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Uranium may pose a hazard to ecosystems and human health due to its chemotoxic and radiotoxic properties. The long half-life of many U isotopes and their ability to migrate raise concerns over disposal of radioactive wastes. This work examines the long-term U bioavailability in aerobic soils following direct deposition or transport to the surface and addresses two questions: (i) to what extent do soil properties control the kinetics of U speciation changes in soils and (ii) over what experimental timescales must U reaction kinetics be measured to reliably predict long-term of impact in the terrestrial environment? Soil microcosms spiked with soluble uranyl were incubated for 1.7 years. Changes in U VI fractionation were periodically monitored by soil extractions and isotopic dilution techniques, shedding light on the binding strength of uranyl onto the solid phase. Uranyl sorption was rapid and strongly buffered by soil Fe oxides, but U VI remained reversibly held and geochemically reactive. The pool of uranyl species able to replenish the soil solution through several equilibrium reactions is substantially larger than might be anticipated from typical chemical extractions and remarkably similar across different soils despite contrasting soil properties. Modelled kinetic parameters indicate that labile U VI declines very slowly, suggesting that the processes and transformations transferring uranyl to an intractable sink progress at a slow rate regardless of soil characteristics. This is of relevance in the context of radioecological assessments, given that soil solution is the key reservoir for plant uptake., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Biosolids application to arable land is a common, and cost-effective, practice but the impact of prolonged disposal remains uncertain. We evaluated the dynamics of potentially toxic elements (PTEs) at a long-established 'dedicated' sewage treatment farm. Soil metal concentrations exceeded regulations governing application of biosolids to non-dedicated arable land. However, measurement of isotopic exchangeability of Ni, Cu, Zn, Cd and Pb demonstrated support for the 'protection hypothesis' in which biosolids constituents help immobilise potential toxic metals (PTMs). Metal concentrations in a maize crop were strongly, and almost equally, correlated with all 'capacity-based' and 'intensity-based' estimates of soil metal bioavailability. This was attributable to high correlations between soil factors controlling bioavailability (organic matter, phosphate etc.) on a site receiving a single source of PTMs. Isotopic analysis of the maize crop suggested contributions to foliar Pb from soil dust originating from neighbouring fields. There was also clear evidence of metal-specific effects of biosolids on soil metal lability. With increasing metal concentrations there was both decreasing lability of Cd and Pb, due to interaction with increasing phosphate concentrations, and increasing lability of Ni, Cu and Zn due to weaker soil binding. Such different responses to prolonged biosolids disposal to arable soil should be considered when setting regulatory limits., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Vegetable fields in and around urban areas in the Kurdistan region of Iraq may have higher than background concentrations of potentially toxic elements (PTEs) from contamination sources including municipal waste disposal and wastewater used for irrigation. The purpose of this study was to assess PTE concentrations in soils and the edible parts of field-grown vegetables to quantify potential health risks to the local population. In this survey, 174 soils and 26 different vegetable and fruit types were sampled from 15 areas around Sulaymaniyah and Halabja cities. Sampling was undertaken from fields in urban, peri-urban and rural locations including sites close to areas of waste disposal. The soils are calcareous (pH 7.67-8.21) and classified as silty loam, sandy or silty clay with organic matter content between 6.62 and 11.4%. Concentrations of PTEs were typically higher in waste disposal areas compared with urban, peri-urban and rural areas. Pollution load indices suggested that agricultural soils near waste disposal sites were contaminated with some trace elements. Potentially toxic element concentrations in vegetables were highly variable. Higher total concentrations of PTEs were measured in vegetables from the waste areas with decreasing concentrations in urban, peri-urban and rural areas. Risks to human health were assessed using hazard quotients (HQ). Vegetable consumption poses no risk for adults, whereas children might be exposed to Ni, As and Cd. Although HQs suggest elevated risk for children from consumption of some vegetables, these risks are likely to be lower when realistic dietary consumption levels are considered.

Wheat farming provides 28.5% of global cereal production. After steady growth in average crop yield from 1950 to 1990, wheat yields have generally stagnated, which prompts the question of whether further improvements are possible. Statistical studies of agronomic parameters such as crop yield have so far exclusively focused on estimating parameters describing the whole of the data, rather than the highest yields specifically. These indicators include the mean or median yield of a crop, or finding the combinations of agronomic traits that are correlated with increasing average yields. In this paper, we take an alternative approach and consider high yields only. We carry out an extreme value analysis of winter wheat yield data collected in England and Wales between 2006 and 2015. This analysis suggests that, under current climate and growing conditions, there is indeed a finite upper bound for winter wheat yield, whose value we estimate to be 17.60 tonnes per hectare. We then refine the analysis for strata defined by either location or level of use of agricultural inputs. We find that there is no statistical evidence for variation of maximal yield depending on location, and neither is there statistical evidence that maximum yield levels are improved by high levels of crop protection and fertilizer use., Competing Interests: The authors declare no competing interests., (© 2020 The Authors.)

Technetium-99 is a significant and long-lived component of spent nuclear fuel relevant to long-term assessments of radioactive waste disposal. Whilst 99 Tc behaviour in poorly aerated environments is well known, the long-term bioavailability in aerobic soils following direct deposition or transport to the surface is less well understood. This work addresses two questions: (i) to what extent do soil properties control 99 Tc kinetics in aerobic soils and (ii) over what experimental timescales must 99 Tc kinetics be measured to make reliable long-term predictions of impact in the terrestrial environment? Soil microcosms spiked with 99 TcO 4 - were incubated for 2.5 years and 99 Tc transformations were periodically monitored by a sequential extraction, which enabled quantification of the reaction kinetics. Reduction in soluble 99 Tc was slow and followed a double exponential kinetic model including a fast component enhanced by low pH, a slow component controlled by pH and organic matter, and a persistently soluble 99 Tc fraction. Complexation with soil humus was key to the progressive immobilisation of 99 Tc. Evidence for slow transfer to an unidentified 'sink' was found, with estimated decadal timeframes. Our data suggest that short-term experiments may not reliably predict long-term 99 Tc solubility in soils with low to moderate organic matter contents., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 The Authors. Published by Elsevier B.V. All rights reserved.)

Assessing the reactions of iodine (I) in soil is critical to evaluate radioiodine exposure and understand soil-to-crop transfer rates. Our mechanistic understanding has been constrained by method limitations in assessing the dynamic interactions of iodine between soil solution and soil solid phase over short periods (hours). We use microdialysis to passively extract soil solution spiked with radioiodine ( 129 I - and 129 IO 3 - ) to monitor short-term (≤40 h) in situ fixation and speciation changes. We observed greater instantaneous adsorption of 129 IO 3 - compared to 129 I - in all soils and the complete reduction of 129 IO 3 - to 129 I - within 5 h of addition. Loss of 129 I from solution was extremely rapid; the average half-lives of 129 I - and 129 IO 3 - in soil solution were 4.06 and 10.03 h, respectively. We detected the presence of soluble organically bound iodine (org- 129 I) with a low molecular weight (MW) range (0.5-5 kDa) in all soils and a slower (20-40 h) time-dependent formation of larger MW org-I compounds (12-18 kDa) in some samples. This study highlights the very short window of immediate availability in which I from rainfall or irrigation remains in soil solution and available to crops, thus presenting significant challenges to phytofortification strategies in soil-based production systems.

To understand the dynamic mechanisms governing soil-to-plant transfer of selenium (Se), technetium-99 ( 99 Tc) and iodine (I), a pot experiment was undertaken using 30 contrasting soils after spiking with 77 Se, 99 Tc and 129 I, and incubating for 2.5 years. Two grass species (Agrostis capillaris and Lolium perenne) were grown under controlled conditions for 4 months with 3 cuts at approximately monthly intervals. Native (soil-derived) 78 Se and 127 I, as well as spiked 77 Se, 99 Tc and 129 I, were assayed in soil and plants by ICP-MS. The grasses exhibited similar behaviour with respect to uptake of all three elements. The greatest uptake observed was for 99 Tc, followed by 77 Se, with least uptake of 129 I, reflecting the transformations and interactions with soil of the three isotopes. Unlike soil-derived Se and I, the available pools of 77 Se, 99 Tc and 129 I were substantially depleted by plant uptake across the three cuts with lower concentrations observed in plant tissues in each subsequent cut. Comparison between total plant offtake and various soil species suggested that 77 SeO 4 2- , 99 TcO 4 - and 129 IO 3 - , in soluble and adsorbed fractions were the most likely plant-available species. A greater ratio of 127 I/ 129 I in the soil solid phase compared to the solution phase confirmed incomplete mixing of spiked 129 I with native 127 I in the soil, despite the extended incubation period, leading to poor buffering of the spiked available pools. Compared to traditional expressions of soil-plant transfer factor (TF total ), a transfer factor (TF available ) expressed using volumetric concentrations of speciated 'available' fractions of each element showed little variation with soil properties., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Metal bioavailability and phytotoxicity may be exaggerated when derived from studies based on amending soils with soluble metal salts. It is therefore important to evaluate soil tests for their consistency in estimating plant uptake and phytotoxicity in both field-contaminated and freshly-spiked soils. This study aimed to compare the effects of zinc (Zn) on plant growth in soils (i) recently spiked with soluble Zn and (ii) historically amended with biosolids. The objective was to reconcile methods for determining bioavailability in both cases by testing a range of 'quantity-based' and 'intensity-based' assays. Soils with a range of Zn concentrations, from an arable farm used for biosolids disposal for over a century, were further amended with Zn added in solution, and were incubated for one month prior to planting with barley seeds in a glasshouse pot trial. The majority (67-90%) of the added Zn remained isotopically exchangeable after 60 days. Zinc in the solution phase of a soil suspension was present mainly as free Zn 2+ ions. Cadmium bioaccumulation factors were inversely proportional to Zn concentration in the soil solution confirming that greater Zn availability suppressed Cd uptake by plants. Measurements of soil Zn 'quantities' (total, EDTA-extractable and isotopically exchangeable) and 'intensity' (solution concentration and free ion activity) were correlated with Zn uptake and toxicity by barley plants. Correlations using Zn intensity were much stronger than those using quantity-based measurements. The free Zn 2+ ion activity appears to be a consistent driver for plant uptake and phytotoxic response for both metal-spiked soils and historically contaminated soils. Surprisingly, soil Zn accumulation of up to 100 times the current regulations for normal arable land only produced a mild toxic response suggesting that constituents in biosolids (e.g. organic matter and phosphates) strongly restrict metal bioavailability., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Iodine is an essential micronutrient for human health; phytofortification is a means of improving humans' nutritional iodine status. However, knowledge of iodine uptake and translocation in plants remains limited. In this paper, plant uptake mechanisms were assessed in short-term experiments (24 h) using labelled radioisotopes; the speciation of iodine present in apoplastic and symplastic root solutions was determined by (HPLC)-ICP-QQQ-MS. Iodine storage was investigated in spinach (Spinacia oleracea L.) treated with I - and IO 3 - . Finally, translocation through the phloem to younger leaves was also investigated using a radioiodine ( 129 I - ) label. During uptake, spinach roots demonstrated the ability to reduce IO 3 - to I - . Once absorbed, iodine was present as org-I or I - with significantly greater concentrations in the apoplast than the symplast. Plants were shown to absorb similar concentrations of iodine applied as I - or IO 3 - , via the roots, grown in an inert growth substrate. We found that whilst leaves were capable of absorbing radioactively labelled iodine applied to a single leaf, less than 2% was transferred through the phloem to younger leaves. In this paper, we show that iodine uptake is predominantly passive (approximately two-thirds of total uptake); however, I - can be absorbed actively through the symplast. Spinach leaves can absorb iodine via foliar fertilisation, but translocation is severely limited. As such, foliar application is unlikely to significantly increase the iodine content, via phloem translocation, of fruits, grains or tubers.

Element cycling in the terrestrial environment is heavily reliant upon processes that occur in soil solution. Here we present the first application of microdialysis to sample iodine from soil solution. In comparison to conventional soil solution extraction methods such as Rhizon™ samplers, centrifugation, and high-pressure squeezing, microdialysis can passively sample dissolved compounds from soil solution without altering the in-situ speciation of trace elements at realistic soil moisture conditions. In order to assess the suitability of microdialysis for sampling iodine, the permeability factors and effect of perfusion flowrate on I - and IO 3 - recovery was examined in stirred solutions. Furthermore, microdialysis was used to sample native soluble iodine at a range of water contents and iodine-enriched soils to investigate iodine soil dynamics. Total iodine concentrations were measured using ICP-MS. Inorganic species and the molecular weight distribution of organically bound iodine were determined by anion exchange and size exclusion chromatography (SEC) coupled to an ICP-MS, respectively. The most effective recovery rates in stirred solution were observed with the slowest perfusion flowrate yielding 66.2 ± 7.1 and 70.5 ± 7.1% for I - and IO 3 - , respectively. Microdialysis was proven to be capable of sampling dissolved iodine from the soil solution, which accounted for <2.5% of the total soil iodine and speciation followed the sequence: organic-I > I -  > IO 3 - . The use of SEC coupled to (i) UV and (ii) ICP-MS analysis provided detail regarding the molecular weight distribution of dissolved org-I compounds. Dissolved org-I was detected with approximate molecular weights between 0.1 and 4.5 kDa. The results in this study show that microdialysis is a suitable technique for sampling dissolved iodine species from soils maintained at realistic moisture contents. In addition, inorganic iodine added to soils was predominately bound with relatively low molecular weight (<4.5 kDa) soluble organic matter., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

Numerous radioecological models have been developed to predict radionuclides transfer from contaminated soils to the food chain, which is an essential step in preparing and responding to nuclear emergencies. However, the lessons learned from applying these models to predict radiocaesium (RCs) soil-to-plant transfer following the Fukushima accident in 2011 renewed interest in RCs transfer modelling. To help guide and prioritise further research in relation to modelling RCs transfer in terrestrial environments, we reviewed existing models focussing on transfer to food crops and animal fodders. To facilitate the review process, we categorised existing RCs soil-to-plant transfer models into empirical, semi-mechanistic and mechanistic, though several models cross the boundaries between these categories. The empirical approach predicts RCs transfer to plants based on total RCs concentration in soil and an empirical transfer factor. The semi-mechanistic approach takes into account the influence of soil characteristics such as clay and exchangeable potassium content on RCs transfer. It also uses 'bioavailable' rather than total RCs in soil. The mechanistic approach considers the physical and chemical processes that control RCs distribution and uptake in soil-plant systems including transport in the root zone and root absorption kinetics. Each of these modelling approaches has its advantages and disadvantages. The empirical approach is simple and requires two inputs, but it is often associated with considerably uncertainty due to the large variability in the transfer factor. The semi-mechanistic approach factorises more soil and plant parameters than the empirical approach; therefore, it is applicable to a wider range of environmental conditions. The mechanistic approach is instrumental in understanding RCs mobility and transfer in soil-plant systems; it also helps to identify influential soil and plant parameters. However, the comlexity and the large amount of specific parameters make this approach impractical for nuclear emergency preparedness and response purposes. We propose that the semi-mechanistic approach is sufficiently robust and practical, hence more fit for the purpose of planning and responding to nuclear emergencies compared with the empirical and mechanistic approaches. We recommend further work to extend the applicability of the semi-mechanistic approach to a wide range of plants and soils., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Following nuclear releases to the environment, 137 Cs (half-life 30 years) is a long-term contaminant of many ecosystems, including forests. We recently sampled soils under pine forests in temperate and tropical climates to test the hypothesis that migration of 137 Cs, 50 years after nuclear weapons fallout, is coupled with organic matter (OM) accumulation in these soils. Depth profiles of 137 Cs, naturally-occurring 210 Pb and weapons-derived 241 Am were measured. After 50 years, migration of 137 Cs into the temperate and tropical soils is limited to half-depths of 7-8 cm and 2-3 cm, respectively. At both locations, most 137 Cs is associated with OM that accumulated from the early to mid-1960s. Illite, which immobilises radiocaesium, was undetectable by X-ray diffraction in the layer of peak 137 Cs accumulation in the temperate forest soil, but apparent in the zone of peak concentration in the tropical soil. Data indicate that long-term (50 year) fate of 137 Cs in organic-rich, temperate forest soil is coupled with OM accumulation; fixation of 137 Cs by illite is more important in the tropical forest soil where OM is rapidly decomposed. Models of long-term radiocaesium migration in forest soils should explicitly account for the role of OM, especially when considering forests under contrasting climatic regimes., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Iodine is an essential micronutrient for human health: insufficient intake can have multiple effects on development and growth, affecting approximately 1.9 billion people worldwide. Previous reviews have focussed on iodine analysis in environmental and biological samples, however, no such review exists for the determination of iodine fractionation and speciation in soils. This article reviews the geodynamics of both stable 127 I and the long-lived isotope 129 I (t 1/2 = 15.7 million years), alongside the analytical methods for determining iodine concentrations in soils, including consideration of sample preparation. The ability to measure total iodine concentration in soils has developed significantly from rudimentary spectrophotometric analysis methods to inductively coupled plasma mass spectrometry (ICP-MS). Analysis with ICP-MS has been reported as the best method for determining iodine concentrations in a range of environmental samples and soils due to developments in extraction procedures and sensitivity, with extremely good detection limits typically <μg L -1 . The ability of ICP-MS to measure iodine and its capabilities to couple on-line separation tools has the significance to develop the understanding of iodine geodynamics. In addition, nuclear-related analysis and recent synchrotron light source analysis are discussed.

Spatially averaged models of root-soil interactions are often used to calculate plant water uptake. Using a combination of X-ray computed tomography (CT) and image-based modelling, we tested the accuracy of this spatial averaging by directly calculating plant water uptake for young wheat plants in two soil types. The root system was imaged using X-ray CT at 2, 4, 6, 8 and 12 d after transplanting. The roots were segmented using semi-automated root tracking for speed and reproducibility. The segmented geometries were converted to a mesh suitable for the numerical solution of Richards' equation. Richards' equation was parameterized using existing pore scale studies of soil hydraulic properties in the rhizosphere of wheat plants. Image-based modelling allows the spatial distribution of water around the root to be visualized and the fluxes into the root to be calculated. By comparing the results obtained through image-based modelling to spatially averaged models, the impact of root architecture and geometry in water uptake was quantified. We observed that the spatially averaged models performed well in comparison to the image-based models with <2% difference in uptake. However, the spatial averaging loses important information regarding the spatial distribution of water near the root system., (© 2017 John Wiley & Sons Ltd.)

In this study, the effects of incubation time and the method of soil solution extraction and filtration on the empirical distribution coefficient (K d ) obtained by de-sorbing indigenous selenium (Se) and iodine (I) from arable and woodland soils under temperate conditions were investigated. Incubation time had a significant soil- and element-dependent effect on the K d values, which tended to decrease with the incubation time. Generally, a four-week period was sufficient for the desorption K d value to stabilise. Concurrent solubilisation of soil organic matter (OM) and release of organically-bound Se and I was probably responsible for the observed decrease in K d with time. This contrasts with the conventional view of OM as a sink for Se and I in soils. Selenium and I K d values were not significantly affected by the method of soil solution extraction and filtration. The results suggest that incubation time is a key criterion when selecting Se and I K d values from the literature for risk assessments. Values derived from desorption of indigenous soil Se and I might be most appropriate for long-term assessments since they reflect the quasi-equilibrium state of their partitioning in soils., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The disposal of biosolids poses a major environmental and economic problem. Agricultural use is generally regarded as the best means of disposal. However, its impact on soil ecosystems remains uncertain. Biosolids can improve soil properties by supplying nutrients and increasing organic matter content but there is also a potentially detrimental effect arising from the introduction of heavy metals into soils. To assess the balance between these competing effects on soil health, we investigated soil bacterial and fungal diversity and community structure at a site that has been dedicated to the disposal of sewage sludge for over 100 years. Terminal restriction fragment length polymorphism (T-RFLP) was used to characterize the soil microbial communities. The most important contaminants at the site were Ni, Cu, Zn, Cd, and Pb. Concentrations were highly correlated and Zn concentration was adopted as a good indicator of the overall (historical) biosolids loading. A biosolids loading, equivalent to 700-1000 mg kg -1 Zn appeared to be optimal for maximum bacterial and fungal diversity. This markedly exceeds the maximum soil Zn concentration of 300 mg kg -1 permitted under the current UK Sludge (use in agriculture) Regulations. Redundancy analysis (RDA) suggested that the soil microbial communities had been altered in response to the accumulation of trace metals, especially Zn, Cd, and Cu. We believe this is the first time the trade-off between positive and negative effects of long term (>100 years) biosolids disposal on soil microorganisms have been observed in the field situation., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Substitution of a species or cultivar with higher uptake of an element by one with lower uptake has been proposed as a remediation strategy following accidental releases of radioactivity. However, despite the importance of pasture systems for radiological dose, species/cultivar substitution has not been thoroughly investigated for forage grasses. 397 cultivars from four forage grass species; hybrid ryegrass (Lolium perenne L. x Lolium multiflorum Lam.), perennial ryegrass (Lolium perenne L.), Italian ryegrass (Lolium multiflorum Lam.) and tall fescue (Festuca arundinacea Shreb.); were sampled from 19 field-based breeding experiments in Aberystwyth and Edinburgh (UK) in spring 2013 and analysed for caesium (Cs) and strontium (Sr) concentrations. In order to calculate concentration ratios (CRs; the concentration of an element in a plant in relation to the concentration in the soil), soils from the experiments were also analysed to calculate extractable concentrations of Cs and Sr. To test if cultivars have consistently low Cs and Sr concentration ratios, 17 hybrid ryegrass cultivars were sampled from both sites again in summer 2013 and spring and summer 2014. Tall fescue cultivars had lower Cs and Sr CRs than the other species. Three of the selected 17 hybrid ryegrass cultivars had consistently low Cs CRs, two had consistently low Sr CRs and one had consistently low Cs and Sr CRs. Cultivar substitution could reduce Cs CRs by up to 14-fold and Sr CRs by 4-fold in hybrid ryegrass. The identification of species and cultivars with consistently low CRs suggests that species or cultivar substitution could be an effective remediation strategy for contaminated areas.

Radiocaesium and radiostrontium enter the foodchain primarily via plant root uptake. Selecting varieties of crop that display low accumulation of these radionuclides has been suggested as an economically and socially acceptable remediation strategy for radiologically contaminated land. However, there is insufficient information available to assess the feasibility of this remediation approach. This paper presents a comprehensive literature-based evaluation of inter-varietal variation in accumulation of Cs and Sr in crop plants. Thirty-seven publications studying 27 plant species were identified as appropriate for these analyses. Inter-varietal variation was expressed at the ratio of the maximum to minimum observed concentrations for a given crop species and element and ranged from 1.0 to 6.3 and from 1.0 to 4.5 for Cs and Sr respectively. This variation suggests that exploitation of inter-varietal variation could be used in some crop species to reduce the transfer of these radionuclides to a similar extent to existing remediation strategies. Low-Sr accumulating varieties were also found to have lower concentrations of Ca, whereas low Cs-accumulating varieties were not shown to have low K accumulation. Concentrations of Cs and Sr in plants were not related, suggesting that finding varieties displaying low accumulation of both Sr and Cs may not be feasible. Varietal selection could be an effective remediation strategy, and could be used in combination with other existing methods, such as fertilisation and ploughing. However, a thorough investigation of species contributing the most to ingestion doses is recommended to fully determine the feasibility of varietal selection as a remediation strategy. The reproducibility of inter-varietal variation between sites and growing seasons should be the focus of future research., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

This research investigates the long-term kinetics of Cd(2+) sorption and desorption by calcium-exchanged clinoptilolite (CaCpt) and Y-type (CaY) zeolite using isotopic exchange with (109)Cd while maintaining pH at circumneutral values. The effects of Si/Al ratio and crystal structure of these zeolitic materials on intracrystalline transport of Cd are discussed. A first-order kinetic model was developed to describe the progressive transfer of Cd(2+) to a less reactive form within the zeolite structure, following initial sorption and subsequent desorption of Cd subject to different initial contact times. The kinetic model differentiates between two forms of sorbed Cd(2+) designated 'labile' and 'non-labile' in which the labile form is in immediate equilibrium with the free Cd(2+) ion activity in solution. A model combining diffusion and first-order kinetics for cation exchange was also employed to determine Cd(2+) diffusivity and intracrystalline exchange rates in CaY and CaCpt. The efficiency of Permeable Reactive Barriers (PRBs) containing zeolitic materials in protecting water systems against lateral flow of metal-contaminated leachate was simulated for three contrasting zeolites. The slow transfer of Cd between labile and non-labile forms was particularly important in moderating high concentration pulses of Cd traversing the PRB. In addition, the reversibility of Cd fixation effectively restored the sorption capability of the zeolite through slow leakage to drainage water., (Copyright © 2010 Elsevier B.V. All rights reserved.)