Exposure and Emissions Monitoring during Carbon Nanofiber Production--Part I: Elemental Carbon and Iron-Soot Aerosols

Division of Applied Research and Technology, National Institute for Occupational Safety and Health, 4676 Columbia Parkway, MS-R5, Cincinnati, OH 45226, USA.
Annals of Occupational Hygiene (Impact Factor: 2.1). 09/2011; 55(9):1016-36. DOI: 10.1093/annhyg/mer073
Source: PubMed


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.

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    • "Samples were analyzed by Sunset Laboratory Inc. (Tigard, OR) using NIOSH Method 5040 (NIOSH, 2003a). Thermal-optical speciation for the quantification of carbonaceous particles has been applied in several recent exposure assessments (Kuhlbusch et al., 2004; Kuhlbusch and Fissan, 2006; Methner et al., 2007; Ono-Ogasawara and Myojo, 2011; Birch et al., 2011; Dahm et al., 2012; Takaya et al., 2012; Hedmer et al., 2014; Lee et al., 2014; Dahm et al., 2015). The limit of detection (LOD) was assumed to be 0.09 µg EC per cm samples with sampling times ranging from 1.9 to 4.9 h during a 12 h shift were compared to the 8-h TWA REL using two assumptions. "
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    ABSTRACT: Recent animal studies have shown that carbon nanotubes (CNTs) may pose a significant health risk to those exposed in the workplace. To further understand this potential risk, effort must be taken to measure the occupational exposure to CNTs. Results from an assessment of potential exposure to multi-walled carbon nanotubes (MWCNTs) conducted at an industrial facility where polymer nanocomposites were manufactured by an extrusion process are presented. Exposure to MWCNTs was quantified by the thermal-optical analysis for elemental carbon (EC) of respirable dust collected by personal sampling. All personal respirable samples collected (n = 8) had estimated 8-h time weighted average (TWA) EC concentrations below the limit of detection for the analysis which was about one-half of the recommended exposure limit for CNTs, 1 µg EC/m(3) as an 8-h TWA respirable mass concentration. Potential exposure sources were identified and characterized by direct-reading instruments and area sampling. Area samples analyzed for EC yielded quantifiable mass concentrations inside an enclosure where unbound MWCNTs were handled and near a pelletizer where nanocomposite was cut, while those analyzed by electron microscopy detected the presence of MWCNTs at six locations throughout the facility. Through size selective area sampling it was identified that the airborne MWCNTs present in the workplace were in the form of large agglomerates. This was confirmed by electron microscopy where most of the MWCNT structures observed were in the form of micrometer-sized ropey agglomerates. However, a small fraction of single, free MWCNTs was also observed. It was found that the high number concentrations of nanoparticles, ~200000 particles/cm(3), present in the manufacturing facility were likely attributable to polymer fumes produced in the extrusion process. © The Author 2015. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.
    Annals of Occupational Hygiene 07/2015; DOI:10.1093/annhyg/mev044 · 2.10 Impact Factor
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    • "Over time, the sampling strategy for EC PBZ samples evolved, as methodologies advanced (Table 1). At sites A–K (excluding Sites G and I), only inhalable EC PBZ samples were collected, using methods described previously (Birch et al., 2011; Dahm et al., 2012). For Sites L–N and G, both inhalable and respirable EC PBZ samples were collected, with sample inlets positioned close together. "
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    ABSTRACT: 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. Published by Oxford University Press on behalf of the British Occupational Hygiene Society 2015.
    Annals of Occupational Hygiene 04/2015; 59(6). DOI:10.1093/annhyg/mev020 · 2.10 Impact Factor
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    • "The dose of 56 μg corresponds to 3 times the life-long dose and 162 μg/mouse corresponds to 9 times the proposed life dose. Work place exposure to CNT are reported in the range of 10–300 μg/m 3 (Birch et al., 2011; Dahm et al., 2013; Erdely et al., 2013; Han et al., 2008; Lee et al., 2010; Maynard et al., 2004; Methner et al., 2010b, 2012), thus 10–300 times above the proposed exposure limit. At an air concentration of 10 μg/m 3 , 162 μg/mouse would correspond to the total dose during a 40-year working life, whereas 162 μg/mouse corresponds to pulmonary deposition during 1.5 work years at 300 μg/m 3 . "
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    ABSTRACT: Adverse lung effects following pulmonary exposure to multi-walled carbon nanotubes (MWCNTs) are well documented in rodents. However, systemic effects are less understood. Epidemiological studies have shown increased cardiovascular disease risk after pulmonary exposure to airborne particles, which has led to concerns that inhalation exposure to MWCNTs might pose similar risks. We analyzed parameters related to cardiovascular disease, including plasma acute phase response (APR) proteins and plasma lipids, in female C57BL/6 mice exposed to a single intratracheal instillation of 0, 18, 54 or 162μg/mouse of small, entangled (CNTSmall, 0.8±0.1μm long) or large, thick MWCNTs (CNTLarge, 4±0.4μm long). Liver tissues and plasma were harvested 1, 3 and 28days post-exposure. In addition, global hepatic gene expression, hepatic cholesterol content and liver histology were used to assess hepatic effects. The two MWCNTs induced similar systemic responses despite their different physicochemical properties. APR proteins SAA3 and haptoglobin, plasma total cholesterol and low-density/very low-density lipoprotein were significantly increased following exposure to either MWCNTs. Plasma SAA3 levels correlated strongly with pulmonary Saa3 levels. Analysis of global gene expression revealed perturbation of the same biological processes and pathways in liver, including the HMG-CoA reductase pathway. Both MWCNTs induced similar histological hepatic changes, with a tendency towards greater response following CNTLarge exposure.Overall, we show that pulmonary exposure to two different MWCNTs induces similar systemic and hepatic responses, including changes in plasma APR, lipid composition, hepatic gene expression and liver morphology. The results link pulmonary exposure to MWCNTs with risk of cardiovascular disease.
    Toxicology and Applied Pharmacology 01/2015; 283(3). DOI:10.1016/j.taap.2015.01.011 · 3.71 Impact Factor
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