Chemical characteristics of haze particles in Xi'an during Chinese Spring Festival: Impact of fireworks burning

Fireworks burning releases massive fine particles and gaseous pollutants, significantly deteriorating air quality during Chinese Lunar New Year(LNY) period. To investigate the impact of the fireworks burning on the atmospheric aerosol chemistry, 1-hr time resolution of PM_(2.5) samples in Xi'an during the winter of 2016 including the LNY were collected and detected for inorganic ions, acidity and liquid water content(LWC) of the fine aerosols. PM_(2.5) during the LNY was 167 ± 87 μg/m~3, two times higher than the China National Ambient Air Quality Standard(75 μg/m~3). K~+(28 wt.% of the total ion mass) was the most abundant ion in the LNY period, followed by SO_4~(2-)(25 wt.%) and Cl-(18 wt.%). In contrast, NO_3~-(34 wt.%) was the most abundant species in the haze periods(hourly PM32-2.5 75 μg/m), followed by SO_4(29.2 wt.%) and NH_4~+(16.3 wt.%), while SO_4~(2-)(35 wt.%) was the most abundant species in the clean periods(hourly PM_(2.5) 75 μg/m~3), followed by NO_3~-(23.1 wt.%) and NH_4~+(11 wt.%). Being different from the acidic nature in the non-LNY periods, aerosol in the LNY period presented an alkaline nature with a pH value of 7.8 ± 1.3. LWC during the LNY period showed a robust linear correlation with K_2SO_4 and KCl, suggesting that aerosol hygroscopicity was dominated by inorganic salts derived from fireworks burning. Analysis of correlations between the ratios of NO--3/SO_4~(2-) and NH_4~+/SO_4~(2-) indicated that heterogeneous reaction of HNO_3 with NH_3 was an important formation pathway of particulate nitrate and ammonium during the LNY period.     

长三角淳安地区二次颗粒物污染形成机制

二次组分是长三角区域PM_(2.5)颗粒物的主要组成部分,研究二次细颗粒物污染特征以及形成机制对污染控制至关重要.本文揭示了长三角背景地区颗粒物的有机与无机组分的构成,实现了对二次有机气溶胶(SOA)总量的核算;并进一步结合气溶胶热力学模型,模拟颗粒物的理化性质,深入探讨颗粒相的水含量与酸碱度对二次污染物形成的影响.结果表明,长三角背景区域细颗粒的年平均浓度为33μg·m~(-3),主要成分为硫酸盐、硝酸盐、铵盐和有机物,其平均贡献分别为19%、15%、12%和19%.颗粒相中的硝酸盐主要为局地生成,其质量浓度主要受到温度与颗粒相铵盐浓度的影响;硫酸盐的生成受到区域传输与局地生成的耦合作用的影响.气溶胶热力学模型模拟的结果显示,长三角背景地区颗粒物总体呈现强酸性,其酸度受季节影响不大,但显著受到了颗粒相水含量的影响;颗粒相水含量对春季SOA生成的促进作用较夏季更为显著;夏季SOA在PM_(2.5)中质量浓度占比高达40%,其形成主要受到大气氧化性的影响.     

石灰石沟-堆肥湿地系统处理酸性矿山废水的研究

为探讨石灰石沟-潜流堆肥湿地系统处理酸性矿山废水(AMD)的效果及影响因素,进行了6个月模拟试验,测定出水水质和植物生长等相关的影响因素.结果表明,石灰石沟可有效提高AMD的pH值,降低其酸度与重金属含量,但随着石灰石沟中氢氧化物的积累,后期处理性能下降;堆肥湿地可显著降低AMD的酸度与重金属,出水酸度随时间持续降低,出水的Cd、Pb在检测限以下,Zn、Cu平均浓度分别为1.8mg/L, 2.6μg/L,均达到农业灌溉水标准,而无前置堆肥的普通湿地后期Cd、Zn、Cu偏高;东南景天在湿地系统也能正常富积Cd/Zn;狭叶香蒲使堆肥湿地的产碱过程受到抑制,出水酸度升高,但其对堆肥湿地的重金属去除没有产生显著影响.     

Influence of the chemical and mineralogical composition on the acidity of an abandoned copper mine in the Bor river valley (eastern Serbia)

Since the end of operations in 1987, the flotation tailing pond in the area of the former Bor River valley has been left without any type of remediation, leading to a great environmental impact on the wider surrounding area. Because the relative abundance of minerals is critical in determining the quality of the water draining from such materials, research to define the influence of the chemical and mineralogical characteristics on the acidity of the Bor flotation tailing was performed. With this aim in mind, core sampling from eight, 20-m deep drilling holes was undertaken, followed by mineralogical analysis of the composites from each drilling hole and chemical analysis of the composites of the holes and samples taken every 5 m. In addition, the tailing acidity was measured on samples from all drilling holes taken every 1 m from the surface to the base of the tailing using distilled water and 1 M KCl. The average tailing acidity was very high, with a pH value between 2.2 and 4.0 along the depth of the holes, indicating that pyrite, as the dominant sulphide mineral, was oxidised even in the deepest layers of flotation tailing.     

ZrO2掺杂的V2O5/TiO2催化剂表征及催化还原NOx

采用共沉淀法制备出不同锆掺杂量的钛锆复合载体(TiO2-ZrO2),运用XRD和BET研究其微观结构,结果显示钛锆物质的量之比1∶1时复合载体具有最大的比表面积,可达256.01 m.2g-1.以此为载体制备了V2O5/TiO2-ZrO2催化剂,并添加少量CeO2对其改性.采用XRD、BET、H2-TPR、原位FT-IR等手段研究其活性组分的表面分散状态、氧化还原特性和表面酸性.结果显示,V2O5高度分散在载体上;与纯V2O5相比,复合载体上V2O5的还原峰向低温方向发生了偏移;催化剂表面包含了大量的B酸和L酸.模拟氨气催化还原NO(NH3-SCR)的脱硝反应活性测试表明,V2O5/TiO2-ZrO2催化剂具有较好的热稳定性和较宽的活性窗口,少量CeO2的加入提高了催化剂的低温活性.     

闽西北邵武市酸雨分布特征及其与气象条件的关系

利用1992-2005年邵武市的探空、降水量和酸雨资料,分析了邵武市不同气象条件对降水酸度、酸雨出现率的影响,结果表明:(1)闽西北是福建省酸雨污染较严重的地区之一,相对于夏、秋二季,冬、春二季的降水酸度更强、酸雨出现率更高。(2)降水的量级对降水酸度、酸雨出现率有明显影响。(3)逆温层对酸雨有较大的影响,逆温特征越明显,降水pH值越低,酸雨出现概率越大。(4)1500 m高空风速、风向在一定程度上影响邵武市降水酸度和酸雨出现机率。(5)邵武市上空850 hPa~700 hPa高度层在暖平流控制下不仅降水酸度强且出现酸雨的机会大。相反,如果850hPa~700 hPa高度层在冷单流控制下不仅降水酸度弱且出现酸雨的机会小。     

Why Critical Loads of Acidity and N for Soils Should be Based on Pollutant Effective Concentrations Rather Than Deposition Fluxes

Numerous assumptions have been made over the past 17 years when calculating critical loads for soils, both for acidity (based upon base cation steady state mass balances (SMB)) and for N (eutrophication, based upon N mass balances), often without all the assumptions being explicitly stated. The tacit assumptions that the author believes to be implicit in the SMB approach are critically reviewed, with particular reference to upland regions where slope processes are highly significant. It is concluded that many of them cannot be justified, especially those that involve ignoring many key processes known to be important to biogeochemical cycling and soil evolution in upland catchments. The evidence presented suggests that critical loads of acidity and of N for soils should be based upon effective pollutant and, for acidity, also effective base cation deposition concentrations, rather than upon pollutant deposition fluxes. This is because of the dominant role of cation exchange equilibria, rather than weathering rate, in regulation of the pH and base status of the more acidification-sensitive soils, and because of the importance of transport down slope of base cations, alkalinity and N species.     

Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH4 in excess oxygen

The reaction mechanisms of selective catalytic reduction (SCR) of nitric oxide (NO) by methane (CH₄) over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models. Catalysts derived from different supports would lead to different reaction pathways, and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities. Higher ratios of Br?nsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation. Strong Br?nsted acid sites would not necessarily lead to better catalytic performance, however, since the active surface NO_y species and the corresponding reaction routes were determined by the overall acidity strength of the support. The reaction routes where NO₂ moiety was engaged as an important intermediate involved moderate oxidation of methane, the rate of which could determine the overall activity. The reaction involving NO moiety was likely to be determined by the step of reduction of NO. Therefore, to enhance the SCR activity of solid superacid catalysts, reactions between appropriate couples of active NO_y species and activated hydrocarbon intermediates should be realized by modification of the support acidity.     

贵州龙里实验区酸性降水特征及变化趋势

以2007年4月～2008年12月贵州龙里实验区的降水监测数据为基础,运用统计学方法对该地区大气降水酸度和化学组成的特征及其季节变化趋势进行分析.结果表明,研究期内当地的降水pH均值为4.70,酸雨占降雨次数的70.1%和总降雨量的76.7%.酸雨的发生呈现一定的季节变化特征,其中春季为酸雨高发季节.降水中SO42-、NO3-、NH4+、Ca2+等含量较高.与相关研究进行对比,初步认为该地区大气降水所带来的S和N的湿沉降量尚未超过当地生态系统的酸沉降临界负荷.     

基于SPAMS探究南京市秋季大气中含草酸重金属颗粒的混合状态

草酸是大气环境中重要的二羧酸,可以与多种非吸湿性的多价金属形成草酸-金属络合物,并对生物健康和大气环境产生重要的影响. 众所周知,光化学反应可以促进草酸的形成. 然而,考虑到草酸与重金属（Heavy Metals, HMs）潜在的络合反应,草酸与HMs颗粒的混合态目前尚不完全清楚. 本研究利用单颗粒气溶胶质谱仪对南京市大气中含有草酸的HMs （Fe、Cu、Pb、Zn） 的粒径和化学组成进行了分析. 结果表明,与采样期间获得的整体颗粒相比（17.16%）,HMs中草酸的数分数（Number fractions, Nfs）更高（29.88%）. 草酸在各类HMs中的Nfs值分别为20.84% （Fe）、45.59% （Cu）、37.16% （Pb）、36.51% （Zn）. 此外,草酸与Cu （ r = 0.53 ）、Pb （ r = 0.55 ）和Zn （ r = 0.79 ）之间存在良好的相关性,这可能归因于它们在环境中可以形成草酸-重金属配合物. 值得注意的是,Fe与草酸在白天（r = 0.29）和夜间（r = 0.71）的相关性差异明显,这可能是因为Fe-草酸配合物在白天发生光解和Fe驱动的Fenton反应有关. 此外,气溶胶酸度（Relative acidity, Ra）和相对湿度（Relative humidity, RH）对形成草酸-重金属配合物也有影响. Ra的增强可能抑制草酸-重金属配合物的形成. 当RH > 70%时,RH增大可能促进草酸-重金属配合物的形成. 本研究为评估草酸在HMs中的增强提供了一些参考依据,同时提高了我们对大气环境中存在的草酸汇的认识.