Surface O3 production has a highly nonlinear relationship with its precursors. The spatial and temporal heterogeneity of O3-NOx-VOC-sensitivity regimes complicates the control-decision making. In this paper, the indicator method was used to establish the relationship between O3 sensitivity and assessment indicators. Six popular ratios indicating ozone-precursor sensitivity, HCHO/NOy, H2O2/ HNO3, O3/NOy, O3/NOz, O3/HNO3, and H2O2/NOz, were evaluated based on the distribution of NOx- and VOC-sensitive regimes. WRF-Chem was used to study a serious ozone episode in fall over the Pearl River Delta (PRD). It was found that the south-west of the PRD is characterized by a VOCsensitive regime, while its north-east is NOx-sensitive, with a sharp transition area between the two regimes. All indicators produced good representations of the elevated ozone hours in the episode on 6 November 2009, with H2O2/HNO3 being the best indicator. The threshold sensitivity levels for HCHO/NOy, H2O2/HNO3, O3/NOy, O3/NOz, O3/HNO3, and H2O2/NOz were estimated to be 0.41, 0.55, 10.2, 14.0, 19.1, and 0.38, respectively. Threshold intervals for the indicators H2O2/HNO3, O3/NOy, O3/NOz, O3/HNO3, and H2O2/NOz were able to identify more than 95% of VOC- and NOx-sensitive grids. The ozone episode on 16 November 16 2008 was used to independently verify the results, and it was found that only H2O2/HNO3 and H2O2/NOz were able to differentiate the ozone sensitivity regime well. Hence, these two ratios are suggested as the most appropriate indicators for identifying fall ozone sensitivity in the PRD. Since the species used for indicators have seasonal variation, the utility of those indicators for other seasons should be investigated in the future work.
We implemented the online coupled WRF-Chem model to reproduce the 2013 January haze event in North China, and evaluated simulated meteorological and chemical fields using multiple observations. The comparisons suggest that temperature and relative humidity (RH) were simulated well (mean biases are–0.2K and 2.7%, respectively), but wind speeds were overestimated (mean bias is 0.5 m?s–1). At the Beijing station, sulfur dioxide (SO2) concentrations were overpredicted and sulfate concentrations were largely underpredicted, which may result from uncertainties in SO2 emissions and missing heterogeneous oxidation in current model. We conducted three parallel experiments to examine the impacts of doubling SO2 emissions and incorporating heterogeneous oxidation of dissolved SO2 by nitrogen dioxide (NO2) on sulfate formation during winter haze. The results suggest that doubling SO2 emissions do not significantly affect sulfate concentrations, but adding heterogeneous oxidation of dissolved SO2 by NO2 substantially improve simulations of sulfate and other inorganic aerosols. Although the enhanced SO2 to sulfate conversion in the HetS (heterogeneous oxidation by NO2) case reduces SO2 concentrations, it is still largely overestimated by the model, indicating the overestimations of SO2 concentrations in the North China Plain (NCP) are mostly due to errors in SO2 emission inventory.
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.
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.
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.
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.
A series of Co-La catalysts were prepared using the wet impregnation method and the synthesis of catalysts were modified by controlling pH with the addition of ammonium hydroxide or oxalic solution. All the catalysts were systematically investigated for NO oxidation and SO2 resistance in a fixed bed reactor and were characterized by Brunanuer–Emmett–Teller (BET) method, Fourier Transform infrared spectroscopy (FTIR), X–ray diffraction (XRD), Thermogravimetric (TG) and Ion Chromatography (IC). Among the catalysts, the one synthesized at pH = 1 exhibited the maximum NO conversion of 43% at 180°C. The activity of the catalyst was significantly suppressed by the existence of SO2 (300 ppm) at 220°C. Deactivation may have been associated with the generation of cobalt sulfate, and the SO2 adsorption quantity of the catalyst might also have effected sulfur resistance. In the case of the compact selective catalytic reduction (SCR), the activity increased from 74% to 91% at the highest gas hourly space velocity (GHSV) of 300000 h–1 when the NO catalyst maintained the highest activity, in excess of 50% more than that of the standard SCR.
Leaching behavior and gastrointestinal bioaccessibility of rare earth elements (REEs) from hospital waste incineration (HWI) fly and bottom ash samples collected from Beijing and Nanjing Cities were assessed. In the same ash sample, the leaching concentrations of individual REEs determined by the Toxicity Characteristic Leaching Procedure (TCLP) were higher than those detected by the European standard protocol (EN-type test), thereby suggesting that the low pH value of leaching solution was an important factor influencing the leachability of REE. The REE bioaccessibility results, which were evaluated using the physiologically based extraction test (PBET), indicated that REEs were highly absorbed during gastric phase by dissolution; and subsequently precipitated and/or re-adsorbed in small intestinal phase. The relative amounts of the total REEs extracted by the TCLP method, EN-type test and PBET test were compared. In addition to the pH value of extraction solutions, the chelating role of REEs with organic ligands used in the PBET method was also an important parameter affecting REE adsorption in human body. Additionally, this study showed that REEs were extracted by these methods as concomitants of heavy metals and anions (NO3–, F–, SO42–, and Cl–) from HWI ash, which probably caused the remarkably complex toxicity on human body by the exposure pathway.
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.
Copper recovery is the core of waste printed circuit boards (WPCBs) treatment. In this study, we proposed a feasible and efficient way to recover copper from WPCBs concentrated metal scraps by direct electrolysis and factors that affect copper recovery rate and purity, mainly CuSO4·5H2O concentration, NaCl concentration, H2SO4 concentration and current density, were discussed in detail. The results indicated that copper recovery rate increased first with the increase of CuSO4·5H2O, NaCl, H2SO4 and current density and then decreased with further increasing these conditions. NaCl, H2SO4 and current density also showed a similar impact on copper purity, which also increased first and then decreased. Copper purity increased with the increase of CuSO4·5H2O. When the concentration of CuSO4·5H2O, NaCl and H2SO4 was respectively 90, 40 and 118 g/L and current density was 80 mA/cm2, copper recovery rate and purity was up to 97.32% and 99.86%, respectively. Thus, electrolysis proposes a feasible and prospective approach for waste printed circuit boards recycle, even for e-waste, though more researches are needed for industrial application.
This first nationwide survey was conducted to evaluate the overall performance of the circulating fluidized bed (CFB) incineration of municipal solid waste (MSW) in 2014-2015 in China. Total 23 CFB incineration power plants were evaluated. The data for monthly average flue gas emission of particles, CO, NOx, SO2 and HCl were collected over 12 consecutive months. The data were analyzed to assess the overall performance of CFB incineration by applying the Mahalanobis distance as a multivariate outlier detection method. Although the flue gas emission parameters had met the Chinese national emission standards, there were 11 total outliers (abnormal behavior) detected in 6 out of 23 CFB incineration power plants from the perspective of the MSWincineration performance. The results demonstrate that it is more important for a better performance of CFBs to reduce the frequencies of the MSW load changes, rather than the magnitudes of the MSW load changes, particularly reducing the frequencies in the range of 10% and more of the load changes, under the same and stable conditions. Furthermore, the overloading occurs more often than the underloading during the operation of the CFB incineration power plants in China. The frequent overloading is 0% to 30% of the designed capacity. To achieve the stable performance of CFBs in practice, an appropriately designed MSW storage capacity is suggested to build in a plant to buffer and reduce the frequency of the load changes.
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.
Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) and microelectrode technology were employed to evaluate the Nitrous oxide (N2O) production in biological aerated filters (BAFs) under varied dissolved oxygen (DO) concentrations during treating wastewater under laboratory scale. The average yield of gasous N2O showed more than 4-fold increase when the DO levels were reduced from 6.0 to 2.0 mg?L–1, indicating that low DO may drive N2O generation. PCR-DGGE results revealed that Nitratifractor salsuginis were dominant and may be responsible for N2O emission from the BAFs system. While at a low DO concentration (2.0 mg?L–1), Flavobacterium urocaniciphilum might play a role. When DO concentration was the limiting factor (reduced from 6.0 to 2.0 mg?L–1) for nitrification, it reduced NO2--N oxidation as well as the total nitrification. The data from this study contribute to explain how N2O production changes in response to DO concentration, and may be helpful for reduction of N2O through regulation of DO levels.
A novel microorganism embedding material was prepared to enhance the biological nitrogen removal through simultaneous nitrification and denitrification. Polyvinyl alcohol (PVA), sodium alginate (SA) and cyclodextrin (CD) were used to compose gel bead with embedded activated sludge. The effects of temperature, CD addition and concentrations of PVA and SA on nitrogen removal were evaluated. Results show that the gel bead with CD addition at 30°C contributed to the highest nitrogen removal efficiency and nitrogen removal rate of 85.4% and 2.08 mgL·(L·h)–1, respectively. Meanwhile, negligible NO3– and NO2– were observed, proving the occurrence of simultaneous nitrification and denitrification. The High-Throughput Sequencing confirms that the microbial community mainly contained Comamonadaceae in the proportion of 61.3%. Overall, CD increased gel bead’s porosity and resulted in the high specific endogenous respiration rate and high nitrogen removal efficiency, which is a favorable additional agent to the traditional embedding material.
Sulfamethoxazole (SMX) and trimethoprim (TMP) are two critical sulfonamide antibiotics with enhanced persistency that are commonly found in wastewater treatment plants. Recently, more scholars have showed interests in how SMX and TMP antibiotics are biodegraded, which is seldom reported previously. Novel artificial composite soil treatment systems were designed to allow biodegradation to effectively remove adsorbed SMX and TMP from the surface of clay ceramsites. A synergy between sorption and biodegradation improves the removal of SMX and TMP. One highly efficient SMX and TMP degrading bacteria strain, Bacillus subtilis, was isolated from column reactors. In the removal process, this bacteria degrade SMX and TMP to NH4+, and then further convert NH4+ to NO3– in a continuous process. Microbial adaptation time was longer for SMX degradation than for TMP, and SMX was also able to be degraded in aerobic conditions. Importantly, the artificial composite soil treatment system is suitable for application in practical engineering.
With extensive use of lithium ion batteries (LIBs), amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content (12%–21%) of anode graphite in spent LIBs, recycling anode graphite from spent LIBs cannot only alleviate the shortage of natural graphite, but also promote the sustainable development of related industries. After calcined at 600°C for 1 h to remove organic substances, anode graphite was used to prepare graphene by oxidation-reduction method. Effect of pH and N2H4·H2O amount on reduction of graphite oxide were probed. Structure of graphite, graphite oxide and graphene were characterized by XRD, Raman and FTIR. Graphite oxide could be completely reduced to graphene at pH 11 and 0.25 mL N2H4·H2O. Due to the presence of some oxygen-containing groups and structure defects in anode graphite, concentrated H2SO4 and KMnO4 consumptions were 40% and around 28.6% less than graphene preparation from natural graphite, respectively.
Atmospheric models are essential tools to study the behavior of air pollutants. To interpret the complicated atmospheric model simulations, a new-generation Model Visualization and Analysis Tool (Model-VAT) has been developed for scientists to analyze the model data and visualize the simulation results. The Model-VAT incorporates analytic functions of conventional tools and enhanced capabilities in flexibly accessing, analyzing, and comparing simulated results from multi-scale models with different map projections and grid resolutions. The performance of the Model-VAT is demonstrated by a case study of investigating the influence of boundary conditions (BCs) on the ambient Hg formation and transport simulated by the CMAQ model over the Pearl River Delta (PRD) region. The alternative BC options are taken from (1) default time-independent profiles, (2) outputs from a CMAQ simulation of a larger nesting domain, and (3) concentration files from GEOS-Chem (re-gridded and re-projected using the Model-VAT). The three BC inputs and simulated ambient concentrations and deposition were compared using the Model-VAT. The results show that the model simulations based on the static BCs (default profile) underestimates the Hg concentrations by ~6.5%, dry depositions by ~9.4%, and wet depositions by ~43.2% compared to those of the model-derived (e. g. GEOS-Chem or nesting CMAQ) BCs. This study highlights the importance of model nesting approach and demonstrates that the innovative functions of Model-VAT enhances the efficiency of analyzing and comparing the model results from various atmospheric model simulations.
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).
The considerable compounds content, abundance, and low costs involved has led to the proposal to use sewage sludge as raw material for biodiesel production. The transesterification reaction is catalyzed using an acid catalyst instead of base catalysts because of the high free fatty acid concentration. However, the use of a base catalyst, particularly a solid base catalyst, has certain advantages, including faster reaction speed and easier separation. In this study, we utilize in situ transesterification by base catalyst (KOH, KOH/activated carbon (AC) and KOH/CaO) with sewage sludge as raw material. Many conditions have been tested to increase biodiesel yield through single-factor tests, including mass fraction and catalyst dosage. Preliminary experiments have optimized reaction time and temperature. However, the three catalysts did not work better than H2SO4, which had a maximum yield of 4.6% (dry sewage sludge base) considering the purity by KOH, KOH/CaO, and KOH/AC. The features of the catalyst were analyzed using XRD, BETand SEM. As to BETof KOH/AC and the good spiculate formation of KOH crystal appears to be essential to its function. As for KOH/CaO, the formation of K2O and absorption points is likely essential.
This work investigates the effect of adding pentanol with biodiesel derived from cashew nut shell on its emissions characteristics is conducted in stationery diesel engine. The main purpose of this work is intended to reduce the emissions by fuelling biodiesel derived from cashew nut shell and the pentanol blends. Cashew nut shell biodiesel is prepared by transesterification process. Oxygenated additive used in the work is Pentanol. The experiment is conducted using four test fuels such as, biodiesel derived from cashew nut shell (CNSBD), a fuel containing 90% cashew nut shell biodiesel and 10% pentanol (CNSBD90P10), a fuel containing 80% cashew nut shell biodiesel and 20% pentanol (CNSBD80P20) and neat diesel. Experimental work concluded that by adding 10% of pentanol to cashew nut shell biodiesel 10.1%, 2.6%, 5.1%and 2.1%reduction in CO, HC, NOx and Smoke emissions were observed respectively. Further by fueling with these blends, no modifications in engines were required.
