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© 2020 American Chemical Society. All rights reserved. Conventional soil solution sampling of species-sensitive inorganic contaminants, such as hexavalent chromium (CrVI), may induce interconversions due to disruption of system equilibrium. The temporal resolution that these sampling methods afford may also be insufficient to capture dynamic interactions or require time-consuming and expensive analysis. Microdialysis (MD) is emerging as a minimally invasive passive sampling method in environmental science, permitting the determination of solute fluxes and concentrations at previously unobtainable spatial scales and time frames. This article presents the first use of MD coupled to high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) for the continuous sampling and simultaneous detection of CrVI in soil solution. The performance criteria of the system were assessed using stirred solutions; good repeatability of measurement (RSD < 2.5%) was obtained for CrVI, with a detection limit of 0.2 μg L-1. The online MD-HPLC-ICP-MS setup was applied to the sampling of native CrVI in three soils with differing geochemical properties. The system sampled and analyzed fresh soil solution at 15 min intervals, offering improved temporal resolution and a significant reduction in analysis time over offline MD. Simple modifications to the chromatographic conditions could resolve additional analytes, offering a powerful tool for the study of solute fluxes in soil systems to inform research into nutrient availability or soil-to-plant transfer of potentially harmful elements.

Iodine deficiency disorders (IDD) in sub-Saharan African countries are related to low dietary I intake and generally combatted through salt iodisation. Agronomic biofortification of food crops may be an alternative approach. This study assessed the effectiveness of I biofortification of green vegetables (Brassica napus L and Amaranthus retroflexus L.) grown in tropical soils with contrasting chemistry and fertility. Application rates of 0, 5 and 10 kg ha−1I applied to foliage or soil were assessed. Leaves were harvested fortnightly for ~ 2 months after I application before a second crop was grown to assess the availability of residual soil I. A separate experiment was used to investigate storage of I within the plants. Iodine concentration and uptake in sequential harvests showed a sharp drop within 28 days of I application in all soil types for all I application levels and methods. This rapid decline likely reflects I fixation in the soil. Iodine biofortification increased I uptake and concentration in the vegetables to a level useful for increasing dietary I intake and could be a feasible way to reduce IDD in tropical regions. However, biofortification of green vegetables which are subject to multiple harvests requires repeated I applications.

Made available in DSpace on 2022-04-28T19:52:03Z (GMT). No. of bitstreams: 0 Previous issue date: 2022-07-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Empresa Brasileira de Pesquisa Agropecuária Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) The Amazon rainforest is a heterogeneous ecosystem and its soils exhibit geographically variable concentrations of trace elements. In this region, anthropic activities - e.g., agriculture and mining - are numerous and varied, and even natural areas are at risk of contamination by trace elements, either of geogenic or anthropogenic origin. A reliable dataset of benchmark values for selenium (Se), barium (Ba), and iodine (I) concentrations in soils is needed for use as a reference in research and public policies in the region. In this study, 9 selected sites in the Brazilian Amazon rainforest within areas represented by Oxisols and Ultisols were assessed for relevant soil physicochemical characteristics, along with the concentrations of total Se (SeTot), total Ba (BaTot), and sequentially-extracted soluble Se (SeSol) and adsorbed Se (SeAd) in 3 different soil layers (0–20, 20–40, and 40–60 cm). In addition, organically bound-Se (SeOrg) and total I (ITot) concentrations in the surface layer (0–20 cm) were measured. Soil Se concentrations (SeTot) were considered safe and are likely a result of contributions of sedimentary deposits from the Andes. Available Se (SeSol + SeAd) accounted for 4.5% of SeTot, on average, while SeOrg in the topsoil accounted for more than 50% of SeTot. Barium in the western Amazon (state of Acre) and central Amazon (Anori, state of Amazonas) exceeded national prevention levels (PVs). Furthermore, the average ITot in the studied topsoils (5.4 mg kg−1) surpassed the worldwide mean. Notwithstanding, the close relationship found between the total content of the elements (Se, Ba, and I) and soil texture (clay, silt, and sand) suggests their geogenic source. Finally, our data regarding SeTot, BaTot, and ITot can be used to derive regional quality reference values for Amazon soils and also for updating prevention (PV) and investigation (IV) values established for selected elements by the Brazilian legislation. Department of Soil Science Federal University of Lavras, MG Embrapa Rondônia, RO Embrapa Amazônia Ocidental, AM Embrapa Roraima, RR Embrapa Amapá, AP Embrapa Amazônia Oriental, PA São Paulo State University (UNESP) School of Sciences and Engineering, SP School of Biosciences University of Nottingham, Sutton Bonington Campus São Paulo State University (UNESP) School of Sciences and Engineering, SP CAPES: 001

Refereed/Peer-reviewed The environmental mobility of Cu and therefore its potential toxicity are closely linked to its attachment to natural organic matter (NOM). Geochemical models assume full lability of metals bound to NOM, especially under strong oxidizing conditions, which often leads to an overestimation of the lability of soil metals. Stable isotope dilution (SID) has been successfully applied to estimate the labile (isotopically exchangeable) pool of soil metals. However, its application to study the lability of NOM-Cu required development of a robust separation and detection approach so that free Cu ions can be discriminated from (the also soluble) NOM-Cu. We developed a SID protocol (with enriched ⁶⁵Cu) to quantify the labile pool of NOM-Cu using size exclusion chromatography coupled to a UV detector (for the identification of different NOM molecular weights) and ICP-MS (for ⁶⁵Cu/⁶³Cu ratio measurement). The Cu isotopic-exchange technique was first characterized and verified using standard NOM (SR-NOM) before applying the developed technique to an “organic-rich” podzol soil extract. The developed protocol indicated that, in contrast to the common knowledge, significant proportions of SR-NOM-Cu (25%) and soil organic-Cu (55%) were not labile, i.e., permanently locked into inaccessible organic structures. These findings need to be considered in defining Cu interactions with the reactive pool of NOM using geochemical models and risk evaluation protocols in which complexed Cu has always been implicitly assumed to be fully labile and exchangeable with free Cu ions.

Iodine and selenium deficiencies are common worldwide. We assessed the iodine and selenium status of Gilgit-Baltistan, Pakistan. We determined the elemental composition (ICP-MS) of locally grown crops (n = 281), drinking water (n = 82), urine (n = 451) and salt (n = 76), correcting urinary analytes for hydration (creatinine, specific gravity). We estimated dietary iodine, selenium and salt intake. Median iodine and selenium concentrations were 11.5 (IQR 6.01, 23.2) and 8.81 (IQR 4.03, 27.6) µg/kg in crops and 0.24 (IQR 0.12, 0.72) and 0.27 (IQR 0.11, 0.46) µg/L in water, respectively. Median iodised salt iodine was 4.16 (IQR 2.99, 10.8) mg/kg. Population mean salt intake was 13.0 g/day. Population median urinary iodine (uncorrected 78 µg/L, specific gravity-corrected 83 µg/L) was below WHO guidelines; creatinine-corrected median was 114 µg/L but was unreliable. Daily selenium intake (from urinary selenium concentration) was below the EAR in the majority (46–90%) of individuals. Iodine and selenium concentrations in all crops were low, but no health-related environmental standards exist. Iodine concentration in iodised salt was below WHO-recommended minimum. Estimated population average salt intake was above WHO-recommended daily intake. Locally available food and drinking water together provide an estimated 49% and 72% of EAR for iodine (95 µg/day) and selenium (45 µg/day), respectively. Low environmental and dietary iodine and selenium place Gilgit-Baltistan residents at risk of iodine deficiency disorders despite using iodised salt. Specific gravity correction of urine analysis for hydration is more consistent than using creatinine. Health-relevant environmental standards for iodine and selenium are needed.

Selenium (Se) biofortification of staple cereal crops can improve the Se nutritional status of populations. A field trial employing an enriched stable isotope of Se (77Se) was undertaken over three consecutive cropping seasons in a coarse-textured, calcareous soil in Gilgit-Baltistan, Pakistan. The objectives were to (1) assess the feasibility and efficiency of Se biofortification, (2) determine the fate of residual Se, and (3) assess the consequences for dietary Se intake. Isotopically enriched 77Se (77SeFert) was applied, either as selenate or as selenite, at three levels (0, 10, and 20 g ha−1) to a wheat crop. Residual 77SeFert availability was assessed in subsequent crops of maize and wheat without further 77SeFert addition. Loss of 77SeFert was c.35% by the first (wheat) harvest, for both selenium species, attributable to the practice of flood irrigation and low adsorption capacity of the soil. No 77SeFert was detectable in subsequent maize or wheat crops. The remaining 77SeFert in soil was almost entirely organically bound and diminished with time following a reversible (pseudo-)first-order trend. Thus, repeat applications of Se would be required to adequately biofortify grain each year. In contrast to native soil Se, there was no transfer of 77SeFert to a recalcitrant form. Grain from control plots would provide only 0.5 µg person−1 day−1 of Se. By contrast, a single application of 20 g ha−1 SeVI could provide c. 47 µg person−1 day−1 Se in wheat, sufficient to avoid deficiency when combined with dietary Se intake from other sources (c. 25 µg day−1).

A field experiment was undertaken on farmers’ fields adjacent to a large mine tailings dam in the Zambian mining town of Kitwe. Experimental plots were located close to the tailings (≤ 200 m) or further away (300–400 m) within the demarcated land farmed by the same community. This study evaluated the uptake of Cd, Cu, Ni, Pb and Zn by pumpkin leaves and maize grown in soil amended with lime and manure applied at agronomic rates, and the subsequent risk of dietary exposure to the local community, typical of many similar situations across the Zambian Copperbelt. Treatments, combinations of lime and manure (present or absent), were applied to subplots selected independently and randomly within each main plot, which represented variable geochemistry across this study site as a result of windblown/rain-driven dust from the tailings. Total elemental concentrations in crops were determined by ICP-MS following microwave-assisted acid digestion. Concentrations of Cu and Pb in pumpkin leaves were above the prescribed FAO/WHO safe limits by 60–205% and by 33–133%, respectively, while all five metals were below the limit for maize grain. Concentration of metals in maize grain was not affected by the amendments. However, lime at typical agronomic application rates significantly reduced concentrations of Cd, Cu, Pb and Zn in the pumpkin leaves by 40%, 33%, 19% and 10%, respectively, and for manure Cd reduced by 16%, while Zn increased by 35%. The uptake of metals by crops in locations further from the tailings was greater than closer to the tailings because of greater retention of metals in the soil at higher soil pH closer to the tailings. Crops in season 2 had greater concentrations of Cu, Ni, Pb and Zn than in season 1 due to diminished lime applied only in season 1, in line with common applications on a biannual basis. Maize as the staple crop is safe to grow in this area while pumpkin leaves as a readily available commonly consumed leafy vegetable may present a hazard due to accumulation of Cu and Pb above recommended safe limits.

Zinc (Zn) deficiency is a widespread nutritional problem in human populations, especially in sub-Saharan Africa (SSA). The Zn concentration of crops consumed depends in part on the Zn status of the soil. Improved understanding of factors controlling the phyto-availability of Zn in soils can contribute to potential agronomic interventions to tackle Zn deficiency, but many soil types in SSA are poorly studied. Soil samples (n=475) were collected from a large part of the Amhara Region of Ethiopia, where there is widespread Zn deficiency. Zinc status was quantified by measuring several fractions, including the pseudo-total (aqua regia digestion; ZnTot), available (DTPA (diethylenetriamine pentaacetate) extractable; ZnDTPA), soluble (dissolved in 0.01 M Ca(NO3); ZnSoln) and isotopically exchangeable Zn, using the enriched stable Zn isotope 70Zn (ZnE). Soil geochemical properties were assessed for their influence on Zn lability and solubility. A parameterized geochemical assemblage model (Windermere Humic Aqueous Model – WHAM) was also employed to predict the solid phase fractionation of Zn in tropical soils rather than using sequential chemical extractions. ZnTot ranged from 14.1 to 291 mg kg−1 (median = 100 mg kg−1), whereas ZnDTPA in the majority of soil samples was less than 0.5 mg kg−1, indicating widespread phyto-available Zn deficiency in these soils. The labile fraction of Zn in soil (ZnE as % ZnTot) was low, with median and mean values of 4.7 % and 8.0 %, respectively. Labile Zn partitioning between the solid and the solution phases of soil was highly pH dependent, where 94 % of the variation in the partitioning coefficient of 70Zn was explained by soil pH. Similarly, 86 % of the variation in ZnSoln was explained by soil pH. Zinc distribution between adsorbed ZnE and ZnSoln was controlled by pH. Notably, Zn isotopic exchangeability increased with soil pH. This contrasts with literature on contaminated and urban soils and may arise from covarying factors, such as contrasting soil clay mineralogy across the pH range of the soils used in the current study. These results could be used to improve agronomic interventions to tackle Zn deficiency in SSA.

Deficiencies of the micronutrients iodine and selenium are particularly prevalent where populations consume local agricultural produce grown on soils with low iodine and selenium availability. This study focussed on such an area, Gilgit-Baltistan in Pakistan, through a geochemical survey of iodine and selenium fractionation and speciation in irrigation water and arable soil. Iodine and selenium concentrations in water ranged from 0.01–1.79 µg L−1 to 0.016–2.09 µg L−1, respectively, which are smaller than levels reported in similar mountainous areas in other parts of the world. Iodate and selenate were the dominant inorganic species in all water samples. Average concentrations of iodine and selenium in soil were 685 µg kg−1 and 209 µg kg−1, respectively, much lower than global averages of 2600 and 400 µg kg−1, respectively. The ‘reactive’ fractions (‘soluble’ and ‘adsorbed’) of iodine and selenium accounted for −1) for iodine (1.07) and selenium (1.27) suggested minimal buffering of available iodine and selenium against leaching losses and plant uptake. These geochemical characteristics suggest low availability of iodine and selenium in Gilgit-Baltistan, which may be reflected in locally grown crops. However, further investigation is required to ascertain the status of iodine and selenium in the Gilgit-Baltistan food supply and population.

Zinc (Zn) deficiency is a widespread nutritional problem in human populations, especially in sub-Saharan Africa (SSA). The Zn concentration of crops consumed depends in part on the Zn status of soil. Improved understanding of factors controlling the phyto-availability of Zn in soils can contribute to potential agronomic interventions to tackle Zn deficiency, although there are major knowledge gaps for many soil types in SSA. Soil samples (n = 475) were collected from a large part of the Amhara Region of Ethiopia where there is widespread Zn deficiency. Zinc status was quantified by measuring several fractions: pseudo-total (Aqua-Regia digestion; ZnTot), available (DTPA-extractable; ZnDTPA), soluble (dissolved in 0.01 M Ca(NO3); ZnSoln) and isotopically exchangeable Zn using the enriched stable Zn isotope 70Zn (ZnE). Soil geochemical properties were assessed for their influence on Zn lability and solubility. ZnTot ranged from 14.1 to 291 mg kg−1 (median = 100 mg kg−1) whereas ZnDTPA in the majority of soil samples was less than 0.5 mg kg−1 indicating widespread phytoavailable Zn deficiency in these soils. The labile fraction of Zn in soil (ZnE as %ZnTot) was low, with median and mean values of 4.7 % and 8.0 % respectively. Labile Zn partitioning between the solid and the solution phases of soil was highly pH-dependent where 94 % of the variation in the partitioning coefficient of 70Zn was explained by soil pH. Similarly, 86 % of the variation in ZnSoln was explained by soil pH. Zinc distribution between adsorbed ZnE and ZnSoln was pH controlled. Notably, Zn isotopic exchangeability increased with soil pH. This contrasts with literature on contaminated and urban soils and may arise from covarying factors such as contrasting soil clay mineralogy across the pH range of the soils used in the current study. These results could be used to improve agronomic interventions to tackle Zn deficiency in SSA.

This study presents an analysis of the effects of manure and lime commonly used to improve agricultural productivity and evaluates the potential for such soil amendments to mobilise/immobilise metal fractions in soils contaminated from nearby mine tailings in the Zambian Copperbelt. Lime and manure were applied at the onset of the study, and their effects were studied over two planting seasons, i.e. 2016-17 and 2017–18. Operationally defined plant-available Cd, Cu, Ni, Pb and Zn in the soil, were determined by extraction with DTPA-TEA (diethylenetriaminepentaacetic acid-triethanolamine) and 0.01 M Ca(NO3)2, before, and after, applying the amendments. In unamended soils, Cd was the most available and Ni the least. Lime application decreased extractable Cd, Cu, Ni, Pb and Zn. The response to lime was greater in soils with an initially acidic pH than in those with approximately neutral pH values. Manure increased DTPA extractable Zn, but decreased DTPA and Ca(NO3)2 extractable Cd, Cu and Pb. Combined lime and manure amendment exhibited a greater reduction in DTPA extractable Cd, Ni, Pb, Zn, as well as for Ca(NO3)2 extractable Cd compared to separate applications of lime and manure. The amendments had a significant residual effect on most of the soil fractions between season 1 and 2. The results obtained in this study showed that soil amendment with minimal lime and manure whilst benefiting agricultural productivity, may significantly reduce the mobility or plant availability of metals from contaminated agricultural soils. This is important in contaminated, typical tropical soils used for crop production by resource poor communities affected by mining or other industrial activities., Copperbelt; Lime; Manure; Mine tailings; Bioavailable metals; Agricultural soil science; Environmental analysis; Environmental assessment; Environmental chemistry; Environmental geochemistry; Environmental hazard; Environmental health; Environmental management; Soil science.

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 IO3−. Finally, translocation through the phloem to younger leaves was also investigated using a radioiodine (129I−) label. During uptake, spinach roots demonstrated the ability to reduce IO3− 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 IO3−, 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.

Elemental composition of food can be used to determine nutritional potential as well as guiding legislation for establishing maximum acceptable limits (MAL) of metals in consumption products. This study aimed to determine the elemental background levels of yerba mate (Ilex paraguariensis A.St.-Hil.) under varied geologic formations in southern Brazil. Mature leaves were randomly collected from four wild-grown plants at thirty native sites in three states and analyzed for 32 elements. Since yerba mate is not washed to obtain the final product, leaves were analyzed with and without washing to assess foliar deposition. Concentration values of As, Ag, Be, Cs, Cr, Li, Se, Tl, U, and V were near detection limits, indicating low potential as a source and/or toxicity to the consumer. Washing decreased concentrations of Fe, Ti, As, Mo, Li, V, and Pb, suggesting atmospheric contributions/dust deposition. Concentrations of Mn (very high), Zn (high), and Ni (high) demonstrated that leaves could be an important source of these elements. Soil parent material affected elemental composition with basalt providing higher concentrations of Mn, P, and Co while Rhyodacite provided higher concentrations of K and Na. All samples exhibited Pb values below the MAL of 0.6 mg kg−1, but 23% of washed leaves and 20% of unwashed leaves had Cd concentrations close to or above the MAL value of 0.4 mg kg−1. Study results indicated that Cd MAL values for yerba mate in southern Brazil should be reassessed.

Background Chromium (Cr) exists in the environment in two chemical forms; CrIII is an essential micronutrient for glucose and lipid metabolism, whereas CrVI is toxic and a recognised carcinogen through inhalation. Numerous studies have attempted to evaluate their transfer mechanisms from soil and solution media into plants, usually with respect to the hyperaccumulation, detoxification and tolerance of the plant to CrVI. Methods Isotopically enriched species of Cr, added as 50CrIII and 53CrVI, were used to investigate transfer from solution into the root systems of Spinacia oleracea. In addition the effect of sulphate (SO42−), as a competitor for CrVI uptake, was investigated. Separation of 50CrIII and 53CrVI was undertaken using HPLC-ICP-QQQ following isolation of root solutions using freeze/thaw centrifugation. Results Irrespective of supplied CrVI concentration (250, 500 or 1000 μg L−1), the dominant species in both apoplastic (routed through cell wall and intercellular space as a passive mechanism) and symplastic (routed through cytoplasm as an active mechanism) root solutions was CrIII. There was evidence for CrVI reduction in the rhizosphere prior to uptake as an additional detoxification mechanism. Sulphate promoted uptake of CrVI through the active pathway, although increases in SO42- concentration did not yield a proportional increase in Cr symplastic solution concentration; CrIII was also the dominant species in these root solutions. Conclusion The results indicate that Spinacia oleracea plants can effectively reduce CrVI to CrIII and that the uptake pathways for both CrIII and CrVI are more complex than previously reported. Further work is required to understand the physiological processes that result in the reduction of CrVI prior to, and during, uptake. The efficacy of sulphate to augment existing agricultural management strategies, such as liming and organic reincorporation, also requires further investigation to establish suitable application rates and applicability to other environmental contaminants.

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.

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 UVI 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 UVI 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 UVI 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., This work was carried out within the TREE (Transfer-Exposure-Effects) consortium within the Radioactivity and the Environment (RATE) programme, funded jointly by the Natural Environment Research Council, Radioactive Waste Management Ltd. and the Environment Agency (grant no. NE/L000504/1). We thank the numerous individuals and agencies who gave permission to sample 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. © 2019 The Authors, This work was carried out within the TREE (Transfer-Exposure-Effects) consortium, one of three projects within the Radioactivity and the Environment (RATE) programme. This study was funded jointly by the Natural Environment Research Council Radioactive Waste Management Ltd . and the Environment Agency in the United Kingdom (grant no. NE/L000504/1 ). We also thank the numerous individuals and agencies in the UK who gave permission to sample soils on their land. Appendix A

The Chernobyl Exclusion Zone (CEZ) represents a unique natural laboratory that received significant 129I contamination across a range of soils and land-use types in a short time period in 1986. Data are presented on 129I and 127I in soil samples collected from highly contaminated areas in the CEZ in 2015. The geometric mean (GM) total concentration of stable iodine (127I) was 6.7 × 10−7 g g−1 and the (GM) total concentration of 129I was 2.39 × 10−13 g g−1, equivalent to 1.56 mBq kg−1. GM total 127I concentration is below the European average soil concentration of 3.94 × 10−6 g g−1, while 129I is significantly higher than the pre-Chernobyl activity concentration for 129I of 0.094 mBq kg−1. Significant differences were found in the extractability of native, stable 127I and 129I almost 30 years after the introduction of 129I to the soils. Both 127I and 129I were predominantly associated with alkaline-extractable soil organic matter, established using a three-step sequential extraction procedure. Whereas 127I was significantly correlated with gross soil organic matter (measured by loss on ignition), however, 129I was not. The ratio of 129I/127I was significantly lower in extracts of soil organic matter than in more labile (soluble and adsorbed) fractions, indicating incomplete equilibration of 129I with native 127I in soil humic substances after 29 years residence time in the CEZ soils. The initial physico-chemical form of 129I in the CEZ soils is unknown, but the widespread presence of uranium oxide fuel particles is unlikely to have influenced the environmental behaviour of 129I. Our findings have implications for long-term radiation dose from 129I in contaminated soils and the use of native, stable 127I as a proxy for the long-term fate of 129I. © 2019 Elsevier B.V., This work was carried out within the TREE (Transfer-Exposure-Effects) consortium, one of three projects within the Radioactivity and the Environment (RATE) programme funded jointly by the Natural Environment Research Council, Radioactive Waste Management Ltd. and the Environment Agency (grant no. NE/L000504/1). We thank M. D. Bondarkov and J. Makluk (Chornobyl Center for Nuclear Safety, Radioactive Waste and Radioecology, Slavutych) and Thawatchai Itthipoonthanakorn (Office of Atoms for Peace, Bangkok, Thailand) for their kind assistance. Finally, we thank four anonymous reviewers for their help in improving the manuscript.

© 2020 Elsevier B.V. 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.

Chemical fractionation via sequential extraction (SEP) combined with isotopic analysis of Pb was used to investigate the origins and reactivity of Pb in 66 topsoil samples collected from 12 different locations in Egypt. The total soil Pb concentrations (TPb) covered a wide range (∼80–16,000 mg kg−1), but were only elevated in four industrial and urban locations within Cairo and Alexandria. In all the other locations values of TPb were generally low and were close to the average crustal Pb concentration of 14 mg kg−1. The largest Pb fraction in all soils, with the exception of two industrial locations, was the ‘residual’ fraction (38–63% of TPb) followed by Pb bound to ‘organic’ and ‘metal oxide’ phases. The Pb isotopic signatures (206Pb/207Pb vs 208Pb/207Pb) of all samples in all SEP fractions were highly variable, suggesting a heterogeneous mix of Pb contamination sources; however, they aligned closely to a binary mixing line between geogenic and petrol Pb sources. There were similar Pb isotopic patterns across all of the non-residual fractions with measureable data (F2 – F4) suggesting that the non-residual anthropogenic-Pb and geogenic-Pb have been assimilated into common pools within the soil. Binary and ternary source-apportionment models based on Pb isotopic ratios and abundances showed that the relative contribution of petrol-Pb and geogenic-Pb can be ascribed with reasonable certainty. However, the contribution of further sources can only be accounted for if the isotopic abundance of all end-members are known and are at the periphery of the soils dataset.

Biochar, a by-product from the production of biofuel and syngas by gasification, was tested as a material for adsorption and fixation of UVI from aqueous solutions. A batch experiment was conducted to study the factors that influence the adsorption and time-dependent fixation on biochar at 20 °C, including pH, initial concentration of UVI and contact time. Uranium (UVI) adsorption was highly dependent on pH but adsorption on biochar was high over a wide range of pH values, from 4.5 to 9.0, and adsorption strength was time-dependent over several days. The experimental data for pH > 7 were most effectively modelled using a Freundlich adsorption isotherm coupled to a reversible first order kinetic equation to describe the time-dependent fixation of UVI within the biochar structure. Desorption experiments showed that UVI was only sparingly desorbable from the biochar with time and isotopic dilution with 233UVI confirmed the low, or time-dependent, lability of adsorbed 238UVI. Below pH 7 the adsorption isotherm trend suggested precipitation, rather than true adsorption, may occur. However, across all pH values (4.5⿿9) measured saturation indices suggested precipitation was possible: autunite below pH 6.5 and either swartzite, liebigite or bayleyite above pH 6.5.

Chemical extractants used to measure labile soil metal must ideally select for and solubilise the labile fraction, with minimal solubilisation of non-labile metal. We assessed four extractants (0.43 M HNO3, 0.43 M CH3COOH, 0.05 M Na2H2EDTA and 1 M CaCl2) against these requirements. For soils contaminated by contrasting sources, we compared isotopically exchangeable Ni, Cu, Zn, Cd and Pb (EValue, mg kg-1), with the concentrations of metal solubilised by the chemical extractants (MExt, mg kg-1). Crucially, we also determined isotopically exchangeable metal in the soil–extractant systems (EExt, mg kg-1). Thus ‘EExt - EValue’ quantifies the concentration of mobilised non-labile metal, while ‘EExt - MExt’ represents adsorbed labile metal in the presence of the extractant. Extraction with CaCl2 consistently underestimated EValue for Ni, Cu, Zn and Pb, while providing a reasonable estimate of EValue for Cd. In contrast, extraction with HNO3 both consistently mobilised non-labile metal and overestimated the EValue. Extraction with CH3COOH appeared to provide a good estimate of EValue for Cd; however, this was the net outcome of incomplete solubilisation of labile metal, and concurrent mobilisation of non-labile metal by the extractant (MExt < EExt > EValue). The Na2H2EDTA extractant mobilised some non-labile metal in three of the four soils, but consistently solubilised the entire labile fraction for all soil-metal combinations (MExt ≈ EExt). Comparison of EValue, MExt and EExt provides a rigorous means of assessing the underlying action of soil chemical extraction methods and could be used to refine long-standing soil extraction methodologies.

Grain and soil were sampled across a large part of Amhara, Ethiopia in a study motivated by prior evidence of selenium (Se) deficiency in the Region's population. The grain samples (teff, Eragrostis tef, and wheat, Triticum aestivum) were analysed for concentration of Se and the soils were analysed for various properties, including Se concentration measured in different extractants. Predictive models for concentration of Se in the respective grains were developed, and the predicted values, along with observed concentrations in the two grains were represented by a multivariate linear mixed model in which selected covariates, derived from remote sensor observations and a digital elevation model, were included as fixed effects. In all modelling steps the selection of predictors was done using false discovery rate control, to avoid over-fitting, and using an α-investment procedure to maximize the statistical power to detect significant relationships by ordering the tests in a sequence based on scientific understanding of the underlying processes likely to control Se concentration in grain. Cross-validation indicated that uncertainties in the empirical best linear unbiased predictions of the Se concentration in both grains were well-characterized by the prediction error variances obtained from the model. The predictions were displayed as maps, and their uncertainty was characterized by computing the probability that the true concentration of Se in grain would be such that a standard serving would not provide the recommended daily allowance of Se. The spatial variation of grain Se was substantial, concentrations in wheat and teff differed but showed the same broad spatial pattern. Such information could be used to target effective interventions to address Se deficiency, and the general procedure used for mapping could be applied to other micronutrients and crops in similar settings., Graphical abstract Unlabelled Image, Highlights • Joint soil and crop sampling was undertaken across Amhara Region, Ethiopia. • Statistical modelling of the resulting data incorporated extensive covariates. • Spatial predictions were made of grain selenium concentration. • These predictions, and their uncertainties, are presented as maps. • The maps show the probability that grain provides adequate dietary Se.

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 IO3− 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 IO3−, respectively. Microdialysis was proven to be capable of sampling dissolved iodine from the soil solution, which accounted for I− > IO3−. 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 (

The distribution of elemental species of chromium (Cr) in potentially-contaminated soil samples warrants investigation due to the differing mobilities and toxicities of trivalent [Cr(III)] and hexavalent chromium [(Cr(VI)]. In addition, the possibility of species interconversions requires the implementation of robust methods that can correct for changes at the point of sampling, extraction and analysis. This work presents the application of speciated isotope dilution mass spectrometry (SIDMS) to accurately quantify Cr(VI) in agricultural soils within close proximity to a mine tailings dam in the Copperbelt Province of Zambia. Interpolated plots of total Cr, produced from data collected through a nested sampling design, were used to optimise the sampling across the spatial domain. Extraction of Cr(VI) was undertaken using a microwave assisted reaction system (80 °C for 5 min) with 50 mM EDTA, to complex Cr(III) and reduce the likelihood of oxidation during the extraction. Isotopically-enriched 53Cr(VI) was added to each sample prior to extraction to account for species interconversions. The accuracy of the method was confirmed using NIST SRM 2700 and 2701. Cr(VI) concentrations in the soil samples ranged between 0.03 and 0.29 mg kg−1, significantly lower than the residential UK screening value for Cr(VI) of 21 mg kg−1. The data indicate that this site poses a low environmental/human health risk with respect to Cr(VI) exposure.

Made available in DSpace on 2019-10-06T15:46:53Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-10-15 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) Arsenic (As) in native soils of the Amazon rainforest is a concern due to its likely origin from the Andean rivers, which transport loads of sediments containing substantial amounts of trace elements coming from the cordilleras. Yet, unveiling soil As baseline concentrations in the Amazon basin is still a need because most studies in Brazil have been performed in areas with predominantly high concentrations and cannot express a real baseline value for the region. In this study, 414 soil samples (0–20, 20–40 and 40–60 cm layers) were collected from different sites throughout the Amazon basin - including native Amazon rainforest and minimally disturbed areas - and used to determine total and extractable (soluble + available) As concentrations along with relevant soil physicochemical properties. Descriptive statistics of the data was performed and Pearson correlation supported by a Principal Component Analysis (PCA) provided an improved understanding of where and how As concentrations are influenced by soil attributes. Total As concentration ranged from 0.98 to 41.71 mg kg−1 with values usually increasing from the topsoil (0–20 cm) to the deepest layer (40–60 cm) in all sites studied. Considering the proportional contribution given by each fraction (soluble and available) on extractable As concentration, it is noticeable that KH2PO4-extractable As represents the most important fraction, with >70% of the As extracted on average in all the sites studied. Still, the extractable fractions (soluble + available) correspond to ~0.24% of the total As, on average. Total, available, and soluble As fractions were strongly and positively correlated with soil Al3+. The PCA indicated that soil pH in combination with CEC might be the key factors controlling soil As concentrations and the occurrence of each arsenic fraction in the soil layers. Department of Soil Science Federal University of Lavras Vale Institute of Technology Embrapa Rondônia Embrapa Amazônia Ocidental Embrapa Roraima Embrapa Amapá Embrapa Amazônia Oriental São Paulo State University (UNESP) School of Sciences and Engineering, Rua Domingos da Costa Lopes 780 School of Biosciences University of Nottingham, Sutton Bonington Campus São Paulo State University (UNESP) School of Sciences and Engineering, Rua Domingos da Costa Lopes 780

Iron intakes calculated from one-day weighed records were compared with those from same day analyzed duplicate diet composites collected from 120 Malawian women living in two rural districts with contrasting soil mineralogy and where threshing may contaminate cereals with soil iron. Soils and diet composites from the two districts were then subjected to a simulated gastrointestinal digestion and iron availability in the digests measured using a Caco-2 cell model. Median analyzed iron intakes (mg/d) were higher (p

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 127I and the long-lived isotope 129I (t1/2 ¼ 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

Widespread potential dietary deficiencies of calcium (Ca), iron (Fe), iodine (I), selenium (Se) and zinc (Zn) have been identified in Malawi. Several deficiencies are likely to be compounded by high phytic acid (PA) consumption. Rice (Oryza sativa) is commonly consumed in some Malawian populations, and its mineral micronutrient content is important for food security. The considerable irrigation requirements and flooded conditions of paddy soils can also introduce or mobilise potentially toxic elements including arsenic (As), cadmium (Cd) and lead (Pb). The aim of this study was to determine the mineral composition of rice sampled from farmers' fields and markets in Malawi. Rice was sampled from 18 extension planning areas across Malawi with 21 white (i.e. polished) and 33 brown samples collected. Elemental composition was determined by inductively coupled plasma-mass spectrometry (ICP-MS). Arsenic speciation was performed using high-performance liquid chromatography (HPLC)-ICP-MS. Concentration of PA was determined using a PA-total phosphorus assay. Median total concentrations (mg kg(-1), dry weight) of elements important for human nutrition in brown and white rice, respectively, were: Ca = 66.5 and 37.8; Cu = 3.65 and 2.49; Fe = 22.1 and 7.2; I = 0.006 and

The current availability of Pb in Egyptian soils and associated plants were studied in 15 locations (n = 159) that had been historically subjected to industrial and automobile Pb emissions. Isotopic dilution with enriched 204Pb was used to estimate the soil Pb labile pool (PbE); results showed that %PbE values were mostly

Metal-salt amended soils (MA, n = 23), and historically-contaminated urban soils from two English cities (Urban, n = 50), were investigated to assess the effects of soil properties and contaminant source on metal lability and solubility. A stable isotope dilution method, with and without a resin purification step, was used to measure the lability of Cd, Cu, Ni, Pb and Zn. For all five metals in MA soils, lability (%E-values) could be reasonably well predicted from soil pH value with a simple logistic equation. However, there was evidence of continuing time-dependent fixation of Cd and Zn in the MA soils, following more than a decade of storage under air-dried conditions, mainly in high pH soils. All five metals in MA soils remained much more labile than in Urban soils, strongly indicating an effect of contaminant source on metal lability in the latter. Metal solubility was predicted for both sets of soil by the geochemical speciation model WHAM-VII, using E-value as an input variable. For soils with low metal solution concentrations, over-estimation of Cd, Ni and Zn solubility was associated with binding to the Fe oxide fraction while accurate prediction of Cu solubility was dependent on humic acid content. Lead solubility was most poorly described, especially in the Urban soils. Generally, slightly poorer estimation of metal solubility was observed in Urban soils, possibly due to a greater incidence of high pH values. The use of isotopically exchangeable metal to predict solubility is appropriate both for historically contaminated soils and where amendment with soluble forms of metal is used, as in toxicological trials. However, the major limitation to predicting solubility may lie with the accuracy of model input variables such as humic acid and Fe oxide contents where there is often a reliance on relatively crude analytical estimations of these variables. Trace metal reactivity in urban soils depends on both soil properties and the original source material; the WHAM geochemical model predicts solubility using isotopically exchangeable metal as an input.

Amazonian Dark Earths (ADEs) are soils studied for archaeological purposes and as a potentially agricultural model for the humid tropic. We investigated the chemical composition of an ADE in comparison to an adjacent Ultisol without anthropic influence for better understanding the origin of ADE fertility and formation process. Three hundred ADE and Ultisol samples were collected at 10 cm depths from 0 to 100 cm soil profiles on the Caldeirao site at the Solimoes River, Brazil and analyzed for elemental composition in an inductively coupled plasma mass spectrometer (ICP-MS). Results showed significantly increased concentrations of P, Ca, K, Mg, Mn, Ba, Zn, Sr, Cu, Rb, Ni, Li, Cd, Cs, Co, Tl, and Be and reduced concentrations of Se along the ADE profile relative to the control Ultisol. Additionally, it was also detected reduced concentrations of Al, U, and V in ADE superficial layers. Elemental enrichment factors in ADE varied from 1.6 to 15.9 times and the enriched elements have mostly been associated with organic residues. Besides the common elements used to characterize ADE sites, our results have shown altered concentrations of other uncommon elements (Al, Be, Cd, Cs, Li, Se, Tl, U, and V) that can be also used to unveil ADE sites and differentiate them from Amazonian soils without anthropic influence.

To understand the dynamic mechanisms governing soil-to-plant transfer of selenium (Se), technetium-99 (99Tc) and iodine (I), a pot experiment was undertaken using 30 contrasting soils after spiking with 77Se, 99Tc and 129I, 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) 78Se and127I, as well as spiked 77Se, 99Tc and 129I, 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 99Tc, followed by 77Se, with least uptake of 129I, reflecting the transformations and interactions with soil of the three isotopes. Unlike soil-derived Se and I, the available pools of 77Se, 99Tc and 129I 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 77SeO42−, 99TcO4− and 129IO3−, in soluble and adsorbed fractions were the most likely plant-available species. A greater ratio of 127I/129I in the soil solid phase compared to the solution phase confirmed incomplete mixing of spiked 129I with native 127I 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 (TFtotal), a transfer factor (TFavailable) expressed using volumetric concentrations of speciated ‘available’ fractions of each element showed little variation with soil properties.

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 Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %. E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (

The isotopically exchangeable metal pool (E-value) of zinc (Zn), cadmium (Cd) and lead (Pb) were simultaneously measured, using stable isotope dilution, in soils contaminated by Pb/Zn mining activities and varying in properties likely to affect metal reactivity, including pH, organic matter content, metal concentration and land use. E-values were compared with single and sequential extraction schemes. Results showed a wide range of metal reactivity (approximately 1–100% of total) depending on the extent of contamination and on the prevailing soil conditions. Across the range of soils, the E-values showed no consistent correspondence to any single chemical extraction procedure (EDTA, DTPA and HNO3) although there was reasonable agreement with the extractants 0.05 m EDTA and 0.43 m HNO3 in acidic organic soils. Extraction with 0.005 m DTPA substantially under-estimated the isotopically exchangeable metal content. E-values corresponded reasonably well with the exchangeable metal (fraction 1 (F1) of the sequential extraction procedure) in calcareous soils but relatively poorly and inconsistently with F1–F2, F1–F3 or F1–F4 in acidic-neutral soils. Operational aspects associated with determination of multi-element E-values are discussed.

The mining and processing of copper in Kilembe, Western Uganda, from 1956 to 1982 left over 15 Mt. of tailings containing cupriferous and cobaltiferous pyrite dumped within a mountain river valley. This pilot study was conducted to assess the nature and extent of risk to local populations from metal contamination arising from those mining activities. We determined trace element concentrations in mine tailings, soils, locally cultivated foods,house dust, drinking water and human biomarkers (toenails) using ICP-MS analysis of acid digested samples. The results showed that tailings, containing higher concentrations of Co, Cu, Ni and As compared with world average crust values had eroded and contaminated local soils. Pollution load indices revealed that 51% of agricultural soils sampled were contaminated with trace elements. Local water supplies were contaminated, with Co concentrations that exceeded Wisconsin (US) thresholds in 25% of domestic water supplies and 40% of Nyamwamba river water samples. Zinc exceeded WHO/FAO thresholds of 99.4 mg kg?1 in 36% of Amaranthus vegetable samples, Cu exceeded EC thresholds of 20 mg kg?1 in 19% of Amaranthus while Pb exceeded WHO thresholds of 0.3 mg kg?1 in 47% of Amaranthus vegetables. In bananas, 20% of samples contained Pb concentrations that exceeded the WHO/FAO recommended threshold of 0.3 mg kg?1. However, risk assessment of local foods and water, based on hazard quotients (HQ values) revealed no potential health effects. The high external contamination of volunteers' toenails with some elements (even after a washing process) calls into question their use as a biomarker for metal exposure in human populations where feet are frequently exposed to soil.

Urban waste disposal occurred on fenland to the west of Manchester, England, between 1900 and 1964. The reclaimed fenland, Chat Moss, is now used for mixed arable farming. A total of 1.92 Mt of waste including privy midden, street sweepings, clinkers and slaughterhouse refuse was incorporated into the moss resulting in a modified topsoil with raised pH and reduced organic matter content compared with the subsoil. Elevated levels of potentially toxic elements (PTEs) are observed in the topsoil beyond the typical depth of atmospheric contamination; Cd and As concentrations exceed soil guideline values (SGVs) at 1.8 and 43 mg/kg, respectively. Sequential extraction indicates that waste-derived Pb, Zn and Ni remain predominantly in the residual fraction, whereas Cu was mainly organically bound. Arsenic was predominately found in oxide and organic matter fractions with Cd in carbonate, oxide, organic matter and residual fractions. Pot trials indicated limited uptake of PTEs by vegetables grown on the waste-amended soil, with the exception of Cd uptake by lettuce (0.22 mg/kg FW) and Pb uptake by radish (0.16 mg/kg FW), which exceeded current EU limits of 0.2 and 0.1 mg/kg FW, respectively. Hazard quotients (HQs) identified no risks to adults from consumption of vegetables grown in these soils with the exception of lettuce consumption with a HQ of 1.4. Risks to children were slightly greater with HQs >1 for Cd in lettuce, spinach, carrots and onion, As in lettuce, parsley and onion and for Zn in spinach.

Trace metal uptake was measured for tropical and temperate leafy vegetables grown on soil from an urban sewage disposal farm in the UK. Twenty-four leafy vegetables from East Africa and the UK were assessed and the five vegetable types that showed the greatest Cd concentrations were grown on eight soils differing in the severity of contamination, pH and other physico-chemical properties. The range of Cd concentrations in the edible shoots was greater for tropical vegetables than for temperate types. Metal uptake was modelled as a function of (i) total soil metal concentration, (ii) CaCl2-soluble metal, (iii) soil solution concentration and (iv) the activity of metal ions in soil pore water. Tropical vegetables were not satisfactorily modelled as a single generic ‘green vegetable’, suggesting that more sophisticated approaches to risk assessment may be required to assess hazard from peri-urban agriculture in developing countries.

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.

Evidence of chloride-enhanced cadmium uptake by plants in soil experiments has been reported. However, it is still unclear whether this finding is due to increased rates of Cd2+ diffusion to plant roots or the direct uptake of complexes such as CdC1+. A controlled hydroponic experiment was undertaken to distinguish and quantify the uptake rates of free and inorganic-complexed cadmium and to model the uptake of cadmium by Indian mustard plants with a 'biotic ligand model'. Plants were treated with NaCl (0 to 200 mM) including equivalent Na2SO4 treatments. Cadmium speciation in solution was calculated using the WHAM-VI model. Results of the current trials showed that higher Cl-concentrations in solution generally resulted in greater cadmium accumulation by plants than predicted by the Cd2+ activity. Activities of Cd-chloro complexes showed the best correlations with the cadmium concentrations in the plants compared with the activity of Cd2+. The biotic ligand model showed a reasonable good fit for the plants when assuming competition by Cd2+ and CdCl+ for sorption sites at root level. The relative values of the two reaction constants suggest that root affinity for Cd2+ is 3.4 times greater than for CdCl+. Nevertheless this clearly indicates a substantial role for chloro-complexed cadmium accumulation.

Dye tracers are widely used for tracing and visualising hydrological flow paths in soils. Despite evidence of non-conservative behaviour (i.e. sorption) in recent years, Brilliant Blue FCF continues to be used extensively for dye tracing in soil. However, previous studies have not considered hysteresis in the sorption mechanism. The objectives of this study were (1) to test the hypothesis that sorption of Brilliant Blue FCF on soils with widely contrasting textures could be described with a single sorption isotherm based solely on sorption by the clay fraction and (2) to determine whether desorption hysteresis is likely to confound the estimation of retardation factor in modelling dye transit through soil. We measured the sorption and desorption of Brilliant Blue on four soils of contrasting texture, ranging from a light sand to a heavy clay, and resolved a single Freundlich sorption isotherm for the clay fraction in all soils. An attempt to include silt and humus fractions as additional adsorbents with independent Freundlich parameters was unsuccessful. The sorption of Brilliant Blue FCF on the four soils studied was not fully reversible; there was apparent sorption–desorption hysteresis in all cases. Therefore, even though the sorption strength of Brilliant Blue in soils might be less than that of other dye tracers, it is possible that the visualised flow pathways may not accurately reflect those of water in soil. From this we suggest that Brilliant Blue may not be well suited for all forms of dye tracing in clay soils and it is therefore crucial that the specific environmental conditions, soil type, dye concentration and objectives of the study are considered each time when choosing the appropriate dye tracer.

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.

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing 109 Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric PCO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd 2+ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R 2 = 0.992). It differentiates between two ‘pools’ of sorbed Cd 2+ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd 2+ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R 2 = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of � 175 d, for release to a ‘zerosink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption. 2008 Published by Elsevier Ltd.

The rate of reactions between humic acid (HA) and iodide (I(-)) and iodate (IO3(-)) have been investigated in suspensions spiked with (129)I at concentrations of 22, 44 and 88 μg L(-1) and stored at 10 °C. Changes in the speciation of (129)I(-), (129)IO3(-) and mixed ((129)I(-) + (129)IO3(-)) spikes were monitored over 77 days using liquid chromatography inductively coupled plasma mass spectrometry (LC-ICP-MS). In suspensions spiked with (129)I(-) 25% of the added I(-) was transformed into organic iodine (Org-(129)I) within 77 days and there was no evidence of (129)IO3(-) formation. By contrast, rapid loss of (129)IO3(-) and increase in both (129)I(-) and Org-(129)I was observed in (129)IO3(-)-spiked suspensions. However, the rate of Org-(129)I production was greater in mixed systems compared to (129)IO3(-)-spiked suspensions with the same total (129)I concentration, possibly indicating IO3(-)I(-) redox coupling. Size exclusion chromatography (SEC) demonstrated that Org-(129)I was present in both high and low molecular weight fractions of the HA although a slight preference to bond with the lower molecular weight fractions was observed indicating that, after 77 days, the spiked isotope had not fully mixed with the native (127)I pool. Iodine transformations were modelled using first order rate equations and fitted rate coefficients determined. However, extrapolation of the model to 250 days indicated that a pseudo-steady state would be attained after ∼200 days but that the proportion of (129)I incorporated into HA was less than that of (127)I indicating the presence of a recalcitrant pool of (127)I that was unavailable for isotopic mixing.

Geochemical speciation models generally include the assumption that all metal bound to humic acid and fulvic acid (HA, FA) is labile. However, in the current study, we determined the presence of a soluble ‘non-labile’ Cu fraction bound to HA extracted from grassland and peat soils. This was quantified by determining isotopically-exchangeable Cu (E-value) and EDTA-extraction of HA-bound Cu, separated by size-exclusion chromatography (SEC) and assayed by coupled ICP-MS. Evidence of time-dependent Cu fixation by HA was found during the course of an incubation study (160 days); up to 50% of dissolved HA-bound Cu was not isotopically exchangeable. This result was supported by extraction with EDTA where approximately 40% of Cu remained bound to HA despite dissolution in 0.05 M Na2-EDTA. The presence of a substantial non-labile metal fraction held by HA challenges the assumption of wholly reversible equilibrium which is central to current geochemical models of metal binding to humic substances.

Using interdisciplinary field research in the Usa Basin, northeast European Russia, we compared local inhabitants' perception of environmental problems with chemical and remote-sensing signatures of environmental pollution and their local impacts. Extensive coal mining since the 1930s around Inta and Vorkuta has left a legacy of pollution, detected by measuring snowpack, topsoil, and lichen chemistry, together with remote-sensing techniques and analysis of lake water and sediments. Vorkuta and its environs suffered the worst impacts, with significant metal loading and alkalization in lakes and topsoils, elevated metals and cations in terricolous (reindeer) lichens, and changes in vegetation communities. Although the coal industry has declined recently, the area boasts a booming oil and gas industry, based around Usinsk. Local perceptions and concerns of environmental pollution and protection were higher in Usinsk, as a result of increased awareness after a major oil spill in 1994, compared with Vorkuta's inhabitants, who perceived air pollution as the primary environmental threat. Our studies indicate that the principal sources of atmospheric emissions and local deposition within 25 to 40 km of Vorkuta were coal combustion from power and heating plants, coal mines, and a cement factory. Local people evaluated air pollution from direct observations and personal experiences, such as discoloration of snow and respiratory problems, whereas scientific knowledge played a minor role in shaping these perceptions.

MBL-MEL, a simple model of ecosystem biogeochemistry, is amended and applied to plant and soil C, 14N and 15N data for the summers of 2001–2003 from Brandalpynten, a maritime high Arctic site on Svalbard following the application of 15N (99 atom%) as 15NO3-N at or 15NH4-N at concentrations of 1 or 5 kg N ha−1. Variants of this Parent model are also developed to incorporate: temperature dependence into equations describing nutrient fluxes (Temp model); cryptogams (Cryp model); both features combined (CrypTemp model). Goodness-of-fit (GOF) statistics suggest that the addition of temperature-dependence improves the utility of models with and without cryptogams: the residual weighted sums of squares per data point were 5.69, 3.91, 4.31 and 3.93 for the Parent, Temp, Cryp and CrypTemp models respectively. The application of model selection criteria confirm that the addition of temperature-dependence also improves model generalisability. Across all models, the principal discrepancies between observation and prediction are associated with the inorganic soil 15N pool. We conclude that models in which fluxes are described using simple equations that can be augmented to include additional complexity, are an ideal starting point from which the relationship between GOF and model generalisability can be assessed.

The chemical composition of terricolous lichens, top-soil and abundance and diversity of lichen communities were assessed at eight sites in the Pechora basin during the summer of 2000 and 2001 to assess local impacts of oil and gas operations. Sites close to industrial areas were compared with areas considered to be pristine. The broad objective of the study was to identify changes in the chemistry of a suite of lichens that could be caused by pollutants from the industrial sites. In particular, increases in the ratios of K:Mg and K:Ca + Mg are indicators of acid deposition and increased N indicates increased N deposition. Lead was also measured in lichens. Other elements measured were Ba, Ca, Cd, Cu, K, Mg, Na, Ni, Pb, Sr and Zn in top-soils. The Pechora basin, north-eastern European Russia, includes the north and east of the Komi Republic and a major portion of the Nenets Autonomous region. It is bounded by the Ural mountains to the east and by the Timan range to the west. The area has extensive natural resources, both renewable (e.g. forests) and non-renewable (e.g. minerals, coal, oil and gas). There were limited modifications in the chemistry of lichens and top-soils and lichen diversity close to an oil and gas industrial complex. Here, there were elevations of lead and nitrogen concentrations in lichen apices and in the apical:basal nitrogen ratio in Flavocetraria cucullata , with lower lichen diversity in epigeal and epiphytic lichens. Elevated concentrations of Ba and Ca were found in soil-ash over the 0–5 cm horizon, probably as a result of local emissions from construction activity and gas flaring, rather than from long-range transport. Virtually all other sites remained unmodified and reflected background concentrations. The ecological impacts of the measured pollution loads were low, as elemental concentrations were generally below detection limits, except for one industrial site, where there were signs of an early indicator of industrial activity.