Block-effective macrodispersion for numerical simulations of sorbing solute transport in heterogeneous porous formations     

Alison E. Lawrence  Yoram Rubin 《Advances in water resources》2007

Heterogeneity is prevalent in aquifers and has an enormous impact on contaminant transport in groundwater. Numerical simulations are an effective way to deal with heterogeneity directly by assigning different hydraulic property values to each numerical grid block. Because hydraulic properties vary on different scales, but they cannot be sampled exhaustively and the number of numerical grid blocks is limited by computational considerations, the dispersive effects of unmodeled heterogeneity need to be accounted for. Dispersion tensors can be used to model the dispersion caused by unmodeled heterogeneity. The concept of block-effective macrodispersion tensors for modeling the effects of small-scale variability on solute transport introduced by Rubin et al. [Rubin Y, Sun A, Maxwell R, Bellin A. The concept of block-effective macrodispersivity and a unified approach for grid-scale- and plume-scale-dependent transport. J Fluid Mech 1999;395:161–80] is extended in this paper for use with reactive solutes. The tensors are derived for reactive solutes with spatially variable retardation factors and for solutes experiencing spatially uniform rate-limited sorption. The longitudinal block-effective macrodispersion coefficient is largest for perfect negative correlation between the log-hydraulic conductivity and the retardation factor. Because dispersion tensors, as they are usually implemented in numerical simulations, produce symmetric spreading, the applicability of the concept depends on the portion of the plume asymmetry caused by small-scale variability. The presented results show that the concept is applicable for rate-limited sorption for block sizes of one and two integral scales.  相似文献   

Reactive transport model of silicification at the Mount Isa copper deposit, Australia     

Michael Kühn  Klaus Gessner   《Journal of Geochemical Exploration》2006,89(1-3):195

A distinct feature of the world-class Mount Isa copper system is the presence of a massive silica body enveloping the chalcopyrite ore body in the Urquhart shale. Because silicification may be genetically linked to the copper mineralization, it is important to understand its formation. It can be shown by numerical simulations of reactive transport processes that both hydraulic head and buoyancy driven flow are capable of generating silicification patterns similar to the field example. Considering the physical conditions required to form the observed patterns we suggest, however, that head-driven flow rather than free thermal convection produced the silica body. Free convection requires very special conditions and only one of several possible scenarios reproduces the observed silicification whereas any of the tested forced flux scenario is capable of doing so.  相似文献   

Kinetic investigation of the OH + CH3Br reaction between 248 and 390 K     

A. Chichinin  S. Teton  G. Le Bras  G. Poulet 《Journal of Atmospheric Chemistry》1994,18(3):239-245

The rate parameters for the reaction of the OH radical with CH₃Br have been measured using the discharge flow-electron paramagnetic resonance method. The result isk ₁=(1.86±0.48)×10^–12 exp[–(1230±150)/T] cm³ molecule^–1 s^–1. This value is compared to earlier data and is found to be in excellent agreement with the most recent results, which greatly increases the accuracy of the ozone depletion potential of CH₃Br which can be derived from these kinetic data.  相似文献   

DOAS Zenith Sky Observations: 1. BrO Measurements over Bremen (53°N) 1993–1994     

M. EISINGER  A. RICHTER  A. LADSTÄTTER-WEIßENMAYER  J. P. BURROWS 《Journal of Atmospheric Chemistry》1997,26(1):93-108

Observations of stratospheric BrO over Bremen (53°N) are reported for winter and early spring periods of 1993 and 1993/94. The BrO was observed by ground-based near-UV absorption spectroscopy of sunlight scattered in the zenith. Differential slant column densities for solar zenith angles 90°/80° in the range of9× 10¹³ (detection limit) to 4.5×10¹⁴ molecules/cm² having a high day-to-day variability were found. For the majority of the measurements no significant difference was observed between the morning and evening behaviour of BrO. Exceptions are the morning measurements from the winter of 1992/93 where an accelerated production of BrO was observed. We believe the latter best to be explained by the early morning rapid photolysis of elevated amounts of photo-labile Br-reservoirs formed during the night. The largest differential slant column densities of BrO were measured in December 1993 when the temperatures at 30 hPa dropped below 205 K. This might be an indication of heterogeneous conversion of bromine compounds on sulfate and other aerosols.  相似文献   

超热中子活化法测定碘和溴   总被引：14，自引：2，他引：14  

侯小琳 《岩矿测试》1995,14(1):31-36

介绍了采用微型反应堆超热中子活化分析膳食样品中Ｉ和Ｂｒ的方法。讨论了热中子屏蔽材料的选择，干扰扣除等问题，计算了不同样品的探测极限及标准偏差。对几种标样进行分析，其结果与推荐值相符。  相似文献   

电感耦合等离子体质谱法同时测定地质样品中痕量碘溴硒砷的研究Ⅰ．不同介质及不同阴离子形态对测定信号的影响   总被引：11，自引：14，他引：11  

李冰  何红蓼  史世云  马新荣  温宏利  吕彩芬 《岩矿测试》2001,20(3):161-166

研究了半熔-电感耦合等离子体质谱法（ICP-MS）同时测定地质样品中痕量碘、溴、硒和砷等非金属元素的可行性。重点研究了不同介质中碘以及溴、砷、硒不同形态对测定信号的影响。比较并讨论了在纯水溶液、0.07mol/LNH  相似文献   

Adsorption Characteristics of Reactive Black 5 from Aqueous Solution onto Chitosan     

Tapan K. Saha  Nikhil C. Bhoumik  Subarna Karmaker  Mahmooda G. Ahmed  Hideki Ichikawa  Yoshinobu Fukumori 《洁净——土壤、空气、水》2011,39(10):984-993

Adsorption of reactive black 5 (RB5) from aqueous solution onto chitosan was investigated in a batch system. The effects of solution pH, initial dye concentration, and temperature were studied. Adsorption data obtained from different batch experiments were modeled using both pseudo first‐ and second‐order kinetic equations. The equilibrium adsorption data were fitted to the Freundlich, Tempkin, and Langmuir isotherms over a dye concentration range of 45–100 µmol/L. The best results were achieved with the pseudo second‐order kinetic and Langmuir isotherm equilibrium models, respectively. The equilibrium adsorption capacity (q_e) was increased with increasing the initial dye concentration and solution temperature, and decreasing solution pH. The chitosan flakes for the adsorption of the dye was regenerated efficiently through the alkaline solution and was then reused for dye removal. The activation energy (E_a) of sorption kinetics was estimated to be 13.88 kJ/mol. Thermodynamic parameters such as changes in free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) were evaluated by applying the van't Hoff equation. The thermodynamics of reactive dye adsorption by chitosan indicates its spontaneous and endothermic nature.  相似文献   

薄膜吸附制样-波长色散X射线荧光光谱法测定卤水中的溴   总被引：2，自引：2，他引：0  

陈景伟  宋江涛  赵庆令  宋双喜  汤云芝  耿楠 《岩矿测试》2015,34(5):570-574

溴主要以离子形式分布在地壳水圈的溴化物型卤水、卤化物硫酸盐型卤水中,目前应用波长色散X射线荧光光谱(WDXRF)测定卤水中的溴,主要采用粉末载体压片法前处理待检样品,制样工作量大,制样均匀性和制样过程中的污染都会影响准确度,方法实用性不强。本文借助薄膜吸附前处理卤水样品,通过优化筛选薄膜材料及卤水取样量,确定移取50μL卤水样品滴于Ф=40 mm的3#层析滤纸的圆心位置,自然晾干后高压压平来前处理待检样品,采用人工配制标准样品校正溴的标准曲线,用WDXRF测定溴的含量。钾钠钙镁氯和硫酸根等共存离子的影响可以忽略,方法检出限(3σ)为0.95 mg/L,精密度(RSD,n=11)不大于0.8%,加标回收率为99.4%~101.2%。本方法操作简便,不需要使用化学试剂,解决了现行卤水中溴的分析方法流程复杂、分析成本高的问题。  相似文献   

Gas BenchⅡ-IRMS测定地下水中溴同位素新技术     

杨杰  马腾  刘玲  刘存富  单慧媚  陈柳竹 《西安地质学院学报》2011,(4):397-401

建立了利用GasBenchⅡ联用同位素比值质谱仪（GasBench Ⅱ-IRMS）用于测定地下水中溴稳定同位素的方法。基于溴比氯更容易被重铬酸钾氧化的性质,将Br-氧化成Br2,而氯残留在原溶液中,从而把溴与氯分离开;再利用AgNO3将溴以AgBr的形式沉淀下来,然后将AgBr转化成CH。Br进行溴稳定同位素质谱测定。反应中,CHsI用量为20μL,AgBr用量为0．5mg。本测试流程需溴4～10mg,质谱测试时问由1．5h缩短为800s,测试精度优于±0．1‰（2σ）。该方法可以用于地下水中溴同位素测定,在水文地质研究中具有广阔的应用前景。  相似文献   

Effect of mineral reactions on the hydraulic properties of unsaturated soils: Model development and application     

L. Wissmeier  D.A. Barry 《Advances in water resources》2009

The selective radius shift model was used to relate changes in mineral volume due to precipitation/dissolution reactions to changes in hydraulic properties affecting flow in porous media. The model accounts for (i) precipitation/dissolution taking place only in the water-filled part of the pore space and further that (ii) the amount of mineral precipitation/dissolution within a pore depends on the local pore volume. The pore bundle concept was used to connect pore-scale changes to macroscopic soil hydraulic properties. Precipitation/dissolution induces changes in the pore radii of water-filled pores and, consequently, in the effective porosity. In a time step of the numerical model, mineral reactions lead to a discontinuous pore-size distribution because only the water-filled pores are affected. The pore-size distribution is converted back to a soil moisture characteristic function to which a new water retention curve is fitted under physically plausible constraints. The model equations were derived for the commonly used van Genuchten/Mualem hydraulic properties. Together with a mixed-form solution of Richards’ equation for aqueous phase flow, the model was implemented into the geochemical modelling framework PHREEQC, thereby making available PHREEQC’s comprehensive geochemical reactions. Example applications include kinetic halite dissolution and calcite precipitation as a consequence of cation exchange. These applications showed marked changes in the soil’s hydraulic properties due to mineral precipitation/dissolution and the dependency of these changes on water contents. The simulations also revealed the strong influence of the degree of saturation on the development of the saturated hydraulic conductivity through its quadratic dependency on the van Genuchten parameter α. Furthermore, it was shown that the unsaturated hydraulic conductivity at fixed reduced water content can even increase during precipitation due to changes in the pore-size distribution.  相似文献