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.

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.

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.

Two kinds of C₈ isomers, di-n-butyl ether (DNBE) and 1-octanol, as potential oxygen-containing alternative fuels, show important value in the trade-off between efficiency and emission. In the present work, the effects of DNBE/1-octanol with different proportions (0, 10%, and 20%) blended into diesel on the combustion characteristics, fuel economy, and emission characteristics in a six-cylinder heavy-duty diesel engine were studied at low, medium, and high loads. 1-Octanol with a 20% blending ratio showed different combustion characteristics in the cylinder compared with the other fuels. The economic analysis showed that the brake specific fuel consumption of DNBE–diesel blend fuels was higher than that of 1-octanol–diesel blend fuels, while brake thermal efficiency was the opposite tendency. The emissions of nitrogen oxides (NOx), hydrocarbons (HC), and carbon monoxide (CO) were affected by the types of blend fuels, blending ratios, and loads. In comparison with 1-octanol–diesel blend fuels, the addition of DNBE in diesel promoted the emission of nitrogen oxides, but inhibited the emissions of soot, HC, and CO. DNBE– and 1-octanol–diesel blend fuels increased the weighted brake specific fuel consumption but decreased the weighted brake thermal efficiency compared with diesel in the World Harmonized Stationary Cycle test cycle of Euro VI regulation. The weighted NOx, HC, soot, and CO emissions of blend fuels depended on the types of blend fuels and blend ratios. The weighted NOx, HC, and soot emissions were reduced by blending 1-octanol into diesel, while the weighted CO emission was increased. The weighted CO and soot emissions of diesel blended with DNBE were reduced than that of diesel.

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.

The main purpose of current study is accurate prediction of NOx emissions from diesel engines considering in-cylinder ion current. To reach this goal, a validated thermodynamic multi-zone model was used. A modified chemical kinetics mechanism of diesel fuel oxidation was used too. A chemical kinetics mechanism of NOX formation including 103 reactions was added to the main mechanism. A set of ions and ionic reactions was added to the developed chemical kinetics mechanism and finally a modified chemical kinetics mechanism with 445 reactions and 100 species was formed. The developed mechanism was coupled to the multi-zone model and a diesel engine was simulated. The importance of Zeldovich mechanism, prompt mechanism, N₂O mechanism and NNH mechanism were investigated. The progress rates of reactions were calculated and important reactions were identified. The results show that the oxygenated ions, NO⁺, O⁺ and O₂⁺, has more effects on NO production than other ions. The prompt mechanism plays an important role in predicting the ion current inside the chamber. Because this mechanism has reactions that can lead to CH production. The CH radicals produced by this mechanism can be employed by basic ionic reactions and lead to ion production. The results show that using NOx related ionic reactions results in accurate prediction of engine exhaust NOx.

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.

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.

Recently it became known that Volkswagen Group has been cheating with emission tests for diesel engines over the last six years, resulting in on-road emissions vastly exceeding legal standards for nitrogen oxides in Europe and the United States. Here, we provide an estimate of the public health consequences caused by this fraud. From 2009 to 2015, approximately nine million fraudulent Volkswagen cars, as sold in Europe and the US, emitted a cumulative amount of 526 ktonnes of nitrogen oxides more than was legally allowed. These fraudulent emissions are associated with 45 thousand disability-adjusted life years (DALYs) and a value of life lost of at least 39 billion US dollars, which is approximately 5.3 times larger than the 7.3 billion US dollars that Volkswagen Group has set aside to cover worldwide costs related to the diesel emissions scandal.