We investigated the biological response of soluble organic fraction (SOF) and water-soluble fraction (WSF) extracted from particulate matter (PM) emitted by an automotive diesel engine operating in a representative urban driving condition. The engine was fueled with ultra-low sulfur diesel (ULSD), and its binary blends by volume with 13% of butanol (Bu13), and with hydrotreated vegetable oil (HVO) at 13% (HVO13) and 20% (HVO20). Cytotoxicity, genotoxicity, oxidative DNA damage and ecotoxicity tests were carried out, and 16 polycyclic aromatic hydrocarbons (PAH) expressed as tbenzo(a)pyrene total toxicity equivalent (BaP-TEQ) were also analyzed. The Hepatocarcinoma epithelial cell line (HepG2) was exposed to SOF for 24 h and analyzed using comet assay, with the inclusion of formamidopyrimidine DNA glycosylase (FPG) and endonuclease III (Endo III) to recognize oxidized DNA bases. The WSF was evaluated through acute ecotoxicity tests with the aquatic microcrustacean Daphnia pulex (D. Pulex). Results showed that there was no cytotoxic activity for all tested SOF concentrations. Genotoxic responses by all the SOF samples were at same level, except for the HVO13 which was weaker in the absence of the enzymes. The addition of the FPG and Endo III enzymes resulted in a significant increase in the comet tail, indicating that the DNA damage from SOF for all tested fuel blends involves oxidative damage including a higher level of oxidized purines for ULSD and Bu13 in comparison with HVO blends, but the oxidized pyrimidines for HVO blends were slightly higher compared to Bu13. The WSF did not show acute ecotoxicity for any of the fuels. Unlike other samples, Bu13-derived particles significantly increase the BaP-TEQ. The contribution to the genotoxic activity and oxidative DNA from SOF was not correlated to BaP-TEQ, which means that the biological activity of PM might be affected also by other toxic compounds present in particulate phase.

In this experimental study, particulate matter (PM) characterizations of different low-temperature combustion (LTC) strategies have been compared with conventional compression ignition (CI) combustion for finding out a sustainable and cleaner transport solution. LTC strategies included premixed charge compression ignition (PCCI) and reactivity-controlled compression ignition (RCCI) combustion. Particulate sampling and characterization were carried out in a single-cylinder diesel engine. All engine tests were performed at 1, 2, 3, 4 bar brake mean effective pressure (BMEP) at 1500 rpm. CI and PCCI combustion experiments were performed using mineral diesel as the test fuel. However, mineral diesel and methanol were used as high reactivity fuel (HRF) and low reactivity fuel (LRF), respectively in the RCCI combustion strategy. For all combustion strategies, fuel injection pressure (FIP) was kept constant at 500 bar. However, the number of injections and start of injection (SoI) timings were varied to optimize the engine performance. Results showed that the RCCI combustion strategy emitted a relatively lower concentration of particles than the other two strategies (PCCI and CI). A relatively higher number concentration of accumulation mode particles (AMP) compared to nucleation mode particles (NMP) in the exhaust of the RCCI combustion strategy was an important finding of this study. Number-size and mass-size distributions of particles emitted from different strategies also exhibited the dominant concentration of particles in the CI combustion strategy. PM bound trace metal analysis was yet another critical aspect of this study, which showed that both RCCI and PCCI strategies emitted a relatively lower concentration of trace metals than the conventional CI combustion strategy. Parametric analysis of different PM characteristics and NOx-PM trade-off analysis also demonstrated the importance of LTC strategies over the conventional CI combustion strategy. Overall, this study demonstrated that all LTC strategies could be used for PM and NOx reduction; however, the RCCI combustion strategy was more dominant in NOx and PM reduction, in addition to having an excellent capability of using alternative fuel in the quest for developing sustainable transport solution.

Biodiesel is considered as a valuable and less toxic alternative to diesel. However, cellular and molecular effects of repeated exposure to biodiesel emissions from a recent engine equipped with a diesel particle filter (DPF) remain to be characterized. To gain insights about this point, the lung transcriptional signatures were analyzed for rats (n = 6 per group) exposed to filtered air, 30% rapeseed biodiesel (B30) blend or reference diesel (RF0), upstream and downstream a DPF, for 3 weeks (3 h/day, 5 days/week).Genomic analysis revealed a modest regulation of gene expression level (lower than a 2-fold) by both fuels and a higher number of genes regulated downstream the DPF than upstream, in response to either RF0 or to B30 exhaust emissions. The presence of DPF was found to notably impact the lung gene signature of rats exposed to B30. The number of genes regulated in common by both fuels was low, which is likely due to differences in concentrations of regulated pollutants in exhausts, notably for compound organic volatiles, polycyclic aromatic hydrocarbons, NO or NOx. Nevertheless, we have identified some pathways that were activated for both exhaust emissions, such as integrin-, IGF-1- and Rac-signaling pathways, likely reflecting the effects of gas phase products. By contrast, some canonical pathways relative to “oxidative phosphorylation” and “mitochondrial dysfunction” appear as specific to B30 exhaust emission; the repression of transcripts of mitochondrial respiratory chain in lung of rats exposed to B30 downstream of DPF supports the perturbation of mitochondria function.This study done with a recent diesel engine (compliant with the European IV emission standard) and commercially-available fuels reveals that the diesel blend composition and the presence of an after treatment system may modify lung gene signature of rats repeatedly exposed to exhaust emissions, however in a rather modest manner.

Seasonal and diurnal variations of carbonyl compounds were investigated in the ambient air of a mountainous city in China, from September 2014 to July 2015. The most abundant carbonyl compounds are formaldehyde, acetaldehyde and acetone, propionaldehyde and methacryladehyde (MACR), which were all measured in most samples. The average concentrations of formaldehyde, acetaldehyde, acetone, propionaldehyde and MACR in the atmosphere in Changsha were broken down into each season: 6.57, 3.29, 3.66, 0.67 and 0.54 μg/m³ respectively during Spring, 14.09, 8.28, 9.02, 1.28 and 0.6 μg/m³, respectively during Summer, 9.24, 5.48, 8.62, 0.73 and 0.62 μg/m³, respectively during Autumn, and 5.88, 4.84, 7.84, 0.87 and 0.26 μg/m³ respectively during Winter. And majority of the species had higher concentration during noon, showing photochemical oxidation and human activities played an important role in diurnal variation. The highest average C1/C2 (formaldehyde/acetaldehyde) ratio was observed in summer (2.10) compared to those (1.33–2.03) in other seasons, implying the photochemical activities had a positive effect on increasing the ratio of C1/C2. In this study, the monthly concentration of formaldehyde produced from isoprene accounts for 4.8%–39.1% of formaldehyde in ambient air. Strong correlation among some carbonyl compounds means that they came from the same sources. Photochemical reaction was the main source of carbonyl compounds in summer and vehicular exhaust (gasoline and diesel engines) in winter. Changsha is not a completely urbanized city and it is rich in vegetation of broadleaf evergreen shrubs. Both atmospheric photochemical reactions and anthropogenic sources, including vehicular exhaust and industrial processes, dominate the levels of carbonyls. The ILTCR and HQ values of formaldehyde and acetaldehyde are 1.23E-04 and 1.34E-05, 2.80E-01 and 1.86E-01, respectively.

Chemical mass balance (CMB) modeling and radiocarbon measurements were combined to evaluate the sources of carbonaceous fine particulate matter (PM2.5) in Shenzhen, China during and after the 2011 summer Universiade games when air pollution control measurements were implemented to achieve air quality targets. Ambient PM2.5 filter samples were collected daily at two sampling sites (Peking University Shenzhen campus and Longgang) over 24 consecutive days, covering the controlled and uncontrolled periods. During the controlled period, the average PM2.5 concentration was less than half of what it was after the controls were lifted. Organic carbon (OC), organic molecular markers (e.g., levoglucosan, hopanes, polycyclic aromatic hydrocarbons), and secondary organic carbon (SOC) tracers were all significantly lower during the controlled period. After pollution controls ended, at Peking University, OC source contributions included gasoline and diesel engines (24%), coal combustion (6%), biomass burning (12.2%), vegetative detritus (2%), biogenic SOC (from isoprene, α-pinene, and β-caryophyllene; 7.1%), aromatic SOC (23%), and other sources not included in the model (25%). At Longgang after the controls ended, similar source contributions were observed: gasoline and diesel engines (23%), coal combustion (7%), biomass burning (17.7%), vegetative detritus (1%), biogenic SOC (from isoprene, α-pinene, and β-caryophyllene; 5.3%), aromatic SOC (13%), and other sources (33%). The contributions of the following sources were smaller during the pollution controls: biogenic SOC (by a factor of 10–16), aromatic SOC (4–12), coal combustion (1.5–6.8), and biomass burning (2.3–4.9). CMB model results and radiocarbon measurements both indicated that fossil carbon dominated over modern carbon, regardless of pollution controls. However, the CMB model needs further improvement to apportion contemporary carbon (i.e. biomass burning, biogenic SOC) in this region. This work defines the major contributors to carbonaceous PM2.5 in Shenzhen and demonstrates that control measures for primary emissions could significantly reduce secondary organic aerosol (SOA) formation.

The contribution of diesel exhaust to atmospheric pollution is a major concern for public health, especially in terms of occurrence of lung cancers. The present study aimed at addressing the toxic effects of a repeated exposure to these emissions in an animal study performed under strictly controlled conditions. Rats were repeatedly exposed to the exhaust of diesel engine. Parameters such as the presence of a particle filter or the use of gasoil containing rapeseed methyl ester were investigated. Various biological parameters were monitored in the lungs to assess the toxic and genotoxic effects of the exposure. First, a transcriptomic analysis showed that some pathways related to DNA repair and cell cycle were affected to a limited extent by diesel but even less by biodiesel. In agreement with occurrence of a limited genotoxic stress in the lungs of diesel-exposed animals, small induction of γ-H2AX and acrolein adducts was observed but not of bulky adducts and 8-oxodGuo. Unexpected results were obtained in the study of the effect of the particle filter. Indeed, exhausts collected downstream of the particle filter led to a slightly higher induction of a series of genes than those collected upstream. This result was in agreement with the formation of acrolein adducts and γH2AX. On the contrary, induction of oxidative stress remained very limited since only SOD was found to be induced and only when rats were exposed to biodiesel exhaust collected upstream of the particle filter. Parameters related to telomeres were identical in all groups. In summary, our results point to a limited accumulation of damage in lungs following repeated exposure to diesel exhausts when modern engines and relevant fuels are used. Yet, a few significant effects are still observed, mostly after the particle filter, suggesting a remaining toxicity associated with the gaseous or nano-particular phases.

Semivolatile organic compounds (SVOCs) represent a dominant category of secondary organic aerosol precursors that are increasingly included in air quality models. In the present study, an experimental system was developed and applied to a light-duty diesel engine to determine the emission factors of particulate SVOCs (pSVOCs) and nonvolatile particulate matter (PM) components at dilution ratios representative of ambient conditions. The engine was tested under three steady-state operation modes, using ultra-low-sulfur diesel (ULSD), three types of pure biodiesels and their blends with ULSD. For ULSD, the contribution of pSVOCs to total particulate organic matter (POM) mass in the engine exhaust ranged between 21 and 85%. Evaporation of pSVOCs from the diesel particles during dilution led to decreases in the hydrogen to carbon ratio of POM and the PM number emission factor of the particles. Substituting biodiesels for ULSD could increase pSVOCs emissions but brought on large reductions in black carbon (BC) emissions. Among the biodiesels tested, tallow/used cooking oil (UCO) biodiesel showed advantages over soybean and canola biodiesels in terms of both pSVOCs and nonvolatile PM emissions. It is noteworthy that PM properties, such as particle size and BC mass fraction, differed substantially between emissions from conventional diesel and biodiesels.

This study investigates the morphology and nanostructure of soot particles during cold-start and hot-start engine operation of a diesel engine using oxygenated fuels. The soot samples were analysed using transmission electron microscopy. The oxygen content in the fuel was varied between 0 and 12%. The results showed that the primary particles during cold-start have significantly smaller size when compared to hot-start engine operation. The addition of oxygenated fuels also resulted in smaller sized primary particles. Smaller radius of gyration and higher fractal dimension of soot aggregates during cold-start would mean smaller aggregate size with a more compact structure. Shorter fringes with a higher inter-fringe spacing for cold-start would mean lower graphitisation of soot particles that could be related to higher oxidation reactivity of soot particles.

In the transportation sector, the share of biofuels such as biodiesel is increasing and it is known that such fuels significantly affect NOx emissions. In addition to NOx emission from diesel engines, which is a significant challenge to vehicle manufacturers in the most recent emissions regulation (Euro 6.2), this study investigates NO₂ which is a toxic emission that is currently unregulated but is a focus to be regulated in the next regulation (Euro 7). This manuscript studies how the increasing share of biofuels affects the NO₂, NOx, and NO₂/NOx ratio during cold-start (in which the after-treatment systems are not well-effective and mostly happens in urban areas). Using a turbocharged cummins diesel engine (with common-rail system) fueled with diesel and biofuel derived from coconut (10 and 20% blending ratio), this study divides the engine warm-up period into 7 stages and investigates official cold- and hot-operation periods in addition to some intermediate stages that are not defined as cold in the regulation and also cannot be considered as hot-operation. Engine coolant, lubricating oil and exhaust temperatures, injection timing, cylinder pressure, and rate of heat release data were used to explain the observed trends. Results showed that cold-operation NOx, NO₂, and NO₂/NOx ratio were 31–60%, 1.14–2.42 times, and 3–8% higher than the hot-operation, respectively. In most stages, NO₂ and the NO₂/NOx ratio with diesel had the lowest value and they increased with an increase of biofuel in the blend. An injection strategy change significantly shifted the in-cylinder pressure and heat release diagrams, aligned with the sudden NOx drop during the engine warm-up. The adverse effect of cold-operation on NOx emissions increased with increasing biofuel share.

NO₂ oxidation of soot exhausted from engines is more efficient than O₂ under low-temperature conditions, and is crucial for diesel particulate filter to control soot pollution. To explore the principle behind accelerating soot oxidation by NO₂, this paper uses density functional theory to reveal soot oxidation process by NO₂. This study contributes to understanding rules of soot oxidation by NO₂ and perfecting soot oxidation models to develop soot emission control technologies. Results show that NO₂ oxidation of pyrene radical involves three steps. Firstly, NO₂ attacks the C∗ atom to form –C (NO₂) with reaction energy of 306.3 kJ/mol, which decomposes to produce a –C (O) compound. Secondly, another NO₂ molecule climbs over an energy barrier of 8.8 kJ/mol, and changes into a –C (ONO₂) intermediate on –C (O). Finally, the N or O atom of NO₂ attacks –C (O) for a second time to help open aromatic ring for releasing CO or CO₂. Further decomposition of –C (NO₂) and –C (ONO₂) requires activation energies of 81.6 kJ/mol, 75.7 kJ/mol, and 53.5 kJ/mol, respectively, on preferential pathways. Calculations prove that attacks of O atom from NO₂ on C∗ help open the aromatic ring more efficiently than N atom.