Manolis N. Romanias
University of Crete
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Featured researches published by Manolis N. Romanias.
Journal of Physical Chemistry A | 2013
Yuri Bedjanian; Manolis N. Romanias; Atallah El Zein
Kinetics and products of the interaction of OH radicals with solid films of Arizona Test Dust (ATD) were studied using a low pressure flow reactor (0.5-3 Torr) combined with a modulated molecular beam mass spectrometer for monitoring of the gaseous species involved. The reactive uptake coefficient of OH was measured from the kinetics of OH consumption on Pyrex rods coated with ATD as a function of OH concentration ((0.4-5.2) × 10(12) molecules cm(-3)), relative humidity (RH = 0.03-25.9%), temperature (T = 275-320 K), and UV irradiance intensity (J(NO(2)) = 0-0.012 s(-1)). Deactivation of ATD surface upon exposure to OH was observed. The initial uptake coefficient was found to be independent of temperature and irradiation conditions and to decrease with relative humidity: γ(0) = 0.2/(1 + RH(0.36)) (calculated using geometric surface area, with 30% estimated conservative uncertainty). H(2)O(2) and H(2)O were observed in the gas phase as products of the OH reaction with ATD surface with yields of (10 ± 3) and (98 ± 25) %, respectively.
Environmental Science & Technology | 2013
Atallah El Zein; Manolis N. Romanias; Yuri Bedjanian
Kinetics and products of the reaction of HONO with solid films of Fe2O3 and Arizona Test Dust (ATD) were investigated using a low pressure flow reactor (1 - 10 Torr) combined with a modulated molecular beam mass spectrometer. The reactive uptake of HONO was studied as a function of HONO concentration ([HONO]0 = (0.6 - 15.0) × 10(12) molecules cm(-3)), relative humidity (RH = 3 × 10(-4) - 84.1%) and temperature (T = 275 - 320 K). Initial reactive uptake coefficients were found to be similar under dark conditions and in the presence of UV irradiation (JNO2 = 0.012 s(-1)) and independent of the HONO concentration and temperature. In contrast, the relative humidity (RH) was found to have a strong impact on the uptake coefficients: γ (ATD) = 3.8 × 10(-6) (RH)(-0.61) and γ (Fe2O3) = 1.7 × 10(-6) (RH)(-0.62) (γ calculated with BET surface area, 30% conservative uncertainty). In both reactions of HONO studied, NO2 and NO were observed as gaseous products with yields of (60 ± 9) and (40 ± 6) %, respectively, independent of relative humidity, temperature, concentration of HONO and UV irradiation intensity. The observed data point to minor importance of the HONO uptake on mineral aerosol compared with other known sinks of HONO in the atmosphere, which are its dry deposition and photolysis in night-time and during the day, respectively.
Journal of Physical Chemistry A | 2016
Manolis N. Romanias; Habib Ourrad; Frederic Thevenet; Véronique Riffault
The heterogeneous interaction of limonene and toluene with Saharan dusts was investigated under dark conditions, pressure of 1 atm, and temperature 293 K. The mineral dust samples were collected from six different regions along the Sahara desert, extending from Tunisia to the western Atlantic coastal areas of Morocco, and experiments were carried out with the smallest sieved fractions, that is, inferior to 100 μm. N2 sorption measurements, granulometric analysis, and X-ray fluorescence and diffraction (XRF and XRD) measurements were conducted to determine the physicochemical properties of the particles. The chemical characterization showed that dust originating from mideastern Sahara has a significantly higher SiO2 content (∼ 82%) than dust collected from the western coastal regions where the SiO2 relative abundance was ∼ 50%. A novel experimental setup combining diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), selected-ion flow-tube mass spectrometry (SIFT-MS), and long path transmission Fourier transform infrared spectroscopy (FTIR) allowed us to follow both the adsorbed and gas phases. The kinetic adsorption/desorption measurements were performed using purified dry air as bath gas, exposing each dust surface to 10 ppm of the selective volatile organic compound (VOC). The adsorption of limonene was independent of the SiO2 content, given the experimental uncertainties, and the coverage measurements ranged between (10 and 18) × 10(13) molecules cm(-2). Experimental results suggest that other metal oxides that could possibly influence dust acidity may enhance the adsorption of limonene. On the contrary, in the case of toluene, the adsorption capacities of the Saharan samples increased with decreasing SiO2 content; however, the coverage measurements were significantly lower than those of limonene and ranged between (2 and 12) × 10(13) molecules cm(-2). Flushing the surface with purified dry air showed that VOC desorption is not a completely reversible process at room temperature. The reversibly adsorbed fraction and the rate coefficients of desorption, kdes, depended inversely on the SiO2 relative abundance for both VOCs.
Journal of Physical Chemistry A | 2012
Manolis N. Romanias; Antonia G. Zogka; Vassileios C. Papadimitriou; Panos Papagiannakopoulos
The adsorption of gaseous acetic acid (CH(3)C(O)OH) on thin ice films and on ice doped with nitric acid (1.96 and 7.69 wt %) was investigated over upper troposphere and lower stratosphere (UT/LS) temperatures (198-208 K), and at low gas concentrations. Experiments were performed in a Knudsen flow reactor coupled to a quadrupole mass spectrometer. The initial uptake coefficients, γ(0), on thin ice films or HNO(3)-doped ice films were measured at low surface coverage. In all cases, γ(0) showed an inverse temperature dependence, and for pure thin ice films, it was given by the expression γ(0)(T) = (4.73 ± 1.13) × 10(-17) exp[(6496 ± 1798)/T]; the quoted errors are the 2σ precision of the linear fit, and the estimated systematic uncertainties are included in the pre-exponential factor. The inverse temperature dependence suggests that the adsorption process occurs via the formation of an intermediate precursor state. Uptakes were well represented by the Langmuir adsorption model, and the saturation surface coverage, N(max), on pure thin ice films was (2.11 ± 0.16) × 10(14) molecules cm(-2), independent of temperature in the range 198-206 K. Light nitration (1.96 and 7.69 wt %) of ice films resulted in more efficient CH(3)C(O)OH uptakes and larger N(max) values that may be attributed to in-bulk diffusion or change in nature of the gas-ice surface interaction. Finally, it was estimated that the rate of adsorption of acetic acid on high-density cirrus clouds in the UT/LS is fast, and this is reflected in the short atmospheric lifetimes (2-8 min) of acetic acid; however, the extent of this uptake is minor resulting in at most a 5% removal of acetic acid in UT/LS cirrus clouds.
Journal of Physical Chemistry A | 2014
Manolis N. Romanias; Auréa Andrade-Eiroa; Roya Shahla; Yuri Bedjanian; Antonia G. Zogka; Aggelos Philippidis; Philippe Dagaut
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.
Journal of Physical Chemistry A | 2013
Manolis N. Romanias; Yuri Bedjanian; Aristotelis M. Zaras; Auréa Andrade-Eiroa; Roya Shahla; Philippe Dagaut; Aggelos Philippidis
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.
Journal of Physical Chemistry A | 2015
Manolis N. Romanias; Philippe Dagaut; Yuri Bedjanian; Auréa Andrade-Eiroa; Roya Shahla; Karafas S. Emmanouil; Vassileios C. Papadimitriou; Apostolos Spyros
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.
Journal of Physical Chemistry A | 2014
Tristan Braure; Yuri Bedjanian; Manolis N. Romanias; Julien Morin; Véronique Riffault; Alexandre Tomas; Patrice Coddeville
The kinetics of the reactions of limonene with OH and OD radicals has been studied using a low-pressure flow tube reactor coupled with a quadrupole mass spectrometer: OH + C10H16 → products (1), OD + C10H16 → products (2). The rate constants of the title reactions were determined using four different approaches: either monitoring the kinetics of OH (OD) radicals or limonene consumption in excess of limonene or of the radicals, respectively (absolute method), and by the relative rate method using either the reaction OH (OD) + Br2 or OH (OD) + DMDS (dimethyl disulfide) as the reference one and following HOBr (DOBr) formation or DMDS and limonene consumption, respectively. As a result of the absolute and relative measurements, the overall rate coefficients, k1 = (3.0 ± 0.5) × 10(-11) exp((515 ± 50)/T) and k2 = (2.5 ± 0.6) × 10(-11) exp((575 ± 60)/T) cm(3) molecule(-1) s(-1), were determined at a pressure of 1 Torr of helium over the temperature ranges 220-360 and 233-353 K, respectively. k1 was found to be pressure independent over the range 0.5-5 Torr. There are two possible pathways for the reaction between OH (OD) and limonene: addition of the radical to one of the limonene double bonds (reactions 1a and 2a ) and abstraction of a hydrogen atom (reactions 1b and 2b ), resulting in the formation of H2O (HOD). Measurements of the HOD yield as a function of temperature led to the following branching ratio of the H atom abstraction channel: k2b/k2 = (0.07 ± 0.03) × exp((460 ± 140)/T) for T = (253-355) K.
ChemPhysChem | 2010
Manolis N. Romanias; Antonia G. Zogka; Vassileios G. Stefanopoulos; Vassileios C. Papadimitriou; Panos Papagiannakopoulos
The adsorption of formic acid on thin ice films and on ice doped with nitric acid (1.96, 7.69 and 53.8 wt%) is studied as a function of temperature T=195-211 K and gas concentration (0.33-10.6)×10(11) molecule cm(-3). Experiments are performed in a Knudsen flow reactor coupled with a quadrupole mass spectrometer. The initial uptake coefficients γ are strongly and inversely dependent on the ice temperature. Initial uptake is determined at low surface coverages and ranges from (0.65-3.78)×10(-3). The adsorption uptake of formic acid on pure ice films and on ice lightly doped with HNO(3) is a reversible process, and the adsorption isotherms exhibit Langmuir behaviour. N(max)(1) is (2.94±0.67)×10(14) molecule cm(-2), in good agreement with previous measurements. The temperature dependence of K(Lin) is very well represented by the expression: K(Lin)(1)=(1.43±0.32)×10(-8) exp[(4720±520)/T] cm(3) molecule(-1); the quoted uncertainty is at the 95% level of confidence and includes systematic uncertainties. Formic acid uptakes on ice films highly doped with HNO(3) (53.8 wt%) are two orders of magnitude higher than those measured on pure ice films and irreversible, thus indicating the formation of a supercooled liquid layer on the ice films upon which dissolution of formic acid occurs. Finally, the atmospheric lifetime of formic acid due to heterogeneous loss on cirrus cloud ice particles and the removal of formic acid by adsorption are estimated under conditions related to the upper troposphere.
Journal of Physical Chemistry A | 2015
Yuri Bedjanian; Julien Morin; Manolis N. Romanias
The kinetics of the reaction of OH radicals with p-cymene has been studied in the temperature range of 243-898 K using a flow reactor combined with a quadrupole mass spectrometer: OH + p-cymene → products. The reaction rate constant was determined as a result of absolute measurements, from OH decay kinetics in excess of p-cymene and employing the relative rate method with OH reactions with n-pentane, n-heptane,1,3-dioxane, HBr, and Br2 as the reference ones. For the rate coefficient of the H atom abstraction channel, the expression k1b = (3.70 ± 0.42) × 10(-11) exp[-(772 ± 72)/T] was obtained over the temperature range of 381-898 K. The total rate constant (addition + abstraction) determined at T = 243-320 K was k1 = (1.82 ± 0.48) × 10(-12) exp[(607 ± 70)/T] or, in a biexponential form, k1 = k1a + k1b = 3.7 × 10(-11) exp(-772/T) + 6.3 × 10(-13) exp(856/T), independent of the pressure between 1 and 5 Torr of helium. In addition, our results indicate that the reaction pathway involving alkyl radical elimination upon initial addition of OH to p-cymene is most probably unimportant.