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

Exposure Group Development in Support of the NIEHS GuLF Study

In the GuLF Study, a study investigating possible adverse health effects associated with work on the oil spill response and clean-up (OSRC) following the Deepwater Horizon disaster in the Gulf of Mexico, we used a job-exposure matrix (JEM) approach to estimate exposures. The JEM linked interview responses of study participants to measurement data through exposure groups (EGs). Here we describe a systematic process used to develop transparent and precise EGs that allowed characterization of exposure levels among the large number of OSRC activities performed across the Gulf of Mexico over time and space. EGs were identified by exposure determinants available to us in our measurement database, from a substantial body of other spill-related information, and from responses provided by study participants in a detailed interview. These determinants included: job/activity/task, vessel and type of vessel, weathering of the released oil, area of the Gulf of Mexico, Gulf coast state, and time period. Over 3000 EGs were developed for inhalation exposure and applied to each of 6 JEMs of oil-related substances (total hydrocarbons, benzene, toluene, ethylbenzene, total xylene, and n-hexane). Subsets of those EGs were used for characterization of exposures to dispersants, particulate matter, and oil mist. The EGs allowed assignment to study participants of exposure estimates developed from measurement data or from estimation models through linkage in the JEM for the investigation of exposure-response relationships

Estimates of Inhalation Exposures to Oil-Related Components on the Supporting Vessels During the Deepwater Horizon Oil Spill

The Deepwater Horizon oil spill response and clean-up (OSRC) involved over 9000 large and small vessels deployed in waters of the Gulf of Mexico across four states (Alabama, Florida, Louisiana, and Mississippi). For the GuLF STUDY, we developed exposure estimates of oil-related components for many work groups to capture a wide range of OSRC operations on these vessels, such as supporting the four rig vessels charged with stopping the spill at the wellhead; skimming oil; in situ burning of oil; absorbing and containing oil by boom; and environmental monitoring. Work groups were developed by: (i) vessel activity; (ii) location (area of the Gulf or state); and (iii) time period. Using Bayesian methods, we computed exposure estimates for these groups for: total hydrocarbons measured as total petroleum hydrocarbons (THC), benzene, toluene, ethylbenzene, xylene, and n-hexane (BTEX-H). Estimates of the arithmetic means for THC ranged from 0.10 ppm [95% credible interval (CI) 0.04, 0.38 ppm] in time periods 2 and 3 (16 July-30 September 2010) to 15.06 ppm (95% CI 10.74, 22.41 ppm) in time period 1a (22 April-15 May 2010). BTEX-H estimates were substantially lower (in the parts per billion range). Exposure levels generally fell over time and differed statistically by activity, location, and time for some groups. These exposure estimates have been used to develop job-exposure matrices for the GuLF STUDY

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

Development of a total hydrocarbon ordinal job-exposure matrix for workers responding to the Deepwater Horizon disaster: The GuLF STUDY

The GuLF STUDY is a cohort study investigating the health of workers who responded to the Deepwater Horizon oil spill in the Gulf of Mexico in 2010. The objective of this effort was to develop an ordinal job-exposure matrix (JEM) of airborne total hydrocarbons (THC), dispersants, and particulates to estimate study participants' exposures. Information was collected on participants' spill-related tasks. A JEM of exposure groups (EGs) was developed from tasks and THC air measurements taken during and after the spill using relevant exposure determinants. THC arithmetic means were developed for the EGs, assigned ordinal values, and linked to the participants using determinants from the questionnaire. Different approaches were taken for combining exposures across EGs. EGs for dispersants and particulates were based on questionnaire responses. Considerable differences in THC exposure levels were found among EGs. Based on the maximum THC level participants experienced across any job held, 1/414% of the subjects were identified in the highest exposure category. Approximately 10% of the cohort was exposed to dispersants or particulates. Considerable exposure differences were found across the various EGs, facilitating investigation of exposure-response relationships. The JEM is flexible to allow for different assumptions about several possibly relevant exposure metrics

Large-scale pharmacogenomic study of sulfonylureas and the QT, JT and QRS intervals: CHARGE Pharmacogenomics Working Group

Sulfonylureas, a commonly used class of medication used to treat type 2 diabetes, have been associated with an increased risk of cardiovascular disease. Their effects on QT interval duration and related electrocardiographic phenotypes are potential mechanisms for this adverse effect. In 11 ethnically diverse cohorts that included 71 857 European, African-American and Hispanic/Latino ancestry individuals with repeated measures of medication use and electrocardiogram (ECG) measurements, we conducted a pharmacogenomic genome-wide association study of sulfonylurea use and three ECG phenotypes: QT, JT and QRS intervals. In ancestry-specific meta-analyses, eight novel pharmacogenomic loci met the threshold for genome-wide significance (P<5 × 10−8), and a pharmacokinetic variant in CYP2C9 (rs1057910) that has been associated with sulfonylurea-related treatment effects and other adverse drug reactions in previous studies was replicated. Additional research is needed to replicate the novel findings and to understand their biological basis

Linear Relationships Between Total Hydrocarbons and Benzene, Toluene, Ethylbenzene, Xylene, and n-Hexane during the Deepwater Horizon Response and Clean-up

Objectives: Our objectives were to (i) determine correlations between measurements of THC and of BTEX-H, (ii) apply these linear relationships to predict BTEX-H from measured THC, (iii) use these correlations as informative priors in Bayesian analyses to estimate exposures. Methods: We used a Bayesian left-censored bivariate framework for all 3 objectives. First, we modeled the relationships (i.e. correlations) between THC and each BTEX-H chemical for various overarching groups of measurements using linear regression to determine if correlations derived from linear relationships differed by various exposure determinants. We then used the same linear regression relationships to predict (or impute) BTEX-H measurements from THC when only THC measurements were available. Finally, we used the same linear relationships as priors for the final exposure models that used real and predicted data to develop exposure estimate statistics for each individual exposure group. Results: Correlations between measurements of THC and each of the BTEX-H chemicals (n = 120 for each of BTEX, 36 for n-hexane) differed substantially by area of the Gulf of Mexico and by time period that reflected different oil-spill related exposure opportunities. The correlations generally exceeded 0.5. Use of regression relationships to impute missing data resulted in the addition of >23 000 n-hexane and 541 observations for each of BTEX. The relationships were then used as priors for the calculation of exposure statistics while accounting for censored measurement data. Conclusions: Taking advantage of observed relationships between THC and BTEX-H allowed us to develop robust exposure estimates where a large amount of data were missing, strengthening our exposure estimation process for the epidemiologic study

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

Theory and simulation of quantum photovoltaic devices based on the non-equilibrium Green's function formalism

This article reviews the application of the non-equilibrium Green's function formalism to the simulation of novel photovoltaic devices utilizing quantum confinement effects in low dimensional absorber structures. It covers well-known aspects of the fundamental NEGF theory for a system of interacting electrons, photons and phonons with relevance for the simulation of optoelectronic devices and introduces at the same time new approaches to the theoretical description of the elementary processes of photovoltaic device operation, such as photogeneration via coherent excitonic absorption, phonon-mediated indirect optical transitions or non-radiative recombination via defect states. While the description of the theoretical framework is kept as general as possible, two specific prototypical quantum photovoltaic devices, a single quantum well photodiode and a silicon-oxide based superlattice absorber, are used to illustrated the kind of unique insight that numerical simulations based on the theory are able to provide.Comment: 20 pages, 10 figures; invited review pape

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