Effect of Humidity on the Reactive Uptake of Ammonia and Dimethylamine by Nitrogen-Containing Secondary Organic Aerosol

This study investigated the uptake of ammonia (NH3) by secondary organic aerosol (SOA) particles generated via limonene photooxidation or ozonolysis as well as the uptake of dimethylamine (DMA) by limonene ozonolysis, α-cedrene photooxidation, or toluene photooxidation SOA in an environmental chamber between 0–50% relative humidity. In addition to the acid-base equilibrium uptake, NH3 and DMA can react with SOA carbonyl compounds converting them into nitrogen-containing organic compounds (NOCs). The effective reactive uptake coefficients for the formation of NOCs from ammonia were measured on the order of 10−5. The observed DMA reactive uptake coefficients ranged from 10−5 to 10−4. Typically, the reactive uptake coefficient decreased with increasing relative humidity. This is consistent with NOC formation by a condensation reaction between NH3 or DMA with SOA, which produces water as a product. Ammonia is more abundant in the atmosphere than amines. However, the larger observed reactive uptake coefficient suggests that amine uptake may also be a potential source of organic nitrogen in particulate matter.

Photocatalytic properties of TiO2 for the degradation of O3: Examined by environmental parameters

Background: This paper describes how environmentally relevant parameters affect titanium dioxide's photocatalytic properties (TiO2) to decompose ozone (O3). Methods: Thus, experiments have been carried out in a box chamber with TiO2 coated roofing membrane samples to determine the significance of light intensity, temperature, initial O3 concentration, and relative humidity. Furthermore, an outdoor experiment has been conducted where the roofing membrane was subjected to natural sunlight. Results: The results show a significant photocatalytic effect of TiO2. The half-life of the O3 decay curve is 5.8 min in near-ambient UV-light exposure compared with 7.1 min in dark conditions. Experiments conducted at higher light intensity show a more extensive degradation of O3, where the value of the reactive uptake coefficient increases from 0.044 to 0.051. Also, the measurements carried out under natural sunlight show a photocatalytic effect where the uptake coefficient value is 0.046. A larger photocatalytic effect is detected for the experiments conducted at 283 K and 303 K temperatures compared with experiments under standard conditions. Conclusion: Experiments carried out with a very high initial concentration of O3 show that 28.1 μg of O3 is decomposed than ambient conditions, where 2.3 μg is destroyed. This demonstrates that light intensity, temperature, ozone concentration, and relative humidity significantly impact TiO2's degradation of O3.

Evaluation and Bias Correction of the Secondary Inorganic Aerosol Modeling over North China Plain in Autumn and Winter

Secondary inorganic aerosol (SIA) is the key driving factor of fine-particle explosive growth (FPEG) events, which are frequently observed in North China Plain. However, the SIA simulations remain highly uncertain over East Asia. To further investigate this issue, SIA modeling over North China Plain with the 15 km resolution Nested Air Quality Prediction Model System (NAQPMS) was performed from October 2017 to March 2018. Surface observations of SIA at 28 sites were obtained to evaluate the model, which confirmed the biases in the SIA modeling. To identify the source of these biases and reduce them, uncertainty analysis was performed by evaluating the heterogeneous chemical reactions in the model and conducting sensitivity tests on the different reactions. The results suggest that the omission of the SO2 heterogeneous chemical reaction involving anthropogenic aerosols in the model is probably the key reason for the systematic underestimation of sulfate during the winter season. The uptake coefficient of the “renoxification” reaction is a key source of uncertainty in nitrate simulations, and it is likely to be overestimated by the NAQPMS. Consideration of the SO2 heterogeneous reaction involving anthropogenic aerosols and optimization of the uptake coefficient of the “renoxification” reaction in the model suitably reproduced the temporal and spatial variations in sulfate, nitrate and ammonium over North China Plain. The biases in the simulations of sulfate, nitrate, ammonium, and particulate matter smaller than 2.5 μm (PM2.5) were reduced by 84.2%, 54.8%, 81.8%, and 80.9%, respectively. The results of this study provide a reference for the reduction in the model bias of SIA and PM2.5 and improvement of the simulation of heterogeneous chemical processes.

Production of HONO from NO₂ uptake on illuminated TiO₂ aerosol particles and following the illumination of mixed TiO₂∕ammonium nitrate particles

The rate of production of HONO from illuminated TiO2 aerosols in the presence of NO2 was measured using an aerosol flow tube system coupled to a photo-fragmentation laser-induced fluorescence detection apparatus. The reactive uptake coefficient of NO2 to form HONO, γNO2→HONO, was determined for NO2 mixing ratios in the range 34–400 ppb, with γNO2→HONO spanning the range (9.97 ± 3.52) × 10−6 to (1.26 ± 0.17) × 10−4 at a relative humidity of 15 ± 1 % and for a lamp photon flux of (1.63 ± 0.09) ×1016 photons cm−2 s−1 (integrated between 290 and 400 nm), which is similar to midday ambient actinic flux values. γNO2→HONO increased as a function of NO2 mixing ratio at low NO2 before peaking at (1.26 ± 0.17) ×10-4 at ∼ 51 ppb NO2 and then sharply decreasing at higher NO2 mixing ratios rather than levelling off, which would be indicative of surface saturation. The dependence of HONO production on relative humidity was also investigated, with a peak in production of HONO from TiO2 aerosol surfaces found at ∼ 25 % RH. Possible mechanisms consistent with the observed trends in both the HONO production and reactive uptake coefficient were investigated using a zero-dimensional kinetic box model. The modelling studies supported a mechanism for HONO production on the aerosol surface involving two molecules of NO2, as well as a surface HONO loss mechanism which is dependent upon NO2. In a separate experiment, significant production of HONO was observed from illumination of mixed nitrate/TiO2 aerosols in the absence of NO2. However, no production of HONO was seen from the illumination of nitrate aerosols alone. The rate of production of HONO observed from mixed nitrate/TiO2 aerosols was scaled to ambient conditions found at the Cape Verde Atmospheric Observatory (CVAO) in the remote tropical marine boundary layer. The rate of HONO production from aerosol particulate nitrate photolysis containing a photocatalyst was found to be similar to the missing HONO production rate necessary to reproduce observed concentrations of HONO at CVAO. These results provide evidence that particulate nitrate photolysis may have a significant impact on the production of HONO and hence NOx in the marine boundary layer where mixed aerosols containing nitrate and a photocatalytic species such as TiO2, as found in dust, are present.

Heterogeneous uptake of NH3 on ambient PM2.5 in Beijing and Shijiazhuang: Possible influence of aerosol acidity

<p>Ammonium salts (NH<sub>4</sub><sup>+</sup>) is the important component of PM<sub>2.5</sub> and has a significant impact on air quality, climate, human health, and natural ecosystems. The contribution of NH<sub>4</sub><sup>+</sup> to PM<sub>2.5</sub> is increasing at urban sites. Ammonia (NH<sub>3</sub>) with global emissions estimated at greater than 33 Tg(N) Yr<sup>-1</sup> is the only precursor of particulate NH<sub>4</sub><sup>+</sup> in the atmosphere. Thus, it is important to understand the conversion kinetics from NH<sub>3</sub> to NH<sub>4</sub><sup>+</sup> in the atmosphere. However, the uptake coefficient of NH<sub>3</sub> (γ<sub>NH3</sub>) on aerosol particles are scarce at the present time. In this work, we reported the γ<sub>NH3</sub> on ambient PM<sub>2.5</sub> in Beijing and Shijiazhuang in China. The γ<sub>NH3</sub> values on ambient PM<sub>2.5</sub> are (1.13±12.4)×10<sup>-4</sup> and (6.88±40.7)×10<sup>-4</sup> in Shijiazhuang and Beijing, respectively. They are significantly lower than those on sulfuric acid droplet (0.1-1), aqueous surface (~5×10<sup>-3</sup>-0.1) and acidified secondary organic aerosol (~10<sup>-3</sup>-~10<sup>-2</sup>), while are comparable with that on ice surface (5.3±2.2 ×10<sup>-4</sup>) and on sulfuric acid in the presence of organic gases (2×10<sup>-4</sup>-4×10<sup>-3</sup>). An annual increase of γ<sub>NH3</sub> in the statistic sense is observed and the possible reason related to the aerosol acidity has also been discussed.</p>

Production of HONO from heterogeneous uptake of NO₂ on illuminated TiO₂ aerosols measured by Photo-Fragmentation Laser Induced Fluorescence

The rate of production of HONO from illuminated TiO2 aerosols in the presence of NO2 was measured using an aerosol flow tube coupled to a photo-fragmentation laser induced fluorescence detection apparatus. The reactive uptake coefficient of NO2 to form HONO, γNO2→HONO, was determined for NO2 mixing ratios in the range 34–400 ppb, with γNO2→HONO spanning the range (9.97 ± 3.52) × 10−6 to (1.26 ± 0.17) × 10−4 at a relative humidity of 15 ± 1 % and for a lamp photon flux of (1.63 ± 0.09) × 1016 photons cm−2 s −1 (integrated between 290 and 400 nm), which is similar to values of ambient actinic flux at midday. γNO2→HONO increased as a function of NO2 mixing ratio at low NO2 before peaking at (1.26 ± 0.17) × 10−4 at 51 ppb NO2 and then sharply decreasing at higher NO2 mixing ratios, rather than levelling off which would be indicative of surface saturation. The dependence of HONO production on relative humidity was also investigated, with a peak in production of HONO from TiO2 aerosol surfaces found at ~25 % RH. Possible mechanisms consistent with the observed trends in both the HONO production and reactive uptake coefficient were investigated using a zero-dimensional kinetic box model. The modelling studies supported a mechanism for HONO production on the aerosol surface involving two molecules of NO2, as well as a surface HONO loss mechanism which is dependent upon NO2. In a separate experiment, significant production of HONO was observed from illumination of mixed nitrate/TiO2 aerosols in the absence of NO2. However, no statistically significant production of HONO was seen from the illumination of pure nitrate aerosols. The rate of production of HONO observed from mixed nitrate/TiO2 aerosols was scaled to ambient conditions found at the Cape Verde Atmospheric Observatory (CVAO) in the remote tropical marine boundary layer. The rate of HONO production from aerosol particulate nitrate photolysis containing a photocatalyst was found to be similar to the missing HONO production rate necessary to reproduce observed concentrations of HONO at CVAO. These results provide evidence that particulate nitrate photolysis may have a significant impact on the production of HONO and hence NOx in the marine boundary layer where mixed aerosols containing nitrate and a photocatalytic species such as TiO2, as found in dust, are present.

Waste Utilization: Insulation Panel from Recycled Polyurethane Particles and Wheat Husks

This study provides a solution for the utilization of two waste materials, namely the residues of soft polyurethane foam from the production of mattresses and winter wheat husks. Thermal insulation panels with a nominal density of 50–150 kg/m3, bonded one-component moisture curing polyurethane adhesive, were developed, and the effect of the ratio between recycled polyurethane foam and winter wheat husk on internal bond strength, compressive stress at 10% strain, water uptake, coefficient of thermal conductivity, and volumetric heat capacity was observed. The developed composite materials make use of the very good thermal insulation properties of the two input waste materials, and the coefficient of thermal conductivity of the resulting boards achieves excellent values, namely 0.0418–0.0574 W/(m.K). The developed boards can be used as thermal insulation in the structures of environmentally friendly buildings.