Assessing indoor gas phase oxidation capacity through real-time measurements of HONO and NOx in Guangzhou, China.

The hydroxyl radical (OH) is one of the most important oxidants controlling the oxidation capacity of the indoor atmosphere. One of the main OH sources indoors is the photolysis of nitrous acid (HONO). In this study, real-time measurements of HONO, nitrogen oxides (NOx) and ozone (O3) in an indoor environment in Guangzhou, China, were performed under two different conditions: (1) in the absence of any human activity and (2) in the presence of cooking. The maximum NOx and HONO levels drastically increased from 15 and 4 ppb in the absence of human activity to 135 and 40 ppb during the cooking event, respectively. The photon flux was determined for the sunlit room, which has a closed south-east oriented window. The photon flux was used to estimate the photolysis rate constants of NO2, J(NO2), and HONO, J(HONO), which span the range between 8 × 10-5 and 1.5 × 10-5 s-1 in the morning from 9:30 to 11:45, and 8.5 × 10-4 and 1.5 × 10-4 s-1 at noon, respectively. The OH concentrations calculated by photostationary state (PSS) approach, observed around noon, are very similar, i.e., 2.4 × 106 and 3.1 × 106 cm-3 in the absence of human activity and during cooking, respectively. These results suggest that under "high NOx" conditions (NOx higher than a few ppb) and with direct sunlight in the room, the NOx and HONO chemistry would be similar, independent of the geographic location of the indoor environment, which facilitates future modeling studies focused on indoor gas phase oxidation capacity.

Illuminating the dark side of indoor oxidants.

The chemistry of oxidants and their precursors (oxidants*) plays a central role in outdoor environments but its importance in indoor air remains poorly understood. Ozone (O3) chemistry is important in some indoor environments and, until recently, ozone was thought to be the dominant oxidant indoors. There is now evidence that formation of the hydroxyl radical by photolysis of nitrous acid (HONO) and formaldehyde (HCHO) may be important indoors. In the past few years, high time-resolution measurements of oxidants* indoors have become more common and the importance of event-based release of oxidants* during activities such as cleaning has been proposed. Here we review the current understanding of oxidants* indoors, including drivers of the formation and loss of oxidants*, levels of oxidants* in indoor environments, and important directions for future research.

Photochemical reaction between biphenyl and N(III) in the atmospheric aqueous phase.

The photochemical reaction between biphenyl (Bp) and N(III) under irradiation at 365 nm UV light was investigated. The results showed that Bp conversion efficiency was strongly influenced by N (III) concentration, Bp initial concentration and pH. Species-specific rate constants determined by reaction of Bp with H2ONO+ (k1), HONO (k2) and NO2- (k3) were k1 = (0.058 ± 0.005 L mol-1 s-1), k2 = (0.12 ± 0.06 L mol-1 s-1) and k3 = (0.0019 ± 0.0003 L mol-1 s-1), respectively. Laser flash photolysis studies confirmed that OH radical deriving from the photolysis of N(III) attacked aromatic ring to form Bp-OH adduct with a rate constant of 9.4 × 109 L mol-1 s-1. The products analysis suggested that Bp-OH adduct could be nitrated by N (III) and NO2 to generate nitro-compounds.

Photolysis of Nitric Acid and Nitrate on Natural and Artificial Surfaces.

Photolysis of nitric acid and nitrate (HNO3/nitrate) was investigated on the surfaces of natural and artificial materials, including plant leaves, metal sheets, and construction materials. The surfaces were conditioned in the outdoor air prior to experiments to receive natural depositions of ambient HNO3/nitrate and other atmospheric constituents. The photolysis rate constant (JHNO3(s)) of the surface HNO3/nitrate was measured based on the production rates of nitrous acid (HONO) and nitrogen oxides (NOx). The JHNO3(s) values, from 6.0 × 10(-6) s(-1) to 3.7 × 10(-4) s(-1), are 1 to 3 orders of magnitude higher than that of gaseous HNO3. The HONO was the major product from photolysis of HNO3/nitrate on most plant leaves, whereas NOx was the major product on most artificial surfaces. The JHNO3(s) values decreased with HNO3/nitrate surface density and could be described by a simple analytical equation. Within a typical range of HNO3/nitrate surface density in the low-NOx forested areas, photolysis of HNO3/nitrate on the forest canopy can be a significant source for HONO and NOx for the overlying atmosphere.

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.

Different reaction mechanisms of diphenylether and 4-bromodiphenylether with nitrous acid in the 355 nm laser flash photolysis of mixed aqueous solution.

The microscopic reaction mechanisms of diphenylether (DPE) and 4-bromodiphenylether (4-BrDPE) with nitrous acid (HNO(2)) in the absence of O(2) have been explored by the 355nm laser flash photolysis. It was proposed that OH radical, from the photolysis of HNO(2), added to DPE forms the C(12)H(10)O-OH adduct while added to 4-BrDPE forms the 4-BrDPE-OH and 4-BrOH-DPE adducts. The first-order decay rate constants of the C(12)H(10)O-OH adduct, 4-BrDPE-OH adduct and 4-BrOH-DPE adduct were measured to be (1.86+/-0.14)x10(5)s(-1), (2.19+/-0.04)x10(5)s(-1) and (1.56+/-0.03)x10(5)s(-1), respectively. The final photolysis products of DPE and HNO(2) identified by GC/MS analysis were phenol, o-hydroxydiphenylether, p-hydroxydiphenylether and p-nitrodiphenylether, while the final photolysis product of 4-BrDPE and HNO(2) identified by LC/MS analysis was mainly the dimer.

Photochemistry in the mixed aqueous solution of nitrobenzene and nitrous acid as initiated by the 355 nm UV light.

The 355 nm photon-initiated microscopic reaction mechanisms of the mixed aqueous solution of nitrobenzene and nitrous acid in the presence or absence of O(2) were studied by the laser flash photolysis technique. The main transient absorption peaks in the recorded spectra were assigned and the growth/decay trends of several transient species were investigated. It was found that the OH radical formed from the photolysis of nitrous acid triggered most of the subsequent radical reactions. The rate constant of the reaction between OH radical and nitrobenzene was measured to be (3.4 +/- 0.1) x 10(9) l mol(-1) s(-1). The product from this reaction, namely C(6)H(5)NO(2)-OH adduct, was found to react with O(2) to yield C(6)H(5)NO(2)-OHO(2) adduct with a rate constant of (1.6 +/- 0.2) x 10(9) l mol(-1) s(-1). Final steady-state products were identified by GC/MS analysis and were in accordance with the transient spectroscopic results. The possible reaction pathways were proposed.