Design of Non-Invasive Systems for Detection of Exogenous and Endogenous Volatile Compounds for Applications in Environmental Exposure and Health Diagnostics

The analysis of volatile organic compounds (VOCs) and semi-VOCs and their relation to health, environmental, and occupational exposure is investigated. The research in this dissertation highlights the endogenous and exogenous volatile organic compounds that are best suited as targets in health and occupational contexts. Target VOCs and the resulting breath profiles are used to produce proof of concept designs for information and diagnostic early-warning systems. Carcinogenic exogenous and semi-VOCs, including polyaromatic hydrocarbons and BTX compounds (i.e., benzene, toluene, and xylene derivatives), were the subjects of exposure monitoring. These compounds were identified and quantified in the firefighter demographic, which is known to exhibit a higher incidence of certain cancers compared to the general population. Silicone-based passive sampling is used in conjunction with chemical diagnostic ratios of sorbed compounds of interest for improved exposure profiles. Endogenous volatile organic compounds result in breath profile changes within exhaled breath. In that regard, a drowsiness detection system was developed that can monitor breath profile changes with the prospect of producing a non-invasive diagnostic system to integrate into the automobile and workplace. Applications of endogenous VOCs for rapid diagnostics for disease and health through the context of breath analysis are also discussed. In both scenarios, real-time and off-line methods of sampling and analysis are utilized for determining profiles in varying matrices.</div

Self‐reported and objectively measured occupational exposures, health, and safety concerns among fishermen: A cross‐sectional Fishing Industry Safety and Health (FISH) pilot study

Background Fishing industry workers are exposed to hazardous working conditions, engage in strenuous labor, and work long hours in variable weather conditions. Despite these known employment challenges, little is known of their perceived occupational health and safety concerns. In this pilot study, we: (1) describe fishermen's perceptions on worker‐ and organizational‐level characteristics that impact occupational health and safety; and (2) estimate environmental exposure to polycyclic aromatic hydrocarbons (PAHs) encountered during fishing activities. Methods We collected both qualitative and quantitative data from Mississippi and Florida fishermen. Using an ethnographic approach, the study team conducted 1‐h key informant interviews, administered a one‐page demographic survey, and collected objective measurements to PAHs using silicone‐based passive sampling wristbands. Results Study participants (n = 17) had a mean age of 50.9 years (SD = 11.7), 88.2% were male, 94.1% white, 100.0% non‐Hispanic/Latino, and 52.9% were married. Approximately, 87.5% reported fishing as their primary job, with a mean of 26.4 years in the industry (SD = 15.3). Four broad themes describing the culture of the fishing industry, common workplace exposures that impact fishermen's safety and health, and facilitators and barriers to safety while working in the fishing industry were documented. Deckhands had the lowest mean exposure to PAHs (8.3 ppb), followed by crew members (11.0 ppb), captains (82.64 ppb), and net makers (208.1 ppb). Conclusions Gulf coast fishermen expressed specific occupational health and safety concerns and were exposed to carcinogenic PAHs during regular work. Opportunities exist and strategies are needed for health protection and health promotion interventions among Gulf fishermen

Abstract A29: Silicone-based wristband passive samplers in the detection of firefighter occupational carcinogenic exposures

Introduction: First responders (i.e., paramedics and firefighters) are exposed to hazardous chemicals such as polycyclic aromatic hydrocarbons (PAHs)in the conduct of their work duties. Linking mixed chemical exposures to health conditions (e.g., cancer) is difficult given the latency period of disease, the magnitude of the potential doses, or interactions of carcinogenic compounds present while firefighting. To understand the relationship between environmental exposures and resulting toxicity, passive personal sampling devices (PSDs) have been used to monitor. In the present study, we 1) describe the type of chemical exposures encountered by firefighters in their work environment, 2) characterize and compare chemical exposures by work-shift activities (e.g., fire suppression, emergency medical services, hazmat), and 3) field test the use of silicone-based wristbands for monitoring chemical exposures in firefighters. Methods: Twenty-four wristbands were deployed across various fire services throughout South Florida. Prior to deployment, bands were cleaned using a standardized cleaning protocol to remove contamination and optimize the surface for absorption. Wristbands were then packaged in airtight bags to prevent contamination. Wristbands were worn on fire service personnel and collected at the end of a 24-hour work shift. Chemical contaminants were then extracted from the wristband and analyzed for PAHs—identified using the EPA IRIS, California Proposition 65, and IRAC datasets—using gas chromatography-mass spectrometry. Results: The average number of chemicals found across all wristbands (n=24) was 23 with 4 categorized as carcinogenic to humans (i.e., benzo[b]fluoranthene, benzo[j]fluoranthene, chrysene, and naphthalene). All bands had at least one PAH present, specifically, 87.5% contained benzo[b]fluoranthene (mean=5.23 ng/band), 50% contained benzo[j]fluoranthene (mean=2.05 ng/band), 79.2% contained chrysene (mean=9.55 ng/band), and 100% contained napthalene (mean=176.53 ng/band). Actual types of exposure compounds are likely to be larger than the observed data as the group of PAHs detected was limited to three existing datasets. Discussion: Silicone-based wristbands are feasible to use within the fire service to detect and characterize ambient hazardous chemical compounds. These personal self-samplers used during a 24-hour collection period identified various PAHs in the firefighter work environment. Objective measures of harmful chemical exposures in the fire service should be monitored with a comprehensive surveillance system that includes personal sampler devices. Citation Format: Alberto J. Caban-Martinez, Katerina M. Santiago, Jeramy Baum, Natasha N. Schaefer Solle, Sylvia Daunert, Sapna Deo, Erin N. Kobetz. Silicone-based wristband passive samplers in the detection of firefighter occupational carcinogenic exposures [abstract]. In: Proceedings of the AACR Special Conference on Environmental Carcinogenesis: Potential Pathway to Cancer Prevention; 2019 Jun 22-24; Charlotte, NC. Philadelphia (PA): AACR; Can Prev Res 2020;13(7 Suppl): Abstract nr A29

O1D.2 Objective measurement of work-environment carcinogenic exposures in florida firefighters using silicone-based passive sampling wristbands

Firefighters are likely to be exposed to many toxic chemicals in the performance of their work duties such as polycyclic aromatic hydrocarbons (PAHs). Chemical exposures may occur through dermal, oral, or inhalation pathways. Passive sampling devices are used to sequester organic molecules through passive diffusion and provide time-weighted averages of chemical concentrations. This pilot study uses silicone-based wristbands as a personal passive sampler to detect known carcinogens during a 24 hour work shift. Twenty-four wristbands were deployed across various fire services throughout South Florida. Prior to deployment, bands were cleaned using a standardized cleaning protocol to remove contamination and optimize the surface for absorption. Wristbands were then packaged in air-tight bags to prevent contamination. Wristbands were worn on fire service personnel and collected at the end of a 24 hour work shift. Chemical contaminants were then extracted from the wristband and analyzed for PAHs—identified using the EPA IRIS, California Proposition 65, and IRAC datasets— using gas chromatography-mass spectrometry. The average number of chemicals found across all wristbands (n=24) was 23 with 4 categorized as carcinogenic to humans (i.e., Benzo[b]fluoranthene, Benzo[j]fluoranthene, Chrysene, and Naphthalene). All bands had at least one PAH present, specifically, 87.5% contained Benzo[b]fluoranthene (mean=5.23 ng/band), 50% contained Benzo[j]fluoranthene (mean=2.05 ng/band), 79.2% contained Chrysene (mean=9.55 ng/band), and 100% contained Napthalene (mean=176.53 ng/band). Actual types of exposure compounds is likely to be larger than the observed data as the group of PAHs detected was limited to three existing datasets. Silicone-based wristbands are feasible to use within the fire service to detect and characterize ambient hazardous chemical compounds. These personal self-samplers used during a 24 hour collection period identified various PAHs in the firefighter work environment. Objective measures of harmful chemical exposures in the fire service should be monitored with a comprehensive surveillance system that includes personal sampler devices

The “Warm Zone” Cases: Environmental Monitoring Immediately Outside the Fire Incident Response Arena by Firefighters

Hazardous work zones (i.e., hot, warm, and cold) are typically established by emergency response teams during hazardous materials (HAZMAT) calls but less consistently for fire responses to segment personnel and response activities in the immediate geographic area around the fire. Despite national guidelines, studies have documented the inconsistent use of respiratory protective equipment by firefighters at the fire scene. In this case-series report, we describe warm zone gas levels using multigas detectors across five independent fire incident responses all occurring in a large South Florida fire department. Multigas detector data collected at each fire response indicate the presence of sustained levels of volatile organic compounds in the “warm zone” of each fire event. These cases suggest that firefighters should not only implement strategies for multigas detector use within the warm zone but also include respiratory protection to provide adequate safety from toxic exposures in the warm zone. Keywords: Firefighters, Multigas detectors, Respiratory protection, Warm zon

Mapping carcinogen exposure across urban fire incident response arenas using passive silicone-based samplers

Carcinogens are emitted in significant quantities at fire scenes and are a major contributor in the increased cancer risk observed in firefighters when compared to the general population. A knowledge gap exists in the current understanding of the distribution of these toxic compounds within a localized fire incident response arena. Here, we employ stationary silicone-based passive samplers at controlled live fire trainings to evaluate the deposition behavior of polyaromatic hydrocarbons (PAHs) emitted by fires. Our findings indicate significantly greater total PAH exposure in fires fueled by biomass and wood compared to fires burning cleaner fuels, such as propane. A 22% increase in total PAH deposition and a 68% increase in high molecular weight PAH deposition was recorded for biomass fueled fires compared to propane fueled fires. Furthermore, we observe that heavier molecular weight PAHs exhibit a pronounced deposition front within a certain radius of the hot zone, whereas low molecular weight PAHs are more uniformly distributed throughout the area. These findings highlight that the warm zones and cold zones of fire situations yield elevated levels of carcinogen exposure to first responders within them. We anticipate that these findings will help inform decisions made by emergency personnel when evaluating risk for the hot zone, warm zone, and cold zone of urban fires helping ease the carcinogenic risk experienced.•Firefighters are occupationally exposed to toxic and carcinogenic compounds during various fire situations.•Fire scenes are divided into safety zones: hot zones, warm zones, and cold zones.•This work assesses the migration and deposition of volatilized carcinogens such as PAHs in fire situations and the surrounding environment.•Passive samplers highlight higher than anticipated PAH levels in various zones at a fire scene.•Provide insights to help with policies to mitigate future exposure for firefighters and the nearby population

Evaluation of silicone-based wristbands as passive sampling systems using PAHs as an exposure proxy for carcinogen monitoring in firefighters: Evidence from the firefighter cancer initiative

Compared to the general population, firefighters are known to sustain greater levels of exposure to hazardous compounds, despite their personal protective equipment, also known as turnout gear. Among the most significant toxins that firefighters are chronically exposed to are polycyclic aromatic hydrocarbons (PAHs). Additionally, firefighters have also been noted to exhibit an increased incidence of certain types of cancer. Considering a probable link between exposure to PAHs and increased rates of cancer in the fire service, we aim to document ambient chemical concentrations in the firefighter work environment. Our strategy involves the use of silicone-based wristbands that have the capacity to passively sorb PAHs. To determine if wristbands can serve as an effective chemical monitoring device for the fire service, silicone wristbands were pilot-tested as personal sampling devices for work environment risk monitoring in active-duty firefighters. Recovered wristbands underwent multiple extraction steps, followed by GC-MS analysis to demonstrate their efficacy in monitoring PAHs in the firefighter environment. Initial findings from all wristband samples taken from firefighters showed multiple exposures to various PAHs of concern for the health of the firefighters when in a fire environment. In addition to PAH monitoring, we examined known and potential sources of PAH contamination in their work environment. To that end, profiles of elevated PAH concentrations were documented at various fire stations throughout South Florida, for individual firefighters both during station duties and active fire response. •Firefighters are occupationally exposed to toxic and carcinogenic compounds such as polyaromatic hydrocarbons (PAHs).•Silicone-based passive sampling presents an easy, affordable means to document firefighter exposure.•PAH exposure observed on wristbands of firefighters reporting to fire scenes was greater than for non-fire wristbands.•Diagnostic PAH ratios support exposure originating from diesel combustion observed in the fire service environment

964 Passive monitoring of chemical exposures in south florida firefighters using silicone wristbands

Introduction Firefighters are likely to be exposed to many toxic chemicals in the performance of their work duties such as polycyclic aromatic hydrocarbons (PAHs). Chemical exposures may occur through dermal, oral, or inhalation pathways. Passive sampling devices are used to sequester organic molecules through passive diffusion and provide time-weighted averages of chemical concentrations. This pilot study uses silicone-based wristbands as a personal passive sampler to detect known carcinogens during a 24 hour work shift. Methods Twenty-four wristbands were deployed across various fire services throughout South Florida. Prior to deployment, bands were cleaned using a standardised cleaning protocol to remove contamination and optimise the surface for absorption. Wristbands were then packaged in air-tight bags to prevent contamination. Wristbands were worn on fire service personnel and collected at the end of a 24 hour work shift. Chemical contaminants were then extracted from the wristband and analysed for PAHs—identified using the EPA IRIS, California Proposition 65, and IRAC datasets—using gas chromatography-mass spectrometry. Results The average number of chemicals found across all wristbands (n=24) was 23 with 4 categorised as carcinogenic to humans (i.e., Benzo[b]fluoranthene, Benzo[j]fluoranthene, Chrysene, and Naphthalene). All bands had at least one PAH present, specifically, 87.5% contained Benzo[b]fluoranthene (mean=5.23 ng/band), 50% contained Benzo[j]fluoranthene (mean=2.05 ng/band), 79.2% contained Chrysene (mean=9.55 ng/band), and 100% contained Napthalene (mean=176.53 ng/band). Actual types of exposure compounds is likely to be larger than the observed data as the group of PAHs detected was limited to three existing datasets. Discussion Silicone-based wristbands are feasible to use within the fire service to detect and characterise ambient hazardous chemical compounds. These personal self-samplers used during a 24 hour collection period identified various PAHs in the firefighter work environment. Objective measures of harmful chemical exposures in the fire service should be monitored with a comprehensive surveillance system that includes personal sampler devices

967 Evaluating temperature changes and volatile organic compound off-gassing in turnout protective gear ensembles among florida firefighters

Introduction Firefighter protective gear ensembles have been shown in controlled laboratory and staged live fire training experiments, to collect and harbour carcinogens such as polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Protective gear is often time transported in the personal vehicle of firefighters, resulting in cross-contamination between the vehicle and the fire incident environment. In the Southern United States particularly, ambient warmer temperatures may influence the rate of VOC gear off-gassing. This pilot study characterises temperature and particle off-gassing of firefighter turnout gear immediately following a 24 hour work shift. Methods Twelve sets of gear were obtained from South Florida career firefighters. Their protective gear, including helmet, gloves, hood, pants, boots and turnout coat, were placed in a large vacuum sealed Pelican case immediately after a 24 hour work shift. Turn-out gear was randomly selected at each fire station regardless of fire exposure. A photoionization gas detector (0.2 to 200 ppm), MetOne particle counter, Chromosorb diffusion patch, and a temperature logger were placed in each case with the ensemble for a 24 hour collection period. Results In two extreme observation points, VOC off-gassing was moderately, but significantly, correlated with temperature changes within the exposed gear (case#1: r=0.50; p Discussion Firefighter turnout gear used during real-life fire incident response events was documented to release VOCs and particles immediately after a 24 hour work shift. These results suggest the importance of the development of robust decontamination procedures immediately following a fire incident response is needed to reduce exposure to potential carcinogens from firefighter protective gear

Characterization of fire investigators’ polyaromatic hydrocarbon exposures using silicone wristbands

Background: Exposures to polyaromatic hydrocarbons (PAHs) contribute to cancer in the fire service. Fire investigators are involved in evaluations of post-fire scenes. In the US, it is estimated that there are up to 9000 fire investigators, compared to approximately 1.1 million total firefighting personnel. This exploratory study contributes initial evidence of PAH exposures sustained by this understudied group using worn silicone passive samplers. Objectives: Evaluate PAH exposures sustained by fire investigators at post-fire scenes using worn silicone passive samplers. Assess explanatory factors and health risks of PAH exposure at post-fire scenes. Methods: As part of a cross-sectional study design, silicone wristbands were distributed to 16 North Carolina fire investigators, including eight public, seven private, and one public and private. Wristbands were worn during 46 post-fire scene investigations. Fire investigators completed pre- and post-surveys providing sociodemographic, occupational, and post-fire scene characteristics. Solvent extracts from wristbands were analyzed via gas chromatography-mass spectrometry (GC-MS). Results were used to estimate vapor-phase PAH concentration in the air at post-fire scenes. Results: Fire investigations lasted an average of 148 minutes, standard deviation ± 93 minutes. A significant positive correlation (r=0.455, p<.001) was found between investigation duration and PAH concentrations on wristbands. Significantly greater time-normalized PAH exposures (p=0.039) were observed for investigations of newer post-fire scenes compared to older post-fire scenes. Regulatory airborne PAH exposure limits were exceeded in six investigations, based on exposure to estimated vapor-phase PAH concentrations in the air at post-fire scenes. Discussion: Higher levels of off-gassing and suspended particulates at younger post-fire scenes may explain greater PAH exposure. Weaker correlations are found between wristband PAH concentration and investigation duration at older post-fire scenes, suggesting reduction of off-gassing PAHs over time. Exceedances of regulatory PAH limits indicate a need for protection against vapor-phase contaminants, especially at more recent post-fire scenes