Contamination, risk, and source apportionment of potentially toxic microelements in river sediments and soil after extreme flooding in the Kolubara River catchment in Western Serbia

Climate change is contributing to an increase in extreme weather events. This results in a higher river flooding risk, causing a series of environmental disturbances, including potential contamination of agricultural soil. In Serbia, the catastrophic floods of 2014 affected six river basins, including the Kolubara River Basin, as one of the larger sub-catchments of the large regional Sava River Basin, which is characterized by large areas under agricultural cultures, various geological substrates, and different types of industrial pollution. The main aim of this study was to establish the sources of potentially toxic elements in soil and flood sediments and the effect of the flood on their concentrations. Field sampling was performed immediately after water had receded from the flooded area in May 2014. In total, 36 soil samples and 28 flood sediment samples were collected. After acid digestion (HNO3), concentrations of the most frequent potentially toxic elements (PTE) in agricultural production (As, Cd, Cr, Cu, Ni, Pb, Zn) and Co which are closely related to the geological characteristics of river catchments, were analyzed. The origin, source, and interrelations of microelements, as well as BACKGROUND: values of the PTE of the river catchment, the pollution index (Pi), enrichment factor (Ef), and geological index (Igeo), were determined, using statistical methods such as Pearson correlations, principal component analysis (PCA), and multiple linear regression (MLRA). The content of the hot acid-extractable forms of the elements, PCA, and MLRA revealed a heavy geological influence on microelement content, especially on Ni, Cr, and Co, while an anthropogenic influence was observed for Cu, Zn, and Cd content. This mixed impact was primarily related to mines and their impact on As and Pb content. The pseudo-total concentrations of all the analyzed elements did not prove to be a danger in the catchment area, except for Cu in some samples, indicating point-source pollution, and Ni, whose pseudo-total content could be a limiting factor in agricultural production. For the Ef, the Ni content in 59% soil and 68% flood sediment samples is classified into influence classes. The similar pseudo-total contents of the elements studied in soil samples and flood sediment and their origin indicate that the long-term soil formation process is subject to periodic flooding in the Kolubara River Basin without any significant changes taking place. This implies that floods are not an endangering factor in terms of the contamination of soil by potentially toxic elements in the explored area

Geochemical assessment of metal transfer from rock and soil to water in serpentine areas of Sabah (Malaysia)

The mobility of metals in ultramafic rock–soil systems and metal contamination in serpentine soils were investigated from the Ranau area in Sabah, East Malaysia. Metal concentrations were analysed after division into seven operationally defined fractions by selective sequential extraction (SSE). Geochemical studies showed that the soils are exceptionally high in Cr (95%) residing in refractory residual fractions. Metal speciation studies will shed further light on toxicities in the Malaysian ultramafic tropical environment, reconciled against elemental metal tenure, adopted by common standards

Linking Ni and Cr concentrations to soil mineralogy: does it help to assess metal contamination when the natural background is high?

In soils from serpentinitic areas the natural background of Ni and Cr is so high that the assessment of contamination by comparing metal concentrations with some fixed thresholds may give unreliable results. We therefore sought a quantitative relation between serpentines and Ni and Cr concentrations in uncontaminated soils, evaluated if the approach may help in establishing a baseline, and discussed if additional anthropogenic inputs of Ni and Cr can be realistically individuated in these areas. We analysed the total, acidextractable and exchangeable concentrations of Ni and the total and acid-extractable concentrations of Cr in 66 soil horizons, belonging to 19 poorly developed and uncontaminated Alpine soils. The soils had different amounts of serpentines, depending on the abundance of these minerals in the parent material. We calculated an index of abundance of serpentines in the clay fraction by XRD and related total metal contents to the mineralogical index. We then tested the regressions on potentially contaminated soils, developed on the alluvial plain of the same watershed. We found extremely high total concentrations of Ni (up to 1,887 mg kg\u20131) and Cr (up to 2,218 mg kg\u20131) in the uncontaminated soils, but only a small proportion was extractable. Total Ni and Cr contents were significantly related to serpentine abundance (r2=0.86 and 0.74, respectively). The regressions indicated that even small amounts of serpentines induced metal contents above 200 mg kg\u20131, and the 95% confidence limits were 75 and 111 mg kg\u20131 of Ni and Cr, respectively. When the regressions were tested on the potentially contaminated soils, a good estimate was obtained for Cr, while the Ni concentration was overestimated, probably because of some leaching of this element. The concentrations of Ni and Cr that can be expected in soils because of the presence of small amounts of serpentines are comparable to the amounts accumulated in the soil because of diffuse contamination and potentially contaminated soils had metal concentrations falling in the range expected from the presence of natural sources. Only in the case of very severe contamination events, the identification of anthropogenic sources adding to the natural background would be feasible

Element Case Studies: Nickel

Initial experiments using Mediterranean Ni-hyperaccumulator plants for the purpose of phytomining were carried out in the 1990s. In order to meet commercial phytoextraction requirements, a technology has been developed using hyperaccumulator species with adapted intensive agronomic practices on natural Ni-rich soils. Ultramafic soils in the Balkans display a great variability in Ni concentrations and available Ni levels, both in Albania and the Pindus Mountains of Greece. In Albania, Vertisols are currently being used for low-productivity agriculture (pasture or arable land) on which phytomining could be included in cropping practices. Alyssum murale occurs widely on these ultramafic Vertisols and is a spontaneous weed that grows among other crops. This review chapter presents the different steps that were investigated during the study of soil suitability, and selection of plants up to optimization of agronomic practices, at field scale, as recently developed to reach the implementation stage of Ni agromining in Albania. During a 7-year study we addressed the following questions: (i) what are the optimal soils for Ni agromining in terms of fertility and Ni availability? (ii) what is the phytoextraction potential of local populations of Ni hyperaccumulator species? (iii) what should be the agronomical practices used to optimize the cropping of A. murale for extensive phytomining adapted to a Balkan agricultural setting

Delimiting soil chemistry thresholds for nickel hyperaccumulator plants in Sabah (Malaysia)

Nickel hyperaccumulator plants have been the focus of considerable research because of their unique ecophysiological characteristics that can be exploited in phytomining technology. Comparatively little research has focussed on the soil chemistry of tropical nickel hyperaccumulator plants to date. This study aimed to elucidate whether the soil chemistry associated with nickel hyperaccumulator plants has distinctive characteristics that could be indicative of specific edaphic requirements. The soil chemistry associated with 18 different nickel hyperaccumulator plant species occurring in Sabah (Malaysia) was compared with local ultramafic soils where nickel hyperaccumulator plants were absent. The results showed that nickel hyperaccumulators in the study area were restricted to circum-neutral soils with relatively high phytoavailable calcium, magnesium and nickel concentrations. There appeared to be a ‘threshold response’ for the presence of nickel hyperaccumulator plants at >20 μg g−1 carboxylic-extractable nickel or >630 μg g−1 total nickel, and >pH 6.3 thereby delimiting their edaphic range. Two (not mutually exclusive) hypotheses were proposed to explain nickel hyperaccumulation on these soils: (1) hyperaccumulators excrete large amounts of root exudates thereby increasing nickel phytoavailability through intense rhizosphere mineral weathering; and (2) hyperaccumulators have extremely high nickel uptake efficiency thereby severely depleting nickel and stimulating re-supply of Ni from diffusion from labile Ni pools. It was concluded that since there was an association with soils with highly labile nickel pools, the available evidence primarily supports hypothesis (2

Current status and challenges in developing nickel phytomining: an agronomic perspective

Nickel (Ni) phytomining operations cultivate hyperaccumulator plants ('metal crops') on Ni-rich (ultramafic) soils, followed by harvesting and incineration of the biomass to produce a high-grade 'bio-ore' from which Ni metal or pure Ni salts are recovered. This review examines the current status, progress and challenges in the development of Ni phytomining agronomy since the first field trial over two decades ago. To date, the agronomy of less than 10 species has been tested, while most research focussed on Alyssum murale and A. corsicum. Nickel phytomining trials have so far been undertaken in Albania, Canada, France, Italy, New Zealand, Spain and USA using ultramafic or Ni-contaminated soils with 0.05-1 % total Ni. N, P and K fertilisation significantly increases the biomass of Ni hyperaccumulator plants, and causes negligible dilution in shoot Ni concentration. Organic matter additions have pronounced positive effects on the biomass of Ni hyperaccumulator plants, but may reduce shoot Ni concentration. Soil pH adjustments, S additions, N fertilisation, and bacterial inoculation generally increase Ni phytoavailability, and consequently, Ni yield in 'metal crops'. Calcium soil amendments are necessary because substantial amounts of Ca are removed through the harvesting of 'bio-ore'. Organic amendments generally improve the physical properties of ultramafic soil, and soil moisture has a pronounced positive effect on Ni yield. Repeated 'metal crop' harvesting depletes soil phytoavailable Ni, but also promotes transfer of non-labile soil Ni to phytoavailable forms. Traditional chemical soil extractants used to estimate phytoavailability of trace elements are of limited use to predict Ni phytoavailability to 'metal crop' species and hence Ni uptake