Short-Term Iodine Dynamics in Soil Solution.

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 (129I- and 129IO3-) to monitor short-term (≤40 h) in situ fixation and speciation changes. We observed greater instantaneous adsorption of 129IO3- compared to 129I- in all soils and the complete reduction of 129IO3- to 129I- within 5 h of addition. Loss of 129I from solution was extremely rapid; the average half-lives of 129I- and 129IO3- in soil solution were 4.06 and 10.03 h, respectively. We detected the presence of soluble organically bound iodine (org-129I) 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.

Assessment of potentially toxic elements in vegetables cultivated in urban and peri-urban sites in the Kurdistan region of Iraq and implications for human health.

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.

Quantification of root water uptake in soil using X-ray computed tomography and image-based modelling.

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.

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

Understanding the dynamics of water distribution in soil is crucial for enhancing our knowledge of managing soil and water resources. The application of X-ray computed tomography (CT) to the plant and soil sciences is now well established. However, few studies have utilized the technique for visualizing water in soil pore spaces. Here this method is utilized to visualize the water in soil in situ and in three-dimensions at successive reductive matric potentials in bulk and rhizosphere soil. The measurements are combined with numerical modelling to determine the unsaturated hydraulic conductivity, providing a complete picture of the hydraulic properties of the soil. The technique was performed on soil cores that were sampled adjacent to established roots (rhizosphere soil) and from soil that had not been influenced by roots (bulk soil). A water release curve was obtained for the different soil types using measurements of their pore geometries derived from CT imaging and verified using conventional methods, such as pressure plates. The water, soil, and air phases from the images were segmented and quantified using image analysis. The water release characteristics obtained for the contrasting soils showed clear differences in hydraulic properties between rhizosphere and bulk soil, especially in clay soil. The data suggest that soils influenced by roots (rhizosphere soil) are less porous due to increased aggregation when compared with bulk soil. The information and insights obtained on the hydraulic properties of rhizosphere and bulk soil will enhance our understanding of rhizosphere biophysics and improve current water uptake models.

Zinc uptake and phyto-toxicity: Comparing intensity- and capacity-based drivers.

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 Zn2+ 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 Zn2+ 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.

The impact of long-term biosolids application (>100 years) on soil metal dynamics.

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.

Operating at the extreme: estimating the upper yield boundary of winter wheat production in commercial practice.

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.

Kinetics of 99Tc speciation in aerobic soils.

Technetium-99 is a significant and long-lived component of spent nuclear fuel relevant to long-term assessments of radioactive waste disposal. Whilst 99Tc 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 99Tc kinetics in aerobic soils and (ii) over what experimental timescales must 99Tc kinetics be measured to make reliable long-term predictions of impact in the terrestrial environment? Soil microcosms spiked with 99TcO4- were incubated for 2.5 years and 99Tc transformations were periodically monitored by a sequential extraction, which enabled quantification of the reaction kinetics. Reduction in soluble 99Tc 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 99Tc fraction. Complexation with soil humus was key to the progressive immobilisation of 99Tc. 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 99Tc solubility in soils with low to moderate organic matter contents.

Fit-for-purpose modelling of radiocaesium soil-to-plant transfer for nuclear emergencies: a review.

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.

Forage grasses with lower uptake of caesium and strontium could provide 'safer' crops for radiologically contaminated areas.

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.

The response of soil microbial diversity and abundance to long-term application of biosolids.

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-1permitted 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.

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.

Kinetics of zinc and cadmium release in freshly contaminated soils.

The kinetics of metal release from the solid phase to solution was measured on two sets of 14 freshly contaminated soils with diverse properties. From measurements of metal concentrations in extracted soil pore water, the amount accumulated from the soil by diffusive gradients in thin-film (DGT) devices, and the distribution coefficient for labile metal, Kdl, estimated by isotopic exchange, we calculated the response time, Tc, of the soil-solution system to the removal of metal by DGT and the rate constant for release from the solid phase, k(-1). Resupply was so fast for Zn that Tc (and k(-1)) could be measured only in three of the soils, with either a silty or a sandy loam texture and low to intermediate pH (4.84-5.66). In only six clay soils was resupply of Cd too fast to measure. The generally slower release rates of Cd compared to Zn may reflect the 100-fold lower concentration of Cd, which allowed a greater proportion of it to occupy stronger binding sites with slower release rates. The rate constants derived indicate that supply from the solid phase to solution will not limit uptake of Cd or Zn by plants in clay soils, but it could be a factor in sandy or silty soils with a low pH. These findings suggest that risk assessment of clay soils could be undertaken using measurements of metals in soil solution. However, devices such as DGT, which respond to the kinetics of supply, are necessary to assess available metal in low pH, sandy, and silty soils.

Derivation of irrigation requirements for radiological impact assessments.

When assessing the radiological impacts of radioactive waste disposal, irrigation using groundwater contaminated with releases from the disposal system is a principal means of crop and soil contamination. In spite of their importance for radiological impact assessments, irrigation data are scarce and often associated with considerable uncertainty for several reasons including limited obligation to measure groundwater abstraction and differences in measuring methodologies. Further uncertainty arises from environmental (e.g. climate and landscape) change likely to occur during the assessment long time frame. In this paper, we derive irrigation data using the crop growth AquaCrop model relevant to a range of climates, soils and crops for use in radiological impact assessments. The AquaCrop estimates were compared with actual irrigation data reported in the literature and with estimates obtained from simple empirical methods proposed for use in radiological impact assessments. Further, the AquaCrop irrigation data were analysed using mixed effects modelling to investigate the effects of climate, soil and crop type on the irrigation requirement. Irrigation estimates from all models were within a reasonable range of the measured values. The AquaCrop estimates, however, were at the higher end of the range and higher than those from the empirical methods. Nevertheless, they may be more appropriate for conservative radiological assessments. The use of mixed effects modelling allowed for the characterisation of crop-specific variability in the irrigation data, and in contrast to the empirical methods, the AquaCrop and the mixed effects models accounted for the soil effect on the irrigation requirement. The approach presented in this paper is relevant for obtaining irrigation data for a specific site under different climatic conditions as well as for generic dose assessments. To the best of our knowledge, this is one of the most comprehensive analyses of irrigation data in the context of radiological impact assessment currently available.

Assessing potential risk of heavy metal exposure from consumption of home-produced vegetables by urban populations.

We performed a risk assessment of metal exposure to population subgroups living on, and growing food on, urban sites. We modeled uptake of cadmium, copper, nickel, lead, and zinc for a selection of commonly grown allotment and garden vegetables. Generalized linear cross-validation showed that final predictions of Cd, Cu, Ni, and Zn content of food crops were satisfactory, whereas the Pb uptake models were less robust. We used predicted concentrations of metals in the vegetables to assess the risk of exposure to human populations from homegrown food sources. Risks from other exposure pathways (consumption of commercially produced foodstuffs, dust inhalation, and soil ingestion) were also estimated. These models were applied to a geochemical database of an urban conurbation in the West Midlands, United Kingdom. Risk, defined as a "hazard index," was mapped for three population subgroups: average person, highly exposed person, and the highly exposed infant (assumed to be a 2-year-old child). The results showed that food grown on 92% of the urban area presented minimal risk to the average person subgroup. However, more vulnerable population subgroups (highly exposed person and the highly exposed infant) were subject to hazard index values greater than unity. This study highlights the importance of site-specific risk assessment and the "suitable for use" approach to urban redevelopment.

Effects of gamma irradiation on Holcus lanatus (Yorkshire fog grass) and associated soil microorganisms.

An investigation was conducted to determine the impact of acute doses of gamma radiation on the microbial community structure of a Holcus lanatus dominated grassland soil. Mesocosms containing soil and established grass were irradiated using a sealed (137)Cs source (7.0 Gy min(-1)). Doses ranged from 5 to 160 Gy, analyses were conducted on the day of irradiation, then 7 and 30 days later. Plant growth and arbuscular mycorrhizal fungal colonisation of roots were reduced by irradiation. Gram-negative bacteria, and microbial metabolic capacity were also negatively affected by treatment. Microbial biomass measured by phospholipid fatty acid (PLFA) analysis, showed an increase at doses above 20 Gy, 7 and 30 days after treatment. Proportions of Gram-positive bacterial and fungal PLFAs fluctuated inversely to each other, in response to both sampling time and radiation dose. We hypothesise that many of the observed soil microbial responses are indirect effects mediated by the influence of ionising radiation on the plants in this system.