Associations between airborne crude oil chemicals and symptom-based asthma.

RATIONALE: The 2010 Deepwater Horizon (DWH) oil spill response and cleanup (OSRC) workers were exposed to airborne total hydrocarbons (THC), benzene, toluene, ethylbenzene, o-, m-, and p-xylenes and n-hexane (BTEX-H) from crude oil and PM2.5 from burning/flaring oil and natural gas. Little is known about asthma risk among oil spill cleanup workers. OBJECTIVES: We assessed the relationship between asthma and several oil spill-related exposures including job classes, THC, individual BTEX-H chemicals, the BTEX-H mixture, and PM2.5 using data from the Gulf Long-Term Follow-up (GuLF) Study, a prospective cohort of 24,937 cleanup workers and 7,671 nonworkers following the DWH disaster. METHODS: Our analysis largely focused on the 19,018 workers without asthma before the spill who had complete exposure, outcome, and covariate information. We defined incident asthma 1-3 years following exposure using both self-reported wheeze and self-reported physician diagnosis of asthma. THC and BTEX-H were assigned to participants based on measurement data and work histories, while PM2.5 used modeled estimates. We used modified Poisson regression to estimate risk ratios (RR) and 95% confidence intervals (CIs) for associations between spill-related exposures and asthma and a quantile-based g-computation approach to explore the joint effect of the BTEX-H mixture on asthma risk. RESULTS: OSRC workers had greater asthma risk than nonworkers (RR: 1.60, 95% CI: 1.38, 1.85). Higher estimated THC exposure levels were associated with increased risk in an exposure-dependent manner (linear trend test p < 0.0001). Asthma risk also increased with increasing exposure to individual BTEX-H chemicals and the chemical mixture: A simultaneous quartile increase in the BTEX-H mixture was associated with an increased asthma risk of 1.45 (95% CI: 1.35,1.55). With fewer cases, associations were less apparent for physician-diagnosed asthma alone. CONCLUSIONS: THC and BTEX-H were associated with increased asthma risk defined using wheeze symptoms as well as a physician diagnosis.

Assessing Exposures from the Deepwater Horizon Oil Spill Response and Clean-up.

The GuLF Study is investigating adverse health effects from work on the response and clean-up after the Deepwater Horizon explosion and oil release. An essential and necessary component of that study was the exposure assessment. Bayesian statistical methods and over 135 000 measurements of total hydrocarbons (THC), benzene, ethylbenzene, toluene, xylene, and n-hexane (BTEX-H) were used to estimate inhalation exposures to these chemicals for >3400 exposure groups (EGs) formed from three exposure determinants: job/activity/task, location, and time period. Recognized deterministic models were used to estimate airborne exposures to particulate matter sized 2.5 µm or less (PM2.5) and dispersant aerosols and vapors. Dermal exposures were estimated for these same oil-related substances using a model modified especially for this study from a previously published model. Exposures to oil mist were assessed using professional judgment. Estimated daily THC arithmetic means (AMs) were in the low ppm range (<25 ppm), whereas BTEX-H exposures estimates were generally <1000 ppb. Potential 1-h PM2.5 air concentrations experienced by some workers may have been as high as 550 µg m-3. Dispersant aerosol air concentrations were very low (maximum predicted 1-h concentrations were generally <50 µg m-3), but vapor concentrations may have exceeded occupational exposure excursion guidelines for 2-butoxyethanol under certain circumstances. The daily AMs of dermal exposure estimates showed large contrasts among the study participants. The estimates are being used to evaluate exposure-response relationships in the GuLF Study.

Comparative analysis of groundwater quality statuses and associated health risk indices of metals and total hydrocarbons at locations of tank farm in Delta State, Nigeria.

The study aimed at assessing the groundwater quality and the associated health implications of oil storage tank farms in Asaba, Oghara, Warri, and Koko towns, in Delta State, Nigeria. Fe, Cr, Cd, Ni, Pb, and V concentrations in the groundwater samples were determined using Atomic Absorption Spectrophotometry (AAS), while total hydrocarbons (THC) concentrations were determined using gas chromatography coupled with a flame ionization detector (GC-FID). The quality index of Warri groundwater was 66.38; being within the range of 51-75 was considered poor quality. The water quality indices (WQI) of Oghara, Koko, and Asaba were 163.79, 161.43, and 129.95 respectively, which were all > 100, hence amounting to very poor water quality status. Results indicated that children in Oghara who are orally exposed to chromium are at risk of cancer. Both adults and children orally exposed to THC in Oghara are also at risk of cancer. Furthermore, THC posed an oral route cancer risk to the children in Koko town. The study showed that chromium posed carcinogenic threats to children in Oghara, while THC posed carcinogenic threats to adults and children in Oghara and children alone in Koko. These risks are liable to be mediated through ingestion of the groundwater of Oghara and Koko by the susceptible groups.

Estimates of Occupational Inhalation Exposures to Six Oil-Related Compounds on the Four Rig Vessels Responding to the Deepwater Horizon Oil Spill.

BACKGROUND: The 2010 Deepwater Horizon (DWH) oil spill involved thousands of workers and volunteers to mitigate the oil release and clean-up after the spill. Health concerns for these participants led to the initiation of a prospective epidemiological study (GuLF STUDY) to investigate potential adverse health outcomes associated with the oil spill response and clean-up (OSRC). Characterizing the chemical exposures of the OSRC workers was an essential component of the study. Workers on the four oil rig vessels mitigating the spill and located within a 1852 m (1 nautical mile) radius of the damaged wellhead [the Discoverer Enterprise (Enterprise), the Development Driller II (DDII), the Development Driller III (DDIII), and the HelixQ4000] had some of the greatest potential for chemical exposures. OBJECTIVES: The aim of this paper is to characterize potential personal chemical exposures via the inhalation route for workers on those four rig vessels. Specifically, we presented our methodology and descriptive statistics of exposure estimates for total hydrocarbons (THCs), benzene, toluene, ethylbenzene, xylene, and n-hexane (BTEX-H) for various job groups to develop exposure groups for the GuLF STUDY cohort. METHODS: Using descriptive information associated with the measurements taken on various jobs on these rig vessels and with job titles from study participant responses to the study questionnaire, job groups [unique job/rig/time period (TP) combinations] were developed to describe groups of workers with the same or closely related job titles. A total of 500 job groups were considered for estimation using the available 8139 personal measurements. We used a univariate Bayesian model to analyze the THC measurements and a bivariate Bayesian regression framework to jointly model the measurements of THC and each of the BTEX-H chemicals separately, both models taking into account the many measurements that were below the analytic limit of detection. RESULTS: Highest THC exposures occurred in TP1a and TP1b, which was before the well was mechanically capped. The posterior medians of the arithmetic mean (AM) ranged from 0.11 ppm ('Inside/Other', TP1b, DDII; and 'Driller', TP3, DDII) to 14.67 ppm ('Methanol Operations', TP1b, Enterprise). There were statistical differences between the THC AMs by broad job groups, rigs, and time periods. The AMs for BTEX-H were generally about two to three orders of magnitude lower than the THC AMs, with benzene and ethylbenzene measurements being highly censored. CONCLUSIONS: Our results add new insights to the limited literature on exposures associated with oil spill responses and support the current epidemiologic investigation of potential adverse health effects of the oil spill.

Using Real-Time Area VOC Measurements to Estimate Total Hydrocarbons Exposures to Workers Involved in the Deepwater Horizon Oil Spill.

Even though the Deepwater Horizon oil spill response and clean-up (OSRC) had one of the largest exposure monitoring efforts of any oil spill, a number of exposure groups did not have sufficient personal data available or there were gaps in days measured to adequately characterize exposures for the GuLF STUDY, an epidemiologic study investigating the health of the OSRC workers. Area measurements were available from real-time air monitoring instruments and used to supplement the personal exposure measurements. OBJECTIVES: The objective was to present a method that used real-time volatile organic compounds (VOCs) area measurements transformed to daily total hydrocarbons (THC) time-weighted averages (TWAs) to supplement THC personal full-shift measurements collected using passive charcoal badges. A second objective was to develop exposure statistics using these data for workers on vessels piloting remotely operated vehicle (ROV) vessels and other marine vessels (MVs) not at the job title level, but at the vessel level. METHODS: From hourly vessel averages derived from ~26 million real-time VOC measurements, we estimated full-shift VOC TWAs. Then, we determined the relationship between these TWAs and corresponding full-shift THC personal measurements taken on the same vessel-day. We used this relationship to convert the full-shift VOC measurements to full-shift 'THC' TWA estimates when no personal THC measurements existed on a vessel-day. We then calculated arithmetic means (AMs) and other statistics of THC exposures for each vessel. RESULTS: The VOC-derived estimates substantially supplemented the THC personal measurements, with the number of vessel-days for which we have exposure estimates increasing by ~60%. The estimates of the AMs are some of the highest observed in the GuLF STUDY. As expected, the AMs decreased over time, consistent with our findings on other vessels. CONCLUSIONS: Despite the inherent limitations of using real-time area measurements, we were able to develop additional daily observations of personal THC exposures for workers on the ROV vessels and other MVs over time. The estimates likely resulted in more representative estimates of the AMs in the GuLF STUDY. The method used here can be applied in other occupational settings and industries for personal exposure estimation where large amounts of area measurements and more limited numbers of personal measurements are available.

Estimation of Dermal Exposure to Oil Spill Response and Clean-up Workers after the Deepwater Horizon Disaster.

The GuLF STUDY is investigating health outcomes associated with oil spill-related chemical exposures among workers involved in the spill response and clean-up following the Deepwater Horizon disaster. Due to the lack of dermal exposure measurements, we estimated dermal exposures using a deterministic model, which we customized from a previously published model. Workers provided information on the frequency of contact with oil, tar, chemical dispersants applied to the oil spill and sea water, as well as the use of protective equipment, by job/activity/task. Professional judgment by industrial hygienists served as a source of information for other model variables. The model estimated dermal exposures to total hydrocarbons (THC), benzene, ethylbenzene, toluene, xylene, n-hexane (BTEX-H), polycyclic aromatic hydrocarbons (PAHs), and dispersants in GuLF DREAM units (GDUs). Arithmetic means (AMs) of THC exposure estimates across study participants ranged from <0.02 to 5.50 GDUs for oil and <0.02 to 142.14 GDUs for tar. Statistical differences in the estimates were observed among the AMs of the estimates for some broad groups of worker activities over time and for some time periods across the broad groups of activities. N-Hexane had ranges similar to THC for oil exposures (e.g. AMs up to 2.22 GDUs) but not for tar (up to 5.56 GDUs). Benzene, ethylbenzene, toluene, and xylene, in contrast, were characterized by higher exposure levels than THC for oil (AMs up to 12.77, 12.17, 17.45, and 36.77 GDUs, respectively) but lower levels than THC to tar (AMs up to 3.69, 11.65, 42.37, and 88.18 GDUs, respectively). For PAHs, the AMs were as high as 219.31 and 587.98 for oil and tar, respectively. Correlations of these seven substances to each other were high (>0.9) for most of the substances in oil but were lower for some of the substances in tar. These data were linked to the study participants to allow investigation of adverse health effects that may be related to dermal exposures.

Estimates of Inhalation Exposures among Land Workers during the Deepwater Horizon Oil Spill Clean-up Operations.

Following the Deepwater Horizon oil spill disaster, thousands of workers and volunteers cleaned the shoreline across four coastal states of the Gulf of Mexico. For the GuLF STUDY, we developed quantitative estimates of oil-related chemical exposures [total petroleum hydrocarbons (THC), benzene, toluene, ethylbenzene, xylene, and n-hexane (BTEX-H)] from personal measurements on workers performing various spill clean-up operations on land. These operations included decontamination of vessels, equipment, booms, and personnel; handling of oily booms; hazardous waste management; beach, marsh, and jetty clean-up; aerial missions; wildlife rescue and rehabilitation; and administrative support activities. Exposure estimates were developed for unique groups of workers by (i) activity, (ii) state, and (iii) time period. Estimates of the arithmetic means (AMs) for THC ranged from 0.04 to 3.67 ppm. BTEX-H estimates were substantially lower than THC (in the parts per billion range). Both THC and BTEX-H estimates were substantially lower than their respective occupational exposure limits. The work group, 'Fueled engines' consistently was one of the higher exposed groups to THC and BTEX-H. Notable differences in the AM exposures were observed by activity, time and, to a lesser degree, by state. These exposure estimates were used to develop job-exposure matrices for the GuLF STUDY.

Lung function in oil spill responders 4-6 years after the Deepwater Horizon disaster.

Oil spill response and clean-up (OSRC) workers were exposed to hazardous airborne chemicals following the 2010 Deepwater Horizon disaster. The aim of this study was to evaluate lung function in workers 4-6 years following the disaster using a prospective cohort. Participants who completed two spirometry test sessions 1-3 years, and 4-6 years after the spill (N = 1,838) were included and forced expiratory volume in 1 s (FEV1; ml), forced vital capacity (FVC; ml), and ratio (FEV1/FVC; %) determined. Linear mixed models were utilized to estimate relationships between OSRC exposures and lung function 4-6 years after the spill and changes since the prior measurement. Despite suggestive reduced lung function at 1-3 years, at the  4-6-year exam workers with total hydrocarbon (THC) exposure 1-2.99 ppm and ≥3 ppm compared to those with ≤0.29 ppm exhibited higher FEV1 (ß: 108 ml, 95% CI: 17, 198) and (ß: 118 ml, 95% CI: 5, 232), respectively. Compared with support workers, those in higher exposed jobs displayed greater improvement in FEV1 between visits: cleanup on water (ß: 143 ml, 95% CI: 35, 250), operations (ß: 132 ml, 95% CI: 30, 234) and response (ß: 149 ml, 95% CI: 43, 256). Greater FEV1 improvement was also associated with higher versus the lowest level THC exposure: 1-2.99 ppm (ß: 134 ml, 95% CI: 57, 210) and ≥3 ppm (ß: 205 ml, 95% CI: 109, 301). Lung function decrements seen shortly after the spill were no longer apparent 4-6 years later, with the greatest improvement among those with the highest exposures.

[Emission Status and Standards of Volatile Organic Compounds from Chinese and Foreign Bulk Petroleum Terminals].

Chinese emission standard of air pollutants for bulk gasoline terminals (GB 20950-2007) stipulate standards for vapor emissions during gasoline storage and receiving in bulk gasoline terminals. However, the standards are not applicable to crude oil, aviation kerosene, naphtha, and other kinds of oil. We assess emission standards or directives for vapor processing equipment in terminals in the United States (US) and European Union (EU), and analyze the emission status of vapor processing equipment in three typical cities in China. We further propose revisions to GB 20950-2007. We made the following observations. ① US and EU standards include scope not only for gasoline, but also crude oil and other organic liquids. ② The emission limits of non-methane hydrocarbons defined in GB 20950-2007 are i) 0.5, 1.8, and 8.9 times those defined in Subpart XX, Subpart R, and Subpart Y in the US federal regulations, ii) 1.8 and 3.1 times those defined in Rule 462 and Rule 1142 in southern California law, and iii) 0.7 and 500 times those defined in EU and German directives, respectively. The vapor leakage limit for general areas of China is 0.5 times that defined in Subpart XX of the US standards, whereas the limits for some other specific areas of China, are 0.7 and 2.0 times those defined by Rule 462 and Rule 1142 in southern California law. ③ The numerical range of P5th-P95th of NMHC emissions from the inlet and outlet of vapor processing equipment in three typical cities of China were 115-811 g·m-3 and 0.1-20.0 g·m-3, respectively. The proportion of NMHC emission concentrations less than or equal to 10 g·m-3 at the outlet of vapor processing equipment was>85%. We suggest that the scope of application of GB 20950-2007 should be extended to crude oil, gasoline (including ethanol gasoline), aviation kerosene, and naphtha. The emission concentration limit of NMHC from vapor processing equipment should be tighten from 25 g·m-3 to 20 g·m-3, with a emission limit of 10 g·m-3 added for particular cases.

Airborne exposures associated with the typical use of an aerosol brake cleaner during vehicle repair work.

Many petroleum-based products are used for degreasing and cleaning purposes during vehicle maintenance and repairs. Although prior studies have evaluated chemical exposures associated with this type of work, most of these have focused on gasoline and exhaust emissions, with few samples collected solely during the use of an aerosol cleaning product. In this case study, we assess the type of airborne exposures that would be expected from the typical use of an aerosol brake cleaner during vehicle repair work. Eight exposure scenarios were evaluated over a 2-day study in which the benzene content of the brake cleaner and potential for dilution ventilation and air flow varied. Both short-term (15 min) and task-based (≥1 hr) charcoal tube samples were collected in the breathing zone and adjacent work area and analyzed for total hydrocarbons (THCs), toluene, and benzene. The majority of personal (N = 48) and area (N = 47) samples had detectable levels of THC and toluene, but no detections of benzene were found. For the personal short-term samples, average airborne concentrations ranged from 3.1-61.5 ppm (13.8-217.5 mg/m3) for THC and 2.2-44.0 ppm (8.2-162.5 mg/m3) for toluene, depending on the scenario. Compared to the personal short-term samples, average concentrations were generally 2-3 times lower for the personal task-based samples and 2-5 times lower for the area short-term samples. The highest exposures occurred when the garage bay doors were closed, floor fan was turned off, or greatest amount of brake cleaner was used. These findings add to the limited dataset on this topic and can be used to bound or approximate worker or consumer exposures from use of aerosol cleaning products with similar compositions and use patterns.

Assessment and ecological indicators of total and polycyclic aromatic hydrocarbons in the aquatic environment of lake Manzala, Egypt.

The study objective was to assess the profile of aliphatic and polycyclic aromatic hydrocarbons in the aquatic environment of Lake Manzala and to determine the potential sources and effects of these hydrocarbons. To reach these objectives 24 surface sediment and 24 tilapia fish were collected and analyzed using GC-FID and GC-MS. The highest concentrations for n-alkanes (∑n-C15-35) (19,625 ng g-1) and PAHs (∑45PAHs) (5,153 ng g-1) were found in sediments collected from Bahr Al-Baqar drain while Al-Temsah and Al-Hamra sites contained the lowest concentrations. Different diagnostic molecular ratios for hydrocarbons were used to evaluate sources of the hydrocarbons. The hydrocarbons were found to have differing proportions of petrogenic, pyrogenic, and biogenic sources. Comparison to sediment quality guidelines indicated PAHs were below the effect range low (ERL) with the exception of acenaphthene, fluorine, and ∑45PAHs in Bahr Al-Baqar drain sediments. Tissue samples had moderate PAH concentrations for ∑45PAHs ranging from 302.5 ng g-1 West of Bashteer (S3) to 596 ng g-1 in Legam (S5). Since fish metabolize PAH quickly, their detection suggest continual or very recent exposure. The PAH in sediment and fish from Lake Manzala are at a low or below level of environmental concern.

Treatment of synthetic refinery wastewater in anoxic-aerobic sequential moving bed reactors and sulphur recovery.

Objective of the present study was to simultaneously biodegrade synthetic petroleum refinery wastewater containing phenol (750 mg/L), sulphide (750 mg/L), hydrocarbon (as emulsified diesel of 300 mg/L), ammonia-nitrogen (350 mg/L) at pH >9 in anoxic-aerobic sequential moving bed reactors. The optimum mixing speed of anoxic reactor was observed at 20 rpm and beyond that, removal rate remained constant. In anoxic reactor the minimum hydraulic retention time was observed to be 2 days for complete removal of sulphide, 40-50% removal of phenol and total hydrocarbons and 52% of sulphur recovery. The optimum HRT of aerobic moving bed reactor was observed as 16 h (total HRT of 64 h for anoxic and aerobic reactors) for complete removals of phenol, total hydrocarbons, COD (chemical oxygen demand) and ammonia-nitrogen with nitrification.

JP8 exposure and neurocognitive performance among US Air Force personnel.

Petroleum-based fuels such as jet propellant (JP) 4, JP5, JP8, and jet A1 (JetA) are among the most common occupational chemical exposures encountered by military and civilian workforces. Although acute toxicity following high-level exposures to JP8 and similar chemical mixtures has been reported, the relationship between persistent low-level occupational exposures to jet fuels and both acute and longer-term central nervous system (CNS) function has been comparatively less well characterized. This paper describes results of neurocognitive assessments acquired repeatedly across a work week study design (Friday to Friday) as part of the Occupational JP8 Exposure Neuroepidemiology Study (OJENES) involving U.S. Air Force (AF) personnel with varying levels of exposure to jet fuel (JP8). JP8 exposure levels were quantified using both personal air monitoring and urinary biomarkers of exposure. Neurocognitive performance was evaluated using an objective, standardized battery of tests. No significant associations with neurocognitive performances were observed between individuals having regular contact and those with minimal/no direct contact with JP8 (measured by average work week levels of personal breathing zone exposure). Also, no significant findings were noted between repeated measures of absorbed dose (multi-day pre-shift urinary 1- and 2-naphthol) and reduced proficiency on neurocognitive tasks across the work week. Results suggest that occupational exposure to lower (than regulated standards) levels of JP8 do not appear to be associated with acute, measurable differences or changes in neurocognitive performance.

Bivariate Left-Censored Bayesian Model for Predicting Exposure: Preliminary Analysis of Worker Exposure during the Deepwater Horizon Oil Spill.

In April 2010, the Deepwater Horizon oil rig caught fire and exploded, releasing almost 5 million barrels of oil into the Gulf of Mexico over the ensuing 3 months. Thousands of oil spill workers participated in the spill response and clean-up efforts. The GuLF STUDY being conducted by the National Institute of Environmental Health Sciences is an epidemiological study to investigate potential adverse health effects among these oil spill clean-up workers. Many volatile chemicals were released from the oil into the air, including total hydrocarbons (THC), which is a composite of the volatile components of oil including benzene, toluene, ethylbenzene, xylene, and hexane (BTEXH). Our goal is to estimate exposure levels to these toxic chemicals for groups of oil spill workers in the study (hereafter called exposure groups, EGs) with likely comparable exposure distributions. A large number of air measurements were collected, but many EGs are characterized by datasets with a large percentage of censored measurements (below the analytic methods' limits of detection) and/or a limited number of measurements. We use THC for which there was less censoring to develop predictive linear models for specific BTEXH air exposures with higher degrees of censoring. We present a novel Bayesian hierarchical linear model that allows us to predict, for different EGs simultaneously, exposure levels of a second chemical while accounting for censoring in both THC and the chemical of interest. We illustrate the methodology by estimating exposure levels for several EGs on the Development Driller III, a rig vessel charged with drilling one of the relief wells. The model provided credible estimates in this example for geometric means, arithmetic means, variances, correlations, and regression coefficients for each group. This approach should be considered when estimating exposures in situations when multiple chemicals are correlated and have varying degrees of censoring.

The phytoremediation of an organic and inorganic polluted soil: A real scale experience.

A phytoremediation process with horse manure, plants (Populus alba, Cytisus scoparius, Paulownia tomentosa) and naturally growing vegetation was carried out at a real-scale in order to phytoremediate and functionally recover a soil contaminated by metals (Zn, Pb, Cd, Ni, Cu, Cr), hydrocarbons (TPH) and polychlorobiphenyls (PCB). All the plants were effective in two years in the reclamation of the polluted soil, showing an average reduction of about 35%, 40%, and 70% in metals, TPH and PCB content, respectively. As regards the plants, the poplar contributed the most to organic removal. In fact, its ability to take up and detoxify organic pollutants is well known. Paulownia tomentosa, instead, showed high metal removal. The Cytisus scoparius was the least effective plant in soil decontamination. The recovery of soil functionality was followed by enzyme activities, expressing the biochemical processes underway, and nutrient content useful for plant growth and development. Throughout the area, an enhancement of metabolic processes and soil chemical quality was observed. All the enzymatic activities showed a general increase over time (until 3-4 fold than the initial value for urease and ß-glucosidase). Moreover, Cytisus scoparius, even though it showed a lower decontamination capability, was the most effective in soil metabolic stimulation.