Purpose: Underground diesel exhaust exposure is an occupational health risk. It is not known how recent intensified emission legislation and use of renewable fuels have reduced or altered occupational exposures. We characterized these effects on multipollutant personal exposure to diesel exhaust and underground ambient air concentrations in an underground iron ore mine. Methods: Full-shift personal sampling (12 workers) of elemental carbon (EC), nitrogen dioxide (NO₂), polycyclic aromatic hydrocarbons (PAHs), and equivalent black carbon (eBC) was performed. The study used and validated eBC as an online proxy for occupational exposure to EC. Ambient air sampling of these pollutants and particle number size distribution and concentration were performed in the vicinity of the workers. Urine samples (27 workers) were collected after 8 h exposure and analyzed for PAH metabolites and effect biomarkers (8-oxodG for DNA oxidative damage, 4-HNE-MA for lipid peroxidation, 3-HPMA for acrolein). Results: The personal exposures (geometric mean; GM) of the participating miners were 7 µg EC m⁻³ and 153 µg NO₂ m⁻³, which are below the EU occupational exposure limits. However, exposures up to 94 µg EC m⁻³ and 1200 µg NO₂ m⁻³ were observed. There was a tendency that the operators of vehicles complying with sharpened emission legislation had lower exposure of EC. eBC and NO₂ correlated with EC, R = 0.94 and R = 0.66, respectively. No correlation was found between EC and the sum of 16 priority PAHs (GM 1790 ng m⁻³). Ratios between personal exposures and ambient concentrations were similar and close to 1 for EC and NO₂, but significantly higher for PAHs. Semi-volatile PAHs may not be effectively reduced by the aftertreatment systems, and ambient area sampling did not predict the personal airborne PAHs exposure well, neither did the slightly elevated concentration of urinary PAH metabolites correlate with airborne PAH exposure. Conclusion: Miners’ exposures to EC and NO₂ were lower than those in older studies indicating the effect of sharpened emission legislation and new technologies. Using modern vehicles with diesel particulate filter (DPF) may have contributed to the lower ambient underground PM concentration and exposures. The semi-volatile behavior of the PAHs might have led to inefficient removal in the engines aftertreatment systems and delayed removal by the workplace ventilation system due to partitioning to indoor surfaces. The results indicate that secondary emissions can be an important source of gaseous PAH exposure in the mine.

Renewable diesel fuels have the potential to reduce net CO₂ emissions, and simultaneously decrease particulate matter (PM) emissions. This study characterized engine-out PM emissions and PM-induced reactive oxygen species (ROS) formation potential. Emissions from a modern heavy-duty diesel engine without external aftertreatment devices, and fueled with petroleum diesel, hydrotreated vegetable oil (HVO) or rapeseed methyl ester (RME) biodiesel were studied. Exhaust gas recirculation (EGR) allowed us to probe the effect of air intake O₂ concentration, and thereby combustion temperature, on emissions and ROS formation potential. An increasing level of EGR (decreasing O₂ concentration) resulted in a general increase of equivalent black carbon (eBC) emissions and decrease of NO_x emissions. At a medium level of EGR (13% intake O₂), eBC emissions were reduced for HVO and RME by 30 and 54% respectively compared to petroleum diesel. In general, substantially lower emissions of polycyclic aromatic hydrocarbons (PAHs), including nitro and oxy-PAHs, were observed for RME compared to both HVO and diesel. At low-temperature combustion (LTC, O₂ < 10%), CO and hydrocarbon gas emissions increased and an increased fraction of refractory organic carbon and PAHs were found in the particle phase. These altered soot properties have implications for the design of aftertreatment systems and diesel PM measurements with optical techniques. The ROS formation potential per mass of particles increased with increasing engine O₂ concentration intake. We hypothesize that this is because soot surface properties evolve with the combustion temperature and become more active as the soot matures into refractory BC, and secondly as the soot surface becomes altered by surface oxidation. At 13% intake O₂, the ROS-producing ability was high and of similar magnitude per mass for all fuels. When normalizing by energy output, the lowered emissions for the renewable fuels led to a reduced ROS formation potential.

Constraining the climate impact of particulate brown carbon (BrC) will require identification of formation mechanisms and isolation of its different components to allow for source apportionment. For fresh combustion aerosols, the light absorption characteristics and the Absorption Ångstrom Exponent (AAE) are principally controlled by the combustion conditions in which the particles formed and evolved. We investigated the influence of combustion temperatures on the BrC or black carbon (BC) emission characteristics for a miniCAST soot generator (propane fuel) and a modern heavy-duty diesel engine (petroleum diesel and two renewable diesel fuels). Changes in the AAE, mass spectral signatures, and thermal-optical characteristics were studied. We show that changing operating parameters to gradually reduce the combustion temperatures in these two fundamentally different combustion devices result in a regression from BC dominated to BrC dominated particle emissions. The regression towards BrC was associated with: 1) an increasing mass fraction of particulate non-refractory polycyclic aromatic hydrocarbons (PAHs), 2) an increasing fraction of refractory organic carbon, 3) more curved soot nanostructures and shorter fringe lengths, and 4) increased signal from (refractory) large carbon fragments in IR laser-vaporization aerosol mass spectra. Based on these results we argue that fresh BrC dominated combustion aerosols are attributed to primary emissions from low temperature combustion, highlighting the influence of refractory constituents and soot nanostructure. Higher temperatures favor the growth of conjugated polyaromatic structures in the soot, a progression hypothesized to control the evolution from BrC to BC character of the emitted aerosols.