Study on Transfer of Ni in Soil—Plant System Using ^63Ni Tracer Method

A study was carried out on the transfer of native and added Ni towards plant both in different soils and at different time by using ^63 Ni tracer technique.The transfer of added Ni in soil was greater than native Ni and declined as time increased.The mobility was greater for soluble plus exchangeable fraction of soil Ni but very smaller for residual and Fe/Mn oxide bound fractions.These indicated that Ni was more mobile and more harmful in soils with a low pH and /or low content of Fe/Mn oxides.     

用63Ni示踪技术研究土壤－植物系统的Ni的转化

A study was carried out on the transfer of native and added Ni towards plant both in different soils and at different time by using ⁶³Ni tracer technique. The transfer of added Ni in soil was greater than native Ni and declined as time increased. The mobility was greater for soluble plus exchangeable fraction of soil Ni but very smaller for residual and Fe/Mn oxide bound fractions. These indicated that Ni was more mobile and more harmful in soils with a low pH and/or low content of Fe/Mn oxides.     

四川省紫色土天然和添加的镍不同形态的分布及转化

The distribution and transformation of added and native Ni in purple soils were investigated with both sequential extraction procedure and isotopic tracer technique.The distribution of added and native Ni was greatly dependent on soil properties.Low soil pH was favorable for soluble plus exchangeable(EX) Fraction,while Fe/Mn oxides and clay for Fe/Mn oxide bound(OX) and residual(RES) fractions.The added Ni,however,has not yet reached the distribution equilibrium up to the 150th day after incubation.This was reflected in the fact that the proportion of EX fraction from added Ni was 150%-600% as much as that of native Ni,while that of RES fraction was only about 80%,Once entering soil,the applied soluble Ni was rapidly transformed into other fractions,but the organic complexe (OM) fraction of added Ni was relatively stable during incubation.The carbonate bound(CAB)fraction showed a progressive increase and attained a peak value after 0-14d of incubation and thereafter decreased gradually.The occurrence time of this peak advanced as initial soil pH increased.but the peak would disappear when initial soil pH was higher than 7.5(or containing free CaCO3).The transformation processes of the EX,OX and RES fractions could be described by Elovich and two-constant rate equations,and the rate were positively correlated with soil pH,CEC and clay.These finding could explain why there are differences in ecological and environmental effects of Ni in different soils and at various intervals.     

受土壤类型和金属负荷量影响的重金属形态分布

Two series of soil subsamples, by spiking copper(Cu),lead(Pb),zinc(Zn)and cadmium(Cd)in an orthogonal design,were prepared using red soil and brown soil,respectively.The results indicated that heavy metal fractions in these soil subsamples depended not only on soil types,but also on metal loading quantity as well as on interactions among metals in soil.Lead and Cu in red soil appeared mostly in weakly specifically adsorbed(WSA),Fe and Mn oxides bound(OX),and residual(RES)fractions.Zine cxisted in all fractions except organic bound one,and Cd was major in water soluble plus exchangeable(SE)one.Different from the results of red soil,Pb and Cu was present in brown soil in all fractions except organic one,but over 75% of Zn and 90% of Cd existed only in SE fraction.Meanwhile,SE fraction for any metal in red soil was lower than that in brown soil and WSA and OX fractions were higher.It is in agreernent with low cation exchange capacity and large amounts of metal oxides included in red soil.Metal fractions in soil,especially for water soluble plus exchangeable one ,were obviously influenced by other coexisting metals.The SE fraction of heavy metals increased with increasing loading amounts of metals in red soil but not obviously in brown soil,which suggest that metal availability be easily affected by their total amounts spiked in red soil.In addition,more metals in red soil were extracted with 0.20 mol L^-1 NH4Cl（pH5.40）than that with 1.0 mol L^-1 Mg(NO3)2(pH7.0),but the reverse happened in brown soil,implicating significantly different mechanisms of metal desorption from red soil and brown soil.     

施用碱稳定固体的酸性土壤的Cu和Zn的形态分布

Fractionation of metals in a granite-derived acid sandy loam soil amended with alkaline-stabilised sewagesIudge biosolids was conducted in order to assess metal bioavailability and environmental mobility soil solution was extracted by a centrifugation and filtration technique. Metal speciation in the soil solution wasdetermined by a cation exchange resin method. Acetic acid and EDTA extracting solutions were used forextraction of metals in soil solid surfaces. Metal distribution in different fractions of soil solid phase was determined using a three-step sequential extraction scheme. The results show that the metals in the soilsolution existed in different fractions with variable lability and metals in the soil solid phase were also presentin various chemical forms with potentially different bioavail ability and environmental mobility Alkaline-stabilised biosolids could elevate solubility of Cu and proportion of Cu in organically complexed fractionsboth in soil liquid and solid phases, and may therefore increase Cu mobility. In contrast, the biosolids lowered the concentrations of water-soluble Zn (labile fraction) and exchangeable Zn and may hence decrease bioavailability and mobility of Zn. However, Fe and Mn oxides bound and organic matter bound fractions are likely to be Zn pools in the sludge-amended soil. These consequences possibly result from the liming effect and metal speciation of the sludge product and the difference in the chemistry between the metals in soil.     

华北矿区残留态铜、铅在土壤剖面中的分布与迁移

Residual heavy metals are commonly considered to be immobile in soils, leading to an underestimation of their environmental risk. This study investigated the distribution and transport of residual heavy metals along soil profiles, using the Xiaoqinling gold mining region in North China as a case study. Soil samples were collected at three depths from three locations near the tailing heap. The speciation of copper (Cu) and lead (Pb) (exchangeable, carbonate-bound, Fe-Mn oxide-bound, organic matter-bound, and residual fractions) was determined using a sequential extraction procedure. The residual fraction’s morphology was observed using scanning electron microscopy (SEM). Results showed that metal fraction distributions along the soil profiles were influenced by each fraction’s mobility. Residual fraction with high chemical stability cannot be transformed from or into other fractions. This led to the conclusion that the high concentration of residual metals in soils mainly resulted from residual fraction transport.The SEM analysis showed that fine particles (submicrons) were mainly attached to large particles and were likely released and transported by water flow. The more sorptive fractions (non-residual fractions) were mainly retained in the top soil, and the more mobile fractions (residual fraction) were mainly leached to the deep soil. Cu and Pb concentrations in the residual fraction decreased slightly and those in the non-residual fractions decreased significantly with soil depth. These suggest a relatively higher residual metal mobility along the soil pro?les. Therefore, residual metals can be transported in soils and their environmental risk can not be ignored in assessing soil contamination.     

化学萃取修复尾渣土壤的金属形态变化特征

The efficiency of EDTA, HNO3 and CaCl2 as extractants to remove Pb, Zn and Cu from tailing soils without varying soil pH was investigated with distributions of Pb, Zn and Cu being determined before and after extraction using the sequential extraction procedure of the optimized European Community Bureau of Reference （BCR）. Results indicated that EDTA and HNO3 were both effective extracting agents.The extractability of extractants for Pb and Zn was in the order EDTA 〉 HNO3 〉 CaCl2, while for Cu it was HNO3 〉 EDTA 〉 CaCl2. After EDTA extraction, the proportion of Pb, Zn and Cu in the four fractions varied greatly, which was related to the strong extraction and complexation ability. Before and after extraction with HNO3 and CaCl2, the percentages of Pb, Zn and Cu in the reducible, oxidizable and residual fractions changed little compared to the acid-extractable fraction. The lability of metal in the soil and the kinds of extractants were the factors controlling the effects of metal extraction.     

在法国前铅和锌冶炼厂附近的城市土壤重金属的污染、分离和利用

smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry （FAAS or ETAAS）, depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical Soil contamination by metals from anthropogenic activities （e.g., mining and smelting） is a major concern for the environment and human health. Environmental availability of cadmium （Cd）, lead （Pb）, zinc （Zn）, copper （Cu）, and indium （In） in 27 urban soils located around two former Pb and Zn smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry （FAAS or ETAAS）, depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical procedure. Metal partitioning was conducted using a four-step sequential extraction procedure. The results showed that Cd and Zn were mainly in the acid-extractable and reducible forms in the urban soils studied. In contrast, Pb and In were largely in the reducible fraction. However, in some samples, the amount of In extracted in the residual or exchangeable fraction was higher than that in the reducible fraction. Copper was mainly found in the reducible and residual fractions. A pot experiment was conducted in a glasshouse with seven soils （six contaminated and one uncontaminated） and two plant species, ryegrass and lettuce. The results showed transfer of metals from the contaminated soils to the shoots of ryegrass and the edible part of lettuce. The metal bioconcentration factor was in the order of Cd Cu > In > Zn Pb for lettuce leaves, whereas for ryegrass shoots, three orders were found, Cd > Zn > Cu In > Pb, Cd ≥ In > Zn > Cu Pb, and Zn > Cd > Cu > In > Pb, depending on the physico-chemical properties of the soils, such as pH, cation exchange capacity, carbonates, and organic matter. It was established that the metal toxicity was related to the contamination levels and the physico-chemical properties, including pH, organic matter, and in a lesser extent, Ca, Mg, and phosphorus contents, of the soils. However, it was shown that lettuce could grow on soils having high Cd and CaCO₃ contents. Cadmium was one of the most available metals while Pb was always the least available in the soils studied.     

氧化节杆菌生物降解苯并芘

A pot experiment was conducted with multi-metal (Pb, Cd, Cu, and Zn) contaminated acidic soil to investigate changes in available metal burden resulting from the application of industrial wastes (fly ash and steel slag). The efficiency of amendments-induced metal stabilization was evaluated by diffusive gradients in thin films (DGT), sequential extraction, and plant uptake. The stability of remediation was assessed by an acidification test and by chemical equilibrium modeling. Addition of fly ash (20 g kg-1 ) and steel slag (3 g kg-1 ) resulted in similar increase in soil pH. Both amendments significantly decreased the concentrations of metals measured with DGT (C DGT) and the metal uptake by Oryza sativa L. Significant correlations were found between C DGT and the concentration of a combination of metal fractions (exchangeable, bound to carbonates, and bound to Fe/Mn oxides), unraveling the labile species that participate in the flux of metal resupply. The capability of metal resupply, as reflected by the R (ratio of C DGT to pore water metal concentration) values, significantly decreased in the amended soils. The C DGT correlated well with the plant uptake, suggesting that DGT is a good indicator for bioavailability. Acidification raised the extractable metal concentration in amended soil but the concentration did not return to the pre-amendment level. Equilibrium modeling indicated that the soil amendments induced the precipitation of several Fe, Al and Ca minerals, which may play a positive role in metal stabilization. Chemical stabilization with alkaline amendments could be an effective and stable soil remediation strategy for attenuating metal bioavailability and reducing plant metal uptake.     

云南滇池沉积物中重金属的形态分布特征

Fractionation of heavy metals in sediments can help in understanding potential hazards of heavy metals. The present study analyzed total concentrations and fractions of selected heavy metals （Cd, Cr, Cu, Pb, and Zn） in surface sediments from Dianchi Lake, Yunnan Province, China, as well as factors that may affect distributions of the various heavy metal fractions. Total concentrations of the heavy metals decreased in the order Zn 〉 Cu 〉 Pb 〉 Cr 〉 Cd. These heavy metals, except Cr, were much higher than their background levels, indicating that Dianchi Lake was polluted by Cd, Zn, Pb, and Cu. Cadmium occurred mainly as the non-residual fraction （sum of the HOAc-soluble, reducible, and oxidizable fractions） （97.6%）, and Zn （55.7%） was also predominantly found in the non-residual fraction. In contrast, most of the Cr （88.5%）, Pb （81.8%）, and Cu （59.2%） occurred in the residual fraction. Correlation analysis showed that total heavy metal concentrations, organic matter and reducible Fe were the main factors affecting the distributions of the various heavy metal fractions. In the Walhai section of Dianchi Lake （comprising 97% of the lake area）, the concentrations of Cd, Zn, Pb, and Cu in the non-residual fraction were significantly lower （P ≤ 0.01 or 0.05） than those of the Caohal section （3% of the lake area）. This indicated that potential heavy metal hazards in the Caohai section were greater than the Waihai section.     

Distribution of Trace Elements in Soils from the Sudbury Smelting Area (Ontario,Canada)

The sequential extraction procedure proposed by the European Commission Measurement and Testing Programme, combined with Scanning Electron Microscopy and Energy Dispersive X-ray Analysis(SEM/EDS), was applied to identify and quantify the chemical andmineralogical forms of Cu, Ni, Fe, Mn, Zn, Pb, Cr and Cd presentin the topsoil from a mining and smelting area near Sudbury (Ontario, Canada). The possible mobility of the chemical forms was also assessed. The metal fractions: (1) soluble and exchangeable, (2) occluded in manganese oxides and in easily reducible iron oxides, (3) organically bound and in form of sulphides, (4) residual mainly present in the mineral lattice structures were separated. Cu and Ni were the major metallic contaminants, occurring in soils in broad ranges of concentrations: Cu 11–1890 and Ni 23–2150 mg kg^-1. Cu was uniformly distributed among allthe extracted fractions. Ni was found associated mainly withthe residual forms, accounting for 17–92%, with an averageof 64%, of the total Ni present in the soils. Fe, Mn, Zn,Pb, Cr and Cd, while occurring in most analysed samples innormal soil concentrations, were primarily held in theresidual mineral fraction (on average >50%). The solubleand exchangeable forms made a small contribution (≤8.1%)to the total content of metals extracted. At least 14% ofthe total Cd, Mn and Pb was mobilised from the reducibleforms. The oxidizable fraction assumed mean values higher than10% only for Pb and Zn. Statistical treatment of the experimental data showed significant correlations between totalmetal content of the soils, some soil properties such as pH value, clay and organic matter content, and metal concentrationsin the various fractions. SEM/EDS analysis showed Fe in form ofoxides and sulphides in soils and Cu, Ni, Mn, Zn and Cr in association with iron oxides. Numerous black carbonaceous particles and precipitates of aluminium fluoride salts, observedin the solid residue left after `total’ digestion, were found tocontain Fe, Ni and Cr.     

Use of the BCR three-step sequential extraction procedure for the study of the partitioning of Cd, Pb and Zn in various soil samples

A slightly modified three-step sequential extraction procedure proposed by the Community Bureau of Reference (BCR) for analysis of sediments was successfully applied to soil samples. Contaminated soil samples from the lead and zinc mining area in the Mezica valley (Slovenia) and natural soils from a non-industrial area were analysed. The total concentrations of Cd, Pb and Zn and their concentrations in fractions after extraction were determined by flame or electrothermal atomic absorption spectrometry (FAAS, ETAAS). Total metal concentrations in natural soils ranged from 0.3 to 2.6 mg kg^-1 for Cd, from 20 to 45 mg kg^-1 for Pb and from 70 to 140 mg kg^-1 for Zn, while these concentrations ranged from 0.5 to 35 mg kg^-1 for Cd, from 200 to 10000 mg kg^-1 for Pb and from 140 to 1500 mg kg^-1 for Zn in soils from contaminated areas. The results of the partitioning study applying the slightly modified BCR three-step extraction procedure indicate that Cd, Pb and Zn in natural soils prevails mostly in sparingly soluble fractions. Cd in natural soils is bound mainly to Fe and Mn oxides and hydroxides, Pb to organic matter, sulphides and silicates, while Zn is predominantly bound to silicates. In contaminated soils, Cd, Pb and Zn are distributed between the easily and sparingly soluble fractions. Due to the high total Cd, Pb and Zn concentrations in contaminated soil close to the smelter, ! and their high proportions in the easily soluble fraction (80% of Cd, 50% of Pb and 70% of Zn), the soil around smelters represents an environmental hazard.     

Trace metal composition and speciation in street sediment: Sault Ste. Marie,Canada

Street sediment collected in Sault Ste. Marie, Ontario was examined for trace element composition (As, Cd, Cr, Cu, Fe, Pb, Hg, Ni and Zn) and the metal partitioning to various sediment properties was determined by sequential extraction. Total Ni, Cu, Zn and Pb concentrations exceeded the lowest effect levels specified in the Ontario Provincial Sediment Quality Guidelines for Metals (Environment Ontario, 1992) and derived from bioassay studies. According to these Guidelines, the disposal of such sediment has to be guided by environmental considerations. A significant fraction of these metals was extractable in 0.5 N HCl over a 12-hour period and considered as potentially bioavailable. The major accumulative phases of toxic metals in this sediment are exchangeable, carbonate, Fe/Mn oxides and organic matter but the relative importance of each phase varied for individual metals. Approximately 20% of the total extractable Cd is found in each of these four fractions. Pb, Zn and Mn are predominantly bound to carbonates, Fe/Mn oxides and organic matter. Cu shows a high affinity for organic matter and to a lesser extent for carbonates. Elevated levels of Cd, Pb, Cu, Zn, Mn and Cr in the exchangeable and/or soluble phase suggest that sediment associated metals, mobilised from streets in Sault Ste. Marie during runoff and snowmelt, would adversely impact water quality in the receiving waters. However, large fractions of the total metal load are associated with coarser particles which are unlikely to be transported through the drainage system into receiving waters.     

PARTITIONING OF HEAVY METALS IN PODZOL SOILS CONTAMINATED BY MINE DRAINAGE WATERS,DALARNA, SWEDEN

The discharge of acidic mine drainage waters onto a hillslope in Dalarna, central Sweden, has lead to the contamination of the podzol soils with Cu, Fe, Ni, Pb, Zn and sulfate. Samples from contaminated and reference soils have been collected for chemical and mineralogical analyses. Jarosite is identified by x-ray diffraction analysis as a precipitate in the upper horizons (A, E, B) of the contaminated soils, where the soil acidity (pH_KCl～2.6) promotes jarosite stability. The sequential chemical extraction of soil samples indicates that, in the reference A horizon, Cu, Pb, Ni and Zn are bound primarily to cation exchange sites and organic matter. In the A horizon of the contaminated soils closest to the rock dump, metal partitioning is dominated by the Fe oxide fractions, despite the high organic matter content; Pb is almost completely bound to crystalline Fe oxides, possibly adsorbed to Fe oxides or occuring in a jarosite solid solution. In the reference B and C horizons, Cu, Ni and Zn are primarily adsorbed/coprecipitated in the Fe oxide fractions, while Pb remains with a large fraction bound to organic matter. In the Fe-rich B horizon of the contaminated soils, the partitioning of the metals in cation exchange sites and to organic matter has greatly increased relative to the reference soils, resulting from the mobilization of organo-metal complexes down the profile.     

Source Identification and Speciation of Metals in the Topsoil of the Khli Ti Watershed, Thailand

The enrichment factor, multivariate analysis and metal speciation studies were used to identify degree, source and dispersal of metal contamination in Khli Ti watershed, Thailand. Topsoil samples were collected throughout the watershed, analyzed for total metal concentration. Sequential extraction was also carried out to determine geochemical phases of metals which were identified as exchangeable and bound to carbonates, Fe–Mn oxides, organic matter and residuals. Soil characteristics including pH, total organic carbon, redox potential, cation exchange capacity and texture were also analyzed. Principal component analysis yielded three metal groups which explained 83% of the variance. The concentrations of metals which were derived from lithogenic origin, such as Co, Cr, Fe, Ni and V were in natural background levels and were mostly bound to the residual phase. The remaining elements (i.e. Ba, Cd, Cu, Pb, Sb and Zn) were associated with the contamination from previous activities of the Pb-ore concentrator and Zn–Pb mining. Anthropogenic contamination mainly increased Pb and Zn bound to Fe–Mn oxides at the expense of residual fraction. Even though low exchangeable Pb contents in Khli Ti soils indicated low availability to plants, Pb bound to Fe–Mn oxides fraction might increase its mobility under reducing conditions.     

Copper and arsenic (enargite) contamination of soils along a toposequence in Chinkuashih,northern Taiwan

This study investigates the species of Cu and As (enargite) residues present in soils of the Chinkuashih area, northern Taiwan. Two pedons, on the shoulder and footslope along a toposequence, were examined for their metal partitioning and geochemical origins. The bulk soils were analyzed by sequential extraction combined with mineralogical analyses, including X-ray diffraction (XRD) and scanning electron microscopy ∕ energy dispersive spectrometer (SEM ∕ EDS) analyses. Soil pH ranged from 4.23 to 4.91 with low base saturation, and the soils can be classified as fine, mixed, thermic, Typic Kandiudults. Mineralogical study indicated that enargite and pyrite particles mainly coexisted in silt and sand fractions, particularly in lower soil horizons of the footslope, showing high contents of Cu and As. Kaolinite and illite were dominant minerals in clay fractions. The footslope accumulated more total Cu and As than that of shoulder pedon. The sequential extraction experiments resulted in high proportions of Cu remaining in residual fractions, while the most of As was bound in amorphous Fe and Al oxyhydroxide fraction. The risk analyses of Cu and As (enargite) contamination in soils of the Chinkuashih area merits further study.     

Speciation and sorption structure of diphenylarsinic acid in soil clay mineral fractions using sequential extraction and EXAFS spectroscopy

Purpose

The mobility of arsenic (As) in soils is fundamentally affected by the clay mineral fraction and its composition. Diphenylarsinic acid (DPAA) is an organoarsenic contaminant derived from chemical warfare agents. Understanding how DPAA interacts with soil clay mineral fractions will enhance understanding of the mobility and transformation of DPAA in the soil-water environment. The objective of this study was to investigate the speciation and sorption structure of DPAA in the clay mineral fractions.

Materials and methods

Twelve soils were collected from nine Chinese cities which known as chemical weapons burial sites and artificially contaminated with DPAA. A sequential extraction procedure (SEP) was employed to elucidate the speciation of DPAA in the clay mineral fractions of soils. Pearson’s correlation analysis was used to derive the relationship between DPAA sorption and the selected physicochemical properties of the clay mineral fractions. Extended X-ray absorption fine structure (EXAFS) L_III-edge As was measured using the beamline BL14W1 at Shanghai Synchrotron Radiation Facility (SSRF) to identify the coordination environment of DPAA in clay mineral fractions.

Results and discussion

The SEP results showed that DPAA predominantly existed as specifically fraction (18.3–52.8%). A considerable amount of DPAA was also released from non-specifically fraction (8.2–46.7%) and the dissolution of amorphous, poorly crystalline, and well-crystallized Fe/Al (hydr)oxides (20.1–46.2%). A combination of Pearson’s correlation analysis and SEP study demonstrated that amorphous and poorly crystalline Fe (hydr)oxides contributed most to DPAA sorption in the clay mineral fractions of soils. The EXAFS results further demonstrated that DPAA formed inner-sphere complexes on Fe (hydr)oxides, with As-Fe distances of 3.18–3.25 Å. It is likely that the steric hindrance caused by phenyl substitution and hence the instability of DPAA/Fe complexes explain why a substantial amount of DPAA presented as weakly bound forms.

Conclusions

DPAA in clay mineral fractions predominantly existed as specifically, amorphous, poorly crystalline, and crystallized Fe/Al (hydr)oxides associated fractions. Amorphous/poorly crystalline Fe rather than total Fe contributed more to DPAA sorption and DPAA formed inner-sphere complexes on Fe (hydr)oxides.

     

Micrometer-scale internal structure and element distribution of Fe-Mn nodules in Quaternary red earth of Eastern China

Purpose

Fe-Mn nodules are the common feature of tropical and subtropical soils and contain abundant information of pedogenic processes, palaeoenvironmental changes, and element geochemistry. The main aim of the present study was to determine the internal structure and spatial distribution of elements in the Fe-Mn nodules to better understand the 3D internal structure, enrichment, and dynamics of heavy metals in nodules and to provide more aspects to explore the possible heavy metal sequestration and pedoenvironmental implications of Fe-Mn nodules in soils.

Materials and methods

The studied Typic Plinthudult was developed on Quaternary red earths in Èastern China. The Fe-Mn nodules in the Bs horizon of soil were separated and classified into four size fractions (5–8, 3–5, 2–3, and 1–2 mm). The 3D microstructure of Fe-Mn nodules was examined by means of synchrotron radiation-based X-ray microcomputed tomography (SR-mCT), and the spatial distribution of Fe and Mn in nodules was studied by scanning electron microscopy (SEM) equipped with an energy-dispersive X-ray spectrometer (EDS). The association of heavy metals with Fe and Mn oxides in nodules was described by selective chemical dissolution, SEM/EDS, and principal component analysis.

Results and discussion

The SR-mCT images indicated that the 5–8, 3–5, and 2–3 mm nodules exhibited well-defined ring structures, while the 1–2 mm nodule exhibited homogeneous fabric. The internal microstructures of nodules could be divided into four parts: Fe-rich ring, Mn-rich ring, Fe and Mn overlapped ring, and the gap between ring structures. The Fe-Mn nodules were significantly enriched in Mn, Pb, Ni, Cu, and Zn relative to the soil matrix. In particular, the concentrations of Mn and Pb in the nodules were 150 and 90 times greater than those in the soil matrix, respectively. A clear partitioning of heavy metals between Mn and Fe oxide phases was observed in the nodules, indicating that Pb was mainly present in Fe oxides, while Ni, Cu, and Zn were mainly associated with Mn oxide phases.

Conclusions

The SR-mCT and SEM-EDS revealed the detailed internal microstructure of the Fe-Mn nodules and geochemical dynamics of heavy metals in the soil system. The Fe-Mn nodules have very high scavenging ability in sequestrating toxic heavy metals in soils, such as Pb and Ni. The microstructure and spatial distribution of Fe and Mn in nodules reflected the cycle of alternating drying and wetting conditions and served as an important basis for inferring the pedogenic processes and pedoenvironmental conditions.

     

Creation of Technosols to Decrease Metal Availability in Pyritic Tailings with Addition of Biochar and Marble Waste

Creation of Technosols with the use of different materials is a sustainable strategy to reclaim mine tailings and reduce metal mobility. For this purpose, a short‐term incubation experiment was designed with biochars derived from pig manure, crop residues and municipal solid waste added to tailings alone or in combination with marble waste. We aimed to assess the efficiency of the different amendments to decrease Cd, Pb and Zn availability in the Technosols and the fractions where metals were retained. Results showed that all amendments reduced metal mobility, directly related to increases in pH. Those materials with higher content of carbonates were more effective to immobilize metals (~99%). Municipal solid waste was highly effective to decrease metal mobility owing to the higher carbonate content, but addition of marble waste was needed to enhance metal immobilization with pig manure and crop residue. Decreases in Cd mobility were related to retention by the carbonate, Mn/Fe oxides and oxidizable (organic compounds) fractions. Decreases in Pb mobility were related to retention in the Mn/Fe oxides and residual fractions, while decreases in Zn mobility were related to retention in Mn/Fe oxides and oxidizable fractions. Association of Zn and Pb with the oxidizable fraction was also related to the recalcitrance of the organic compounds and so dependent on biochar type. Scanning electron microscopy coupled with energy dispersive X‐ray showed that biochar showed great affinity to interact with iron oxides, calcium sulfates and phyllosilicates. Copyright © 2017 John Wiley & Sons, Ltd.     

Metalliferous Constituents of Rhizosphere Soils Contaminated by Zn–Pb Mining in Southern Poland

Industrial soils near Zn–Pb mines and metallurgical plants in the vicinity of Olkusz (southern Poland) are exposed to high environmental stress related to heavy metal pollution (Zn, Pb, Cd, Mn, Fe, Tl and As) from waste disposal sites and primary ores. X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectrometry analyses (EDS) and Atomic Absorption Spectroscopy (AAS) were used to analyse rhizosphere soil samples from the area. The mineral composition of the rhizosphere soils was determined. Carbonates of lead, cadmium and zinc, arsenic–lead sulphosalts and other minerals occurring on the root epiderm are described. Mineral aggregates of secondary origin include polymineralic spherules containing high concentrations of Zn (up to 2.3%), Pb (up to 0.7%), Fe (up to 23%), Cd (up to 427 mg kg^?1) and Tl (up to 139 mg kg^?1). Processes on the rhizoplane, and in the zone where plant-root exudation solutions are active, promote the crystallization of metalliferous minerals. ESEM is recommended as an efficient method for examining alteration occurring in the rhizosphere environment.