Physicochemical characterization and genotoxicity of the broad class of carbon nanotubes and nanofibers used or produced in U.S. facilities.

BACKGROUND: Carbon nanotubes and nanofibers (CNT/F) have known toxicity but simultaneous comparative studies of the broad material class, especially those with a larger diameter, with computational analyses linking toxicity to their fundamental material characteristics was lacking. It was unclear if all CNT/F confer similar toxicity, in particular, genotoxicity. Nine CNT/F (MW #1-7 and CNF #1-2), commonly found in exposure assessment studies of U.S. facilities, were evaluated with reported diameters ranging from 6 to 150 nm. All materials were extensively characterized to include distributions of physical dimensions and prevalence of bundled agglomerates. Human bronchial epithelial cells were exposed to the nine CNT/F (0-24 µg/ml) to determine cell viability, inflammation, cellular oxidative stress, micronuclei formation, and DNA double-strand breakage. Computational modeling was used to understand various permutations of physicochemical characteristics and toxicity outcomes. RESULTS: Analyses of the CNT/F physicochemical characteristics illustrate that using detailed distributions of physical dimensions provided a more consistent grouping of CNT/F compared to using particle dimension means alone. In fact, analysis of binning of nominal tube physical dimensions alone produced a similar grouping as all characterization parameters together. All materials induced epithelial cell toxicity and micronuclei formation within the dose range tested. Cellular oxidative stress, DNA double strand breaks, and micronuclei formation consistently clustered together and with larger physical CNT/F dimensions and agglomerate characteristics but were distinct from inflammatory protein changes. Larger nominal tube diameters, greater lengths, and bundled agglomerate characteristics were associated with greater severity of effect. The portion of tubes with greater nominal length and larger diameters within a sample was not the majority in number, meaning a smaller percentage of tubes with these characteristics was sufficient to increase toxicity. Many of the traditional physicochemical characteristics including surface area, density, impurities, and dustiness did not cluster with the toxicity outcomes. CONCLUSION: Distributions of physical dimensions provided more consistent grouping of CNT/F with respect to toxicity outcomes compared to means only. All CNT/F induced some level of genotoxicity in human epithelial cells. The severity of toxicity was dependent on the sample containing a proportion of tubes with greater nominal lengths and diameters.

Evaluation of total and inhalable samplers for the collection of carbon nanotube and carbon nanofiber aerosols.

A growing number of carbon nanotubes and nanofibers (CNT/F) exposure and epidemiologic studies have utilized 25-mm and 37-mm open-faced cassettes (OFC) to assess the inhalable aerosol fraction. It has been previously established that the 37-mm OFC under-samples particles greater than 20 µm in diameter, but the size-selective characteristics of the 25-mm OFC have not yet been fully evaluated. This article describes an experimental study conducted to determine if the 25- and 37-mm OFCs performed with relative equivalence to a reference inhalable aerosol sampler when challenged with CNT/F particles. Side-by-side paired samples were collected within a small Venturi chamber using a 25-mm styrene OFC, 37-mm styrene OFC, 25-mm aluminum OFC, and Button Inhalable Aerosol Sampler. Three types of CNT/F materials and an Arizona road dust were used as challenge aerosols for the various sampler configurations. Repeated experiments were conducted for each sampler configuration and material. The OFC samplers operated at flow rates of 2 and 5 liters per minute. Results showed that the 25-mm OFC performed comparably to the Button Sampler when challenged with CNT/F aerosols, which was demonstrated in five of the six experimental scenarios with an average error of 20%. Overall, the results of this study indicate that the sampling efficiency of the 25- and 37-mm OFCs adequately followed the ISO/ACGIH/CEN inhalable sampling convention when challenged with CNT/F aerosols. Past exposure and epidemiologic studies that used these OFC samplers can directly compare their results to studies that have used other validated inhalable aerosol samplers.

Association of pulmonary, cardiovascular, and hematologic metrics with carbon nanotube and nanofiber exposure among U.S. workers: a cross-sectional study.

BACKGROUND: Commercial use of carbon nanotubes and nanofibers (CNT/F) in composites and electronics is increasing; however, little is known about health effects among workers. We conducted a cross-sectional study among 108 workers at 12 U.S. CNT/F facilities. We evaluated chest symptoms or respiratory allergies since starting work with CNT/F, lung function, resting blood pressure (BP), resting heart rate (RHR), and complete blood count (CBC) components. METHODS: We conducted multi-day, full-shift sampling to measure background-corrected elemental carbon (EC) and CNT/F structure count concentrations, and collected induced sputum to measure CNT/F in the respiratory tract. We measured (nonspecific) fine and ultrafine particulate matter mass and count concentrations. Concurrently, we conducted physical examinations, BP measurement, and spirometry, and collected whole blood. We evaluated associations between exposures and health measures, adjusting for confounders related to lifestyle and other occupational exposures. RESULTS: CNT/F air concentrations were generally low, while 18% of participants had evidence of CNT/F in sputum. Respiratory allergy development was positively associated with inhalable EC (p=0.040) and number of years worked with CNT/F (p=0.008). No exposures were associated with spirometry-based metrics or pulmonary symptoms, nor were CNT/F-specific metrics related to BP or most CBC components. Systolic BP was positively associated with fine particulate matter (p-values: 0.015-0.054). RHR was positively associated with EC, at both the respirable (p=0.0074) and inhalable (p=0.0026) size fractions. Hematocrit was positively associated with the log of CNT/F structure counts (p=0.043). CONCLUSIONS: Most health measures were not associated with CNT/F. The positive associations between CNT/F exposure and respiratory allergies, RHR, and hematocrit counts may not be causal and require examination in other studies.

Carbon nanotube and nanofiber exposure and sputum and blood biomarkers of early effect among U.S. workers.

BACKGROUND: Carbon nanotubes and nanofibers (CNT/F) are increasingly used for diverse applications. Although animal studies suggest CNT/F exposure may cause deleterious health effects, human epidemiological studies have typically been small, confined to single workplaces, and limited in exposure assessment. OBJECTIVES: We conducted an industrywide cross-sectional epidemiological study of 108 workers from 12 U.S. sites to evaluate associations between occupational CNT/F exposure and sputum and blood biomarkers of early effect. METHODS: We assessed CNT/F exposure via personal breathing zone, filter-based air sampling to measure background-corrected elemental carbon (EC) (a CNT/F marker) mass and microscopy-based CNT/F structure count concentrations. We measured 36 sputum and 37 blood biomarkers. We used factor analyses with varimax rotation to derive factors among sputum and blood biomarkers separately. We used linear, Tobit, and unconditional logistic regression models to adjust for potential confounders and evaluate associations between CNT/F exposure and individual biomarkers and derived factors. RESULTS: We derived three sputum and nine blood biomarker factors that explained 78% and 67%, respectively, of the variation. After adjusting for potential confounders, inhalable EC and total inhalable CNT/F structures were associated with the most sputum and blood biomarkers, respectively. Biomarkers associated with at least three CNT/F metrics were 72 kDa type IV collagenase/matrix metalloproteinase-2 (MMP-2), interleukin-18, glutathione peroxidase (GPx), myeloperoxidase, and superoxide dismutase (SOD) in sputum and MMP-2, matrix metalloproteinase-9, metalloproteinase inhibitor 1/tissue inhibitor of metalloproteinases 1, 8-hydroxy-2'-deoxyguanosine, GPx, SOD, endothelin-1, fibrinogen, intercellular adhesion molecule 1, vascular cell adhesion protein 1, and von Willebrand factor in blood, although directions of associations were not always as expected. CONCLUSIONS: Inhalable rather than respirable CNT/F was more consistently associated with fibrosis, inflammation, oxidative stress, and cardiovascular biomarkers.

Airborne contaminants during controlled residential fires.

In this study, we characterize the area and personal air concentrations of combustion byproducts produced during controlled residential fires with furnishings common in 21st century single family structures. Area air measurements were collected from the structure during active fire and overhaul (post suppression) and on the fireground where personnel were operating without any respiratory protection. Personal air measurements were collected from firefighters assigned to fire attack, victim search, overhaul, outside ventilation, and command/pump operator positions. Two different fire attack tactics were conducted for the fires (6 interior and 6 transitional) and exposures were compared between the tactics. For each of the 12 fires, firefighters were paired up to conduct each job assignment, except for overhaul that was conducted by 4 firefighters. Sampled compounds included polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs, e.g., benzene), hydrogen cyanide (HCN), and particulate (area air sampling only). Median personal air concentrations for the attack and search firefighters were generally well above applicable short-term occupational exposure limits, with the exception of HCN measured from search firefighters. Area air concentrations of all measured compounds decreased after suppression. Personal air concentrations of total PAHs and benzene measured from some overhaul firefighters exceeded exposure limits. Median personal air concentrations of HCN (16,300 ppb) exceeded the exposure limit for outside vent firefighters, with maximum levels (72,900 ppb) higher than the immediately dangerous to life and health (IDLH) level. Median air concentrations on the fireground (including particle count) were above background levels and highest when collected downwind of the structure and when ground-level smoke was the heaviest. No statistically significant differences in personal air concentrations were found between the 2 attack tactics. The results underscore the importance of wearing self-contained breathing apparatus when conducting overhaul or outside ventilation activities. Firefighters should also try to establish command upwind of the structure fire, and if this cannot be done, respiratory protection should be considered.

Exposure assessments for a cross-sectional epidemiologic study of US carbon nanotube and nanofiber workers.

BACKGROUND: Recent animal studies have suggested the potential for wide-ranging health effects resulting from exposure to carbon nanotubes and nanofibers (CNT/F). To date, no studies in the US have directly examined the relationship between occupational exposure and potential human health effects. OBJECTIVES: Our goal was to measure CNT/F exposures among US workers with representative job types, from non-exposed to highly exposed, for an epidemiologic study relating exposure to early biologic effects. METHODS: 108 participants were enrolled from 12 facilities across the US. Personal, full-shift exposures were assessed based on the mass of elemental carbon (EC) at the respirable and inhalable aerosol particle size fractions, along with quantitatively characterizing CNT/F and estimating particle size via transmission electron microscopy (TEM). Additionally, sputum and dermal samples were collected and analyzed to determine internal exposures and exposures to the hands/wrists. RESULTS: The mean exposure to EC was 1.00 µg/m3 at the respirable size fraction and 6.22 µg/m3 at the inhalable fraction. Analysis by TEM found a mean exposure of 0.1275 CNT/F structures/cm3, generally to agglomerated materials between 2 and 10 µm. Internal exposures to CNT/F via sputum analysis were confirmed in 18% of participants while ∼70% had positive dermal exposures. CONCLUSIONS: We demonstrated the occurrence of a broad range of exposures to CNT/F within 12 facilities across the US. Analysis of collected sputum indicated internal exposures are currently occurring within the workplace. This is an important first step in determining if exposures in the workforce have any acute or lasting health effects.

In Vivo Toxicity Assessment of Occupational Components of the Carbon Nanotube Life Cycle To Provide Context to Potential Health Effects.

Pulmonary toxicity studies on carbon nanotubes focus primarily on as-produced materials and rarely are guided by a life cycle perspective or integration with exposure assessment. Understanding toxicity beyond the as-produced, or pure native material, is critical, due to modifications needed to overcome barriers to commercialization of applications. In the first series of studies, the toxicity of as-produced carbon nanotubes and their polymer-coated counterparts was evaluated in reference to exposure assessment, material characterization, and stability of the polymer coating in biological fluids. The second series of studies examined the toxicity of aerosols generated from sanding polymer-coated carbon-nanotube-embedded or neat composites. Postproduction modification by polymer coating did not enhance pulmonary injury, inflammation, and pathology or in vitro genotoxicity of as-produced carbon nanotubes, and for a particular coating, toxicity was significantly attenuated. The aerosols generated from sanding composites embedded with polymer-coated carbon nanotubes contained no evidence of free nanotubes. The percent weight incorporation of polymer-coated carbon nanotubes, 0.15% or 3% by mass, and composite matrix utilized altered the particle size distribution and, in certain circumstances, influenced acute in vivo toxicity. Our study provides perspective that, while the number of workers and consumers increases along the life cycle, toxicity and/or potential for exposure to the as-produced material may greatly diminish.

Ultrafine and respirable particle exposure during vehicle fire suppression.

Vehicle fires are a common occurrence, yet few studies have reported exposures associated with burning vehicles. This article presents an assessment of firefighters' potential for ultrafine and respirable particle exposure during vehicle fire suppression training. Fires were initiated within the engine compartment and passenger cabins of three salvaged vehicles, with subsequent water suppression by fire crews. Firefighter exposures were monitored with an array of direct reading particle and air quality instruments. A flexible metallic duct and blower drew contaminants to the instrument array, positioned at a safe distance from the burning vehicles, with the duct inlet positioned at the nozzle operator's shoulder. The instruments measured the particle number, active surface area, respirable particle mass, photoelectric response, aerodynamic particle size distributions, and air quality parameters. Although vehicle fires were suppressed quickly (<10 minutes), firefighters may be exposed to short duration, high particle concentration episodes during fire suppression, which are orders of magnitude greater than the ambient background concentration. A maximum transient particle concentration of 1.21 × 10(7) particles per cm(3), 170 mg m(-3) respirable particle mass, 4700 µm(2) cm(-3) active surface area and 1400 (arbitrary units) in photoelectric response were attained throughout the series of six fires. Expressed as fifteen minute time-weighted averages, engine compartment fires averaged 5.4 × 10(4) particles per cm(3), 0.36 mg m(-3) respirable particle mass, 92 µm(2) cm(-3) active particle surface area and 29 (arbitrary units) in photoelectric response. Similarly, passenger cabin fires averaged 2.04 × 10(5) particles per cm(3), 2.7 mg m(-3) respirable particle mass, 320 µm(2) cm(-3) active particle surface area, and 34 (arbitrary units) in photoelectric response. Passenger cabin fires were a greater potential source of exposure than engine compartment fires. The wind direction and the relative position of the fire crew to the stationary burning vehicle played a primary role in fire crews' potential for exposure. We recommend that firefighters wear self-contained breathing apparatus during all phases of the vehicle fire response to significantly reduce their potential for particulate, vapor, and gaseous exposures.

Carbon Nanotube and Nanofiber Exposure Assessments: An Analysis of 14 Site Visits.

Recent evidence has suggested the potential for wide-ranging health effects that could result from exposure to carbon nanotubes (CNT) and carbon nanofibers (CNF). In response, the National Institute for Occupational Safety and Health (NIOSH) set a recommended exposure limit (REL) for CNT and CNF: 1 µg m(-3) as an 8-h time weighted average (TWA) of elemental carbon (EC) for the respirable size fraction. The purpose of this study was to conduct an industrywide exposure assessment among US CNT and CNF manufacturers and users. Fourteen total sites were visited to assess exposures to CNT (13 sites) and CNF (1 site). Personal breathing zone (PBZ) and area samples were collected for both the inhalable and respirable mass concentration of EC, using NIOSH Method 5040. Inhalable PBZ samples were collected at nine sites while at the remaining five sites both respirable and inhalable PBZ samples were collected side-by-side. Transmission electron microscopy (TEM) PBZ and area samples were also collected at the inhalable size fraction and analyzed to quantify and size CNT and CNF agglomerate and fibrous exposures. Respirable EC PBZ concentrations ranged from 0.02 to 2.94 µg m(-3) with a geometric mean (GM) of 0.34 µg m(-3) and an 8-h TWA of 0.16 µg m(-3). PBZ samples at the inhalable size fraction for EC ranged from 0.01 to 79.57 µg m(-3) with a GM of 1.21 µg m(-3). PBZ samples analyzed by TEM showed concentrations ranging from 0.0001 to 1.613 CNT or CNF-structures per cm(3) with a GM of 0.008 and an 8-h TWA concentration of 0.003. The most common CNT structure sizes were found to be larger agglomerates in the 2-5 µm range as well as agglomerates >5 µm. A statistically significant correlation was observed between the inhalable samples for the mass of EC and structure counts by TEM (Spearman ρ = 0.39, P < 0.0001). Overall, EC PBZ and area TWA samples were below the NIOSH REL (96% were <1 µg m(-3) at the respirable size fraction), while 30% of the inhalable PBZ EC samples were found to be >1 µg m(-3). Until more information is known about health effects associated with larger agglomerates, it seems prudent to assess worker exposure to airborne CNT and CNF materials by monitoring EC at both the respirable and inhalable size fractions. Concurrent TEM samples should be collected to confirm the presence of CNT and CNF.

Volatile Organic Compounds Off-gassing from Firefighters' Personal Protective Equipment Ensembles after Use.

Firefighters' personal protective equipment (PPE) ensembles will become contaminated with various compounds during firefighting. Some of these compounds will off-gas following a response, which could result in inhalation exposure. This study was conducted to determine the magnitude and composition of volatile organic compounds (VOCs) generated during controlled structure burns that subsequently off-gassed from the firefighters' PPE, and were systemically absorbed and exhaled in firefighters' breath. Three crews of five firefighters performed entry, suppression, and overhaul during a controlled burn. We used evacuated canisters to sample air inside the burn structure during active fire and overhaul. After each burn, we placed PPE from two firefighters inside clean enclosures and sampled the air using evacuated canisters over 15 min. Firefighters' exhaled breath was collected ∼1 hr before and 4-14 min after each burn. Using gas chromatography/mass spectrometry, the evacuated canister samples were analyzed for 64 VOCs and the exhaled breath samples were analyzed for benzene, toluene, ethylbenzene, xylene, and styrene (BTEXS). Fourteen of the same VOCs were detected off-gassing from PPE in 50% or more of the samples. Compared to background levels, we measured >5 fold increases in mean off-gas concentrations of styrene, benzene, 1,4-dichlorobenzene, acetone, and cyclohexane. Several of the compounds detected off-gassing from PPE were also measured at concentrations above background during active fire and overhaul, including benzene, propene, and styrene. The overhaul and off-gas air concentrations were well below applicable short-term occupational exposure limits. Compared to pre-burn levels, we measured >2 fold increases in mean breath concentrations of benzene, toluene, and styrene after the burns. Air concentrations of BTEXS measured off-gassing from firefighters' used PPE and in firefighters' post-burn exhaled breath were significantly correlated. The firefighters may have absorbed BTEXS through both the dermal route (during firefighting) and inhalation route (from off-gassing PPE after firefighting). Firefighters should be made aware of the potential for inhalation exposure when doffing and traveling in confined vehicles with contaminated PPE and take measures to minimize this exposure pathway.

Carbon nanotube dosimetry: from workplace exposure assessment to inhalation toxicology.

BACKGROUND: Dosimetry for toxicology studies involving carbon nanotubes (CNT) is challenging because of a lack of detailed occupational exposure assessments. Therefore, exposure assessment findings, measuring the mass concentration of elemental carbon from personal breathing zone (PBZ) samples, from 8 U.S.-based multi-walled CNT (MWCNT) manufacturers and users were extrapolated to results of an inhalation study in mice. RESULTS: Upon analysis, an inhalable elemental carbon mass concentration arithmetic mean of 10.6 µg/m3 (geometric mean 4.21 µg/m3) was found among workers exposed to MWCNT. The concentration equates to a deposited dose of approximately 4.07 µg/d in a human, equivalent to 2 ng/d in the mouse. For MWCNT inhalation, mice were exposed for 19 d with daily depositions of 1970 ng (equivalent to 1000 d of a human exposure; cumulative 76 yr), 197 ng (100 d; 7.6 yr), and 19.7 ng (10 d; 0.76 yr) and harvested at 0, 3, 28, and 84 d post-exposure to assess pulmonary toxicity. The high dose showed cytotoxicity and inflammation that persisted through 84 d after exposure. The middle dose had no polymorphonuclear cell influx with transient cytotoxicity. The low dose was associated with a low grade inflammatory response measured by changes in mRNA expression. Increased inflammatory proteins were present in the lavage fluid at the high and middle dose through 28 d post-exposure. Pathology, including epithelial hyperplasia and peribronchiolar inflammation, was only noted at the high dose. CONCLUSION: These findings showed a limited pulmonary inflammatory potential of MWCNT at levels corresponding to the average inhalable elemental carbon concentrations observed in U.S.-based CNT facilities and estimates suggest considerable years of exposure are necessary for significant pathology to occur at that level.

Dustiness of fine and nanoscale powders.

Dustiness may be defined as the propensity of a powder to form airborne dust by a prescribed mechanical stimulus; dustiness testing is typically intended to replicate mechanisms of dust generation encountered in workplaces. A novel dustiness testing device, developed for pharmaceutical application, was evaluated in the dustiness investigation of 27 fine and nanoscale powders. The device efficiently dispersed small (mg) quantities of a wide variety of fine and nanoscale powders, into a small sampling chamber. Measurements consisted of gravimetrically determined total and respirable dustiness. The following materials were studied: single and multiwalled carbon nanotubes, carbon nanofibers, and carbon blacks; fumed oxides of titanium, aluminum, silicon, and cerium; metallic nanoparticles (nickel, cobalt, manganese, and silver) silicon carbide, Arizona road dust; nanoclays; and lithium titanate. Both the total and respirable dustiness spanned two orders of magnitude (0.3-37.9% and 0.1-31.8% of the predispersed test powders, respectively). For many powders, a significant respirable dustiness was observed. For most powders studied, the respirable dustiness accounted for approximately one-third of the total dustiness. It is believed that this relationship holds for many fine and nanoscale test powders (i.e. those primarily selected for this study), but may not hold for coarse powders. Neither total nor respirable dustiness was found to be correlated with BET surface area, therefore dustiness is not determined by primary particle size. For a subset of test powders, aerodynamic particle size distributions by number were measured (with an electrical low-pressure impactor and an aerodynamic particle sizer). Particle size modes ranged from approximately 300 nm to several micrometers, but no modes below 100 nm, were observed. It is therefore unlikely that these materials would exhibit a substantial sub-100 nm particle contribution in a workplace.

Occupational exposure assessment in carbon nanotube and nanofiber primary and secondary manufacturers: mobile direct-reading sampling.

UNLABELLED: RESEARCH SIGNIFICANCE: Toxicological evidence suggests the potential for a wide range of health effects from exposure to carbon nanotubes (CNTs) and carbon nanofibers (CNFs). To date, there has been much focus on the use of direct-reading instruments (DRIs) to assess multiple airborne exposure metrics for potential exposures to CNTs and CNFs due to their ease of use and ability to provide instantaneous results. Still, uncertainty exists in the usefulness and interpretation of the data. To address this gap, air-monitoring was conducted at six sites identified as CNT and CNF manufacturers or users and results were compared with filter-based metrics. METHODS: Particle number, respirable mass, and active surface area concentrations were monitored with a condensation particle counter, a photometer, and a diffusion charger, respectively. The instruments were placed on a mobile cart and used as area monitors in parallel with filter-based elemental carbon (EC) and electron microscopy samples. Repeat samples were collected on consecutive days, when possible, during the same processes. All instruments in this study are portable and routinely used for industrial hygiene sampling. RESULTS: Differences were not observed among the various sampled processes compared with concurrent indoor or outdoor background samples while examining the different DRI exposure metrics. Such data were also inconsistent with results for filter-based samples collected concurrently at the same sites [Dahm MM, Evans DE, Schubauer-Berigan MK et al. (2012) Occupational exposure assessment in CNT and nanofiber primary and secondary manufacturers. Ann Occup Hyg; 56: 542-56]. Significant variability was seen between these processes as well as the indoor and outdoor backgrounds. However, no clear pattern emerged linking the DRI results to the EC or the microscopy data (CNT and CNF structure counts). CONCLUSIONS: Overall, no consistent trends were seen among similar processes at the various sites. The DRI instruments employed were limited in their usefulness in assessing and quantifying potential exposures at the sampled sites but were helpful for hypothesis generation, control technology evaluations, and other air quality issues. The DRIs employed are nonspecific, aerosol monitors, and, therefore, subject to interferences. As such, it is necessary to collect samples for analysis by more selective, time-integrated, laboratory-based methods to confirm and quantify exposures.

Investigation of Aerosol Surface Area Estimation from Number and Mass Concentration Measurements: Particle Density Effect.

For nanoparticles with nonspherical morphologies, e.g., open agglomerates or fibrous particles, it is expected that the actual density of agglomerates may be significantly different from the bulk material density. It is further expected that using the material density may upset the relationship between surface area and mass when a method for estimating aerosol surface area from number and mass concentrations (referred to as "Maynard's estimation method") is used. Therefore, it is necessary to quantitatively investigate how much the Maynard's estimation method depends on particle morphology and density. In this study, aerosol surface area estimated from number and mass concentration measurements was evaluated and compared with values from two reference methods: a method proposed by Lall and Friedlander for agglomerates and a mobility based method for compact nonspherical particles using well-defined polydisperse aerosols with known particle densities. Polydisperse silver aerosol particles were generated by an aerosol generation facility. Generated aerosols had a range of morphologies, count median diameters (CMD) between 25 and 50 nm, and geometric standard deviations (GSD) between 1.5 and 1.8. The surface area estimates from number and mass concentration measurements correlated well with the two reference values when gravimetric mass was used. The aerosol surface area estimates from the Maynard's estimation method were comparable to the reference method for all particle morphologies within the surface area ratios of 3.31 and 0.19 for assumed GSDs 1.5 and 1.8, respectively, when the bulk material density of silver was used. The difference between the Maynard's estimation method and surface area measured by the reference method for fractal-like agglomerates decreased from 79% to 23% when the measured effective particle density was used, while the difference for nearly spherical particles decreased from 30% to 24%. The results indicate that the use of particle density of agglomerates improves the accuracy of the Maynard's estimation method and that an effective density should be taken into account, when known, when estimating aerosol surface area of nonspherical aerosol such as open agglomerates and fibrous particles.

Occupational exposure assessment in carbon nanotube and nanofiber primary and secondary manufacturers.

UNLABELLED: RESEARCH SIGNIFICANCE: Toxicological evidence suggests the potential for a wide range of health effects, which could result from exposure to carbon nanotubes (CNTs) and carbon nanofibers (CNFs). The National Institute for Occupational Safety and Health (NIOSH) has proposed a recommended exposure limit (REL) for CNTs/CNFs at the respirable size fraction. The current literature is lacking exposure information, with few studies reporting results for personal breathing zone (PBZ) samples in occupational settings. To address this gap, exposure assessments were conducted at six representative sites identified as CNT/CNF primary or secondary manufacturers. METHODS: Personal and area filter-based samples were collected for both the inhalable mass concentration and the respirable mass concentration of elemental carbon (EC) as well as CNT structure count analysis by transmission electron microscopy to assess exposures. When possible, full-shift PBZ samples were collected; area samples were collected on a task-based approach. RESULTS: The vast majority of samples collected in this study were below the proposed REL (7 µg m(-3)). Two of the three secondary manufacturers' surveyed found concentrations above the proposed REL. None of the samples collected at primary manufacturers were found to be above the REL. Visual and microscopy-based evidence of CNTs/CNFs were found at all sites, with the highest CNT/CNF structure counts being found in samples collected at secondary manufacturing sites. The statistical correlations between the filter-based samples for the mass concentration of EC and CNT structure counts were examined. A general trend was found with a P-value of 0.01 and a corresponding Pearson correlation coefficient of 0.44. CONCLUSIONS: CNT/CNF concentrations were above the proposed NIOSH REL for PBZ samples in two secondary manufacturing facilities that use these materials for commercial applications. These samples were collected during dry powder handling processes, such as mixing and weighing, using fairly large quantities of CNTs/CNFs.

A strategy for assessing workplace exposures to nanomaterials.

This article describes a highly tailorable exposure assessment strategy for nanomaterials that enables effective and efficient exposure management (i.e., a strategy that can identify jobs or tasks that have clearly unacceptable exposures), while simultaneously requiring only a modest level of resources to conduct. The strategy is based on strategy general framework from AIHA® that is adapted for nanomaterials and seeks to ensure that the risks to workers handling nanomaterials are being managed properly. The strategy relies on a general framework as the basic foundation while building and elaborating on elements essential to an effective and efficient strategy to arrive at decisions based on collecting and interpreting available information. This article provides useful guidance on conducting workplace characterization; understanding exposure potential to nanomaterials; accounting methods for background aerosols; constructing SEGs; and selecting appropriate instrumentation for monitoring, providing appropriate choice of exposure limits, and describing criteria by which exposure management decisions should be made. The article is intended to be a practical guide for industrial hygienists for managing engineered nanomaterial risks in their workplaces.

Exposure and emissions monitoring during carbon nanofiber production--Part I: elemental carbon and iron-soot aerosols.

Production of carbon nanofibers and nanotubes (CNFs/CNTs) and their composite products is increasing globally. High volume production may increase the exposure risks for workers who handle these materials. Though health effects data for CNFs/CNTs are limited, some studies raise serious health concerns. Given the uncertainty about their potential hazards, there is an immediate need for toxicity data and field studies to assess exposure to CNFs/CNTs. An extensive study was conducted at a facility that manufactures and processes CNFs. Filter, sorbent, cascade impactor, bulk, and microscopy samples, combined with direct-reading instruments, provided complementary information on air contaminants. Samples were analyzed for organic carbon (OC) and elemental carbon (EC), metals, and polycyclic aromatic hydrocarbons (PAHs), with EC as a measure of CNFs. Transmission electron microscopy with energy-dispersive X-ray spectroscopy also was applied. Fine/ultrafine iron-rich soot, PAHs, and carbon monoxide were production byproducts. Direct-reading instrument results were reported previously [Evans DE et al. (Aerosol monitoring during carbon nanofiber production: mobile direct-reading sampling. Ann Occup Hyg 2010;54:514-31.)] Results for time-integrated samples are reported as companion papers in this Issue. OC and EC, metals, and microscopy results are reported here, in Part I, while results for PAHs are reported in Part II [Birch ME. (Exposure and Emissions Monitoring during Carbon Nanofiber Production-Part II: Polycyclic Aromatic Hydrocarbons. Ann. Occup. Hyg 2011; 55: 1037-47.)]. Respirable EC area concentrations inside the facility were about 6-68 times higher than outdoors, while personal breathing zone samples were up to 170 times higher.

Assessing the risk to firefighters from chemical vapors and gases during vehicle fire suppression.

Despite the frequent occurrence of vehicle fires, very few studies investigating firefighters' potential inhalation exposures during vehicle fire suppression have been conducted. In this paper, we present an assessment of firefighters' health risk from vehicle fire suppression that accounts for the mixture of gases and vapors likely to be found in these fires. Summa canisters were used to collect emissions from the engine and cabin fires of a single vehicle and were analyzed for 75 volatile organic compounds (VOCs). Firefighters' breathing zone concentrations (BZCs) of aromatic hydrocarbons, aldehydes, isocyanates, and carbon monoxide were measured during the suppression of three vehicle fires. The Summa canister and BZC data were used to develop a simple model for predicting BZCs for the compounds that were not measured in the firefighters' breathing zones. Hazard quotients (HQs) were calculated by dividing the predicted and measured BZCs by the most conservative short-term exposure limits (STELs) or ceiling limits. Hazard indices (HIs) were determined by adding HQs for compounds grouped by the target organ for acute health effects. Any HIs above unity represented unacceptable risks. According to this mixture analysis, the estimated 95(th) percentile of the exposure distribution for the study population represents ≥ 9.2 times the acceptable level of risk to the respiratory tract and eyes. Furthermore, chemicals known or reasonably anticipated to be human carcinogens contributed to > 45% of these HIs. While STELs are not usually based on carcinogenicity, maintaining exposures below STELs may protect individuals from the biological stress that could result from short-term exposures to carcinogens over time. Although vehicle fires are suppressed quickly (<10 min), this assessment suggests that firefighters have the potential to be overexposed to acute toxins during vehicle fire suppression and should therefore wear self-contained breathing apparatus at all times during vehicle fire response.

Aerosol monitoring during carbon nanofiber production: mobile direct-reading sampling.

Detailed investigations were conducted at a facility that manufactures and processes carbon nanofibers (CNFs). Presented research summarizes the direct-reading monitoring aspects of the study. A mobile aerosol sampling platform, equipped with an aerosol instrument array, was used to characterize emissions at different locations within the facility. Particle number, respirable mass, active surface area, and photoelectric response were monitored with a condensation particle counter (CPC), a photometer, a diffusion charger, and a photoelectric aerosol sensor, respectively. CO and CO(2) were additionally monitored. Combined simultaneous monitoring of these metrics can be utilized to determine source and relative contribution of airborne particles (CNFs and others) within a workplace. Elevated particle number concentrations, up to 1.15 x 10(6) cm(-3), were found within the facility but were not due to CNFs. Ultrafine particle emissions, released during thermal treatment of CNFs, were primarily responsible. In contrast, transient increases in respirable particle mass concentration, with a maximum of 1.1 mg m(-3), were due to CNF release through uncontrolled transfer and bagging. Of the applied metrics, our findings suggest that particle mass was probably the most useful and practical metric for monitoring CNF emissions in this facility. Through chemical means, CNFs may be selectively distinguished from other workplace contaminants (Birch et al., in preparation), and for direct-reading monitoring applications, the photometer was found to provide a reasonable estimate of respirable CNF mass concentration. Particle size distribution measurements were conducted with an electrical low-pressure impactor and a fast particle size spectrometer. Results suggest that the dominant CNF mode by particle number lies between 200 and 250 nm for both aerodynamic and mobility equivalent diameters. Significant emissions of CO were also evident in this facility. Exposure control recommendations were described for processes as required.