水体中挥发酚测定中的流动注射分光光度法研究进展

挥发酚是水体中的重要污染物,对生态环境和人体健康有着严重的危害,美国环保署已将11种酚类化合物列入环境优先污染物之中。文章概括了挥发酚的气相色谱法、蒸馏后溴化容量法、重量法、薄层色谱法、液相色谱法、光度法等检测方法的特点,重点介绍了流动注射分光光度法在挥发酚测定中的原理及在水质分析中的应用,讨论了该法的影响因素,包括缓冲溶液pH、氧化剂、空气峰以及实际水样的影响,并对这一领域的发展趋势进行了展望。引用文献54篇。     

流动注射分析在分光光度法中的应用

流动注射分析是近年发展起来的新分析方法,具有准确、精密、快速的优点,能实现化学分析测定自动化。 本文采用中国科学院科学仪器厂的FIA—21型流动注射分析仪配接721分光光度计,探索了工作条件,可用在岩石土壤等地质样品中0.00X—0.X％磷的测定。测定频率为120次分,对含3ppm磷的标准溶液测定20次,RSD为0.54％;对磷的含量为226ppm的样品(GSR—6)测定9次,其RSD为3.16％。     

流动注射—速差动力学研究：分光光度法测定岩矿中痕量锆

探讨了以二甲酚橙（ＸＯ）为显色剂时，一些常见金属离子与试验剂的显色反应动力学特性，利用Ｚｒ（Ⅳ）和其它金属离子与ＸＯ的反应在动力学上的差异，及Ｚｒ－ＸＯ络合物灵敏的亚稳态，采用流动注射－分光光度联用技术，测定了岩矿中痕量Ｚｒ。方法经ＧＳＲ，ＧＳＳ，ＧＳＤ系列部分地质标准参考物质验证，其结果与推荐值吻合。对含Ｚｒ量为２７２μｇ／ｇ的ＧＳＲ－３进行了５次测定，其ＲＳＤ为２．２％。     

流动注射快速分析水体中挥发酚及样品保存的研究

采用模块化流动注射分光光度法对环境水中的挥发酚进行测定,并与国家标准方法4-氨基安替比林分光光度法进行对照,测定结果经统计学处理(t=1.94t0.05(6)=2.45,P0.05),两种方法无显著性差异;精密度(RSD为1.25%,n=7)、准确度(回收率91%~105%)等各项分析指标符合分析标准。对不同水体中挥发酚保存条件进行了研究,结果表明,水样采集后应立即测试;不能立即测试的水样,加碱(NaOH)保存在低于20℃条件下不超过7天,或加磷酸和硫酸铜保存在4℃条件下不超过3天。     

流动注射—催化光度法测定痕量锰

在非离子表面活性剂吐温－８０存在的Ｈ３ＰＯ４介质中,Ｍｎ＾２＋对Ｖ（Ｖ）氧化二安替比林苯乙烯甲烷（ＤＡＶＰＭ）成红色化合物的反应具有较强的催化作用,基于此采用流动注射－催化光度法测定了痕量Ｍｎ＾２＋,该方法的检测波长为５５５ｎｍ,检出限为０．０２μｇ／Ｌ Ｍｎ,线性范围为０．０２￣６μｇ／Ｌ Ｍｎ,进样频率为６０次／ｈ,对５μｇ／Ｌ Ｍｎ进行１０次测定的相对标准偏差为１．８％。经环境标准样品分析验     

反向流动注射分析法连续测定氰化物和硫氰化物的研究

运用反向流动注射分析法以吡啶－巴比舀酸和Ｆｅ（Ⅲ）作为显色剂建立了连续测定ＣＮ＾－和ＳＣ＾－的方法，借助于聚四氟乙烯微孔膜分离ＣＮ＾－和ＳＣＮ＾－，经切换阀实现测定转换。通过优化实验找到了两者连续测定的适宜条件，ＣＮ＾－和ＳＣＮ＾－的测定范围分别为：５－２０ｍｇ／Ｌ和０－８０ｍｇ／Ｌ．     

流动注射HG-AFS法同时测定化探样品中的砷和汞

建立了流动注射HG-AFS测定痕量砷和汞的分析方法。把砷和汞放入20%的王水介质中,它们被硫脲-抗坏血酸预还原,待测量溶液澄清之后,将溶液与硼氢化钾一起导入反应器,产生的氢化物载气导入原子化器中测定,测定结果符合国家标准。本法改进了流动注射HG-AFS法测定砷、汞的分析方法。     

Temporal change in permeability of the Nojima fault zone by repeated water injection experiments

Three boreholes were drilled near the Nojima fault, which the 1995 Hyogoken–Nanbu earthquake occurred on. In order to research the properties and the healing process of the fault, water injection experiments were conducted every 3 years. In this report, we researched the permeability of the fault as a measurement of crack density or porosity of the fault zone. Pore water pressure changes in rock due to the water injections at one borehole were observed as discharge changes or groundwater level changes at the other borehole. Using numerical calculations, the permeability of the fault fracture zone was estimated for each experiment. The permeability has been decreasing as time passed, which is thought to show the fault healing process of the Nojima fault after the 1995 Hyogoken–Nanbu earthquake.     

北方泥炭沼泽中酚类物质释放的热敏感性研究:以英国威尔士地区雨养和矿养泥炭沼泽为例

利用高精度多梯度热培养系统,对英国威尔士地区两类典型的北方泥炭沼泽中酚类物质和溶解有机碳释放的热敏感性进行了为期1年的调查研究.研究结果表明,雨养泥炭沼泽(Bog)酚类物质释放的热敏感性Q10(总酚)月变化为0.92～1.57,而矿养泥炭沼泽(Fen)的月变化范围为0.93～1.30.酚类释放的热敏感性与土壤温度大致呈正相关关系.此外,土壤温度与溶解有机碳释放的热敏感性Q10(DOC)也呈正相关关系.总体上,雨养泥炭沼泽的热敏感性比矿养泥炭沼泽略高.除温度外,水文条件和植被等多种环境因子对酚类物质和溶解有机碳释放的热敏感性也有较大影响.研究结果还表明酚碳热敏感性比值Q10o(总酚)/Q10(DOC)相对稳定,土壤温度的变化对其影响有限.     

Secular change of permeability in the fracture zone near the Nojima fault estimated using strain changes due to water injection experiments

Water injection experiments were performed in 1997, 2000 and 2003 at the 1800 m borehole near the fracture zone of the 1995 Hyogo-ken Nanbu earthquake. During these experiments, a contraction of about 10^− 8–10^− 7 was observed with three-component strainmeters at a bottom of the 800 m borehole, 70 m southwest of the 1800 m borehole. We estimated hydraulic properties of the fracture zone near the Nojima fault by using the strain data to investigate a healing of the fault during the postseismic stage. We calculated pore pressure changes due to the water injection using Darcy's equation and obtained strain changes due to the pore pressure changes as elastic deformations of the crust. The calculated strain changes have a nearly agreement with the observed strain changes. Hydraulic conductivity in 1997, 2000 and 2003 was determined to be 0.9 ± 0.2 × 10^− 6, 0.8 ± 0.2 × 10^− 6 and 0.4 ± 0.1 × 10^− 6 m/s, respectively. The reduced hydraulic conductivities in 2000 and 2003 suggest that the fractures had been healing.     

Numerical analysis of thermal fracturing in subsurface cold water injection by finite element methods

Integration of poromechanics and fracture mechanics plays an important role in understanding a series of thermal fracturing phenomena in subsurface porous media such as cold water flooding for enhanced oil recovery, produced‐water reinjection for waste disposal, cold water injection for geothermal energy extraction, and CO₂ injection for geosequestration. Thermal fracturing modeling is important to prevent the potential risks when fractures propagate into undesired zones, and it involves the coupling of heat transfer, mass transport, and stress change as well as the fracture propagation. Analytical method, finite element method, and finite difference method as well as boundary element method have been used to perform the thermal fracturing modeling considering different degrees and combinations of coupling. In this paper, extended finite element method is employed for the thermal fracturing modeling in a fully coupled fashion with remeshing avoided, and the stabilized finite element method is employed to account for the convection‐dominated heat transfer in the fracturing process with numerical oscillation circumvented. With the thermal fracturing model, a hypothetical numerical experiment on cold water injection into a deep warm aquifer is conducted. Results show that parameters such as injection rate, injection temperature, aquifer stiffness, and permeability can affect the fracture development in different ways and extended finite element method and stabilized finite element method provide effective tools for thermal fracturing simulation. Copyright © 2012 John Wiley & Sons, Ltd.     

单井注水改变填埋场中垃圾土温度的模拟

为了加速填埋场降解的稳定化,渗滤液回灌常被应用在工程实践中。使用竖井进行回灌是较为有效的方式之一。伴随着液体的注入,由于对流的产生,垃圾土温度势必会发生改变。基于无锡填埋场注水试验,对该现场试验过程中垃圾土温度的改变进行模拟。为此,建立了考虑渗透系数和孔隙率随深度变化的渗流模型,以及考虑渗流影响的热对流-热传导模型,并利用数值计算方法进行求解。在对比计算值和试验值之后,发现所建立的模型能较好地模拟注水期间渗滤液水位和垃圾土温度的变化规律。结果表明：在离注水井超过6 m处的位置,显现的液位相对滞后,至少滞后0.15 d,而且距离越远滞后的时间越长;在液位以下,注水井周围的垃圾土温度均低于初始温度。但是在径向上远离注水井3.6 m之外的垃圾土温度并不是全低于初始温度,在新老垃圾土交界处之上2 m范围内,会出现温度高于初始温度的现象,温度差可达3 ℃;新填垃圾土的已降解时长对单井注水工况下温度分布的影响较为显著。     

永安井水位记录水震波能力及分析

本文主要在对永安井水位记录的水震波进行统计分析 ,在此基础上 ,择出有代表性震例的水震波进行分析探讨 ,并提出一些假设进行讨论     

Micromechanical approach to unsaturated water flow in structured geomaterials by two-scale computations

This article presents a micromechanical approach to the problem of unsaturated water flow in heterogeneous porous media in transient conditions. The numerical formulation is based on the two-scale model obtained previously by periodic homogenization. It allows for a coupled solution of the non-linear flow equations at macroscopic and microscopic scales and takes into account the macroscopic anisotropy of the medium and the local non-equilibrium of the capillary pressure. The model was applied to simulate two-dimensional water infiltration at constant flux into an initially dry medium containing inclusions of square and rectangular shapes. The numerical results showed the influence of the inclusion–matrix conductivity ratio and the local geometry on the macroscopic behavior. The influence of the conductivity ratio manifested itself by the acceleration or retardation of the onset of the macroscopic water flux at the outlet, while the local geometry (anisotropy) significantly affected the macroscopic spatial distribution of the water flux. Such type of approach can be extended to simulate coupled phenomena (for example hydro-mechanical problems) with evolving local geometry.     

水压式双栓塞止水压水技术的研究与实践

国内工程钻孔压水多结合造孔采用单栓塞止水,按0.3、0.6和1.0MPa 3个压力点5个压力阶段进行试验,我们称其为常规压水试验.目前,进行勘测设计和施工的高坝高水头电站、抽水蓄能电站已有多座,查明岩体在实际水头作用下的透水率和渗透特性是工程设计的一项重要工作.因为一些低压力下不渗透的岩层在高压下可能渗透甚至会产生水力劈裂,常规压水试验结果已不能完全满足工程设计的需要.为此,我们研制了水压式双栓塞止水压水技术.实践证明,该技术具有止水效果好、操作简单、可在终孔后连续进行试验等优点.本文给出了使用该技术进行的常规压水、高压压水和水力劈裂三个方面的试验资料,简单分析了这些试验资料在工程设计中的作用和意义.     

The distribution and natural degradation of cyanide in goldmine tailings and polluted soil in arid and semiarid areas

Farmlands and rivers have been seriously polluted by cyanide from a goldmine tailings dam that collapsed in early spring of 1995 in Yining County, Xinjiang Autonomous Region of China. The cyanide distribution in the polluted farmland and the abandoned tailings dam was studied, three and 4 years after the accident occurred. The results indicated that natural degradation of cyanide in soils is slower than in natural water bodies. The cyanide transport in the soil section is similar to freely soluble salts. In arid and semiarid areas, cyanide can be highly enriched in the salt crust in which the concentration is even higher than the fresh tailings debris though cyanide has decomposed for 4 years. In the polluted farmland, the sticky layer in the soil section can highly adsorb and enrich cyanide so it can partly prevent cyanide transfer to groundwater. According to the characteristics of cyanide natural degradation in soil, the measures for prevention and cure of soil polluted by goldmine tailing dam collapse have been discussed.