Estrogen equivalent concentration of 13 branched para-nonylphenols in three technical mixtures by isomer-specific determination using their synthetic standards in SIM mode with GC-MS and two new diasteromeric isomers

Thirteen isomers of branched para-nonylphenols (para-NP) in three technical mixtures were isomer-specifically determined using their synthesized standards by SIM of structurally specific ions, m/z 135, 149 or 163 with GC–MS. Of the 13 isomers, four isomers, 4-(2,4-dimethylheptan-4-yl)phenol, 4-(4-methyloctan-4-yl)phenol, 4-(3-ethyl-2-methylhexan-2-yl)phenol (3E22NP) and 4-(2,3-dimethylheptan-2-yl)phenol synthesized for their determinations were first used as standard substances. The 13 isomers in the technical mixtures individually occurred at mass percent portion of more than 2%. The total mass percent portions in the mixtures from Tokyo Chemical Industry (TCI), Aldrich, and Fluka covered with 89 ± 2%, 75 ± 4% and 77 ± 2%, respectively. The abundance of 4-(3,6-dimethylheptan-3-yl)phenol in the three mixtures was the largest with 11.1 ± 2% to 9.9 ± 0.3%, while that of 4-(2-methyloctan-2-yl)phenol was the smallest with 2.9 ± 0.3% to 3.0 ± 0.2%. Additionally, structures of four new isomers of more than 1% portion present in a technical mixture were elucidated as two pairs of diastereomeric isomers: two types of 4-(3,4-dimethylheptan-4-yl)phenol (344NP) and those of 4-(3,4-dimethylheptan-3-yl)phenol (343NP). By estrogenic assay of 13 isomers with yeast estrogen screen system, the activity of 3E22NP was the highest, while that of 4-(3-methyloctan-3-yl)phenol was the least. Their relative activities to that of 3E22NP were individually calculated. Estrogenic equivalent concentrations of the three technical mixtures were predictively evaluated. The ratio of the EEC to the conventional concentration, total mass percent portions of the 13 isomers in technical mixtures were 0.208 for TCI, 0.206 for Aldrich and 0.205 for Fluka. The predicted estrogenic activity of measured concentration of para-NP in technical mixtures was approximately 5-fold greater than the measured estrogen agonist activity.     

山梨酸废水在ABR中的基质降解行为

稳态条件下,采用厌氧折流板反应器(anaerobic baffled reactor,ABR)处理山梨酸废水并进行基质降解动力学研究.实验表明,在污泥负荷为0.54～1.63 kg COD/(kg VSS·d)的范围内,COD去除率随着负荷的增加从85%降到55%.各隔室出水COD沿程递减,前3个隔室承担了去除COD的重要作用,但随着污泥负荷的增加,后部承担的COD去除率比例增大.基于各串联隔室完全混合的假定,推导ABR中山梨酸废水的基质降解动力学方程,并通过实验确定相关动力学参数及相应的动力学方程.实测值与预测值基本吻合.     

Seasonal variation in dissolved gaseous mercury and total mercury concentrations in Juam Reservoir, Korea

Dissolved gaseous mercury (DGM) and total mercury (TM) concentrations were measured in Juam Reservoir, Korea. DGM concentrations were higher in spring (64+/-13pgL(-1)) and summer (109+/-15pgL(-1)), and lower in fall (20+/-2pgL(-1)) and winter (23+/-6pgL(-1)). In contrast, TM concentrations were higher in fall (3.2+/-0.1ngL(-1)) and winter (3.3+/-0.1ngL(-1)) than in spring (2.3+/-0.1ngL(-1)) and summer (2.2+/-0.4ngL(-1)). DGM concentrations were correlated with water temperature (p<0.0001), ORP (p<0.0001), UV intensity (UV-A: p=0.008; UV-B: p=0.003), and DOC concentration (p=0.0107). DGM concentrations varied diurnally with UV intensity. The average summer DGM (109+/-15pgL(-1)) and TM (2.2+/-0.4ngL(-1)) concentrations in Juam Reservoir were higher than the averages for North American lakes (DGM=38+/-16pgL(-1); TM=1.0+/-1.2ngL(-1)), but lower than levels reported for Baihua Reservoir in China.     

Laboratory longitudinal diffusion tests: 2. Parameter estimation by inverse analysis

This study focuses on the verification of test interpretations for different state analyses of diffusion experiments. Part 1 of this study identified that steady, quasi-steady and equilibrium state analyses for the through- and in-diffusion tests with solution reservoirs are generally feasible where the tracer is not highly sorptive. In Part 2 we investigate parameter identifiability in transient-state analysis of reservoir concentration variation using a numerical approach. For increased generality, the analytical models, objective functions and Jacobian matrix necessary for inverse analysis of transient-state data are reformulated using unified dimensionless parameters. In these dimensionless forms, the number of unknown parameters is reduced and a single dimensionless parameter represents the sorption property. The dimensionless objective functions are evaluated for individual test methods and parameter identifiability is discussed in relation to the sorption property. The effects of multiple minima and measurement error on parameter identifiability are also investigated. The main findings are that inverse problems for inlet and outlet reservoir concentration analyses are generally unstable and well-posed, respectively. Where the tracer is sorptive, the inverse problem for the inlet reservoir concentration analysis may have multiple minima. When insufficient measurement data is collected, multiple solutions may result and this should be taken into consideration when inversely analyzing data including that of inlet reservoir concentration. Verification of test interpretation by cross-checking different state analyses is feasible where the tracer is not highly sorptive. In an actual experiment, test interpretation validity is demonstrated through consistency between theory and practice for different state analyses.     

New metallothionein assay in Scrobicularia plana: heating effect and correlation with other biomarkers

Metallothionein (MT) and other biomarker levels were measured in Scrobicularia plana clams to assess pollution of the Guadalquivir Estuary possibly affected by metals released from Aznalcóllar pyrite mine in 1998. After optimizing reagent concentrations for monobromobimane derivatization, MT levels were quantified by reversed-phase high-performance liquid chromatography coupled to fluorescence detection (RP-HPLC-FD) in heated or unheated digestive gland extracts and compared to those obtained by differential pulse polarography (DPP). MT content assayed by RP-HPLC-FD in unheated samples was higher than that obtained by DPP and correlated better with metals and anti-oxidant activities. MT assay by RP-HPLC-FD in unheated extracts would be preferable for assessing metal pollution, due to its greater sensitivity and specificity. In addition to MT induction, glyoxalase II inhibition was well correlated with metal contents. Our results suggest that metals at the estuary do not originate from Aznalcóllar spill, but from those carried along by the river and deposited at its concave bank.     

基于我国物种毒性数据的多溴联苯醚预测无效应浓度分析

采用多溴联苯醚(PBDEs)对我国广泛分布生物物种的生态毒性数据,根据欧盟现有化学物质风险评价技术指导文件,对不同环境介质中PBDEs预测无效应浓度(PNEC)进行了推导。结果表明:我国淡水环境PBDEs(四溴、五溴、八溴)的PNEC水分别为50μg·L~(-1)、0.53μg·L~(-1)、0.017μg·L~(-1)。沉积物环境PBDEs(四溴、五溴、八溴和十溴)的PNEC沉积物分别为823.35 mg·kg~(-1)wt、1.55 mg·kg~(-1)dw、12.72 mg·kg~(-1)dw、38.41 mg·kg~(-1)dw。土壤环境PBDEs(四溴、五溴、八溴和十溴)的PNEC土壤分别为668.3mg·kg~(-1)wt、0.38 mg·kg~(-1)dw、147 mg·kg~(-1)dw、98 mg·kg~(-1)dw。次生毒性PBDEs(五溴、八溴和十溴)的PNEC经口分别为0.3~0.7 mg·kg~(-1)、0.56 mg·kg~(-1)、2 500 mg·kg~(-1)。该数值期为我国PBDEs的环境风险评价提供科学基础。     

浓度效应对卡马西平在生物炭上的吸附动力学影响

为了解人工合成药物在生物炭上的吸附动力学特征及其浓度效应的影响,选择卡马西平(CBZ)为目标污染物。探讨不同初始质量浓度(2、4、25、50 mg·L~(-1))在不同裂解温度(200、300、500℃)下制备的生物炭上的吸附动力学特征。结果表明,双室一级动力学模型可以精确地描述CBZ在生物炭上的吸附动力学特征。CBZ的快室吸附对总体吸附的贡献随初始浓度的增大而减小,而慢室吸附贡献则增大。π-π作用可能对CBZ的吸附贡献较大。孔隙填充可以描述慢室吸附过程,可能是吸附速率的控制环节。     

珠穆朗玛峰北坡绒布冰川区水体的化学特征

１９９７－０５在珠峰地区绒布冰川采集的４类水样的实测资料表明,本区各类水体都呈碱性,ＰＨ值的大小顺序为：湖水〉湖水〉表层雪。河水和湖水的阴离子以ＳＯ＾２－４为最大,而表层雪样品以Ｃｌ－最大;     

厌氧条件下活性黑(KBR)染料脱色的批量投料研究

在厌氧条件下，进行了微生物降解染料活性黑（ＫＢＲ）的试验研究。试验中研究了氯离子浓度、染料浓度、生物量、特别是投加易降解物对染料降解的影响，并且对厌氧降解该染料的过程进行了分析，着重探讨了易降解物葡萄糖投加量对该染料脱色降解的作用     

阳离子共聚物的反相悬浮聚合

采用反相悬浮聚合方法合成颗粒状的阳离子型高分子絮凝剂。选用丙烯酰胺(Am)和氯化[N,N,N-三甲基乙醇丙烯酸酯]盐(AQ)两种单体,研究反应体系的特征及影响分子量的基本因素,诸如温度、单体浓度、引发剂浓度、分散剂浓度、水相和油相的体积比(Vw/Vo)对分子量的影响。为了选择出最佳原料比,本文对两种单体的原料比进行了研究。实验中还发现亚硫酸钠是一种优良的缩短反应诱导期、加速反应进程的试剂。