离子液体吸收废印刷线路板热拆解过程中挥发性有机物——基于COSMO-RS模型

模拟废印刷线路板（WPCB）的热拆解过程,分析热拆解过程中的挥发性有机物（VOCs）组分;利用真实溶剂似导体屏蔽（COSMO-RS）模型对浓度较高的污染物进行量子力学模拟,研究离子液体（ILs）组成单元对目标污染物溶解度的影响差异,分析溶解过程中主导分子间作用力类型,确定优选吸收剂;测定不同溶剂进行溶解性,验证模型适用性.结果表明：①乙酸乙酯和环戊酮是浓度较高的VOCs组分,在240和250℃时浓度分别为43.1,153mg/m³和105,252mg/m³,质量百分比总和分别为76.3%和67.3%.②高表面屏蔽电荷密度分布峰、长烷基链阴阳离子和亲电基团的存在可提高乙酸乙酯和环戊酮在ILs中的溶解度.双三氟甲磺酰基亚胺盐（NTf₂^-）类ILs是一类优良吸收剂.静电力和范德华力对溶解过程起主导作用.③COSMO-RS模型可定性和半定量用于预测乙酸乙酯和环戊酮的溶解度.     

Quantitative structure-property relationship of aromatic sulfur-containing carboxylates

IntroductionItiswidelyrecognizedthatthephysicochemicalprofileoforganicchemicalslargelydeterminestheirdistributionbetweenenvironmentalmedia .Fortheenvironmentalbehaviorsoforganiccontaminants,watersolubility(SW)andoctanol waterpartitioncoefficient(KOW)aretremendouslyimportant.Octanol waterpartitioncoefficienthasbeenwidelyrelatedtobiochemicaland orbiologicalactivityinquantitativestructure activityrelationships(QSARs) (Leo ,1 971 ) .Watersolubilitycorrespondstothedispersiontendencyandtothereca…     

热液中金的沉淀机理研究综述

金的沉淀机理是了解热液金矿床成矿机制的关键。本文总结了金从热液中沉淀机理的最新研究成果，介绍了各种主要含金配合物的溶解度拨制机制，阐述了矿物表面吸附／还原以及电化学富集等矿物表面作用对金沉淀行为的制约。     

Reversibly enhanced aqueous solubilization of volatile organic compounds using a redox-reversible surfactant

Surfactant-enhanced remediation (SER) is an effective method for the removal of volatile organic compounds (VOCs) from contaminated soils and groundwater. To reuse the surfactant the VOCs must be separated from the surfactant solutions. The water solubility of VOCs can be enhanced using reversible surfactants with a redox-acive group, (ferrocenylmethyl)dodecyldimethylammonium bromide (Fcl2) and (ferrocenylmethyl)tetradecanedimethylammonium bromide (Fcl4), above and below their critical micelle concentrations (CMC) under reducing (I⁺) and oxidative (I²⁺) conditions. The CMC values of Fcl2 and Fcl4 in I⁺ are 0.94 and 0.56 mmol/L and the solubilization of toluene by Fcl2 and Fcl4 in I⁺ for toluene is higher than the solubilization achieved with sodium dodecyl sulfate, cetyltrimethylammonium bromide and Trition X-114. The solubilization capacity of the ferrocenyl surfactants for each tested VOCs ranked as follows: ethylbenzene > toluene > benzene. The solubilities of VOCs by reversible surfactant in I⁺ were 30% higher than those in I²⁺ at comparable surfactant concentrations. The effects of Fcl4 concentrations on VOCs removal efficiency were as follows: benzene > toluene > ethylbenzene. However, an improved removal efficiency was achieved at low ferrocenyl surfactant concentrations. Furthermore, the reversible surfactant could be recycled through chemical approaches to remove organic pollutants, which could significantly reduce the operating costs of SER technology.     

表面活性剂Burkholderia xenoborans LB400体系对低氯代PCBs的好氧强化降解

增强多氯联苯(PCBs)的水溶性是强化PCBs微生物降解的主要控制因素之一,本研究选取了PCB5(2,3-CB)和PCB31(2,4',5-CB)作为低氯代PCBs的典型代表,以曲拉通100(TX-100)、吐温80(Tween 80)、鼠李糖脂粗提物(RL crude)3种表面活性剂和β-环糊精( HPCD)联合Burkholderia xenoνorans LB400构建PCBs好氧降解体系,测试了它们对PCB5和PCB31的溶出率及微生物生长的影响.结果表明,TX-100(CMC＝194 mg·L-1)、 Tween 80(CMC＝13.1 mg·L-1)、 RL crude(CMC＝50 mg·L-1)浓度在1~7 CMC 时和 HPCD 浓度在500~1500 mg·L-1时对 PCB5和 PCB31溶出率分别达到54.7％~100％、59.8％~100％;10.5％~40.8％、6.8％~31.6％;10.3％~19.9％、3.3％~11.6％和19.5％~34.2％、4.2％~10.7％. TX-100浓度在1~7 CMC时对B. xenoνorans LB400生长的抑制率达到30.3％~45.8％,而Tween 80浓度在0.1~1 CMC时对其生长的抑制率为10.0％~15.4％; RL crude 本身能作为底物促进 LB400的生长,而 HPCD 对其生长无明显影响. B. xenoνorans LB400对PCB31(5 mg·L-1)的降解效率在添加表面活性剂后有不同程度的提高：TX-100,23.7％~65.5％; Tween 80,14.6％~44.3％;RL crude,9.6％~27.2％;HPCD,15.3％~20.7％;而表面活性剂对PCB5(10 mg·L-1)的降解效率则无明显影响.表面活性剂主要通过增大溶液中PCBs-表面活性剂的胶束浓度来提高LB400对PCBs的降解效率,在水溶液培养体系中当设置TX-100和Tween 80浓度分别在1和7 CMC时,PCB31的降解效率达到100％和81.7％,而此时B. xenoνorans LB400生长的抑制率为30.3％和5.4％.     

北京大气颗粒物和重金属铅干沉降通量及季节变化

为了解大气颗粒物和重金属铅(Pb)干沉降通量的变化规律,采用聚氨酯泡沫膜片为代用面联合干湿沉降自动观测设备,于2013年12月~2014年11月在北京城区采集了颗粒物干沉降,利用微波消解和电感耦合等离子体质谱仪对样品中全量Pb和水溶性Pb进行了测试分析.结果表明,北京大气颗粒物和Pb干沉降通量分别为0.84 t·(hm~2·a)~(-1)和7.56mg·(m~2·a)~(-1),呈现出春季冬季秋季~夏季的特征.大气颗粒物中水溶性Pb干沉降通量为3.14 mg·(m~2·a)~(-1),占Pb干沉降总量的43%,这一比例呈现出冬春季高于夏秋季的特征.人为源排放不仅增加了大气颗粒物和Pb的干沉降通量,也改变了水溶性Pb干沉降通量的季节分布.研究结果对科学评估重金属沉降的生态影响和健康效应提供了科学基础,同时凸显了消减人为源重金属排放的重要性.     

Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs)     

Fingerprinting of Gasoline and Coal Tar NAPL Volatile Hydrocarbons Dissolved in Groundwater

Accidental spills and chronic leaks of fuel oil or other hydrocarbon material (e.g., coal tar) often result in subsurface accumulation of nonaqueous phase liquid (NAPL), which can be a subsequent source of contamination in groundwater. Linking hydrocarbons in groundwater to a source NAPL has been difficult when using standard target analytes (e.g., BTEX) because of differences in partitioning properties of the analytes between the source NAPL and groundwater. Because aqueous solubility is predicted to be the controlling influence in the partitioning of hydrocarbons from NAPL to groundwater, a solubility-based approach to matching dissolved hydrocarbons in groundwater to their source NAPL has been developed and validated for two sites with commonly encountered types of NAPL contamination. Specifically, a gasoline LNAPL and a coal tar DNAPL from two separate sites (West Virginia and California) and groundwater interfaced with these NAPLs were analyzed for approximately 50 gasoline-range hydrocarbons consisting of paraffin, isoparaffin, (mono-) aromatic, naphthene, and olefin compounds (PIANO). Solubility characteristics of selected alkyl aromatic hydrocarbons from the PIANO analysis were used to identify a set of diagnostic hydrocarbons, expressed as hydrocarbon ratios, which were found to be useful in distinguishing the source(s) of hydrocarbons in groundwater. At the West Virginia site, the diagnostic ratios in a downgradient groundwater sample were similar to those of a gasoline NAPL at that site, indicating the source of hydrocarbons to the groundwater was the upgradient gasoline NAPL. The diagnostic ratios of the groundwater in contact with the gasoline NAPL and the remote groundwater were also similar, providing evidence that the diagnostic ratios were retained during transport in the aquifer. At the California site, diagnostic ratios in a cross-gradient groundwater sample differed from those of the coal tar NAPL at that site, indicating that the remote groundwater hydrocarbons did not originate from the coal tar contamination. Environmental factors such as selective degradation of specific isomers and various geological conditions (e.g., soil mineralogy, and organic content) may confound the application of this solubility-based fingerprinting approach. Thus, it is recommended that multiple diagnostic pairs be simultaneously evaluated when considering this fingerprinting approach for specific sites and product types.     

一个新的拓扑指数用于芳烃化合物溶解度、分配系数及生物毒性的研究

在分子拓扑理论的基础上，提出了一个新的拓扑指数Yx，并用Yx研究了芳烃化合物的溶解度、分配系数及生物毒(活）性，给出了相关方程。结果表明，新方法计算方便，物理意义明确，预测值与相应的实验值较吻合。     

阳离子表面活性剂十六烷基三甲基溴化铵对酞酸酯类化合物增溶性研究

用阳离子表面活性剂十六烷基三甲基溴化铵对六种酞酸酯类化合物(五种脂肪链酞酸酯和一种苯基酞酸酯)进行了增溶性实验．结果表明,在表观浓度(Ｃｓ)小于临界胶速浓度(ＣＭＣ)时,十六烷基三甲基溴化铵对四种酞酸酯(ＤＭＰ和ＤＰｈＰ除外)有一定程度的增溶作用;当Ｃｓ大于ＣＭＣ时,对六种化合物的增溶性显著增强．其增溶性(Ｓｔ/Ｓｗ)随Ｃｓ增大而线性递增:当Ｃｓ＜ＣＭＣ时,Ｓｔ/Ｓｗ＝ａ＋Ｋｍｎ·Ｃｓ,ｒ＞０．９０,ｎ＝５;当Ｃｓ＞ＣＭＣ时,Ｓｔ/Ｓｗ＝ａ＋Ｋｍｃ·Ｃｓ,ｒ＞０．９９,ｎ＝５． 各化合物增溶系数随各自固有水溶性(Ｓｗ)减小而增大(苯基酞酸酯有所反常),ｌｇＫｍｎ和ｌｇＫｍｃ与各自ｌｇｌ/Ｓｗ具有良好的线性正相关性．本文进一步对增溶机理进行了分析解释．