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.     

硬质聚氨酯泡沫和组合聚醚中消耗臭氧层物质的便携式GC-MS测定方法

建立了便携式顶空/气相色谱-质谱法测定硬质聚氨酯泡沫和组合聚醚中一氟三氯甲烷（CFC-11）、二氟二氯甲烷（CFC-12）、二氟一氯甲烷（HCFC-22）及一氟二氯乙烷（HCFC-141b）的定性分析方法，系统考察了色谱柱、顶空体系、顶空温度和顶空时间对测定结果的影响。结果表明，DB-WAX色谱柱对目标物质的分离效果最好，顶空温度为50℃、顶空时间为10 min条件下，目标物质的检测灵敏度最高。在优化条件下，硬质聚氨酯泡沫取样体积为1 cm³时，4种目标物的方法检出限为0.6~0.8 μg；组合聚醚取样量为10 mg时，4种目标物的方法检出限为0.5~0.6 μg。该方法具有较高的灵敏度，定性准确，适用于实际样品的现场快速定性分析。     

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。     

基于响应曲面法的遗煤自燃分析与研究*

为研究高瓦斯易自燃煤层不同供风量、高抽巷抽采流量、低抽巷抽采流量3因素对采空区自燃“三带”分布影响规律，选取阳煤五矿8406工作面为研究对象，在数值模拟研究基础上，采用Design Expert软件进行Box Behnken试验设计，构建采空区氧化升温带宽度在3因素、3水平条件下的二次回归响应曲面模型，并对不同条件下采空区氧化升温带宽度进行预测与分析。结果表明:二次回归方程P值为0.001 6，预测模型显著，模型的失拟项为0.606 3，不显著，回归方程具有统计学意义；当供风量为1 500~2 000 m3/min，低抽流量为450~650 m3/min，高抽流量为100~200 m3/min时，对氧化升温带宽度一次项重要度排序为C（高抽巷抽采流量）>A（供风量）>B（低抽巷抽采流量），二次项重要度排序为AC（供风量和高抽巷抽采流量）>AB（供风量和低抽巷抽采流量）>BC（低抽巷抽采流量和高抽巷抽采流量），且AB,AC,BC之间均无交互作用。     

基于复合治理理论的基层应急管理模式优化*

为弥补传统基层应急管理模式的短板，解决信息壁垒、协调困难、公众参与不足等问题。从复合性视角出发，阐述复合治理理论内涵，探讨复合治理与应急管理在主体、思维、过程、空间、目标上的契合性，并进一步分析基层应急管理的现实背景和困境，进而构建基于复合治理理论的基层应急管理模式，阐明模式基本结构和工作流程，最终提出理念树立、平台搭建、机制保障、队伍建设、制度安排、文化营造、技术支撑方面的优化路径。结果表明:复合治理理论的应用可以加强基层应急管理能力，促进多元主体协同共治。     

肥煤自燃全过程热动力学特征参数研究

实验测定了林西矿肥煤样品30~900℃煤自燃全过程热动力学特征参数,得出:TG/DTG曲线显示煤样DTG初始临界温度45℃,干裂温度122℃,活性温度195℃,增速温度265℃,质量极大值温度342℃,着火温度465℃,最大热失重速率温度515℃和燃尽温度690℃;DSC曲线显示,煤样初始放热温度60℃、最大热释放速率温度511℃。结合TG-DTG-DSC曲线综合分析可知,煤温达到510℃左右时煤样反应最剧烈。由煤自燃标志气体测定实验系统得出:煤温130℃后CO,CO 2释放量迅速增加,210℃增加速度下降;CH 4,C 2 H 6含量变化具有规律性且两者变化相近;C 2 H 4出现温度为130℃;C 2 H 4/C 2 H 6比值在190~350℃有较强的规律性,呈上升趋势且上升速度较快;350℃之后,CH 4,C 2 H 6,C 2 H 4体积分数均开始急剧增大;C 2 H 4/CO与C 2 H 4/CO 2变化趋势大致相同,在130~350℃时缓慢增长,达到350℃后比值呈指数形式上升。经拟合曲线,得到活化能的3个突变点温度:70,180,220℃,其中180℃与交叉点温度相吻合。通过以上研究,得到了肥煤自燃全过程的热力学特征参数,为实际生产中防治煤自燃提供了理论依据。     

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。     

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.     

汽车用聚合物材料火灾燃烧特性研究

为研究车用聚合物材料的燃烧特性，并对材料的火灾危险性进行全方位的评估，采用锥形量热仪，对汽车上常用的ABS，PP-PVC，PVC革-无纺毡以及无纺布-PVC聚合物材料进行分析表征，测得点燃时间、热释放速率、总热释放量、质量损失速率、烟气生成速率等参数。结果表明:ABS材料的点燃危险性相对最低，PVC革-无纺毡材料相对最高；随热辐射强度的增加，各样品的热释放速率和烟气生成速率明显加快；结合热释放速率峰值、均值和总热释放量可知，无纺布-PVC材料的热危险性相对最低；结合烟气生成速率和总烟释放量可知，ABS材料的发烟危害性相对最高，无纺布-PVC的相对最低；综合比较各样品的FGI和FPI值，安全等级由高到低依次为ABS，PP-PVC，PVC革-无纺毡，无纺布-PVC。