Dispersion and Dosimetric Challenges of Hydrophobic Carbon-Based Nanoparticles in In Vitro Cellular Studies.

Methodologies across the dispersion preparation, characterization, and cellular dosimetry of hydrophilic nanoparticles (NPs) have been developed and used extensively in the field of nanotoxicology. However, hydrophobic NPs pose a challenge for dispersion in aqueous culture media using conventional methods that include sonication followed by mixing in the culture medium of interest and cellular dosimetry. In this study, a robust methodology for the preparation of stable dispersions of hydrophobic NPs for cellular studies is developed by introducing continuous energy over time via stirring in the culture medium followed by dispersion characterization and cellular dosimetry. The stirring energy and the presence of proteins in the culture medium result in the formation of a protein corona around the NPs, stabilizing their dispersion, which can be used for in vitro cellular studies. The identification of the optimal stirring time is crucial for achieving dispersion and stability. This is assessed through a comprehensive stability testing protocol employing dynamic light scattering to evaluate the particle size distribution stability and polydispersity. Additionally, the effective density of the NPs is obtained for the stable NP dispersions using the volumetric centrifugation method, while cellular dosimetry calculations are done using available cellular computational modeling, mirroring approaches used for hydrophilic NPs. The robustness of the proposed dispersion approach is showcased using a highly hydrophobic NP model (black carbon NPs) and two culture media, RPMI medium and SABM, that are widely used in cellular studies. The proposed approach for the dispersion of hydrophobic NPs results in stable dispersions in both culture media used here. The NP effective density of 1.03-1.07 g/cm3 measured here for black carbon NPs is close to the culture media density, resulting in slow deposition on the cells over time. So, the present methodology for dispersion and dosimetry of hydrophobic NPs is essential for the design of dose-response studies and overcoming the challenges imposed by slow particle deposition.

Toward Elimination of Soot Emissions from Jet Fuel Combustion.

Soot from jet fuel combustion in aircraft engines contributes to global warming through the formation of contrail cirrus clouds that make up to 56% of the total radiative forcing from aviation. Here, the elimination of such emissions is explored through N2 injection (containing 0-25 vol % O2) at the exhaust of enclosed spray combustion of jet fuel that nicely emulates aircraft soot emissions. It is shown that injecting N2 containing 5 vol % of O2 enhances the formation of polyaromatic hydrocarbons (PAHs) that adsorb on the surface of soot. This increases soot number density and volume fraction by 25 and 80%, respectively. However, further increasing the O2 concentration to 20 or 25 vol % enhances oxidation and nearly eliminates soot emissions from jet fuel spray combustion, reducing the soot number density and volume fraction by 87.3 or 95.4 and 98.3 or 99.6%, respectively. So, a judicious injection of air just after the aircraft engine exhaust can drastically reduce soot emissions and halve the radiative forcing due to aviation, as shown by soot mobility, X-ray diffraction, Raman spectroscopy, nitrogen adsorption, microscopy, and thermogravimetric analysis (for the organic to total carbon ratio) measurements.

Comprehensive analysis of the air quality impacts of switching a marine vessel from diesel fuel to natural gas.

New environmental regulations are mandating cleaner fuels and lower emissions from all maritime operations. Natural gas (NG) is a fuel that enables mariners to meet regulations; however, emissions data from maritime operations with natural gas is limited. We measured emissions of criteria, toxic and greenhouse pollutants from a dual-fuel marine engine running either on diesel fuel or NG as well as engine activity and analyzed the impacts on pollutants, health, and climate change. Results showed that particulate matter (PM), black carbon (BC), nitric oxides (NOx), and carbon dioxide (CO2) were reduced by about 93%, 97%, 92%, and 18%, respectively when switching from diesel to NG. Reductions of this magnitude provide a valuable tool for the many port communities struggling with meeting air quality standards. While these pollutants were reduced, formaldehyde (HCHO), carbon monoxide (CO) and methane (CH4) increased several-fold. A health risk assessment of exhaust plume focused on when the vessel was stationary, and at-berth showed the diesel plume increased long-term health risk and the NG plume increased short-term health risk. An analysis of greenhouse gases (GHGs) and BC was performed and revealed that, on a hundred year basis, the whole fuel cycle global warming potential (GWP) per kWh including well-to-tank and exhaust was 50% to few times higher than that of diesel at lower engine loads, but that it was similar at 75% load and lower at higher loads. Mitigation strategies for further reducing pollutants from NG exhaust are discussed and showed potential for reducing short-term health risks and climate impacts.

On determining soot maturity: A review of the role of microscopy- and spectroscopy-based techniques.

Incomplete combustion is the main source of airborne soot, which has negative impacts on public health and the environment. Understanding the morphological and chemical evolution of soot is important for assessing and mitigating the impact of soot emissions. Morphological and chemical structures of soot are commonly studied using microscopy or spectroscopy, and the best technique depends on the parameter of interest and the stage of soot formation considered (i.e., maturity). For the earliest stages of soot formation, particles exhibit simple morphology yet complex and reactive chemical composition, which is best studied by spectroscopic techniques sensitive to the large number of soot precursor species. The only microscope that can offer some morphological information at this stage is the scanning probe microscopy, which can image single polycyclic aromatic hydrocarbons, the precursors of soot. A broader range of types of spectrometers and microscopes can be used by increasing the soot maturity. Mature soot is primarily carbon, and exhibits complex fractal-like morphology best studied with electron microscopy and techniques sensitive to thin oxide or organic coatings. Each characterization technique can target different morphological and chemical properties of soot, from the early to the late stage of its formation. Thus, a guideline for the selection of the appropriate technique can facilitates studies on environmental samples involving the presence of soot.