Environmental and health risk implications of unregulated emissions from advanced biofuels in a Euro 6 engine.

The use of conventional and advanced biofuels is part of the efforts to reduce greenhouse gases and harmful exhaust gaseous emissions. This study investigates the unregulated emissions in gas and particles from a Euro 6b diesel engine, operated with four unconventional and advanced biofuels (two hydrogenated terpenic biofuels, a polyoxymethylene dimethyl ether, and a glycerol-derived biofuel), blended with diesel fuel and pure hydrotreated vegetable oil as base biofuel. The engine was operated following WLTC starting from cold-engine conditions. Gas phase samples were collected at each phase of the driving cycle and particulate matter (PM) samples were collected from a dilution tunnel at the end of the driving cycle. A total of 16 PAH and 13 carbonyls were analyzed. In addition, the apoptotic index induced by gas and particle emissions was determined. In the gaseous phase, the total PAH and carbonyl emission factors were higher at the low-speed phase for all fuels. Gas-phase PAH emission factors exceeded particle-bound PAH. Carbonyl emission factors ranged from 0.12 ± 0.012 to 25.3 ± 4.2 mg/km, markedly exceeding gaseous PAH emissions, which ranged from 20.7 ± 1.5 to 51.7 ± 8.9 µg/km. Diesel fuel exhibited the highest carbonyl emissions and its blend with 20% of hydrogenated turpentine exhibited the highest PAH emissions at the end of the WLTC, both due to high emissions at the low-speed phase. Although particle-bound PAH comprise only a small fraction of total PAH emissions, both phases (gas and particles) contributed approximately equal to the toxicity associated with carcinogenic PAH. The apoptotic cells percentage increased in a dose-dependent manner and was significantly higher in cells exposed to gas phase-derived samples. The apoptotic index induced by particulate matter samples did not show a concentration-response effect for any of the fuels.

WLTC and real-driving emissions for an autochthonous biofuel from wine-industry waste.

Residues from the wine industry constitute an abundant feedstock for biodiesel production in wine-producing countries. The use of grapeseed oil, together with bioethanol obtained from distillation of wine surplus or grape skins and stalks and wine lees, as reagents in the transesterification reaction, results in a mixture of fatty acid ethyl esters (FAEE), which is a fully renewable, autochthonous, and waste-derived biofuel. In this work, a blend of FAEE produced from grape seed oil with diesel fuel was selected based on a study of fuel properties, and the optimal blend, with 30% v/v of FAEE, was tested in a Euro 6 engine following the Worldwide harmonized Light-duty Test Cycle (WLTC) and a Real Driving Emissions Cycle (RDE), as required in the new certification procedures. Engine performance and emissions from this blend and a commercial diesel fuel were compared. The FAEE blend showed a significant potential to reduce particle emissions, both in mass and number (from 23% in number to 46.5% in mass for WLTC, and from 56% in number to 61% in mass for RDE), and CO (25.5% for WLTC and 39% for RDE) but penalized NOx (32% higher in WLTC and 26.4% higher in RDE).

Hydrogenated or oxyfunctionalized turpentine: options for automotive fuel components.

Many concerns, such as economic and technical viability and social and ethical aspects, must be considered for a feedstock selection for advanced biofuels. Industrialized countries promote the use of industrial waste or by-products for this purpose. In particular, turpentine has several properties which make it an attractive source for biofuels, including its possible industrial waste origin. Nevertheless, turpentine has shown some disadvantages when blended directly with diesel, especially because it increases the sooting tendency. On the contrary, some derivatives of turpentine can be suitable for diesel blends. Thus, the evaluation of their properties is necessary. In the present work, the properties of hydrogenated and oxyfunctionalized turpentine have been analysed and compared with the purpose of elucidating their benefits and drawbacks in diesel fuel applications, using European standards as a reference. The results show a promising application of both hydroturpentine and oxyturpentine as diesel components. While hydroturpentine significantly improves the diesel cold flow properties, oxyturpentine noticeably reduces the sooting tendency.

Optimized Production of Fatty Acid Ethyl Esters (FAEE) from Waste Frying Oil by Response Surface Methodology.

ABSTRACT: In Europe, recent regulations on advanced biofuels have prompted a search for new fuel sources and the development of synthesis methods meeting the demanding specifications of the sector. However, in developing countries such as Algeria, where a significant stock of frying oil is unused, the use of diesel engines powered with waste-oil-derived biofuels must be explored. In this work, the variables related to the transesterification reaction from this frying oil with ethanol are analyzed using response surface methodology. From this analysis, only the reaction time and temperature have been determined as relevant parameters. In addition, FT-IR analysis has proven a useful tool to analyse the conversion in the transesterification reaction of waste frying oil with ethanol and is cheaper and quicker than GC-FID. This sustainable biofuel (FAEE), mixed with a diesel and pure fuel, has been physically characterized. The mixture of FAEE at 30% by volume with diesel meets the requirements demanded in standard EN 590 and can be classified as winter diesel class D. As a pure biofuel, only its high cold flow temperatures could constitute a drawback for exporting to temperate climates but not for internal consumption.

Oxidation Stability: The Bottleneck for the Development of a Fully Renewable Biofuel from Wine Industry Waste.

Wine industry generates a large amount of biowaste, such as grape marc and wine lees, which is considered in the Directive (EU) 2018/2001 as an adequate feedstock to produce advanced biofuels. Grapeseed oil fatty acid ethyl esters (FAEEs) can be obtained from oil extracted from grape marc and bioethanol distilled from wine lees or wine surplus. Although FAEE still has no specific standard, grapeseed oil FAEE would fulfill all of the properties set by the standard EN 14214, except oxidation stability. This work analyzes the effect of natural antioxidants on the oxidation stability of grapeseed oil FAEE, using grapeseed oil fatty acid methyl esters (FAMEs) as a reference for comparison. On the one hand, the biofuel, produced with conventional transesterification, was mixed with FAME and FAEE produced via in situ transesterification. On the other hand, antioxidants extracted from grapeseed or defatted grapeseed flour were added to the biofuel. The results show that (1) FAEE has worse oxidation stability than FAME, (2) in situ transesterification improves the oxidation stability, and (3) addition of natural antioxidants is hindered by their low solubility in alkyl esters. Finally, the concentration of antioxidants, measured by UV-vis spectroscopy, showed a correlation between the absorbance at 285 nm (characteristic of phenolic compounds) and the induction time (IT) of the samples.

Influence of molecular structure of oleoresin-derived compounds on flame properties and emissions from laminar flames.

The search for renewable fuels or components which may improve or replace fossil fuels is an important step towards a sustainable future. In particular, the pine oleoresin produced by conifer trees, which is composed by turpentine oil and non-volatile rosin, may be transformed into alternative fuels. In this work, combustion of six molecules which can be obtained from oleoresin either by distillation (i.e., α- and ß-pinene) or by further oxyfunctionalization (nopol, terpineol, myrtenol, and borneol) was studied to assess the potential of pine oleoresin as raw material for biofuels. Emission indices of the main pollutants (carbon monoxide-CO, unburned hydrocarbons-UHC, and nitrogen oxides-NOx) were obtained in non-premixed co-flow laminar flames of the oleoresin-derived molecules blended with n-heptane. The main characteristics of the flames (i.e., temperature and height) were also determined. Significant increase in flame temperature and reduction in CO and UHC emissions with respect to n-heptane were observed with nopol, terpineol, and myrtenol, along an increase in NOx emissions, suggesting an improvement in combustion performance. In addition, differences in emission indices, evidenced for these molecules (even between α- and ß-pinene), suggest the importance of the molecular structure in the combustion reaction.

Optical determination of black carbon mass concentrations in snow samples: A new analytical method.

Black carbon (BC) aerosols in the atmosphere strongly affect direct radiative forcing and climate, not only while suspended in the atmosphere but also after deposition onto high albedo surfaces. Snow surfaces are especially sensitive to BC deposition, because of their high surface albedo and additional positive feedbacks further enhance faster snowpack melting caused by BC deposition, resulting in modifications in water resources and recession of glaciers. For the analysis of BC deposition on snow, a precise quantification of BC mass is needed. Instead, optical methods have the potential of quantifying only BC, based on its characteristic spectral absorption. Commercial optical transmissometers commonly use quartz filters to filter BC and measure its optical attenuation. They are calibrated for the determination of BC mass concentrations in air, but not adapted or calibrated for their determination in water or snowmelt samples. Additionally, they are generally calibrated using BC-simulating materials that are not representative of ambient BC particles. Here, a new analytical method is demonstrated for the quantitative determination of BC mass concentration in snow samples that considers filtering of melted snow with polycarbonate filters in a new device, and optical filter attenuation BC mass concentration measurement (880 nm). The attenuation can be obtained with any optical equipment that can measure the 880-nm attenuation of filters impacted with BC/snow impurities. This method has been calibrated using real diesel vehicle exhaust soot with well-known optical properties as reference material, yielding a multipoint calibration curve for common BC concentration levels in snow. The limits of detection (0.011 mg of BC), quantification (0.036 mg of BC) and reproducibility (96.39%) of this new analytical method have been determined. Real surface snow samples collected at different locations in "Los Andes" mountains of Chile were measured with this method given a BC concentrations ranged from 151 to 5987 µg kg-1.

Diesel particulate emissions from used cooking oil biodiesel.

Two different biodiesel fuels, obtained from waste cooking oils with different previous uses, were tested in a DI diesel commercial engine either pure or in 30% and 70% v/v blends with a reference diesel fuel. Tests were performed under a set of engine operating conditions corresponding to typical road conditions. Although the engine efficiency was not significantly affected, an increase in fuel consumption with the biodiesel concentration was observed. This increase was proportional to the decrease in the heating value. The main objective of the work was to study the effect of biodiesel blends on particulate emissions, measured in terms of mass, optical effect (smoke opacity) and size distributions. A sharp decrease was observed in both smoke and particulate matter emissions as the biodiesel concentration was increased. The mean particle size was also reduced with the biodiesel concentration, but no significant increases were found in the range of the smallest particles. No important differences in emissions were found between the two tested biodiesel fuels.

Emission factors from different burning stages of agriculture wastes in Mexico.

Open-air burning of agricultural wastes from crops like corn, rice, sorghum, sugar cane, and wheat is common practice in Mexico, which in spite limiting regulations, is the method to eliminate such wastes, to clear the land for further harvesting, to control grasses, weeds, insects, and pests, and to facilitate nutrient absorption. However, this practice generates air pollution and contributes to the greenhouse effect. Burning of straws derived from the said crops was emulated in a controlled combustion chamber, hence determining emission factors for particles, black carbon, carbon dioxide, carbon monoxide, and nitric oxide throughout the process, which comprised three apparent stages: pre-ignition, flaming, and smoldering. In all cases, maximum particle concentrations were observed during the flaming stage, although the maximum final contributions to the particle emission factors corresponded to the smoldering stage. The comparison between particle size distributions (from laser spectrometer) and black carbon (from an aethalometer) confirmed that finest particles were emitted mainly during the flaming stage. Carbon dioxide emissions were also highest during the flaming stage whereas those of carbon monoxide were highest during the smoldering stage. Comparing the emission factors for each straw type with their chemical analyses (elemental, proximate, and biochemical), some correlations were found between lignin content and particle emissions and either particle emissions or duration of the pre-ignition stage. High ash or lignin containing-straw slowed down the pre-ignition and flaming stages, thus favoring CO oxidation to CO2.

Emission factors for PM2.5, CO, CO2, NOx, SO2 and particle size distributions from the combustion of wood species using a new controlled combustion chamber 3CE.

The objective of this research was to determine emission factors (EF) for particulate matter (PM2.5), combustion gases and particle size distribution generated by the combustion of Eucalyptus globulus (EG), Nothofagus obliqua (NO), both hardwoods, and Pinus radiata (PR), softwood, using a controlled combustion chamber (3CE). Additionally, the contribution of the different emissions stages associated with the combustion of these wood samples was also determined. Combustion experiments were performed using shaving size dried wood (0% humidity). The emission samples were collected with a tedlar bag and sampling cartridges containing quartz fiber filters. High reproducibility was achieved between experiment repetitions (CV<10%, n=3). The EF for PM2.5 was 1.06gkg-1 for EG, 1.33gkg-1 for NO, and 0.84gkg-1 for PR. Using a laser aerosol spectrometer (0.25-34µm), the contribution of particle emissions (PM2.5) in each stage of emission process (SEP) was sampled in real time. Particle size of 0.265µm were predominant during all stages, and the percentages emitted were PR (33%), EG (29%), and NO (21%). The distributions of EF for PM2.5 in pre-ignition, flame and smoldering stage varied from predominance of the flame stage for PR (77%) to predominance of the smoldering stage for NO (60%). These results prove that flame phase is not the only stage contributing to emissions and on the contrary, pre-ignition and in especial post-combustion smoldering have also very significant contributions. This demonstrates that particle concentrations measured only in stationary state during flame stage may cause underestimation of emissions.

Polycyclic Aromatic Hydrocarbons (PAHs) produced in the combustion of fatty acid alkyl esters from different feedstocks: Quantification, statistical analysis and mechanisms of formation.

Polycyclic Aromatic Hydrocarbons (PAHs) are pollutants of concern due to their carcinogenic and mutagenic activity. Their emissions are mainly related with the combustion or pyrolysis of the organic matter, such as in fossil fuels combustion. It is important to characterize PAHs in the combustions of biofuels due to their increasing importance in the actual energetic setting. There is a lot of research focused in PAHs emission due to the combustion in diesel engines; but only few of them have analyzed the effect of raw material and type of alcohol used in the transesterification process. Different raw materials (i.e. animal fat, palm, rapeseed, linseed, peanut, coconut, and soybean oils) have been used for obtaining FAME and FAEE. A method for measuring PAHs generated during combustion in a bomb calorimeter has been developed. Combustion was made at different oxygen pressures and the samples were taken from the bomb after each combustion. Samples were extracted and the PAHs amounts formed during combustion were analyzed by GC-MS. This research shows the statistical relationships among the 16 PAHs of concern, biodiesel composition and oxygen pressure during combustion.

A method to determine the fractal dimension of diesel soot agglomerates.

Soot agglomerates emitted by diesel engines are composed of primary particle forming irregular clusters. Such irregularity can be quantified by the fractal dimension, whose determination depends on certain parameters not unanimously established, such as the prefactor of the power law relationship. Mean values of the fractal dimension of large collections of agglomerates are usually determined in literature by least-square regression fittings to the power law relationship. In this paper, an iterative method to determine the fractal dimension of individual agglomerates is proposed instead, thus making possible a better discrimination of effects. Functions depending on the fractal dimension and the number of primary particles are proposed for the prefactor and for the overlapping parameter (a measure of the overlap that the primary particles provoke among themselves when projected). Therefore, extreme cases (agglomerates forming a compact sphere and an aligned chain of primary particles) were taken as boundary conditions, for which a geometrical analysis has been performed. The method has been adjusted by comparison with cluster-cluster aggregation models taken from literature, and has proved to have good sensitivity and low loss of information. Some examples are shown from transmission electron microscopy (TEM) images of agglomerates obtained with thermophoretic sampling from the exhaust gas of a diesel engine under different operating conditions.

Correlation for the estimation of the density of fatty acid esters fuels and its implications. A proposed Biodiesel Cetane Index.

Biodiesel fuels (methyl or ethyl esters derived from vegetables oils and animal fats) are currently being used as a means to diminish the crude oil dependency and to limit the greenhouse gas emissions of the transportation sector. However, their physical properties are different from traditional fossil fuels, this making uncertain their effect on new, electronically controlled vehicles. Density is one of those properties, and its implications go even further. First, because governments are expected to boost the use of high-biodiesel content blends, but biodiesel fuels are denser than fossil ones. In consequence, their blending proportion is indirectly restricted in order not to exceed the maximum density limit established in fuel quality standards. Second, because an accurate knowledge of biodiesel density permits the estimation of other properties such as the Cetane Number, whose direct measurement is complex and presents low repeatability and low reproducibility. In this study we compile densities of methyl and ethyl esters published in literature, and proposed equations to convert them to 15 degrees C and to predict the biodiesel density based on its chain length and unsaturation degree. Both expressions were validated for a wide range of commercial biodiesel fuels. Using the latter, we define a term called Biodiesel Cetane Index, which predicts with high accuracy the Biodiesel Cetane Number. Finally, simple calculations prove that the introduction of high-biodiesel content blends in the fuel market would force the refineries to reduce the density of their fossil fuels.

Geometrical determination of the lacunarity of agglomerates with integer fractal dimension.

Different agglomerates composed by a variable number of spherical primary particles corresponding to extreme and intermediate values of fractal dimension (D(f)=1, D(f)=2 and D(f)=3) are analysed in this work. In each case, the moment of inertia, diameter of gyration and prefactor of the power-law relationship are determined as a function of the number of composing primary particles. The obtained results constitute the geometrical data base for the development of a method for the determination of the fractal dimension of individual agglomerates from their planar projections, although it is not the aim of this paper to describe the method itself. As a result of these calculations, the prefactor of the power-law relationship was shown not to be a constant parameter, but to tend asymptotically to a limit value with increasing number of primary particles. This limit value is closely related with the compactness of the initial geometrical arrangement in the agglomerate, this justifying the historical association of this parameter with the lacunarity of the agglomerate. A correlation for the determination of the prefactor as a function of the fractal dimension and the number of elementary structures is proposed and compared with other methods proposed in the literature.

Determination of enthalpy of formation of methyl and ethyl esters of fatty acids.

Biofuels composed by fatty acid methyl esters are widely used as partly substituting fuels for diesel fossil fuels. Additionally, it is expected that the diesel biofuel norms will be extended to ethyl esters produced from bioethanol in the upcoming years. A precise knowledge of the standard enthalpy of formation is necessary for the calculation of some parameters useful for the analysis of the combustion process and emissions of a diesel engine operating with different fuels, such as the heating value, the adiabatic flame temperature or the kinetic mechanisms. However, experimental data for this property are scarce, and only available for short-chain, saturated methyl esters. In this work, four estimation methods for the calculation of the enthalpy of formation are examined and compared. Three of them are simple methods based on groups or bonds contribution, and another one is a computational method (with Gaussian 03 software). After presenting the implementation rules for each of them, conclusions are stated based on the results attained. Gaussian and Benson-Groups methods seem to be more accurate in predicting the actual values of the enthalpy of formation, both methods considering the separation between double bonds and the edge effects in the molecule. However, only the Gaussian method considers the effect of the position of the double bond in the molecule for all the unsaturated esters.