Polycyclic aromatic compounds (PACs) are known due to their mutagenic activity. Among them, 2-nitrobenzanthrone (2-NBA) and 3-nitrobenzanthrone (3-NBA) are considered as two of the most potent mutagens found in atmospheric particles. In the present study 2-NBA, 3-NBA and selected PAHs and Nitro-PAHs were determined in fine particle samples (PM 2.5) collected in a bus station and an outdoor site. The fuel used by buses was a diesel-biodiesel (96:4) blend and light-duty vehicles run with any ethanol-to-gasoline proportion. The concentrations of 2-NBA and 3-NBA were, on average, under 14.8 µg g−1 and 4.39 µg g−1, respectively. In order to access the main sources and formation routes of these compounds, we performed ternary correlations and multivariate statistical analyses. The main sources for the studied compounds in the bus station were diesel/biodiesel exhaust followed by floor resuspension. In the coastal site, vehicular emission, photochemical formation and wood combustion were the main sources for 2-NBA and 3-NBA as well as the other PACs. Incremental lifetime cancer risk (ILCR) were calculated for both places, which presented low values, showing low cancer risk incidence although the ILCR values for the bus station were around 2.5 times higher than the ILCR from the coastal site.

Around the world, there is a growing increase in biofuels consumption, mainly ethanol and biodiesel as well as their blends with diesel that reduce the cost impact of biofuels while retaining some of the advantages of the biofuels. This increase is due to several factors like decreasing the dependence on imported petroleum; providing a market for the excess production of vegetable oils and animal fats; using renewable and biodegradable fuels; reducing global warming due to its closed carbon cycle by CO2 recycling; increasing lubricity; and reducing substantially the exhaust emissions of carbon monoxide, unburned hydrocarbons, and particulate emissions from diesel engines. However, there are major drawbacks in the use of biofuel blends as NOx tends to be higher, the intervals of motor parts replacement such as fuel filters are reduced and degradation by chronic exposure of varnish deposits in fuel tanks and fuel lines, paint, concrete, and paving occurs as some materials are incompatible. Here, fuel additives become indispensable tools not only to decrease these drawbacks but also to produce specified products that meet international and regional standards like EN 14214, ASTM D 6751, and DIN EN 14214, allowing the fuels trade to take place. Additives improve ignition and combustion efficiency, stabilize fuel mixtures, protect the motor from abrasion and wax deposition, and reduce pollutant emissions, among other features. Two basic trends are becoming more relevant:  the progressive reduction of sulfur content and the increased use of biofuels. Several additives' compositions may be used as long as they keep the basic chemical functions that are active.

No abstract

The presence of carbonyl compounds (CCs) in wines has sparked the interest of researchers in several countries. The quantification of some of these compounds has been used as a parameter of quality for many fermented beverages. Although present in minute quantities (except for acetaldehyde), they have a strong olfactory impact. In addition, the CCs found in wines have a strong affinity for bisulfite and can form stable adducts, which will also interfere in the characteristics of aroma. The greatest challenge, however, is to predict which CCs have the strongest affinity for S(IV) and what conditions favor this interaction. To better understand the reaction of CC-bisulfite adduct formation (HASA), this study has evaluated the profile of 22 CCs in a "synthetic wine" containing bisulfite and in 10 real samples of different wines from the São Francisco Valley, northeastern Brazil. On the basis of principal component analysis (PCA) and dissociation constants, the results revealed that aliphatic aldehydes form adducts with S(IV), whereas ketones, cyclic aldehydes, and trans-alkenes interact weakly and are found predominantly in their free form. These results revealed also that pH 10 and 11 were defined as the most appropriate for CC-SO 2 adduct dissociation, and the total CCs were quantified reliably.

The size distributed composition of ambient aerosols is used to explore seasonal differences in particle chemistry and to show that dry deposition fluxes of soluble species, including important plant nutrients, increase during periods of biomass (sugar cane trash) burning in São Paulo State, Brazil. Measurements were made at a single site centrally located in the State's sugar cane growing region but away from the immediate vicinity of burns, so that the airsampled was representative of the regional background. Calculation of ion equivalent balances showed that during burning periods smaller particles (Aitken and accumulation modes) were more acidic, containing higher concentrations of SO4(2-), oxalate, NO3-, HCOO-, CH3COO-, and CI-, but insufficient NH4+ and K+ to achieve neutrality. Larger particles showed an anion deficit due to the presence of unmeasured ions and comprised resuspended dusts modified by accumulation of nitrate, chloride, and organic anions. Increases of resuspended particles during the burning season were attributed to release of earlier deposits from the surfaces of burning vegetation as well as increased vehicle movement on unsurfaced roads. During winter months the relative contribution of combined emissions from road transport and industry diminished due to increased emissions from biomass combustion and other activities specifically associated with the harvest period. Positive increments in annual particulate dry deposition fluxes due to higher fluxes during the sugar cane harvest were 44.3% (NH4+), 42.1% (K+), 31.8% (Mg2+), 30.4% (HCOO-), 12.8% (CI-), 6.6% (CH3COO-), 5.2% (Ca2+), 3.8% (SO4(2-)), and 2.3% (NO3-). Na+ and oxalate fluxes were seasonally invariant. Annual aerosol dry deposition fluxes (kg ha(-1)) were 0.5 (Na+), 0.25 (NH4+), 0.39 (K+), 0.51 (Mg2+), 3.19 (Ca2+), 1.34 (Cl-), 4.47 (NO3-), 3.59 (SO4(2-)), 0.58 (oxalate), 0.71 (HCOO-), and 1.38 (CH3COO-). Contributions of this mechanism to combined aerosol dry deposition and precipitation scavenging (inorganic species, excluding gaseous dry deposition) were 31% (Na+), 8% (NH4+), 26% (K+), 63% (Mg2+), 66% (Ca2+), 32% (Cl-), 33% (NO3-), and 36% (SO4(2-)).

Abstract. São Paulo in Brazil has relatively relaxed regulations for ambient air pollution standards and often experiences high air pollution levels due to emissions of particulate pollutants from local sources and long-range transport of air masses impacted by biomass burning. In order to evaluate the sources of particulate air pollution and related health risks, a year-round sampling was done at the University of São Paulo campus (20 m a.g.l.), a green area near an important expressway. The sampling was performed for PM 2.5 (≤ 2.5 µm) and PM 10 (≤ 10 µm) in 2014 through intensive (everyday sampling in wintertime) and extensive campaigns (once a week for the whole year) with 24 h of sampling. This year was characterized by having lower average precipitation compared to meteorological data, and high-pollution episodes were observed all year round, with a significant increase in pollution level in the intensive campaign, which was performed during wintertime. Different chemical constituents, such as carbonaceous species, polycyclic aromatic hydrocarbons (PAHs) and derivatives, water-soluble ions, and biomass burning tracers were identified in order to evaluate health risks and to apportion sources. The species such as PAHs, inorganic and organic ions, and monosaccharides were determined using chromatographic techniques and carbonaceous species using thermal-optical analysis. Trace elements were determined using inductively coupled plasma mass spectrometry. The risks associated with particulate matter exposure based on PAH concentrations were also assessed, along with indexes such as the benzo[a]pyrene equivalent (BaPE) and lung cancer risk (LCR). High BaPE and LCR were observed in most of the samples, rising to critical values in the wintertime. Also, biomass burning tracers and PAHs were higher in this season, while secondarily formed ions presented low variation throughout the year. Meanwhile, vehicular tracer species were also higher in the intensive campaign, suggesting the influence of lower dispersion conditions in that period. Source apportionment was performed using positive matrix factorization (PMF), which indicated five different factors: road dust, industrial emissions, vehicuPublished by Copernicus Publications on behalf of the European Geosciences Union. 11944 G. M. Pereira et al.: Particulate pollutants in the Brazilian city of São Paulo lar exhaust, biomass burning and secondary processes. The results highlighted the contribution of vehicular emissions and the significant input from biomass combustion in wintertime, suggesting that most of the particulate matter is due to local sources, in addition to the influence of pre-harvest sugarcane burning.

No abstract

Hydroxyl radicals (. OH) are key players in chemistry in surface waters, clouds and aerosols. Additionally,. OH may contribute to the inflammation underlying adverse health outcomes associated with particulate matter exposure. Terephthalate is a particularly sensitive probe for hydroxyl radicals, with a detection limit as low as 2 nM. However, there is uncertainty in. OH quantification using this method, and potential for interference from fluorescent compounds and from some transition metals. Terephthalate reacts with. OH to form a fluorescent product, 2-hydroxylterephthalic acid (hTA), with a moderate dependence on pH and temperature. However, there 1 is disagreement in the literature on the yield of the fluorescent product (Y hTA), which introduces a large uncertainty in the quantification of OH. Additionally, TA and similar organic probes are known to complex Cu(II) at high concentrations, thus if this reaction is important at lower concentrations, Cu(II) could reduce apparent hTA formation, and reduce activity of Cu(II) in target samples. Using a pH 3.5 dark ferrous Fenton system to generate. OH radicals, we find that Y hTA = 31.5 ± 7%. This is about double the recent literature value measured, but in excellent agreement with earlier measurements. Additionally, we find that interactions between Cu(II) and hTA are small enough to be ignored at Cu(II) concentrations below ~50 µM.