Ambient PM2.5 samples were collected at four sites in Xiamen, including Gulangyu (GLY), Hongwen (HW), Huli (HL) and Jimei (JM) during January, April, July and October 2013. Local source samples were obtained from coal burning power plants, industries, motor vehicles, biomass burning, fugitive dust, and sea salt for the source apportionment studies. The highest value of PM2.5 mass concentration and species related to human activities (SO42–, NO3–, Pb, Ni, V, Cu, Cd, organic carbon (OC) and elemental carbon (EC)) were found in the ambient samples from HL, and the highest and lowest loadings of PM2.5 and its components occurred in winter and summer, respectively. The reconstructed mass balance indicated that ambient PM2.5 consisted of 24% OM (organic matter), 23% sulfate, 14% nitrate, 9% ammonium, 9% geological material, 6% sea salt, 5% EC and 10% others. For the source profiles, the dominant components were OC for coal burning, motor vehicle, biomass burning and sea salt; SO42– for industry; and crustal elements for fugitive dust. Source contributions were calculated using a chemical mass balance (CMB) model based on ambient PM2.5 concentrations and the source profiles. GLY was characterized by high contributions from secondary sulfate and cooking, while HL and JM were most strongly affected by motor vehicle emissions, and biomass burning and fugitive dust, respectively. The CMB results indicated that PM2.5 from Xiamen is composed of 27.4% secondary inorganic components, 20.8% motor vehicle emissions, 11.7% fugitive dust, 9.9% sea salt, 9.3% coal burning, 5.0% biomass burning, 3.1% industry and 6.8% others.
Porous carbon material facilitates the reaction SO2 + O2 + H2O → H2SO4 in coal-burned flue gas for sulfur resources recovery at mild conditions. It draws a long-term mystery on its heterogeneous catalysis due to the complicated synergic effect between its microstructure and chemical components. To decouple the effects of geometric structure from chemical components, classical molecular dynamics method was used to investigate the static and dynamic characteristics of the reactants (H2O, SO2 and O2) in the confined space truncated by double-layer graphene (DLG). Strong adsorption of SO2 and O2 by the DLG was observed, which results in the filling of the solute molecules into the interior of the DLG and the depletion of H2O. This effect mainly results from the different affinity of the DLG to the species and can be tuned by the separation of the two graphene layers. Such dimension dependence of the static and dynamic properties like distribution profile, molecular cluster, hydrogen bond and diffusion coefficient were also studied. The conclusions drawn in this work could be helpful to the further understanding of the underlying reaction mechanism of desulfurization process in porous carbon materials and other applications of carbon-based catalysts.
First-principles calculations were performed to investigate the mechanism of Hg0 adsorption and oxidation on CeO2(111). Surface oxygen activated by the reduction of Ce4+ to Ce3+ was vital to Hg0 adsorption and oxidation processes. Hg0 was fully oxidized by the surface lattice oxygen on CeO2(111), without using any other oxidizing agents. HCl could dissociate and react with the Hg adatom on CeO2(111) to form adsorbed Hg–Cl or Cl–Hg–Cl groups, which promoted the desorption of oxidized Hg and prevented CeO2 catalyst deactivation. In contrast, O–H and H–O–H groups formed during HCl adsorption consumed the active surface oxygen and prohibited Hg oxidation. The consumed surface oxygen was replenished by adding O2 into the flue gas. We proposed that oxidized Hg desorption and maintenance of sufficient active surface oxygen were the rate-determining steps of Hg0 removal on CeO2-based catalysts. We believe that our thorough understanding and new insights into the mechanism of the Hg0 removal process will help provide guidelines for developing novel CeO2-based catalysts and enhance the Hg0 removal efficiency.
A new type of Au/TiO2/reduced graphene oxide (RGO) nanocomposite was fabricated by the hydrothermal synthesis of TiO2 on graphene oxide followed by the photodeposition of Au nanoparticles. Transmission electron microscopy images showed that Au nanoparticles were loaded onto the surface of both TiO2 and RGO. Au/TiO2/RGO had a better photocatalytic activity than Au/ TiO2 for the degradation of phenol. Electrochemical measurements indicated that Au/TiO2/RGO had an improved charge transfer capability. Meanwhile, chemiluminescent analysis and electron spin resonance spectroscopy revealed that Au/TiO2/RGO displayed high production of hydrogen peroxide and hydroxyl radicals in the photocatalytic process. This high photocatalytic performance was achieved via the addition of RGO in Au/TiO2/RGO, where RGO served not only as a catalyst support to provide more sites for the deposition of Au nanoparticles but also as a collector to accept electrons from TiO2 to effectively reduce photogenerated charge recombination.
Based on the activity level and technical information of coal-fired power-generating units (CFPGU) obtained in China from 2011 to 2015, we, 1) analyzed the time and spatial distribution of SO2 and NOx emission performance of CFPGUs in China; 2) studied the impact of installed capacity, sulfur content of coal combustion, and unit operation starting time on CFPGUs’ pollutant emission performance; and 3) proposed the SO2 and NOx emission performance standards for coal-fired power plants based on the best available control technology. Our results show that: 1) the larger the capacity of a CFPGU, the higher the control level and the faster the improvement; 2) the CFPGUs in the developed eastern regions had significantly lower SO2 and NOx emission performance values than those in other provinces due to better economic and technological development and higher environmental management levels; 3) the SO2 and NOx emission performance of the Chinese thermal power industry was significantly affected by the single-unit capacity, coal sulfur content, and unit operation starting time; and 4) based on the achievability analysis of best available pollution control technology, we believe that the CFPGUs’ SO2 emission performance reference values should be 0.34 g/kWh for active units in general areas, 0.8 g/kWh for active units in high-sulfur coal areas, and 0.13 g/kWh for newly built units and active units in key areas. In addition, the NOx emission performance reference values should be 0.35 g/kWh for active units in general areas and 0.175 g/kWh for new units and active units in key areas.
Heterogeneous Fenton-like reaction has been extensively investigated to eliminate refractory organic contaminants in wastewater, but it usually shows low catalytic performance due to difficulty in reduction from Fe(III) to Fe(II). In this study, enhanced catalytic efficiency was obtained by employing Cu-doped BiFeO3 as heterogeneous Fenton-like catalysts, which exhibited higher catalytic performance toward the activation of H2O2 for phenol degradation than un-doped BiFeO3. BiFe0.8Cu0.2O3 displayed the best performance, which yielded 91% removal of phenol (10 mg L–1) in 120 min. The pseudo first-order kinetic rate constant of phenol degradation in BiFe0.8Cu0.2O3 catalyzed heterogeneous Fenton-like reaction was 5 times higher than those of traditional heterogeneous Fenton-like catalysts, such as Fe3O4 and goethite. The phenol degradation efficiency could still reach 83% after 4 cycles, which implied the good stability of BiFe0.8Cu0.2O3. The high catalytic activity of BiFe0.8Cu0.2O3 was attributed to the fact that the doping Cu into BiFeO3 could promote the generation of Fe(II) in the catalyst and then facilitate the activation of H2O2 to degrade the organic pollutants.
The photolysis frequency of NO2, j(NO2), is an important analytical parameter in the study of tropospheric chemistry. A chemical actinometer (CA) was built to measure the ambient j(NO2) based on a high precision NOx instrument with 1 min time resolution. Parallel measurements of the ambient j(NO2) by using the CA and a commercial spectroradiometer (SR) were conducted at a typical urban site (Peking University Urban Environmental Monitoring Station) in Beijing. In general, good agreement was achieved between the CA and SR data with a high linear correlation coefficient (R2 = 0.977) and a regression slope of 1.12. The regression offset was negligible compared to the measured signal level. The j(NO2) data were calculated using the tropospheric ultraviolet visible radiation (TUV) model, which was constrained to observe aerosol optical properties. The calculated j(NO2) was intermediate between the results obtained with CA and SR, demonstrating the consistency of all the parameters observed at this site. The good agreement between the CA and SR data, and the consistency with the TUV model results, demonstrate the good performance of the installed SR instrument. Since a drift of the SR sensitivity is expected by the manufacturer, we propose a regular check of the data acquired via SR against those obtained by CA for long-term delivery of a high quality series of j(NO2) data. Establishing such a time series will be invaluable for analyzing the long-term atmospheric oxidation capacity trends as well as O3 pollution for urban Beijing.
In this study, FeVO4 was prepared and used as Fenton-like catalyst to degrade orange G (OG) dye. The removal of OG in an aqueous solution containing 0.5 g·L–1 FeVO4 and 15 mmol·L–1 hydrogen peroxide at pH 7.0 reached 93.2%. Similar rates were achieved at pH 5.7 (k = 0.0471 min–1), pH 7.0 (k = 0.0438 min–1), and pH 7.7 (k = 0.0434 min–1). The FeVO4 catalyst successfully overcomes the problem faced in the heterogeneous Fenton process, i.e., the narrow working pH range. The data for the removal of OG in FeVO4 systems containing H2O2 conform to the Langmuir–Hinshelwood model (R2 = 0.9988), indicating that adsorption and surface reaction are the two basic mechanisms for OG removal in the FeVO4–H2O2 system. Furthermore, the irradiation of FeVO4 by visible light significantly increases the degradation rate of OG, which is attributed to the enhanced rates of the iron cycles and vanadium cycles.
Ammonia has emerged as a promising hydrogen carrier with applications as an energy source in recent years. However, in addition to being toxic, gaseous ammonia is a precursor of secondary inorganic aerosols. The concentration of ambient fine particulate matter (PM2.5) is intrinsically connected to public health. In this study, PM2.5-related health impacts of utilizing ammonia-hydrogen energy in Kanto Region, Japan, were investigated. It was assumed that 20% of the electricity consumption in Kanto Region, the most populated area in Japan, was supplied by ammonia-hydrogen energy. The PM2.5 resulted from incomplete ammonia decomposition was simulated by a chemical transport model: ADMER-PRO (modified version). Based on the incremental PM2.5 concentration, health impacts on the elderly (individuals over 65 years old) were quantitatively evaluated. The ammonia emission in this scenario increased PM2.5 by 11.7% (0.16 μg·m–3·y–1) in winter and 3.5% (0.08 μg ·m–3·y–1) in summer, resulting in 351 premature deaths per year. This study suggests that costeffective emissions control or treatment and appropriate land planning should be considered to reduce the associated health impacts of this type of energy generation. In addition, further in-depth research, including cost-benefit analysis and security standards, is needed.
The Pearl River Delta (PRD) is one of the most industrialized, urbanized and populated regions in China, and thus has been long suffering from severe air pollutions. Space data provide a unique perspective for investigating the atmospheric environment at a regional scale. By utilizing multiple satellite retrievals from 2005 to 2013, this study presented, for the first time, the spatial patterns and temporal trends of typical air pollutants over PRD and its vicinity. As viewed from space, aerosol optical depth (AOD), NO2 and SO2 all had their higher values at the central part of PRD, and showed clear descending gradients as moving to the outskirt of this region. As to the inter-annual variation, all these pollutants had decreasing trends in PRD during the study period, which generally agreed with the relevant in situ measurements. However, the satellite retrievals differed from ground measurements when addressing NO2 and SO2 in the vicinity of PRD. This work also provides the inter-comparison among PRD and three other metropolitan clusters in China: PRD had relatively high AOD, moderate NO2 and low SO2 levels, and it was the only region achieving the effective reduction of NO2 and SO2 during last decade. Unlike the previous three pollutants, HCHO observed by satellite showed very special patterns: it had a relatively homogeneous spatial distribution over both of PRD and its vicinity, and presented an opposite increasing trend from 2005 to 2010. Moreover, PRD had the highest HCHO level among all the metropolitan clusters, hinting a considerable contribution of biogenic origins of HCHO in PRD.
A sampling campaign including summer, autumn and winter of 2014 and spring of 2015 was accomplished to obtain the characteristic of chemical components in PM2.5 at three sites of Kunming, a plateau city in South-west China. Nine kinds of water-soluble inorganic ions (WSI), organic and element carbon (OC and EC) in PM2.5 were analyzed by ion chromatography and thermal optical reflectance method, respectively. Results showed that the average concentrations of total WSI, OC and EC were 22.85±10.95 µg·m-3, 17.83±9.57 µg·m-3 and 5.11±4.29 µg·m-3, respectively. They totally accounted for 53.0% of PM2.5. Secondary organic and inorganic aerosols (SOA and SIA) were also assessed by the minimum ratio of OC/EC, nitrogen and sulfur oxidation ratios. The annual average concentrations of SOA and SIA totally accounted for 28.3% of the PM2.5 concentration. The low proportion suggested the primary emission was the main source of PM2.5 in Kunming. However, secondary pollution in the plateau city should also not be ignorable, due to the appropriate temperature and strong solar radiation, which can promote the atmospheric photochemical reactions.
Direct individual analysis using Scanning Electron Microscopy combined with online observation was conducted to examine the S-rich particles in PM2.5 of two typical polluted haze episodes in summer and winter from 2014 to 2015 in Beijing. Four major types of S-rich particles, including secondary CaSO4 particles (mainly observed in summer), S-rich mineral particles (SRM), S-rich water droplets (SRW) and (C, O, S)-rich particles (COS) were identified.We found the different typical morphologies and element distributions of S-rich particles and considered that (C, O, S)-rich particles had two major mixing states in different seasons. On the basis of the S-rich particles’ relative abundances, S concentrations and their relationships with PM2.5 as well as the seasonal comparison, we revealed that the S-participated formation degrees of SRM and SRW would enhance with increasing PM2.5 concentration. Moreover, C-rich matter and sulfate had seasonally different but significant impacts on the formation of COS.
Because the efficiency of biological nutrient removal is always limited by the deficient carbon source for the low carbon/nitrogen (C/N) ratio in real domestic sewage, the denitrifying phosphorus removal (DNPR) was developed as a simple and efficient method to remove nitrogen and phosphorous. In addition, this method has the advantage of saving aeration energy while reducing the sludge production. In this context, a pre-denitrification anaerobic/anoxic/post-aeration + nitrification sequence batch reactor (pre-A2NSBR) system, which could also reduce high ammonia effluent concentration in the traditional two-sludge DNPR process, is proposed in this work. The pre-A2NSBR process was mainly composed of a DNPR SBR and a nitrifying SBR, operating as alternating anaerobic/anoxic/post-aeration + nitrification sequence. Herein, the long-term performance of different nitrate recycling ratios (0–300%) and C/N ratios (2.5–8.8), carbon source type, and functional microbial community were studied. The results showed that the removal efficiency of total inorganic nitrogen (TIN, including NH4+-N, NO2– -N, and NO3– -N) gradually increased with the nitrate recycling ratios, and the system reached the highest DNPR efficiency of 94.45% at the nitrate recycling ratio of 300%. The optimum C/N ratio was around 3.9–7.3 with a nitrogen and phosphorus removal efficiency of 80.15% and 93.57%, respectively. The acetate was proved to be a high-quality carbon source for DNPR process. The results of fluorescence in situ hybridization (FISH) analysis indicated that nitrifiers and phosphorus accumulating organisms (PAOs) were accumulated with a proportion of 19.41% and 26.48%, respectively.
In the recent years, photocatalytic self-cleaning and “depolluting” materials have been suggested as a remediation technology mainly for NOx and aromatic VOCs in urban areas. A number of products incorporating the aforementioned technology have been made commercially available with the aim to improve urban air quality. These commercial products are based on the photocatalytic properties of a thin layer of TiO2 at the surface of the material (such as glass, pavement, etc.) or embedded in paints or concrete. The use of TiO2 photocatalysts as an emerging air pollution control technology has been reported in many locations worldwide. However, up to now, the effectiveness measured in situ and the expected positive impact on air quality of this relatively new technology has only been demonstrated in a limited manner. Assessing and demonstrating the effectiveness of these depolluting techniques in real scale applications aims to create a real added value, in terms of policy making (i.e., implementing air quality strategies) and economics (by providing a demonstration of the actual performance of a new technique).
Various pretreatments methods including sonication and grinding were performed on red seaweed Gelidium amansii for the subsequent extraction of agarose. The agarose products are usually extracted from agar powder products from seaweeds. In this study, the agarose was extracted using a direct polyethylene glycol (PEG) method without the need to first process the agar from seaweed. The agar extract was frozen then thawed and mixed directly with PEG solution to precipitate the agarose. The quality of agarose obtained was evaluated through physico-chemical properties analysis which includes spectral technique (FTIR), melting and boiling point, gel strength and sulfate content. These properties were compared with a non-pretreated sample and it was found that the addition of pretreatment steps improved the quality of agarose but gave a slightly lower yield. The gel strength of pretreated samples was much higher and the sulfate content was lower compared to non-pretreated samples. The best pretreatment method was sonication which gave gel strength of 742 g cm-2 and sulfate content of 0.63%. The extraction of agarose can be further improved with the use of different neutralizing agents. Pretreating the seaweed shows potential in improving the quality of agarose from seaweed and can be applied for future extraction of the agarose.
The spontaneous oxidation process of pristine silicon (Si) limits its application as photocatalyst or electrode in aqueous solution or moist air. Covering a protection layer on Si surface is an effective approach to overcome this disadvantage. In this paper, α-Fe2O3 is demonstrated to be an excellent alternative as a protection material. α-Fe2O3 layer was deposited around each p-type Si micropillar (SiMP) in well-ordered array by chemical bath deposition method. The diameter of SiMP was 5 mm and the thickness of α-Fe2O3 layer was about 20 nm. The photoeletrochemical stability of SiMP/α-Fe2O3 was proved by 10 circles cyclic voltammetry testing. Compared with SiMP, its optical absorption and photocurrent density improved 2 times and 4 times, respectively, and its onset potential for hydrogen evolution moved positively about 0.4 V. These improved performances could be ascribed to the enhanced photogenerated-charge-separation efficiency deriving from built-in electric field at the interface between Si and α-Fe2O3. The above results show an effective strategy to utilize Si material as photocatalyst or electrode in aqueous solution or moist air.
Fe-BEA catalysts are active for the NH3-SCR of NO. For industrial application, a binder should be added to the Fe-BEA catalysts to make them tightly adhere to the monoliths. The addition of alumina and zirconia as binders to the Fe-BEA led to a different effect on NO conversion. The catalytic activity of the mixed samples was evaluated by the temperature programmed procedure in a flow-reactor system, and the mechanism was analyzed via SEM, BET, XRD and XPS. It was found that larger iron particles were formed by the migration of parent iron particles in the Fe-BEA catalyst with alumina. This led to the increase of Fe3+ magnitude and iron cluster, enhancing the abilities of NO oxidation and storage. Accordingly, the SCR activity increased slightly in low temperature but decreased sharply in high temperature. For the Fe-BEA with zirconia sample, NO oxidation and storage abilities decreased due to the less iron clusters. The increase of Fe3+ magnitude resulted in higher catalytic oxidation ability, which gave rise to little change in the SCR activity compared with the Fe-BEA.
This work presents an overall introduction to the Station for Observing Regional Processes of the Earth System–SORPES in Nanjing, East China, and gives an overview about main scientific findings in studies of air pollution-weather/climate interactions obtained since 2011. The main results summarized in this paper include overall characteristics of trace gases and aerosols, chemical transformation mechanisms for secondary pollutants like O3, HONO and secondary inorganic aerosols, and the air pollution–weather/climate interactions and feedbacks in mixed air pollution plumes from sources like fossil fuel combustion, biomass burning and dust storms. The future outlook of the development plan on instrumentation, networking and data-sharing for the SORPES station is also discussed.
Chromium oxide and manganese oxide promoted ZrO2-CeO2 catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NOx with NH3. A series of characterization including X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), Brunauer–Emmett–Teller (BET) surface area analysis, H2 temperatureprogrammed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS) were used to evaluate the influence of the physicochemical properties on NH3-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO2-CeO2 binary oxide for the low temperature NH3-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO2 and H2O. Cr-Zr-Ce mixed oxide exhibited>80% NOx conversion at a wide temperature window of 100°C–300°C. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence of Cr6 +. The present mixed oxide can be a candidate for the low temperature abatement of NOx.
Effect of different carbon sources on purification performance and change of microbial community structure in a novel A2N-MBR process were investigated. The results showed that when fed with acetate, propionate or acetate and propionate mixed (1:1) as carbon sources, the effluent COD, NH4+-N, TN and TP were lower than 30, 5, 15 and 0.5 mg?L–1, respectively. However, taken glucose as carbon source, the TP concentration of effluent reached 2.6 mg?L–1. Process analysis found that the amount of anaerobic phosphorus release would be the key factor to determine the above effectiveness. The acetate was beneficial to the growth of Candidatus Accumulibacter associated with biological phosphorus removal, which was the main cause of high efficiency phosphorus removal in this system. In addition, it could eliminate the Candidatus Competibacter associated with glycogen-accumulating organisms and guarantee high efficiency phosphorus uptake of phosphorus accumulating organisms in the system with acetate as carbon source.
