水中邻苯二甲酸酯类化合物的预富集

首次采用国产新型Ｄ４０２０大孔吸附树脂吸附水中邻苯二甲酸酯类化合物,结果表明,Ｄ４０２０树脂具有吸附速度快,吸附容量大,省时,费用低,操作简便等优点,用自制的下班富集柱研究了各因素对吸附率及洗脱率的影响,柱长,流速,ＰＨ值及洗脱速率影响显著。     

Resource utilization of typical biomass wastes as biochars in removing plasticizer diethyl phthalate from water: characterization and adsorption mechanisms

● Six largely produced agricultural biomass wastes were pyrolyzed into biochars. ● Feedstock type significantly determined physiochemical properties of biochars. ● The biochars showed powerful adsorption capabilities to Plasticizer DEP. ● Giant reed biochar with higher DEP adsorption was a prominent sorbent. Plastic pollution as a global environmental issue has become a research hotspot, among which the removal of inherent plasticizer (e.g., phthalic acid esters, PAEs) received increasing attention. However, the effects of biochars derived from different feedstocks on the adsorption of PAEs are poorly understood. Thus, the characteristics of biochars derived from six largely produced biomass wastes in China at 400 °C, as well as their performance in adsorption of diethyl phthalate (DEP), one of frequently detected PAEs in aqueous environment, were investigated. The results indicated that the variation in feedstock type showed significant changes in the properties (e.g., porosity, specific surface area, surface functional groups) of biochars, which affected DEP adsorption and desorption. Pseudo-second order and Freundlich models fitted the adsorption data well, and adsorption mechanisms mainly included hydrophobic effect, followed by micropore filling, hydrogen bonding, and π-π EDA interactions. Adsorption thermodynamics revealed that the adsorption was a spontaneous and exothermic the adsorption capacities of DEP on these biochars slightly decreased with the increasing pH but increased with the increasing ionic strength. Among these biochars, the giant reed biochar with relatively higher DEP adsorption and low desorption exhibited the great efficiency for DEP removal as an environment-friendly sorbent. These results highlighted the significant roles of micropore filling and hydrogen bond in determining adsorption capacity of designed biochars prepared from selecting suitable agricultural straws and wetland plant waste to typical plasticizer. The findings are useful for producing designed biochars from different biomass wastes for plasticizer pollution control.     

太滆运河表层沉积物中的酞酸酯类增塑剂和溴系、有机磷系阻燃剂残留特征初探

分别采用微波萃取-气相色谱/质谱法、加速溶剂萃取提取-液相色谱/质谱法对采自太滆运河5个沉积物样品中的6种邻苯二甲酸酯类(PAEs)、13种多溴联苯醚(PBDEs)和9种有机磷酸酯(OPEs)的质量比及分布进行研究。结果表明,所有样品中均检测到PAEs、PBDEs和OPEs(以总量计),其总质量比分别为1.99~6.90μg/g,47~572和17.1~69.7 ng/g;十溴联苯醚(BDE-209)和磷酸三异辛酯(TEHP)分别是质量比最高的PBDEs和OPEs;对于PAEs,入太湖点位处邻苯二甲酸二(2-乙基己基)酯(DEHP)质量比较高,其余点位则是邻苯二甲酸二正丁酯(DBP)质量比较高;ω(PAEs)、ω(PBDEs)和ω(OPEs)两两间线性相关性较好,指示其来源相同;下游沉积物中污染物的质量比均高于上游,沿岸生产、生活中增塑剂和阻燃剂对太湖的污染应引起更多关注。     

电气石球负载纳米二氧化钛光催化剂的制备及其对水中邻苯二甲酸酯的降解作用

以电气石微球为载体,采用溶胶–凝胶法制备电气石负载纳米二氧化钛(TiO_2)光催化材料。用X射线衍射分析、扫描电镜对微球负载TiO_2光催化剂的晶型结构和形貌进行了表征。以6种邻苯二甲酸酯为降解对象,考察了热处理温度、辐射强度对TiO_2光催化活性的影响。发现TiO_2以纳米颗粒的形式牢固负载在电气石微球表面;以天然电气石微球为载体所制得的TiO_2光催化剂对于6种邻苯二甲酸酯具有较好的光催化降解效果。     

邻苯二甲酸二甲酯在离体人红细胞内的分布和含量研究

邻苯二甲酸酯类污染物(PAEs)在环境中普遍存在,可沿食物链富集,危害人体健康。本文利用荧光光谱法和高效液相色谱法(HPLC)探究了邻苯二甲酸二甲酯(DMP)在离体人红细胞内的分布情况。结果表明,红细胞在310 nm、490 nm和609nm处各具有一个荧光特征峰,其来源分别为:红细胞内的蛋白;还原型烟酰胺腺嘌呤二核苷酸磷酸(NADPH)、黄素腺嘌呤二核苷酸(FAD)和膜脂;锌卟啉和原卟啉。DMP染毒后,310 nm处的荧光峰出现明显下降,其原因为进入红细胞内的DMP与蛋白发生了结合;490 nm和609 nm处的荧光峰变化很小。高效液相色谱(HPLC)实验结果表明,DMP能透过红细胞膜进入细胞内部,其进入量随暴露量增加而增加,进入量和暴露量的比值随暴露量增加而减少。上述研究成果能加深对PAEs在血液运输过程中与红细胞毒性作用的理解,可为PAEs的危险性评估和相关疾病预防提供数据参考。     

加压流体萃取-气相色谱法测定土壤中酞酸酯类化合物

建立了土壤中15种酞酸酯的加压流体萃取-弗罗里硅土柱净化-气相色谱测定方法。就萃取条件探讨了溶剂、温度、时间和循环次数对萃取效率的影响,就净化条件探讨了净化柱和洗脱溶剂对萃取效率的影响。根据研究结果,确定萃取条件以二氯甲烷为萃取溶剂,在萃取温度120℃、压强1 500 psi时,预热5 min,静态提取5 min,循环萃取2次,用体积为60%萃取池体积的萃取溶剂冲洗萃取池,之后用氮气吹扫萃取池90 s;净化条件为萃取溶液过弗罗里硅土固相萃取柱净化后,以正己烷∶丙酮(体积比为5∶1)洗脱。15种酞酸酯类化合物加标回收率为67.1%~124%,方法检出限为0.017~0.048 mg/kg。     

Pollution characteristics of 15 gas- and particle-phase phthalates in indoor and outdoor air in Hangzhou

Phthalate esters (PAEs), typical pollutants widely used as plasticizers, are ubiquitous in various indoor and outdoor environments. PAEs exist in both gas and particle phases, posing risks to human health. In the present study, we chose four typical kinds of indoor and outdoor environments with the longest average human residence times to assess the human exposure in Hangzhou, including newly decorated residences, ordinary residences, offices and outdoor air. In order to analyze the pollution levels and characteristics of 15 gas- and particle-phase PAEs in indoor and outdoor environments, air and particulate samples were collected simultaneously. The total PAEs concentrations in the four types of environments were 25,396, 25,466.8, 15,388.8 and 3616.2?ng/m³, respectively. DEHP and DEP were the most abundant, and DMPP was at the lowest level. Distinct variations in the distributions of indoor/outdoor, gas/particle-phase and different molecular weights of PAEs were observed, showing that indoor environments were the main sources of PAEs pollution. While most PAEs tended to exsit in indoor sites and gas-phase, the high-molecular-weight chemicals tended to exist in the particle-phase and were mainly found in PM_2.5. PAEs were more likely adsorbed by small particles, especially for the indoor environments. There existed a good correlation between the particle matter concentrations and the PAEs levels. In addition, neither temperature nor humidity had obvious effects on the distributions of the PAEs concentrations.     

3DBER-S-Fe同步脱氮除磷及去除邻苯二甲酸酯的工艺特性

为探究三维电极生物膜耦合硫铁新工艺(3DBER-S-Fe)脱氮除磷并同步去除邻苯二甲酸酯(PAEs)的工艺特性,在水力停留时间(HRT)分别为8、6、4 h条件下,研究分析了系统内总氮(TN)、总磷(TP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基)己酯(DEHP)、NO-3-N、SO2-4及pH的变化情况.结果表明,3DBER-S-Fe系统具有较好的脱氮除磷及PAEs去除效果.当水力停留时间为8、6、4 h时,TN去除率分别为80.99%、78.85%、64.76%;TP去除率分别为65.18%、67.17%、43.44%;DBP去除率分别为96.72%、97.32%、96.53%;DEHP去除率分别为91.89%、81.57%、74.30%.在3DBER-S-Fe系统内,存在异养、氢自养、硫自养反硝化脱氮过程,当HRT由8h缩短到4h时,单质硫可以弥补进水NO-3-N负荷增加所导致的反硝化电子供体相对不足问题,维持系统高效的脱氮效率;系统中海绵铁填料腐蚀产生的铁离子能够高效持续沉淀除磷;3DBER-S-Fe工艺结合了物理吸附、生物降解及电化学作用,使其在不同HRT条件下具有较高的DBP与DEHP去除率.     

邻苯二甲酸酯在三峡库区消落带非淹水期土壤中污染特征及健康风险

本研究利用超高效液相色谱飞行时间质谱(UPLC-Q-TOF~-MS)分析了三峡库区8个消落带河段土壤样品中邻苯二甲酸酯(PAEs)的浓度水平,探讨了其组成特征,通过相关性分析和主成分分析阐明了其可能的来源,并且采用健康风险模型评价了PAEs在消落带土壤中的人群健康风险.结果表明,ΣPAEs在三峡库区消落带的含量(以干重计,下同)范围为322.0~737.3 ng·g~(-1),平均值为497.2 ng·g~(-1),处于文献报道的较低水平;DIBP是丰度最高的同系物单体,其次是DBP和DEHP,三者平均贡献率为94.5%,然而DEHP并不是主要污染物,这可能由于在淹水状态下消落带土壤向水体释放DEHP,但DEHP在土壤微生物中降解也不能完全排除;DMP、DEP、DBP和DIBP两两之间具有极显著正相关性,同时结合主成分分析,表明4种PAEs可能具有相同来源.人群暴露6种PAEs的日均摄入量均未超过美国EPA规定的参考剂量(Rf D),并且6种PAEs单体的致癌风险均远低于美国EPA规定的可接受致癌风险值,但是DBP的日均摄入量占总PAEs的60%~84%,因此,在三峡库区消落带耕作过程中应预防DBP带来的潜在健康风险.     

污泥中有机磷酸酯检测的预处理优化

基于“富集（加速溶剂萃取）+净化+检测”的步骤，进行污泥取样量、萃取条件、净化柱类型、淋洗液极性和洗脱液极性的优化.确定了0.2g污泥取样量、130℃萃取温度、1：1（V/V）的丙酮/二氯甲烷混合溶液为萃取剂、氨基柱净化、2：5（V/V）的二氯甲烷/正己烷混合溶液为淋洗液、二氯甲烷为洗脱液，最后用超高效液相色谱-串联质谱对有机磷酸酯进行定性定量检测.结果表明，各物质的基质加标回收率均在60%~120%之间，基质效应也基本控制在±15%.净化方法同样适用于污水样品，用此方法成功测定了北京市某污水处理厂各工艺单元的水相及固相样品，显示出良好的适用性.