Determination of policyclic aromatic compounds, (PAH, nitro-PAH and oxy-PAH) in soot collected from a diesel engine operating with different fuels.

A qualitative and quantitative analysis of polycyclic aromatic compounds (PACs; polycyclic aromatic hydrocarbons (PAHs), oxygenated and nitrated polycyclic aromatic hydrocarbons (OPAHs and NPAHs)) present in the soluble organic fraction (SOF) of different soot samples has been carried out to determine the effect of soot-generation conditions on their composition and health effects. The soot samples were generated using a diesel engine bench powered by diesel (DS) and biodiesel (BS) fuels under different combustion conditions. To optimize the procedure, a surrogate soot (Printex-U) and a certified reference material (SRM1650b) were also tested. Different extraction methods were used to extract the PAHs, OPAHs and NPAHs, and the Soxhlet technique using pyridine:acetic acid 1 % was found to be the most suitable procedure to extract the highest concentration (ng mg-1) and more types of PAHs and OPAHs from the soot. The results show that the PACs identified, and their concentrations, depend on the formation and collection conditions. The predominant compounds in all soot samples studied were fluorene (Flo), phenanthrene (Phe), fluoranthene (Fla), pyrene (Pyr), 9-fluorenone (9Flo) and 9,10-anthraquinone (9,10Anq). As such, the presence of these PACs in the atmosphere of urban and rural areas can mainly be attributed to the emissions from diesel vehicles. The percentage of OPAHs with respect to total PACs was highest in the soot generated from a biofuel. These oxidized compounds favor regeneration of the diesel particulate filter (DPF). The results also indicate that the carcinogenicity of the soot depends on the combustion conditions and type of fuel.

Chemical characterization of diesel and hydrotreated vegetable oil (HVO) soot after reactive gas probing using diffuse reflectance FTIR spectroscopy (DRIFTS).

A chemical characterization of diesel and hydrotreated vegetable oil (HVO) soot has been developed using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) before and after the reaction with different probe gases. Samples were generated under combustion conditions corresponding to an urban operation mode of a diesel engine and were reacted with probe gas-phase molecules in a Knudsen flow reactor. Specifically, NH2OH, O3 and NO2 were used as reactants (probes) and selected according to their reactivities towards specific functional groups on the sample surface. Samples of previously ground soot were diluted with KBr and were introduced in a DRIFTS accessory. A comparison between unreacted and reacted soot samples was made in order to establish chemical changes on the soot surface upon reaction. It was concluded that the interface of diesel and HVO soot before reaction mainly consists polycyclic aromatic hydrocarbons, nitro and carbonyl compounds, as well as ether functionalities. The main difference between both soot samples was observed in the band of the C=O groups that in diesel soot was observed at 1719 cm-1 but not in HVO soot. After reaction with probe gases, it was found that nitro compounds remain on the soot surface, that the degree of unsaturation decreases for reacted samples, and that new spectral bands such as hydroxyl groups are observed.

Molecular Characterization of the Gas-Particle Interface of Soot Sampled from a Diesel Engine Using a Titration Method.

Surface functional groups of two different types of combustion aerosols, a conventional diesel (EN 590) and a hydrotreated vegetable oil (HVO) soot, have been investigated using heterogeneous chemistry (i.e., gas-particle surface reactions). A commercial sample of amorphous carbon (Printex XE2-B) was analyzed as a reference substrate. A Knudsen flow reactor was used to carry out the experiments under molecular flow conditions. The selected gases for the titration experiments were: N(CH3)3 for the identification of acidic sites, NH2OH for the presence of carbonyl groups, CF3COOH and HCl for basic sites of different strength, and O3 and NO2 for reducing groups. Reactivity with N(CH3)3 indicates a lower density of acidic functionalities for Printex XE2-B in relation to diesel and HVO soot. Results for NH2OH experiments indicates that commercial amorphous carbon exhibits a lower abundance of available carbonyl groups at the interface compared to the results from diesel and HVO soot, the latter being the one with the largest abundance of carbonyl functions. Reactions with acids indicate the presence of weak basic oxides on the particle surface that preferentially interact with the strong acid CF3COOH. Finally, reactions with O3 and NO2 reveal that diesel and especially HVO have a significantly higher reactivity with both oxidizers compared to that of Printex XE2-B because they have more reducing sites by roughly a factor of 10 and 30, respectively. The kinetics of titration reactions have also been investigated.

The use of heterogeneous chemistry for the characterization of functional groups at the gas/particle interface of soot from a diesel engine at a particular running condition.

Two gases, O3 and NO2, were selected to probe the surface of a diesel fuel combustion aerosol sample, diesel soot, and amorphous carbon nanoparticles (PRINTEX XE2-B) using heterogeneous (i.e., gas-surface reactions). The gas uptake to saturation of the probes was measured under molecular flow conditions using a Knudsen flow reactor in order to quantify and characterize surface functional groups. Specifically, O3 and NO2 are used for the titration of oxidizable groups. Diesel soot samples interacted with the probe gases to various extents which points to the coexistence of different functional groups on the same aerosol surface such as reduced groups. The carbonaceous particles displayed significant differences: PRINTEX XE2-B amorphous carbon had a significantly lower surface functional group density of both total and strongly reducing groups despite its significantly larger internal surface area, compared to diesel soot. The uptake kinetics of the gas-phase probe molecules (uptake probabilities) were also measured in order to obtain further information on the reactivity of emitted soot aerosols in order to enable the potential prediction of health effects.

FTIR gas-phase kinetic study on the reactions of some acrylate esters with OH radicals and Cl atoms.

Acrylate esters are α,ß-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon. These compounds are widely used in the production of plastics and resins. Atmospheric degradation processes of these compounds are currently not well understood. The kinetics of the gas phase reactions of OH radicals with methyl 3-methylacrylate and methyl 3,3-dimethylacrylate were determined using the relative rate technique in a 50 L Pyrex photoreactor using in situ FTIR spectroscopy at room temperature (298 ± 2 K) and atmospheric pressure (708 ± 8 Torr) with air as the bath gas. Rate coefficients obtained were (in units cm(3) molecule(-1) s(-1)): (3.27 ± 0.33) × 10(-11) and (4.43 ± 0.42) × 10(-11), for CH3CH═CHC(O)OCH3 and (CH3)2CH═CHC(O)OCH3, respectively. The same technique was used to study the gas phase reactions of hexyl acrylate and ethyl hexyl acrylate with OH radicals and Cl atoms. In the experiments with Cl, N2 and air were used as the bath gases. The following rate coefficients were obtained (in cm(3) molecule(-1) s(-1)): k3 (CH2═CHC(O)O(CH2)5CH3 + Cl) = (3.31 ± 0.31) × 10(-10), k4(CH2═CHC(O)OCH2CH(CH2CH3)(CH2)3CH3 + Cl) = (3.46 ± 0.31) × 10(-10), k5(CH2═CHC(O)O(CH2)5CH3 + OH) = (2.28 ± 0.23) × 10(-11), and k6(CH2═CHC(O)OCH2CH(CH2CH3)(CH2)3CH3 + OH) = (2.74 ± 0.26) × 10(-11). The reactivity increased with the number of methyl substituents on the double bond and with the chain length of the alkyl group in -C(O)OR. Estimations of the atmospheric lifetimes clearly indicate that the dominant atmospheric loss process for these compounds is their daytime reaction with the hydroxyl radical. In coastal areas and in some polluted environments, Cl atom-initiated degradation of these compounds can be significant, if not dominant. Maximum Incremental Reactivity (MIR) index and global warming potential (GWP) were also calculated, and it was concluded that these compounds have significant MIR values, but they do not influence global warming.

Sorption of nickel and cobalt ions onto cobalt and nickel ferrites.

The corrosion of the metal parts in the primary circuit of pressurized water reactors leads to the release of colloidal particles (NiFe(2)O(4), CoFe(2)O(4), NiO, Ni...) and ionic species (Co, Ni, Cr...). Particles can interact with ionic species in the primary medium, contributing to their transport and to their deposition onto surfaces outside the neutron flux generating radioactive contamination. Sorption and zetametry experiments at 25 °C were performed on the Ni(2+)/CoFe(2)O(4) and Co(2+)/NiFe(2)O(4) systems in order to determine the behaviour of corrosion products in the fluid of the primary circuit. Sorption appears as surface complexation starting from pH 6 and is followed by precipitation of hydroxide above pH 7.5. Complexation and solubility constants were obtained from the modelling of sorption curves. The two oxide systems present a very similar sorption behaviour, but some differences, due to their different isoelectric points, could be observed on zetametric measurements.

Night-time atmospheric fate of acrolein and crotonaldehyde.

The absolute rate coefficients for the gas-phase reaction of the NO3 radical with acrolein and crotonaldehyde have been measured overthe temperature range 249-330 K, using a discharge flow system and monitoring the NO3 radical by laser induced fluorescence (LIF). The obtained rate coefficients at 298 K for NO3 reactions with acrolein and crotonaldehyde were (3.30 +/- 0.39) x 10(-15) cm3 molecule(-1) s(-1) for acrolein and (1.35 +/- 0.04) x 10(-14) cm3 molecule(-1) s(-1) for crotonaldehyde, and the proposed Arrhenius expressions are k(T) = (1.72 +/- 0.5) x 10(-13) exp[(-1190 +/- 43)/T] and k(T) = (5.02 +/- 0.7) x 10(-13) exp[(-1076 +/- 47)/T], respectively, in units of cm3 molecule(-1) s(-1). In addition, the products and mechanisms were investigated using an environmental chamber/FTIR absorption system. Formaldehyde, CO, and acryloylperoxy nitrate were identified as the main products for the acrolein reaction with molar yields of 31.6 +/- 2.0, 20.9 +/- 1.9, and 47 +/- 3, respectively. In the crotonaldehyde reaction the main products detected were crotonylperoxy nitrate and CO with yields of 93.6 +/- 4.3 and 8.3 +/- 1.1, respectively. On the basis of the rate constant measured, the activation energy calculated, and the identified products, abstraction of the aldehydic H seems to be the main degradation pathway at room temperature for the reaction of acrolein with NO3. For crotonaldehyde, the mechanism is unclear on the basis of the experimental results. The atmospheric implications of the reactions in question are also discussed.

Dental caries and caries-associated microorganisms in Uruguayan preschool children.

The prevalence of dental caries was studied in 3-5-year-old Uruguayan children (n = 76) living in 2 areas with different socioeconomic and cultural conditions. More children from the low socioeconomic area of Las Acacias had caries (68%) than children from the middle- to high-class neighborhood of Pocitos (19%). They also had poorer oral hygiene and a significantly higher caries prevalence (P < 0.05) than those from Pocitos. The occurrence of mutans streptococci and lactobacilli was determined in whole unstimulated saliva and compared with that in debris collected with a loop from the dorsum of the tongue. Mutans streptococci were detected in 42% of the children with significant correlations between the salivary levels of the microorganism and caries experience. Lactobacilli were recovered less frequently (18%). The detection of mutans streptococci in the tongue-loop samples was significantly correlated with that in whole saliva.

[Evaluation of oral health status of a preschool group with a predictive test based on mutans group and clinical studies]. / Relevamiento del estado de salud bucal de una población pre-escolar con test predictivo en base al grupo mutans y a estudios clinicos.

A children's population, aged from 2 to 5 years, was studied for three years. Bacteriological and clinical criteria were followed, with a determination of the M. st level in non-stimulated saliva in the age-groups of 3, 4 and 5 years. We found, as Alaluusua did, a correlation between the M. st level in saliva and the number of caries. With this study, a large number of caries-free children had a low M. st level. The largest amount of caries appears in children with a high M. st level. The highest caries incidence in this population appears at the 4 year children group. It has to be remembered that this is an age-group with specific characteristics. Caries is a disease depending on many factors and the M. st level would be very significant to an early detection of risks, but should be evaluated considering all the parameters as a whole. Its predictive value is not sufficient by itself but it has an unquestionable value when detecting risk patients of an early age. Therefore, treatment has to be the result of an etiological diagnosis addressed to prevention after an evaluation of all the factors related with the caries disease.