Exposure monitoring of graphene nanoplatelets manufacturing workplaces

Abstract Graphenes have emerged as a highly promising, two-dimensional engineered nanomaterial that can possibly substitute carbon nanotubes. They are being explored in numerous R&D and industrial applications in laboratories across the globe, leading to possible human and environmental exposures to them. Yet, there are no published data on graphene exposures in occupational settings and no readily available methods for their detection and quantitation exist. This study investigates for the first time the potential exposure of workers and research personnel to graphenes in two research facilities and evaluates the status of the control measures. One facility manufactures graphene using graphite exfoliation and chemical vapor deposition (CVD), while the other facility grows graphene on a copper plate using CVD, which is then transferred to a polyethylene terephthalate (PET) sheet. Graphene exposures and process emissions were investigated for three tasks – CVD growth, exfoliation, and transfer – using a multi-metric approach, which utilizes several direct reading instruments, integrated sampling, and chemical and morphological analysis. Real-time instruments included a dust monitor, condensation particle counter (CPC), nanoparticle surface area monitor, scanning mobility particle sizer, and an aethalometer. Morphologically, graphenes and other nanostructures released from the work process were investigated using a transmission electron microscope (TEM). Graphenes were quantified in airborne respirable samples as elemental carbon via thermo-optical analysis. The mass concentrations of total suspended particulate at Workplaces A and B were very low, and elemental carbon concentrations were mostly below the detection limit, indicating very low exposure to graphene or any other particles. The real-time monitoring, especially the aethalometer, showed a good response to the released black carbon, providing a signature of the graphene released during the opening of the CVD reactor at Workplace A. The TEM observation of the samples obtained from Workplaces A and B showed graphene-like structures and aggregated/agglomerated carbon structures. Taken together, the current findings on common scenarios (exfoliation, CVD growth, and transfer), while not inclusive of all graphene manufacturing processes, indicate very minimal graphene or particle exposure at facilities manufacturing graphenes with good manufacturing practices.

[1]  P. J. Ollivier,et al.  Layer-by-Layer Assembly of Ultrathin Composite Films from Micron-Sized Graphite Oxide Sheets and Polycations , 1999 .

[2]  Jong Seong Lee,et al.  Persistent DNA damage measured by comet assay of Sprague Dawley rat lung cells after five days of inhalation exposure and 1 month post-exposure to dispersed multi-wall carbon nanotubes (MWCNTs) generated by new MWCNT aerosol generation system. , 2012, Toxicological sciences : an official journal of the Society of Toxicology.

[3]  Tung-Sheng Shih,et al.  Six-month follow-up study of health markers of nanomaterials among workers handling engineered nanomaterials , 2014, Nanotoxicology.

[4]  Ken Donaldson,et al.  Graphene-based nanoplatelets: a new risk to the respiratory system as a consequence of their unusual aerodynamic properties. , 2012, ACS nano.

[5]  Jae Hoon Shin,et al.  5-Day repeated inhalation and 28-day post-exposure study of graphene , 2015, Nanotoxicology.

[6]  Determination of airborne fibre number concentrations , 2004 .

[7]  B. van Ravenzwaay,et al.  Comparative inhalation toxicity of multi-wall carbon nanotubes, graphene, graphite nanoplatelets and low surface carbon black , 2013, Particle and Fibre Toxicology.

[8]  I. Yu,et al.  In vivo Genotoxicity of Silver Nanoparticles after 90-day Silver Nanoparticle Inhalation Exposure , 2011, Safety and health at work.

[9]  I. Yu,et al.  Three-Day Continuous Exposure Monitoring of CNT Manufacturing Workplaces , 2015, BioMed research international.

[10]  Young Hee Lee,et al.  Monitoring multiwalled carbon nanotube exposure in carbon nanotube research facility. , 2008, Inhalation toxicology.

[11]  Kang L. Wang,et al.  A chemical route to graphene for device applications. , 2007, Nano letters.

[12]  Jong Seong Lee,et al.  Health surveillance study of workers who manufacture multi-walled carbon nanotubes , 2015, Nanotoxicology.

[13]  Jong Seong Lee,et al.  28-Day inhalation toxicity of graphene nanoplatelets in Sprague-Dawley rats , 2016, Nanotoxicology.

[14]  S. Fukushima,et al.  Development of a new multi-walled carbon nanotube (MWCNT) aerosol generation and exposure system and confirmation of suitability for conducting a single-exposure inhalation study of MWCNT in rats , 2014, Nanotoxicology.

[15]  Darrell R Boverhof,et al.  A review and perspective of existing research on the release of nanomaterials from solid nanocomposites , 2014, Particle and Fibre Toxicology.

[16]  P. Baron,et al.  Observation and measurement of anomalous responses in a differential mobility analyzer caused by ultrafine fibrous carbon aerosols , 2007 .

[17]  M. Schubauer-Berigan,et al.  Occupational exposure assessment in carbon nanotube and nanofiber primary and secondary manufacturers: mobile direct-reading sampling. , 2013, The Annals of occupational hygiene.

[18]  H. Chiang,et al.  Epidemiological study of health hazards among workers handling engineered nanomaterials , 2012, Journal of Nanoparticle Research.

[19]  W. McKinney,et al.  Computer controlled multi-walled carbon nanotube inhalation exposure system , 2009, Inhalation toxicology.

[20]  G. Bae,et al.  Exposure assessment of carbon nanotube manufacturing workplaces , 2010, Inhalation toxicology.

[21]  M. Schubauer-Berigan,et al.  Occupational exposure assessment in carbon nanotube and nanofiber primary and secondary manufacturers. , 2012, The Annals of occupational hygiene.

[22]  Jong Seong Lee,et al.  Pulmonary Responses of Sprague-Dawley Rats in Single Inhalation Exposure to Graphene Oxide Nanomaterials , 2015, BioMed research international.

[23]  I. Yu,et al.  Multi-Walled Carbon Nanotube (MWCNT) Dispersion and Aerosolization with Hot Water Atomization without Addition of Any Surfactant , 2011, Safety and health at work.