过硫酸钠缓释材料的释放性能及其对2, 4-二硝基甲苯的降解效果

针对原位化学氧化技术修复土壤和地下水时氧化剂因释放过快而导致的利用率低等问题,通过熔化成型法制备过硫酸钠缓释材料,分析石蜡、硅砂和过硫酸钠不同配比对材料成型度和释放性能的影响,研究缓释过程中溶液pH的变化,探讨其在水溶液中的缓释行为及其对2,4-二硝基甲苯（2,4-DNT）的降解效果.结果表明:当固定过硫酸钠质量为6 g、硅砂质量为18 g、蜡砂比（石蜡、硅砂质量之比）为1:4~1:8时,过硫酸钠缓释材料成型度适中,且过硫酸钠的累积缓释量随着时间的延长而逐渐增大,第31天时过硫酸钠累积释放百分比为74.67%~88.40%,可实现过硫酸钠的持续可控释放.当硅砂质量为18 g、蜡砂比为1:1~1:6时,过硫酸钠累积释放百分比随着过硫酸钠质量的增加而增大,且溶液中的pH呈先降低后上升的变化规律.缓释材料缓释前后实物图和显微镜分析结果显示,过硫酸钠缓释材料的释放是一个由外到内、速率由快变慢最终趋于平稳的过程.过硫酸钠质量为12 g、硅砂质量为18 g、蜡砂比为1:4的缓释材料对2,4-DNT具有较好的降解效果,第16次置换浓度为0.2 mg/L的2,4-DNT水溶液时,2,4-DNT的降解率为56.38%.研究显示,改变制备材料的配比可有效实现缓释材料中过硫酸钠的缓慢释放及对污染物的有效降解,可为原位化学氧化修复土壤和地下水提供理论支撑.      

取代苯胺和苯酚类化合物对大型■(Daphnia magna Straus)的定量结构-活性关系研究

研究了３６个取代苯胺和苯酚类化合物对大型的急性毒性，应用正辛醇／水分配系数、线性溶解能关系参数和分子连接性指数得出了该类化合物的定量构效关系方程，这些方程可以用来进行该类化合物危害性初评．ＬＳＥＲ法得到的ＱＳＡＲ方程拟合效果较好，增大分子体积及偶极性极化性，均可增大毒性．化合物与蛋白质等生物大分子的氢键键合作用是导致该类化合物毒性高于其基本毒性的原因．     

水中氯仿的活性炭电增强吸附特性

讨论了活性炭在电场作用下对水中微量的三氯甲烷的吸附 ,测定不同控制电位下活性炭的吸附量 ,并讨论了吸附动力学与吸附等温方程 .实验结果表明 :活性炭的吸附量与活性炭上所加的控制电位相关 .在阳极极化时 ,活性炭的吸附量增大 ;在阴极极化时 ,活性炭吸附量减少 .吸附起始浓度为 10 0 μg L的氯仿溶液 ,同样数量的活性炭在阳极极化下可得到最大吸附量 ,其值为无电场时的 1 6倍 .分析了电场影响活性炭吸附的机理 .     

The interaction effects of FEN1 rs174538 polymorphism and polycyclic aromatic hydrocarbon exposure on damage in exon 19 and 21 of EGFR gene in coke oven workers

Polycyclic aromatic hydrocarbon (PAH) exposure and genetic susceptibility were conductive to genotoxic effects including gene damage, which can increase mutational probability. We aimed to explore the dose-effect associations of PAH exposure with damage of exons of epidermal growth factor receptor (EGFR) and breast cancer susceptibility gene 1 (BRCA1), as well as their associations whether modified by Flap endonuclease 1 (FEN1) genotype. Two hundred eighty-eight coke oven male workers were recruited, and we detected the concentration of 1-hydroxypyrene (1-OH-pyr) as PAH exposure biomarker in urine and examined base modification in exons of EGFR and BRCA1 respectively, and genotyped FEN1 rs174538 polymorphism in plasma. We found that the damage indexes of exon 19 and 21 of EGFR (EGFR-19 and EGFR-21) were both significantly associated with increased urinary 1-OH-pyr (both P_trend < 0.001). The levels of urinary 1-OH-pyr were both significantly associated with increased EGFR-19 and EGFR-21 in both smokers and nonsmokers (both P < 0.001). Additionally, we observed that the urinary 1-OH-pyr concentrations were linearly associated with both EGFR-19 and EGFR-21 only in rs174538 GA+AA genotype carriers (both P < 0.001). Moreover, FEN1rs rs174538 showed modifying effects on the associations of urinary 1-OH-pyr with EGFR-19 and EGFR-21 (both P_interaction < 0.05). Our findings revealed the linear dose-effect association between exon damage of EGFR and PAH exposure and highlight differences in genetic contributions to exon damage and have the potential to identify at-risk subpopulations who are susceptible to adverse health effects induced by PAH exposure.

     

南昌市移动源排放清单研究

根据收集的南昌市移动源活动水平数据,采用合适的估算方法、排放因子和GIS技术,建立了南昌市2007—2014年移动源排放清单,并对2014年移动源清单进行了空间化处理与分析,空间分辨率为1 km×1 km.结果表明,2007—2014年南昌市移动源共向大气排放CO、HC、NO_x、PM_(2.5)、PM_(10)、SO_2分别为18.26×10~4、5.07×10~4、18.46×10~4、0.99×10~4、1.08×10~4、3.31×10~4t.其中,2014年移动源向大气中排放的这6种污染物总量分别为2.14×10~4、0.76×10~4、1.97×10~4、0.08×10~4、0.09×10~4、0.55×10~4t.道路移动源中,汽油小型客车是CO、HC和SO_2最大的贡献源,排放量分别占机动车排放总量的55.1%、78.5%和56.1%;柴油重型货车是NO_x、PM_(2.5)和PM_(10)排放贡献率最大的车型,分别占43.2%、40%和40%.非道路移动源中,小型拖拉机对CO、HC、NO_x、PM_(2.5)和PM_(10)的贡献率均较大,分别占非道路移动源排放总量的29.9%、26.9%、23.4%、29.5%和29.8%;SO_2排放主要来源于船舶,占非道路移动源SO_2排放总量的45.1%.高污染排放集中的区域,主要是青山湖区、西湖区和东湖区.     

植物的非传统稳定同位素前处理及测定技术研究进展

一直以来植物都是多领域的研究重点,随着非传统稳定同位素的不断发展,植物非传统稳定同位素研究日益增加。但因植物样品中有机物含量高,同位素分馏复杂,样品前处理及测定中存在诸多难题。本文对植物样品非传统稳定同位素工作中常用的前处理方法和测定技术进行了总结。综述了直接萃取法、湿法消解和高温灰化法的原理、操作和优缺点;以K、Ca、Mg、Fe、B等典型非传统稳定同位素为例介绍了非传统稳定同位素常用测定技术,旨在为植物样品的非传统稳定同位素测定进行梳理,最后对其应用方向和测试方法的发展方向进行了展望。     

Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters

• Selective molecularly imprinted polymer (MIP) binding gel was prepared. • MIP-DGT showed excellent uptake performance for antibiotics. • In situ measurement of antibiotics in wastewaters via MIP-DGT was developed. • The MIP-DGT method was robust, reliable, and highly sensitive. Urban wastewater is one of main sources for the introduction of antibiotics into the environment. Monitoring the concentrations of antibiotics in wastewater is necessary for estimating the amount of antibiotics discharged into the environment through urban wastewater treatment systems. In this study, we report a novel diffusive gradient in thin films (DGT) method based on molecularly imprinted polymers (MIPs) for in situ measurement of two typical antibiotics, fluoroquinolones (FQs) and sulfonamides (SAs) in urban wastewater. MIPs show specific adsorption toward their templates and their structural analogs, resulting in the selective uptake of the two target antibiotics during MIP-DGT deployment. The uptake performance of the MIP-DGTs was evaluated in the laboratory and was relatively independent of solution pH (4.0–9.0), ionic strength (1–750 mmol/L), and dissolved organic matter (DOM, 0–20 mg/L). MIP-DGT samplers were tested in the effluent of an urban wastewater treatment plant for field trials, where three SA (sulfamethoxazole, sulfapyridine, and trimethoprim) and one FQ (ofloxacin) antibiotics were detected, with concentrations ranging from 25.50 to 117.58 ng/L, which are consistent with the results measured by grab sampling. The total removal efficiency of the antibiotics was 80.1% by the treatment plant. This study demonstrates that MIP-DGT is an effective tool for in situ monitoring of trace antibiotics in complex urban wastewaters.     

Octanol–air partition coefficients of polybrominated biphenyls

The octanol–air partition coefficients (K_OA) for PBB15, PBB26, PBB31, PBB49, PBB103 and PBB153 were determined as a function of temperature using a gas chromatographic retention time technique with 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (p,p′-DDT) as a reference substance. The internal energies of phase change from octanol to air (Δ_OAU) were calculated for the six compounds and were in the range from 74 to 116 kJ mol⁻¹. Simple regression equations of log K_OA versus relative retention times (RRTs) on gas chromatography (GC), and log K_OA versus molecular connectivity indexes (MCI) were obtained, for which the correlation coefficients (r²) were greater than 0.985 at 283.15 K and 298.15 K. Thus the K_OA values of the remaining PBBs can be predicted by using their RRTs and MCI according to these relationships.     

Important role of reaction field in photodegradation of deca-bromodiphenyl ether: Theoretical and experimental investigations of solvent effects

Photolysis of deca-bromodiphenyl ether (BDE-209) was investigated in tetrahydrofuran, dichloromethane, isopropanol, acetone, ethanol, methanol, acetonitrile and dimethylsulfoxide. Noticeable differences of the photolytic rates and quantum yields were found in the diverse solvents. Different to the previous deductions, hydrogen donating efficiency and electron donating efficiency of solvents were not the decisive factors for the photolytic rate in this study, which was proved by the fast photolysis of BDE-209 in CCl₄, a solvent without hydrogen and difficult to donate electrons. Besides hydrogen addition process, intermolecular polymerization might occur during the photolysis. Density functional theory (DFT) calculation was performed to understand the molecular properties of BDE-209 in different solvents. The lowest singlet vertical excitation energy (E_ex) and the average formal charge on Br () of BDE-209, reflecting the difficulty for the excitation of BDE-209 and for the departing of Br atom, respectively, were changed by the reaction fields formed by the different solvents. E_ex and linearly correlated with the photolytic activity (log k). This study is helpful to better understand the photolytic behavior of BDE-209 in different media.     

几类有机污染物的微塑料/水分配系数的线性溶解能关系模型

水体中的微塑料会吸附其中的有机污染物,影响有机污染物和微塑料的环境归趋和生态毒性。研究微塑料对有机污染物的吸附行为,对于评价有机污染物和微塑料的环境赋存、迁移及生物有效性有重要意义。污染物在微塑料与水之间的平衡分配系数(Kd),是表征微塑料对有机污染物吸附能力的重要参数。实验方法难以逐个测定众多有机污染物的Kd值,有必要发展其预测模型。本研究搜集了有机污染物的线性溶解能关系(LSER)参数及Kd值,构建了可预测有机污染物在聚丙烯微塑料与海水、聚乙烯微塑料与海水、聚乙烯微塑料与淡水之间Kd值的LSER模型。模型具有良好的拟合优度(R2adj介于0.794~0.903)、稳健性(Q2LOO和Q2BOOT分别介于0.763~0.863和0.720~0.804)和预测能力(R2ext和Q2ext分别介于0.886~0.971和0.825~0.954),能够用于预测多氯联苯、多环芳烃、六氯环已烷和氯苯类有机污染物的Kd值。