A new hazard assessment workflow to assess soil contamination from large and artisanal scale gold mining.

Gold mining activities are undertaken both at large and artisanal scale, often resulting in serious 'collateral' environmental issues, including environmental pollution and hazard to human and ecosystem health. Furthermore, some of these activities are poorly regulated, which can produce long-lasting damage to the environment and local livelihoods. The aim of this study was to identify a new workflow model to discriminate anthropogenic versus geogenic enrichment in soils of gold mining regions. The Kedougou region (Senegal, West Africa) was used as a case study. Ninety-four soil samples (76 topsoils and 18 bottom soils) were collected over an area of 6,742 km2 and analysed for 53 chemical elements. Robust spatial mapping, compositional and geostatistical models were employed to evaluate sources and elemental footprint associated with geology and mining activities. Multivariate approaches highlighted anomalies in arsenic (As) and mercury (Hg) distribution in several areas. However, further interpretation with enrichment factor (EFs) and index of geoaccumulation (IGeo) emphasised high contamination levels in areas approximately coinciding with the ones where artisanal and small scale mining (ASGM) activities occur, and robust compositional contamination index (RCCI) isolated potentially harmful elements (PHE) contamination levels in very specific areas of the Kedougou mining region. The study underlined the importance of complementary approaches to identify anomalies and, more significantly, contamination by hazardous material. In particular, the analyses helped to identify discrete areas that would require to be surveyed in more detail to allow a comprehensive and thorough risk assessment, to investigate potential impacts to both human and ecosystem health.

Environmental and human iodine and selenium status: lessons from Gilgit-Baltistan, North-East Pakistan.

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.

Multiple geochemical factors may cause iodine and selenium deficiency in Gilgit-Baltistan, Pakistan.

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 < 7% and < 5% of their total concentrations in soil. More than 90% of reactive iodine was organic; iodide was the main inorganic species. By contrast, 66.9 and 39.7% of 'soluble' and 'adsorbed' selenium, respectively, were present as organic species; inorganic selenium was mainly selenite. Very low distribution coefficients (kd = adsorbed/soluble; L kg-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.

Fate of selenium in biofortification of wheat on calcareous soil: an isotopic study.

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).

Urine selenium concentration is a useful biomarker for assessing population level selenium status.

Plasma selenium (Se) concentration is an established population level biomarker of Se status, especially in Se-deficient populations. Previously observed correlations between dietary Se intake and urinary Se excretion suggest that urine Se concentration is also a potentially viable biomarker of Se status. However, there are only limited data on urine Se concentration among Se-deficient populations. Here, we test if urine is a viable biomarker for assessing Se status among a large sample of women and children in Malawi, most of whom are likely to be Se-deficient based on plasma Se status. Casual (spot) urine samples (n = 1406) were collected from a nationally representative sample of women of reproductive age (WRA, n =741) and school aged children (SAC, n=665) across Malawi as part of the 2015/16 Demographic and Health Survey. Selenium concentration in urine was determined using inductively coupled plasma mass spectrometry (ICP-MS). Urinary dilution corrections for specific gravity, osmolality, and creatinine were applied to adjust for hydration status. Plasma Se status had been measured for the same survey participants. There was between-cluster variation in urine Se concentration that corresponded with variation in plasma Se concentration, but not between households within a cluster, or between individuals within a household. Corrected urine Se concentrations explained more of the between-cluster variation in plasma Se concentration than uncorrected data. These results provide new evidence that urine may be used in the surveillance of Se status at the population level in some groups. This could be a cost-effective option if urine samples are already being collected for other assessments, such as for iodine status analysis as in the Malawi and other national Demographic and Health Surveys.

Using human hair and nails as biomarkers to assess exposure of potentially harmful elements to populations living near mine waste dumps.

Potentially harmful elements (PHEs) manganese (Mn), cobalt (Co), copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn) were measured in human hair/nails, staple crops and drinking water to ascertain the level of exposure to dust transference via wind and rain erosion for members of the Mugala community living near a mine waste dump in the Zambian Copperbelt. The mean PHE concentrations of hair in decreasing order were Zn (137 ± 21 mg/kg), Cu (38 ± 7 mg/kg), Mn (16 ± 2 mg/kg), Pb (4.3 ± 1.9 mg/kg), Ni (1.3 ± 0.2 mg/kg) and Cr (1.2 ± 0.2 mg/kg), Co (0.9 ± 0.2 mg/kg) and Cd (0.30 ± 0.02 mg/kg). Whilst for toenails the decreasing order of mean concentrations was Zn (172 ± 27 mg/kg), Cu (30 ± 5 mg/kg), Mn (12 ± 2 mg/kg), Pb (4.8 ± 0.5 mg/kg), Ni (1.7 ± 0.14 mg/kg) and Co (1.0 ± 0.02 mg/kg), Cr (0.6 ± 0.1 mg/kg) and Cd (0.1 ± 0.002 mg/kg). The concentration of these potentially harmful elements (PHEs) varied greatly among different age groups. The results showed that Mn, Co, Pb, Cd and Zn were above the interval values (Biolab in Nutritional and environmental medicine, Hair Mineral Analysis, London, 2012) at 0.2-2.0 mg/kg for Mn, 0.01-0.20 mg/kg for Co, < 2.00 mg/kg for Pb, < 0.10 mg/kg for Cd and 0.2-2.00 mg/kg for Zn, whilst Ni, Cu and Cr concentrations were within the normal range concentrations of < 1.40 mg/kg, 10-100 mg/kg and 0.1-1.5 mg/kg, respectively. Dietary intake of PHEs was assessed from the ingestion of vegetables grown in Mugala village, with estimated PHE intakes expressed on a daily basis calculated for Mn (255), Pb (48), Ni (149) and Cd (33) µg/kg bw/day. For these metals, DI via vegetables was above the proposed limits of the provisional tolerable daily intakes (PTDIs) (WHO in Evaluation of certain food additive and contaminants, Seventy-third report of the Joint FAO/WHO Expert Committee on Food Additives, 2011) for Mn at 70 µg/kg bw/day, Pb at 3 µg/kg bw/day, Ni and Cd 5 µg/kg bw/day and 1 µg/kg bw/day, respectively. The rest of the PHEs listed were within the PTDIs limits. Therefore, Mugala inhabitants are at imminent health risk due to lead, nickel and cadmium ingestion of vegetables and drinking water at this location.

Source apportionment of micronutrients in the diets of Kilimanjaro,Tanzania and Counties of Western Kenya.

Soil, water and food supply composition data have been combined to primarily estimate micronutrient intakes and subsequent risk of deficiencies in each of the regions studied by generating new data to supplement and update existing food balance sheets. These data capture environmental influences, such as soil chemistry and the drinking water sources to provide spatially resolved crop and drinking water composition data, where combined information is currently limited, to better inform intervention strategies to target micronutrient deficiencies. Approximately 1500 crop samples were analysed, representing 86 food items across 50 sites in Tanzania in 2013 and >230 sites in Western Kenya between 2014 and 2018. Samples were analysed by ICP-MS for 58 elements, with this paper focussing on calcium (Ca), copper (Cu), iron (Fe), magnesium (Mg), selenium (Se), iodine (I), zinc (Zn) and molybdenum (Mo). In general, micronutrient supply from food groups was higher from Kilimanjaro,Tanzania than Counties in Western Kenya, albeit from a smaller sample. For both countries leafy vegetable and vegetable food groups consistently contained higher median micronutrient concentrations compared to other plant based food groups. Overall, calculated deficiency rates were <1% for Cu and Mo and close to or >90% for Ca, Zn and I in both countries. For Mg, a slightly lower risk of deficiency was calculated for Tanzania at 0 to 1% across simplified soil classifications and for female/males, compared to 3 to 20% for Kenya. A significant difference was observed for Se, where a 3 to 28% risk of deficiency was calculated for Tanzania compared to 93 to 100% in Kenya. Overall, 11 soil predictor variables, including pH and organic matter accounted for a small proportion of the variance in the elemental concentration of food. Tanzanian drinking water presented several opportunities for delivering greater than 10% of the estimated average requirement (EAR) for micronutrients. For example, 1 to 56% of the EAR for I and up to 10% for Se or 37% for Zn could be contributed via drinking water.

The risk of selenium deficiency in Malawi is large and varies over multiple spatial scales.

Selenium (Se) is an essential human micronutrient. Deficiency of Se decreases the activity of selenoproteins and can compromise immune and thyroid function and cognitive development, and increase risks from non-communicable diseases. The prevalence of Se deficiency is unknown in many countries, especially in sub-Saharan Africa (SSA). Here we report that the risk of Se deficiency in Malawi is large among a nationally representative population of 2,761 people. For example, 62.5% and 29.6% of women of reproductive age (WRA, n = 802) had plasma Se concentrations below the thresholds for the optimal activity of the selenoproteins glutathione peroxidase 3 (GPx3; <86.9 ng mL-1) and iodothyronine deiodinase (IDI; <64.8 ng mL-1), respectively. This is the first nationally representative evidence of widespread Se deficiency in SSA. Geostatistical modelling shows that Se deficiency risks are influenced by soil type, and also by proximity to Lake Malawi where more fish is likely to be consumed. Selenium deficiency should be quantified more widely in existing national micronutrient surveillance programmes in SSA given the marginal additional cost this would incur.

Elemental composition of Malawian rice.

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 <0.005; Mg = 1130 and 265; Mn = 18.2 and 9.6; Se = 0.025 and 0.028; and Zn = 17.0 and 14.4. In brown and white rice samples, respectively, median PA concentrations were 5438 and 1906 mg kg-1, and median PA:Zn molar ratios were 29 and 13. Concentrations of potentially toxic elements (mg kg-1, dry weight) in brown and white rice samples, respectively, were: As = 0.030 and 0.006; Cd  ≤ 0.002 and 0.006; Pb = 0.008 and 0.008. Approximately 95 % of As was found to be inorganic As, where this could be quantified. Malawian rice, like the more widely consumed staple grain maize, contains inadequate Ca, I, Se or Zn to meet dietary requirements. Biofortification strategies could significantly increase Se and Zn concentrations and require further investigation. Concentrations of Fe in rice grain varied greatly, and this was likely due to contamination of rice samples with soil. Risk of As, Cd or Pb toxicity due to rice consumption in Malawi appears to be minimal.

Africa's Oesophageal Cancer Corridor: Geographic Variations in Incidence Correlate with Certain Micronutrient Deficiencies.

BACKGROUND: The aetiology of Africa's easterly-lying corridor of squamous cell oesophageal cancer is poorly understood. Micronutrient deficiencies have been implicated in this cancer in other areas of the world, but their role in Africa is unclear. Without prospective cohorts, timely insights can instead be gained through ecological studies. METHODS: Across Africa we assessed associations between a country's oesophageal cancer incidence rate and food balance sheet-derived estimates of mean national dietary supplies of 7 nutrients: calcium (Ca), copper (Cu), iron (Fe), iodine (I), magnesium (Mg), selenium (Se) and zinc (Zn). We included 32 countries which had estimates of dietary nutrient supplies and of better-quality GLOBCAN 2012 cancer incidence rates. Bayesian hierarchical Poisson lognormal models were used to estimate incidence rate ratios for oesophageal cancer associated with each nutrient, adjusted for age, gender, energy intake, phytate, smoking and alcohol consumption, as well as their 95% posterior credible intervals (CI). Adult dietary deficiencies were quantified using an estimated average requirements (EAR) cut-point approach. RESULTS: Adjusted incidence rate ratios for oesophageal cancer associated with a doubling of mean nutrient supply were: for Fe 0.49 (95% CI: 0.29-0.82); Mg 0.58 (0.31-1.08); Se 0.40 (0.18-0.90); and Zn 0.29 (0.11-0.74). There were no associations with Ca, Cu and I. Mean national nutrient supplies exceeded adult EARs for Mg and Fe in most countries. For Se, mean supplies were less than EARs (both sexes) in 7 of the 10 highest oesophageal cancer ranking countries, compared to 23% of remaining countries. For Zn, mean supplies were less than the male EARs in 8 of these 10 highest ranking countries compared to in 36% of other countries. CONCLUSIONS: Ecological associations are consistent with the potential role of Se and/or Zn deficiencies in squamous cell oesophageal cancer in Africa. Individual-level analytical studies are needed to elucidate their causal role in this setting.

Soil-type influences human selenium status and underlies widespread selenium deficiency risks in Malawi.

Selenium (Se) is an essential human micronutrient with critical roles in immune functioning and antioxidant defence. Estimates of dietary Se intakes and status are scarce for Africa although crop surveys indicate deficiency is probably widespread in Malawi. Here we show that Se deficiency is likely endemic in Malawi based on the Se status of adults consuming food from contrasting soil types. These data are consistent with food balance sheets and composition tables revealing that >80% of the Malawi population is at risk of dietary Se inadequacy. Risk of dietary Se inadequacy is >60% in seven other countries in Southern Africa, and 22% across Africa as a whole. Given that most Malawi soils cannot supply sufficient Se to crops for adequate human nutrition, the cost and benefits of interventions to alleviate Se deficiency should be determined; for example, Se-enriched nitrogen fertilisers could be adopted as in Finland.

A high prevalence of zinc- but not iron-deficiency among women in rural Malawi: a cross-sectional study.

BACKGROUND: Zinc deficiency is often associated with nutritional iron deficiency (ID), and may be exacerbated by low selenium status. AIM: To investigate risk of iron and zinc deficiency in women with contrasting selenium status. METHODS: In a cross-sectional study, 1-day diet composites and blood samples were collected from self-selected Malawian women aged 18-50 years from low- (Zombwe) (n=60) and high-plant-available soil selenium (Mikalango) (n=60) districts. Diets were analyzed for trace elements and blood for biomarkers. RESULTS: Zinc deficiency (>90 %) was greater than ID anemia (6 %), or ID (5 %), attributed to diets low in zinc (median 5.7 mg/day) with high phytate:zinc molar ratios (20.0), but high in iron (21.0 mg/day) from soil contaminant iron. Zombwe compared to Mikalango women had lower (p<0.05) intakes of selenium (6.5 vs. 55.3 µg/day), zinc (4.8 vs. 6.4 mg/day), iron (16.6 vs. 29.6 mg/day), lower plasma selenium (0.72 vs. 1.60 µmol/L), and higher body iron (5.3 vs. 3.8 mg/kg), although plasma zinc was similar (8.60 vs. 8.87 µmol/L). Body iron and plasma zinc were positive determinants of hemoglobin. CONCLUSION: Risk of zinc deficiency was higher than ID and was shown not to be associated with selenium status. Plasma zinc was almost as important as body iron as a hemoglobin determinant.

Maize grain and soil surveys reveal suboptimal dietary selenium intake is widespread in Malawi.

Selenium is an essential element in human diets but the risk of suboptimal intake increases where food choices are narrow. Here we show that suboptimal dietary intake (i.e. 20-30 µg Se person(-1) d(-1)) is widespread in Malawi, based on a spatial integration of Se concentrations of maize (Zea mays L.) grain and soil surveys for 88 field sites, representing 10 primary soil types and >75% of the national land area. The median maize grain Se concentration was 0.019 mg kg(-1) (range 0.005-0.533), a mean intake of 6.7 µg Se person(-1) d(-1) from maize flour based on national consumption patterns. Maize grain Se concentration was up to 10-fold higher in crops grown on soils with naturally high pH (>6.5) (Eutric Vertisols). Under these less acidic conditions, Se becomes considerably more available to plants due to the greater solubility of Se((IV)) species and oxidation to Se((VI)).

Earthworms and in vitro physiologically-based extraction tests: complementary tools for a holistic approach towards understanding risk at arsenic-contaminated sites.

The relationship of the total arsenic content of a soil and its bioaccumulation by earthworms (Lumbricus rubellus and Dendrodrilus rubidus) to the arsenic fraction bioaccessible to humans, measured using an in vitro physiologically-based extraction test (PBET), was investigated. Soil and earthworm samples were collected at 24 sites at the former arsenic mine at the Devon Great Consols (DGC) in southwest England (UK), along with an uncontaminated site in Nottingham, UK, for comparison. Analysis of soil and earthworm total arsenic via inductively coupled plasma mass spectrometry (ICP-MS) was performed following a mixed acid digestion. Arsenic concentrations in the soil were elevated (204-9,025 mg kg(-1)) at DGC. The arsenic bioaccumulation factor (BAF) for both earthworm species was found to correlate positively with the human bioaccessible fraction (HBF), although the correlation was only significant (P < or = 0.05) for L. rubellus. The potential use of both in vitro PBETs and earthworms as complementary tools is explored as a holistic and multidisciplinary approach towards understanding risk at contaminated sites. Arsenic resistant earthworm species such as the L. rubellus populations at DGC are presented as a valuable tool for understanding risk at highly contaminated sites.