Dimitri Bacco

Seasonal variation and source estimation of organic compounds in urban aerosol of Augsburg, Germany.

This study reports a general assessment of the organic composition of the PM(2.5) samples collected in the city of Augsburg, Germany in a summer (August-September 2007) and a winter (February-March 2008) campaign of 36 and 30 days, respectively. The samples were directly submitted to in-situ derivatisation thermal desorption gas chromatography coupled with time of flight mass spectrometry (IDTD-GC-TOFMS) to simultaneously determine the concentrations of many classes of molecular markers, such as n-alkanes, iso- and anteiso-alkanes, polycyclic aromatic hydrocarbons (PAHs), oxidized PAHs, n-alkanoic acids, alcohols, saccharides and others. The PCA analysis of the data identified the contributions of three emission sources, i.e., combustion sources, including fossil fuel emissions and biomass burning, vegetative detritus, and oxidized PAHs. The PM chemical composition shows seasonal trend: winter is characterized by high contribution of petroleum/wood combustion while the vegetative component and atmospheric photochemical reactions are predominant in the hot season.

Thermodynamics of Self-Assembly of Copper(II) 15-Metallacrown-5 of Eu(III) or Gd(III) with (S)-α-Alaninehydroxamic Acid in Aqueous Solution

The equilibria of self-assembly of 15-metallacrown-5 (15-MC-5) complexes of Cu(2+) and (S)-alpha-alaninehydroxamic acid (alpha-Alaha, HL) with the lanthanide (Ln) ions Eu(3+) or Gd(3+) in aqueous solution are described. The binary Ln(3+)/alpha-Alaha systems were first studied by potentiometric and calorimetric in-cell titrations; the latter technique allowed us to define the most suitable speciation model. On the contrary, because the kinetics of formation of the Ln(3+) 15-MC-5 complexes is slow, their stability constants were determined by out-of-cell (batch) potentiometric titrations. Two 15-MC-5 complexes are formed with both Eu(3+) and Gd(3+), namely, {Ln[Cu(5)L(5)H(-5)]}(3+) and {Ln[Cu(5)L(5)H(-5)](OH)}(2+), with the latter being the hydroxo species of the former. The acidity of the former to give the hydroxo species is remarkably high (log K = 4.40-4.69). Moreover, our potentiometric and spectrophotometric investigations clearly indicate that the hydroxide ion is coordinated to the central Ln ion, as was reported for several 15-MC-5 in the solid state. The formation of {Ln[Cu(5)L(5)H(-5)]}(3+) starts at ca. pH 3.5, which converts at ca. pH 4.5 into the {Ln[Cu(5)L(5)H(-5)](OH)}(2+) species, which predominates up to pH 7, where a purple precipitate occurs. The coexistence of both 15-MC-5 species and the copper(II) 12-MC-4 species of alpha-Alaha ([Cu(5)L(4)H(-4)](2+)) was observed under appropriate experimental conditions (pH and ligand and metal concentrations). A complete ESI-MS investigation of the Ln(3+)/Cu(2+)/alpha-Alaha system at different pHs confirmed the formation of the two 15-MC-5 species. The 15-MC-5 stability constants were employed to quantitatively evaluate the solution behavior of Ln(III) MCs regarding their integrity, ligand substitution, and transmetalation processes. In particular, EDTA or DOTA, added in equimolar amounts, should not appreciably interfere with the MC integrity, as found in previous experimental investigations, although it is expected that at higher amounts of EDTA, the MC should be disrupted. Our results also demonstrate that an excess of alpha-aminohydroxamate does not interfere with the integrity of the MC, and the disappearance of the CD spectra upon addition of the R enantiomer to 15-MC-5 containing the S enantiomer is due to a very rapid ligand exchange with formation of all possible isomers with no selectivity. The stability of the 15-MC-5 complexes in the presence of transferrin, serum albumin, or an excess of Zn(2+) is also discussed. With regards to the latter metal ion, we found that the MCs are stable toward Gd(3+)/Zn(2+) transmetalation. although the presence of a phosphate buffer promotes the disruption of the MC scaffold by formation of stable Gd(3+)/phosphate species.

Copper(II) 12-metallacrown-4 complexes of alpha-, beta- and gamma-aminohydroxamic acids: a comparative thermodynamic study in aqueous solution.

A complete thermodynamic study of the protonation and Cu(II) complex formation equilibria of a series of alpha- and beta-aminohydroxamic acids in aqueous solution was performed. The thermodynamic parameters obtained for the protonation of glycine-, (S)-alpha-alanine-, (R,S)-valine-, (S)-leucine-, beta-alanine- and (R)-aspartic-beta-hydroxamic acids were compared with those previously reported for gamma-amino- and (S)-glutamic-gamma-hydroxamic acids. The enthalpy/entropy parameters calculated for the protonation microequilibria of these three types of ligands are in very good agreement with the literature values for simple amines and hydroxamic acids. The pentanuclear complexes [Cu5L4H(-4)]2+ contain the ligands acting as (NH2,N-)-(O,O-) bridging bis-chelating and correspond to 12-metallacrown-4 (12-MC-4) which are formed by self-assembly between pH 4 and 6 with alpha-aminohydroxamates (HL), while those with beta- and gamma-derivatives exist in a wider pH range (4-11). The stability order of these metallomacrocycles is beta- >> alpha- > gamma-aminohydroxamates. The formation of 12-MC-4 with alpha-aminohydroxamates is entropy-driven, and that with beta-derivatives is enthalpy-driven, while with gamma-GABAhydroxamate both effects occur. These results are interpreted on the basis of specific enthalpies or entropy contributions related to chelate ring dimensions, charge neutralization and solvation-desolvation effects. The enthalpy/entropy parameters of 12-MC-4 with alpha-aminohydroxamic acids considered are also dependent on the optical purity of the ligands. Actually, that with (R,S)-valinehydroxamic acid presents an higher entropy and a lower enthalpy value than those of enantiopure ligands, although the corresponding stabilities are almost equivalent. Moreover, DFT calculations are in agreement with a more exothermic enthalpy found for metallacrowns with enantiomerically pure ligands.

GC-MS analysis of water-soluble organics in atmospheric aerosol: response surface methodology for optimizing silyl-derivatization for simultaneous analysis of carboxylic acids and sugars.

This paper describes the development of a derivatization procedure - silylation using N,O-bis(trimethylsilyl)-trifluoroacetamide (BSTFA) - for the simultaneous GC-MS analysis of a wide range of water-soluble organics in atmospheric aerosols. The reaction operating conditions were optimized using the response surface methodology (RSM) including central composite design (CCD) in order to achieve the highest response for a large number of dicarboxylic acids and sugars. The factors considered were: (i) reaction temperature (50-90°C), (ii) the reaction duration (60-120 min), (iii) reagent concentrations (10-100% of the total solution volume) and (iv) pyridine concentration (0-50% of the derivatization reagent). On the basis of RSM and experimental evidence, the optimum derivatization conditions were defined as reaction temperature of 75°C, reaction duration of 70 min, BSTFA reagent concentration of 55% and pyridine concentration of 35%. The optimized protocol was extended to a broader range of 22 target analytes that are relevant chemical markers, i.e., 15 carboxylic acids and 7 sugars. In addition, the applicability of the optimized procedure was verified in environmental matrices from PM filters collected under different conditions, i.e., different seasons (summer vs. winter), different sampling sites (urban vs. rural), different particle size dimensions (PM(2.5) vs. PM(1)).

The complex-formation behaviour of His residues in the fifth Cu2+ binding site of human prion protein: a close look

Human Prion Protein (hPrPC) is able to bind up to six Cu2+ ions. Four of them can be allocated in the “octarepeat domain”, a region of the unstructured N-terminal domain containing four tandem-repetitions of the sequence PHGGGWGQ. It is widely accepted that the additional binding sites correspond to His-96 and His-111 residues. However, recent literature does not agree on the role and the behavior of these sites in Cu2+ complexation to hPrPC. In order to shed more light on this topic, some peptidic analogues of the PrP92–113 fragment were synthesized: (H96A)PrP92–113, (H111A)PrP92–113, (H96Nτ-Me-His)PrP92–113, (H111Nτ-Me-His)PrP92–113, (H96Nτ-Me-His)PrP92–100, (H111Nτ-Me-His)PrP106–113, where an alanine or a histidine methylated at the τ nitrogen atom of its imidazole ring have been substituted to His-96 or His-111. The first two ligands allowed to confirm that His-111 binding site is stronger than His-96 one: they act as independent sites even at Cu2+-ion substoichiometric levels. Neither multi-histidine binding nor bis-complex formation has been detected at neutral pH. Nτ methylation gave evidence that τ nitrogens of imidazole residues can participate in complex-formation only at acidic pH, where displacement of amidic protons by Cu2+ ions is not allowed. Finally, the length of the fragment does not appear to have any significant influence on the behavior of the two His-96 and His-111 binding sites, from the point of view of either the coordination geometry or their relative strength.

Characteristics and major sources of carbonaceous aerosols in PM2.5 in Emilia Romagna Region (Northern Italy) from four-year observations

The concentrations of organic and elemental carbon in PM2.5 aerosol samples were measured in two sites of Emilia Romagna (Po Valley, Northern Italy) in eight campaigns during different seasons from 2011 to 2014. Strong seasonality was observed with the highest OC concentrations during the cold periods (≈ 5.5 μg m(-3)) and the lowest in the warm months (≈ 2.7 μg m(-3)) as well as with higher EC levels in fall/winter (≈ 1.4 μg m(-3)) in comparison with spring/summer (≈ 0.6 μg m(-3)). Concerning spatial variability, there were no statistically significant difference (p<0.05) between OC concentrations at the two sampling sites in each campaign, while the EC values were nearly twofold higher levels at the urban site than those at the rural one. Specific molecular markers were investigated to attempt the basic apportionment of OC by discriminating between the main emission sources of primary OC, such as fossil fuels burning - including traffic vehicle emission - residential wood burning, and bio-aerosol released from plants and microorganisms, and the atmospheric photo-oxidation processes generating OCsec. The investigated markers were low-molecular-weight carboxylic acids - to describe the contribution of secondary organic aerosol - anhydrosugars - to quantify primary emissions from biomass burning - bio-sugars - to qualitatively estimate biogenic sources - and Polycyclic Aromatic Hydrocarbons - to differentiate among different combustion emissions. Using the levoglucosan tracer method, contribution of wood smoke to atmospheric OC concentration was computed. Wood burning accounts for 33% of OC in fall/winter and for 3% in spring/summer. A clear seasonal trend is also observed for the impact of secondary processes with higher contribution in the warm seasons (≈ 63%) in comparison with that in colder months (≈ 33%), that is consistent with enhanced solar radiation in spring/summer.

Preliminary Results Of The Project “Supersito” Concerning The Atmospheric Aerosol Composition In Emilia-Romagna Region, Italy: PM Source Apportionment And Aerosol Size Distribution

The Emilia-Romagna region and its Agency for Prevention and Environment are running a project – called Supersito – the purpose of which is to gain further knowledge about the components of fine and ultrafine particles in the atmosphere. Supersito began the measurements at the end of 2011, in this paper we summarize the preliminary results observed for the aerosol size distribution and source apportionment of PM2.5 in Bologna’s urban background. Results show that nitrates, sulphates and ammonium accounts for more than 40% of the mass of PM2.5 in the cold season and for about 30% in the summer. The carbonaceous fraction (organic aerosol plus elemental carbon) is about 40% in both seasons. PMF analysis of the data coming from the results of the mass composition shows that important fractions of PM2.5 during the cold season come from

Higher health effects of ambient particles during the warm season: The role of infiltration factors

A large number of studies have shown much higher health effects of particulate matter (PM) during the warm compared to the cold season. In this paper we present the results of an experimental study carried out in an unoccupied test apartment with the aim of understanding the reasons behind the seasonal variations of the health effects due to ambient PM2.5 exposure. Measurements included indoor and outdoor PM2.5 mass and chemical composition as well as particle size distribution of ultrafine particles. Monitoring campaigns were carried out during summer and winter following a ventilation protocol developed to replicate typical occupant behaviour according to a questionnaire-based survey. Our findings showed that seasonal variation of the relationship between ambient and indoor mass concentrations cannot entirely explain the apparent difference in PM toxicity between seasons and size distribution and chemical composition of particles were identified as other possible causes of changes in the apparent PM toxicity. A marked decrease of ultrafine particles (<100 nm) passing from outdoors to indoors was observed during winter; this resulted in higher indoor exposure to nanoparticles (<50 nm) during summer. With regards to the chemical composition, a pooled analysis showed infiltration factors of chemical species similar to that obtained for PM2.5 mass with values increasing from 0.73 during winter to 0.90 during summer and few deviations from the pooled estimates. In particular, significantly lower infiltration factors and sink effect were found for nitrates and ammonium during winter. In addition, a marked increase in the contribution of indoor and outdoor sulfates to the total mass was observed during summer.

2D autocovariance function for comprehensive analysis of two-way GC-MS data matrix: application to environmental samples.

This paper describes a signal processing method for comprehensive analysis of the large data set generated by hyphenated GC-MS technique. It is based on the study of the 2D autocovariance function (2D-EACVF) computed on the raw GC-MS data matrix, extending the procedure previously developed for 1D to 2D signals. It appears specifically promising for GC-MS investigation, in particular to single out ordered patterns in complex data: such patterns can be simply identified by visual inspection from deterministic peaks in the 2D-EACVF plot. A case of order along the retention time axis (x=t(R)) is represented by a horizontal sequence of peaks, located at the same interdistance Δt(R)=b(x), e.g., b(x) is the CH(2) retention time increment between subsequent terms of an homologous series. The order along the fragment mass axis (y=m/z) contains information on analyte fragmentation patterns. Deterministic peaks appear in the 2D-EACVF plot at Δm/z values corresponding to the most abundant ion fragments - dominating fragments in MS spectrum - or to ions generated by repetitive loss of the same ion fragment, i.e., Δm/z=14 amu produced by the [CH(2)]() group loss in n-alkanes. Method applicability was tested by processing GC-MS data of organic extracts of atmospheric aerosol samples: attention is focused on identifying and characterizing homologous series of organics, i.e., n-alkanes and n-alkanoic acids, since they are considered molecular tracers able to track the origin and fate of different organics in the environment.

Vertical variation of PM2.5 mass and chemical composition, particle size distribution, NO2, and BTEX at a high rise building

Substantial efforts have been made in recent years to investigate the horizontal variability of air pollutants at regional and urban scales and epidemiological studies have taken advantage of resulting improvements in exposure assessment. On the contrary, only a few studies have investigated the vertical variability and their results are not consistent. In this study, a field experiment has been conducted to evaluate the variation of concentrations of different particle metrics and gaseous pollutants on the basis of floor height at a high rise building. Two 15-day monitoring campaigns were conducted in the urban area of Bologna, Northern Italy, one of the most polluted areas in Europe. Measurements sites were operated simultaneously at 2, 15, 26, 44 and 65 m a.g.l. Several particulate matter metrics including PM2.5 mass and chemical composition, particle number concentration and size distribution were measured. Time integrated measurement of NO2 and BTEX were also included in the monitoring campaigns. Measurements showed relevant vertical gradients for most traffic related pollutants. A monotonic gradient of PM2.5 was found with ground-to-top differences of 4% during the warm period and 11% during the cold period. Larger gradients were found for UFP (∼30% during both seasons) with a substantial loss of particles from ground to top in the sub-50 nm size range. The largest drops in concentrations for chemical components were found for Elemental Carbon (-27%), iron (-11%) and tin (-36%) during winter. The ground-to-top decline of concentrations for NO2 and benzene during winter was equal to 74% and 35%, respectively. In conclusion, our findings emphasize the need to include vertical variations of urban air pollutants when evaluating population exposure and associated health effects, especially in relation to some traffic related pollutants and particle metrics.