Biomarkers of Organophosphate and Polybrominated Diphenyl Ether (PBDE) Flame Retardants of American Workers and Associations with Inhalation and Dermal Exposures.

This study evaluated workers' exposures to flame retardants, including polybrominated diphenyl ethers (PBDEs), organophosphate esters (OPEs), and other brominated flame retardants (BFRs), in various industries. The study aimed to characterize OPE metabolite urinary concentrations and PBDE serum concentrations among workers from different industries, compare these concentrations between industries and the general population, and evaluate the likely route of exposure (dermal or inhalation). The results showed that workers from chemical manufacturing had significantly higher (p <0.05) urinary concentrations of OPE metabolites compared to other industries. Spray polyurethane foam workers had significantly higher (p <0.05) urinary concentrations of bis(1-chloro-2-propyl) phosphate (BCPP) compared to other industries. Electronic scrap workers had higher serum concentrations of certain PBDE congeners compared to the general population. Correlations were observed between hand wipe samples and air samples containing specific flame-retardant parent chemicals and urinary metabolite concentrations for some industries, suggesting both dermal absorption and inhalation as primary routes of exposure for OPEs. Overall, this study provides insights into occupational exposure to flame retardants in different industries and highlights the need for further research on emerging flame retardants and exposure reduction interventions.

Evaluating workplace protection factors (WPFs) of different firefighter PPE interface control measures for select volatile organic compounds (VOCs).

Structural firefighters are exposed to a complex set of contaminants and combustion byproducts, including volatile organic compounds (VOCs). Additionally, recent studies have found structural firefighters' skin may be exposed to multiple chemical compounds via permeation or penetration of chemical byproducts through or around personal protective equipment (PPE). This mannequin-based study evaluated the effectiveness of four different PPE conditions with varying contamination control measures (incorporating PPE interface design features and particulate blocking materials) to protect against ingress of several VOCs in a smoke exposure chamber. We also investigated the effectiveness of long-sleeve base layer clothing to provide additional protection against skin contamination. Outside gear air concentrations were measured from within the smoke exposure chamber at the breathing zone, abdomen, and thigh heights. Personal air concentrations were collected from mannequins under PPE at the same general heights and under the base layer at abdomen and thigh heights. Sampled contaminants included benzene, toluene, styrene, and naphthalene. Results suggest that VOCs can readily penetrate the ensembles. Workplace protection factors (WPFs) were near one for benzene and toluene and increased with increasing molecular weight of the contaminants. WPFs were generally lower under hoods and jackets compared to under pants. For all PPE conditions, the pants appeared to provide the greatest overall protection against ingress of VOCs, but this may be due in part to the lower air concentrations toward the floor (and cuffs of pants) relative to the thigh-height outside gear concentrations used in calculating the WPFs. Providing added interface control measures and adding particulate-blocking materials appeared to provide a protective benefit against less-volatile chemicals, like naphthalene and styrene.

Characterization of inhalation exposures at a wildfire incident during the Wildland Firefighter Exposure and Health Effects (WFFEHE) Study.

Wildland firefighters (WFFs) are exposed to many inhalation hazards working in the wildland fire environment. To assess occupational exposures and acute and subacute health effects among WFFs, the wildland firefighter exposure and health effects study collected data for a 2-year repeated measures study. This manuscript describes the exposure assessment from one Interagency Hotshot Crew (N = 19) conducted at a wildfire incident. Exposures to benzene, toluene, ethylbenzene, xylene isomers, formaldehyde, acetaldehyde, and naphthalene were measured through personal air sampling each work shift. Biological monitoring was done for creatinine-adjusted levoglucosan in urine pre- and post-shift. For 3 days sampling at the wildfire incident, benzene, toluene, ethylbenzene, xylene isomers (m and p, and o) exposure was highest on day 1 (geometric mean [GM] = 0.015, 0.042, 0.10, 0.42, and 0.15 ppm, respectively) when WFFs were not exposed to smoke but used chainsaws to remove vegetation and prepare fire suppression breaks. Exposure to formaldehyde and acetaldehyde was highest on day 2 (GM = 0.03 and 0.036 ppm, respectively) when the WFFs conducted a firing operation and were directly exposed to wildfire smoke. The greatest difference of pre- and post-shift levoglucosan concentrations were observed on day 3 (pre-shift: 9.7 and post-shift: 47 µg/mg creatinine) after WFFs conducted mop up (returned to partially burned area to extinguish any smoldering vegetation). Overall, 65% of paired samples (across all sample days) showed a post-shift increase in urinary levoglucosan and 5 firefighters were exposed to benzene at concentrations at or above the National Institute for Occupational Safety and Health (NIOSH) recommended exposure limit. Our findings further demonstrate that exposure to inhalation hazards is one of many risks that wildland firefighters experience while suppressing wildfires.

Evaluating Exposure to VOCs and Naphthalene for Firefighters Wearing Different PPE Configurations through Measures in Air, Exhaled Breath, and Urine.

Firefighters are at an increased risk of cancer due to their occupational exposure to combustion byproducts, especially when those compounds penetrate the firefighter personal protective equipment (PPE) ensemble. This has led to questions about the impact of base layers (i.e., shorts vs. pants) under PPE ensembles. This study asked 23 firefighters to perform firefighting activities while wearing one of three different PPE ensembles with varying degrees of protection. Additionally, half of the firefighters unzipped their jackets after the scenario while the other half kept their jackets zipped for five additional minutes. Several volatile organic compound (VOC) and naphthalene air concentrations outside and inside of hoods, turnout jackets, and turnout pants were evaluated; biological (urinary and exhaled breath) samples were also collected. VOCs and naphthalene penetrated the three sampling areas (hoods, jackets, pants). Significant (p-value < 0.05) increases from pre- to post-fire for some metabolites of VOCs (e.g., benzene, toluene) and naphthalene were found. Firefighters wearing shorts and short sleeves absorbed higher amounts of certain compounds (p-value < 0.05), and the PPE designed with enhanced interface control features appeared to provide more protection from some compounds. These results suggest that firefighters can dermally absorb VOCs and naphthalene that penetrate the PPE ensemble.

Use of Preliminary Exposure Reduction Practices or Laundering to Mitigate Polycyclic Aromatic Hydrocarbon Contamination on Firefighter Personal Protective Equipment Ensembles.

Chronic health risks associated with firefighting continue to be documented and studied, however, the complexity of occupational exposures and the relationship between occupational exposure and contaminated personal protective equipment (PPE) remains unknown. Recent work has revealed that common PPE cleaning practices, which are becoming increasingly more common in the fire service, are not effective in removing certain contaminants, such as polycyclic aromatic hydrocarbons (PAHs), from PPE. To better understand the relationship between contaminated firefighter PPE and potential exposure to PAHs, and to gain further understanding of the efficacy of cleaning practices, we used a standardized fire exposure simulator that created repeatable conditions and measured PPE surface contamination levels via wipe sampling and filters attached to firefighter gear worn by standing mannequins. This study examined the effects of repeated (40 cycles) PPE cleaning (laundering and on-scene preliminary exposure reduction (PER) techniques) and repeated exposures on PAH concentration on different surfaces. Further exploration included examination of contamination breakthrough of turnout jackets (comparing outer shell and interior liner) and evaluation of off-gassing PAHs from used gear after different cleaning treatments. When compared by jacket closure type (zipper and hook and dee), total PAH concentration wiped from gear after exposure and cleanings showed no significant differences. Regression analysis indicated that there was no effect of repeated exposures on PAH contamination levels (all sampling sites combined; before fire 10, 20, and 40; after fire 1, 10, 20, and 40; p-value > 0.05). Both laundering and on-scene PER significantly reduced contamination levels on the exterior pants and helmets and were effective at reducing PAH contamination. The jacket outer shell had significantly higher PAH contamination than the jacket liner. Both laundering and wet soap PER methods (post-fire) are effective in reducing surface contamination and appear to prevent accumulation of contamination after repeated exposures. Semi-volatile PAHs deep within the fibers of bulky PPE are not effectively reduced via PER or machine laundering, therefore, permitting continued off-gassing of these compounds. Further research is needed to identify the most effective laundering methods for firefighter turnout gear that considers the broad spectrum of common contaminants.

Firefighters' urinary concentrations of VOC metabolites after controlled-residential and training fire responses.

INTRODUCTION: Firefighters are exposed to volatile organic compounds (VOCs) during structural fire responses and training fires, several of which (e.g., benzene, acrolein, styrene) are known or probable carcinogens. Exposure studies have found that firefighters can absorb chemicals like benzene even when self-contained breathing apparatus (SCBA) are worn, suggesting that dermal absorption contributes to potentially harmful exposures. However, few studies have characterized VOC metabolites in urine from firefighters. OBJECTIVES: We quantified VOC metabolites in firefighters' urine following live firefighting activity across two field studies. METHODS: In two separate controlled field studies, spot urine was collected before and 3 h after firefighters and firefighter students responded to simulated residential and training fires. Urine was also collected from instructors from the training fire study before the first and 3 h after the last training scenario for each day (instructors led three training scenarios per day). Samples were analyzed for metabolites of VOCs to which firefighters may be exposed. RESULTS: In the residential fire study, urinary metabolites of xylenes (2MHA), toluene (BzMA), and styrene (MADA) increased significantly (at 0.05 level) from pre- to post-fire. In the training fire study, MADA concentrations increased significantly from pre- to post-fire for both firefighter students and instructors. Urinary concentrations of benzene metabolites (MUCA and PhMA) increased significantly from pre- to post-fire for instructors, while metabolites of xylenes (3MHA+4MHA) and acrolein (3HPMA) increased significantly for firefighter students. The two highest MUCA concentrations measured post-shift from instructors exceeded the BEI of 500 µg/g creatinine. CONCLUSIONS: Some of the metabolites that were significantly elevated post-fire are known or probable human carcinogens (benzene, styrene, acrolein); thus, exposure to these compounds should be eliminated or reduced as much as possible through the hierarchy of controls. Given stringent use of SCBA, it appears that dermal exposure contributes in part to the levels measured here.

Airborne contamination during post-fire investigations: Hot, warm and cold scenes.

Fire investigators may be occupationally exposed to many of the same compounds as the more widely studied fire suppression members of the fire service but are often tasked with working in a given exposure for longer periods ranging from hours to multiple days and may do so with limited personal protective equipment. In this study, we characterize the area air concentrations of contaminants during post-fire investigation of controlled residential fires with furnishings common to current bedroom, kitchen and living room fires in the United States. Area air sampling was conducted during different investigation phases including when investigations might be conducted immediately after fire suppression and extended out to 5 days after the fire. Airborne particulate over a wide range of dimensions, including sub-micron particles, were elevated to potentially unhealthy levels (based on air quality index) when averaged over a 60 min investigation period shortly after fire suppression with median PM2.5 levels over 100 µg/m3 (range 16-498 µg/m3) and median peak transient concentrations of 1,090 µg/m3 (range 200-23,700 µg/m3) during drywall removal or shoveling activities. Additionally, airborne aldehyde concentrations were elevated compared to volatile organic compounds with peak values of formaldehyde exceeding NIOSH ceiling limits during the earliest investigation periods (median 356 µg/m3, range: 140-775 µg/m3) and occasionally 1 day post-fire when the structure was boarded up before subsequent investigation activities. These results highlight the need to protect investigators' airways from particulates when fire investigation activities are conducted as well as during post-fire reconstruction activities. Additionally, vapor protection from formaldehyde should be strongly considered at least through investigations occurring 3 days after the fire and personal formaldehyde air monitoring is recommended during investigations.

Characterizing exposure to benzene, toluene, and naphthalene in firefighters wearing different types of new or laundered PPE.

The fire service has become more aware of the potential for adverse health outcomes due to occupational exposure to hazardous combustion byproducts. Because of these concerns, personal protective equipment (PPE) manufacturers have developed new protection concepts like particulate-blocking hoods to reduce firefighters' exposures. Additionally, fire departments have implemented exposure reduction interventions like routine laundering of PPE after fire responses. This study utilized a fireground exposure simulator (FES) with 24 firefighters performing firefighting activities on three consecutive days wearing one of three PPE ensembles (stratified by hood design and treatment of PPE): 1) new knit hood, new turnout jacket and new turnout pants 2) new particulate-blocking hood, new turnout jacket and new turnout pants or 3) laundered particulate-blocking hood, laundered turnout jacket and laundered turnout pants. As firefighters performed the firefighting activities, personal air sampling on the outside and inside the turnout jacket was conducted to quantify exposures to volatile organic compounds (VOCs) and naphthalene. Pre- and immediately post-fire exhaled breath samples were collected to characterize the absorption of VOCs. Benzene, toluene, and naphthalene were found to diffuse through and/or around the turnout jacket, as inside jacket benzene concentrations were often near levels reported outside the turnout jacket (9.7-11.7% median benzene reduction from outside the jacket to inside the jacket). The PPE ensemble did not appear to affect the level of contamination found inside the jacket for the compounds evaluated here. Benzene concentrations in exhaled breath increased significantly from pre to post-fire for all three groups (p-values < 0.05). The difference of pre-to post-fire benzene exhaled breath concentrations were positively associated with inside jacket and outside jacket benzene concentrations, even though self-contained breathing apparatus (SCBA) were worn during each response. This suggests the firefighters can absorb these compounds via the dermal route.

Characterizing exposures to flame retardants, dioxins, and furans among firefighters responding to controlled residential fires.

Firefighters may encounter items containing flame retardants (FRs), including organophosphate flame retardants (OPFRs) and polybrominated diphenyl ethers (PBDEs), during structure fires. This study utilized biological monitoring to characterize FR exposures in 36 firefighters assigned to interior, exterior, and overhaul job assignments, before and after responding to controlled residential fire scenarios. Firefighters provided four urine samples (pre-fire and 3-h, 6-h, and 12-h post-fire) and two serum samples (pre-fire and approximately 23-h post-fire). Urine samples were analyzed for OPFR metabolites, while serum samples were analyzed for PBDEs, brominated and chlorinated furans, and chlorinated dioxins. Urinary concentrations of diphenyl phosphate (DPhP), a metabolite of triphenyl phosphate (TPhP), bis(1,3-dichloro-2-propyl) phosphate (BDCPP), a metabolite of tris(1,3-dichloro-2-propyl) phosphate (TDCPP), and bis(2-chloroethyl) phosphate (BCEtP), a metabolite of tris(2-chloroethyl) phosphate (TCEP), increased from pre-fire to 3-hr and 6-hr post-fire collection, but only the DPhP increase was statistically significant at a 0.05 level. The 3-hr and 6-hr post-fire concentrations of DPhP and BDCPP, as well as the pre-fire concentration of BDCPP, were statistically significantly higher than general population levels. BDCPP pre-fire concentrations were statistically significantly higher in firefighters who previously participated in a scenario (within the past 12 days) than those who were responding to their first scenario as part of the study. Similarly, firefighters previously assigned to interior job assignments had higher pre-fire concentrations of BDCPP than those previously assigned to exterior job assignments. Pre-fire serum concentrations of 2,3,4,7,8-pentachlorodibenzofuran (23478-PeCDF), a known human carcinogen, were also statistically significantly above the general population levels. Of the PBDEs quantified, only decabromodiphenyl ether (BDE-209) pre- and post-fire serum concentrations were statistically significantly higher than the general population. These results suggest firefighters absorbed certain FRs while responding to fire scenarios.

Impact of select PPE design elements and repeated laundering in firefighter protection from smoke exposure.

As the Fire Service becomes more aware of the potential health effects from occupational exposure to hazardous contaminants, personal protective equipment (PPE) manufacturers, and fire departments have responded by developing and implementing improved means of firefighter protection, including more frequent laundering of PPE after exposures. While laboratory testing of new PPE designs and the effect of laundering on PPE fabric provides a useful way to evaluate these approaches, laboratory scale testing does not necessarily translate to full garment protection. Utilizing a fireground smoke exposure simulator, along with air and/or filter-substrate sampling for polycyclic aromatic hydrocarbons (PAHs) and benzene, this pilot study tested the chemical-protective capabilities of firefighting PPE of different designs (knit hood vs. particulate-blocking hood, turnout jacket with zipper closure vs. hook & dee closure), including the impact of repeatedly exposing and cleaning (through laundering or decontamination on-scene) PPE 40 times. Overall, PAH contamination on filters under hoods in the neck region were higher (median PAHs = 14.7 µg) than samples taken under jackets in the chest region (median PAHs = 7.05 µg). PAH levels measured under particulate-blocking hoods were lower than levels found under knit hoods. Similarly, zippered closures were found to provide a greater reduction in PAHs compared to hook & dee closures. However, neither design element completely eliminated contaminant ingress. Measurements for benzene under turnout jackets were similar to ambient chamber air concentrations, indicating little to no attenuation from the PPE. The effect of laundering or on-scene decontamination on contaminant breakthrough appeared to depend on the type of contaminant. Benzene breakthrough was negatively associated with laundering, while PAH breakthrough was positively associated. More research is needed to identify PPE features that reduce breakthrough, how targeted changes impact exposures, and how fireground exposures relate to biological absorption of contaminants.

Assessment of spray polyurethane foam worker exposure to organophosphate flame retardants through measures in air, hand wipes, and urine.

Tris(1-chloro-2-propyl) phosphate (TCPP, also referenced as TCIPP), a flame retardant used in spray polyurethane foam insulation, increases cell toxicity and affects fetal development. Spray polyurethane foam workers have the potential to be exposed to TCPP during application. In this study, we determined exposure to TCPP and concentrations of the urinary biomarker bis(1-chloro-2-propyl) phosphate (BCPP) among 29 spray polyurethane foam workers over 2 work days. Work was conducted at residential or commercial facilities using both open-cell (low density) and closed-cell (high density) foam. Study participants provided two personal air samples (Day 1 and Day 2), two hand wipe samples (Pre-shift Day 2 and Post-shift Day 2), and two spot urine samples (Pre-shift Day 1 and Post-shift Day 2). Bulk samples of cured spray foam were also analyzed. Sprayers were found to have significantly higher TCPP geometric mean (GM) concentration in personal air samples (87.1 µg/m3), compared to helpers (30.2 µg/m3; p = 0.025). A statistically significant difference was observed between TCPP pre- and post-shift hand wipe GM concentrations (p = 0.004). Specifically, TCPP GM concentration in post-shift hand wipe samples of helpers (106,000 ng/sample) was significantly greater than pre-shift (27,300 ng/sample; p < 0.001). The GM concentration of the urinary biomarker BCPP (23.8 µg/g creatinine) was notably higher than the adult male general population (0.159 µg/g creatinine, p < 0.001). Urinary BCPP GM concentration increased significantly from Pre-shift Day 1 to Post-shift Day 2 for sprayers (p = 0.013) and helpers (p = 0.009). Among bulk samples, cured open-cell foam had a TCPP GM concentration of 9.23% by weight while closed-cell foam was 1.68%. Overall, post-shift BCPP urine concentrations were observed to be associated with TCPP air and hand wipe concentrations, as well as job position (sprayer vs. helper). Spray polyurethane foam workers should wear personal protective equipment including air-supplied respirators, coveralls, and gloves during application.

Firefighter hood contamination: Efficiency of laundering to remove PAHs and FRs.

Firefighters are occupationally exposed to products of combustion containing polycyclic aromatic hydrocarbons (PAHs) and flame retardants (FRs), potentially contributing to their increased risk for certain cancers. Personal protective equipment (PPE), including firefighter hoods, helps to reduce firefighters' exposure to toxic substances during fire responses by providing a layer of material on which contaminants deposit prior to reaching the firefighters skin. However, over time hoods that retain some contamination may actually contribute to firefighters' systemic dose. We investigated the effectiveness of laundering to reduce or remove contamination on the hoods, specifically PAHs and three classes of FRs: polybrominated diphenyl ethers (PBDEs), non-PBDE flame retardants (NPBFRs), and organophosphate flame retardants (OPFRs). Participants in the study were grouped into crews of 12 firefighters who worked in pairs by job assignment while responding to controlled fires in a single-family residential structure. For each pair of firefighters, one hood was laundered after every scenario and one was not. Bulk samples of the routinely laundered and unlaundered hoods from five pairs of firefighters were collected and analyzed. Residual levels of OPFRs, NPBFRs, and PAHs were lower in the routinely laundered hoods, with total levels of each class of chemicals being 56-81% lower, on average, than the unlaundered hoods. PBDEs, on average, were 43% higher in the laundered hoods, most likely from cross contamination. After this initial testing, four of the five unlaundered exposed hoods were subsequently laundered with other heavily exposed (unlaundered) and unexposed (new) hoods. Post-laundering evaluation of these hoods revealed increased levels of PBDEs, NPBFRs, and OPFRs in both previously exposed and unexposed hoods, indicating cross contamination. For PAHs, there was little evidence of cross contamination and the exposed hoods were significantly less contaminated after laundering (76% reduction; p = 0.011). Further research is needed to understand how residual contamination on hoods could contribute to firefighters' systemic exposures.