The present study investigates the transesterification of corn oil with methanol over two oxides of MgO and ZnO at 65 ͦC and 1 atm. These two catalysts have been prepared via a conventional co-precipitation process. As for MgO, the corresponding mixed metal nitrate solution has been mixed and heated at the presence of urea. ZnO has also been synthesized by co-precipitation of metal acetate at the presence of oxalic acid and ethanol. The catalysts then have been characterized by means of X-Ray Diffraction (XRD) and Scanning Electron Microscope (SEM). XRD results indicate high purity for both catalysts. Also, catalytic activity has been evaluated in methanol reflux temperature through corn oil transesterification, with the impacts of reaction variables, like catalyst amount, methanol/oil molar ratio, and reaction time on biodiesel yield, investigated by means of HNMR spectrum. Under appropriate transesterification conditions at 65 °C (catalyst amount= 5%, methanol/ oil ratio= 20, and reaction time= 10 hr), an ME content of 62.61% can be achieved, using MgO catalyst. Similarly, the experiments have been repeated to achieve the best yield, using ZnO catalyst, with the highest rate, equal to 53.1%, obtained in 9% of catalyst and methanol/oil ratio of 30 over 10 hr. Furthermore, reusability of ZnO and MgO has been evaluated in transesterification reaction.

Biodiesel side stream waste glycerol was identified as a cheap carbon source for rhamnolipids (RLs) production which at the same time could improve the management of waste. The present study aimed to produce RLs by using Pseudomonas aeruginosa RS6 utilizing waste glycerol as a substrate and to evaluate their physico-chemicals properties. Fermentation conditions such as temperature, initial medium pH, waste glycerol concentration, nitrogen sources and concentrations resulted in different compositions of the mono- and di-RLs produced. The maximum RLs production of 2.73 g/L was obtained when P. aeruginosa RS6 was grown in a basal salt medium supplemented with 1% waste glycerol and 0.2 M sodium nitrate at 35 °C and pH 6.5. At optimal fermentation conditions, the emulsification index (E₂₄) values of cooking oil, diesel oil, benzene, olive oil, petroleum, and kerosene were all above E₂₄₌50%. The surface tension reduction obtained from 72.13 mN/m to 29.4–30.4 mN/m was better than the surface activity of some chemical-based surfactants. The RLs produced possessed antimicrobial activities against Gram-negative and Gram-positive bacteria with values ranging from 37% to 77% of growth inhibition when 1 mg/mL of RLs was used. Concentrations of RLs below 1500 μg/mL did not induce phytotoxicity effects on the tested seeds (Vigna radiata) compared to the chemical-based- surfactant, SDS. Furthermore, RLs tested on zebrafish (Danio rerio) embryos only exhibited low acute toxicity with an LC₅₀ value of 72.97 μg/mL at 48 h of exposure suggesting a green and eco-biochemical worthy of future applications to replace chemical-based surfactants.

Recycling of waste glycerol derived from biodiesel production to high value-added chemicals is essential for sustainable development of Bio-Circular-Green Economy. This work studied the conversion of glycerol to 1,3-propanediol over Pt/WOₓ/Al₂O₃ catalysts, pointing out the impacts of catalyst pore sizes and operating conditions for maximizing the yield of 1,3-propanediol. The results suggested that both pore confinement effect and number of available reactive metals as well as operating conditions determined the glycerol conversion and 1,3-propanediol selectivity. The small-pore 5Pt/WOₓ/S–Al₂O₃ catalyst (6.1 nm) gave a higher Pt dispersion (32.0%), a smaller Pt crystallite size (3.5 nm) and a higher number of acidity (0.47 mmol NH₃ g⁻¹) compared to those of the large-pore 5Pt/WOₓ/L-Al₂O₃ catalyst (40.3 nm). However, glycerol conversion and 1,3-propanediol yield over the small-pore 5Pt/WOₓ/S–Al₂O₃ catalyst were significantly lower than those of the large-pore Pt/WOₓ/L-Al₂O₃ catalyst, suggesting that the diffusional restriction within the small-pore catalyst suppressed transportation of molecules to expose catalytic active sites, favoring the excessive hydrogenolysis of 1,3-propanediol, giving rise to undesirable products. The best 1,3-propanediol yield of 32.8% at 78% glycerol conversion were achieved over the 5Pt/WOₓ/L-Al₂O₃ under optimal reaction condition of 220 °C, 6 MPa, 5 h reaction time and amount of catalyst to glycerol ratio of 0.25 g mL⁻¹. However, the 1,3-propanediol yield and glycerol conversion decreased to 19.6% and 51% after the 4th reaction-regeneration which were attributed to the carbonaceous deposition and the agglomeration of Pt particles.

In this work, valorisation pathways of brewers’ spent grains (BSG) towards biofuels production under the biorefinery concept were studied utilizing experimental data that provide a common base for straightforward comparison. The dehydration and the recovery of used oil, bioethanol and biogas from BSG were studied. The process units involved were thoroughly investigated and optimized. The oil extraction efficiency reached up to 70% using solid-liquid extraction process with hexane as solvent. The optimal ethanol yield achieved was 45% after the application of acid pretreatment, enzymatic hydrolysis with CellicCTec2 and fermentation with S. Cerevisiae. As far as biogas potential is concerned, the raw BSG, defatted BSG and stillage presented values equal to 379 ± 19, 235 ± 21 and 168 ± 39 mL biogas/g for respectively. Through the combination of the proposed schemes, three biorefinery scenarios were set up able to produce biodiesel, bioethanol and/or biogas. Material flow diagrams were set up in order to assess these schemes. Given that BSG could ensure ‘green’ energy production in the range of 4.5–7.0 million MJ/y if the European BSG potential is fully valorised, BSG could substantially contribute to the biofuel energy strategy.

The influence of palm oil biodiesel content on the cytotoxicity, mutagenicity and genotoxicity of particle- and gas-phase diesel vehicle emissions was investigated. The emissions were collected on-board of a EURO IV diesel truck, fuelled with mixtures of 10% (B10), 20% (B20) and 100% (B100) of palm oil biodiesel, under real driving conditions. Organic extracts of the particulate matter (PM) and gases were characterised for 17 PAH (including EPA priority) and used for the biological assay. Increasing biodiesel content in the fuel mixture results in a decrease in the PM and PAH emission factors, both in the particulate and gas-phase. The majority of the PAH are present in the gas-phase. The mutagenic potencies, in TA98 bacteria, are higher for B20 in both phases, whereas the mutagenicity emission factor, that takes into account the lower emission of PM and PAH, is not significantly different between the fuels. Higher direct mutagenicity (TA98 + S9) is observed in all the tested fuels, indicating the action of carcinogenic compounds other than non-substituted PAH. The gas-phase extracts present higher cytotoxicity and genotoxicity in lung epithelial cell A549, which may be related to the higher PAH content in the gas-phase. The increase in biodiesel content have a different impact on cytotoxicity, being larger in the gas-phase and lower in the particle-phase. This indicates that pulmonary toxicity may be higher for the gaseous emissions, due to the role of different toxic compounds compared to the PM. The adverse biological effects when biodiesel content increases are not consequent with the reduction of the PAH characterised, indicating that other toxic compounds are more relevant. Further investigations to identify these compounds are required in order to update and focus the efforts regarding emission targets and controls.

We report on commuters’ exposure to black carbon (BC), PM₂.₅ and particle number (PN, with aerodynamic diameter, dₐ, in the range 0.01 <dₐ< 1.0 μm) collected on-board diesel- and biodiesel-fuelled buses of the Bus Rapid Transit (BRT) system of the city of Curitiba, Brazil. Particulate concentrations measured at high sampling rates allowed the capture of fine gradients along the route and the comparison of in-cabin air pollution on buses of different technologies.Of all metrics, BC showed the largest discrepancies, with mean concentrations of 20.1 ± 20.0 μg m⁻³ and 3.9 ± 26.0 μg m⁻³ on diesel- and biodiesel-fuelled buses, respectively. Mean PM₂.₅ concentrations were similar (31.6 ± 28.5 μg m⁻³ and 29.0 ± 17.8 μg m⁻³), whilst mean PN concentrations were larger on the biodiesel buses (56,697 ± 26,800 # cm⁻³vs. 43,322 ± 32,243 # cm⁻³). The results are in line with studies on biodiesel emission factors that reported lower BC mass but more particles with smaller diameters. Our hypothesis is that different emission factors of diesel and biodiesel engines reflected in differences of in-cabin particulate concentrations. We found that the passenger exposure during the bus commutes was affected not only by the fuel used but also by the street geometry along the route, with segments with canyon configurations resulting in peak exposure to particulates. The results suggest that i) switching from diesel to biodiesel may help abate commuters’ exposure to BC particles on-board buses of the BRT system, whilst it would need to be complemented with after-treatment technologies to reduce emissions; ii) further reductions in exposure (to peaks in particular) could be achieved by changing bus routes to ones that avoid passing through narrow urban street canyons.

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.

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.

We tested the hypothesis that the biodegradation of volatile petroleum hydrocarbons (VPHs) in aerobic sandy soil is affected by the blending with 10 percent ethanol (E10) or 20 percent biodiesel (B20). When inorganic nutrients were scarce, competition between biofuel and VPH degraders temporarily slowed monoaromatic hydrocarbon degradation. Ethanol had a bigger impact than biodiesel, reflecting the relative ease of ethanol compared to methyl ester biodegradation. Denaturing gradient gel electrophoresis (DGGE) of bacterial 16S rRNA genes revealed that each fuel mixture selected for a distinct bacterial community, each dominated by Pseudomonas spp. Despite lasting impacts on soil bacterial ecology, the overall effects on VHP biodegradation were minor, and average biomass yields were comparable between fuel types, ranging from 0.40 ± 0.16 to 0.51 ± 0.22 g of biomass carbon per gram of fuel carbon degraded. Inorganic nutrient availability had a greater impact on petroleum hydrocarbon biodegradation than fuel composition.