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Abstract: Natural attenuation processes resulting from the afforestation of some U-waste rock piles have the potential to limit the linkage of radioelements and other trace pollutants, thereby minimizing exposure risks. We determined the evolution of pH and organic matter and compared the 226Ra and Ca extractability in pyrite-containing mining debris which was revegetated 35 years ago with Scots pine. Oxidation of sulphidic minerals remaining in the substrate appeared to dominate over acidification processes due to vegetation inputs and litter decomposition. The accumulation of organic matter in forest floor had a negligible effect on the 226Ra upward recycling compared to the migration losses observed mainly from decarbonatation of the surface mining debris. 226Ra was overall less soluble than Ca in the soil profile but NH4Ac-pH 5 had the capacity to extract a 226Ra fraction of 31.1–41.5%, i.e. at least twice as much as for Ca. In deeper layers, a majority of both Ca and 226Ra were extractable from the same non-specific adsorption pool, which mainly involved carbonate. In the upper acidified layer, the incorporation of organic matter had no effect on 226Ra extractability. A further specific adsorption pool for 226Ra was attributed to the formation of sparingly soluble Fe–Al oxyhydroxides. However, that specific 226Ra-bearing phase was readily dissolved in NH4Ac-pH 5, indicating a relatively reversibility of the precipitation reaction of 226Ra with amorphous oxide. Trees are effective at reducing hydrological release of many pollutants but in the mining debris studied, four decades of pine growth did not significantly promote 226Ra remediation in the soil. [Copyright &y& Elsevier]

The 2011 nuclear accident at Japan's Fukushima Daiichi Nuclear Power Plant (FDNPP) prompted inquiries about the long-term transfer of Cesium-137 ( 137 Cs) from soil to agricultural plants. In this context, numerical modeling is particularly useful for the long-term evaluation of the consequences of agroecosystem contamination. Agricultural practices, such as tillage and cover cropping, play key roles in 137 Cs recycling in agroecosystems. In this study, we used 10-year monitoring data to develop a dynamic model to predict 137 Cs redistribution (via uptake, litterfall, translocation, and percolation) under different tillage (no-tillage, NT; rotary cultivation, RC; moldboard plow, MP) and cover crop (rye; hairy vetch; fallow weed) treatments. The verification exercise and assessment results indicated the model's reliability, as the temporal dynamics of predicted values agreed with observed values. Tillage significantly influenced the 137 Cs distribution in soil, thereby decreasing plant uptake of 137 Cs, whereas cover crop exerted a minimal effect on 137 Cs cycling. Furthermore, while the 137 Cs concentrations in soybean grain under RC and NT treatments were comparable 62 years after the FDNPP accident, the concentration under MP treatment remained consistently the lowest. Despite natural decay being the main cause of the decreased global 137 Cs level in the agroecosystem, with minimal losses from percolation to deeper soil layers and soybean harvesting, adopting an appropriate tillage practice was shown to promote a long-term reduction of 137 Cs concentration in crops. Finally, to improve the model's accuracy, further research should consider incorporating the effects of soil properties and extreme weather events on 137 Cs flow into the model, as these factors are essential for realizing improved agroecosystem predictions., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Masakazu Komatsuzaki reports financial support was provided by Ibaraki University. Masakazu Komatsuzaki reports financial support was provided by Japan Atomic Energy Agency. Masakazu Komatsuzaki reports financial support was provided by Tojuro Iijima Foundation for Food Science and Technology. Yves Thiry reports financial support was provided by French National Research Agency., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Accidental release of radionuclides caused by nuclear accidents like those in Fukushima and Chernobyl can result in pulses of radioactivity entering the forest environment. Due to intense recycling in the forest, equilibrium between radioactivity concentrations in trees and in soil may not be reached during the period of short-term radionuclide transport following the accident. Another question arises as to whether the equilibrium hypothesis using empirical concentration ratios (CRs) can be applied to the long-term period. Using two atmospheric 137 Cs fallout scenarios in the Fukushima and Chernobyl sites, this study investigated whether the CR approach could provide conservative predictions of 137 Cs levels in trees following 137 Cs fallout events by comparing predictions from the CR approach using data gathered for trees by the IAEA to those from dynamic transfer models and actual measured data. The inter-comparisons also aimed to investigate whether the CR approach could account for the variability of 137 Cs levels across different tree organs. The results showed that caution may be necessary when using the CR approach, which relies on the IAEA dataset, to estimate 137 Cs accumulation in forest trees in the short - and long term following atmospheric 137 Cs fallout events. A calculation by TRIPS 2.0 demonstrated the importance of considering the distribution within tree organs for in-depth analysis of radiological impact of forest trees. Our findings suggest that it may be preferable to use CR values based on site-specific data rather than generic data collected from various sites. This is particularly relevant when studying the sites where the bioavailability of 137 Cs for trees and thus possible exposures are higher. This study also showed that dynamic modeling approaches could offer an alternative means of estimating CR values of the entire tree or specific tree organs in situations where empirically derived values are not available., 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 © 2023 Elsevier B.V. All rights reserved.)

Differences in the source and behaviour of 129 I compared to 127 I isotopes have been described for a variety of surface environments, but little is known about the cycling rates of each isotope in terrestrial ecosystems. We developed a compartment model of the iodine cycle in a forest ecosystem, with a labile and non-labile pool to simplify the complex fate of iodine in the forest floor and soil. Simulations were performed using atmospheric 127 I and 129 I inputs for sites differing in climate, vegetation, and soil. In general, considering dry deposition in addition to wet deposition improved model simulations. Model results support the view that soil is the sink for atmospheric iodine deposited in forest ecosystems, while tree vegetation has little influence on long-term iodine budgets. Modelling also showed that iodine cycling reaches equilibrium after a period of about 5000 years, mainly due to a gradual incorporation of iodine into the bulk stabilised soil organic matter. At steady state, this pool of non-labile iodine in soil can retain about 20% of total deposition with a mean residence time of 900 years, while the labile iodine pool is renewed after 90 years. The proportions of modern anthropogenic 129 I in each modelled pool reflect those of stable 127 I at least several decades after input to the forest; this result explains why isotopic disequilibrium is common in field data analysis. Volatilisation plays a central role in regulating iodine storage in soil and, therefore, its residence time, while drainage is a minor export pathway, except at some calcareous sites. Dynamic modelling has been particularly helpful for gaining insight into the long-term response of iodine partitioning to continuous, single or even varying deposition. Our modelling study suggested that better estimates of dry deposition of atmospheric iodine, weathering of parent rock, and volatilisation of the deposited iodine from soil and vegetation will be required for reliable predictions of iodine cycling in specific forests, because these processes remain insufficiently explored., Competing Interests: Declaration of competing interest There is no conflict of interest., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Storage of selenium and iodine can greatly vary between forest ecosystems, but the influence of tree species on partitioning and recycling of those elements remains elusive. In this study, contents of Se and I were measured in tree compartments, litterfall, humus, and soil horizons in monospecific stands of Douglas fir, pine, spruce, beech, and oak under identical climatic and edaphic conditions. The cycle of each element was characterized in terms of stocks and fluxes. Lowest concentrations were in wood (Se: 8-13 μg kg -1 ; I: <16.5 μg kg -1 ). Senescing organs had higher Se and I content, than the living parts of trees due to direct exposure to atmospheric deposition, with some variation between coniferous and deciduous trees. For all stands, low amounts of Se and I were involved in biological cycle as reflected by low root uptake. In humus, the enrichment of elements greatly increased with the stage of organic matter (OM) degradation with average factors of 10 and 20 for Se and I. OM degradation and element persistence in humus was influenced by tree species. Deciduous trees, with low biomass, and fast degradation of OM stored less Se and I in humus compared to fir and spruce with high humus biomass. Interestingly, tree species did not affect soil reserves of Se and I. Concentration ranges were 331-690 μg Se kg -1 and 4.3-14.5 mg I kg -1 . However, the divergent vertical profiles of the elements in the soil column indicated greater mobility of I. Selenium concentrations regularly decreased with depth in correlation with OM and Fe oxides content. For iodine, the maximum iodine concentration at a soil depth of 15 to 35 cm was caused by a parallel precipitation/sorption behavior of aluminium and organic iodine dissolved in the topsoil., 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 © 2021 Elsevier B.V. All rights reserved.)

The levels of natural organic chlorine (Cl org ) typically exceed levels of chloride in most soils and is therefore clearly of high importance for continental chlorine cycling. The high spatial variability raises questions on soil organic matter (SOM) chlorination rates among topsoils with different types of organic matter. We measured Cl org formation rates along depth profiles in six French temperate soils with similar Cl deposition using 36 Cl tracer experiments. Three forest sites with different humus types and soils from grassland and arable land were studied. The highest specific chlorination rates (fraction of chlorine pool transformed to Cl org per time unit) among the forest soils were found in the humus layers. Comparing the forest sites, specific chlorination was highest in mull-type humus, characterized by high microbial activity and fast degradation of the organic matter. Considering non-humus soil layers, grassland and forest soils had similar specific chlorination rates in the uppermost layer (0-10 cm below humus layer). Below this depth the specific chlorination rate decreased slightly in forests, and drastically in the grassland soil. The agricultural soil exhibited the lowest specific chlorination rates, similar along the depth profile. Across all sites, specific chlorination rates were correlated with soil moisture and in combination with the patterns on organic matter types, the results suggest an extensive Cl cycling where humus types and soil moisture provided best conditions for microbial activity. Cl org accumulation and theoretical residence times were not clearly linked to chlorination rates. This indicates intensive Cl cycling between organic and inorganic forms in forest humus layers, regulated by humic matter reactivity and soil moisture, while long-term Cl org accumulation seems more linked with overall deep soil organic carbon stabilization. Thus, humus types and factors affecting soil carbon storage, including vegetation land use, could be used as indicators of potential Cl org formation and accumulation in soils., 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 © 2021. Published by Elsevier B.V.)

Selenium is a trace element and an essential nutrient. Its long-lived radioisotope, selenium 79 is of potential radio-ecological concern in surface environment of deep geological repository for high-level radioactive waste. In this study, the influence of environmental, climatic and geochemical conditions on stable Se (as a surrogate of 79 Se) accumulation was statistically assessed (PCA analysis, Kruskall-Wallis and Spearman tests) based on the analysis of its concentration in litterfall, humus, and soil samples collected at 51 forest sites located in France. Selenium concentrations were in the ranges: 22-369, 57-1608 and 25-1222 μg kg -1 respectively in litterfall, humus, and soil. The proximity of the ocean and oceanic climate promoted Se enrichment of litterfall, likely due to a significant reaction of wet deposits with forest canopy. Se content was enhanced by humification (up to 6 times) suggesting that Se concentrations in humus were affected by atmospheric inputs. Selenium stock in humus decreased in the order of decreasing humus biomass and increasing turnover of organic matter: mor > moder > mull. Positive correlations between Se content and geochemical parameters such as organic carbon content, total Al and total Fe confirmed the important role of organic matter (OM) and mineral Fe/Al oxides in Se retention in soils., 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 © 2021. Published by Elsevier B.V.)

It is unclear to what extent chlorine (Cl) and its long-lived isotope 36 Cl are recycled in different terrestrial environments in response to time-variable inputs. A new version of a dynamic compartment model was developed to examine the transformation and transfer processes influencing the partitioning and persistence of both Cl and 36 Cl in forest ecosystems. The model's performance was evaluated by comparing simulations and field observations of scenarios of stable Cl atmospheric deposition and of global 36 Cl fallout. The model reproduced Cl storage in soil reasonably well, despite wide heterogeneity in environmental conditions and atmospheric deposits. Sensitivity analysis confirmed that the natural production of organochlorine in soil plays a major role in Cl build-up and affects long-term Cl dynamics. The timeframe required for the soil organochlorine pool to reach equilibrium in a steady-state system was several thousands of years. Interestingly, root uptake flux, a predominant pathway of the inorganic cycle, was found to affect both inorganic and organic pools in soil, highlighting the importance of plant-soil interactions in Cl dynamics. Model outputs agreed well with local 36 Cl measurements, and demonstrated that 90% of the 36 Cl found in soil may have come from bomb-test fallout. The pattern of estimated 36 Cl/Cl ratios showed that soil 36 Cl was not in equilibrium with 36 Cl levels in rain input in the post-bomb period. Complete recovery of a natural isotopic ratio in drainage water will need a time close to the residence time of organic 36 Cl in soil: i.e., 800 years. A simple dynamic model concept was found to be suitable to illustrate the plant-soil interactions combining both the inorganic and organic Cl cycles acting over different time scales., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Radioiodine is of health concerns in case of nuclear events. Possible pathways and rates of flow are essential information for risk assessment. Forest ecosystems could influence the global cycle of long-lived radioiodine isotope ( 129 I) with transfer processes similar to stable isotope ( 127 I). Understanding iodine cycling in forest involves study of the ecosystem as a whole. In this context, we determined the 127 I contents and distribution in soil, tree compartments and atmospheric inputs during a three years in situ monitoring of a temperate beech forest stand. The iodine cycle was first characterized in terms of stocks by measuring its concentrations in: tree, litterfall, humus, soil, rainfall, throughfall, stemflow and soil solutions. Main annual fluxes (requirement, uptake and internal transfers) and forest input-output budget were also estimated using conceptual model calculations. Our findings show that: (i) soil is the main I reservoir accounting for about 99.9% of ecosystem total stock; (ii) iodine uptake by tree represents a minor fraction of the available pool in soil (<0.2%); (iii) iodine allocation between tree compartments involves low immobilization in wood and restricted location in the roots; (iv) translocation of excess iodine towards senescing foliage appears as an elimination process for trees, and (v) litterfall is a major pathway in the I biological cycling. In our soil conditions, the input - output budget shows that the ecosystem behaves as a potential source of I for groundwater., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A better understanding of selenium fate in soils at both short and long time scales is mandatory to consolidate risk assessment models relevant for managing both contamination and soil fertilization issues. The purpose of this study was thus to investigate Se retention processes and their kinetics by monitoring time-dependent distribution/speciation changes of both ambient and freshly added Se, in the form of stable enriched selenite-77, over a 2-years field experiment. This study clearly illustrates the complex reactivity of selenium in soil considering three methodologically defined fractions (i.e. soluble, exchangeable, organic). Time-dependent redistribution of Se-77 within solid-phases having different reactivity could be described as a combination of chemical and diffusion controlled processes leading to its stronger retention. Experimental data and their kinetic modeling evidenced that transfer towards less labile bearing phases are controlled by slow processes limiting the overall sorption of Se in soils. These results were used to estimate time needed for (77)Se to reach the distribution of naturally present selenium which may extend up to several decades. Ambient Se speciation accounted for 60% to 100% of unidentified species as function of soil type whereas (77)Se(IV) remained the more abundant species after 2-years field experiment. Modeling Se in the long-term without taking account these slow sorption kinetics would thus result in underestimation of Se retention. When using models based on Kd distribution coefficient, they should be at least reliant on ambient Se which is supposed to be at equilibrium., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Much of the total pool of chlorine (Cl) in soil consists of naturally produced organic chlorine (Clorg). The chlorination of bulk organic matter at substantial rates has been experimentally confirmed in various soil types. The subsequent fates of Clorg are important for ecosystem Cl cycling and residence times. As most previous research into dechlorination in soils has examined either single substances or specific groups of compounds, we lack information about overall bulk dechlorination rates. Here we assessed bulk organic matter chlorination and dechlorination rates in coniferous forest soil based on a radiotracer experiment conducted under various environmental conditions (additional water, labile organic matter, and ammonium nitrate). Experiment results were used to develop a model to estimate specific chlorination (i.e., fraction of Cl(-) transformed to Clorg per time unit) and specific dechlorination (i.e., fraction of Clorg transformed to Cl(-) per time unit) rates. The results indicate that chlorination and dechlorination occurred simultaneously under all tested environmental conditions. Specific chlorination rates ranged from 0.0005 to 0.01 d(-1) and were hampered by nitrogen fertilization but were otherwise similar among the treatments. Specific dechlorination rates were 0.01-0.03d(-1) and were similar among all treatments. This study finds that soil Clorg levels result from a dynamic equilibrium between the chlorination and rapid dechlorination of some Clorg compounds, while another Clorg pool is dechlorinated more slowly. Altogether, this study demonstrates a highly active Cl cycling in soils., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Selenium adsorption onto oxy-hydroxides mainly controls its mobility in volcanic soils, red earths and soils poor in organic matter (OM) while the influence of OM was emphasized in podzol and peat soils. This work aims at deciphering how those solid phases influence ambient Se mobility and speciation under less contrasted conditions in 26 soils spanning extensive ranges of OM (1-32%), Fe/Al oxy-hydroxides (0.3-6.1%) contents and pH (4.0-8.3). The soil collection included agriculture, meadow and forest soils to assess the influence of OM quality as well. Trace concentrations of six ambient Se species (Se(IV), Se(VI) and 4 organo-Se compounds) were analyzed by HPLC-ICP-MS in three extractants (ultrapure water, phosphate and sodium hydroxide) targeting Se associated to different soil phases. The Kd values determined from ultrapure water extraction were higher than those reported in commonly used short-term experiments after Se-spiking. Correlations of ambient Se content and distribution with soil parameters explained this difference by an involvement of slow processes in Se retention in soils. The 26 Kd values determined here for a wide variety of soils thus represent a relevant database for long-term prediction of Se mobility. For soils containing less than 20% OM, ambient Se solubility is primarily controlled by its adsorption onto crystalline oxy-hydroxides. However, OM plays an important role in Se mobility by forming organo-mineral associations that may protect adsorbed Se from leaching and/or create anoxic zones (aggregates) where Se is immobilized after its reduction. Although for the first time, inorganic Se(IV), Se(VI) and organo-Se compounds were simultaneously investigated in a large soil collection, high Se proportions remain unidentified in each soil extract, most probably due to Se incorporation and/or binding to colloidal-sized OM. Variations of environmental factors regulating the extent of OM-mineral associations/aggregation may thus lead to changes in Se mobility and bio-availability., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In a large forested area affected by the Chernobyl radioactive fallout, especially in CIS, the lasting recycling of radiocaesium (137Cs) by the trees is a source of long-term contamination of woody products. The quantitative description of the 137Cs dynamics in contaminated forest is a prerequisite to predictive modelling and further management of such territories. Three even-aged mono-specific Scots pine stands (17, 37 and 57 years old) were selected in a contaminated woodland in southeastern Belarus to constitute an adequate chronosequence. We determined the potassium and radiocaesium annual fluxes involved in the biological cycling in each stand using a well-documented calculation methodology. Qualitatively, 137Cs was shown to be rapidly recycled in trees through the same pathways as K and to redistribute similarly between the tree components. Compared to K, a higher fraction of 137Cs, corresponding to about the half of the annual uptake, is immobilised in perennial organs. With tree development, trunk wood and bark become prevailing sinks for 137Cs since they represent an increasing pool of biomass. In the pine chronosequence, the current root absorption, respectively, mobilizes 0.53, 0.32 and 0.31% year(-1) of the total 137Cs pool in soil. Variations in the 137Cs uptake do not reflect differences in the 137Cs balance between stands. In the two older stands, 51 and 71% of the current tree contamination are related to earlier accumulation subsequent to the initial fallout interception and recycling. The soil is the dominant source of long-term tree contamination. A simple modelling based on the measured 137Cs fluxes indicates that, for young stands, radioactive decay-corrected contamination would stabilize after reaching a maximum of 25 years after the 137Cs deposition. Stemwood presents a maximum of 15 years after the deposition and decrease afterwards mainly through radioactive decay. In the older stands, the decontamination is constant without local maximum of 137Cs level in the wood. The 137Cs contamination of tree components is the result of different influential processes like root uptake, internal translocation and immobilisation. For more accurate predictions, the calibration of existing models would be benefited by comparing with the 137Cs annual fluxes instead of the simple transfer factor coefficients. In the perspective of other applications, there is a need of such data for other radionuclides as well as for heavy metals., (Copryright 2003 Elsevier B.V.)