A comparison of non-linear least square and GLUE for model calibration and uncertainty estimation for pesticide transport in soils

The problems of calibrating soil hydraulic and transport parameters are well documented, particularly when data are limited. Programs such as CXTFIT, UUCODE and PEST, based on well established principles of statistical inference, will often provide good fits to limited observations giving the impression that a useful model of a particular soil system has been obtained. This may be the case, but such an approach may grossly underestimate the uncertainties associated with future predictions of the system and resulting dependent variables. In this paper, this is illustrated by an application of CXTFIT within the generalised likelihood uncertainty estimation (GLUE) approach to model calibration which is based on a quite different philosophy. CXTFIT gives very good fits to the observed breakthrough curves for several different model formulations, resulting in very small parameter uncertainty estimates. The application of GLUE, however, shows that much wider ranges of parameter values can provide acceptable fits to the data. The wider range of potential outcomes should be more robust in model prediction, especially when used to constrain field scale models.     

基于室内土柱穿透实验的优先流定量评价

土壤优先流对包气带水流和污染物运移的影响已引起广泛关注,但大多数研究还停留在定性描述上,缺乏对优先流定量评价的标准。基于室内土柱实验获取的穿透曲线,分析了饱和条件下土壤溶质优先运移的一般规律,采用解析法模拟软件CX-TFIT拟合了溶质优先运移的参数,同时结合时间矩方法计算了定量评价优先流的指标PFSP。研究结果表明:时间矩方法中的一阶标准矩μ′1、二阶中间矩μ2以及偏态系数S可以定量刻画穿透曲线的特征,从而指示优先流的程度;PFSP能很好地刻画优先流作用的大小。该研究对优先流的定量评价具有重要指导意义。     

Evaluating the transport and removal of chromate using pyrite and biotite columns

To remove chromate from a wastewater, a porous permeable reactive barrier system (PRBS), using pyrite and biotite, was adapted. This study included bench‐scale column experiments to evaluate the efficiency of the PRBS and investigate the reaction process. The total chromium concentration of the effluent from the biotite and pyrite columns reached the influent concentration of 0·10 mM after passing through more than 150 pore volumes (PVs) and 27 PVs respectively, and remained constant thereafter. The Cr^VI concentration in the effluent from the biotite column became constant at about 0·08 mM , accounting for approximately 80% of the influent concentration, after passing through 200 PVs. Moreover, in the pyrite column, the Cr^VI concentration remained at about 0·01 mM , 10% of the input level, after passing through 116 PVs. This shows that both columns maintained their levels of chromate reduction once the Cr^VI breakthrough curves (BTCs) had reached the steady state, though the steady‐state output concentration of total chromium had reached the influent level. The variances of the iron concentration closely followed those of the chromium. The observed data for both columns were fitted to the predicted BTCs calculated by CXTFIT, a program for estimating the solute transport parameters from experimental data. The degradation coefficient µ of the total chromium BTCs for both columns was zero, suggesting the mechanisms for the removal of chromate limit the µ of the Cr^VI BTCs. The Cr^VI degradation of the pyrite column (6·60) was much greater than that of the biotite column (0·27). In addition, the Cr^VI retardation coefficient R of the pyrite column (253) was also larger than that of the biotite column (125). The R values for the total chromium BTCs from both columns were smaller than those of the Cr^VI BTC. Whereas the total chromium BTC for the pyrite column showed little retardation (1·5), the biotite column showed considerable retardation (80). The results for the 900 °C heat‐treated biotite column were analogous to those of the control column (quartz sand). This suggests that the heat‐treated biotite played no role in the retardation and removal of hexavalent chromium. The parameters of the heat‐treated biotite were calculated to an R of 1·2 and µ of 0·01, and these values confirmed quantitatively that the heated biotite had little effect on the transport of Cr^VI. These solute transport parameters, calculated by CXTFIT from the data obtained from the column tests, can provide quantitative information for the evaluation of bench‐ or field‐scale columns as a removal technology for Cr^VI in wastewater or contaminated groundwater. Copyright © 2006 John Wiley & Sons, Ltd.