Improving simulations of sulfate aerosols during winter haze over Northern China: the impacts of heterogeneous oxidation by NO<Subscript>2</Subscript>

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.

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Permitted emissions of major air pollutants from coal-fired power plants in China based on best available control technology

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 NO_x 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 NO_x 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 NO_x emission performance values than those in other provinces due to better economic and technological development and higher environmental management levels; 3) the SO₂ and NO_x 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 NO_x 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.

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Did the Clean Air Act cause the remarkable decline in sulfur dioxide concentrations?

Over the last three decades, ambient concentrations of sulfur dioxide (SO₂) air pollution have declined by approximately 80%. This paper tests whether the 1970 Clean Air Act and its subsequent amendments caused this decline. The centerpiece of this legislation is the annual assignment of all counties to SO₂ nonattainment or attainment categories. Polluters face stricter regulations in nonattainment counties. There are two primary findings. First, regulators pay little attention to the statutory selection rule in their assignment of the SO₂ nonattainment designations. Second, SO₂ nonattainment status is associated with modest reductions in SO₂ air pollution, but a null hypothesis of zero effect generally cannot be rejected. This finding holds whether the estimated effect is obtained with linear adjustment or propensity score matching. Overall, the evidence suggests that the nonattainment designation played a minor role in the dramatic reduction of SO₂ concentrations over the last 30 years.     

Estimation of the amount of dry deposition in an urban area (Kobe city, Japan) by the inferential method

The amount of dry deposition of SO₂(g) and HNO₃(g) in an urban area in Japan has been estimated by the inferential method. The mean annual dry deposition of SO₂(g) (2.91 kgS/ha/year) was close to or less than that in the Clean Air Status and Trends Network (CASTNet) of the U.S. (3.59 kgS/ha/year). The mean annual dry deposition of HNO₃(g) (10.8 kgN/ha/year) was approximately six times larger than that in CASTNet (1.85 kgN/ha/year). The proportions of dry/(dry+wet) deposition for sulfur and nitrogen were 0.301 and 0.785, respectively.     

Sulphur isotope mass balance of dissolved sulphate ion in a freshwater dam reservoir

We show that sulphur isotopic composition can be a useful tool to discriminate between various sources of sulphate and a tool for better understanding of the sulphur cycling and mass balance. Our investigations, carried out in a dam reservoir, demonstrate differences in sulphur biogeochemistry between different seasons, caused by recharge water supply in spring and intensive sulphate reduction in summer. In the riverine-affected part of the reservoir δ³⁴S(SO₄ ²⁻) varied from 4.7 to 5.9‰ in spring, and from 4.1 to 4.6‰ in summer. In the lacustrine-affected part δ³⁴S(SO₄²⁻) varied from 4.0 to 5.0‰ in spring, and from 4.5 to 5.4‰ in summer. Diurnal variations of δ³⁴S(SO₄ ²⁻) were negligible as compared to seasonal variations.     

Ambient air particulates-bound metallic elements sources identifications during winter and summer at a Science Park

The ambient air particulates pollutants of total suspended particulates (TSP) and PM_2.5 were collected by using PS-1 and Wilbur PM_2.5 sampler, simultaneously during the year of 2015–2017 at a photoelectric factory in Science Park of central Taiwan. And those of the ambient air atmospheric metallic elements (Cr, Mn, Ni, Cu, Zn, Pb) concentrations which attached on the TSP and PM_2.5 were analyzed by using inductively coupled plasma optical emission spectrometer. In addition, identifying anthropogenic and natural pollutants sources were conducted by using the enrichment factor (EF) and principal component analysis (PCA) methods. The results indicated that the average TSP and PM_2.5 concentrations were ranked highest in winter season, while summer season was ranked lowest during the year of 2015–2016. In addition, the average highest metallic element concentrations were occurred in winter season for both TSP and PM_2.5 during the year of 2015–2016, while the average lowest metallic elements concentrations in TSP and PM_2.5 were also occurred in winter season during the year of 2016–2017. Moreover, the EF analysis results showed that the metallic element Zn came from anthropogenic emission source. As for metallic element Mn, the results showed that metallic element Mn was mainly attributed to natural emission in this study. Finally, the PCA results showed that metallic elements Cr, Zn and Pb were the dominant emissions metallic elements in this study. As for PM_2.5, the results showed that the metallic elements Cr, Cu and Pb were the dominant emissions metallic elements at this HPB sampling site.

     

Rate evaluation of marble damage by SO2-acidity in the vicinity of stacks

A laboratory modelling for the assessment of damage to marble by the SO₂-acidity in the vicinity of stacks has been devised. The modelling is based on the role of metal oxide particulates (also emitted by smoke-stacks) which catalytically convert SO₂ to SO₃ forming H₂SO₄ (in presence of water), which has an excessively high selectivity, compared with HNO₃, for corroding marble. The requisites of the modelling are: (1) determination of composition of the marble, (2) immersion of samples of marble blocks (after measurement of surface areas) in H₂SO₄ solutions of known concentrations, maintaining pH and temperature at their initial values, (3) determination of concentrations of Ca and Mg (major components of marble) in the leachate, and thereby evaluating the mass loss of the marble, in terms of mg marble cm^–2 day^–1, for each level of H₂S0₄ concentration, (4) application of derived data for evaluation of duration (in years) for the decay of 1 cm thickness of marble block by the process of surface corrosion. From the modelling, it was found that the duration for the damage of 1 cm thickness of the marble sample used here by SO₂ acidities of 1, 5, 10, 50 and 100 ppm are 83.01, 69.02, 31.24, 8.19 and 4.31 years respectively.     

Air pollution-oriented ecological risk assessment in Xiamen city,China

Urban energy consumption is one of the most important causes of air pollution. Air pollution-oriented ecological risk assessment is of great significance to the promotion of urban environmental protection. This paper focuses on ecological risk in Xiamen city caused by air pollutant discharge from urban energy consumption. The Long-range Energy Alternatives Planning model was used to establish two scenarios of energy consumption in Xiamen city, and based on different scenarios, we estimated urban energy consumption and discharge quantity of air pollutant (DQAP). A box model and an expert scoring method were used to calculate the air pollution burden (APB) of SO₂, NO₂, CO, PM₁₀ and PM_2.5 and to obtain the probabilities of different air pollution loads. An ecological risk assessment model was developed and utilized to predict Xiamen city’s ecological risks in 2020. The results showed that under an energy-saving scenario, the ecological risks for PM_2.5, SO₂ and NO₂ are high, whereas the ecological risks for CO and PM₁₀ are low. Under a baseline scenario, the ecological risks for PM_2.5, SO₂ and NO₂ are moderate, whereas the ecological risks for CO and PM₁₀ are low. In addition, the APB of SO₂, NO₂, CO, and PM_2.5, but not of PM₁₀, is predicted to rise. In the simulation, energy generation from coal is the main source of air pollution. Although the DQAP from automobiles is not high, it is predicted to rise year-on-year. In summary, the ecological risk due to pollution in Xiamen city is high, and the main pollutants are SO₂, NO₂ and PM_2.5.     

Characterization and performance of V2O5/CeO2 for NH3-SCR of NO at low temperatures

A series of CeO₂ supported V₂O₅ catalysts with various loadings were prepared with different calcination temperatures by the incipient impregnation. The catalysts were evaluated for low temperature selective catalytic reduction (SCR) of NO with ammonia (NH₃). The effects of O₂ and SO₂ on catalytic activity were also studied. The catalysts were characterized by specific surface areas (S_BET) and X-ray diffraction (XRD) methods. The experimental results showed that NO conversion changed significantly with the different V₂O₅ loading and calcination temperature. With the V₂O₅ loading increasing from 0 to 10 wt%, NO conversion increased significantly, but decreased at higher loading. The optimum calcination temperature was 400°C. The best catalyst yielded above 80% NO conversion in the reaction temperature range of 160°C–300°C. The formation of CeVO₄ on the surface of catalysts caused the decrease of redox ability.     

Evaluation of porous cup soil‐water samplers under laboratory conditions: Comparison of ceramic and PTFE cups

Three different types of soil solution samplers (two ceramic cups and PTFE) were tested in the laboratory to validate their use for collecting soil‐water samples and for monitoring the chemical composition of soil solutions. Interactions between porous materials and chemical solutions were examined under different experimental conditions for several major cations (Ca²⁺, Mg²⁺, Na⁺ and K⁺) and anions (HCO^‐ ₃, NO^‐ ₃, SO₄ ^2‐ and Cl^‐) and for several minor ions (NH⁺ ₄, NO^‐ ₄, PO₄ ^3‐and B).

The results show that ceramic cups are not inert for bicarbonate, calcium and phosphate ions. Their use is only valid for a limited number of ions such as chloride and nitrate which, however, are the most studied ions in field experiments. PTFE cups have less restrictions although their use in measuring sulphates, phosphates and ammonium presents some problems.

Choosing the appropriate type of cup depends on the objectives. In any case, laboratory experiments must be performed before installation.     

Comparative study between using natural and synthetic zeolites for the improvement of soil salinity and crop yield

The effects of natural zeolite (clinoptilolite, NZ) and synthetic zeolite (Y, SZ) on salinity and the presence of the harmful salts in the soil were compared on Raphanus sativus L. Nine soil treatments were studied: 1 (control), 2 (NaCl), 3 (Na₂SO₄), 4 (NZ), 5 (SZ), 6 (NZ?+?NaCl), 7 (SZ?+?NaCl), 8 (NZ?+?Na₂SO₄), and 9 (SZ?+?Na₂SO₄). Five radish seeds were planted in each pot. Each treatment was repeated 10 times. After 50 days under equal conditions some parameters consisting of the number of leaves (NL), total leaf area (TLA), total fresh weight (TFW), total dry weight (TDW), root fresh weight (RFW), air fresh weight (AFW), root dry weight (RDW) and air dry weight (ADW) were determined. Results showed that adding either NZ or SZ to salinic soil (treatments NZNaCl, NZNa₂SO₄, SZNaCl and SZNa₂SO₄) increased AFW, TFW and TDW. Using both NZ and SZ in normal soil increased the weight of plants by developing AFW. Further NZ was more effective on soil with NaCl than SZ.     

Bioavailability of metals and As from acidified multicontaminated soils: Use of white lupin to validate several extraction methods

White lupin is an annual crop that has been used for phytostabilization of acidified multicontaminated (heavy metals and As) soils from the Aznalcóllar spill-affected area, Southern Spain. One of the most important factors for successful phytostabilization is monitoring the pollutant bioavailability in the soil. The aim of this work was to determine the best-suited method for assessing the bioavailability of heavy metals together with As in the Aznalcóllar spill-affected area, by means of a systematic comparison between different extraction methods (Ammonium bicarbonate-diethylenetriamine pentaacetic acid (AB-DTPA), CaCl₂, NaNO₃, BCR, (NH₄)₂SO₄ and rhizo). Both AB-DTPA and the first step of the BCR method were found to be unsuitable for assessing the bioavailability of heavy metals and As to plants growing in acidic soils. However, CaCl₂-extractable As, Cu, and Zn and NaNO₃-extractable As and Zn were well correlated with their concentrations in plant organs. Rhizo and (NH₄)₂SO₄, with the highest determination coefficients, were the most recommended simple extraction methods to assess the bioavailability of As, Cu, Fe, Mn, and Zn in acidified multicontaminated soils using white lupin as an excluder model plant.     

Static and dynamic characteristics of SO<Subscript>2</Subscript>-O<Subscript>2</Subscript> aqueous solution in the microstructure of porous carbon materials

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.

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山西工矿区土壤二氧化硫与多环芳烃复合污染对小麦种子萌发和幼苗生长的影响

以小麦为供试植物,山西工矿区生黄土为供试土壤,进行了土壤中二氧化硫(SO2)与多环芳烃(PAHs)单一及复合污染对小麦种子萌发率及小麦幼苗株高、根伸长和地下生物量影响的研究,以期考察复合污染的生态毒性效应。结果表明,小麦种子萌发对SO2与PAHs单一及复合污染均不敏感;SO2和PAHs单一污染时,小麦幼苗的株高与根伸长均受到一定程度的影响,低浓度SO2或PAHs处理对小麦生长起促进作用,高浓度则为抑制作用;小麦幼苗株高与SO2浓度呈显著负相关(r=-0.954,P<0.05),但与PAHs浓度的相关性不显著;SO2与PAHs复合污染条件下,对小麦幼苗株高或根伸长的联合作用多体现为协同作用,在低浓度情况下(SO2<500mg·kg-1)表现为协同促进;当SO2达到500～1000mg·kg-1时,对小麦幼苗株高或根伸长的联合作用均体现为协同抑制。SO2和PAHs单一污染时,小麦幼苗地下生物量与SO2、PAHs浓度均为显著负相关(rPAHs=-0.953,rSO2=-0.916,P<0.05);复合污染条件下,在SO2浓度为10mg·kg-1时,对地下生物量的联合作用多体现协同促进作用;而在SO2浓度为1000mg·kg-1,PAHs为50～100mg·kg-1时,对地下生物量的联合作用均体现为协同抑制作用。多元逐步回归分析进一步表明,SO2与PAHs复合污染条件下,小麦幼苗株高、根伸长都受到了SO2及PAHs的共同影响,而SO2是影响小麦幼苗地下生物量的主要因素。     

Photoelectrocatalytic degradation of camphor on TiO2/RuO2 electrodes

The degradation of camphor using titanium/ruthenium dioxide (TiO₂/RuO₂; 70:30) electrodes was investigated in a photoelectrochemical thin-film reactor under near UV light irradiation. Two different electrolytes (Na₂SO₄ and NaCl) were used in this work. Camphor degradation was monitored by solvent extraction methods and gas chromatography (GC) analysis. Comparative studies between photoelectrochemical, electrochemical, photolytic, and heterogeneous photocatalytical process were carried out. When NaCl was used, the degradation efficiency of camphor was improved, probably on account of electrochemical generation of active chlorine species and their photochemical conversion to chlorine radicals. Under these conditions camphor was completely mineralized at reaction times of 30 min.     

Acute associations between air pollution on premature rupture of membranes in Hefei,China

Numerous studies had focused on the association between air pollution and health outcomes in recent years. However, little evidence is available on associations between air pollutants and premature rupture of membranes (PROM). Therefore, we performed time-series analysis to evaluate the association between PROM and air pollution. The daily average concentrations of PM_2.5, SO₂ and NO₂ were 54.58 μg/m³, 13.06 μg/m³ and 46.09 μg/m³, respectively, and daily maximum 8-h average O₃ concentration was 95.67 μg/m³. The strongest effects of SO₂, NO₂ and O₃ were found in lag4, lag06 and lag09, and an increase of 10 μg/m³ in SO₂, NO₂ and O₃ was corresponding to increase in incidence of PROM of 8.74% (95% CI 2.12–15.79%), 3.09% (95% CI 0.64–5.59%) and 1.68% (95% CI 0.28–3.09%), respectively. There were no significant effects of PM_2.5 on PROM. Season-specific analyses found that the effects of PM_2.5, SO₂ and O₃ on PROM were more obvious in cold season, but the statistically significant effect of NO₂ was observed in warm season. We also found the modifying effects by maternal age on PROM, and we found that the effects of SO₂ and NO₂ on PROM were higher among younger mothers (<?35 years) than advanced age mothers (≥?35 years); however,?≥?35 years group were more vulnerable to O₃ than?<?35 years group. This study indicates that air pollution exposure is an important risk factor for PROM and we wish this study could provide evidence to local government to take rigid approaches to control emissions of air pollutants.

     

Oxidative stress-mediated cardiac mast cell degranulation

Pulmonary mast cell degranulation is a well-characterized response to diesel exhaust exposure. A primary constituent of fossil fuel combustion is sulfur dioxide (SO₂). SO₂ was shown to induce mast cell degranulation in an immortalized cell line secondary to induction of intracellular oxidative stress; however, it is not known whether SO₂-induced oxidative stress directly triggers the activation of cardiac mast cells. Accordingly, this study sought to determine whether Na₂SO₃ induces degranulation of cardiac mast cells, and furthermore whether cardiac mast cell activation may be prevented by inhibition of oxidative stress. To this end, cardiac mast cells were isolated from epicardial surface of the heart and incubated with increasing concentrations of Na₂SO₃ (0, 0.5, or 5 mM). Antioxidant compounds targeting different mechanisms of free radical generation, including ebselen, diphenyleneiodonium (DPI), or α-tocopherol, were incubated with 5 mM of Na₂SO₃ in order to determine their efficacy in preventing mast cell degranulation. Na₂SO₃ induced a significant concentration-dependent histamine release from cardiac mast cells ranging from 8.87% to 18.86%, which was prevented by ebselen. No effect was observed with DPI and α-tocopherol under these conditions. In conclusion, these findings indicate that SO₂ is capable of producing cardiac mast cell degranulation in vitro; however, the variable effectiveness of the three antioxidants evaluated is indicative of a multifactorial mechanism mediating SO₂-induced cardiac mast cell degranulation. The particular effectiveness of ebselen in preventing mast cell degranulation may be related to its multiple mechanisms of preventing oxidative stress.     

电镀企业周边大气颗粒物PM_(2.5)、PM_(10)和TSP中重金属分布特征及健康风险评价

以东莞市5个镇区为研究对象,采集电镀企业周边大气样品,分析了样品中重金属(包括As、Co、Cd、Cr、Cu、Mn、Ni、Pb、Sb、V、Zn和Hg)的含量分布,使用富集因子(enrich factor)、地累积指数(index of geoaccumulation)、Hakanson法和美国国家环境保护局(US EPA)的人体暴露健康风险评价模型,对PM_(2.5)、PM_(10)、总悬浮颗粒物(TSP)中重金属进行人体健康风险评价。结果表明,PM_(2.5)、PM_(10)和TSP中As、Cd和Cr平均浓度皆超标。Cr、Ni和V元素在3种颗粒物中非富集,主要为自然源;As、Co、Cu、Pb和Zn,可能来源于自然源和叠加的工业污染。Cd、Hg和Sb浓度受人为污染影响严重。Cd、Sb、Cu、Zn、Pb为生物可利用元素(K>0.6),在环境中的可迁移性高且易于被生物体和人体吸收。Mn元素的非致癌风险值较其他重金属要高1~4个数量级,且儿童的非致癌暴露风险值HQ均高于成人的。3种颗粒物中重金属元素通过呼吸吸入途径产生的非致癌风险HI值均高于人体可接受的上限1.0,其主要贡献来源于Mn的影响,研究区非致癌风险较为严重。除PM_(10)中Co元素和TSP中Co、Cr的成人致癌风险CR值大于10-4之外,其余大部分重金属元素通过呼吸途径产生的致癌风险CR值均在可接受范围之内,此外,3种颗粒物中的成人的致癌暴露风险值CRT均高于儿童的CRT值,并且除了PM_(2.5)中儿童的重金属致癌暴露风险CRT值(4.70E-05)低于人体可接受范围的上限(10-4),其余CRT值均高于10-4,致癌风险较为严重。     

Full scale treatment of hazardous wastewater through thermal reduction

An attempt has been made to present the data relating to full scale application of evaporation‐incineration technology for containment of wastewater emanating from H‐acid (mono sodium salt of 1 amino‐8‐hydroxynapthalene 3,6‐disulphonic acid) production with recourse to zero wastewater discharge. The wastewater is acidic with high concentrations of COD and total dissolved salts and BOD/COD ratio of 0.11. NO_x, SO_x, SPM and CO from stack emissions are within the standards stipulated by the statutory bodies.     

Study on particulate and metallic elements variation at daytime and nighttime period in urban atmosphere

Daily PM_2.5, PM_2.5–10 and TSP have been collected by Universal and PS‐1 sampler simultaneously at a site within Taichung between February and March 1999. The filters were analyzed by atomic absorption spectrophotometry for the elemental analysis of Ca, Fe, Mn, Pb, Cu, Zn and Cr. In general, the concentration of these metallic elements are higher in fine particles than in coarse particles. On average, PM₁₀ accounted for 67% of the TSP at daytime, while at nighttime PM₁₀ accounted for only 44% of the TSP. For PM_2.5, PM₂._5–10 and TSP concentrations, there were no significant differences between day and night period. The averaged concentrations of metallic elements in PM_2.5 at daytime were all higher than that at nighttime. Ca, Fe and Zn have large and variable PM_2.5 concentrations at both daytime and nighttime. For the daytime Zn and Pb account for the largest portion of the heavy metal elements. For the nighttime, Zn and Cr make the largest portion of the heavy metal elements. The concentrations of Mn were higher on fine particulates. The trace metals Cu and Cr in Taichung are probably due to particulates emitted by Taichung Fire Power Plants transported into the sampling area by the prevailing northwesterly wind.