Particulate matter, gas-phase and particle-bound polycyclic aromatic hydrocarbons in an urban environment heavily impacted by vehicular traffic (Bologna, Italy)

A set of 8 polycyclic aromatic hydrocarbons (PAHs) has been analysed in a traffic-limited area in Bologna downtown, both in the gas-phase and in the particulate phase (PM10), and gas-to-particle partitioning has been investigated. From Sep 2002 to May 2003, 28 high volume PM10 samplings were carried out, and in 50 % of the samplings, PM10 concentrations exceeded the limit of 50 microg/m3 established by a 1999 EU directive. A precisely defined sampling strategy was adopted to limit artifacts (8 h sampling in the same time interval) in the 28 samplings carried out in different meteorological conditions. A linear log-log correlation was found between gas-particle partitioning coefficients KBp and the subcooled liquid vapour pressures pB0LB, with rP2P = 0.82 and slope = -0.59. This empirical correlation may be used to anticipate the total (gas + particle-bound) concentration of each PAHs in this urban site, once PM10 and the particle-bound concentration is measured. Parallel samplings of PM10 and of PM2.5 allowed us to ascertain that PM2.5 represents the gross contribution to PM10 and that most of the particle-bound PAHs reside on the finest fraction of particulate matter.     

A simultaneous correlation of vapour pressures and thermal data: application to 1-alkanols

R∪žička, K. and Majer, V., 1986. A simultaneous correlation of vapour pressures and thermal data: application to 1-alkanols. Fluid Phase Equilibria, 28: 253-264Possibilities of simultaneous correlation of vapour pressures and thermal data (enthalpy of vaporization and difference between heat capacity of idea gas and liquid) are investigated. This approach permits a reliable evaluation of vapour pressures and/or enthalpies of vaporization far below the normal boiling point and can serve also as a consistency test of experimental data. A simple procedure using smoothed input data is proposed which can be implemented in a software of the data bank of thermodynamic properties. The method is demonstrated on a group of eight 1-alkanols.     

Phase equilibria in binary mixtures of propane + acenaphthene

In the near-critical region of propane, phase equilibria of binary mixtures of propane + acenaphthene have been investigated experimentally. Apart from the three-phase equilibrium solid acenaphthene + liquid + vapour, two-phase boundaries liquid + vapour and solid acenaphthene + liquid have been investigated over the entire mole fraction range. The measurements were performed in the temperature region 350–420 K with pressures up to 10 MPa.     

Adsorption of a diverse set of organic vapors on the bulk water surface

The bulk water surface is of fundamental interest to physical as well as environmental chemistry. As there is a lack of wide-ranging adsorption data from the air to the bulk water surface, a large and diverse data set of adsorption coefficients of nonionic, organic compounds has been produced with inverse gas chromatography. The 61 compounds were chosen to cover a large range of properties, considering the intermolecular interactions between the compounds and the bulk water surface, i.e., van der Waals and electron-donor/acceptor interactions. The data set gained in this work was interpreted with a linear free energy relationship (LFER) based on these intermolecular interactions. From this LFER, a general adsorption model is derived, including compound (i) and surface (surf) properties: log K(i surf/air)(m(3)/m(2)) = 0.135(+/-0.003) log K(i hexadecane/air)(gamma(surf)(vdW))(0.5) + 5.11(+/-0.15)Sigma beta(i2)(H)EA(surf) + 3.60(+/-0.28)Sigma alpha(i2)(H)ED(surf) - 8.47. This adsorption model can be used for the characterization of adsorption to any other surface. The adsorption model for bulk water surface adsorption as well as the general adsorption model can be used as prediction tools in natural or technical systems.     

Phase equilibria in binary mixtures of ethane + docosane and molar volumes of liquid docosane

Experimental results for various types of phase behaviour which can occur in the binary ethane + docosane system are presented. The experimental data cover various two-phase boundaries and the three-phase equilibria solid docosane + liquid + vapour and liquid + liquid + vapour. In addition, p,V,T measurements of liquid docosane are carried out. The experimental work is performed within a temperature range of ∼ 290–370 K and at pressures of up to 16 MPa.     

Solid vapor pressure for five heavy PAHs via the Knudsen effusion method

Polycyclic aromatic hydrocarbons (PAHs) are compounds resulting from incomplete combustion and many fuel processing operations, and they are commonly found as subsurface environmental contaminants at sites of former manufactured gas plants. Knowledge of their vapor pressures is the key to predict their fate and transport in the environment. The present study involves five heavy PAHs, i.e. benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and dibenz[a,h]anthracene, which are all as priority pollutants classified by the US EPA. The vapor pressures of these heavy PAHs were measured by using Knudsen effusion method over the temperature range of 364 K to 454 K. The corresponding values of the enthalpy of sublimation were calculated from the Clausius-Clapeyron equation. The enthalpy of fusion for the 5 PAHs was also measured by using differential scanning calorimetry and used to convert earlier published sub-cooled liquid vapor pressure data to solid vapor pressure in order to compare with the present results. These adjusted values do not agree with the present measured actual solid vapor pressure values for these PAHs, but there is good agreement between present results and other earlier published sublimation data.     

Development of a stabilized low temperature infrared absorption cell for use in low temperature and collisional cooling experiments

We have constructed a stabilized low temperature infrared absorption cell cooled by an open cycle refrigerator, which can run with liquid nitrogen from 250 to 80K or with liquid helium from 80K to a few kelvin. Several CO infrared spectra were recorded at low temperature using a tunable diode laser spectrometer. These spectra were analyzed taking into account the detailed effects of collisions on the line profile when the pressure increases. We also recorded spectra at very low pressure to accurately model the diode laser emission. Spectra of the R(2) line in the fundamental band of 13CO cooled by collisions with helium buffer gas at 10.5K and at pressures near 1 Torr have been recorded. The He-pressure broadening parameter (gamma(0) = 0.3 cm(-1) atm(-1)) has been derived from the simultaneous analysis of four spectra at different pressures.     

Onsager heat of transport at the aniline liquid–vapour interface

The heat of transport for passage of matter through a gas–liquid interface has been determined for the aniline liquid–vapour system, by measuring stationary-state pressure differences produced by known temperature differences over a distance of 2 mm on the vapour side of the interface. For the range of pressures used, 2 mm is between 6 and 34 mean free paths. Coupling of the heat and matter fluxes is significant over the whole of this range. At the higher pressures the heat of transport is more than 20% of the heat of condensation; at the lower pressures it is more than 50%.     

The interaction of monosubstituted benzenes with the stationary liquid in gas liquid chromatography

In gas liquid chromatography (GLC), the relative retention values log gamma was mainly expressed by van der Waals energy (the sum of the dispersion E(dis) and repulsive E(rep) energies) to the interactions between monosubstituted benzene derivatives and the nonpolar stationary liquid as squalane. The single exception was that of anilines, and it was corrected by the electrostatic energy (E(ES)) due to C-H/pi hydrogen bond. When the stationary liquid changed from the nonpolar to polar, log gamma was estimated by the inductive interaction energy (included in E(ES)) in addition to the sum of E(dis) and E(rep). In the benzene solution, the relative equilibrium values log K/K(o) introduced from the interactions between phenol and substituted benzene derivatives were estimated by E(ES). The E(ES) of COCH(3), CO(2)C(2)H(5) groups is especially originated in the excited dipole moments micro(e). The relative frequency values log nu/nu(o) derived from O-H or O-D stretching vibration of phenol or methanol-D gave the correlation to E(ES) as well as log K/K(o). That of anilines-methanol-D however had been out of a linear relation to E(ES). The cause is concluded that the aniline-methanol-D is making the proton transfer structure from the discussion about the proton affinity (PA) of the base.     

A kinetic study of the reactions of Ca+ ions with O3, O2, N2, CO2 and H2O

The reactions between Ca(+)(4(2)S(1/2)) and O(3), O(2), N(2), CO(2) and H(2)O were studied using two techniques: the pulsed laser photo-dissociation at 193 nm of an organo-calcium vapour, followed by time-resolved laser-induced fluorescence spectroscopy of Ca(+) at 393.37 nm (Ca(+)(4(2)P(3/2)-4(2)S(1/2))); and the pulsed laser ablation at 532 nm of a calcite target in a fast flow tube, followed by mass spectrometric detection of Ca(+). The rate coefficient for the reaction with O(3) is essentially independent of temperature, k(189-312 K) = (3.9 +/- 1.2) x 10(-10) cm(3) molecule(-1) s(-1), and is about 35% of the Langevin capture frequency. One reason for this is that there is a lack of correlation between the reactant and product potential energy surfaces for near coplanar collisions. The recombination reactions of Ca(+) with O(2), CO(2) and H(2)O were found to be in the fall-off region over the experimental pressure range (1-80 Torr). The data were fitted by RRKM theory combined with quantum calculations on CaO(2)(+), Ca(+).CO(2) and Ca(+).H(2)O, yielding the following results with He as third body when extrapolated from 10(-3)-10(3) Torr and a temperature range of 100-1500 K. For Ca(+) + O(2): log(10)(k(rec,0)/cm(6) molecule(-2) s(-1)) = -26.16 - 1.113log(10)T- 0.056log(10)(2)T, k(rec,infinity) = 1.4 x 10(-10) cm(3) molecule(-1) s(-1), F(c) = 0.56. For Ca(+) + CO(2): log(10)(k(rec,0)/ cm(6) molecule(-2) s(-1)) = -27.94 + 2.204log(10)T- 1.124log(10)(2)T, k(rec,infinity) = 3.5 x 10(-11) cm(3) molecule(-1) s(-1), F(c) = 0.60. For Ca(+) + H(2)O: log(10)(k(rec,0)/ cm(6) molecule(-2) s(-1)) = -23.88 - 1.823log(10)T- 0.063log(10)(2)T, k(rec,infinity) = 7.3 x 10(-11)exp(830 J mol(-1)/RT) cm(3) molecule(-1) s(-1), F(c) = 0.50 (F(c) is the broadening factor). A classical trajectory analysis of the Ca(+) + CO(2) reaction is then used to investigate the small high pressure limiting rate coefficient, which is significantly below the Langevin capture frequency. Finally, the implications of these results for calcium chemistry in the mesosphere are discussed.     

Measurement of low vapour pressures according to the Knudsen effusion method

The exact measurement of low vapour pressures during recent years has become increasingly important, particularly for environmental problems caused by organic chemicals. Not only for this but for many other fields information about the phase transition solid - gas and liquid - gas is of great scientific interest. In this work a brief survey of the determination of vapour pressures with thermo-analytical methods is made. In particular the thermo-gravimetric vapour pressure measurements by means of a Knudsen cell and a newly developed vapour pressure balance for exact measurement of very low vapour pressures are described. Applications for organic materials (fungicides, benzoic acid, oils) are discussed.     

Temperature dependence of anisotropy decay and solvation dynamics of coumarin 153 in gamma-cyclodextrin aggregates

Effect of temperature on the fluorescence anisotropy decay and the ultraslow component of solvation dynamics of coumarin 153 (C153) in a gamma-cyclodextrin (gamma-CD) nanocavity are studied using a picosecond set up. The steady-state anisotropy (0.13 +/- 0.01) and residual anisotropy (0.14 +/- 0.01) in fluorescence anisotropy decay in an aqueous solution containing 7 microM C153 and 40 mM gamma-CD are found to be quite large. This indicates formation of large linear nanotube aggregates of gamma-CD linked by C153. It is estimated that >53 gamma-CD units are present in each aggregate. In these aggregates with rise in temperature, the average solvation time ((obs)) decreases markedly from 680 ps at 278 K to 160 ps at 318 K. The dynamic Stokes shift is found to decrease from 800 cm(-1) at 278 K to 250 cm(-1) at 318 K. The fraction of dynamic Stokes shift (f(d)) detected in a picosecond set up is calculated using the Fee-Maroncelli procedure. The corrected solvation time ((corr) = f(d)<(tau(s)>(obs)) displays an Arrhenius type temperature dependence. From the temperature variation, the activation energy and entropy of the solvation process are determined to be 12.5 kcal M(-1) and 28 cal M(-1) K(-1), respectively. The ultraslow component and its temperature dependence are ascribed to a dynamic exchange between bound and free water molecules.     

Carrier gas as a new factor influencing the selectivity of the gas-stationary liquid phase chromatographic system

This paper generalizes studies on the influence of carrier gas on relative and absolute retention values. This line of research is also of importance due to the fact that, in the opinion of many chromatographers, the role of the carrier gas is limited only to transporting analyzed compounds along the column. However, even under conditions of the conventional capillary gas-liquid chromatography (i.e. at column pressures under 5 atm) carrier gas (its nature and pressure) significantly influences retention and separation of the analyzed compounds. First, carrier gas (N2 and CO2, for example) dramatically affects relative retention values. For this reason, one should use limit values of alpha(ij) (0) = lim alpha(ij)(P(av)) and I(i)(0) = lim Ii(Pav) I(0) = limI(i) (Pav) with Pav-->0 as chromatographic constants, rather than traditional relative retention values alpha(ij)(P(av)) and I(i)(P(av)). Second, the average pressure Pav of the carrier gas in a column and the nature of the carrier gas influence the selectivity of the gas-stationary liquid phase chromatographic system. Third, wishing to maximize the role of the carrier gas as a factor that improves separation of analyzed compounds, we should design a special gas chromatograph that would allow work with pressures in the column up to 30-50 atm.     

New pressure-density-temperature measurements and new rational equations for the saturated liquid and vapour densities of oxygen

The results of pressure, density, temperature (p, ?, T) measurements in the temperature range from 65 K to 300 K, for pressures up to 7.2 MPa, and for densities from 0.3 mol dm^?3 to 39 mol dm^?3, are presented for pure oxygen. Using the experimental results, new values for the densities of saturated liquid and vapour are evaluated. To check the accuracy of these results, corresponding sets reported in the literature are critically analysed to determine the most reliable p, ?, T set for oxygen. Finally, new equations for the densities of saturated liquid and vapour are developed using a statistical procedure.     

Development and optimisation of a dopant assisted liquid chromatographic-atmospheric pressure photo ionisation-tandem mass spectrometric method for the determination of 15+1 EU priority PAHs in edible oils

European food legislation defines a set of 16 polycyclic aromatic hydrocarbons (PAHs) as of high concern for human health. The EU set contains structurally very similar PAHs with ring numbers between 4 and 6, and so raises some separation aspects and problems, which were not experienced with traditionally analysed PAHs. Many of the currently applied gas chromatographic mass spectrometric (GC-MS) methods suffer from separation problems, while high performance liquid chromatography with fluorescence detection (HPLC-FLD) is neither capable of detecting the whole set of EU priority PAHs nor does it (compared to GC-MS) allow structural identification. In addition HPLC-FLD shows limitations with difficult matrices due to interferences. The aim of this paper is to fill this gap by describing a liquid chromatographic dopant assisted atmospheric pressure photo ionisation tandem mass spectrometric (LC-DA-APPI-MS/MS) method for the determination of 15+1 EU priority PAHs in edible oil, which complies with the requirements set by European food legislation. Measurements were performed in positive ion mode. Anisole at a flow rate of 30 μl/min was used as dopant. Sample preparation was performed offline by donor-acceptor complex chromatography (DACC). Compared to HPLC-FLD methods the presented method enables the determination of all 15+1 EU priority PAHs at the low μg/kg concentration range including less fluorescence active compounds like benzo[j]fluoranthene and indeno[1,2,3-cd]pyrene. By analysing four reference materials it could be demonstrated that this method provides accurate results and is sufficiently sensitive for food control purposes. Statistically significant differences between the reference values and the measured analyte contents were not found. The method performs well also for very complex samples. Repeatability relative standard deviations (RSDr) of the determination of the target PAHs in olive oil were for most analytes below 5%. The limit of detection (LOD) of the method met the requirement set by EU legislation (0.3 μg/kg).