Preferential flow and aging of NAPL in the unsaturated soil zone of a hazardous waste site: implications for contaminant transport

Flow of non‐aqueous phase liquids (NAPL) in the unsaturated zone is thought to be driven by gravity with a dominant vertical flow direction, and lateral spreading to be limited to the gradient of the relative permeabilities. The effect of soil profile build‐up, preferential flow, aging, and groundwater level fluctuations is mostly neglected. The objective of our study was to check the effects of such processes on the fate of NAPL in the unsaturated soil zone. At a hazardous waste site, we conducted a field survey of the unsaturated soil zone and monitored the groundwater for a two year period. We conducted spatially resolved and depth dependent soil sampling and analysis and the evaluation of former ram and core drilling protocols. The samples were analyzed for the 16 EPA PAH and alkanes with GC‐MS and GC‐FID. ¹³C‐NMR spectroscopy was used to assess structural changes of the NAPL phase. Flow of bulk NAPL along macropores and along preferential permeability structures, like sedimentation discontinuities, are the dominant transport pathways which cause large lateral spreading beyond those expected by the relative permeability gradient. Accumulation of NAPL was found at locations with abrupt textural changes and within the zone of capillary rise. Aging of NAPL results in the depletion in soluble and volatile compounds but also in oxidation and polymerization. It increases the chemical diversity and decreases the mobility of the NAPL. Thus, NAPL flow ceases much earlier than expected from the capillary forces. As chemical transformation is restricted to the NAPL water/air interface, a skin‐like thin film is formed which encapsulates and preserves the bulk NAPL from further hardening, limiting contaminant mass transfer from the NAPL to the aqueous phase.     

Emission of groundwater‐derived nitrous oxide into the atmosphere: model simulations based on a 15N field experiment

Indirect emissions of the major greenhouse gas nitrous oxide (N₂O) occurring from aquatic ecosystems are considered to be a highly uncertain component in the global N₂O budget. In this study, we investigated the fate of N₂O produced by denitrification in a sandy shallow aquifer in northern Germany. The experimental data from a previous ¹⁵N field study and site‐specific diffusion coefficients were used to simulate upward fluxes of groundwater‐derived (¹⁵N‐)N₂O in the soil as well as its ultimate emission into the atmosphere. The one‐dimensional simulation model considered gas diffusion and gas retardation by dissolution in the water phase. The modelled concentration gradients and emissions were in good agreement with the experimental data, indicating that diffusion was the dominant transport process in the soil, and that our model approach was thus suitable for simulating N₂O fluxes from the unsaturated zone to the atmosphere. Furthermore, the results revealed that there was no evidence for consumption of ¹⁵N‐N₂O during upward diffusion from the surface groundwater to the atmosphere. Simulated concentrations and emissions of groundwater‐derived N₂O were found to be very small and a negligible component of total N₂O.     

土壤性质对砂土亚表层磷迁移的影响

The soil factors influencing the potential migration of dissolved and particulate phosphorus （P） from structurallyweak sandy subsoils were evaluated by means of soil column leaching experiments. Soil colloids were extracted from two types of soils to make the colloid-bound forms of P solution. Eight sandy soils with diverse properties were collected for packing soil columns. The effects of influent solutions varying in concentrations of colloids, P, and electrolyte, on the transport of P and quality of leachates were characterized. P migration in the soils was soil property-dependent. High soil electrical conductivity values retarded the mobility of colloids and transportability of colloid-associated P （particulate P）. Soil electrical conductivity was negatively correlated with colloids and reactive particulate P （RPP） concentrations in the leachates, whereas, the total reactive P （TRP） and dissolved reactive P （DRP） concentrations in the leachates were mainly controlled by the P adsorption capacity and the P levels in the subsoil. The reactive particulate P in the leachates was positively correlated with the colloidal concentration. Increased colloidal concentration in the influent could significantly increase the colloidal concentration in the leachates. Elevated P concentration in the influent had little effect on P recovery in the leachates, but it resulted in significant increases in the absolute P concentration in the leachates.     

Initial Effects of a New Highway Section on Soil and Groundwater

The environmental impacts of 16 different contaminants originating from the E18 Highway (17,510 annual average daily traffic) were studied over the initial months of the highway??s operational life. Investigative methods used included electrical resistivity surveying, water chemistry analyses, soil analyses, distribution modeling, and transportation modeling of contaminants. The study conclusively showed a year-round infiltration due to melting of the snowpack from road salt, and a strong preferential, anthropogenic pathway due to increased hydraulic conductivities of road construction materials relative to in situ soils. The resistivity surveys produced values well below the expected values for the highway materials, indicating increased ionic content within the unsaturated zone. Time lapse resistivity modeling showed a clear downwards spreading of contamination from the roadway to subsurface distances greater than 5?m. Elevated concentrations of nearly every studied contaminant relative to baseline values were observed, with many metal concentrations within the snow pack averaging values in excess of the Swedish Environmental Protection Agency??s groundwater limitations. Distribution modeling demonstrated a potential offset of peak values from the road surface due to plowing and splash transport processes, and indicated different distribution behavior during winter months than during summer months. One-dimensional transport modeling demonstrated the importance of adsorption and other retentive factors to the migration of contaminants to groundwater and provided an estimate for potential long-term contaminant concentrations.     

Adsorption controls mobilization of colloids and leaching of dissolved phosphorus

Loss of phosphorus (P) from agriculture contributes to the eutrophication of surface waters. We have assessed the magnitude and controls of P leaching and the risk of colloid‐facilitated transport of P from sandy soils in Münster. Concentrations of soluble reactive P in drainage water and groundwater were monitored from 0.9 to 35 m depth. Total P concentrations, P saturation, and P sorption isotherms of soil samples were determined. Concentrations of dispersible soil P and colloidal P in drainage water and groundwater were investigated. The concentrations of soluble reactive P in drainage water and groundwater were close to background concentrations (< 20 µg P l^?1). Median concentrations in excess of 100 µg P l^?1 were found down to 5.6 m depth at one of four research sites and in the lower part of the aquifer. Experimentally determined equilibrium concentrations and the degree of P saturation were good predictors of P concentrations of drainage water. Large concentrations of dispersible P were released from soil with large concentrations of oxalate‐extractable P and addition of P induced further dispersion. Colloidal P was transported in a P‐rich subsoil when there was a large flow of water and after nitrate had been flushed from the soil profile and total solute concentrations were small. We conclude that the concentration of soluble reactive P in drainage water is controlled by rapid adsorption in the sandy soils. Subsurface transport of dissolved P contributes substantially to the loss of P from the soils we investigated. Accumulation of P in soils increases the risk of colloid‐facilitated leaching of P.     

Mobilization of Cd upon acidification of agricultural soils: column study and field modelling

The potential effect of acidification of contaminated sandy soils on Cd transport in the unsaturated zone was assessed. Forty‐eight soil profiles were sampled at five depths in a polluted field that was set aside in 1992. The Cd concentration in the top 30 cm of this field was, on average, 10 mg kg⁻¹. A column experiment was carried out with one of the topsoil samples. Homogeneously packed columns were leached with 0.001 m CaCl₂, adjusted to pH 3 or pH 5.7, at a pore water velocity of 6 cm day⁻¹. The Cd and proton transport was predicted with coupled transport equations. The Cd transport was modelled by assuming local equilibrium and by using sorption parameters derived from batch experiments, while acidification was modelled with a kinetic approach, on the assumption that proton buffering was due to cation exchange and mineral weathering. Organic matter was the main contributor to the cation exchange capacity of these soils. Observed and predicted pH and Cd profiles in the columns agreed well. With the same model, the proton and Cd transport at field scale was calculated for each of the 48 profiles sampled (‘grid model’). It was predicted that the field‐averaged Cd concentration in the seepage water will increase from 6 μg litre⁻¹ at present to 200 μg litre⁻¹ over 260 years, which greatly exceeds the maximum permissible concentration (MPC) in groundwater of 5 μg litre⁻¹. Predictions of Cd transport using field‐averaged soil properties yielded a later breakthrough time and a larger peak Cd concentration than predicted with the grid model, which illustrates the impact of spatial variability on solute transport. Continuation of liming practices is a possible solution to prevent breakthrough of Cd at concentrations far in excess of the MPC.     

Tracing Pharmaceuticals in the Unsaturated Zone (10 pp)

Background, Aim and Scope   One of the first occurrences of pharmaceutically active compounds in groundwater was reported from the sewage irrigation farms south of Berlin. At these sewage irrigation farms treated sewage effluent passed the soil and unsaturated zone before reaching the aquifer. Clofibric acid was detected in pore water from soils of those sewage irrigation farms in concentrations between 65 ng/L and 1430 ng/L. The aim of this study was to investigate the transport behavior of regularly detected clofibric acid, diclofenac, ibuprofen, and propyphenazone under conditions comparable to those at the sewage irrigation farms in a multiple compound sand column laboratory experiment. Materials and Methods   Sediment column experiments were conducted to study the transport of pharmaceuticals in the unsaturated zone. The migration was measured in fine to medium grained sand and leaching solution containing 1 mg/L of pharmaceutically active compounds and 61 mg/L of the tracer lithium chloride (LiCl). For the analysis of the pharmaceutical compounds the water samples were adjusted to a pH value of 2 and then extracted by solid-phase extraction (SPE). Before extraction, the samples were spiked with a surrogate standard for analytical quality control. The sample extracts were analyzed by capillary gas chromatography-mass spectrometry (GC-MS) with selected ion monitoring (SIM). Depending on the sample volume (100 to 200 mL) and the matrix, the limits of detection were between 1 and 10 ng/L, and the limits of quantitation were between 5 and 25 ng/L. Analysis for calcium, magnesium and lithium were carried out using a 'Trace Scan' ICP-AES from Thermo Jarrel Ash. Sodium, potassium, iron and manganese were analyzed using a Philips PU 9400 flame AAS. Analysis of anions was performed on a Dionex ion chromatograph DX 120. Results   At the sewage irrigation farms the average concentrations of clofibric acid in the unsaturated zone declined from higher values near ground surface (480 ng/L) to lower values near the groundwater table (65 ng/L). From the pharmaceuticals analyzed only clofibric acid, primidone and propyphenazone could be analyzed in the first (upper) aquifer at the sewage irrigation farms. All other pharmaceuticals could neither be detected in the first aquifer nor in the deeper aquifers. Breakthrough curves from soil column experiments revealed no transformation and no retardation for clofibric acid, whereas transformation of diclofenac was so high (79%) that no retardation factor could be calculated. Ibuprofen was significantly transformed (37%), transformation of propyphenazone (17%) was quite low and retardation (Rf = 2.05) was in the range of previously conducted column experiments. Discussion   The results confirm previously conducted experiments with clofibric acid where this compound was identified as highly mobile and persistent. The results that diclofenac and ibuprofen are significantly transformed where unexpected as other studies exhibited much lower transformation under saturated conditions at least for diclofenac. However, lower pH values and higher oxygen contents in the unsaturated zone compared to the aquifer may explain this observed high transformation of these compounds at the column experiments. Conclusions   We conclude that irrigation with sewage effluent containing the compounds used in our experiments will lead to an input into groundwater of clofibric acid, whereas diclofenac and ibuprofen will most likely be transformed during the passage. Propyphenazone will be retarded but will most likely occur in groundwater. These results from the column experiments coincide very well with the occurrence of the pharmaceuticals clofibric acid, primidone, and propyphenazone in the first aquifer. Recommendations and Perspective  : The results underline the need to study the sorption of pharmaceuticals on various materials. e.g. organic matter, surfaces at pH values occurring in the unsaturated zone. Future field studies will also include the investigation of desorption behavior in the unsaturated zone.     

Modeling gas migration through unsaturated soils from waste disposal sites

The movement of gases away from waste disposal sites and hazardous waste spills through soils can result in serious safety and health hazards. As in the analogous problem of contaminant transport in groundwater, mathematical models are useful in predicting future gas excursion distances at existing sites and evaluating gas migration control alternatives. This paper presents a mathematical model for simulating the migration of gases from waste disposal sites through the unsaturated zone. The system equations used to represent gas migration through the unsaturated zone are an amalgam of the traditional groundwater flow-contaminant transport equations with the representation of gaseous flows in molar quantities. The model accounts for gas migration due to gas pressure, concentration and velocity gradients. The system equations are solved with the Galerkin finite element technique. The mathematical model successfully reproduced observed historical gas pressure and concentration data at two landfill sites. These two applications tested the mathematical model for both summer and winter flow conditions and under both natural and forced gas potential gradients.     

干旱区重度和轻度盐碱地包气带水分运移规律

为揭示干旱区不同灌溉模式下的包气带水分运移规律,该研究综合使用原位观测、同位素示踪和数值模拟等方法,对跨流域调水背景下,克拉玛依农业开发区重度和轻度盐碱地棉田的土壤水势、土壤含水率和土壤水同位素组成特征,包气带水量平衡以及水分运移规律进行了研究。研究表明,土壤基质势调控的滴灌模式下,重度和轻度盐碱地的灌溉入渗主要影响深度是地表以下0~150 cm,土壤含水率和土壤水势对灌溉和蒸散发动态变化的响应明显,具有前期土壤水和观测期内灌溉入渗水的混合特征。深层(重度盐碱地150~260 cm;轻度盐碱地250~350 cm)受地下水毛细作用影响,土壤水势和土壤含水率对地下水埋深动态变化的响应明显,具有前期土壤水与地下水的混合特征。轻度盐碱地中间层(150~250 cm),几乎不受灌溉入渗和地下水毛细作用的影响,土壤水势和土壤含水率处于动态平衡,主要为前期土壤水的特征。HYDRUS-1D数值模拟结果表明,深层土壤水与地下水之间存在双向交换,地下水对土壤水以补给作用为主,重度和轻度盐碱地地下水补给占包气带水分来源的比例分别为7.9%和15.0%。该灌溉模式对农业开发区地下水补给有一定的抑制作用,但观测期内区域地下水位抬升幅度在50~60 cm之间,说明存在一定的土壤次生盐渍化和地下水咸化的潜在风险。     

再生水灌溉区农田包气带及地下水中硝酸盐分布特征及来源研究

本文通过对华北平原典型再生水灌溉区(河北省石家庄洨河流域)的包气带土壤、地表水和地下水进行采样分析,对硝酸盐在多种环境介质中的来源与环境行为进行了研究,识别了再生水灌溉区地下水硝酸盐污染来源,明确了不同灌溉条件对包气带土壤中硝酸盐迁移的影响。在受到城市再生水严重影响的洨河流域,地下水中的硝酸盐浓度分布范围在4.0 mg·L?1到156.6 mg·L?1之间,已经形成了距离河道2 km、深度70 m的硝酸盐高值区域,经过计算硝酸盐的垂向扩散速率为每年1～2 m。硝酸盐与氯离子的相关性表明,城市再生水是再生水灌溉区包气带、地表水和地下水中硝酸盐的主要来源。利用Geoprobe获取利用不同灌溉水农田土壤剖面样品,研究再生水对厚包气带NO3?-N垂向分布影响,再生水灌溉区和地下水灌溉区中包气带土壤的NO3?-N的平均含量为137.0 mg·kg-1和107.7 mg·kg-1,最高含量523.2 mg·L?1和725.9 mg·L?1,分别出现1.20 m和0.85 m深度,分布规律有着明显的差别。包气带土壤硝酸盐与氯离子的相关性分析表明,再生水灌溉区土壤硝酸盐主要来源于城市再生水,而地下水灌溉区可能来源于农田氮肥。地下水年龄和硝酸盐之间关系表明,地下水中1975年以前补给的硝酸盐浓度低于1975年以后补给,地下水硝酸盐污染与包气带氮入渗的历史过程密切相关。在华北平原特殊的地质水文背景下,农田面源污染对地下水的影响有限,但再生水灌溉区地下水硝酸盐污染的风险较高。     

Remediation Actions by a Risk Assessment Approach: A Case Study of Mercury Contamination

The risk assessment procedure for identifying the remediation actions which may be adopted at a mercury contaminated site, when the plants are upgraded in the future, is proposed. The potentially active exposure/migration pathways in the future arrangement of the area will be due to Hg contaminated subsoil as a primary source (vapor inhalation and groundwater leaching) and to groundwater as a possible secondary source (transport to the point of compliance). The data of mercury concentration in the soil were acquired through environmental monitoring campaigns, and were processed to establish the three-dimensional distribution of contamination in subsoil, to locate sources and to define their geometrical and chemical characteristics. Speciation tests of mercury in the soil indicated that the most abundant species present were poorly leachable under the site-specific environmental conditions, confirming the coefficient distribution value obtained by the leaching tests. Analytical and numerical fate and transport modeling tools were used to locate digging zones in the contaminated subsoil, so as to reduce the possible groundwater contaminant loading and to avoid the down-gradient exceeding the concentration limit according to regulations. Remediation actions additional to civil works were required, which consists of soil digging within one contamination source, for about 22,200 m³ of soil. In order to evaluate the Hazard Index (HI) for human receptors due to Hg vapor inhalation, the air concentration of volatile mercury at the exposure point was estimated, based on direct measurements carried out at the site. Simulation gave HI values below 1 for all tested scenarios, suggesting that public health is protected without any additional actions to the already scheduled plant upgrading and digging for groundwater protection.     

Influence of fertilized short-rotation forest plantations on nitrogen concentrations in groundwater

Abstract. The influence of intensively fertilized short-rotation forest plantations on nitrogen concentrations in groundwater was studied by piezometer readings and water sampling over a two-year period in a sandy field growing willow ( Salix spp.) and other species. The mineral-N content of the unsaturated zone was measured in soil samples collected to 0.9 m depth. Although piezometer readings suggested that deep groundwater could be affected, the concentrations of nitrate-N and ammonium-N were usually less than 1 mg per litre. There was also little mineral-N in the unsaturated zone, except for occasional peaks in the topsoil (0–30 cm) after application of fertilizer. We conclude that there is little risk of nitrogen contamination of groundwater in intensively cultured tree stands receiving up to 150 kg N/ha/yr as fertilizer. This is probably because willow can take up water and nitrogen from deep parts of the soil profile.     

A new method to quantify how water repellency compromises soils' filtering function

Soil water repellency (SWR) is known to lead to preferential flow and to degrade the soil's filtering efficiency. However, no method is available to quantify directly how SWR affects the transport of reactive solutes. We propose a new method for conducting solute transport experiments in water‐repellent soils. It involves sequentially applying two liquids, one water, the other a reference fully wetting liquid, namely aqueous ethanol, to the same intact soil core with air‐drying between liquids. We applied this approach to quantify the impact of SWR on the filtering of the herbicide 2,4‐Dichlorophenoxyacetic acid (2,4‐D) in two Andosols. In batch experiments conducted prior to the transport experiments, 2,4‐D sorption was not influenced by aqueous ethanol for one soil. However, sorption in the second soil followed the co‐solvency theory, which predicts decreasing sorption with increasing solvent fractions. Thus, sorption experiments are necessary to complement our new method. Breakthrough curves were characterized by preferential flow with large initial concentrations, tailing and a long prevalence of solutes remaining in the soil. In the soil in which 2,4‐D sorption was unaffected by aqueous ethanol, SWR increased 2,4‐D losses by four and 50 times in the first 5‐mm outflow compared with the 2,4‐D losses with water. After 50‐mm outflow, the 2,4‐D losses were similar for one core, but in the other core they were still about four times greater with water than with aqueous ethanol. This method to quantify the reduction of the soil's filtering efficiency by SWR is needed for assessing the increased risk of groundwater contamination by solutes exogenously applied to water‐repellent soils.     

Model‐based evaluation of agri‐environmental measures in the Federal State of Brandenburg (Germany) concerning N pollution of groundwater and surface water

GIS‐based modeling of soil‐crop interactions and hydrological processes is a valuable instrument to assess land‐use effects on N pollution of water resources from the agricultural sector. A case study is presented using spatial information on soils, climatic zones, land use, and distribution of agri‐environmental measures within the federal State of Brandenburg (Germany) to assess the reduction effect of EU‐funded measures on N pollution of water resources. In a first step, the area was classified concerning the risk for groundwater and surface‐water pollution. For this, spatially distributed model calculations of the soil‐solution exchange frequency were intersected to a vulnerability map for groundwater derived from geological data and zones of different transit times from the root zone into surface waters. In a second step, model calculations of water and N dynamics in the soil‐crop system for different crop and management systems were performed to calculate nitrate leaching from the root zone and to estimate the effect of present agri‐environmental measures to reduce N pollution on groundwater and surface waters. The results indicated that 75% of the agri‐environmental measures were placed in areas with low impact on groundwater and surface waters. Therefore, the effectiveness of the agri‐environmental measures concerning water‐protection aims was moderate.     

Short‐term transport of cadmium during a heavy‐rain event simulated by a dual‐continuum approach

The transport of solutes in soils, and its intensification due to preferential flow, plays crucial role when problems related to the groundwater pollution are dealt with. The objective of this study was to examine transport of cadmium (Cd) in response to an extreme rainfall event for three different soils using numerical modeling. The ^115mCd²⁺ concentration profile had been measured in the Bodiky reference site (Danubian Lowland, Slovakia) by the radioactive‐tracer technique and used for the calibration of the dual‐continuum model S1D. The Cd transport during a single rain event was predicted with the S1D model for light, medium‐heavy, and heavy soil in the same region. The Cd transport through the soil profile was simulated by the one‐dimensional dual‐permeability model, which assumes the existence of two pore domains: the soil‐matrix domain and the preferential‐flow domain. The model is based on Richards' equation for water flow and advection‐dispersion equation for solute transport. A modified batch technique enables to distinguish process of adsorption in the matrix domain and the preferential pathways. Modeling with classical single‐permeability approach and dual‐continuum approach without considering the particle‐facilitated transport led to negligible Cd penetration. The rainfall event with extremely high rainfall intensity induced deep penetration of Cd in the medium‐heavy and heavy soil, which may indicate increased vulnerability to shallow groundwater pollution for the respective sites in Danubian Lowland region. The highest Cd leaching was predicted for heavy clay soil, where the preferential particle‐facilitated transport of Cd through the soil profile was significant due to the contrasting properties of the soil‐matrix domain and the preferential‐flow domain. The results of the sensitivity analysis suggested only slight effect of the transfer rate coefficients on simulated Cd leaching.     

Effects of Different Factors on Water Flow and Solute Transport Investigated by Time Domain Reflectometry in Sandy Clay Loam Field Soil

Factors affecting preferential flow and transport in the vadose zone need to be investigated by experiments and simulations to protect groundwater against surface applied chemicals. The objectives of this study were to investigate the effects of several factors (soil structure, initial soil water content (SWC), and application rate) and their interactions on the extent of preferential flow and transport in a sandy clay loam field soil using the time domain reflectometry (TDR) for measuring SWC and electrical conductivity (EC) in 12 treatments, modeling (by HYDRUS-1D and VS2DTI) the measured SWC and EC, and conducting statistical tests for comparing the means of the measured and modeled SWC and EC and solute transport parameters (pore water velocity and dispersion coefficient) obtained by inversely fitting in the CXTFIT program. The study results showed that the applied solution moved faster in the undisturbed, wet initial SWC, and higher application rate experimental conditions than in the disturbed, dry initial SWC, and lower application rate, respectively, based on the analysis of the changes in TDR measured SWC and EC with depth at 1, 2, 5, and 15?h of the experiments. However, the effects of interactive factors or treatments on water flow and solute transport were not clear enough. The modeling results showed that HYDRUS-1D was better than VS2DTI in the estimation of EC and especially SWC, but overall the models had relatively low performances in the simulations. Statistical test results also showed that the treatments had different flow and transport characteristics because they were divided into different groups in terms of the means of SWC and EC and solute transport parameters. These results suggest that similar experiments with more distinct interactions and modeling studies with different approaches need to be considered for better understanding the complex flow and transport processes in the vadose zone.     

Willow stands as an alternative method for the reduction of leachate at contaminated sites — numerical investigations

The commonly used multiple‐liner‐system of modern top sealings of contaminated sites is expensive and in many cases (minor hazardousness of pollutants), not necessary. As an alternative, we investigated the performance of willow stands as the only measure to reduce percolating soil water and therewith pollutant transport to underlying ground water resources. It is well accepted that willows have a high water demand and may considerably reduce percolation. On the basis of experimentally determined soil physical properties of a landfill site, we performed water balance calculations with the physically based HYDRUS‐code and a simple bucket approach. The 20 yr annual leachate rate for bare soil was calculated to vary from 336 (HYDRUS) to 451 mm yr^—1 (bucket‐model). Willows were able to reduce the annual leachate to 146 (HYDRUS) and 186 mm yr^—1 (bucket‐model), indicating their great performance compared to a grass‐ or beechwood cover. However, legal regulations (TASi) in Germany cannot be met with the proposed method. In minor hazardous cases, official authorities may accept willow stands as an alternative system for protection.     

Hydraulic and transport properties of the plant–soil system estimated by inverse modelling

Modelling soil water flow and solute transport under field conditions requires the knowledge of many parameters that are difficult to determine directly. Values determined on small isolated samples in the laboratory are often not representative of field situations. We investigated the applicability of inverse modelling to a soil–plant system in lysimeter experiments. We also tested whether parameters obtained from one experiment could be applied to another with the same soil. In a lysimeter planted with young trees, we first did a multistep drainage experiment and then a long‐term bromide tracer experiment with atmospheric boundary conditions at the soil surface. To estimate the unsaturated hydraulic properties, we linked the inverse program SUFI (Sequential Uncertainty FItting) to the flow and transport model HYDRUS5. A comparison of several scenarios showed that the resulting values of parameters depended strongly on the data used for calibration and the formulation of the objective function. The results suggested that inverse modelling could be used to identify important processes. Inversely obtained parameters gave better predictions for a second experiment when more variables were considered in the objective function and when the range of hydraulic conditions was wider. Furthermore, with retention curves directly fitted to measured water retention data we achieved acceptable results. Despite some limitations, the inverse approach was found to be a sound and useful procedure for estimating parameters of a complex system involving water uptake by roots, solute transport and unsaturated flow.     

A transfer-function method for analysing breakthrough data in the time domain of the transport process

A transfer‐function method is proposed to determine transport parameters from solute breakthrough data. The method is based on the assumptions that a linear process governs the transport of solute through soil and that the soil is homogeneous. It needs breakthrough data at two different vertical locations from a pulse input of solute to the soil. The method predicts the response by convoluting the input with the transfer function in the time domain. Solute breakthrough data were measured in unsaturated soil columns by time‐domain reflectometry (TDR). An experimental soil column was placed over a supporting column filled with sandy soil. A constant hanging water table, maintained in the lower column, created suction in the upper column and maintained unsaturated conditions. A solution of calcium chloride (CaCl₂) was spread over the soil in the upper column during steady flow of water in the column. Resident concentrations of solute in terms of electrical conductivity were measured at two depths by TDR sensors. We analysed breakthrough curves of CaCl₂ in 81 experiments to determine the transport parameters in coarse sand, sandy loam soil and clay loam soil by the transfer‐function method. The transport parameters obtained were compared with those determined by the widely used deterministic equilibrium model of the CXTFIT program. The transfer‐function method provided a better fit between the measured and estimated breakthrough curves in almost all cases and resulted in stable values of the parameters. The method is robust against small errors in measurements. It is a mathematically sound and efficient method for analysing breakthrough data.