Investigation of the photochemical reactivity of soot particles derived from biofuels toward NO2. A kinetic and product study.

In the current study, the heterogeneous reaction of NO2 with soot and biosoot surfaces was investigated in the dark and under illumination relevant to atmospheric conditions (J(NO2) = 0.012 s(-1)). A flat-flame burner was used for preparation and collection of soot samples from premixed flames of liquid fuels. The biofuels were prepared by mixing 20% v/v of (i) 1-butanol (CH3(CH2)3OH), (ii) methyl octanoate (CH3(CH2)6COOCH3), (iii) anhydrous diethyl carbonate (C2H5O)2CO and (iv) 2,5 dimethyl furan (CH3)2C4H2O additive compounds in conventional kerosene fuel (JetA-1). Experiments were performed at 293 K using a low-pressure flow tube reactor (P = 9 Torr) coupled to a quadrupole mass spectrometer. The initial and steady-state uptake coefficients, γ0 and γ(ss), respectively, as well as the surface coverage, N(s), were measured under dry and humid conditions. Furthermore, the branching ratios of the gas-phase products NO (∼80-100%) and HONO (<20%) were determined. Soot from JetA-1/2,5-dimethyl furan was the most reactive [γ0 = (29.1 ± 5.8) × 10(-6), γ(ss)(dry) = (9.09 ± 1.82) × 10(-7) and γ(ss)(5.5%RH) = (14.0 ± 2.8)(-7)] while soot from JetA-1/1-butanol [γ0 = (2.72 ± 0.544) × 10(-6), γ(ss)(dry) = (4.57 ± 0.914) × 10(-7), and γ(ss)(5.5%RH) = (3.64 ± 0.728) × 10(-7)] and JetA-1/diethyl carbonate [γ0 = (2.99 ± 0.598) × 10(-6), γ(ss)(dry) = (3.99 ± 0.798) × 10(-7), and γ(ss)(5.5%RH) = (4.80 ± 0.960) × 10(-7)] were less reactive. To correlate the chemical reactivity with the physicochemical properties of the soot samples, their chemical composition was analyzed employing Raman spectroscopy, NMR, and high-performance liquid chromatography. In addition, the Brunauer-Emmett-Teller adsorption isotherms and the particle size distributions were determined employing a Quantachrome Nova 2200e gas sorption analyzer. The analysis of the results showed that factors such as (i) soot mass collection rate, (ii) porosity of the particles formed, (iii) aromatic fraction, and (iv) pre-existence of nitro-containing species in soot samples (formed during the combustion process) can be used as indicators of soot reactivity with NO2.

Photodegradation of pyrene on Al2O3 surfaces: a detailed kinetic and product study.

In the current study, the photochemistry of pyrene on solid Al2O3 surface was studied under simulated atmospheric conditions (pressure, 1 atm; temperature, 293 K; photon flux, JNO2 = 0.002-0.012 s(-1)). Experiments were performed using synthetic air or N2 as bath gas to evaluate the impact of O2 to the reaction system. The rate of pyrene photodegradation followed first order kinetics and was enhanced in the presence of O2, kd(synthetic air) = 7.8 ± 0.78 × 10(-2) h(-1) and kd(N2) = 1.2 ± 0.12 × 10(-2) h(-1) respectively, due to the formation of the highly reactive O2(•-) and HO(•) radical species. In addition, kd was found to increase linearly with photon flux. A detailed product study was realized and for the first time the gas/solid phase products of pyrene oxidation were identified using off-line GC-MS and HPLC analysis. In the gas phase, acetone, benzene, and various benzene-ring compounds were determined. In the solid phase, more than 20 photoproducts were identified and their kinetics was followed. Simulation of the concentration profiles of 1- and 2-hydroxypyrene provided an estimation of their yields, 33% and 5.8%, respectively, with respect to consumed pyrene, and their degradation rates were extracted. Finally, the mechanism of heterogeneous photodegradation of pyrene is discussed.

Mineral oxides change the atmospheric reactivity of soot: NO2 uptake under dark and UV irradiation conditions.

The heterogeneous reactions between trace gases and aerosol surfaces have been widely studied over the past decades, revealing the crucial role of these reactions in atmospheric chemistry. However, existing knowledge on the reactivity of mixed aerosols is limited, even though they have been observed in field measurements. In the current study, the heterogeneous interaction of NO2 with solid surfaces of Al2O3 covered with kerosene soot was investigated under dark conditions and in the presence of UV light. Experiments were performed at 293 K using a low-pressure flow-tube reactor coupled with a quadrupole mass spectrometer. The steady-state uptake coefficient, γ(ss), and the distribution of the gas-phase products were determined as functions of the Al2O3 mass; soot mass; NO2 concentration, varied in the range of (0.2-10) × 10(12) molecules cm(-3); photon flux; and relative humidity, ranging from 0.0032% to 32%. On Al2O3/soot surfaces, the reaction rate was substantially increased, and the formation of HONO was favored compared with that on individual pure soot and pure Al2O3 surfaces. Uptake of NO2 was enhanced in the presence of H2O under both dark and UV irradiation conditions, and the following empirical expressions were obtained: γ(ss,BET,dark) = (7.3 ± 0.9) × 10(-7) + (3.2 ± 0.5) × 10(-8) × RH and γ(ss,BET,UV) = (1.4 ± 0.2) × 10(-6) + (4.0 ± 0.9) × 10(-8) × RH. Specific experiments, with solid sample preheating and doping with polycyclic aromatic hydrocarbons (PAHs), showed that UV-absorbing organic compounds significantly affect the chemical reactivity of the mixed mineral/soot surfaces. A mechanistic scheme is proposed, in which Al2O3 can either collect electrons, initiating a sequence of redox reactions, or prevent the charge-recombination process, extending the lifetime of the excited state and enhancing the reactivity of the organics. Finally, the atmospheric implications of the observed results are briefly discussed.

Improved optimization of polycyclic aromatic hydrocarbons (PAHs) mixtures resolution in reversed-phase high-performance liquid chromatography by using factorial design and response surface methodology.

A new procedure for optimizing PAHs separation in very complex mixtures by reverse phase high performance (RPLC) is proposed. It is based on changing gradually the experimental conditions all along the chromatographic procedure as a function of the physical properties of the compounds eluted. The temperature and speed flow gradients allowed obtaining the optimum resolution in large chromatographic determinations where PAHs with very different medium polarizability have to be separated. Whereas optimization procedures of RPLC methodologies had always been accomplished regardless of the physico-chemical properties of the target analytes, we found that resolution is highly dependent on the physico-chemical properties of the target analytes. Based on resolution criterion, optimization process for a 16 EPA PAHs mixture was performed on three sets of difficult-to-separate PAHs pairs: acenaphthene-fluorene (for the optimization procedure in the first part of the chromatogram where light PAHs elute), benzo[g,h,i]perylene-dibenzo[a,h]anthracene and benzo[g,h,i]perylene-indeno[1,2,3-cd]pyrene (for the optimization procedure of the second part of the chromatogram where the heavier PAHs elute). Two-level full factorial designs were applied to detect interactions among variables to be optimized: speed flow, temperature of column oven and mobile-phase gradient in the two parts of the studied chromatogram. Experimental data were fitted by multivariate nonlinear regression models and optimum values of speed flow and temperature were obtained through mathematical analysis of the constructed models. An HPLC system equipped with a reversed phase 5 microm C18, 250 mm x 4.6mm column (with acetonitrile/water mobile phase), a column oven, a binary pump, a photodiode array detector (PDA), and a fluorimetric detector were used in this work. Optimum resolution was achieved operating at 1.0 mL/min in the first part of the chromatogram (until 45 min) and 0.5 mL/min in the second one (from 45 min to the end) and by applying programmed temperature gradient (15 degrees C until 30 min and progressively increasing temperature until reaching 40 degrees C at 45 min).

Determination of polycyclic aromatic hydrocarbons in kerosene and bio-kerosene soot.

Here we report a new, efficient and reliable analytical methodology for sensitive and selective quantification of Polycyclic Aromatic Hydrocarbons (PAHs) in soot samples. The methodology developed is based on ultrasonic extraction of the soot-bound PAHs into small volumes of acetonitrile, purification of the extracts through C(18) Solid Phase Extraction (SPE) cartridges and analysis by Reverse Phase Liquid Chromatography (RPLC) with UV and fluorimetric detection. For the first time, we report the convenience of adapting the SPE procedure to the nature of the soot samples. As a matter of fact, extracts containing high percentage of unpolar material are recommended to be cleaned with acetone, whereas extracts poor in unpolar compounds can be efficiently cleaned with methanol. The method was satisfactorily applied to kerosene and bio-kerosene soot from atmospheric open diffusion flames (pool fires) and premixed flames achieving Quantification and Detection limits in the range ng mg(-1) soot and recoveries about 90% for most of the PAHs studied.