菏泽市秋冬季PM2.5水溶性离子化学特征分析

为深入研究菏泽市秋冬季PM_2.5中水溶性离子污染特征,于2017年10月15日-2018年1月31日对菏泽市3个监测点同步进行PM_2.5的采集和分析,分析探讨了不同污染程度下ρ（PM_2.5）及水溶性离子化学特征.结果表明:①菏泽市秋冬季PM_2.5呈区域污染特征.②整个观测期间,ρ（PM_2.5）范围为26.72~284.10 μg/m3,平均值为103.27 μg/m3,其中水溶性离子对ρ（PM_2.5）贡献率较大,为44.65%~49.87%;SNA（NO₃-、NH₄+、SO₄2-的统称）的占比较高,SNA占总水溶性离子质量浓度的86.88%,说明二次气溶胶为菏泽市大气PM_2.5中的重要组成部分.③SNA三角图解和水溶性离子相关性结果表明,采样期间大气中NO₃-、SO₄2-可能以NH₄NO₃、（NH₄）₂SO₄形式存在;ρ（Cl-）与ρ（K+）相关性较高（清洁天和污染天的相关系数分别为0.79和0.81）,由此推测Cl-与K+具有同源性,二者主要源于生物质燃烧.④重度及以上污染天的SOR（硫氧化率）和NOR（氮氧化率）分别为0.54和0.37,分别是清洁天的2.08和2.06倍;轻/中污染天的SOR和NOR分别为0.37和0.29,分别是清洁天的1.42和1.61倍.随着污染程度的加重,SO₂和NO₂向SO₄2-和NO₃-的二次转化增强.重污染日SOR、NOR和相对湿度均大于清洁天和轻/中度污染天,而温度则未表现出相似的变化趋势,说明非均相反应是菏泽市秋冬季SO₄2-和NO₃-形成的重要原因.研究显示,菏泽市污染呈区域性污染特征,二次气溶胶是菏泽市大气PM_2.5的重要组成部分,污染天ρ（NO₃-）、ρ（SO₄2-）、ρ（NH₄+）均与相对湿度呈显著正相关（P < 0.05）,均与温度呈负相关,表明在污染天高湿低温对SO₂、NO₂转化为SO₄2-、NO₃-有推动作用.      

Linking the electron donation capacity to the molecular composition of soil dissolved organic matter from the Three Gorges Reservoir areas, China

Soil dissolved organic matter(DOM) plays an essential role in the Three Gorges Reservoir(TGR) as a linkage between terrestrial and aquatic systems.In particular,the reducing capacities of soil DOM influence the geochemistry of contaminants such as mercury(Hg).However,few studies have investigated the molecular information of soil DOM and its relationship with relevant geochemic al reactivities,including redox properties.We collected samples from eight sites in the TGR areas and studied the link between the molecular characteristics of DOM and their electron donation capacities(EDCs) toward Hg(II).The average kinetic rate and EDC of soil DOM in TGR areas were(0.004±0.001) hr~(-1) and(2.88±1.39) nmol e~-/mg DOM_(bulk),respectively.Results suggest that higher EDCs and relatively rapid kinetics were related to the greater electron donating components of ligninderived and perhaps pyrogenic DOM,which are the aromatic constituents that influenced the reducing capacities of DOM in the present study.Molecular details revealed that even the typical autochthonous markers are important for the EDCs of DOM as well,in contrast to what is generally assumed.More studies identifying specific DOM molecular components involved in the abiotic reduction of Hg(II) are required to further understand the relations between DOM sources and their redox roles in the environmental fate of contaminants.     

典型金属离子对漆酶催化降解溴代阻燃剂四溴双酚A的影响研究

研究了自然环境、垃圾渗滤液及工业废水中广泛存在的金属离子对真菌漆酶（Trametes versicolor）酶活性以及对漆酶催化降解典型溴代阻燃剂四溴双酚A（TBBPA）的影响.金属离子包括Na⁺、K⁺、Zn²⁺、Cd²⁺、Cu²⁺、Hg²⁺、Fe²⁺、Fe³⁺、Pb²⁺、Al³⁺能抑制漆酶酶活性和降低TBBPA的降解转化率,抑制效应随着金属离子浓度的升高而增大;Ca²⁺、Mg²⁺、Mn²⁺则对漆酶活性和TBBPA去除率均没有显著影响.金属离子的抑制作用主要是通过干扰漆酶的电子传递过程产生的.其中,Fe²⁺和Hg²⁺的抑制效应尤为明显,而二者的抑制机制不同,Fe²⁺竞争消耗O₂,Hg²⁺则通过与漆酶结构中氨基酸络合,改变其构型从而抑制其活性.此外,通过加入介体物质2,2-联氮-二（3-乙基-苯并噻唑-6-磺酸）二铵盐（ABTS）、2,2,6,6-四甲基哌啶-氮-氧化物（TEMPO）等物质能够显著提高金属离子存在下漆酶对TBBPA的去除率.     

基于高分辨率MARGA分析成都市PM2.5中水溶性离子污染特征

利用高分辨率MARGA对2019年成都市PM_(2.5)中水溶性离子展开连续监测,结合气象参数分析水溶性离子污染特征.结果表明,MARGA监测的8种水溶性离子质量浓度与PM_(2.5)变化趋势一致,水溶性离子年均浓度为(23.1±13.6)μg·m~(-3),在PM_(2.5)中占比为48.6%,表明水溶性离子为PM_(2.5)重要组分.各离子质量浓度大小顺序依次为:NO~-_3、 SO_4~(2-)、 NH~+_4、 Cl~-、 Ca~(2+)、 K~+、 Mg~(2+)和Na~+,其中二次离子(NO~-_3、 SO_4~(2-)和NH~+_4)年均质量浓度为(20.2±2.7)μg·m~(-3),在水溶性离子占比为87.2%.水溶性离子质量浓度季节变化趋势为:冬季春季≈秋季夏季,逐月变化呈"U"型, 1月和12月浓度最高, 6～8月浓度最低.无论有无降雨,能见度均随水溶性离子浓度的增加呈幂指数递减规律,且SNA为首要影响因素.降小雨(日累计降雨量10 mm)对水溶性离子无清除作用,中雨及以上时清除作用显著.SNA在0.01水平上显著相关(两两之间相关系数均大于0.7),表明二次离子生成机制及在大气中演变过程具有较高的相似性.硫氧化率(SOR)和氮氧化率(NOR)年均值分别为0.42和0.12,与温度和O_3均呈负相关性,与湿度均呈正相关性,表明SO_4~(2-)来源主要为液相非均相氧化反应,NO~-_3来源主要为夜间非均相氧化反应.阳离子和阴离子电荷比(CE/AE)年均值为1.2,二次离子中和率(NR)年均值为1.1,表明气溶胶整体呈弱碱性.成都市大气环境处于富氨状态,二次离子存在形式主要为(NH_4)_2SO_4和NH_4NO_3.     

临安夏季霾和清洁天气PM2.5化学组成特征比较

本研究对长江三角洲背景地区临安大气本底站夏季PM_(2.5)进行连续采集,并对其分别进行OC/EC和水溶性离子测试分析.研究结果发现,临安夏季PM_(2.5)中OC和EC平均质量浓度分别为(14.3±3.95)μg·m-3和(3.33±1.47)μg·m-3.与城市地区相比,本研究临安背景地区夏季气溶胶中OC和EC相关性较弱(R2=0.31,P0.01).二次无机离子,即SO_4~(2-)、NO_3~-、NH_4~+(SNA),明显高于其它水溶性无机离子,平均浓度分别为(8.70±5.66)、(2.04±1.07)和(3.25±2.29)μg·m-3.基于对临安夏季PM_(2.5)连续加密观测、气团后向轨迹以及火点图研究分析,发现静稳天气条件和区域传输都可以影响临安地区PM_(2.5)的化学组成特征.此外,通过对临安本底站霾天和清洁天PM_(2.5)化学组成特征比较发现,与清洁天相比,霾污染天气POC和EC占PM_(2.5)的质量分数没有明显变化,而SOC占PM_(2.5)的质量分数却呈现了明显的下降趋势.与SOC不同,SO_4~(2-)和NH_4~+占PM_(2.5)的质量分数在霾污染天气均呈现了上升的趋势,说明二次无机离子有另一种明显增强的化学生成路径,即非均相化学反应.     

典型“组群式”城市夏季大气颗粒物中水溶性离子化学特征及来源

为探究典型“组群式”城市——淄博市夏季大气颗粒物中水溶性离子化学特征及来源,于2016年8月对淄博市6个城市点（桓台、张店、临淄、淄川、博山、周村）、2个郊区点（沂源、高青）及1个清洁对照点（鲁山）同步进行PM_2.5和PM₁₀采样,分析了大气颗粒物质量浓度及9种水溶性离子的空间分布特征,并利用主成分分析方法探讨了PM_2.5和PM₁₀中水溶性离子的主要来源.结果表明:①淄博夏季各点位（清洁对照点除外）PM_2.5和PM₁₀质量浓度日均值范围分别为57.2~112和77.4~163 μg/m3,空间分布特征表现为城市点>郊区点>清洁对照点;各点位PM_2.5/PM₁₀（质量浓度之比）在0.61~0.80之间,表明淄博夏季大气颗粒物污染以PM_2.5为主.②水溶性离子在PM_2.5和PM₁₀中占比分别为53.3%和48.5%,其中二次无机离子分别占总离子浓度的91.4%和83.7%,表明大气颗粒物主要以二次离子为主,并且主要富集在PM_2.5中;PM_2.5中∑阴离子/∑阳离子（摩尔浓度之比）为1.07,PM₁₀中该比值为0.87,说明PM_2.5接近中性,而PM₁₀呈弱碱性.③淄博夏季各点位离子来源具有一定的空间差异性,城市点、郊区点与清洁对照点间的CD（分歧系数）均高于0.2,而城市点间CD值低于0.2,说明城市点位间的水溶性离子的化学性质较为相似.④主成分分析表明,淄博夏季大气PM_2.5中的水溶性离子可能主要来源于工业源、生物质锅炉、燃煤、二次源、道路尘及建筑尘,而PM₁₀中的离子主要来源于道路尘、建筑尘、海盐及二次源.研究显示,淄博市颗粒物污染严重,具有明显的空间分布特征,水溶性离子来源复杂,应采取分区、多源控制的污染防治对策.      

聊城市冬季PM2.5及水溶性离子污染特征及来源分析

为研究聊城市冬季PM_2.5污染特征,于2016年1月7-29日在聊城市区对PM_2.5样品进行了采集,并对其水溶性离子（包括F-、Cl-、NO₃-、SO₄2-、NH₄+、Ca2+、Na+、Mg2+、K+）进行了分析.结果显示:观测期间聊城市ρ（PM_2.5）平均值为（192.4±88.9）μg/m3,超过GB 3095-2012《环境空气质量标准》日均二级标准限值的1.6倍.水溶性离子质量浓度为（77.4±46.9）μg/m3,占ρ（PM_2.5）的40.2%,其中SNA（NO₃-、SO₄2-和NH₄+）为主要离子,占水溶性离子比例达82.5%.轻度、中度、重度及严重污染时PM_2.5中水溶性离子质量浓度分别为（32.49±3.67）（46.26±17.66）（77.11±11.64）和（139.21±51.71）μg/m3,SNA分别占ρ（PM_2.5）的24.4%、26.7%、30.4%和39.0%,随着污染程度加重,SNA比例升高.观测期间SOR（硫转化率）与NOR（氮转化率）的平均值分别为0.18和0.20,随着ρ（PM_2.5）升高,SOR及NOR明显上升,表明冬季PM_2.5污染越严重时SO₂与NO₂的转化速率越强,二次无机污染严重.主成分分析结果表明,二次转化、扬尘源及工业生产为水溶性离子的主要来源.后向气流轨迹结果显示,观测期间污染气团主要来源于西北方向,受内蒙古及河北城市影响较大,但当污染气团来源于周边城市且天气静稳时,颗粒物浓度最高.研究显示,聊城市冬季PM_2.5污染较为严重.      

UiO-66/UiO-66-PYDC的制备及其对UO22+吸附性研究

通过水热法合成了两种锆基有机骨架材料,采用XRD、SEM、IR、TG、EDS、BET等技术对材料的结构和形貌进行了表征,并通过静态吸附实验在不同条件下测试所制材料对UO2+2的吸附性能,考察了时间、温度、初始铀浓度、pH、CO2-3对吸附的影响.结果表明:Ui O-66体系对铀酰离子的吸附以化学吸附为主,通过表面的羧基官能团与铀酰离子结合从而达到吸附的目的.此外,本实验中材料的比表面积对吸附的影响不明显.在初始最佳pH为10.5的条件下,通过热力学模型拟合发现,低浓度下Ui O-66拥有更大的吸附量.随着溶液中初始铀酰离子浓度的升高,Ui O-66-PYDC展现出更好的吸附效果.     

Chemical characteristics and source apportionment of PM2.5 between heavily polluted days and other days in Zhengzhou, China

PM_(2.5) samples were collected in Zhengzhou during 3 years of observation, and chemical characteristics and source contribution were analyzed. Approximately 96% of the daily PM_(2.5) concentrations and annual average values exceeded the Chinese National Ambient Air Quality Daily and Annual Standards, indicating serious PM_(2.5) pollution. The average concentration of water-soluble inorganic ions was 2.4 times higher in heavily polluted days(daily PM32.5 concentrations 250 μg/mand visibility 3 km) than that in other days, with sulfate, nitrate, and ammonium as major ions. According to the ratio of NO-3/SO2-4,stationary sources are still the dominant source of PM_(2.5) and vehicle emission could not be ignored. The ratio of secondary organic carbon to organic carbon indicated that photochemical reactivity in heavily polluted days was more intense than in other days.Crustal elements were the most abundant elements, accounting for more than 60% of 23 elements. Chemical Mass Balance results indicated that the contributions of major sources(i.e., nitrate, sulfate, biomass, carbon and refractory material, coal combustion, soil dust,vehicle, and industry) of PM_(2.5) were 13%, 16%, 12%, 2%, 14%, 8%, 7%, and 8% in heavily polluted days and 20%, 18%, 9%, 2%, 27%, 14%, 15%, and 9% in other days, respectively.Extensive combustion activities were the main sources of polycyclic aromatic hydrocarbons during the episode(Jan 1-9, 2015) and the total benzo[a]pyrene equivalency concentrations in heavily polluted days present significant health threat. Because of the effect of regional transport, the pollution level of PM_(2.5) in the study area was aggravated.     

Mutual detoxification of mercury and selenium in unicellular Tetrahymena

Selenium(Se) is commonly recognized as a protective element with an antagonistic effect against mercury(Hg) toxicity. However, the mechanisms of this Hg–Se antagonism are complex and remain controversial. To gain insight into the Hg–Se antagonism, a type of unicellular eukaryotic protozoa(Tetrahymena malaccensis, T. malaccensis) was selected and individually or jointly exposed to two Hg and three Se species. We found that Se species showed different toxic effects on the proliferation of T. malaccensis with the toxicity following the order:selenite(Se(IV)) selenomethionine(SeMeth) selenate(Se(VI)). The Hg–Se antagonism in Tetrahymena was observed because the joint toxicity significantly decreased under co-exposure to highly toxic dosages of Hg and Se versus individual toxicity. Unlike Se(IV) and Se(VI), non-toxic dosage of SeM eth significantly decreased the Hg toxicity, revealing the influence of the Se species and dosages on the Hg–Se antagonism. Unexpectedly, inorganic divalent Hg(Hg~(2+)) and monomethylmercury(MeHg) also displayed detoxification towards extremely highly toxic dosages of Se, although their detoxifying efficiency was discrepant. These results suggested mutual Hg–Se detoxification in T. malaccensis, which was highly dependent on the dosages and species of both elements. As compared to other species, SeM eth and MeHg promoted the Hg–Se joint effects to a higher degree. Additionally, the Hg contents decreased for all the Hg–Se co-exposed groups, revealing a sequestering effect of Se towards Hg in T. malaccensis.