Henri Wortham

Atmospheric Photosensitized Heterogeneous and Multiphase Reactions: From Outdoors to Indoors

This proposal involves direct photolysis processes occurring in the troposphere incorporating photochemical excitation and intermolecular energy transfer. The study of such processes could provide a better understanding of ·OH radical formation pathways in the atmosphere and in consequence, of a more accurate prediction of the oxidative capacity of the atmosphere. Compounds that readily absorb in the tropospheric actinic window (ionic organic complexes, PAHs, aromatic carbonyl compounds) acting as potential photosensitizers of atmospheric relevant processes are explored. The impact of hotosensitation on relevant systems which could act as powerful atmospheric reactors,that is, interface ocean-atmosphere, urban and forest surfaces and indoor air environments is also discussed.

Emission characteristics of air pollutants from incense and candle burning in indoor atmospheres

Volatile organic compounds (VOCs) and particles emitted by incense sticks and candles combustion in an experimental room have been monitored on-line and continuously with a high time resolution using a state-of-the-art high sensitivity-proton transfer reaction-mass spectrometer (HS-PTR-MS) and a condensation particle counter (CPC), respectively. The VOC concentration–time profiles, i.e., an increase up to a maximum concentration immediately after the burning period followed by a decrease which returns to the initial concentration levels, were strongly influenced by the ventilation and surface interactions. The obtained kinetic data set allows establishing a qualitative correlation between the elimination rate constants of VOCs and their physicochemical properties such as vapor pressure and molecular weight. The emission of particles increased dramatically during the combustion, up to 9.1(±0.2)u2009×u2009104 and 22.0(±0.2)u2009×u2009104 part cm−3 for incenses and candles, respectively. The performed kinetic measurements highlight the temporal evolution of the exposure level and reveal the importance of ventilation and deposition to remove the particles in a few hours in indoor environments.

Formation of indoor nitrous acid (HONO) by light-induced NO2 heterogeneous reactions with white wall paint

Gaseous nitrogen dioxide (NO2) represents an oxidant that is present in relatively high concentrations in various indoor settings. Remarkably increased NO2 levels up to 1.5xa0ppm are associated with homes using gas stoves. The heterogeneous reactions of NO2 with adsorbed water on surfaces lead to the generation of nitrous acid (HONO). Here, we present a HONO source induced by heterogeneous reactions of NO2 with selected indoor paint surfaces in the presence of light (300xa0nmu2009<u2009λu2009<u2009400xa0nm). We demonstrate that the formation of HONO is much more pronounced at elevated relative humidity. In the presence of light (5.5xa0Wxa0m−2), an increase of HONO production rate of up to 8.6u2009·u2009109 molecules cm−2xa0s−1 was observed at [NO2]u2009=u200960xa0ppb and 50xa0% relative humidity (RH). At higher light intensity of 10.6 (Wxa0m−2), the HONO production rate increased to 2.1u2009·u20091010 molecules cm−2xa0s−1. A high NO2 to HONO conversion yield of up to 84xa0% was observed. This result strongly suggests that a light-driven process of indoor HONO production is operational. This work highlights the potential of paint surfaces to generate HONO within indoor environments by light-induced NO2 heterogeneous reactions.

Combustion Processes as a Source of High Levels of Indoor Hydroxyl Radicals through the Photolysis of Nitrous Acid

Hydroxyl radicals (OH) are known to control the oxidative capacity of the atmosphere but their influence on reactivity within indoor environments is believed to be of little importance. Atmospheric direct sources of OH include the photolysis of ozone and nitrous acid (HONO) and the ozonolysis of alkenes. It has been argued that the ultraviolet light fraction of the solar spectrum is largely attenuated within indoor environments, thus, limiting the extent of photolytic OH sources. Conversely, the ozonolysis of alkenes has been suggested as the main pathway of OH formation within indoor settings. According to this hypothesis the indoor OH radical concentrations span in the range of only 10(4) to 10(5) cm(-3). However, recent direct OH radical measurements within a school classroom yielded OH radical peak values at moderate light intensity measured at evenings of 1.8 × 10(6) cm(-3) that were attributed to the photolysis of HONO. In this work, we report results from chamber experiments irradiated with varying light intensities in order to mimic realistic indoor lighting conditions. The exhaust of a burning candle was introduced in the chamber as a typical indoor source causing a sharp peak of HONO, but also of nitrogen oxides (NOx). The photolysis of HONO yields peak OH concentration values, that for the range of indoors lightning conditions were estimated in the range 5.7 ×· 10(6) to 1.6 × 10(7) cm(-3). Excellent agreement exists between OH levels determined by a chemical clock and those calculated by a simple PSS model. These findings suggest that significant OH reactivity takes place at our dwellings and the consequences of this reactivity-that is, formation of secondary oxidants-ought to be studied hereafter.

Photolysis and Heterogeneous Reaction of Coniferyl Aldehyde Adsorbed on Silica Particles with Ozone

The pseudo-first-order loss of coniferyl aldehyde, adsorbed on silicon dioxide particles, upon heterogeneous ozonolysis was monitored at various ozone mixing ratios in the absence and presence of simulated sunlight. For the first time we investigated the effect of light on the heterogeneous ozonolysis of coniferyl aldehyde adsorbed on silica particles. We found that UV-VIS light (λ>300 nm) does not impact the degradation of coniferyl aldehyde by ozone but induces an additional, slow photolysis of the aldehyde with a photolytic rate constant of ~10(-5) s(-1). In both cases, that is, in presence and/or absence of light, the heterogeneous ozonation kinetics are well described by an immediate gas-surface reaction formalism with light-independent rate constants of k(2nd)=(7.2±0.9)×10(-19) cm(3) molec(-1) s(-1) and (7.6±1.7)×10(-19) cm(3) molec(-1) s(-1) in the absence and presence of light, respectively. Five oxidation products: glycolic acid, oxalic acid, vanillin, vanillic acid and 3,4-dihydroxybenzoic acid were identified and confirmed by their corresponding standards. Vanillin and vanillic acid absorb light in the region λ>300 nm and thus can further participate in the direct and indirect photolysis processes of atmospheric relevance. A reaction mechanism is proposed in order to elucidate the ozonolysis reaction and to explain the reaction products.

Transfluthrin indoor air concentration and inhalation exposure during application of electric vaporizers.

Different household insecticide applications via two electric vaporizers emitting transfluthrin were realized in a full-scale experimental room under controlled air exchange rate conditions. On-line high-time resolved measurements of the gas-phase concentrations of the active substance during and immediately after the spreading periods were performed with a High Sensitivity Proton-Transfer-Reaction Mass Spectrometer (HS-PTR-MS). Experimental and modelled data from the ConsExpo 4.0 software were also compared to evaluate the sources of differences. Different application scenarios were also compared. Averaged inhaled concentrations over 1h, 1week, and 5months were estimated to be 8.3, 1.8, and 1.8μg.m(-3), respectively. Corresponding margins of exposures range from 1000 to 10,000, claiming for the absence of effect. Dermal and dust ingestion pathways, although roughly estimated, seems being non-negligible. This claims for a more in-depth integrated risk assessment.

Validation of thermodesorption method for analysis of semi-volatile organic compounds adsorbed on wafer surface.

To prevent the degradation of the device characteristics it is important to detect the organic contaminants adsorbed on the wafers. In this respect, a reliable qualitative and quantitative analytical method for analysis of semi-volatile organic compounds which can adsorb on wafer surfaces is of paramount importance. Here, we present a new analytical method based on Wafer Outgassing System (WOS) coupled to Automated Thermal Desorber-Gas chromatography-Mass spectrometry (ATD-GC-MS) to identify and quantify volatile and semi-volatile organic compounds from 6, 8 and 12 wafers. WOS technique allows the desorption of organic compounds from one side of the wafers. This method was tested on three important airborne contaminants in cleanroom i.e. tris-(2-chloroethyl) phosphate (TCEP), tris-(2-chloroisopropyl) phosphate (TCPP) and diethyl phthalate (DEP). In addition, we validated this method for the analysis and quantification of DEP, TCEP and TCPP and we estimated the backside organic contamination which may contribute to the front side of the contaminated wafers. We are demonstrating that WOS/ATD-GC-MS is a suitable and highly efficient technique for desorption and quantitative analysis of organophosphorous compounds and phthalate ester which could be found on the wafer surface.

Use of the HS-PTR-MS for online measurements of pyrethroids during indoor insecticide treatments

A high-sensitivity proton transfer reaction mass spectrometer (HS-PTR-MS) has been used to study the temporal evolution of pesticide concentrations in indoor environments. Because of the high time variability of the indoor air concentrations during household pesticide applications, the use of this online high time resolution instrument is found relevant. Four pyrethroid pesticides of the latest generation that are commonly found in electric vaporizer refills, namely, transfluthrin, empenthrin, tetramethrin, and prallethrin, were considered. A controlled pesticide generation system was settled and coupled to a HS-PTR-MS analyzer, and a calibration procedure based on the fragmentation patterns of the protonated molecules was performed. To illustrate the functionality of the method, measurements of the concentration–time profiles of transfluthrin contained in an electric vaporizer were carried out in a full-scale environmental room under air exchange rate-controlled conditions. This study demonstrates that the HS-PTR-MS technique can provide online and high time-resolved measurements of semi-volatile organic compounds such as pyrethroid insecticides.

Validation of Direct Analysis Real Time source/Time-of-Flight Mass Spectrometry for organophosphate quantitation on wafer surface.

Microelectronic wafers are exposed to airborne molecular contamination (AMC) during the fabrication process of microelectronic components. The organophosphate compounds belonging to the dopant group are one of the most harmful groups. Once adsorbed on the wafer surface these compounds hardly desorb and could diffuse in the bulk of the wafer and invert the wafer from p-type to n-type. The presence of these compounds on wafer surface could have electrical effect on the microelectronic components. For these reasons, it is of importance to control the amount of these compounds on the surface of the wafer. As a result, a fast quantitative and qualitative analytical method, nondestructive for the wafers, is needed to be able to adjust the process and avoid the loss of an important quantity of processed wafers due to the contamination by organophosphate compounds. Here we developed and validated an analytical method for the determination of organic compounds adsorbed on the surface of microelectronic wafers using the Direct Analysis in Real Time-Time of Flight-Mass Spectrometry (DART-ToF-MS) system. Specifically, the developed methodology concerns the organophosphate group.

Chronic Drought Decreases Anabolic and Catabolic BVOC Emissions of Quercus pubescens in a Mediterranean Forest

Biogenic volatile organic compounds (BVOC) emitted by plants can originate from both anabolism (metabolite production through anabolic processes) and catabolism (metabolite degradation by oxidative reactions). Drought can favor leaf oxidation by increasing the oxidative pressure in plant cells. Thus, under the precipitation decline predicted for the Mediterranean region, it can be expected both strong oxidation of anabolic BVOC within leaves and, as a result, enhanced catabolic BVOC emissions. Using an experimental rain exclusion device in a natural forest, we compared the seasonal course of the emissions of the main anabolic BVOC released by Q. pubescens (isoprene and methanol) and their catabolic products (MACR+MVK+ISOPOOH and formaldehyde, respectively) after 3 years of precipitation restriction (−30% of rain). Thus, we assume that this repetitive amplified drought promoted a chronic drought. BVOC emissions were monitored, on-line, with a PTR-ToF-MS. Amplified drought decreased all BVOC emissions rates in spring and summer by around 40–50 %, especially through stomatal closure, with no effect in autumn. Moreover, ratios between catabolic and anabolic BVOC remained unchanged with amplified drought, suggesting a relative stable oxidative pressure in Q. pubescens under the water stress applied. Moreover, these results suggest a quite good resilience of this species under the most severe climate change scenario in the Mediterranean region.