Predicting octanol/water partition coefficient using solvation free energy and solvent-accessible surface area

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应用线性溶剂化能参数预测多氯有机物的分配性质

应用线性溶剂化能方法构建定量结构-性质相关(QSPR)模型.该模型能较好地预测多氯有机物的正辛醇/水分配系数(K_ow)和沉积物吸附系数(K_oc). K_ow和K_oc平均误差分别为0.43和0.37个对数单位.模型的稳健性检验结果表明,模型中自变量不存在相关关系,残差呈正态分布;对K_oc来说,PCB和PCDD/PCDF在构建模型中起核心作用,剔除该类化合物导致模型相关系数明显下降,农药类和氯硝基苯类化合物的存在降低了模型的精度.     

水溶性有机物对菲的表观溶解度和正辛醇/水分配系数的影响

以农业上常用有机物料绿肥、猪粪和污泥作为水溶性有机物(DOM)的提取材料,以菲(Phe)作为多环芳烃(PAHs)的代表,通过摇瓶法研究了不同来源的DOM对菲在水中的表观溶解度和正辛醇/水分配系数的影响.结果表明,菲在超纯水中的溶解近似一级反应动力学过程.超纯水体系中添加了DOM后,菲溶解的平衡时间相对滞后,但却明显增加了菲的表观溶解度.当DOM浓度为150 mg·L-1(以DOC计)时,在含Tween-80、猪粪DOM、污泥DOM和绿肥DOM的体系中菲的表观溶解度分别是纯水体系的20.39、2.082、1.838和1.549倍.菲的表观溶解度随着外加DOM浓度的增加而增大,它们之间存在着明显的线性关系.回归直线的斜率可以用来表征DOM对菲的增溶效果,本试验4种体系中DOM的增溶效果大小依次为表面活性剂Tween-80＞猪粪DOM＞污泥DOM＞绿肥DOM.同时,DOM可降低菲的正辛醇/水溶液分配系数,各体系中logKow值的高低顺序与增溶效果的顺序恰好相反.研究结果显示,DOM的存在可明显地改变PAHs在水相中的溶解度和正辛醇/水溶液分配系数.     

利用CDOM吸收系数估算博斯腾湖水体表层DOC浓度

基于2021年夏秋两季西部干旱区博斯腾湖表层50个采样点位实测数据,通过对DOC特征的统计学分析、内外源因素影响的时空差异以及电导率相关性验证,将博斯腾湖划分为河口和非河口区域.然后以CDOM特征波长吸收系数a₂₅₀和a₃₆₅为自变量,以DOC浓度（c_DOC）为因变量,分别构建了基于CDOM的河口和非河口水域DOC浓度估算模型.结果表明：河流与湖泊进行水体交换的同时,会将大量陆源DOC输送到博斯腾湖中,使得河口区域DOC浓度明显高于非河口区域（t-tests,P<0.01）,河口区域的DOC浓度（c_DOC）约是非河口区域的2.2~2.3倍,且在河口区域c_DOC与电导率呈现显著相关关系（夏季：R²=0.81,P<0.01;秋季：R²=0.84,P<0.01）.本文构建拟合模型（c_DOC=α+β·α₂₅₀+γ·α₃₆₅）,并通过交叉验证的方法来检验模型精度.将夏季和秋季同区域数据统一建模,河口和非河口区域CDOM与DOC均存在较好的相关关系,且模型精度较高（河口区域：R²=0.60,RMSE=8.56%;非河口区域：R²=0.66,RMSE=8.77%）.本文所建立的模型可以在不增加环境因子变量的前提下提高精度,有利于实现卫星遥感反演.同时,本研究揭示了河流输入对博斯腾湖DOC分布和估算的时空影响,提出可利用CDOM估算DOC浓度,但需根据水文特征和c_DOC等因素区分河口和非河口区域.本研究对实现新疆水资源合理开发、有效保护以及综合治理提供科学依据,对我国西部干旱区湖泊DOC遥感动态监测具有重要意义.     

应用分子拓扑理论预测卤代芳烃的正辛醇/水分配系数

以分子拓扑理论为基础，提出了一个新的拓扑指数Ｙ，并用Ｙ研究了部分卤代芳烃的正辛醇／水分配系数ＫＯＷ。研究表明，Ｙ与卤代芳烃的正辛醇／水分配系数ＫＯＷ的ｌｏｇＫＯＷ呈良好的线性关系，并给出了相关方程。新方法计算方便、精确度高、物理意义明确     

应用多元线性溶剂化能关系研究有机膨润土的吸附特征

以十六烷基三甲基溴化铵(CTMAB)制备的有机膨润土为代表,设置有机膨润土中CTMAB的负载量为1.0倍的阳离子交换量(CEC),测试了其吸附酚类、胺类、硝基类等25种有机物的有机碳标化的吸附系数(K∝)值.在此基础上,运用多元线性回归方法得到了有机膨润土吸附有机物的多元线性溶剂化能关系(LSER)模型,以明确各种作用...     

用碳链准长度估算多环芳烃的分配系数

根据极化效应指数理论计算出多环芳烃的分子极化指数和碳链准长度（N＇）,研究发现,碳链准长度N’与多环芳烃在正辛醇/水两相的分配系数logK_ow有良好的线性关系,它可表示为logK_ow＝0.5441＋0.3767N’n＝32R＝0.9804s＝0.2214。用N’估算和预测多环芳烃的分配系数logK_ow与测定值和Leo碎片法估算值一致,并且准碳链长度N’可直接从分子结构计算得到,经验成分较少,也不需要引入其它结构校正因子。     

取代苯类分配系数的估算和预测

首先计算出取代苯化合物的分子极化指数和碳链准长度N′,然后以苯为参考化合物计算取代苯的相对碳链次长度Nr′。发现用Nr′参数能较好地估算和预测烷基苯、卤代苯、取代苯酚和取代苯胺等各类化合物的正辛醇／水的分配系数logKow。     

Enhanced flushing of polychlorinated biphenyls contaminated sands using surfactant foam: Effect of partition coefficient and sweep efficiency

Foam flushing is an in situ soil remediation technology based on the traditional surfactant flushing method. The contribution of mobility control to contaminant removal by foam is helpful for improving this technology. Foam flushing of polychlorinated biphenyl (PCB)-contaminated unconsolidated media was performed to evaluate the effect of the partition coefficient (PC) and sweep efficiency (SE) on PCB removal. Column flushing with surfactant solution and foam with different types and concentrations of surfactant was carried out for PCB removal. Two types of quartz sand were investigated to evaluate the Jamin effect on the SE value of the washing agent. The results demonstrate that a small PC value and large SE value are necessary to achieve high PCB removal for foam flushing. Compared with solution flushing, the introduction of foam can effectively control the mobility of the washing agent. Similar to solution flushing, solubilization is a key factor which dominates the removal of PCBs in foam flushing. In addition, the SE value and PCB removal by foam flushing is less affected by particle size. Therefore, foam flushing was proved to be more effective in porous media with low hydraulic conductivity and high porosity. An integrated flushing with water, surfactant solution and foam was performed and the results prove that this technology successfully combines the advantages of solution solubilization and mobility control by foam, and thus further increases the remediation efficiency of PCBs to 94.7% for coarse sand.     

舟山海域表层海水正构烷烃、甾萜烷特征参数研究

本文选择舟山海域作为研究对象,对舟山海域的表层海水中有机物特征参数进行了研究。采集的表层海水样品,经正己烷洗脱后,旋转蒸发和氮吹浓缩定容转移至气相分析样品瓶中待GC-MS上机分析。结果表明,从正构烷烃分布来看,峰型为双峰优势碳型和后峰优势碳型,Pr、Ph丰度相对较高,可能是受到石油污染的影响。碳优势指数（CPI）均在1左右,结合Σn-Alk/C₁₆、陆生与水生类脂物比值（TAR）、Pr/Ph、奇偶优势指数（OEP）参数,指示了舟山海域石油污染的存在。舟山海域各站位甾烷萜烷分布趋势上相似,大部分站位检出了18α（H）-奥利烷,Ts/Tm、C₃₁αβ（S/（S+R））、C₃₂αβ（S/（S+R））、C₂₉甾ααα（S/（S+R））等参数指示了该区域有机物成熟度较高,可能与石油污染有关。     

岩溶区不同水体有机氯农药对比研究

为研究岩溶区地下水、地表水之间有机氯农药的差异,用气相色谱-微池电子捕获检测器(GC-μECD)分析了水中OCPs含量.结果表明:研究区水样中有机氯农药检出率达100%.OCPs浓度范围32.13~319.53ng/L,均值为134.17ng/L.OCPs浓度季节差异明显,枯水期高于丰水期.水井(sj)中OCPs,DDTs、HCHs浓度均大于水池(sc).通过采样点间的对比可知,雨季水池、水井间OCPs含量相当,旱季水池小于水井.水池、水井间DDTs、HCHs对比没有明显的季节性,表现为水池的DDTs含量小于水井,但HCHs含量大于水井.水井中的OCPs、DDTs、HCHs的最小值与水池相比均表现出了滞后性.地表水与地下水有机氯农药表现出的差异,是由于两采样点的环境不同.通过比值法得出HCHs来自于混合源,地表水的比值更能准确的反映出HCHs的来源.DDTs可能来自于混合DDTs,且为历史残留,降解环境为好氧环境.水井中DDTs、HCHs百分比组成由于土壤的影响发生了变化.     

卤代苯化合物水溶解度及正辛醇/水分配系数的三维构效关系研究

对卤代苯化合物的水溶解度(-lg Sw)和正辛醇/水分配系数(lg Kow)分别进行了基于三维结构的比较分子场(Co MFA)和比较分子相似性指数(Co MSIA)分析,建立了三维定量结构-性质相关(3D-QSPR)模型,并将所获结果与密度泛函理论(DFT)方法得到的2D-QSPR模型进行了比较.结果表明:-lg Sw的Co MFA和Co MSIA模型交叉验证相关系数Q2分别为0.902和0.940,决定系数R2分别为0.982和0.986,模型稳定性和估算能力较好;lg Kow的Co MFA和Co MSIA模型Q2分别为0.926和0.988,R2分别为0.983和0.997;本研究所建的3D-QSPR模型的估算能力优于2D-QSPR模型;Co MFA和Co MSIA模型三维等势图表明,取代基的疏水效应对该类化合物的水溶解性能及正辛醇/水分配系数的影响更为显著,立体效应次之,静电场效应影响较小.     

融入变异系数的空气和地表水质量评价方法

空气质量指数和综合污染指数为近些年国内最常用的环境质量评价方法,二者分别取各监测指标质量分指数的最大值和平均值,使得前者只重视首要污染物,后者忽略了污染物之间的重要性差异。为解决上述问题,将变异系数融入其中,动态调整了污染物项目之间的权重分布,总质量指数为各分指数的加权平均。通过设定滑动抽取的天数/月数,根据实地情况调节评价指数对长期/短期污染物的敏感度,提高了这2种评价方法的合理性和实用性。以2015—2019年北京市密云和西帽山的环境监测数据为例,验证了这2种改进方法的有效性,运用改进的方法分析了该5年北京市空气质量的时空分布变化。结果表明:北京市空气监测指标中的PM_2.5和PM₁₀以及地表水监测指标中的溶解氧、总磷和总氮的变异系数较大;空气质量持续向好,并呈现从北到南逐渐变好的梯度分布。     

Relationships of nitrous oxide fluxes with water quality parameters in free water surface constructed wetlands

The effects of chemical oxygen demand (COD) concentration in the influent on nitrous oxide (N₂O) emissions, together with the relationships between N₂O and water quality parameters in free water surface constructed wetlands, were investigated with laboratoryscale systems. N₂O emission and purification performance of wastewater were very strongly dependent on COD concentration in the influent, and the total N₂O emission in the system with middle COD influent concentration was the least. The relationships between N₂O and the chemical and physical water quality variables were studied by using principal component scores in multiple linear regression analysis to predict N₂O flux. The multiple linear regression model against principal components indicated that different water parameters affected N₂O flux with different COD concentrations in the influent, but nitrate nitrogen affected N₂O flux in all systems.     

Study of specific energy and friction coefficient in minimum quantity lubrication grinding using oil-based nanolubricants

An investigation on minimum quantity lubrication (MQL) grinding was carried out with the scope of documenting the process efficiency of oil-based nanolubricants. The nanolubricants were composed of MoS₂ nanoparticles (<100 nm) over coated with organic agents, dispersed in two different base oils—mineral oil (paraffin) and vegetable oil (soybean). Surface grinding tests were carried out on cast iron and EN 24 steel under different lubrication conditions—MQL using nanolubricants (varying compositional chemistry and concentration of nanoparticles), pure base oils (without nanoparticles) and base oils containing MoS₂ microparticles (3–5 μm), and flood grinding using water-based coolant. Specific energy, friction coefficient in grinding and G-ratio were used as measurands for determining the process efficiency. Results show that MQL grinding with nanolubricants increases the process efficiency by reducing energy consumption, frictional losses at the wheel–workpiece interface and tool wear. The process efficiency is also found to increase with increasing nanoparticle concentration. Soybean and paraffin based-nanolubricant performed best for steel and cast iron, respectively, showing a possible functional relationship between the compositional chemistry of nanolubricant and the workpiece material, which will be the goal of future work.     

应用量子化学参数预测多氯有机物的分配性质

应用量子化学AM1算法求得多氯有机物的量化参数，以此来构建定量结构－性质相关（QSPR）模型。该模型能较好地预测多氯有机物的正辛醇／水分配系数（Kow)和沉积物吸附系数（Koc).Kow和Koc平均误差分别为0．31和0．33个对数单位。模型的稳健性检验结果表明：模型中自变量不存在相关关系；残差呈正态分布；对Koc来说，PCB和PCDD／F在构建模型中起核心作用，剔除该类化合物导致模型相关系数明显下降，农药类及氯硝基苯类化合物的存在降低了模型的精度。     

Multivariate analysis of surface water quality in the Three Gorges area of China and implications for water management

Multivariate statistical techniques, cluster analysis, non-parametric tests, and factor analysis were applied to analyze a water quality dataset including 13 parameters at 37 sites of the Three Gorges area, China, from 2003–2008 to investigate spatio-temporal variations and identify potential pollution sources. Using cluster analysis, the twelve months of the year were classified into three periods of lowflow (LF), normal-flow (NF), and high-flow (HF); and the 37 monitoring sites were divided into low pollution (LP), moderate pollution (MP), and high pollution (HP). Dissolved oxygen (DO), potassium permanganate index (CODMn), and ammonia-nitrogen (NH4 +-N) were identified as significant variables affecting temporal and spatial variations by non-parametric tests. Factor analysis identified that the major pollutants in the HP region were organic matters and nutrients during NF, heavy metals during LF, and petroleum during HF. In the MP region, the identified pollutants primarily included organic matter and heavy metals year-around, while in the LP region, organic pollution was significant during both NF and HF, and nutrient and heavy metal levels were high during both LF and HF. The main sources of pollution came from domestic wastewater and agricultural activities and runoff; however, they contributed differently to each region in regards to pollution levels. For the HP region, inputs from wastewater treatment plants were significant; but for MP and LP regions, water pollution was more likely from the combined effects of agriculture, domestic wastewater, and chemical industry. These results provide fundamental information for developing better water pollution control strategies for the Three Gorges area.     

基于自组织映射与哈斯图方法的地表水水质评价研究

地表水水质评价是水资源管理与保护中的非常重要的问题.本研究主要目的是应用自组织映射(Self-Organizing Map,SOM)与哈斯图方法(Hasse Diagram Technique,HDT)对地表水水质监测数据集进行分类、建模、解释与评估.以西苕溪流域为例,对其50个断面于2010年6月-2011年5月进行月频率的水质监测.应用SOM分析发现,水质参数可分成10个聚类组,反映了西苕溪流域水质丰、平与枯水期特征,pH、高锰酸盐指数(CODMn)在各个水期变化不大;溶解氧(DO)在枯水期与平水期相对较高,水质具有一定的自净能力;丰水期的氨氮(NH4+-N)、总氮(TN)与总磷(TP)值相对较小;西苕溪流域TN:TP(氮磷质量比)平均为46,监测期间变幅较大为2～482,监测期内有66.7％的水质样本处于磷限制状态,仅有3.2％处于氮限制状态,存在氮限制与磷限制交替出现的状态,表明流域总体处于磷限制状态.选取CODMn、NH4+-N、TN 与TP指标进行HDT综合分析,反映流域上游水质较好,中、下游水质相对较差;敏感性分析结果表明,CODMn敏感性数值最大为235,其次是TN为156,、NH4+-N与TP分别是61与34,表明西苕溪流域的CODMn、TN存在较大的环境风险.建议在西苕溪流域即将开展的环境整治与规划时应考虑开发相关的削减技术与制定相关措施政策以减少CODMn、TN污染.     

典型城郊土地利用格局对水体抗生素的影响研究

阐明城郊地区土地利用格局对水环境中抗生素的影响,对维持城乡共生体水土安全和保障人居环境健康有重要意义.本研究基于典型城郊流域的定位监测,比较了不同等级子流域水体抗生素的组成、浓度和分布特征,探讨了土地利用格局对水体抗生素的影响.结果表明,研究区水体中抗生素浓度为1.126~54.236 ng·L^-1,不同等级子流域水体抗生素的种类和浓度有较大的差异.子流域土地利用结构与水体抗生素的种类和浓度密切相关,由主坐标分析（PCoA）可知,具有相似土地利用结构的子流域水体抗生素组成和浓度具有相似性.相关分析表明,子流域中城镇、农田和林地的面积比例与水体中四环素类抗生素（TCs）的浓度密切相关,而园地面积比例与水体中磺胺类抗生素（SAs）的浓度关系密切.耦合景观格局分析表明,水体抗生素总浓度与香农多样性指数（SHDI）和蔓延度指数（CONTAG）呈显著相关性（p<0.05）;四环素类抗生素与边界密度（ED）、香农多样性指数、均匀度指数（SHEI）、蔓延度指数和聚集度指数（AI）呈显著相关性（p<0.05）.通过构建逐步回归模型进一步表明,水体抗生素的浓度与园地、林地面积和香农多样性指数关系密切.研究结果表明受人类活动干扰程度大、景观破碎化较为严重的区域水体抗生素的浓度较高.