Polycyclic aromatic hydrocarbons and trace elements dietary intake in inhabitants of Athens, Greece, based on a duplicate portion study.

Concentration levels of 26 polycyclic aromatic hydrocarbons and 20 trace elements were measured in dietary samples, in order to estimate the dietary intake and the potential exposure risk of the Greek population. Dietary samples were collected with the help of 30 volunteers inhabitants of Athens, Greece, according to the duplicate portion study (DPS) method where the determination of the compounds is conducted in the final consumed meal. DPS was selected as an alternative to a total diet study for its feasibility, low cost and realistic image that it provides. PAHs determination was performed by gas chromatography tandem mass spectrometry (GC-MS/MS) and trace elements determination by inductively coupled plasma mass spectrometry (ICP-MS). The estimated mean daily dietary exposure on 26 PAHs for an adult was estimated at 101.47 ng kg-1 body weight day-1, while moderate to low exposure was related to the type and amount of food consumed. Exposure levels to PAHs do not indicate a possible risk for the health of the study group. For toxic, potentially essential and/or essential trace elements the daily exposure calculated for Greek population was in accordance with the reference values of the health-based guidances and compared to previous diet studies reported for the population of other countries was in general similar to the lower bound exposure.

PM2.5-bound organosulfates in two Eastern Mediterranean cities: The dominance of isoprene organosulfates.

PM2.5 samples were collected during 2017-2018 at two Eastern Mediterranean urban sites in Greece, Athens and Patra, in order to study the abundances, the seasonal trends, the sources and the possible impact of gas phase pollutants on organosulfate formation. Each of the studied groups, except that of aromatic organosulfates, presented higher concentrations in Patra compared to those measured in Athens, from 1.1 (nitro-oxy organosulfates) to 3.6 times (isoprene organosulfates). At both sites, isoprene organosulfates was the dominant group which accounted on average for more than 50% of the total measured organosulfates, with the contribution being more than 80% during summer. Strong seasonality was observed at both sites, regarding the isoprene organosulfates, with an almost 21-fold increase from winter to summer. The same pattern, but to a lesser extent, was also observed for monoterpenes organosulfates at both sites. Alkyl organosulfates followed an identical seasonal trend with the highest mean concentrations observed during spring followed by autumn. The seasonality of anthropogenic organosulfates, multisource organosulfates and nitro-oxy organosulfates differed among the two sites or presented a more compound-specific variation. The isoprene-epoxydiol pathway appeared to be the dominant pathway of isoprene transformation, with the compounds iOS211, iOS213 and iOS215 being the major isoprene organosulfate compounds at both sites. Organosulfate contribution to the concentration of particulate matter presented common variation at both sites, ranging from 0.20 ± 0.14% (winter) to 2.5 ± 1.2% (summer) and from 0.21 ± 0.13% (winter) to 5.0 ± 2.5% (summer) for Athens and Patra, respectively. The increased NOx levels in Athens, appeared to affect isoprene organosulfate formation as well as the formation of monoterpene and decalin nitro-oxy organosulfates. Principal component analysis followed by multiple linear regression analysis highlighted the dominance of isoprene organosulfates. In Athens, the possible impact of transportation emissions on the formation of monoterpene nitro-oxy organosulfates is indicated while the correlation of naphthalene organosulfates with low molecular weight polycyclic aromatic hydrocarbons suggests that vehicle emissions may be a significant source. In Patra, the possible contribution of sea on methyl sulfate levels is denoted.

Monitoring of Polycyclic Aromatic Hydrocarbon Levels in Mussels (Mytilus galloprovincialis) from Aquaculture Farms in Central Macedonia Region, Greece, Using Gas Chromatography-Tandem Mass Spectrometry Method.

A new sensitive and selective gas chromatography tandem mass spectrometry (GC-MS/MS) method was developed for the analysis of 26 polycyclic aromatic hydrocarbons (PAHs), including 16 Environmental Protection Agency (EPA) and 15 + 1 European Union (EU) PAHs, in mussel samples from aquaculture farms in Thermaikos and Strymonian Gulf, Central Macedonia Region, in three sampling periods. Concentrations were found at moderate to low values at all sampling sites, without exceeding maximum levels set by EU. Low molecular weight PAHs were predominant in all samples. Seasonal variation of the concentrations was observed; values were slightly higher in the winter period. Use of diagnostic ratios for potential sources of PAHs showed both petrogenic and pyrolitic origin. In comparison to other related studies of mussels from the Mediterranean Sea, Greek mussels cultivated in the studied gulfs are low in contaminants due to minimal environmental pollution effects. Low concentrations of PAHs are in compliance with the low values of other POPs which were found in the mussels.

Human serum elements' levels and leukemia: A first pilot study from an adult Greek cohort.

BACKGROUND: The present study focuses on the evaluation of potential relationships between trace elements and acute and chronic types of leukemia, via the determination of their levels in human blood serum. METHODS: A total of 199 serum samples from a Greek cohort were examined, including both leukemia cases and controls. Elements' analysis was carried out using inductively coupled plasma mass spectrometry (ICP-MS) and demographic features such as age, gender, smoking habits and area of residence were recorded and statistically treated applying Shapiro-Wilk, Kolmogorov-Smirnov, Mann Whitney and Kruskal Wallis tests (p < 0.05). Spearman correlation and principal component analysis (PCA) were also performed to investigate possible associations. RESULTS: The results demonstrated significantly higher (p < 0.05) trace elements concentrations in cases' serum compared to that of controls excluding Ba, with Cu (median concentration 1295 µg L-1) being the most abundant in cases. Additionally, concentration of toxic Pb and Cd were found at seven and four fold higher concentrations in cases, respectively. Among the trace elements examined, only Rb (164 µg L-1) was detected in higher concentrations in controls. Ba, Cd and Co presented the lowest concentrations (lower than 1 µg L-1). PCA was performed for overall and classified data, indicating a stronger relation among the toxic As, Cd, Ni and Pb in cases than controls, particularly referring to smokers and industrial sites' residents. Hematological parameters and factors such as age and gender did not present any significant outcome or correlation. CONCLUSIONS: The findings from this pilot study suggest a potential relationship between metals and leukemia, especially concerning the toxic ones. Results from the employed source apportionment tools imply that smoking and atmospheric degradation may be positively related with higher metal serum levels in leukemia patients.

Heart Failure and PAHs, OHPAHs, and Trace Elements Levels in Human Serum: Results from a Preliminary Pilot Study in Greek Population and the Possible Impact of Air Pollution.

Cardiovascular diseases (CVDs) have been associated with environmental pollutants. The scope of this study is to assess any potential relation of polycyclic aromatic hydrocarbons (PAHs), their hydroxylated derivatives, and trace elements with heart failure via their direct determination in human serum of Greek citizens residing in different areas. Therefore, we analyzed 131 samples including cases (heart failure patients) and controls (healthy donors), and the respective demographic data were collected. Significantly higher concentrations (p < 0.05) were observed in cases' serum regarding most of the examined PAHs and their derivatives with phenanthrene, fluorene, and fluoranthene being the most abundant (median of >50 µg L-1). Among the examined trace elements, As, Cd, Cu, Hg, Ni, and Pb were measured at statistically higher concentrations (p < 0.05) in cases' samples, with only Cr being significantly higher in controls. The potential impact of environmental factors such as smoking and area of residence has been evaluated. Specific PAHs and trace elements could be possibly related with heart failure development. Atmospheric degradation and smoking habit appeared to have a significant impact on the analytes' serum concentrations. PCA-logistic regression analysis could possibly reveal common mechanisms among the analytes enhancing the hypothesis that they may pose a significant risk for CVD development.

Primary and secondary organic aerosol in an urban/industrial site: Sources, health implications and the role of plastic enriched waste burning.

PM10 samples were collected from an urban/industrial site nearby Athens, where uncontrolled burning activities occur. PAHs, monocarboxylic, dicarboxylic, hydroxycarboxylic and aromatic acids, tracers from BVOC oxidation, biomass burning tracers and bisphenol A were determined. PAH, monocarboxylic acids, biomass burning tracers and bisphenol A were increased during autumn/winter, while BSOA tracers, dicarboxylic- and hydroxycarboxylic acids during summer. Regarding aromatic acids, different sources and formation mechanisms were indicated as benzoic, phthalic and trimellitic acids were peaked during summer whereas p-toluic, isophthalic and terephthalic were more abundant during autumn/winter. The Benzo[a]pyrene-equivalent carcinogenic power, carcinogenic and mutagenic activities were calculated showing significant (p < 0.05) increases during the colder months. Palmitic, succinic and malic acids were the most abundant monocarboxylic, dicarboxylic and hydrocarboxylic acids during the entire sampling period. Isoprene oxidation was the most significant contributor to BSOA as the isoprene-SOA compounds were two times more abundant than the pinene-SOA (13.4 ± 12.3 and 6.1 ± 2.9 ng/m3, respectively). Ozone has significant impact on the formation of many studied compounds showing significant correlations with: isoprene-SOA (r = 0.77), hydrocarboxylic acids (r = 0.69), pinene-SOA (r = 0.63),dicarboxylic acids (r = 0.58), and the sum of phthalic, benzoic and trimellitic acids (r = 0.44). PCA demonstrated five factors that could explain sources including plastic enriched waste burning (30.8%), oxidation of unsaturated fatty acids (23.0%), vehicle missions and cooking (9.2%), biomass burning (7.7%) and oxidation of VOCs (5.8%). The results highlight the significant contribution of plastic waste uncontrolled burning to the overall air quality degradation.

Secondary organic aerosol tracers and related polar organic compounds between urban and rural areas in the Eastern Mediterranean region: source apportionment and the influence of atmospheric oxidants.

Fine particle samples were collected during summer at an urban (LIM) and a rural/background (AGM) site of Cyprus. They were analyzed for pinene and isoprene secondary organic aerosol (PSOA-ISOA) tracers, linear dicarboxylic acids (DCAs), hydroxyacids (HAs), aromatic acids (AAs), monocarboxylic acids (MCAs) and levoglucosan by GC/MS with prior 3-step derivatization. DCAs, AAs, MCAs and levoglucosan exhibited significantly higher concentrations (p < 0.05) in LIM, PSOAs and ISOAs in AGM (p < 0.05), whereas mixed trends were found for HAs. Among DCAs, succinic was the most abundant in both sites, accounting for 42.5% and 36.5% of the total DCAs in LIM and AGM respectively, followed by adipic in LIM (20.1%) and azelaic in AGM (22.4%). Malic, phthalic and palmitic acids were the dominant HA, AA and MCA, respectively. Regarding PSOAs, significant differences were observed between the two sites, with the first-generation products accounting for 59.8% of the total measured PSOAs in AGM, but were remarkably lowered (10.3%) in LIM indicating that they were highly oxidized. 2-Methylerythritol was the dominant ISOA tracer in both sites; nevertheless the elevated relative abundance of 2-methylglyceric acid in LIM implies the influences of higher NOx levels. The increased O3 levels observed in AGM appear to have a significant impact on SOA formation. Source apportionment tools employed revealed factors related to secondary formation processes including oxidation of unsaturated fatty acids, pinene, isoprene and anthropogenic VOCs and factors associated with primary sources such as biomass burning, plant emissions and/or cooking and motor exhaust, with noteworthy differences observed between the two areas.

Determination of anabolic androgenic steroids as imidazole carbamate derivatives in human urine using liquid chromatography-tandem mass spectrometry.

Anabolic androgenic steroids are widely abused substances in sports doping. Their detection present limitations regarding the use of soft ion sources such as electrospray or atmospheric pressure chemical ionization by liquid chromatography-tandem mass spectrometry. In the current study, a novel derivatization method was developed for the ionization enhancement of selected anabolic androgenic steroids. The proposed method aims at the introduction of an easily ionizable moiety into the steroid molecule by converting the hydroxyl groups into imidazole carbamates using 1,1'-carbonyldiimidazole as derivatization reagent. The proposed method was applied to water and urine samples spiked with exogenous anabolic androgenic steroids in various concentration levels. Steroid imidazole carbamate derivatives have shown intensive [M+H]+ signals under electrospray ionization and common fragmentation patterns in tandem mass spectrometry mode with [M-CO2 +H]+ and [M-ΙmCO2 +H]+ as major ions with low collision energy. The obtained results showed that the majority of steroids were detectable at concentrations equal or lower to their minimum required performance level according to the World Anti-Doping Agency technical document. The proposed method is sensitive with a preparation procedure that could be easily applied to the analysis of doping control samples.

Trace elements, polycyclic aromatic hydrocarbons, mineral composition, and FT-IR characterization of unrefined sea and rock salts: environmental interactions.

Unrefined sea salt originates from seawater, typically by natural evaporation. Being minimally processed, it contains the natural minerals and impurities of seawater. Despite the wide applications of salt for culinary and food preservation purposes, the available composition data is particularly limited. Since seawater often contains various harmful substances at a trace or ultra-trace level, their determination in unrefined salt is significant in terms of quality control and food safety. Twenty-four (24) samples of unrefined sea and rock salts retailed in Greece were studied in terms of their trace metals and polycyclic aromatic hydrocarbon (PAH) content, which constitute the usual pollutants examined in seawater. In addition, samples' color and mineralogy were recorded and their attenuated total reflectance Fourier transform infrared (ATR FT-IR) spectra were obtained. No statistically significant differences were found between sea and rock salts regarding their trace metal (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) content (excluding V) and the 15 PAHs examined. ATR FT-IR succeeded to discriminate among sea, rock, flower, and underground salty water salts. Compared with the typical trace metal concentrations in seawater, quite high Pb values were determined in both sea and rock salts, whereas outliers in the rest of the trace elements examined were scarce. Median values of the sum of PAH (ΣPAHs) concentrations were calculated equal to 2.1 and 2.6 ng g-1 for sea and rock salts, respectively. Environmental interactions of salt production with trace elements and PAHs are also discussed.

Identification of thiocyanates by Gas Chromatography - Mass Spectrometry in explosive residues used as a possible marker to indicate black powder usage.

Black Powder (BP) is one of the most common improvised explosives, due to broad access in precursors and simple home-made preparation. Deflagration of black powder results in residues the chemical analysis of which presents limitations and has been performed with several techniques until today; nevertheless, Gas Chromatography-Mass Spectrometry (GC-MS) has never been used. In this study, a simple experimental protocol has been developed towards black powder residues identification, using GC-MS. The sample preparation does not require specialized equipment. Derivatization of thiocyanates coming from BP deflagration and identification of the relative derivative (PBF-SCN) was achieved by monitoring ions m/z 239, 181 and 161. This characteristic derivative was used as a marker to indicate BP usage. The protocol was optimized by investigating individually all experimental parameters and it was evaluated for false positives and negatives. Repeatability and limit of detection were calculated to be %RSD 7.67 and < 1 mg, respectively. No interference coming from other ingredients that might co-exist in BP residues was observed. This protocol may be applied directly and without previous preparation to evidence coming from cases of explosions, thus practically contributing in BP residues identification.

An effective and low cost carbon based clean-up method for PCDD/Fs and PCBs analysis in food.

Sample preparation is of critical importance in dioxin analysis of food and feed samples. It is a complex procedure that includes lipid extraction followed by the application of chromatographic separation techniques, aiming in removing undesirable interferences from the matrix. The separation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from polychlorinated biphenyls (PCBs) is achieved by carbon-based materials which should have high fat capacity in order to be suitable for lipid-containing matrices. Automated methods are available but due to high cost and use of high amounts of solvents, manual methods are also applied. An active carbon material (Carbosphere) with high fat capacity that has been used in the past for manual methods is no longer commercially available. The present study assesses an alternative active carbon material, FU 4652, that can be used for the separation of PCDD/Fs and non-ortho PCBs. Mono-ortho and 6 non-dioxin-like PCBs are also analyzed. The method was validated according to the analytical criteria set in EU regulations 589/2014 and 709/2014. Control samples analyzed for the evaluation of the above material were olive oil reference samples spiked with PCDD/Fs and dioxin-like PCBs at two concentration levels. The new method was tested successfully on food samples of interlaboratory trials organized in previous years. Farmed fish samples collected within national surveillance programs for the years 2016-2017 were analyzed with the method developed. The results obtained indicate that the FU 4652 carbon sorbent has high fat capacity and is capable of separating congeners with good recoveries.

Characterization of PM2.5 chemical composition at the Demokritos suburban station, in Athens Greece. The influence of Saharan dust.

The aim of this work is to study the atmospheric concentrations of selected major and trace elements and ions found in PM2.5, at a suburban site in Athens, Greece, and discuss on the impact of the different sources. Special focus is given to the influence of Saharan dust episodes. The seasonal variability in the metal and ion concentrations is also examined. The results show that PM2.5 mass concentrations are significantly influenced by Saharan dust events; it is observed that when the PM2.5 concentration is higher than 25 µg/m3, five out of six times, the air mass crossed North Africa at an altitude within the boundary layer. Fe is found to be the element with the more significant seasonal variability, displaying much higher concentrations during cold period. The frequent Saharan dust intrusions in the cold period of this dataset may explain this result. Mineral dust and secondary aerosol are the main PM2.5 components (29 and 34%, respectively). During Saharan dust events, the concentration of mineral dust is increased by 35% compared to the days without dust intrusions, while an increase of 68% of the sea salt is also observed. During event days, PM2.5 concentrations are also increased by 14%. Anthropogenic components do not decrease during those days, while sulfate displays even a slight increase, suggesting enrichment of mineral dust with secondary sulfates. The results indicate that African dust intrusions add a rather significant PM pollution load even in the PM2.5 fraction, with implication to population exposure and human health.

A rapid method for the identification of nitrocellulose in high explosives and smokeless powders using GC-EI-MS.

Nitrocellulose (NC) is one of the most common ingredients in explosive mixtures, however because of its non-volatility, its detection using Gas Chromatography-Electron Ionization-Mass Spectrometry (GC-EI-MS) has not been achieved until today. A rapid method for the identification of NC in bulk explosives using GC-EI-MS was developed. The sample preparation is simple and takes place in a test tube, employing standard equipment of a forensics laboratory. The protocol was optimized and applied to seven, both high and low, commercial explosives, which contained the substance of interest. Moreover, three explosives in the absence of NC were tested to cross check for false positives. Fourteen different standard explosive substances that are usually found in explosive mixtures were then employed in order to monitor the effect of the method on these compounds and check for interferences. Results showed that NC was detected, by its trimethylsilyl (TMS) derivatives, in all the explosive mixtures analyzed and no false positives were observed. The proposed method showed selectivity for NC, as it had no interference coming from other ingredients of explosive mixtures. The protocol introduced offers considerable improvement in identifying the individual components of an explosive mixture and contributes in successful classification of explosives.

Determination of perfluorinated compounds (PFCs) in various foodstuff packaging materials used in the Greek market.

Perfluorinated compounds (PFCs) are used in food packaging materials as coatings/additives for oil and moisture resistance. In the current study, foodstuff-packaging materials collected from the Greek market, made of paper, paperboard or aluminum foil were analyzed for the determination of PFCs. For the analysis of the samples, pressurized liquid extraction (PLE), liquid chromatography­tandem mass spectrometry (LC­MS/MS) and isotope dilution method were applied to develop a specific and sensitive method of analysis for the quantification of 12 PFCs: perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoA), perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS) and the qualitative detection of 5 more: perfluorotridecanoic acid (PFTrDA), perfluorotetradecanoic acid (PFTeDA), perflyohexadecanoic acid (PFHxDA), perfluorooctadecanoic acid (PFODA) and perfluorodecane sulfonate (PFDS). No PFCs were quantified in aluminum foil wrappers, baking paper materials or beverage cups. PFTrDA, PFTeDA and PFHxDA were detected in fast food boxes. In the ice cream cup sample only PFHxA was found. On the other hand, several PFCs were quantified and detected in fast food wrappers, while the highest levels of PFCs were found in the microwave popcorn bag. PFOA and PFOS were not detected in any of the samples. Compared to other studies from different countries, very low concentrations of PFCs were detected in the packaging materials analyzed. Our results suggest that probably no serious danger for consumers' health can be associated with PFCs contamination of packaging materials used in Greece.

Regulated, carbonyl and polycyclic aromatic hydrocarbon emissions from a light-duty vehicle fueled with diesel and biodiesel blends.

This study investigates the impact of low concentration biodiesel blends on the regulated, carbonyl and PAH emissions from a modern passenger vehicle. The vehicle was a Euro 4 compliant SUV type fitted with a common-rail diesel engine and a diesel oxidation catalyst. Emission and fuel consumption measurements were performed on a chassis dynamometer using a constant volume sampling (CVS) technique, following the European regulations. All measurements were conducted over the NEDC and Artemis driving cycles. Aiming to evaluate the fuel impact on emissions, a soy-based biodiesel was blended with an ultra low sulphur diesel at proportions of 10 and 30% by volume. The experimental results revealed that emissions of PM, HC and CO decreased with biodiesel over most driving conditions. Some increases were observed over the NEDC which may be attributed to the cold-start effect and to certain fuel characteristics. NO x emissions were found to be higher with biodiesel especially during Artemis operation. CO 2 emissions and fuel consumption followed similar patterns and increased with biodiesel. Most carbonyl compound emissions increased with biodiesel, with the exception of aromatic aldehydes. It was found that carbonyl emissions decreased as the mean speed and load of the driving cycle was increased. Most PAH emissions were found to be lower with biodiesel, however, some increases were observed for certain toxic compounds.

Biodiesel emissions profile in modern diesel vehicles. Part 1: Effect of biodiesel origin on the criteria emissions.

This paper presents the regulated emissions profile of a Euro 4 compliant common rail passenger car, fuelled with low concentration biodiesel blends. Four biodiesels of different origin and quality blended with a typical automotive diesel fuel at proportions of 10, 20, and 30% v/v. Emission and fuel consumption measurements were conducted on a chassis dynamometer with constant volume sampling (CVS) technique, over the New European Driving Cycle (NEDC) and the real traffic-based Artemis driving cycles. Limited effects were observed on CO(2) emissions, while fuel consumption marginally increased with biodiesel. PM, HC and CO emissions improved with the addition of biodiesel, with some exceptions. Some increases with biodiesel were observed over the NEDC, as a consequence of biodiesel characteristics and engine conditions. NO(x) emissions were increased with the use of biodiesel blends and positively correlated with fuel unsaturation levels.

Biodiesel emissions profile in modern diesel vehicles. Part 2: Effect of biodiesel origin on carbonyl, PAH, nitro-PAH and oxy-PAH emissions.

In the present study, the effects of different biodiesel blends on the unregulated emissions of a Euro 4 compliant passenger car were examined. Two fresh and two oxidized biodiesel fuels of different source materials were blended with an ultra low sulphur automotive diesel fuel at proportions of 10, 20, and 30% v/v. Emission measurements were conducted on a chassis dynamometer with a constant volume sampling (CVS) technique, over the New European Driving Cycle (NEDC) and the Artemis driving cycles. The experimental results revealed that the addition of biodiesel led to important increases in most carbonyl compounds. Sharp increases were observed with the use of the oxidized biodiesel blends, especially those prepared from used frying oil methyl esters. Similar to carbonyl emissions, most PAH compounds increased with the addition of the oxidized biodiesel blends. It can be assumed that the presence of polymerization products and cyclic acids, along with the degree of unsaturation were the main factors that influenced carbonyl and PAH emissions profile.

Influence of oxidized biodiesel blends on regulated and unregulated emissions from a diesel passenger car.

This paper investigates the effects of biodiesel blends on regulated and unregulated emissions from a Euro 4 diesel passenger car, fitted with a diesel oxidation catalyst and a diesel particle filter (DPF). Emission and fuel consumption measurements were conducted for the New European Driving Cycle (NEDC) and the Artemis driving cycles. Criteria pollutants, along with carbonyl, polycyclic aromatic hydrocarbon (PAH) and nitrate PAH and oxygenate PAH emissions, were measured and recorded. A soy-based biodiesel and an oxidized biodiesel, obtained from used frying oils, were blended with an ultra low sulfur diesel at proportions of 20, 30, and 50% by volume. The results showed that the DPF had the ability to significantly reduce particulate matter (PM) emissions over all driving conditions. Carbon monoxide (CO) and hydrocarbon (HC) emissions were also reduced with biodiesel; however, a notable increase in nitrogen oxide (NO(x)) emissions was observed with biodiesel blends. Carbon dioxide (CO(2)) emissions and fuel consumption followed similar patterns and increased with biodiesel. The influence of fuel type and properties was particularly noticeable on the unregulated pollutants. The use of the oxidized biodiesel blends led to significant increases in carbonyl emissions, especially in compounds which are associated with potential health risks such as formaldehyde, acetaldehyde, and acrolein. Sharp increases in most PAH compounds and especially those which are known for their toxic and carcinogenic potency were observed with the oxidized blends. The presence of polymerization products and cyclic acids were the main factors that influenced the PAH emissions profile.

Effects of low concentration biodiesel blend application on modern passenger cars. Part 1: feedstock impact on regulated pollutants, fuel consumption and particle emissions.

Five biodiesels from different feedstocks (rapeseed, soy, sunflower, palm, and used fried oils) blended with diesel at 10% vol. ratio (B10), were tested on a Euro 3 common-rail passenger car. Limited effects (-2% to +4%) were observed on CO(2) emissions. CO and HC emissions increased between 10% and 25% on average, except at high speed - high power where emissions were too low to draw conclusions. NOx emissions increased by up to 20% for two out of the five blends, decreased by up to 15% for two other blends, and remained unchanged for one blend. Particulate matter (PM) was reduced for all blends by up to 25% and the reductions were positively correlated with the extent of biodiesel saturation. PM reductions are associated with consistent reductions in non-volatile particle number. A variable behaviour in particle number is observed when volatile particles are also accounted.

Effects of low concentration biodiesel blends application on modern passenger cars. Part 3: impact on PAH, nitro-PAH, and oxy-PAH emissions.

This study explores the impact of five different types of methyl esters on polycyclic aromatic hydrocarbon (PAH), nitrated-PAH and oxygenated PAH emissions. The measurements were conducted on a chassis dynamometer, according to the European regulation. Each of the five different biodiesels was blended with EN590 diesel at a proportion of 10-90% v/v (10% biodiesel concentration). The vehicle was a Euro 3 compliant common-rail diesel passenger car. Emission measurements were performed over the NEDC and compared with those of the real traffic-based Artemis driving cycles. The experimental results showed that the addition of biodiesel led to some important increases in low molecular-weight PAHs (phenanthrene and anthracene) and to both increases and reductions in large PAHs which are characterised by their carcinogenic and mutagenic properties. Nitro-PAHs were found to reduce with biodiesel whereas oxy-PAH emissions presented important increases with the biodiesel blends. The impact of biodiesel source material was particularly clear on the formation of PAH compounds. It was found that most PAH emissions decreased as the average load and speed of the driving cycle increased. Cold-start conditions negatively influenced the formation of most PAH compounds. A similar trend was observed with particulate alkane emissions.