天津冬季一次重污染过程颗粒物中水溶性离子粒径分布特征

为研究天津冬季重污染天气过程中颗粒物水溶性离子的粒径谱分布及二次离子生成机制,于2014年1月利用Anderson撞击式分级采样器在中国气象局天津大气边界层观测站内采集颗粒物样品,并使用离子色谱仪分析Na~+、NH_4~+、K~+、Mg~(2+)、Ca~(2+)、Cl~-、NO_3~-、SO_4~(2-)等8种水溶性无机离子(TWSII).结果表明,采样期间PM_(2.5)和PM_(10)质量浓度均值分别为(138±100)μg·m~(-3)和(227±142)μg·m~(-3),粗、细粒子中TWSII的平均浓度分别为(34.07±6.16)μg·m~(-3)和(104.16±51.76)μg·m~(-3).细粒子中SO_4~(2-)、NO_3~-和NH_4~+这3种离子的浓度远高于其他离子,且相关性较好,粗粒子中NO_3~-、SO_4~(2-)、Cl~-浓度较高.随着污染程度加剧,细粒子中TWSII浓度增加明显,粗粒子中则变化不大.水溶性离子的粒径谱分布显示,SO_4~(2-)以单模态分布,优良天峰值出现在0.43~0.65μm,NO_3~-在优良日呈现三模态分布,峰值分别出现在0.43~0.65、2.1~3.3和5.8~9.0μm,NH_4~+呈双模态分布,优良日峰值出现在0.43~0.65μm和4.7~5.8μm,污染日3种二次离子峰值均以0.65~1.1μm的单模态分布为主,与三者之间的热动力平衡过程有关.细粒子中NH_4~+除与SO_4~(2-)和NO_3~-结合外,还与部分Cl~-结合,粗粒子中NH_4~+全部与NO_3~-和SO_4~(2-)结合后,剩余的NO_3~-和SO_4~(2-)与其他阳离子结合.     

华北地区乡村站点(曲周)夏季PM2.5中二次无机组分的生成机制与来源解析

利用大气PM2.5水溶性组分及其气态前体物在线测量系统(GAC-IC)于2014年6月9日~7月11日对华北地区乡村站点曲周大气PM2.5中水溶性组分及其气态前体物进行了在线测量,分析了PM2.5中水溶性组分与气态前体物日变化规律及其相互作用,探讨了当地细颗粒物的气粒转化机制并分析了其来源.结果表明夏季曲周大气PM2.5中水溶性无机离子与相关气态前体物的浓度呈现明显的日变化规律.观测期间,PM2.5中SO2-4、NH+4和NO-3的平均浓度分别是26.28、18.08和16.36μg·m-3,是PM2.5中最主要的水溶性无机离子,约占PM2.5质量浓度的76.23%;气态前体物中,NH3浓度明显偏高、平均值为44.85μg·m-3,主要来源于当地的农业活动排放;硫氧化率(SOR)和氮氧化率(NOR)平均值分别是0.60和0.30,表现出明显的二次污染特征.经相关性分析发现:曲周大气PM2.5中NH+4与NO-3、SO2-4有良好的相关性,且表现为富氨状态,NH+4以(NH4)2SO4形式存在,NO-3的生成主要受HNO3的限制.对NH4NO3平衡进行研究发现:与夜间相反,白天曲周大气环境不利于NH4NO3生成和保持.结果也表明,二次转化是曲周夏季细颗粒物的主要来源,堆肥与农田释放的NH3是导致高浓度二次无机颗粒物(SNA)的重要因素.     

烟花禁燃对南京市春节期间PM2.5及其组分的影响研究

对2014年、2015年两年春节期间南京市空气质量监测数据进行分析,探讨禁止燃放烟花爆竹规定实施前后空气质量变化情况.结果表明:烟花爆竹燃放使得空气质量达重污染,且空气中的PM2.5质量浓度迅速上升,出现局地短时间峰值,同时会使PM2.5中的水溶性离子组分含量也急剧升高,其中与烟花爆竹主要成分基本一致的SO2-4、Cl-、K+和Mg2+攀升迅速;禁止燃放烟花爆竹对空气质量改善有显著作用,2015年春节禁燃后,南京市空气质量均达标率同比上升4成以上,春节期间PM2.5平均质量浓度,同比改善56%;PM2.5中的水溶性离子组分也基本处于正常监测范围,较少出现波动.     

武汉市儿童多途径铅暴露风险评估

在武汉市区设置70个采样点,采集土壤、灰尘、大气及食品样品.根据美国EPA推荐的儿童铅暴露参数,应用美国EPA人体暴露风险评估方法对武汉市儿童多途径铅暴露进行了风险评估,结果表明,武汉市区儿童每天的铅暴露量为1.20×10-3mg.（kg.d）-1.经消化道途径是儿童摄入铅的主要途径,其暴露量为1.04×10-3mg.（kg.d）-1,其次为经呼吸道途径及皮肤吸收途径,其暴露量分别为0.153×10-3mg.（kg.d）-1和8.56×10-7mg.（kg.d）-1.在消化道途径中,摄入土壤或灰尘铅暴露量占占总暴露量的52.0%,通过消化道途径摄入土壤或灰尘是最主要的暴露途径.用Monte Carlo法进行模拟,在消化道途径中,通过摄取土壤铅暴露量为2.48×10-2mg.d-1.超过JECFA指定的PTDI的概率为2.1%.风险水平R计算结果表明,从消化道、呼吸道、皮肤吸收这3个途径的铅暴露风险均小于最大可接受风险水平5.0×10-5,其中经过皮肤吸收途径的铅暴露风险值小于可忽略风险水平1×10-8.应用Kriging插值法获得武汉市中心城区儿童铅日暴露量的空间分布,运用指示Kriging方法获得了武汉市儿童铅暴露危险指数图,显示武汉市青山区及江岸区儿童铅暴露水平较高.     

天山乌鲁木齐河源1号冰川区气溶胶水溶性离子变化特征及来源分析

基于2007年4、8和10月这3个时段不同季节的野外考察取样和实验室分析测试,探讨了天山乌鲁木齐河源1号冰川区气溶胶样品中水溶性离子成分的浓度组成、变化特征及其可能来源.结果表明,气溶胶水溶性离子平均浓度为2.76μg·m-3,化学组成以Ca2+、NO-3和SO2-4为主.Ca2+、SO2-4、NH+4、Na+、Mg2+、Cl-在春、夏、秋这3个季节的变化趋势与总离子浓度的变化趋势一致,均为夏季最高、秋季次之、春季最低,而K+与NO-3却呈现出秋季最高、夏季和春季浓度次之的季节变化特征.分析认为,气溶胶中Ca2+、Na+、Mg2+、K+和Cl-主要可能来自陆源矿物;而NO-3和NH+4则很大程度上以人为源为主.并且发现,SO2-4可能同时受陆地源与人类活动来源的影响.     

摩擦清洗修复铅污染土壤的参数优化及清洗效率评价

采用摩擦清洗法修复铅污染场地土壤,主要目的是将细颗粒和铅污染物从砂粒表面去除.通过正交实验优化清洗参数,并对3份不同铅含量土壤进行摩擦清洗实验.优化的清洗参数为:水土比70%干物质、温度25℃、搅拌时间30 min、搅拌速率1 200 r.mim-1.摩擦清洗前土壤经过筛分化验分析表明,3份土壤铅主要富集在砂粒和粉黏粒中;铅的分布与有机质有极大相关性.结果表明,经过摩擦清洗后,3份原状铅污染土壤砂粒的清洗效率分别为:67.61%、31.71%、41.01%,摩擦清洗从砂粒表面去除一部分细粒土壤和铅污染物,使铅浓缩至粉黏粒中;扫描电镜(SEM)分析表明,摩擦清洗后砂粒表面变光滑.以上结论说明摩擦清洗对于铅污染场地的砂粒土壤具有较好的清洗效果.     

聚磷污泥去除高浓度铅的影响因素研究

利用聚磷活性污泥去除废水中的铅[ρ(Pb2+)=150.0 mg·L-1],研究了反应体系内不同溶解氧状况和初始pH值对污泥除铅的效率和稳定性的影响.结果表明,厌氧条件下,pH 6时,铅的去除率随时间增长呈上升趋势,32 d后铅去除率达99.8%,其中有机物及硫化物结合态铅、残渣态分别占41.8%和52.6%,污泥中铅的稳定性良好.好氧条件下,在相对较短时间内铅的去除率随pH上升而增加,反应2 h时,pH 6、pH 4和pH 2对应的铅的去除率分别为99.9%、96.9%和30.3%;而好氧32 d后pH 6、pH 4和pH 2的污泥中残渣态铅含量分别为3 072.3、4 726.8和2 359.1 mg·kg-1,分别占污泥中总铅的41.8%、65.8%和88.8%.综合考虑除铅率和除铅后污泥稳定性,好氧且pH 4理论上是聚磷污泥除铅的最佳条件.     

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: Kinetics, isotherms and thermodynamics

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qm /SSA) and SSA-normalized adsorption coefficient (Kd /SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (△ G0 ) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (△ H0 ), G0 and free energy of adsorption (Ea ), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and K d /SSA or q m /SSA.     

Phytoremediation potential of charophytes: Bioaccumulation and toxicity studies of cadmium, lead and zinc

The ability for usage of common freshwater charophytes,Chara aculeolata and Nitella opaca in removal of cadmium (Cd),lead (Pb) and zinc (Zn) from wastewater was examined.C.aculeolata and N.opaca were exposed to various concentrations of Cd (0.25 and 0.5 mg/L),Pb (5 and 10 mg/L) and Zn (5 and 10 mg/L) solutions under hydroponic conditions for 6 days.C.aculeolata was more tolerant of Cd and Pb than N.opaca.The relative growth rate of N.opaca was drastically reduced at high concentrations of Cd and Pb although both were tolerant of Zn.Both macroalgae showed a reduction in chloroplast,chlorophyll and carotenoid content after Cd and Pb exposure,while Zn exposure had little effects.The bioaccumulation of both Cd and Pb was higher in N.opaca (1544.3 μg/g at 0.5 mg/L Cd,21657.0 μg/g at 10 mg/L Pb) whereas higher Zn accumulation was observed in C.aculeolata (6703.5 μg/g at 10 mg/L Zn).In addition,high bioconcentration factor values (> 1000) for Cd and Pb were observed in both species.C.aculeolata showed higher percentage of Cd and Pb removal (> 95%) than N.opaca and seemed to be a better choice for Cd and Pb removal from wastewater due to its tolerance to these metals.     

Simultaneous preconcentration of cadmium and lead in water samples with silica gel and determination by flame atomic absorption spectrometry

A new method that utilizes pretreated silica gel as an adsorbent has been developed for simultaneous preconcentration of trace Cd(II) and Pb(II) prior to the measurement by flame atomic absorption spectrometry. The effects of pH, the shaking time, the elution condition and the coexisting ions on the separation/preconcentration conditions of analytes were investigated. Under optimized conditions, the static adsorption capacity of Cd(II) and Pb(II) were 45.5 and 27.1mg/g, the relative standard deviations were 3.2% and 1.7% (for n = 11), and the limits of detection obtained were 4.25 and 0.60 ng/mL, respectively. The method was validated by analyzing the certified reference materials GBW 07304a (stream sediment) and successfully applied to the analysis of various treated wastewater samples with satisfactory results.