Comparison of personal air benzene and urine t,t-muconic acid as a benzene exposure surrogate during turnaround maintenance in petrochemical plants.

Previous studies have shown that biomarkers of chemicals with long half-lives may be better surrogates of exposure for epidemiological analyses, leading to less attenuation of the exposure-disease association, than personal air samples. However, chemicals with short half-lives have shown inconsistent results. In the present study, we compared pairs of personal air benzene and its short-half-life urinary metabolite trans,trans-muconic acid (t,t-MA), and predicted attenuation bias of theoretical exposure-disease association. Total 669 pairs of personal air benzene and urine t,t-MA samples were taken from 474 male workers during turnaround maintenance operations held in seven petrochemical plants. Maintenance jobs were classified into 13 groups. Variance components were calculated for personal air benzene and urine t,t-MA separately to estimate the attenuation of the theoretical exposure-disease association. Personal air benzene and urine t,t-MA showed similar attenuation of the theoretical exposure-disease association. Analyses for repeated measurements showed similar results, while in analyses for values above the limits of detection (LODs), urine t,t-MA showed less attenuation of the theoretical exposure-disease association than personal air benzene. Our findings suggest that there may be no significant difference in attenuation bias when personal air benzene or urine t,t-MA is used as a surrogate for benzene exposure.

Exposure Characteristics of Construction Painters to Organic Solvents.

BACKGROUND: Construction painters have not been studied well in terms of their hazards exposure. The objective of this study was to evaluate the exposure levels of total volatile organic compounds (TVOCs) for painters in the construction industry. METHODS: Activity-specific personal air samplings were carried out in three waterproofing activities [polyurethane (PU), asphalt, and cement mortar] and three painting activities (epoxy, oil based, and water based) by using organic-vapor-monitor passive-sampling devices. Gas chromatograph with flame ionization detector could be used for identifying and quantifying individual organic chemicals. The levels of TVOCs, by summing up 15 targeted substances, were expressed in exposure-index (EI) values. RESULTS: As arithmetic means in the order of concentration levels, the EIs of TVOCs in waterproofing works were 10.77, 2.42, 1.78, 1.68, 0.47, 0.07, and none detected (ND) for indoor PU-primer task, outdoor PU-primer task, outdoor PU-resin task, indoor PU-resin task, asphalt-primer task, asphalt-adhesive task, and cement-mortar task, respectively. The highest EI for painting works was 5.61 for indoor epoxy-primer task, followed by indoor epoxy-resin task (2.03), outdoor oil-based-spray-paint task (1.65), outdoor water-based-paint task (0.66), and indoor oil-based-paint task (0.15). Assuming that the operations were carried out continuously for 8 hours without breaks and by using the arithmetic means of EIs for each of the 12 tasks in this study, 58.3% (7 out of 12) exceeded the exposure limit of 100% (EI > 1.0), while 8.3% (1 out of 12) was in 50-100% of exposure limit (0.5 > EI > 1.0), and 4 tasks out of 12 were located in less than 50% of the limit range (EI < 0.5). CONCLUSION: From this study, we recognized that construction painters are exposed to various solvents, including carcinogens and reproductive toxins, and the levels of TVOC concentration in many of the painting tasks exceeded the exposure limits. Construction workers need to be protected from chemical agents during their painting works by using personal protective devices and/or work practice measures. Additional studies should focus on the exposure assessment of other hazards for construction workers, in order to identify high-risk tasks and to improve hazardous work environments.

Amines as occupational hazards for visual disturbance.

Various amines, such as triethylamine and N,N-dimethylethylamine, have been reported to cause glaucopsia in workers employed in epoxy, foundry, and polyurethane foam industries. This symptom has been related to corneal edema and vesicular collection of fluid within the corneal subepithelial cells. Exposure to amine vapors for 30 min to several hours leads to blurring of vision, a blue-grey appearance of objects, and halos around lights, that are probably reversible. Concentration-effect relationships have been established. The visual disturbance is considered a nuisance, as it could cause onsite accidents, impair work efficiency, and create difficulties in driving back home. Occupational exposure limits have been established for some amines, but there is shortage of criteria. Volatility factors, such as vapor pressure, should be considered in industrial settings to prevent human ocular risks, while trying to reduce levels of hazardous amines in the atmosphere.

Cancer incidence and mortality among temporary maintenance workers in a refinery/petrochemical complex in Korea.

BACKGROUND: Petrochemical plant maintenance workers are exposed to various carcinogens such as benzene and metal fumes. In Korea, maintenance operations in petrochemical plants are typically performed by temporary employees hired as contract workers. OBJECTIVES: The purpose of this retrospective study was to evaluate cancer risk in temporary maintenance workers in a refinery/petrochemical complex in Korea. METHODS: Subjects consisted of 14 698 male workers registered in a regional petrochemical plant maintenance workers union during 2002-2007. Cancer mortality and incidence were identified by linking with the nationwide death and cancer registries during 2002-2007 and 2002-2005, respectively. Standardized mortality ratios (SMRs) and standardized incidence ratios (SIRs) were calculated for each cancer. RESULTS: Increased SMR 3·61 (six cases, 95% CI: 1·32-7·87) and SIR 3·18 (five cases, 95% CI: 1·03-7·42) were observed in oral and pharyngeal cancers. CONCLUSION: Our findings may suggest a potential association between oral and pharyngeal cancers and temporary maintenance jobs in the petrochemical industry. Future studies should include a longer follow-up period and a quantitative exposure assessment.

Quantitative exposure assessment of various chemical substances in a wafer fabrication industry facility.

OBJECTIVES: This study was designed to evaluate exposure levels of various chemicals used in wafer fabrication product lines in the semiconductor industry where work-related leukemia has occurred. METHODS: The research focused on 9 representative wafer fabrication bays among a total of 25 bays in a semiconductor product line. We monitored the chemical substances categorized as human carcinogens with respect to leukemia as well as harmful chemicals used in the bays and substances with hematologic and reproductive toxicities to evaluate the overall health effect for semiconductor industry workers. With respect to monitoring, active and passive sampling techniques were introduced. Eight-hour long-term and 15-minute short-term sampling was conducted for the area as well as on personal samples. RESULTS: The results of the measurements for each substance showed that benzene, toluene, xylene, n-butyl acetate, 2-methoxyethanol, 2-heptanone, ethylene glycol, sulfuric acid, and phosphoric acid were non-detectable (ND) in all samples. Arsine was either "ND" or it existed only in trace form in the bay air. The maximum exposure concentration of fluorides was approximately 0.17% of the Korea occupational exposure limits, with hydrofluoric acid at about 0.2%, hydrochloric acid 0.06%, nitric acid 0.05%, isopropyl alcohol 0.4%, and phosphine at about 2%. The maximum exposure concentration of propylene glycol monomethyl ether acetate (PGMEA) was 0.0870 ppm, representing only 0.1% or less than the American Industrial Hygiene Association recommended standard (100 ppm). CONCLUSION: Benzene, a known human carcinogen for leukemia, and arsine, a hematologic toxin, were not detected in wafer fabrication sites in this study. Among reproductive toxic substances, n-butyl acetate was not detected, but fluorides and PGMEA existed in small amounts in the air. This investigation was focused on the air-borne chemical concentrations only in regular working conditions. Unconditional exposures during spills and/or maintenance tasks and by-product chemicals were not included. Supplementary studies might be required.

Characteristics of Occupational Exposure to Benzene during Turnaround in the Petrochemical Industries.

OBJECTIVES: The level of benzene exposure in the petrochemical industry during regular operation has been well established, but not in turnaround (TA), where high exposure may occur. In this study, the characteristics of occupational exposure to benzene during TA in the petrochemical companies were investigated in order to determine the best management strategies and improve the working environment. This was accomplished by evaluating the exposure level for the workers working in environments where benzene was being produced or used as an ingredient during the unit process. METHODS: From 2003 to 2008, a total of 705 workers in three petrochemical companies in Korea were studied. Long- and short-term (< 1 hr) samples were taken during TAs. TA was classified into three stages: shut-down, maintenance and start-up. All works were classified into 12 occupation categories. RESULTS: The long-term geometric mean (GM) benzene exposure level was 0.025 (5.82) ppm (0.005-42.120 ppm) and the short-term exposure concentration during TA was 0.020 (17.42) ppm (0.005-61.855 ppm). The proportions of TA samples exceeding the time-weighted average, occupational exposure level (TWA-OEL in Korea, 1 ppm) and the short-term exposure limit (STEL-OEL, 5 ppm) were 4.1% (20 samples of 488) and 6.0% (13 samples of 217), respectively. The results for the benzene exposure levels and the rates of exceeding the OEL were both statistically significant (p < 0.05). Among the 12 job categories of petrochemical workers, mechanical engineers, plumbers, welders, fieldman and scaffolding workers exhibited long-term samples that exceeded the OEL of benzene, and the rate of exceeding the OEL was statistically significant for the first two occupations (p < 0.05). CONCLUSION: These findings suggest that the periodic work environment must be assessed during non-routine works such as TA.

Cancer morbidity in iron and steel workers in Korea.

BACKGROUND: In the iron and steel industry, workers are potentially exposed to a number of carcinogens and are involved in a number of processes of a hazardous nature. The cancer morbidity of iron and steel workers from modern plants in a developing country is described. METHODS: Cancer morbidity at two Korean iron and steel complexes was analyzed using Poisson regression methods. Work histories were merged with the national cancer registry for 44,974 workers who were followed from 1988-2001. RESULTS: Four hundred sixty-four cancers, in 1% of the population, were diagnosed over 14 years. Based on national cancer rates, the cohort exhibited a healthy worker effect for all cancer (SIR = 0.87, 95% CI = 0.79-0.95) reflecting relative good health, particularly for lung cancer (SIR = 0.58, 95% CI = 0. 04-0.82), stomach cancer (SIR = 0.78, 95% CI = 0.64-0.93), and liver cancer (SIR = 0.83, 95% CI = 0.68-1.01). Lung cancer morbidity was significantly elevated at the affiliated plants versus the parent plants (SRR = 2.35, 95% CI = 1.07-4.92), and all-cancer morbidity was significantly elevated for maintenance workers compared to office and production workers (SRR = 1.27, 95% CI = 1.00-1.60). Lymphohematopoietic cancer incidence was higher in the coke plants (SRR = 3.46, 95% CI = 1.02-8.91) and stomach cancer incidence was higher in the maintenance departments (SRR = 1.66, 95% CI = 1.05-2.56). CONCLUSIONS: This recent steelworker cohort exhibits possible excess cancer morbidity in some processing areas. Further follow-up of this cohort and alternate study designs such as case-control study will be needed to elucidate the relationship of exposure and health risks of iron and steel workers.

Mortality of iron and steel workers in Korea.

BACKGROUND: The mortality experience of iron and steel workers from modern plants in developing countries has not been extensively described. METHODS: Mortality at two Korean iron and steel manufacturing complexes was analyzed using Poisson regression methods with both direct and indirect standardization. Work histories were linked with a national mortality registry. Workers (44,974) hired beginning in 1968 were followed from 1992 to 2001. RESULTS: The 806 deaths observed during 10 years of follow-up comprised 2% of the population at risk and represented a large healthy worker effect (HWE) for all causes (SMR = 0.59, 95% CI = 0.55-0.63) and for cancer (SMR = 0.79, 95% CI = 0.70-0.90). Mortality at subsidiaries was considerably higher than at the parent plants (SRR = 1.71, 95% CI = 1.47-1.99). Relative mortality rates declined with employment duration: > 20 years had significantly reduced mortality (SRR = 0.59, 95% CI = 0.43-0.82) compared to duration < 1 year (test for trend: P = 0.0006). Fatal injury deaths in the first year were highly elevated (SMR = 3.10, 95% CI = 2.17-4.26) declining to less than that expected after 5 years. Cancer mortality was elevated in stainless steel production (SRR = 3.26, 95% CI = 1.37-6.49) and overall mortality was elevated for work in plant maintenance departments (SRR = 1.17, 95% CI = 1.00-1.37), particularly for fatal injuries (SRR = 1.67, 95% CI = 1.29-2.14). All-cause mortality increased with employment duration in the steel-production departments, as did fatal injuries in material handling/construction. CONCLUSIONS: This steelworker cohort exhibits excess mortality in some process areas. More detailed retrospective exposure assessment and future follow-up of this cohort will better define health risks in the modern iron and steel manufacturing.

Application of EPA CMB8.2 model for source apportionment of sediment PAHs in Lake Calumet, Chicago.

A chemical mass balance model developed by the U.S. EPA, CMB8.2, was used to apportion the major sources of PAHs found in the sediments of Lake Calumet and surrounding wetlands in southeast Chicago. The results indicate the feasibility of applying CMB8.2 to pollutants found in aquatic sediments. To establish the fingerprints of PAH sources, 28 source profiles were collected from the literature. Some of the source profiles were modified based on the gas/particle partitioning of individual PAHs. The profiles under the same source category were averaged, and the fingerprints of six sources were established, including coke oven, residential coal burning, coal combustion in power generation, gasoline engine exhaust, diesel engine exhaust, and traffic tunnel air. Nine model operations with a total of 422 runs were made, differing in the choice of fitting species and the sources involved. Modeling results indicate that coke ovens and traffic are the two major sources of PAHs in the area. For traffic sources, either traffic tunnel alone or both diesel and gasoline engine exhausts were entered into the model. These two groups of model operations produced comparable results with regard to the PAH contributions from road traffic. Although the steel industries have shrunk in recent years, closed and still-active coke plants continue to contribute significantly to the PAH loadings. Overall, the average contribution from coke oven emissions calculated by different operations ranges from 21% to 53% of all sources, and that from traffic ranges from 27% to 63%. The pattern of source contributions shows spatial and temporal variations.

Large-volume injection PTV-GC-MS analysis of polycyclic aromatic hydrocarbons in air and sediment samples.

For the analysis of trace organic pollutants in environmental samples using a gas chromatographic (GC) instrument, large-volume injection using the programmable temperature vaporization (PTV) technique has many advantages over the traditional split/splitless injection. By increasing the injection volume from 1 or 2 microL with a split/splitless inlet to 60 microL or higher with the PTV inlet, analytical sensitivity is greatly enhanced for analytes with low concentrations. Results obtained from optimization of instrument operational parameters for analyzing polycyclic aromatic hydrocarbons (PAHs) are reported in this paper. The laboratory method detection limits for 16 PAHs and six deuterated PAH surrogates were determined using seven replicate spike samples. The initial temperature of the inlet was found to be critical in determining the analytical sensitivity of PAHs with two or three rings due to loss of these relatively highly volatile compounds during solvent vaporization. For most PAHs, the response of the mass spectrometry detector increased proportionally as the total injected volume was increased up to 150 microL. Significant interference from rubber material of the sample vial septa was observed.