Crop uptake of heavy metals in response to the environment and agronomic practices on land near mine tailings in the Zambian Copperbelt Province.

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.

Do soil amendments used to improve agricultural productivity have consequences for soils contaminated with heavy metals?

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.

Reconnaissance sampling and determination of hexavalent chromium in potentially-contaminated agricultural soils in Copperbelt Province, Zambia.

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.

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.

Review: mine tailings in an African tropical environment-mechanisms for the bioavailability of heavy metals in soils.

Heavy metals are of environmental significance due to their effect on human health and the ecosystem. One of the major exposure pathways of Heavy metals for humans is through food crops. It is postulated in the literature that when crops are grown in soils which have excessive concentrations of heavy metals, they may absorb elevated levels of these elements thereby endangering consumers. However, due to land scarcity, especially in urban areas of Africa, potentially contaminated land around industrial dumps such as tailings is cultivated with food crops. The lack of regulation for land-usage on or near to mine tailings has not helped this situation. Moreover, most countries in tropical Africa have not defined guideline values for heavy metals in soils for various land uses, and even where such limits exist, they are based on total soil concentrations. However, the risk of uptake of heavy metals by crops or any soil organisms is determined by the bioavailable portion and not the total soil concentration. Therefore, defining bioavailable levels of heavy metals becomes very important in HM risk assessment, but methods used must be specific for particular soil types depending on the dominant sorption phases. Geochemical speciation modelling has proved to be a valuable tool in risk assessment of heavy metal-contaminated soils. Among the notable ones is WHAM (Windermere Humic Aqueous Model). But just like most other geochemical models, it was developed and adapted on temperate soils, and because major controlling variables in soils such as SOM, temperature, redox potential and mineralogy differ between temperate and tropical soils, its predictions on tropical soils may be poor. Validation and adaptation of such models for tropical soils are thus imperative before such they can be used. The latest versions (VI and VII) of WHAM are among the few that consider binding to all major binding phases. WHAM VI and VII are assemblages of three sub-models which describe binding to organic matter, (hydr)oxides of Fe, Al and Mn and clays. They predict free ion concentration, total dissolved ion concentration and organic and inorganic metal ion complexes, in soils, which are all important components for bioavailability and leaching to groundwater ways. Both WHAM VI and VII have been applied in a good number of soils studies with reported promising results. However, all these studies have been on temperate soils and have not been tried on any typical tropical soils. Nonetheless, since WHAM VII considers binding to all major binding phases, including those which are dominant in tropical soils, it would be a valuable tool in risk assessment of heavy metals in tropical soils. A discussion of the contamination of soils with heavy metals, their subsequent bioavailability to crops that are grown in these soils and the methods used to determine various bioavailable phases of heavy metals are presented in this review, with an emphasis on prospective modelling techniques for tropical soils.