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A proper understanding of the residual value of zinc (Zn) is necessary for sustainable biofortification of food crops. This study aimed to establish the extent to which application of Zn at the national rate, plus two experimentally elevated rates, in one year provided any benefit to plant yield and nutritional quality in the following growing season. Residual effects of soil-applied Zn on grain Zn concentration and uptake were estimated by an experiment in which maize was grown in successive seasons at two agricultural research stations in Malawi, with Zn applied to the soil in the first season but not the second. At each site two common soil types were used: Lixisols and Vertisols. The study used three Zn fertilizer rates of 1, 30 and 90 kg Zn ha -1 applied to the soil in the previous cropping season, arranged in a randomized complete block design (RCBD) with 10 replications at each experimental site. At harvest, maize grain yield and Zn concentration in grain and stover were measured; Zn uptake by maize grain and stover were determined and Zn harvest index was calculated. Effects on grain yield and Zn uptake by the crop were assessed in relation to residual Zn fertilizer and soil type. Maize grain yield on plots in the second season where 30 kg Zn ha -1 had been applied exceeded that on second season plots where 1 kg Zn ha -1 had been applied by 25%. The grain Zn concentration and Zn uptake in the second season after fertilizer application were larger by 13% and 30% respectively on the plots which had received 30 kg Zn ha -1 than those which had received 1 kg Zn ha -1 . There was no evidence that applying Zn at 90 kg Zn ha -1 resulted in larger crop yield, grain Zn concentration, or Zn uptake the second year after application than was seen in plots the second year after application of 30 kg Zn ha -1 . The magnitude of the benefits attributed to residual effects of soil-applied Zn did not depend on soil type. Conclusively, the residual effects of 30 kg ha -1 of soil-applied Zn in the preceding season benefited the subsequent maize compared to the national recommendation of 1 kg Zn ha -1 . The benefits of larger applications of Zn than the current national recommendations should be considered across at least two seasons and for different crops.

Amazonian Dark Earths (ADEs) are unusually fertile soils characterised by elevated concentrations of microscopic charcoal particles, which confer their distinctive colouration. Frequent occurrences of pre-Columbian artefacts at ADE sites led to their ubiquitous classification as Anthrosols (soils of anthropic origin). However, it remains unclear how indigenous peoples created areas of high fertility in one of the most nutrient-impoverished environments on Earth. Here, we report new data from a well-studied ADE site in the Brazilian Amazon, which compel us to reconsider its anthropic origin. The amounts of phosphorus and calcium—two of the least abundant macronutrients in the region—are orders of magnitude higher in ADE profiles than in the surrounding soil. The elevated levels of phosphorus and calcium, which are often interpreted as evidence of human activity at other sites, correlate spatially with trace elements that indicate exogenous mineral sources rather than in situ deposition. Stable isotope ratios of neodymium, strontium, and radiocarbon activity of microcharcoal particles also indicate exogenous inputs from alluvial deposition of carbon and mineral elements to ADE profiles, beginning several thousands of years before the earliest evidence of soil management for plant cultivation in the region. Our data suggest that indigenous peoples harnessed natural processes of landscape formation, which led to the unique properties of ADEs, but were not responsible for their genesis. If corroborated elsewhere, this hypothesis would transform our understanding of human influence in Amazonia, opening new frontiers for the sustainable use of tropical landscapes going forward., Amazonian Dark Earth is soil that has had mysteriously high fertility since ancient times, despite the fact that surrounding soils have very low nutrients. Here the authors’ use of isotope reconstructions indicate that these soils predate human settlement and could have alluvial and burning origins.

Consumption of yerba mate occurs mostly in the form of hot infusion (chimarrao). Water solubility of elements found in commercialized yerba mate is needed to establish nutritional value and risks associated with potentially toxic elements. In this study, yerba mate products marketed in three Brazilian states (Parana, Santa Catarina, and Rio Grande do Sul) for chimarrao were analyzed. Total (dry product) and hot water-soluble concentrations of Al, As, B, Ba, Ca, Cd, Co, Cs, Cu, Fe, K, Li, Mg, Mn, Mo, Ni, P, Pb, Rb, S, Se, Sr, Ti, V, and Zn were determined by inductively coupled plasma mass spectroscopy (ICP-MS). Total concentrations of the ten top elements followed the order of K>Ca>Mg>Mn>P>S>Al>Fe>Ba>Zn. The most soluble elements were B, Cs, Ni, Rb, and K, with values greater than 80%. The lowest water-soluble elements were V, Fe, and Ti (values

© 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

Multiple micronutrient deficiencies are widespread in Ethiopia. However, the distribution of Se and Zn deficiency risks has previously shown evidence of spatially dependent variability, warranting the need to explore this aspect for wider micronutrients. Here, blood serum concentrations for Ca, Mg, Co, Cu and Mo were measured (n 3102) on samples from the Ethiopian National Micronutrient Survey. Geostatistical modelling was used to test spatial variation of these micronutrients for women of reproductive age, who represent the largest demographic group surveyed (n 1290). Median serum concentrations were 8·6 mg dl−1 for Ca, 1·9 mg dl−1 for Mg, 0·4 µg l−1 for Co, 98·8 µg dl−1 for Cu and 0·2 µg dl−1 for Mo. The prevalence of Ca, Mg and Co deficiency was 41·6 %, 29·2 % and 15·9 %, respectively; Cu and Mo deficiency prevalence was 7·6 % and 0·3 %, respectively. A higher prevalence of Ca, Cu and Mo deficiency was observed in north western, Co deficiency in central and Mg deficiency in north eastern parts of Ethiopia. Serum Ca, Mg and Mo concentrations show spatial dependencies up to 140–500 km; however, there was no evidence of spatial correlations for serum Co and Cu concentrations. These new data indicate the scale of multiple mineral micronutrient deficiency in Ethiopia and the geographical differences in the prevalence of deficiencies suggesting the need to consider targeted responses during the planning of nutrition intervention programmes.

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.

A controlled in-vitro experiment was conducted to determine the bioaccessibility of extrinsic soil iron in pearl millet contaminated with typical Malawian soils. Pearl millet was contaminated with soils at ratios typically encountered in real life. Iron concentrations of soil-contaminated flour increased such that soil-derived iron contributed 56, 83 and 91% of the total iron when the proportions of soil were 0.1, 0.5 and 1% (soil: grain w/w), respectively. When soils were digested alone, the concentration of bioaccessible iron differed depending on the type of soil. However, the concentration of bioaccessible iron in soil-contaminated flours did not exceed that of uncontaminated flour and there was no effect of soil type. This suggests that knowledge of the proportion of extrinsic soil iron in soil-contaminated grains would be useful for iron bioavailability estimations. Vanadium is a reliable indicator of the presence of extrinsic soil iron in grains and has potential applications in this regard.

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.

Foliar selenium (Se) fertilisation has been shown to be more efficient than soil-applied fertilisation, but the dynamics of absorption and translocation have not yet been explored. An experiment was undertaken to investigate time-dependent changes in the absorption, transformation, and distribution of Se in wheat when 77Se-enriched sodium selenate (Sefert) was applied to the leaves at a rate of 3.33 μg Se per kg soil (equivalent to 10 g ha−1) and two growth stages, namely stem elongation, Zadoks stage 31/32 (GS1), and heading stage, Zadoks stage 57 (GS2). The effect of urea inclusion in foliar Se fertilisers on the penetration rates of Se was also investigated. Wheat was harvested at 3, 10, and 17 days and 3, 10, and 34 days after Se applications at GS1 and GS2, respectively. Applying foliar Se, irrespective of the formulation, brought grain Se concentration to a level high enough to be considered adequate for biofortification. Inclusion of N in the foliar Se solution applied at an early growth stage increased recoveries in the plants, likely due to improved absorption of applied Se through the young leaves. At a later growth stage, the inclusion of N in foliar Se solutions was also beneficial as it improved the assimilation of applied inorganic Se into bioavailable selenomethionine, which was then rapidly translocated to the grain. The practical knowledge gained about the optimisation of Se fertiliser formulation, method, and timing of application will be of importance in refining biofortification programs across different climatic regimes.

Aim Magnesium (Mg) deficiency (known as grass tetany) is a serious metabolic disorder that affects grazing ruminants. We tested whether Mg-fertiliser can increase Mg concentration of Italian ryegrasses (Lolium multiflorum L.) including a cultivar (cv. Bb2067; ‘Magnet’), bred to accumulate larger concentrations of Mg. Methods Under controlled environment (CE) conditions, three cultivars (cv. Bb2067, cv. Bb2068, cv. RvP) were grown in low-nutrient compost at six fertiliser rates (0–1500 μM MgCl2.6H2O). Under field conditions, the three cultivars in the CE condition and cv. Alamo were grown at two sites, and four rates of MgSO4 fertiliser application rates (0–200 kg ha−1 MgO). Multiple grass cuts were taken over two-years. Results Grass Mg concentration increased with increasing Mg-fertiliser application rates in all cultivars and conditions. Under field conditions, cv. Bb2067 had 11–73% greater grass Mg concentration and smaller forage tetany index (FTI) than other cultivars across the Mg-fertiliser application rates, sites and cuts. Grass dry matter (DM) yield of cv. Bb2067 was significantly (p p ≥ 0.05). Conclusions Biofortification of grass with Mg through breeding and agronomy can improve the forage Mg concentration for grazing ruminants, even in high-growth spring grass conditions when hypomagnesaemia is most prevalent. Response to agronomic biofortification varied with cultivar, Mg-fertiliser rate, site and weather. The cost:benefit of these approaches and farmer acceptability, and the impact on cattle and sheep grazing on grasses biofortified with Mg requires further investigation.

Iodine is an essential trace element for humans and grazing animals and is often deficient. Our aim was to investigate the role of soil properties in retaining and ‘fixing' iodine in soils and thereby controlling its phyto-availability to grass. Soils were spiked with labelled 129IO3− and rye grass (Lolium perenne L.) was grown to measure iodine uptake by grass as a function of yield, soil properties and continuous 127I inputs from irrigation water. Iodine-129 added at the start of the uptake trial was rapidly fixed (t1/2 c. 40 h) into non-labile humus-bound forms in soil. The 129I/127I isotopic ratio in grass, compared to the ratio in soil, declined over time confirming progressive 129I fixation into the soil solid phase. The rate of fixation was controlled by soil properties. A model describing iodine dynamics and uptake accounted for c. 75% of the variation in iodine concentration in grass. For most of the soils studied, the main source of iodine in herbage probably arises from the transient availability of periodic rainfall inputs rather than from soil sources. This is expected to improve biofortification strategies.

BACKGROUND Selenium (Se) is a nutrient for animals and humans, and is considered beneficial to higher plants. Selenium concentrations are low in most soils, which can result in a lack of Se in plants, and consequently in human diets. Phytic acid (PA) is the main storage form of phosphorus in seeds, and it is able to form insoluble complexes with essential minerals in the monogastric gut. This study aimed to establish optimal levels of Se application to cowpea, with the aim of increasing Se concentrations. The efficiency of agronomic biofortification was evaluated by the application of seven levels of Se (0, 2.5, 5, 10, 20, 40, and 60 g ha-1 ) from two sources (selenate and selenite) to the soil under field conditions in 2016 and 2017. RESULTS Application of Se as selenate led to greater plant Se concentrations than application as selenite in both leaves and grains. Assuming human cowpea consumption of 54.2 g day-1 , Se application of 20 g ha-1 in 2016 or 10 g ha-1 in 2017 as selenate would have provided a suitable daily intake of Se (between 20 and 55 μg day-1 ) for humans. Phytic acid showed no direct response to Se application. CONCLUSION Selenate provides greater phytoavailability than selenite. The application of 10 g Se ha-1 of selenate to cowpea plants could provide sufficient seed Se to increase daily human intake by 13-14 μg d-1 . © 2019 Society of Chemical Industry.

Correlations between juvenile wheat root traits, and grain yield and yield component traits under optimal field conditions have previously been reported in some conditions. The aim of this study was to test the hypothesis that juvenile wheat root traits correlate with yield, yield components and grain mineral composition traits under a range of soil environments in India. A diverse panel of 36 Indian wheat genotypes were grown for ten days in ‘pouch and wick’ high-throughput phenotyping (HTP) system (20 replicates). Correlations between juvenile root architecture traits, including primary and lateral root length, and grain yield, yield components and grain mineral composition traits were determined, using field data from previously published experiments at six sites in India. Only a limited number of juvenile root traits correlated with grain yield (GYD), yield components, and grain mineral composition traits. A narrow root angle, potentially representing a ‘steep’ phenotype, was associated with increased GYD and harvest index (HI) averaged across sites and years. Length related root traits were not correlated with GYD or HI at most sites, however, the total length of lateral roots and lateral root number correlated with GYD at a sodic site of pH 9.5. The total length of lateral roots (TLLR) correlated with grain zinc (Zn) concentration at one site. A wider root angle, representing a shallow root system, correlated with grain iron (Fe) concentration at most sites. The total length of all roots (TLAR) and total length of primary roots (TLPR) correlated with grain S concentration at most sites. Narrow root angle in juvenile plants could be a useful proxy trait for screening germplasm for improved grain yield. Lateral root and shallow root traits could potentially be used to improve grain mineral concentrations. The use of juvenile root traits should be explored further in wheat breeding for diverse environments.

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.

The aim of this work was to assess the origins, mobility, bioavailability and potential health risks of V, Cr, Co, As, Se, Mo, Cd, Sn and Sb, which are not sufficiently studied in the terrestrial environment of Egypt. This has been carried out by employing a combination of chemical fractionation, plants uptake, mathematical modeling and risk assessment approaches on a wide range of soils and plants sampled from industrial, urban and agricultural locations across Egypt. The contents of As, Cd, Sn and Sb were elevated in the soils of some urban and industrial locations within Cairo, although their soil geo-accumulation (I

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.

© 2021 The Author(s) The purpose of this research was to explore the speciation and bioaccessibility of native soil-derived selenium (Se) versus Se applied via fertiliser in the edible portions of maize, groundnut and cowpea grown in Malawi. Fertiliser-derived Se, applied as isotopically labelled selenate, contributed 88–97% of the total Se in the edible portions. Both soil and fertiliser-derived Se were transformed into similar species, with more than 90% of the extracted Se in an organic form. The main form of fertiliser-derived Se in grain was selenomethionine with an abundance of 92.0 ± 7.6% in maize, 63.7 ± 6.2% in cowpea and 85.2 ± 1.9% in groundnut. In addition, cowpea contained 32.7 ± 6.2% of Se-methyl-selenocysteine. The mean bioaccessibility of fertiliser-derived Se was 73.9 ± 8.5% with no statistically-significant difference across all crops despite some variation in speciation. Understanding the contribution of fertiliser-derived Se to the formation of organic forms of Se in crops is crucial, given that organic Se species are more bioaccessible than inorganic forms.

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.

A survey of wheat grain from 120 fields in Sulaimanyah province, Kurdistan region, Iraq was undertaken in 2017. We evaluated the concentrations of phosphorus (P), Zn and phytic acid (PA) and the estimated Zn bioavailability in wheat grain grown in the calcareous soils of the region. Concentrations of P in wheat grain were higher than the recommended value of 3570 mg kg− 1; PA was within the range of other countries but Zn concentration in 88% of wheat grain samples fell below the value recommended for human nutrition of 41.6 mg kg− 1. Bioavailable Zn intake (mg d− 1) was estimated assuming bread consumption of 300 g day− 1 in the region. Considering PA and Zn intake suggested only 21.5 ± 2.9% of whole grain flour Zn was bioavailable. Thus the effective Zn intakes from whole wheat was only 1.25–2.05 mg d− 1 for the local population. Typical dietary Zn was below recommended levels (11 mg d− 1), due to low soil Zn uptake by wheat and the large concentrations of PA in wheat grains, probably from over-use of phosphate fertilizer.

Made available in DSpace on 2021-06-25T10:25:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-05-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Dietary zinc (Zn) deficiency is widespread globally, and is particularly prevalent in low- and middle-income countries (LMICs). Cowpea (Vigna unguiculata (L.) Walp) is consumed widely in LMICs due to its high protein content, and has potential for use in agronomic biofortification strategies using Zn. This study aimed to evaluate the effect of Zn biofortification on grain nutritional quality of 29 cowpea genotypes. Zn application did not increase cowpea yield. In 11 genotypes sucrose concentration, in 12 genotypes total sugar concentration, and in 27 genotypes storage protein concentration increased in response to Zn supply. Fifteen genotypes had lower concentrations of amino acids under Zn application, which are likely to have been converted into storage proteins, mostly comprised of albumin. Phytic acid (PA) concentration and PA/Zn molar ratio were decreased under Zn application. Six genotypes increased shoot ureides concentration in response to Zn fertilization, indicating potential improvements to biological nitrogen fixation. This study provides valuable information on the potential for Zn application to increase cowpea grain nutritional quality by increasing Zn and soluble storage protein and decreasing PA concentration. These results might be useful for future breeding programs aiming to increase cowpea grain Zn concentrations through biofortification. São Paulo State University (UNESP) São Paulo State University (UNESP), Rua Domingos da Costa Lopes 780, Jd. Itaipu Embrapa Meio-Norte School of Biosciences University of Nottingham, Sutton Bonington The James Hutton Institute, Invergowrie National Key Laboratory of Crop Genetic Improvement Huazhong Agricultural University São Paulo State University (UNESP) São Paulo State University (UNESP), Rua Domingos da Costa Lopes 780, Jd. Itaipu FAPESP: 18/18936-6 CNPq: 309380/2017-0

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.

IntroductionMicronutrient deficiencies, commonly referred to as ‘hidden hunger’, affect more than two billion people worldwide, with zinc and iron-deficiency frequently reported. The aim of this study is to examine the impact of consuming zinc biofortified flour (Zincol-2016) on biochemical and functional measures of status in adolescent girls and children living in a low-resource setting in Pakistan.Methods and analysisWe are conducting a pragmatic, cluster-randomised, double-blind, controlled trial. A total of 482 households have been recruited from two catchment areas approximately 30–40 km distance from Peshawar. Household inclusion criteria are the presence of both an adolescent girl, aged 10–16 years, and a child aged 1–5 years. The study duration is 12 months, divided into two 6-month phases. During phase 1, all households will be provided with locally procured flour from standard varieties of wheat. During phase 2, clusters will be paired, and randomised to either the control or intervention arm of the study. The intervention arm will be provided with zinc biofortified wheat flour, with a target zinc concentration of 40 mg/kg. The control arm will be provided with locally procured wheat flour from standard varieties with an expected zinc concentration of 20 mg/kg. The primary outcome measure is plasma zinc concentration. Secondary outcomes include anthropometric measurements, biomarkers of iron and zinc status, and the presence and duration of respiratory tract infections and diarrhoea.Ethics and disseminationEthical approval was granted from the University of Central Lancashire STEMH Ethics Committee (reference number: STEMH 1014) and Khyber Medical University Ethics Committee (DIR/KMU-EB/BZ/000683). The final study methods will be published in peer-reviewed journals, alongside the study outcomes. In addition, findings will be disseminated to the scientific community via conference presentations and abstracts and communicated to the study participants through the village elders at an appropriate community forum.Trial registration numberISRCTN17107812; Pre-results.

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.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

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.

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.

Selenium (Se) is an essential element for human health and livestock productivity. Globally, human Se status is highly variable, mainly due to the influence of soil types on the Se content of crops, suggesting the need to identify areas of deficiency to design targeted interventions. In sub-Saharan Africa, including Ethiopia, data on population Se status are largely unavailable, although previous studies indicated the potential for widespread Se deficiency. Serum Se concentration of a nationally representative sample of the Ethiopian population was determined, and these observed values were combined with a spatial statistical model to predict and map the Se status of populations across the country. The study used archived serum samples (n = 3269) from the 2015 Ethiopian National Micronutrient Survey (ENMS). The ENMS was a cross-sectional survey of young and school-age children, women and men. Serum Se concentration was measured using inductively coupled plasma mass spectrometry (ICPMS). The national median (Q1, Q3) serum Se concentration was 87.7 (56.7, 123.0) &mu, g L&minus, 1. Serum Se concentration differed between regions, ranging from a median (Q1, Q3) of 54.6 (43.1, 66.3) &micro, 1 in the Benishangul-Gumuz Region to 122.0 (105, 141) &micro, 1 in the Southern Nations, Nationalities, and Peoples&rsquo, Region and the Afar Region. Overall, 35.5% of the population were Se deficient, defined as serum Se &lt, 70 &micro, 1. A geostatistical analysis showed that there was marked spatial dependence in Se status, with serum concentrations greatest among those living in North-East and Eastern Ethiopia and along the Rift Valley, while serum Se concentrations were lower among those living in North-West and Western Ethiopia. Selenium deficiency in Ethiopia is widespread, but the risk of Se deficiency is highly spatially dependent. Policies to enhance Se nutrition should target populations in North-West and Western Ethiopia.

Selenium (Se) is an essential element for human health. However, our knowledge of the prevalence of Se deficiency is less than for other micronutrients of public health concern such as iodine, iron and zinc, especially in sub-Saharan Africa (SSA). Studies of food systems in SSA, in particular in Malawi, have revealed that human Se deficiency risks are widespread and influenced strongly by geography. Direct evidence of Se deficiency risks includes nationally representative data of Se concentrations in blood plasma and urine as population biomarkers of Se status. Long-range geospatial variation in Se deficiency risks has been linked to soil characteristics and their effects on the Se concentration of food crops. Selenium deficiency risks are also linked to socio-economic status including access to animal source foods. This review highlights the need for geospatially-resolved data on the movement of Se and other micronutrients in food systems which span agriculture–nutrition–health disciplinary domains (defined as a GeoNutrition approach). Given that similar drivers of deficiency risks for Se, and other micronutrients, are likely to occur in other countries in SSA and elsewhere, micronutrient surveillance programmes should be designed accordingly.

Novel ANOVA methodology was used to benchmark ICP-QMS against MC-ICP-MS for Pb isotope ratios, demonstrating “fitness-for-purpose” in environmental source apportionment. The precision and accuracy of lead (Pb) isotope measurements obtained from quadrupole-based mass spectrometers (ICP-QMS) are considered to be limited by a number of factors originating in different components of the instruments. In this study, experimental and instrumental protocols were optimised for determining lead isotope ratios in urban soil digests. Experimental measures included individual dilution of all samples and isotopic standards (SRM-981, NIST) to a single Pb concentration intended to produce an intensity which was high enough to negate blanks and interferences but low enough to ensure the detector operated only in pulse counting mode. Instrumental protocols included batch dead time correction, optimisation of dwell time and the number of scans employed and correction of mass discrimination by sequential application of both internal (203Tl/205Tl ratio) and external (SRM-981, NIST) standards. This optimised methodology was benchmarked against multi-collector mass spectrometer (MC-ICP-MS) measurements of Pb isotope ratios using replicate digest solutions of the same soil; but after these had been subjected to Pb separation using an ion-exchange procedure. On the assumption that MC-ICP-MS measurements are more accurate, small additive and multiplicative differences were observed in only the 4th decimal place. ANOVA was used to compare the precisions of the two techniques demonstrating equal precisions c. 0.08% for 207Pb/206Pb, suggesting a sample heterogeneity limitation. By contrast, for 207Pb/204Pb, the worst-case ratio, ICP-QMS had a 10-fold poorer precision, despite negligible interference from 204Hg, implying an instrumental limitation. The study concludes that ICP-QMS can provide valuable source apportionment information for most Pb isotope ratios but further efforts should focus on improving assay of the 207Pb/204Pb ratio.

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.

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.

Selenium biofortification of crops is a proven technology for improving dietary nutrition. This study used isotopically labelled selenate (>99% enriched 77Se) to assess uptake and Se availability to two green vegetables, Brassica napus L (B. napus) and Amaranthus retroflexus L (A. retroflexus) grown in three contrasting Malawi soils: a Vertisol (calcareous), Alfisol (moderately acidic) and Oxisol (acidic). Plants were grown under glasshouse conditions (4 replicates; 6 kg soil per pot) following application of 77Se-enriched selenate at rates equivalent to 0, 10 and 20 g ha−1. Leaves were harvested at fortnightly intervals and the plants were then allowed to re-grow, to simulate cultivation practice. Leaf samples were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) for selenium isotopes (77Se and 78Se). The isotopic data were processed to quantify the contribution to plant Se concentration from the fertilizer and the soil. Both concentration and uptake of the fertilizer 77Se declined sharply with sequential harvests due to progressive fixation of 77Se in the soil rather than exhaustion (by uptake) of the Se applied. Initially the bioavailability of fertilizer Se was three orders of magnitude greater than the soil Se but this declined to the same order of magnitude by the end of the trial. Application of 77Se had no effect on uptake of soil-derived Se. There were marked differences between the three soils studied. The relative bio-availability of the fertilizer Se followed the sequence (Vertisol > Alfisol > Oxisol) but the two crops showed the same trend in decline of fertilizer Se uptake. Thus, fixation of selenium in the soils studied was sufficiently rapid that Se biofortification of green vegetables subject to several harvests would require multiple applications during the growing season.