Heterogeneous reactions of ozone with commonly used pesticides adsorbed on silica particles

Socorro, Joanna; Gligorovski, Sasho; Wortham, Henri; Quivet, Étienne

doi:10.1016/j.atmosenv.2014.10.044

Cited by 27 publications

(35 citation statements)

References 38 publications

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“…The rate constants for the reaction with ozone were available for 25 target SVOCs (13 biocides, 11 PAHs, and di(2‐ethylhexyl) phthalate (DEHP)). Thirty‐two second‐order rate constants were retrieved from the literature for the gas‐phase (four measured values) and particle‐phase (28 measured values) reactions . Twelve second‐order rate constants were predicted using the AOPWIN calculator.…”

Section: Resultsmentioning

confidence: 99%

“…The SVOC reaction mechanism on the particle phase in air can be simulated using the Langmuir–Rideal model or the Langmuir–Hinshelwood model . The Langmuir–Rideal model assumes that particle‐phase SVOCs react directly with gas‐phase reactants, thereby calculating R f, n and the pseudo–first‐order reaction rate constant, k 1f, n (s −1 ), from the second‐order reaction rate constant, k 2f, n (cm 3 /(molecule·s)); C gr, n ; and F .

\begin{matrix} true \\ right R_{normalf, n} = k_{1 normalf, n} F = k_{2 normalf, n} C_{gr, n} F \end{matrix}

…”

Section: Methodsmentioning

confidence: 99%

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Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air

Wei

Mandin

Ramalho

2017

Int. J. Chem. Kinet.

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Indoor semivolatile organic compounds (SVOCs) originate from indoor and outdoor sources. These SVOCs partition among different phases and available surfaces, which increases their residence time indoors to several years. SVOCs may also react with indoor oxidants, such as hydroxyl radicals (OH), nitrate radicals (NO3), and ozone. In the present study, the second‐order reaction rate constants of 72 SVOCs in indoor air (gas and particle phases) at room temperature and ambient air pressure were retrieved from the literature. The pseudo–first‐order reaction rate constants of these SVOCs were calculated for the indoor concentration ranges of OH, NO3, and ozone. Then, the extent to which the chemical reaction had a meaningful impact on the removal of SVOCs from the indoor environment was quantitatively analyzed. The orders of magnitude of the second‐order rate constant ranged between 10−15 and 10−10 cm3/(molecule·s) for OH/SVOC reactions, 10−17 and 10−12 cm3/(molecule·s) for NO3/SVOC reactions, and 10−20 and 10−16 cm3/(molecule·s) for ozone/SVOC reactions in indoor air. Assuming that the highest indoor reactant concentrations were 1.8 × 106 molecules/cm3 (7.3 × 10−5 ppb) for OH, 2.5 × 108 molecules/cm3 (10−2 ppb) for NO3, and 1.4 × 1012 molecules/cm3 (58 ppb) for ozone, the highest pseudo–first‐order rate constants in the gas phase for the studied reactions of OH/SVOCs (n = 72), NO3/SVOCs (n = 3), and ozone/SVOCs (n = 14) reached 1.5 h−1 (OH/benzo[a]pyrene), 0.41 h−1 (NO3/acenaphthene), and 1.0 h−1 (ozone/aldrin and ozone/heptachlor), respectively. The pseudo–first‐order rate constants in the particle phase for the studied reactions of OH/SVOCs (n = 13), NO3/SVOCs (n = 6), and ozone/SVOCs (n = 14) at the high indoor reactant concentrations reached 0.09 h−1 (OH/DEHP), 5.8 h−1 (NO3/pyrene), and 11 h−1 (ozone/benzo[a]pyrene), respectively. These results indicate that the chemical reactions of some SVOCs in indoor air have a meaningful impact compared to the air exchange rate, which should be considered in future studies on indoor air quality modeling.

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Section: Resultsmentioning

confidence: 99%

\begin{matrix} true \\ right R_{normalf, n} = k_{1 normalf, n} F = k_{2 normalf, n} C_{gr, n} F \end{matrix}

…”

Section: Methodsmentioning

confidence: 99%

Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air

Wei

Mandin

Ramalho

2017

Int. J. Chem. Kinet.

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“…Both kinetic patterns were used for this purpose: Langmuir-Rideal (L-R) mechanism (Palm et al [12,13]; Pflieger et al [14][15][16]; Yang et al [17]) and Langmuir-Hinshelwood (L-H) mechanism (Pflieger et al [14][15][16]). , reporting the difficulty of modeling by L-H mechanism (Socorro et al [11]). The k (max) values, i.e., the maximum rate constant that may be attained, range between 0.42  10 .…”

Section: Kinetics Studymentioning

confidence: 99%

“…Atmospheric lifetimes of cyprodinil, deltamethrin and permethrin are higher than one week and higher than one month for pendimethalin, fipronil, tetraconazole, oxadiazon and difenoconazole which suggests inclusion of these pesticides in the persistent organic pollutants (POP). For more details see Socorro et al [11].…”

Section: Kinetics Studymentioning

confidence: 99%

“…The obtained pseudo-first order rate constants of the four degraded pesticides due to ozone reaction allowed (Socorro et al [11]) to determine the second order rate constants. Both kinetic patterns were used for this purpose: Langmuir-Rideal (L-R) mechanism (Palm et al [12,13]; Pflieger et al [14][15][16]; Yang et al [17]) and Langmuir-Hinshelwood (L-H) mechanism (Pflieger et al [14][15][16]).…”

Section: Kinetics Studymentioning

confidence: 99%

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Heterogeneous oxidation of pesticides on the aerosol condensed phase

Socorro

2015

WIT Transactions on Ecology and the Environment

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Pesticides are widely used all over the world. It is known that they exhibit adverse health effects and environmental risks due to their physico-chemical properties and their extensive use, which is growing every year. They are distributed in the atmosphere, an important vector of dissemination, over long distances away from the target area. The partitioning of pesticides between the gas and particulate phases influences their atmospheric fate. Most of the pesticides are semi-volatile compounds, emphasizing the importance of assessing their heterogeneous reactivity towards atmospheric oxidants. The photolysis processing and heterogeneous reactivity towards O3 and OH, was evaluated of eight commonly used pesticides adsorbed in silica particles. Silica particles are present in airborne mineral dust in atmospheric aerosols, and heterogeneous reactions can be different in the presence of these mineral particles. Depending on their origin and conditioning, aerosol particles containing pesticides can have complex and highly porous microstructures, which are influenced by electric charge effects and interaction with water vapour. Therefore, the kinetic experiments and consecutive product studies were performed at atmospherically relevant relative humidity (RH) of 55%. The identification of surface-bound products was performed using GC-(QqQ)-MS/MS and the gas-phase products were monitored on-line by PTRToF-MS. The obtained results will allow a better understanding of the impact of pesticides and their degradation products on human health, and to make recommendations in order to reduce population exposure to the pesticide plume and the pollution by phyto-sanitary products on the regional scale, which constitutes a necessary step in the development of environmental strategies.

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