Determination of 27 pharmaceuticals and personal care products (PPCPs) in water: The benefit of isotope dilution

• Isotope dilution method was developed for the determination of 27 PPCPs in water. • The established method was successfully applied to different types of water samples. • The correction effect of corresponding 27 ILSs over 70 d was investigated. • Benefit of isotopic dilution method was illustrated for three examples. Pharmaceuticals and personal care products (PPCPs) are a unique group of emerging and non-persistent contaminants. In this study, 27 PPCPs in various water samples were extracted by solid phase extraction (SPE), and determined by isotope dilution method using liquid chromatography coupled to tandem triple quadruple mass spectrometer (LC-MS/MS). A total of 27 isotopically labeled standards (ILSs) were applied to correct the concentration of PPCPs in spiked ultrapure water, drinking water, river, effluent and influent sewage. The corrected recoveries were 73%–122% with the relative standard deviation (RSD)<16%, except for acetaminophen. The matrix effect for all kinds of water samples was<22% and the method quantitation limits (MQLs) were 0.45–8.6 ng/L. The developed method was successfully applied on environmental water samples. The SPE extracts of spiked ultrapure water, drinking water, river and wastewater effluent were stored for 70 days, and the ILSs-corrected recoveries of 27 PPCPs were obtained to evaluate the correction ability of ILSs in the presence of variety interferences. The recoveries of 27 PPCPs over 70 days were within the scope of 72%–140% with the recovery variation<37% in all cases. The isotope dilution method seems to be of benefit when the extract has to be stored for long time before the instrument analysis.     

固相萃取-超高效液相色谱/三重四极杆质谱法同时测定地表水中8种亚硝胺类化合物

建立了固相萃取（SPE）-超高效液相色谱/三重四极杆串联质谱（UPLC-MS/MS）同时测定地表水中8种亚硝胺类化合物的方法。水样中目标物经椰壳活性炭固相萃取小柱吸附富集，小柱经氮气吹干后采用二氯甲烷洗脱。待测样品采用Atlantis T₃柱，以水-甲醇作为流动相进行梯度洗脱，大气压力化学电离源（APCI）正离子模式多反应监测方式（MRM）进行检测，内标法定量分析。8种目标物在相关线性范围内线性良好(r≥0.9950)，地表水加标回收率为55.4%~90.4%，相对标准偏差为3.1%~14.3%，方法检出限为1.1 ~1.8 ng/L。本方法准确度和灵敏度高，适用于快速测定地表水中8种亚硝胺类化合物含量。     

煤对CO2，N2和CH4的吸附速率经验公式与异同性研究*

为了解决吸附速率拟合公式缺乏而解吸经验公式众多的问题，通过替换解吸参数、定性和对比分析各经验公式对煤吸附CO₂，N₂，CH₄吸附速率的适用性，选取4种不同煤质的煤样在0.5，1.0和2.0 MPa下进行定温吸附实验，分析压力和煤质对吸附速率的影响规律。研究结果表明:时间函数式对3种气体在不同压力和煤质下的吸附速率拟合效果最佳；压力和煤质对3种气体吸附速率的影响既存在共性又具有差异性，气体吸附速率与压力符合指数函数关系，与挥发分呈现出二次函数关系，并且压力升高会导致最低吸附速率趋向于较高变质程度煤样；CH₄和N₂的吸附速率随压力升高而升高，而CO₂的吸附速率因煤样而不同，且在同压下，不同气体的最高和最低吸附速率煤样的变质程度也不同。     

不同类型活性炭处理废水中重金属离子的研究进展

重金属对人体的显著毒性和难降解的特性,使重金属水体污染成为全球性关注的环境问题。本文综述了重金属废水的危害、来源及常用处理方法,比较了不同类型活性炭处理废水中重金属离子的差异,阐述了不同类型活性炭处理技术的优势和特点,并对今后的重金属废水处理技术研究方向进行了展望。     

山东省主要河流中抗生素污染组成及空间分布特征

采用固相萃取-液相色谱/串联质谱法研究了山东省境内四大流域主要河流中抗生素污染组成及空间分布特征,涉及我国用量最大的6类共20种抗生素。结果表明:20种抗生素均有检出,且大环内酯类、喹诺酮类和四环素类抗生素整体检出浓度较高。就流域而言,半岛诸河流域抗生素污染较小,平均总质量浓度61.4 ng/L;海河流域、小清河流域和淮河流域相对较为严重,平均总质量浓度分别为232、175、118 ng/L。抗生素空间分布呈现一定的规律,检出浓度较高的点位主要集中在人口密集区下游,抗生素污染与周边生活污水、养殖企业废水和城市污水处理厂排水密切相关,而且抗生素组成可从一定程度上反映出污染来源。     

交通限行对大气颗粒物及PM2.5中二NFDA1英的影响

为了研究北京大气颗粒物和二NFDA1英(PCDD/Fs)的污染状况以及评估交通限行对大气颗粒物和PCDD/Fs的影响。利用同位素稀释高分辨率气相色谱/高分辨率质谱(HRGC/HRMS)联用法和USEPA 1613B 标准方法,以中国地质大学(北京)东门为采样点,采集大气PM_2.5、PM₁₀、TSP样品,对北京市交通限行期间以及交通限行前后等不同交通状况下颗粒物浓度及大气PM_2.5中17种2,3,7,8-PCDD/Fs污染特征进行了监测。结果表明,PM_2.5、PM₁₀、TSP的日均质量浓度在交通限行前分别为126、202、304 μg/m³,限行期间分别为39、78、93 μg/m³,限行结束后分别为79、126 μg/m³。PM_2.5中17种PCDD/Fs的质量浓度(毒性浓度)3个时段分别为1 804 fg/m³(70 fg I-TEQ/m³)、252 fg/m³ (9 fg I-TEQ/m³)和1 196 fg/m³ (48 fg I-TEQ/m³)。北京市交通限行期间颗粒物浓度和二 NFDA1 英浓度显著低于交通限行前后,交通源减排措施的实施是大气颗粒物和二 NFDA1英污染水平降低的主要原因,从减排效果看,交通源减排措施对大气细颗粒物(PM_2.5)的控制效果明显好于大气粗颗粒物。     

含氮生物降解促进剂对土壤吸附正十六烷的影响

选用正十六烷模拟润滑油,通过振荡平衡实验,考察了两种含氮脂肪酸型生物降解促进剂（甲基二乙醇胺油酸酯（MDEAO）和油酸二乙醇酰胺（ODEA））对水土体系中正十六烷吸附行为的影响。实验结果表明：正十六烷在水土体系中的有机质标化分配系数与土壤种类无关,与生物降解促进剂种类有关;土壤对正十六烷的吸附过程更符合Freundlich等温吸附模型;MDEAO的临界胶束浓度为2.0 mg/L,对土壤吸附正十六烷有一定的促进作用,ODEA的临界胶束浓度为0.7 mg/L,形成的胶束对正十六烷的增溶效果明显,促进了正十六烷在土壤中的解吸。     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

羊八井地热区典型植物对氟的吸附富集特征探究

采用水浴提取法处理羊八井地热区土壤和植物样品中可溶性氟，并用离子选择性电极法测定提取液及地热水中的氟。结果表明，地热水中氟离子最高为162 mg/L，土壤和植物中水溶性氟分别为347 mg/kg~937 mg/kg和189 mg/kg~164 mg/kg。氟离子在不同植物中的分布差异较大，嵩草属植物富集氟离子的能力最强，故可利用植物修复技术对高氟地热水、土壤净化处理，以降低氟污染。     

MoS_2/Bi_2S_3异质结光催化剂的制备及其光催化性能

以五水硝酸铋为铋源、钼酸钠为钼源、硫脲为硫源,采用简单的一步水热法合成了MoS_2/Bi_2S_3异质结光催化剂,采用XRD,SEM,TEM,BET,UV-Vis DRS技术对其进行了表征。表征结果显示,MoS_2纳米片在Bi_2S_3微棒表面生长,增加了比表面积和活性位点,并形成异质结构,促进了光生载流子的迁移,抑制了电子-空穴对的再复合。实验结果表明:钼酸钠与五水硝酸铋的质量比为1∶2时制备的复合光催化剂性能最好,反应180min时对亚甲基蓝的去除率可达96.4%,明显高于MoS_2和Bi_2S_3,且具有较高的稳定性;该催化剂对罗丹明B、甲基橙和4-硝基苯酚的去除率分别为97.1%、93.1%和90.5%,表明其对污染物具有普适性。