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The effects of NOx on the volatility of the secondary organic aerosol (SOA) formed from isoprene photooxidation are investigated in environmental chamber experiments. Two types of experiments are performed. In HO2-dominant experiments, organic peroxy radicals (RO2) primarily react with HO2. In mixed experiments, RO2 reacts through multiple pathways, including with NO, NO2, and HO2. The volatility and oxidation state of isoprene SOA are sensitive to and exhibit a nonlinear dependence on NOx levels. Depending on the NOx levels, the SOA formed in mixed experiments can be of similar or lower volatility compared to that formed in HO2-dominant experiments. The dependence of SOA yield, volatility, and oxidation state on the NOx level likely arises from gas-phase RO2 chemistry and succeeding particle-phase oligomerization reactions. The NOx level also plays a strong role in SOA aging. While the volatility of SOA in mixed experiments does not change substantially over time, SOA becomes less volatile and more oxidized as oxidation progresses in HO2-dominant experiments.

In the present work, we report a quantitative understanding on how to generate hydroxyl radicals from NO(2) and H(2)O in the troposphere upon photoexcitation at 410 nm by using multiconfigurational perturbation theory and density functional theory. The conical intersections dominate the nonadiabatic relaxation processes after NO(2) irradiated at approximately 410 nm in the troposphere and further control the generation of OH radical by means of hydrogen abstraction. In agreement with two-component fluorescence observed by laser techniques, there are two different photophysical relaxation channels along decreasing and increasing O-N-O angle of NO(2). In the former case, the conical intersection between B(2)B(1) and A(2)B(2) (CI ((2)B(2)/(2)B(1)) first funnels NO(2) out of the Franck-Condon region of B(2)B(1) and relaxes to the A(2)B(2) surface. Following the primary relaxation, the conical intersection between A(2)B(2) and X(2)A(1) (CI((2)B(2)/(2)A(1))) drives NO(2) to decay into highly vibrationally excited X(2)A(1) state that is more than 20,000 cm(-1) above zeroth-order |n(1),n(2),n(3) = 0 vibrational level. In the latter case, increasing the O-N-O angle leads NO(2) to relax to a minimum of B(2)B(1) with a linear O-N-O arrangement. This minimum point is also funnel region between B(2)B(1) and X(2)A(1) (CI((2)B(1)/(2)A(1))) and leads NO(2) to relax into a highly vibrationally excited X(2)A(1) state. The high energetic level of vibrationally excited state has enough energy to overcome the barrier of hydrogen abstraction (40-50 kcal/mol) from water vapor, producing OH ((2)Pi(3/2)) radicals. The collision between NO(2) and H(2)O molecules not only is a precondition of hydrogen abstraction but induces the faster internal conversion (CIIC) via conical intersections. The faster internal conversion favors more energy transfer from electronically excited states into highly vibrationally excited X(2)A(1) states. The collision (i.e., the heat motion of molecules) functions as the trigger and accelerator in the generation of OH radicals from NO(2) and H(2)O in the troposphere.

Clay-supported TiO2 photocatalysts can potentially improve the performance of air treatment technologies via enhanced adsorption and reactivity of target volatile organic compounds (VOCs). In this study, a benchtop photocatalytic flow reactor was used to evaluate the efficiency of hectorite-TiO2 and kaolinite-TiO2, two novel composite materials synthesized in our laboratory. Toluene, a model hydrophobic VOC and a common indoor air pollutant, was introduced in the air stream at realistic concentrations, and reacted under UVA (lamda(max) = 365 nm) or UVC (lamda(max) = 254 nm) irradiation. The UVC lamp generated secondary emission at 185 nm, leading to the formation of ozone and other short-lived reactive species. Performance of clay-Ti02 composites was compared with that of pure TiO2 (Degussa P25), and with UV irradiation in the absence of photocatalyst under identical conditions. Films of clay-TiO2 composites and of P25 were prepared by a dip-coating method on the surface of Raschig rings, which were placed inside the flow reactor. An upstream toluene concentration of approximately 170 ppbv was generated by diluting a constant flow of toluene vapor from a diffusion source with dry air, or with humid air at 10, 33, and 66% relative humidity (RH). Toluene concentrations were determined by collecting Tenax-TA sorbent tubes downstream of the reactor, with subsequent thermal desorption--GC/MS analysis. The fraction of toluene removed, %R, and the reaction rate, Tr, were calculated for each experimental condition from the concentrations measured with and without UV irradiation. Use of UVC light (UV/TiO2/O3) led to overall higher reactivity, which can be partially attributed to the contribution of gas phase reactions by short-lived radical species. When the reaction rate was normalized to the light irradiance, Tr/Ilamda,the UV/TiO2 reaction under UVA irradiation was more efficient for samples with a higher content of TiO2 (P25 and Hecto-TiO2), but notfor Kao-TiO2. In all cases, reaction rates peaked at 10% RH, with Tr values between 10 and 50% higherthan those measured under dry air. However, a net inhibition was observed as RH increased to 33% and 66%, indicating that water molecules competed effectively with toluene for reactive surface sites and limited the overall photocatalytic conversion. Compared to P25, inhibition by coadsorbed water was less significant for Kao-TiO2 samples, but was more dramatic for Hecto-TiO2 due to the high water uptake capacity of hectorite.

In this study, the photodegradation of a typical nonaqueous phase liquid (NAPL)-trichloroethene (TCE) by ultraviolet irradiation was investigated. The decay of NAPL-TCE was studied in a RPR-200 Rayonet photochemical reactor, at three different monochromatic UV lamps (254, 300, and 350 nm). Among the three UV wavelengths used, the highest photodecay rate was obtained at 254 nm. The effect of the initial NAPL dosage was also analyzed to determine the photodecay of NAPL-TCE in batch experiments by ultraviolet irradiation at preselected wavelengths. The direct photolysis of NAPL-TCE followed two-stage pseudo first-order decay kinetics. The photodegradation rates of TCE were found to decrease with the increment of NAPL dosage. It is interesting to find that the NAPL dosage is critical to determine the process performance due to the NAPL size or cage effect, which will control the diffusion of TCE/intermediates between NAPL and aqueous phases and therefore the overall reaction rates. Mathematical models were developed for the prediction of the two-stage photodegradation, in which the remaining fraction of TCE (C/C0) in the system becomes predictable.

The reduction of indoor air pollutants by air cleaning systems has received considerable interest, and a number of techniques are now available. So far, the method of photocatalysis was mainly applied by use of titanium dioxide (TiO2) in flow reactors under UV light of high intensity. Nowadays, indoor wall paints are equipped with modified TiO2 to work as a catalyst under indoor daylight or artificial light. In chamber experiments carried out under indoor related conditions itwas shown thatthe method works for nitrogen dioxide with air exchange and for formaldehyde without air exchange at high concentrations. In further experiments with volatile organic compounds (VOCs), a small effect was found for terpenoids with high kOH rate constants. For other VOCs and carbon monoxide there was no degradation at all or the surface acted as a reversible sink. Secondary emissions from the reaction of paint constituents were observed on exposure to light. From the results it is concluded that recipes of photocatalytic wall paints need to be optimized for better efficiency under indoor conditions.

The formation and volatilization of dissolved gaseous mercury (DGM) is an important mechanism by which freshwaters may naturally reduce their mercury burden. Continuous analysis of surface water for diurnal trends in DGM concentration (ranging from 0 to 60.4 pg L(-1); n=613), mercury volatilization (ranging from 0.2 to 1.1 ng m(-2) h(-1); n=584), and a suite of physical and chemical measurements were performed during a 68 h period in the St. Lawrence River near Cornwall (Ontario, Canada) to examine the temporal relationships governing mercury volatilization. No lag-time was observed between net radiation and OGM concentrations (highest cross-correlation of 0.817), thus supporting previous research indicating faster photoreduction kinetics in rivers as compared to lakes. A significant lag-time (55-145 min; maximum correlation = 0.625) was observed between DGM formation and mercury volatilization, which is similar to surface water Eddy diffusion times of 42-132 min previously measured in the St. Lawrence River. A depth-integrated DGM model was developed using the diffuse integrated vertical attenuation coefficients for UVA and UVB (K(dI UVA) = 1.45 m(-1) K(dI UVB)= 3.20 m(-1)) Low attenuation of solar radiation was attributed to low concentrations of dissolved organic carbon (mean = 2.58 mg L(-1) and particulate organic carbon (mean = 0.58 mg L(-1) in the St. Lawrence River. The depth-integrated DGM model developed found that the top 0.3 m of the water column accounted for only 26% of the total depth-integrated DGM. A comparison with volatilization data indicated that a large portion (76% or 10.5 ng m(-2) of the maximum depth-integrated DGM (13.8 ng m(-2))is volatilized over a 24 h period. Therefore, at least 50% of all DGM volatilized was produced at depths below 0.3 m. These results highlight the importance of solar attenuation in regulating DGM formation with depth. The results also demonstrate both the fast formation of DGM in rivers and the importance of understanding DGM dynamics with depth as opposed to surface waters.