Conversion of nitrogen oxides on commercial photocatalytic dispersion paints

In the present study, photocatalytic reactions of nitrogen oxides (NO_x = NO + NO₂) were studied on commercial TiO₂ doped facade paints in a flow tube photoreactor under simulated atmospheric conditions. Fast photocatalytic conversion of NO and NO₂ was observed only for the photocatalytic paints and not for non-catalytic reference paints. Nitrous acid (HONO) was formed in the dark on all paints studied, however, it efficiently decomposes under irradiation only on the photocatalytic samples. Thus, it is concluded that photocatalytic paint surfaces do not represent a daytime source of HONO, in contrast to other recent studies on pure TiO₂ surfaces. As main final product, the formation of adsorbed nitric acid/nitrate anion (HNO₃/NO₃^?) was observed with near to unity yield. In addition, traces of H₂O₂ were observed in the gas phase only in the presence of O₂. Formation of the greenhouse gas nitrous oxide (N₂O) could be excluded. The uptake kinetics of NO, NO₂ and HONO was very fast under atmospheric conditions (e.g. γ(NO + TiO₂) > 10^?5). Thus, the uptake on urban surfaces (painted houses, etc.) will be limited by transport. For a hypothetically painted street canyon, an average reduction of nitrogen oxide levels of ca. 5% is estimated. Since the harmful HNO₃/NO₃^? is formed on the surface of the photoactive paints, whereas it is formed in the gas phase in the atmosphere, the use of photocatalytic paints may also help to reduce acid deposition, e.g. on plants, or nitric acid related health issues.     

Transformations,Lifetimes, and Sources of NO2, HONO,and HNO3 in Indoor Environments

Recent research has demonstrated that nitrogen oxides are transformed to nitrogen acids in indoor environments, and that significant concentrations of nitrous acid are present in indoor air. The purpose of the study reported in this paper has been to investigate the sources, chemical transformations and lifetimes of nitrogen oxides and nitrogen acids under the conditions existing in buildings. An unoccupied single family residence was instrumented for monitoring of NO, NO₂, NO_y, MONO, HNO₃, CO, temperature, relative humidity, and air exchange rate. For some experiments, NO₂ and HONO were injected into the house to determine their removal rates and lifetimes. Other experiments investigated the emissions and transformations of nitrogen species from unvented natural gas appliances. We determined that HONO is formed by both direct emissions from combustion processes and reaction of NO₂ with surfaces present indoors. Equilibrium considerations influence the relative contributions of these two sources to the indoor burden of HONO. We determined that the lifetimes of trace nitrogen species varied in the order NO ~ HONO > NO₂ >HNO₃. The lifetimes with respect to reactive processes are on the order of hours for NO and HONO, about an hour for NO₂, and 30 minutes or less for HNO3. The rapid removal of NO₂ and long lifetime of HONO suggest that HONO may represent a significant fraction of the oxidized nitrogen burden in indoor air.     

The effects and the toxicity increases caused by bicarbonate,chloride, and other water components during the UV/TiO<Subscript>2</Subscript> degradation of oxazaphosphorine drugs

The influences of HCO₃ ^?, Cl^?, and other components on the UV/TiO₂ degradation of the antineoplastic agents ifosfamide (IFO) and cyclophosphamide (CP) were studied in this work. The results indicated that the presence of HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2? in water bodies resulted in lower degradation efficiencies. The half-lives of IFO and CP were 1.2 and 1.1 min and increased 2.3–7.3 and 3.2–6.3 times, respectively, in the presence of the four anions (initial compound concentration = 100 μg/L, TiO₂ loading =100 mg/L, anion concentration = 1000 mg/L, and pH = 8). Although the presence of HCO₃ ^? in the UV/TiO₂/HCO₃ ^? system resulted in a lower degradation rate and less byproduct formation for IFO and CP, two newly identified byproducts, P11 (M.W. = 197) and P12 (M.W. = 101), were formed and detected, suggesting that additional pathways occurred during the reaction of ?CO₃ ^? in the system. The results also showed that ?CO₃ ^? likely induces a preferred ketonization pathway. Besides the inorganic anions HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2?, the existence of dissolved organic matter in the water has a significant effect and inhibits CP degradation. Toxicity tests showed that higher toxicity occurred in the presence of HCO₃ ^? or Cl^? during UV/TiO₂ treatment and within 6 h of reaction time, implying that the effects of these two anions should not be ignored when photocatalytic treatment is applied to treat real wastewater.     

Potential interferences in photolytic nitrogen dioxide converters for ambient air monitoring: Evaluation of a prototype

ABSTRACT

Mixing ratios of the criteria air contaminant nitrogen dioxide (NO₂) are commonly quantified by reduction to nitric oxide (NO) using a photolytic converter followed by NO-O₃ chemiluminescence (CL). In this work, the performance of a photolytic NO₂ converter prototype originally designed for continuous emission monitoring and emitting light at 395 nm was evaluated. Mixing ratios of NO₂ and NO_x (= NO + NO₂) entering and exiting the converter were monitored by blue diode laser cavity ring-down spectroscopy (CRDS). The NO₂ photolysis frequency was determined by measuring the rate of conversion to NO as a function of converter residence time and found to be 4.2 s^?1. A maximum 96% conversion of NO₂ to NO over a large dynamic range was achieved at a residence time of (1.5 ± 0.3) s, independent of relative humidity. Interferences from odd nitrogen (NO_y) species such as peroxyacyl nitrates (PAN; RC(O)O₂NO₂), alkyl nitrates (AN; RONO₂), nitrous acid (HONO), and nitric acid (HNO₃) were evaluated by operating the prototype converter outside its optimum operating range (i.e., at higher pressure and longer residence time) for easier quantification of interferences. Four mechanisms that generate artifacts and interferences were identified as follows: direct photolysis, foremost of HONO at a rate constant of 6% that of NO₂; thermal decomposition, primarily of PAN; surface promoted photochemistry; and secondary chemistry in the connecting tubing. These interferences are likely present to a certain degree in all photolytic converters currently in use but are rarely evaluated or reported. Recommendations for improved performance of photolytic converters include operating at lower cell pressure and higher flow rates, thermal management that ideally results in a match of photolysis cell temperature with ambient conditions, and minimization of connecting tubing length. When properly implemented, these interferences can be made negligibly small when measuring NO₂ in ambient air.

Implications: A new near-UV photolytic converter for measurement of the criteria pollutant nitrogen dioxide (NO₂) in ambient air by CL was characterized. Four mechanisms that generate interferences were identified and investigated experimentally: direct photolysis of HONO which occurred at a rate constant 6% that of NO₂, thermal decomposition of PAN and N₂O₅, surface promoted chemistry involving HNO₃, and secondary chemistry involving NO in the tubing connecting the converter and CL analyzer. These interferences are predicted to occur in all NO₂ P-CL systems but can be avoided by appropriate thermal management and operating at high flow rates.     

Heterogeneous reaction of NO2 with soot at different relative humidity

The influences of relative humidity (RH) on the heterogeneous reaction of NO₂ with soot were investigated by a coated wall flow tube reactor at ambient pressure. The initial uptake coefficient (γ _initial) of NO₂ showed a significant decrease with increasing RH from 7 to 70%. The γ _initial on “fuel-rich” and “fuel-lean” soot at RH = 7% was (2.59 ± 0.20) × 10^?5 and (5.92 ± 0.34) × 10^?6, respectively, and it decreased to (5.49 ± 0.83) × 10^?6 and (7.16 ± 0.73) × 10^?7 at RH = 70%, respectively. Nevertheless, the HONO yields were almost independent of RH, with average values of (72 ± 3)% for the fuel-rich soot and (60 ± 2)% for the fuel-lean soot. The Langmuir-Hinshelwood mechanism was used to demonstrate the negative role of RH in the heterogeneous uptake of NO₂ on soot. The species containing nitrogen formed on soot can undergo hydrolysis to produce carboxylic species or alcohols at high RH, accompanied by the release of little gas-phase HONO and NO.

     

An observational study of the HONO–NO2 coupling at an urban site in Guangzhou City,South China

The temporal behavior of HONO and NO₂ was investigated at an urban site in Guangzhou city, China, by means of a DOAS system during the Pearl River Delta 2006 intensive campaign from 10 to 24 July 2006. Within the whole measurement period, unexpected high HONO mixing ratios up to 2 ppb were observed even during the day. A nocturnal maximum concentration of about 8.43 ± 0.4 ppb was detected on the night of 24 July 2006. Combining the data simultaneously observed by different instruments, the coupling of HONO–NO₂ and the possible formation sources of HONO are discussed. During the measurement period, concentration ratios of HONO to NO₂ ranged from (0.03 ± 0.1) to (0.37 ± 0.09), which is significantly higher than previously reported values (0.01–0.1). Surprisingly, in most cases a strong daytime correlation between HONO and NO₂ was found, contrary to previous observations in China. Aerosol was found to have a minor impact on HONO formation during the whole measurement period. Using a pseudo steady state approach for interpreting the nocturnal conversion of NO₂ to HONO suggests a non-negligible role of the relative humidity for the heterogeneous HONO formation from NO₂.     

Investigations of emissions and heterogeneous formation of HONO in a road traffic tunnel

Simultaneous measurements of nitrous acid (HONO) and nitrogen dioxide (NO₂) using a differential optical absorption spectroscopy system, nitrogen oxide (NO) by an in situ chemiluminescence analyser and carbon dioxide (CO₂) by a gas chromatographic technique were carried out in the Wuppertal Kiesbergtunnel. At high traffic density HONO concentrations of up to 45 ppbV were observed. However, at low traffic density unexpectedly high HONO concentrations of up to 10 ppbV were measured caused by heterogeneous HONO formation on the tunnel walls. In addition to the tunnel campaigns, emission measurements of HONO, NO₂, NO and CO₂ from different single vehicles (a truck, a diesel and a gasoline passenger car) were also performed. For the correction of the HONO emission data, the heterogeneous HONO formation on the tunnel walls was quantified by two different approaches (a) in different NO₂ emission experiments in the tunnel without traffic and (b) on tunnel wall residue in the laboratory. The HONO concentration corrected for heterogeneous formation on the tunnel walls, in relation to the CO₂ concentration can be used to estimate the amount of HONO, which is directly emitted from the vehicle fleet. From the measured data, emission ratios (e.g. HONO/NO_x) and emission indices (e.g. mg HONO kg⁻¹ fuel) were calculated. The calculated emission index of 88±18 mg HONO kg⁻¹ fuel allows an estimation of the HONO emission rates from traffic into the atmosphere. Furthermore, the heterogeneous formation of HONO from NO₂ on freshly emitted exhaust particles is discussed.     

Influence of environmental factors on net N2 and N2O production in sediment of freshwater rivers

Denitrification is an important N removal process in aquatic systems but is also implicated as a potential source of global N₂O emissions. However, the key factors controlling this process as well as N₂O emissions remain unclear. In this study, we identified the main factors that regulate the production of net N₂ and N₂O in sediments collected from rivers with a large amount of sewage input in the Taihu Lake region. Net N₂ and N₂O production were strongly associated with the addition of NO₃ ^?-N and NH₄ ⁺-N. Specifically, NO₃ ^?-N controlled net N₂ production following Michaelis–Menten kinetics. The maximum rate of net N₂ production (V _max) was 116.3 μmol N₂-N m^?2 h^?1, and the apparent half-saturation concentration (k _m) was 0.65 mg N L^?1. N₂O to N₂ ratios increased from 0.18?±?0.03 to 0.68?±?0.16 with the addition of NO₃ ^?-N, suggesting that increasing NO₃ ^?-N concentrations favored the production of N₂O more than N₂. The addition of acetate enhanced net N₂ production and N₂O to N₂ ratios, but the ratios decreased by about 59.5 % when acetate concentrations increased from 50 to 100 mg C L^?1, suggesting that the increase of N₂O to N₂ ratios had more to do with the net N₂ production rate rather than acetate addition in this experiment. The addition of Cl^? did not affect the net N₂ production rates, but significantly enhanced N₂O to N₂ ratios (the ratios increased from 0.02?±?0.00 to 0.10?±?0.00), demonstrating that the high salinity effect might have a significant regional effect on N₂O production. Our results suggest that the presence of N-enriching sewage discharges appear to stimulate N removal but also increase N₂O to N₂ ratios.     

Impacts of a strong cold front on concentrations of HONO,HCHO, O3, and NO2 in the heavy traffic urban area of Beijing

Much rain and strong winds caused by a cold front occurred in Beijing during the period of Sep. 27 to Oct. 4, 2004 and led to sharp drops in maximum and mean concentrations of HONO, HCHO, O₃, and NO₂, i.e., the maximum concentrations were reduced by 5.9, 21.3, 45.6, and 44.4 ppb, respectively, and the mean concentrations were decreased by 4.0, 5.5, 30.3, and 32.3 ppb, respectively. For daily HO_x production rates HONO photolysis was the largest contributor and over 90% contributions were from photolysis of HONO and HCHO. Large number and area percentages of soot aggregate from PM10, and high correlations between concentrations of PM10 and chemical formation of HONO suggested that heterogeneous reactions of NO₂ on surfaces of soot aggregate could be a key source of HONO in the heavy traffic areas of Beijing during the night and should be considered in air quality simulations for such areas.     

Possible particulate nitrite formation and its atmospheric implications inferred from the observations in Seoul,Korea

Simultaneous measurements of gaseous species and fine-mode, particulate inorganic components were performed at the University of Seoul, Seoul in Korea. In the simultaneous measurements, a certain level of nitrous acid (HONO) was observed in the gas-phase, indicating possible heterogeneous HONO production on the surface of the ambient aerosols. On the other hand, high particulate nitrite (NO^2?) concentrations of 1.41(±2.26) μg/m³ were also measured, which sometimes reached 18.54 μg/m³. In contrast, low HONO-to-NO₂ ratios of 0.007(±0.006) were observed in Seoul. This indicates that a significant fraction of HONO is dissolved in atmospheric aerosols. Around the Seoul site, sufficient alkalinity may have been provided to the atmospheric aerosols from the excessive presence of NH₃ in the gas-phase. Due to the alkaline particulate conditions (defined in this study as a particle pH >～3.29), the HONO molecules produced at the surface of the atmospheric aerosols appeared to have been converted into particulate nitrite, thereby preventing their further participation in the atmospheric O₃/NO_y/HO_x photochemical cycles. It was estimated that a minimum average of 65% of HONO was captured by alkaline, anthropogenic, urban particles in the Seoul measurements.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River,São Paulo,Brazil)

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO^●), singlet oxygen (¹O₂), and triplet excited states of chromophoric dissolved organic matter (³CDOM^*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23?±?0.07)?×?10^–2 and (7.99?±?1.61)?×?10^–3 mol Einstein^?1, respectively. In contrast, reactions with HO^● radicals and ³CDOM* dominate their degradation, with ¹O₂ exhibiting rates three to five orders of magnitude lower. The values of k_IMD,HO● and k_AMT,HO● were (3.51?±?0.06)?×?10⁹ and (4.97?±?0.37)?×?10⁹ L mol^?1 s^?1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with k_IMD,3AQ2S*?=?(1.02?±?0.08)?×?10⁹ L mol^?1 s^?1 and k_IMD,3CBBP*?=?(3.17?±?0.14)?×?10⁸ L mol^?1 s^?1; on the contrary, the values found for AMT are close, k_AMT,3AQ2S*?=?(8.13?±?0.35)?×?10⁸ L mol^?1 s^?1 and k_AMT,3CBBP*?=?(7.75?±?0.80)?×?10⁸ L mol^?1 s^?1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO₃^?, NO₂^?, CO₃^2?, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

     

Heterogeneous NOx chemistry in the polluted PBL

The significance of heterogeneous mechanisms in controlling gas-phase NO_x (NO, NO₂) mixing ratios in polluted urban air, especially during nighttime, is not well established. Several recent studies have suggested that carbon soot can provide an effective surface for mediating the inter conversion among several NO_y members. However, a number of such reactions reported in the literature have widely varying reaction probabilities and often conflicting pathways. We evaluated several of these reactions and choose the NO₂ conversion to HONO on the surface of soot particles for further analysis with a box photochemical model. These calculations show that the conversion of NO₂ to HONO on particle surfaces produces a large, measurable signal (up to several parts per billion) in nighttime HONO mixing ratios. Inclusion of this reaction was also shown to have significant impacts on ozone, OH and HO₂ in the polluted planetary boundary layer (PBL). The sensitivity of these results to the different reaction rate probabilities (γ) and particle surface areas was also examined. Results are then evaluated to find the combination of γ and surface areas that would mostly likely occur in the PBL within the limitations of the model.     

Effects of a constructional intervention on airborne and deposited particulate matter in the Portuguese National Tile Museum, Lisbon

In the 1970s, a large ambulatory of the National Tile Museum, Lisbon, was closed with glass panes on both ground and first floor. Although this design was meant to protect the museum collection from ambient air pollutants, small openings between the glass panes remain, creating a semi-enclosed corridor. The effects of the glass panes on the indoor air quality were evaluated in a comparative study by monitoring the airborne particle concentration and the extent of particle deposition at the enclosed corridor as well as inside the museum building. Comparison of the indoor/outdoor ratio of airborne particle concentration demonstrated a high natural ventilation rate in the enclosed corridor as well as inside the museum building. PM₁₀ deposition velocities on vertical surfaces were estimated in the order of 3?×?10^?4 m s^?1 for both indoor locations. Also, the deposition rates of dark-coloured and black particles in specific were very similar at both indoor locations, causing visual degradation. The effectiveness of the glass panes in protecting the museum collection is discussed.     

Sources of submicron aerosol during fog-dominated wintertime at Kanpur

The main objective of this atmospheric study was to determine the major sources of PM₁ (particles having aerodynamic diameter <1.0 μm) within and near the city of Kanpur, in the Indo-Gangetic Plain. Day and night, 10 h long each, filter-based aerosol samples were collected for 4 months (November 2009 to February 2010) throughout the winter season. These samples were subjected to gravimetric and quantitative chemical analyses for determining water-soluble ions (NH₄ ⁺, F^?, Cl^?, NO₃ ^?, and SO₄ ^2?) using an ion chromatograph and trace elements using an inductively coupled plasma–optical emission spectrometer. The mean PM₁ mass concentrations were recorded as 114?±?71 μg/m³ (day) and 143?±?86 μg/m³ (night), respectively. A significantly higher diurnal contribution of ions (NH₄ ⁺, F^?, Cl^?, NO₃ ^?, and SO₄ ^2?) in PM₁ mass was observed during the fog-affected days and nights throughout the winter season, for which the average values were recorded as 38.09?±?13.39 % (day) and 34.98?±?12.59 % (night), respectively, of the total PM₁ mass. This chemical dataset was then used in a source-receptor model, UNMIX, and the model results are described in detail. UNMIX provided a maximum number of five source factors, including crustal material, composite vehicle, secondary aerosol, coal combustion, and iron/steel production and metallurgical industries, as the dominant air pollution sources for this study.     

FTIR gas-phase kinetic study on the reactions of some acrylate esters with OH radicals and Cl atoms

Acrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon. These compounds are widely used in the production of plastics and resins. Atmospheric degradation processes of these compounds are currently not well understood. The kinetics of the gas phase reactions of OH radicals with methyl 3-methylacrylate and methyl 3,3-dimethylacrylate were determined using the relative rate technique in a 50 L Pyrex photoreactor using in situ FTIR spectroscopy at room temperature (298?±?2 K) and atmospheric pressure (708?±?8 Torr) with air as the bath gas. Rate coefficients obtained were (in units cm³ molecule^?1 s^?1): (3.27?±?0.33)?×?10^?11 and (4.43?±?0.42)?×?10^?11, for CH₃CH═CHC(O)OCH₃ and (CH₃)₂CH═CHC(O)OCH_3, respectively. The same technique was used to study the gas phase reactions of hexyl acrylate and ethyl hexyl acrylate with OH radicals and Cl atoms. In the experiments with Cl, N₂ and air were used as the bath gases. The following rate coefficients were obtained (in cm³ molecule^?1 s^?1): k₃ (CH₂═CHC(O)O(CH₂)₅CH₃?+?Cl)?=?(3.31?±?0.31)?×?10^?10, k₄(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?Cl)?=?(3.46?±?0.31)?×?10^?10, k₅(CH₂═CHC(O)O(CH₂)₅CH₃?+?OH)?=?(2.28?±?0.23)?×?10^?11, and k₆(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?OH)?=?(2.74?±?0.26)?×?10^?11. The reactivity increased with the number of methyl substituents on the double bond and with the chain length of the alkyl group in –C(O)OR. Estimations of the atmospheric lifetimes clearly indicate that the dominant atmospheric loss process for these compounds is their daytime reaction with the hydroxyl radical. In coastal areas and in some polluted environments, Cl atom-initiated degradation of these compounds can be significant, if not dominant. Maximum Incremental Reactivity (MIR) index and global warming potential (GWP) were also calculated, and it was concluded that these compounds have significant MIR values, but they do not influence global warming.     

Light-induced heterogeneous ozone processing on organic coated particles: Kinetics and condensed-phase products

For the first time we investigated the effect of solar irradiation upon the heterogeneous ozonation of adsorbed 3,4,5-trimethoxybenzaldehyde on solid surface. Light-induced heterogeneous reactions between gas-phase ozone and 3,4,5-trimethoxybenzaldehyde adsorbed on silica particles were performed and the consecutive reaction products were identified. At an ozone mixing ratio of 250 ppb, the loss of 3,4,5-trimethoxybenzaldehyde ranged from 1.0 · 10^?6 s^?1 in the dark to 2.9 · 10^?5 s^?1 under light irradiation. Such large enhancement of 29 times clearly shows the importance of light (λ > 300 nm) during the heterogeneous ozonolysis on organic coated particles.The reaction products identified in this study (3,4,5-trimethoxybenzoic acid, syringic acid, methyl 3,4,5-trimethoxybenzoate) absorb light in the spectral window (λ > 300 nm) which implies that light-induced heterogeneous ozone processing can have an influence on the aerosol surfaces by changing their physico-chemical properties.The main identified product of the heterogeneous reactions between gas-phase ozone and 3,4,5-trimethoxybenzaldehyde under dark conditions and in presence of light was 3,4,5-trimethoxybenzoic acid. For this reason we estimated the carbon yield of 3,4,5-trimethoxybenzoic acid. Carbon yields of 3,4,5-trimethoxybenzoic acid decreased with increasing ozone mixing ratio; from 40% at 250 ppb to 15% at ≥2.5 ppm under dark conditions. At ozone mixing ratio (250 ppb–1 ppm), carbon yields of 3,4,5-trimethoxybenzaldehyde are relatively higher in the experiment under dark condition than under simulated solar light.     

Performance evaluation of a continuous flow photocatalytic reactor for wastewater treatment

A novel photocatalytic reactor for wastewater treatment was designed and constructed. The main part of the reactor was an aluminum tube in which 12 stainless steel circular baffles and four quartz tube were placed inside of the reactor like shell and tube heat exchangers. Four UV–C lamps were housed within the space of the quartz tubes. Surface of the baffles was coated with TiO₂. A simple method was employed for TiO₂ immobilization, while the characterization of the supported photocatalyst was based on the results obtained through performing some common analytical methods such as X-ray diffraction (XRD), scanning electron microscope (SEM), and BET. Phenol was selected as a model pollutant. A solution of a known initial concentration (20, 60, and 100 ppmv) was introduced to the reactor. The reactor also has a recycle flow to make turbulent flow inside of the reactor. The selected recycle flow rate was 7?×?10^?5 m³.s^?1, while the flow rate of feed was 2.53?×?10^?7, 7.56?×?10^?7, and 1.26?×?10^?6 m³.s^?1, respectively. To evaluate performance of the reactor, response surface methodology was employed. A four-factor three-level Box–Behnken design was developed to evaluate the reactor performance for degradation of phenol. Effects of phenol inlet concentration (20–100 ppmv), pH (3–9), liquid flow rate (2.53?×?10^?7?1.26?×?10^?6 m³.s^?1), and TiO₂ loading (8.8–17.6 g.m^?2) were analyzed with this method. The adjusted R ² value (0.9936) was in close agreement with that of corresponding R ² value (0.9961). The maximum predicted degradation of phenol was 75.50 % at the optimum processing conditions (initial phenol concentration of 20 ppmv, pH?～?6.41, and flow rate of 2.53?×?10^?7 m³.s^?1 and catalyst loading of 17.6 g.m^?2). Experimental degradation of phenol determined at the optimum conditions was 73.7 %. XRD patterns and SEM images at the optimum conditions revealed that crystal size is approximately 25 nm and TiO₂ nanoparticles with visible agglomerates distribute densely and uniformly over the surface of stainless steel substrate. BET specific surface area of immobilized TiO₂ was 47.2 and 45.8 m² g^?1 before and after the experiments, respectively. Reduction in TOC content, after steady state condition, showed that maximum phenol decomposition occurred at neutral condition (pH?～?6). Figure

The schematic view of the experimental set-up     

Particulate matter in the indoor and outdoor air of a gymnasium and a fronton

An indoor/outdoor monitoring programme of PM₁₀ was carried out in two sports venues (a fronton and a gymnasium). Levels always below 50 μg m^?3 were obtained in the fronton and outdoor air. Due to the climbing chalk and the constant process of resuspension, concentrations above 150 μg m^?3 were registered in the gymnasium. The chalk dust contributed to CO₃ ^2? concentrations of 32?±?9.4 μg m^?3 in this sports facility, which represented, on average, 18 % of the PM₁₀ mass. Here, the carbonate levels were 128 times higher than those registered outdoors. Much lower concentrations, around 1 μg m^?3, were measured in the fronton. The chalk dust is also responsible for the high Mg²⁺ concentrations in the gym (4.7?±?0.89 μg m^?3), unfolding a PM₁₀ mass fraction of 2.7 %. Total carbon accounted for almost 30 % of PM₁₀ in both indoor spaces. Aerosol size distributions were bimodal and revealed a clear dependence on physical activities and characteristics of the sports facilities. The use of climbing chalk in the gymnasium contributed significantly to the coarse mode. The average geometric mean diameter, geometric standard deviation and total number of coarse particles were 0.77 μm, 2.79 cm^?3 and 28 cm^?3, respectively.     

Measurements of nitrogen oxides from Hudson Bay: Implications for NOx release from snow and ice covered surfaces

Measurements of NO and NO₂ were made at a surface site (55.28 °N, 77.77 °W) near Kuujjuarapik, Canada during February and March 2008. NO_x mixing ratios ranged from near zero to 350 pptv with emission from snow believed to be the dominant source. The amount of NO_x was observed to be dependent on the terrain over which the airmass has passed before reaching the measurement site. The 24 h average NO_x emission rates necessary to reproduce observations were calculated using a zero-dimensional box model giving rates ranging from 6.9 × 10⁸ molecule cm^?2 s^?1 to 1.2 × 10⁹ molecule cm^?2 s^?1 for trajectories over land and from 3.8 × 10⁸ molecule cm^?2 s^?1 to 6.6 × 10⁸ molecule cm^?2 s^?1 for trajectories over sea ice. These emissions are higher than those suggested by previous studies and indicate the importance of lower latitude snowpack emissions. The difference in emission rate for the two types of snow cover shows the importance of snow depth and underlying surface type for the emission potential of snow-covered areas.