N.M.J. Crout

Predicting the activity of Cd2+ and Zn2+ in soil pore water from the radio-labile metal fraction

Abstract Cadmium and zinc were added at 3 and 300 mg kg −1 , respectively, to 23 soils and incubated at 16°C and 80% field capacity for 818 d. Following addition of metal, changes in the radio-labile concentrations of both elements were examined on seven separate sampling occasions over 818 d. At each sample time, soil pore water was extracted using Rhizon soil solution samplers, and concentrations of Cd, Zn, dissolved organic carbon, and major cations and anions were determined. The chemical speciation program WHAM 6 was used to determine free metal ion activity, (M 2+ ). Similar measurements were made on a set of historically contaminated soils from old mining areas, sewage sludge disposal facilities, and industrial sources. The two data sets were combined to give a range of values for p (Cd 2+ ) and p (Zn 2+ ) that covered 5 and 4 log 10 units, respectively. A pH-dependent Freundlich model was used to predict Zn 2+ and Cd 2+ ion activity in soil pore water. Total and radio-labile metal ion concentration in the solid phase was assumed to be adsorbed on the “whole soil,” humus, or free iron oxides to provide alternative model formats. The most successful models assumed that solubility was controlled by adsorption on soil humus. Inclusion of ionic strength as a model variable provided small improvements in model fit. Considering competition with Ca 2+ and between Zn 2+ and Cd 2+ produced no apparent improvement in model fit. Surprisingly, there was little difference between the use of total and labile adsorbed metal as a model determinant. However, this may have been due to a strong correlation between metal lability and pH in the data set used. Values of residual standard deviation for the parameterized models using labile metal adsorbed on humus were 0.26 and 0.28 for prediction of p (Cd 2+ ) and p (Zn 2+ ), respectively. Solubility control by pure Zn and Cd minerals was not indicated from saturation indices. However there may have been fixation of metals to non-radio-labile forms in CaCO 3 and Ca-phosphate compounds in the soils in the higher pH range. Independent validation of the Cd model was carried out using an unpublished data set that included measurements of isotopically exchangeable Cd. There was good agreement with the parameterized model.

Predicting the transfer of radiocaesium from organic soils to plants using soil characteristics

A model predicting plant uptake of radiocaesium based on soil characteristics is described. Three soil parameters required to determine radiocaesium bioavailability in soils are estimated in the model: the labile caesium distribution coefficient (kd1), K+ concentration in the soil solution [mK] and the soil solution-->plant radiocaesium concentration factor (CF, Bq kg-1 plant/Bq dm-3). These were determined as functions of soil clay content, exchangeable K+ status, pH, NH4+ concentration and organic matter content. The effect of time on radiocaesium fixation was described using a previously published double exponential equation, modified for the effect of soil organic matter as a non-fixing adsorbent. The model was parameterised using radiocaesium uptake data from two pot trials conducted separately using ryegrass (Lolium perenne) on mineral soils and bent grass (Agrostis capillaris) on organic soils. This resulted in a significant fit to the observed transfer factor (TF, Bq kg-1 plant/Bq kg-1 whole soil) (P < 0.001, n = 58) and soil solution K+ concentration (mK, mol dm-3) (P < 0.001, n = 58). Without further parameterisation the model was tested against independent radiocaesium uptake data for barley (n = 71) using a database of published and unpublished information covering contamination time periods of 1.2-10 years (transfer factors ranged from 0.001 to 0.1). The model accounted for 52% (n = 71, P < 0.001) of the observed variation in log transfer factor.

Evaluating a free ion activity model applied to metal uptake by Lolium perenne L. grown in contaminated soils.

We investigated several formulations of the ‘free ion activity model’ (FIAM) as a means of describing plant uptake of soil Cd and Zn from contaminated soils. Lolium perenne was grown on a range of urban and metal-spiked agricultural soils selected to provide a wide range of Cd and Zn concentrations, pH values and other physico-chemical properties. Plants were grown under controlled conditions and above-ground biomass was harvested at regular intervals. Concentrations of Cd and Zn in the grass were compared with estimates of metal ‘capacity’ (total or radio-labile metal content in the soil) and ‘intensity’ (metal concentration in the soil solution or free divalent ion activity). The results suggested that ‘capacity’ terms alone were poor predictors of plant metal uptake (r2 values between 0.001 and 0.43), while metal ion ‘intensity’ provided quite reasonable predictions of the variation observed for several harvests of the grass (r2=0.60–0.87). Soil solution-to-plant transfer factors were highly pH-dependent which may suggest significant competition between trace metals and protons for sorption sites on roots. However, resolution of this question was confounded because of the strong co-variance between pH and p(M2+) in the soil pore water. Thus the influence of pH could not be separated from the effect of changing metal ion activity on uptake rate. Other possible effects on metal uptake such as dilution from increased biomass during growth and competition for uptake between different metal ions (Zn vs. Cd), or with Ca2+, appeared to play very minor roles in determining bioavailability. Several formulations of the FIAM failed to provide a consistently superior prediction of metal uptake when compared to purely empirical regression with pH and p(M2+) within the range of the data used to parameterise the models.

Is my model too complex? Evaluating model formulation using model reduction

While mechanistic models tend to be detailed, they are less detailed than the real systems they seek to describe, so judgements are being made about the appropriate level of detail within the process of model development. These judgements are difficult to test, consequently it is easy for models to become over-parameterised, potentially increasing uncertainty in predictions. The work we describe is a step towards addressing these difficulties. We propose and implement a method which explores a family of simpler models obtained by replacing model variables with constants (model reduction by variable replacement). The procedure iteratively searches the simpler model formulations and compares models in terms of their ability to predict observed data, evaluated within a Bayesian framework. The results can be summarised as posterior model probabilities and replacement probabilities for individual variables which lend themselves to mechanistic interpretation. This provides powerful diagnostic information to support model development, and can identify areas of model over-parameterisation with implications for interpretation of model results. We present the application of the method to 3 example models. In each case reduced models are identified which outperform the original full model in terms of comparisons to observations, suggesting some over-parameterisation has occurred during model development. We argue that the proposed approach is relevant to anyone involved in the development or use of process based mathematical models, especially those where understanding is encoded via empirically based relationships.

Technical assessment and evaluation of environmental models and software

This letter details the collective views of a number of independent researchers on the technical assessment and evaluation of environmental models and software. The purpose is to stimulate debate and initiate action that leads to an improved quality of model development and evaluation, so increasing the capacity for models to have positive outcomes from their use. As such, we emphasize the relationship between the model evaluation process and credibility with stakeholders (including funding agencies) with a view to ensure continued support for modelling efforts.Many journals, including EM&S, publish the results of environmental modelling studies and must judge the work and the submitted papers based solely on the material that the authors have chosen to present and on how they present it. There is considerable variation in how this is done with the consequent risk of considerable variation in the quality and usefulness of the resulting publication. Part of the problem is that the review process is reactive, responding to the submitted manuscript. In this letter, we attempt to be proactive and give guidelines for researchers, authors and reviewers as to what constitutes best practice in presenting environmental modelling results. This is a unique contribution to the organisation and practice of model-based research and the communication of its results that will benefit the entire environmental modelling community. For a start, our view is that the community of environmental modellers should have a common vision of minimum standards that an environmental model must meet. A common vision of what a good model should be is expressed in various guidelines on Good Modelling Practice. The guidelines prompt modellers to codify their practice and to be more rigorous in their model testing. Our statement within this letter deals with another aspect of the issue - it prompts professional journals to codify the peer-review process. Introducing a more formalized approach to peer-review may discourage reviewers from accepting invitations to review given the additional time and labour requirements. The burden of proving model credibility is thus shifted to the authors. Here we discuss how to reduce this burden by selecting realistic evaluation criteria and conclude by advocating the use of standardized evaluation tools as this is a key issue that needs to be tackled.

Three‐dimensional quantification of soil hydraulic properties using X‐ray Computed Tomography and image‐based modeling

We demonstrate the application of a high-resolution X-ray Computed Tomography (CT) method to quantify water distribution in soil pores under successive reductive drying. We focus on the wet end of the water release characteristic (WRC) (0 to −75 kPa) to investigate changes in soil water distribution in contrasting soil textures (sand and clay) and structures (sieved and field structured) and to determine the impact of soil structure on hydraulic behavior. The 3-D structure of each soil was obtained from the CT images (at a 10 μm resolution). Stokes equations for flow were solved computationally for each measured structure to estimate hydraulic conductivity. The simulated values obtained compared extremely well with the measured saturated hydraulic conductivity values. By considering different sample sizes we were able to identify the smallest possible representative sample size which is required to determine a globally valid hydraulic conductivity.

Urban geochemistry: research strategies to assist risk assessment and remediation of brownfield sites in urban areas.

Urban geochemical maps of Wolverhampton and Nottingham, based on multielement analysis of surface soils, have shown distribution patterns of “total” metals concentrations relating to past and present industrial and domestic land use and transport systems. Several methods have been used to estimate the solubility and potential bioavailability of metals, their mineral forms and potential risks to urban population groups. These include sequential chemical extraction, soil pore water extraction and analysis, mineralogical analysis by scanning electron microscopy, source apportionment by lead isotope analysis and the development of models to predict metal uptake by homegrown vegetables to provide an estimate of risk from metal consumption and exposure. The results from these research strategies have been integrated with a geographical information system (GIS) to provide data for future land-use planning.

Assessing the influence of the rhizosphere on soil hydraulic properties using X-ray computed tomography and numerical modelling

Highlight Using non-destructive imaging techniques and numerical modelling, we quantify differences in hydraulic and structural properties of bulk and rhizosphere soil for sand and clay loam soils.

Kinetics of metal fixation in soils: Measurement and modeling by isotopic dilution

The bioavailability of metal contaminants in soils varies widely, depending on soil characteristics and the source of the contaminant. As a consequence, site-specific risk assessment requires accurate prediction of the bioavailable (or labile) fraction of soil metal. Moreover, metals in soil are subject to time-dependent processes, which affect their bioavailability and thereby complicate the prediction of future risk. The aim of the present study was to describe the development of simple, readily applicable models for the time-dependent changes in lability of Cd and Zn in soils. We present data showing the time-dependent behavior of radiolabile and soil solution concentrations of Cd and Zn during an incubation study over a period of 813 d in 23 diverse soils. The data are used to parameterize candidate models of metal fixation in soils designed to be readily applicable and therefore relevant to risk assessment. We conclude that the final extent of metal fixation increases with pH and generally is greater for Zn than for Cd; however, the rate of fixation is independent of pH and equivalent to a half-time to equilibrium of 29 and 89 d for Cd and Zn, respectively. It is possible that longer-term processes occur, especially for Zn, but these could not be detected in the present study.

The uptake by vegetation of Chernobyl and aged radiocaesium in upland West Cumbria

The uptake into vegetation of radiocaesium originating from the Chernobyl accident and from previous sources was compared at two upland sites in west Cumbria during November/December 1989. Both sites were in an area where restrictions are in place on the movement and slaughter of sheep due to high radiocaesium activities, and were known to have received comparatively high levels of deposition from both the 1957 Windscale accident and weapons fallout. The proportion of Chernobyl derived radiocaesium in the total radiocaesium inventory at each site was estimated using a 134Cs:137Cs ratio of 0–53 in Chernobyl fallout. Aged radiocaesium, mostly present for over 20 years, accounted for 59 ± 2·3 and 44 ± 2·8% (mean ± SE) of the 137Cs deposit at the two sites. Initially, after the Chernobyl accident, the transfer of the recently deposited radiocaesium was reported to be greater than that of aged deposits. However, four years after the accident, the extent of transfer of Chernobyl radiocaesium from the top 4 cm of soil to vegetation is now similar to that of the aged radiocaesium. The similarity in behaviour of Chernobyl derived and aged radiocaesium suggests that future reductions in radiocaesium levels in vegetation, and therefore in sheep, will be slow. The total deposit, measured per square metre down to bedrock or 40 cm. of aged radiocaesium was less available for plant uptake than that from Chernobyl. This is because a greater proportion of the earlier deposit has migrated further down the soil profile. The movement of Chernobyl radiocaesium down the soil profile and its radioactive decay will be the two major factors which contribute to its decline in vegetation and hence sheep.