A wide spectrum of quality changes of river Rhine and Meuse water is presented, on a global scale... more A wide spectrum of quality changes of river Rhine and Meuse water is presented, on a global scale after pre-treatment, dune infiltration and post-treatment. Attention is focussed on the performance of subsystems of the dune infiltration process, the dependency of quality changes upon detention time or flow path length, long term changes in effects of dune infiltration and the accumulation of substances. As far as the main constituents of water are concerned, this is established using a nearly 30 years long record of intensive monitoring on different scales (whole system, subsystems and streamlines). Data on trace inorganics, organic micro-contaminants and mutagenic activity are available (and considered here), since resp. 1971, 1973 and 1981.
This article describes the post audit and inverse modeling of a 1-D forward reactive transport mo... more This article describes the post audit and inverse modeling of a 1-D forward reactive transport model. The model simulates the changes in water quality following artificial recharge of pre-treated water from the river Rhine in the Amsterdam Water Supply Dunes using the PHREEQC-2 numerical code. One observation dataset is used for model calibration, and another dataset for validation of model predictions. The total simulation time of the model is 50 years, from 1957 10 2007, with recharge composition varying on a monthly basis and the post audit is performed 26 years after the former model simulation period. The post audit revealed that the original model could reasonably predict conservative transport and kinetic redox reactions (oxygen and nitrate reduction coupled to the oxidation of soil organic carbon), but showed discrepancies in the simulation of cation exchange. Conceptualizations of the former model were inadequate to accurately simulate water quality changes controlled by cation exchange, especially concerning the breakthrough of potassium and magnesium fronts. Changes in conceptualization and model design, including the addition of five flow paths, to a total of six, and the use of parameter estimation software (PEST), resulted in a better model to measurement fit and system representation. No unique parameter set could be found for the model, primarily due to high parameter correlations, and an assessment of the predictive error was made using a calibration constrained Monte-Carlo method, and evaluated against field observations. The predictive error was found to be low for Na+ and Ca2+, except for greater travel times, while the K+ and Mg2+ error was restricted to the exchange fronts at some of the flow paths. Optimized cation exchange coefficients were relatively high, especially for potassium, but still within the observed range in literature. The exchange coefficient for potassium agrees with strong fixation on illite, a main clay mineral in the area. Optimized CEC values were systematically lower than clay and organic matter contents indicated, possibly reflecting preferential flow of groundwater through the more permeable but less reactive aquifer parts. Whereas the artificial recharge initially acted as an intrusion of relatively saline water triggering Na+ for Ca2+ exchange, further increasing total hardness of the recharged water, the gradual long-term reduction in salinity of the river Rhine since the mid 1970s has shifted to an intrusion of fresher water causing Ca2+ for Na+ exchange. As a result, seasonal and longer term reversal of the initial cation exchange processes was observed adding to the general long-term reduction in total hardness of the recharged Rhine water. (C) 2012 Elsevier B.V. All rights reserved.
A wide spectrum of quality changes of river Rhine and Meuse water is presented, on a global scale... more A wide spectrum of quality changes of river Rhine and Meuse water is presented, on a global scale after pre-treatment, dune infiltration and post-treatment. Attention is focussed on the performance of subsystems of the dune infiltration process, the dependency of quality changes upon detention time or flow path length, long term changes in effects of dune infiltration and the accumulation of substances. As far as the main constituents of water are concerned, this is established using a nearly 30 years long record of intensive monitoring on different scales (whole system, subsystems and streamlines). Data on trace inorganics, organic micro-contaminants and mutagenic activity are available (and considered here), since resp. 1971, 1973 and 1981.
This article describes the post audit and inverse modeling of a 1-D forward reactive transport mo... more This article describes the post audit and inverse modeling of a 1-D forward reactive transport model. The model simulates the changes in water quality following artificial recharge of pre-treated water from the river Rhine in the Amsterdam Water Supply Dunes using the PHREEQC-2 numerical code. One observation dataset is used for model calibration, and another dataset for validation of model predictions. The total simulation time of the model is 50 years, from 1957 10 2007, with recharge composition varying on a monthly basis and the post audit is performed 26 years after the former model simulation period. The post audit revealed that the original model could reasonably predict conservative transport and kinetic redox reactions (oxygen and nitrate reduction coupled to the oxidation of soil organic carbon), but showed discrepancies in the simulation of cation exchange. Conceptualizations of the former model were inadequate to accurately simulate water quality changes controlled by cation exchange, especially concerning the breakthrough of potassium and magnesium fronts. Changes in conceptualization and model design, including the addition of five flow paths, to a total of six, and the use of parameter estimation software (PEST), resulted in a better model to measurement fit and system representation. No unique parameter set could be found for the model, primarily due to high parameter correlations, and an assessment of the predictive error was made using a calibration constrained Monte-Carlo method, and evaluated against field observations. The predictive error was found to be low for Na+ and Ca2+, except for greater travel times, while the K+ and Mg2+ error was restricted to the exchange fronts at some of the flow paths. Optimized cation exchange coefficients were relatively high, especially for potassium, but still within the observed range in literature. The exchange coefficient for potassium agrees with strong fixation on illite, a main clay mineral in the area. Optimized CEC values were systematically lower than clay and organic matter contents indicated, possibly reflecting preferential flow of groundwater through the more permeable but less reactive aquifer parts. Whereas the artificial recharge initially acted as an intrusion of relatively saline water triggering Na+ for Ca2+ exchange, further increasing total hardness of the recharged water, the gradual long-term reduction in salinity of the river Rhine since the mid 1970s has shifted to an intrusion of fresher water causing Ca2+ for Na+ exchange. As a result, seasonal and longer term reversal of the initial cation exchange processes was observed adding to the general long-term reduction in total hardness of the recharged Rhine water. (C) 2012 Elsevier B.V. All rights reserved.
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