Fine Particulate Matter-Induced Oxidative Stress Mediated by UVA-Visible Light Leads to Keratinocyte Damage.

The human skin is exposed to various environmental factors including solar radiation and ambient air pollutants. Although, due to its physical and biological properties, the skin efficiently protects the body against the harm of environmental factors, their excessive levels and possible synergistic action may lead to harmful effects. Among particulate matter present in ambient air pollutants, PM2.5 is of particular importance for it can penetrate both disrupted and intact skin, causing adverse effects to skin tissue. Although certain components of PM2.5 can exhibit photochemical activity, only a limited amount of data regarding the interaction of PM2.5 with light and its effect on skin tissue are available. This study focused on light-induced toxicity in cultured human keratinocytes, which was mediated by PM2.5 obtained in different seasons. Dynamic Light Scattering (DLS) and Atomic Force Microscopy (AFM) were employed to determine sizes of the particles. The ability of PM2.5 to photogenerate free radicals and singlet oxygen was studied using EPR spin-trapping and time-resolved singlet oxygen phosphorescence, respectively. Solar simulator with selected filters was used as light source for cell treatment to model environmental lightning conditions. Cytotoxicity of photoexcited PM2.5 was analyzed using MTT assay, PI staining and flow cytometry, and the apoptotic pathway was further examined using Caspase-3/7 assay and RT-PCR. Iodometric assay and JC-10 assay were used to investigate damage to cell lipids and mitochondria. Light-excited PM2.5 were found to generate free radicals and singlet oxygen in season-dependent manner. HaCaT cells containing PM2.5 and irradiated with UV-Vis exhibited oxidative stress features-increased peroxidation of intracellular lipids, decrease of mitochondrial membrane potential, enhanced expression of oxidative stress related genes and apoptotic cell death. The data indicate that sunlight can significantly increase PM2.5-mediated toxicity in skin cells.

Investigating photo-driven arsenics' behavior and their glucose metabolite toxicity by the typical metallic oxides in ambient PM2.5.

It is essential and challenged to understand the atmospheric arsenic pollution because it is much more complicated than in water and top-soil. Herein the different behavior of arsenic species firstly were discovered within the ambient PM2.5 collected during daytime and nighttime, winter and summer. The diurnal variation of arsenic species in PMs is significantly correlated with the presence of metallic oxides, specifically, ferrous, titanium and zinc oxides, which might play a key role in the process of the photo-oxidation of As(III) to As(V) with the meteorological parameters and regional factors excluded. Subsequently, the photo conversion of arsenite was detected on metal-loaded glass-fiber filters under visible light. The photo-generated superoxide radical was found to be predominantly responsible for the oxidation of As(III). In order to reveal toxicity differences induced by oxidation As(III), HepG2 cells were exposed to various arsenic mixture solution. We found that the antioxidant enzyme activities suppressed with increasing the As(III)/As(V) ratio in total, followed by the accumulation of intracellular ROS level. The glucose consumption and glycogen content also displayed an obvious reduction in insulin-stimulated cells. Compared to the expression levels of IRS-1, AKT and GLUT4, GLUT2 might be more vulnerable to arsenic exposure and lead to the abnormalities of glucose metabolism in HepG2 cells. Taken together, these findings clarify that the health risk posed by inhalation exposure to As-pollution air might be alleviated owing to the photo-driven conversion in presence of metal oxides.

Degradation of ammonia from gas stream by advanced oxidation processes.

The reduction of ammonia emissions from air was experimentally investigated by advanced oxidation processes (AOPs) utilizing the combination of ultraviolet irradiation with ozone. The influence of operating conditions such as initial ammonia concentration and flow rate of gas on the reduction of ammonia concentration was investigated in homemade photochemical unit. The conversion of ammonia decreased with increasing initial concentration of ammonia and with increasing flow rate of air (decreasing retention time). The highest conversion of ammonia (97%) was achieved under lower initial concentration of ammonia (30 ppm) and lower flow rate of air (28 m3/h). The energy per order was evaluated for the advanced oxidation process too. The energy consumption was about 0.037 kWh/m3/order for the 97% ammonia conversion at 30 ppm of initial ammonia concentration and 28 m3/h flow rate of air. Based on the results, the advanced oxidation process combining the UV irradiation and ozone was effective for mitigation of ammonia concentration and presents a promising technology for the reduction of odor emissions from livestock buildings. Moreover, the AOPs are suitable for application for high flow rate of air, especially for ammonia abatement from livestock buildings, where very high efficiency is expected.

Tricrystalline TiO2 with enhanced photocatalytic activity and durability for removing volatile organic compounds from indoor air.

It is important to develop efficient and economic techniques for removing volatile organic compounds (VOCs) in indoor air. Heterogeneous TiO2-based semiconductors are a promising technology for achieving this goal. Anatase/brookite/rutile tricrystalline TiO2 with mesoporous structure was synthesized by a low-temperature hydrothermal route in the presence of HNO3. The obtained samples were characterized by X-ray diffraction and N2 adsorption-desorption isotherm. The photocatalytic activity was evaluated by photocatalytic decomposition of toluene in air under UV light illumination. The results show that tricrystalline TiO2 exhibited higher photocatalytic activity and durability toward gaseous toluene than bicrystalline TiO2, due to the synergistic effects of high surface area, uniform mesoporous structure and junctions among mixed phases. The tricrystalline TiO2 prepared at RHNO3=0.8, containing 80.7% anatase, 15.6% brookite and 3.7% rutile, exhibited the highest photocatalytic activity, about 3.85-fold higher than that of P25. The high activity did not significantly degrade even after five reuse cycles. In conclusion, it is expected that our study regarding gas-phase degradation of toluene over tricrystalline TiO2 will enrich the chemistry of the TiO2-based materials as photocatalysts for environmental remediation and stimulate further research interest on this intriguing topic.

Determination of the photolysis rate coefficient of monochlorodimethyl sulfide (MClDMS) in the atmosphere and its implications for the enhancement of SO2 production from the DMS + Cl2 reaction.

In this work, the photolysis rate coefficient of CH3SCH2Cl (MClDMS) in the lower atmosphere has been determined and has been used in a marine boundary layer (MBL) box model to determine the enhancement of SO2 production arising from the reaction DMS + Cl2. Absorption cross sections measured in the 28000-34000 cm(-1) region have been used to determine photolysis rate coefficients of MClDMS in the troposphere at 10 solar zenith angles (SZAs). These have been used to determine the lifetimes of MClDMS in the troposphere. At 0° SZA, a photolysis lifetime of 3-4 h has been obtained. The results show that the photolysis lifetime of MClDMS is significantly smaller than the lifetimes with respect to reaction with OH (≈ 4.6 days) and with Cl atoms (≈ 1.2 days). It has also been shown, using experimentally derived dissociation energies with supporting quantum-chemical calculations, that the dominant photodissocation route of MClDMS is dissociation of the C-S bond to give CH3S and CH2Cl. MBL box modeling calculations show that buildup of MClDMS at night from the Cl2 + DMS reaction leads to enhanced SO2 production during the day. The extra SO2 arises from photolysis of MClDMS to give CH3S and CH2Cl, followed by subsequent oxidation of CH3S.

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.

Nanocatalysis for detoxification technologies.

Transition metal based nanomaterials have been used in concurrence with Atmospheric Pressure Non Equilibrium Plasma (APNEP) generated using microwaves to detoxify volatile organic compound (VOC) polluted gas streams. Sol-gel synthesized titania nanostructured surfaces using reverse micelles alone or with further surface modification on alumina and cordierite substrate geometries, have been developed. By the construction of a pilot reactor which contains the heterogeneous catalyst after the plasma generation chamber, it was shown that the nanostructured titania greatly enhanced the destruction of the model VOC compounds (Toluene and 1,2 dichlorobenzene) as opposed to the plasma stream alone. Experiments presented show the effect of microwave power, gas stream composition (N2, N2/O2 and N2/H2O) and temperature on the effectiveness of the catalyst. These experimental variables cause a change in the Fermi electron (e-) and electron hole density (h+) of the nanostructured material, therefore, causing enhanced redox VOC destruction to occur on the surface of the nanoparticles. It was observed that the catalyst is greatly enhanced at low microwave plasma power by doping the surface of the nanoparticles with noble metals at low concentrations by chemical vapour deposition (CVD). These results demonstrate that APNEP microwave technology performance is greatly enhanced with the use of nanostructured heterogeneous catalysis for detoxification of VOC polluted gas streams.

Experimental study on removals of SO2 and NO(x) using adsorption of activated carbon/microwave desorption.

UNLABELLED: Experimental studies on desulfurization and denitrification were carried out using activated carbon irradiated by microwave. The influences of the concentrations of nitric oxide (NO) and sulfur dioxide (SO2), the flue gas coexisting compositions, on adsorption properties of activated carbon and efficiencies of desulfurization and denitrification were investigated. The results show that adsorption capacity and removal efficiency of NO decrease with the increasing of SO2 concentrations in flue gas; adsorption capacity of NO increases slightly first and drops to 12.79 mg/g, and desulfurization efficiency descends with the increasing SO2 concentrations. Adsorption capacity of SO2 declines with the increasing of O2 content in flue gas, but adsorption capacity of NO increases, and removal efficiencies of NO and SO2 could be larger than 99%. Adsorption capacity of NO declines with the increase of moisture in the flue gas, but adsorption capacity of SO2 increases and removal efficiencies of NO and SO2 would be relatively stable. Adsorption capacities of both NO and SO2 decrease with the increasing of CO2 content; efficiencies of desulfurization and denitrification augment at the beginning stage, then start to fall when CO2 content exceeds 12.4%. The mechanisms of this process are also discussed. IMPLICATIONS: The prominent SO2 and NOx treatment techniques in power plants are wet flue gas desulfurization (FGD) and the catalytic decomposition method like selective catalytic reduction (SCR) or nonselective catalytic reduction (NSCR). However, these processes would have some difficulties in commercial application due to their high investment, requirement of expensive catalysts and large-scale equipment, and so on. A simple SO2 and NOx reduction utilizing decomposition by microwave energy method can be used. The pollutants control of flue gas in the power plants by the method of microwave-induced decomposition using adsorption of activated carbon/microwave desorption can meet the requirements of environmental protection, which will be stricter in the future.

Decomposition of dichlorobenzene in a dielectric barrier discharge.

This paper presents a decomposition study of 1,2-dichlorobenzene (DCB) using a dielectric barrier discharge (DBD). The discussion is focused on the effects of variations of carrier gases, DCB concentrations and input voltages on the decomposition performance. The DCB conversion was conducted inside a cylindrical reactor consists of silver film as the outside electrode and a spring coil as the inside electrode. Two carrier gases, i.e. air and nitrogen, were introduced to the reactor at a total flow rate of 500 mL/min with DCB concentrations of 100, 300 and 500 ppm. Gaseous products, before and after plasma treatment, were analysed by a gas chromatography and FT-IR spectroscopy, and the consumed power was calculated from Lissajous' figure analysis. In order to improve the decomposition performance, various TiO2-supported catalysts were employed.

Modeling of a combined ultraviolet-biofilter system to treat gaseous chlorobenzene I: model development and parametric sensitivity.

A new type of a combined ultraviolet (UV)-biofilter system for air pollution control is developed. In this paper, two conceptual mathematical submodels of the UV reactor and standalone biofilter are developed. All model parameters have been determined by independent experiments or have been taken from literature. Results from UV and the standalone biofilter submodels are in a good agreement with experimental data. However, the performance of the combined system has significantly deviated from those of the UV or standalone submodels because of the stimulating effects of UV irradiation products on the subsequent biofilter performance. A modified model that considers the stimulating effects has agreed well with experimental data over a wide range of operating conditions. Further analysis of the primary parametric sensitivity of the model has shown that inlet chlorobenzene concentrations, gas empty-bed residence time in the UV reactor, and light intensity are important operating conditions.

Removal of high concentrations of NH(3) by a combined photoreactor and biotrickling filter system.

Average emission levels as high as 800 ppm(v) NH(3) have often been found during the anaerobic fermentation process. At these levels, NH(3) is regarded as an environmental toxic compound. High concentrations of NH(3) gas are difficult to treat in a single treatment process, suggesting that, in terms of economic cost and treatment performance, a coupled system may be a feasible technological alternative. In the coupled TiO(2) photocatalytic-biological treatment system evaluated here, the optimal gas retention time for NH(3) removal--in terms of removal efficiency and capital cost--was 26 s. High gas temperatures, high NH(3) concentrations, and low oxygen contents were unfavorable conditions for NH(3) removal by the photoreactor. The coupled system successfully removed concentrated NH(3) gas (R % > 97 %) under disrupted and shutdown conditions. The photoreactor component of the system successfully fulfilled its role as a pretreatment process and enhanced the performance of the biotrickling filter at a high inlet NH(3) load (2,277 g-N m(-3) day(-1)). Potential ammonia-oxidizing bacteria, including Bacillus cereus, Pseudomonas aeruginosa, and Stenotrophomonas sp., were isolated under the high inlet NH(3) load condition. These microbial strains have a potential as biological agents in the removal of high concentrations of NH(3) in waste gas or wastewater.

A short review of bioaerosol emissions from gas bioreactors: Health threats, influencing factors and control technologies.

Bioaerosols have widely been a concern due to their potential harm to human health caused by the carrying and spreading of harmful microorganisms. Biofiltration has been generally used as a green and effective technology for processing VOCs. However, bioaerosols can be emitted into the atmosphere as secondary pollutants from the biofiltration process. This review presents an overview of bioaerosol emissions from gas bioreactors. The mechanism of bioaerosols production and the effect of biofiltration on bioaerosol emissions were analyzed. The results showed that the bioaerosol emission concentrations were generally exceeded 104 CFU m-3, which would damage to human health. Biomass, inlet gas velocity, moisture content, temperature, and some other factors have significant influences on bioaerosol emissions. Moreover, as a result of the analysis done herein, different inactivation technologies and microbial immobilization of bioaerosols were proposed and evaluated as a potential solution for reducing bioaerosols emissions. The purpose of this paper is to make more people realize the importance of controlling the emissions of bioaerosols in the biofiltration process and to make the treatment of VOCs by biotechnology more environmentally friendly. Additionally, the present work intends to increase people's awareness in regards to the control of bioaerosols, including microbial fragment present in bioaerosols.

Simultaneous SO2 and NO removal from flue gas based on TiO2 photocatalytic oxidation.

A new approach to the simultaneous removal of SO2 and NO from flue gas, by TiO2 photocatalysis based on UV irradiation technology, is presented. Experiments on the simultaneous desulphurization and denitrification were carried out using this photocatalyst in a self-designed photocatalytic reactor. Under the optimal experimental conditions, a removal efficiency of 98% for SO2 and 50% for NO was achieved. Scanning electron microscopy, transmission electron microscopy and X-ray energy spectrometry were used to observe the surface characteristics of the TiO2 photocatalyst. It was found that the surface of the quartz sand carrier was covered with Ti, on which the Si content of the quartz sand carrier was similar to the Ti content, indicating that the quartz sand supported the TiO2 membrane well. Based on the results of X-ray photoelectron spectroscopy (XPS) and chemical analysis of the resulting products, the SO2 and NO removal mechanisms were revealed. Sulphate was the main desulphurization product and nitrite was the main denitrification product. In the removal reaction, NO was rapidly oxidized to NO2 and absorbed in the chemical reaction.

Photochemical removal of acetaldehyde using 172 nm vacuum ultraviolet excimer lamp in N2 or air at atmospheric pressure.

The photochemical removal of acetaldehyde was studied in N2 or air (O2 1-20%) at atmospheric pressure using side-on and head-on types of 172 nm Xe2 excimer lamps. When CH3CHO was decomposed in N2 using the head-on lamp (HL), CH4, CO, and CO2 were observed as products in FTIR spectra. The initial removal rate of CH3CHO in N2 was ascertained as 0.37 min-1. In air (1-20% O2), HCHO, HCOOH, CO, and CO2 were observed as products in FTIR spectra. The removal rate of CH3CHO in air using the side-on lamp (SL) increased from 3.2 to 18.6 min-1 with decreasing O2 concentration from 20 to 1%. It also increased from 2.5 to 3.7 min-1 with increasing CH3CHO concentration from 150 to 1000 ppm at 20% O2. The best energy efficiency of the CH3CHO removal using the SL in a flow system was 2.8 g/kWh at 1% O2. Results show that the contribution of O(1D) and O3 is insignificant in the initial decomposition of CH3CHO. It was inferred that CH3CHO is initially decomposed by the O(3P) + CH3CHO reaction at 5-20% O2, whereas the contribution of direct vacuum ultraviolet (VUV) photolysis increases concomitantly with decreasing O2 pressure at < 5% O2. After initial decomposition of CH3CHO, it was oxidized further by reactions of O(3P), OH, and O3 with various intermediates such as HCHO, HCOOH, and CO, leading to CO2 as a final product.

The Study of an Ultraviolet Radiation Technique for Removal of the Indoor Air Volatile Organic Compounds and Bioaerosol.

This study examined the use of high dosages of ultraviolet germicidal irradiation (UVGI) (253.7 nm) to deal with various concentrations of air pollutants, such as formaldehyde (HCHO), total volatile organic compounds (TVOC), under various conditions of humidity. A number of irradiation methods were applied for various durations in field studies to examine the efficiency of removing HCHO, TVOC, bacteria, and fungi. The removal efficiency of air pollutants (HCHO and bacteria) through long-term exposure to UVGI appears to increase with time. The effects on TVOC and fungi concentration were insignificant in the first week; however, improvements were observed in the second week. No differences were observed regarding the removal of HCHO and TVOC among the various irradiation methods in this study; however significant differences were observed in the removal of bacteria and fungi.

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.

A comparison between the four Geldart groups on the performance of a gas-phase annular fluidized bed photoreactor for volatile organic compound oxidation.

Heterogeneous photocatalytic oxidation (PCO) is a widely studied alternative for the elimination of volatile organic compounds (VOC) in air. In this context, research on novel photoreactor arrangements to enhance PCO rates is desired. Annular fluidized bed photoreactors (AFBPR) have yielded prominent results when compared to conventional thin film reactors. However, very few works aimed at optimizing AFBPR operation. In this study, TiO2 photocalytic agglomerates were synthesized and segregated in specific size distributions to behave as Geldart groups A, B, C, and D fluidization. The TiO2 agglomerates were characterized by XRD, FTIR spectra, and N2 adsorption. Photocatalyst performances were compared in a 10-mm gapped AFBPR for degrading the model pollutant methyl-ethyl-ketone (MEK), using a 254-nm radiation source. Geldart group C showed to be inadequate for AFBPR operation due to the short operation range between fluidization and elutriation. In all the cases, photocatalytic reaction rates were superior to sole UV photolysis. Group A and group B demonstrated the highest reaction rates. Considerations based on mass transfer suggested that the reasons were enhanced UV distribution within the bed at lower flow rates and superior catalyst surface area at higher flow rates. Results also revealed that groups A, B, and D perform equally per catalyst area within an AFBPR if the fluidization numbers (FN) are high enough.

Inactivation of airborne bacteria using different UV sources: Performance modeling, energy utilization, and endotoxin degradation.

Airborne bacteria-containing bioaerosols have attracted increased research attention on account of their adverse effects on human health. Ultraviolet germicidal irradiation (UVGI) is an effective method to inactivate airborne microorganisms. The present study models and compares the inactivation performance of three UV sources in the UVGI for aerosolized Escherichia coli. Inactivation efficiency of 0.5, 2.2 and 3.1 logarithmic order was obtained at an exposure UV dose of 370 J/m3 under UVA (365 nm), UVC (254 nm) and UVD (185 nm) sources, respectively. A Beer-Lambert law-based model was developed and validated to compare the inactivation performances of the UV sources, and modeling enabled prediction of inactivation efficiency and analysis of the sensitivity of several parameters. Low influent E. coli concentrations and high UV doses resulted in high energy consumption (EC). The change in airborne endotoxin concentration during UV inactivation was analyzed, and UVC and UVA irradiation showed no marked effect on endotoxin degradation. By contrast, both free and bound endotoxins could be removed by UVD treatment, which is attributed to the ozone generated by the UVD source. The results of this study can provide a better understanding of the air disinfection and airborne endotoxin removal processes.

S-incorporated TiO2 coatings grown by plasma electrolytic oxidation for reduction of Cr(VI)-EDTA with sunlight.

The plasma electrolytic oxidation (PEO) technique was used to prepare photocatalytic S-TiO2 coatings on Ti sheets; the incorporation of the S ions was possible from the electrolyte for modifying the structural and optics characteristics of the material. In this work, substrates of Ti (ASME SB-265 of 20 × 20 × 1 mm) were used in a PEO process in 10 min, using constant voltage pulses of 340 V with frequency of 1 kHz and duty cycles of 10% and of 30%. Solutions with H2SO4 (0.1 M) and CH4N2S (52 and 79 mM) were used as electrolytes. X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy (EDS) were utilized to analyze the surface morphology, crystalline phase, and chemical composition of the samples. According to the results, the catalyst coatings had microporous structure and contained anatase-rutile TiO2 nanocrystalline mixture, until 73.2% rutile and 26.8% anatase in the samples grown with 30% duty cycle and the lowest concentration of CH4N2S. From the EDS measurements, the incorporation of sulfur ions to the coatings was 0.08 wt%. 99.5% reduction efficiency of Cr(VI)-EDTA with sunlight was observed after 2 h; it was determined by diphenyl carbazide spectrophotometric method. These coatings have potential for effective sunlight heterogeneous photoreduction of this toxic, cumulative, and non-biodegradable heavy metal that contaminates the soil and water and is a serious risk to sustainability, ecosystems, and human health.

Photocatalytic porcelain grés large slabs digitally coated with AgNPs-TiO2.

TiO2 is employed as both photocatalytic and structural materials, leading to its applications in external coatings or in interior furnishing devices, including cement mortar, tiles, floorings, and glass supports. The authors have already demonstrated the efficiency of photoactive micro-sized TiO2 and here its industrial use is reported using the digital printing to coat porcelain grés slabs. Many advantages are immediately evident, namely rapid and precise deposition, no waste of raw materials, thus positively affecting the economy of the process. Data for the thin films deposited by digital printing were compared with those obtained for the conventional spray method. The use of metal-doped TiO2 is also reported so that the photoactivity of these materials can be exploited even under LED light. The digital inkjet printed coatings exhibited superior photocatalytic performance owing to both higher exposed surface area and greater volume of deposited anatase, as well as the greater areal distribution density of thinly and thickly coated regions. Moreover, the presence of TiO2 doped silver increased the efficiency of the materials in NOx degradation both under UVA and LED lights.