Martina Vítková

Lead and cadmium sorption mechanisms on magnetically modified biochars.

This paper discusses Cd(II) and Pb(II) sorption efficiency of biochars modified by impregnation with magnetic particles. All selected biochar characteristics were significantly affected after the modification. More specifically, the cation exchange capacity increased after the modification, except for grape stalk biochar. However, the changes in the pH value, PZC, and BET surface after modification process were less pronounced. The metal loading rate was also significantly improved, especially for Cd(II) sorption on/in nut shield and plum stone biochars (10- and 16-times increase, respectively). The results indicated that cation exchange (as a metal sorption mechanism) was strengthened after Fe oxide impregnation, which limited the desorbed amount of tested metals. In contrast, the magnetization of grape stalk biochar reduced Pb(II) sorption in comparison with that of pristine biochar. Magnetic modification is, therefore, more efficient for biochars with well-developed structure and for more mobile metals, such as Cd(II).

Primary and secondary phases in copper-cobalt smelting slags from the Copperbelt Province, Zambia

Abstract Pyrometallurgical slags from three Cu-Co smelters (Nkana, Mufulira, Chambishi) in the Copperbelt Province, Zambia, were studied from mineralogical and chemical points of view. The slags were enriched in metals and metalloids, mainly Cu (up to 35 wt.%), Co (up to 2.4 wt.%) and As (up to 3650 ppm). The following primary phases were observed in slags: Ca-Fe silicates (clinopyroxene, olivine) and leucite, oxides (spinel-series phases), ubiquitous silicate glass and sulphide/metallic droplets of various sizes. The presence of glass and skeletal/dendritic crystal shapes indicated rapid cooling of the slag melt. Copper and cobalt were found in low concentrations in the majority of silicates (olivine, clinopyroxene) and oxides, substituting for Fe in their structures (up to 7.15 wt.% CoO in olivine, 4.11 wt.% CuO in spinel). Similarly, up to 0.91 wt.% CoO and 6.90 wt.% CuO were observed in the interstitial glass. Nevertheless, the main carriers of these metals in the slags studied were Cu sulphides (digenite, chalcocite, bornite, chalcopyrite), Co-Fe sulphides (cobaltpentlandite), Co-bearing intermetallic phases ((Fe,Co)2As) and alloys. Weathering features corresponding to the presence of secondary metal-bearing phases, such as malachite (Cu2(CO3)(OH)2), brochantite (Cu4SO4(OH)6) and sphaerocobaltite (CoCO3), were observed on the slag surfaces. They indicate that the slags studied are reactive on contact with water/atmosphere and that their environmental stability and release of potentially harmful metals and metalloids must be evaluated further.

The pH-dependent leaching of inorganic contaminants from secondary lead smelter fly ash

The leaching behaviour of fly ash (FA) from a secondary Pb smelter was assessed using the pH-static leaching experiment according to prEN 14997 (pH range 3-11) coupled with mineralogical investigation of the leached FA by XRD and Rietveld analyses and thermodynamic modelling using PHREEQC-2. The procedure was performed on fresh FA and FA washed at a cumulative L/S ratio of 60l/kg to remove readily soluble salts. For both fresh and washed FA, high amounts of inorganic contaminants were released under acidic conditions, exhibiting L-shaped leaching patterns: up to 300g Pb/kg, 4.5g Cd/kg, 4g Zn/kg, 1.05g As/kg and 70mg Sb/kg. The washing of soluble salts significantly decreased the leachability of Cd, Zn, As and Sb and increased the release of Pb, especially under acidic conditions. The leaching of fresh FA removed part of primary caracolite and all the KPb(2)Cl(5) and NaCl. The Pb release was controlled by the precipitation of anglesite and PbSO(3) under acidic conditions and of laurionite and carbonates (hydrocerussite and phosgenite) under alkaline conditions. In contrast, the washed FA was composed mainly of anglesite and PbSO(3), both phases being the main solubility-controlling phases for Pb over the whole studied pH range.

Interactions of nano-oxides with low-molecular-weight organic acids in a contaminated soil

Various low-molecular-weight organic acids (LMWOAs) play an important role in the mobilisation of contaminants and their subsequent uptake by plants. Nano-maghemite (NM) and an amorphous Mn oxide (AMO) were investigated for their stabilisation potential under simulated rhizosphere conditions in terms of their use during chemical stabilisation and aided phytostabilisation of metal(loid)s in contaminated soils. In order to understand the reactivity of these potential sorbents of contaminants in soils and subsequent mobility of metal(loid)s, a set of time-dependent batch leaching experiments was performed using a mix of acetic, lactic, citric, malic and formic acids simulating root exudates. Despite being relatively unstable under given conditions, the AMO proved to be an efficient amendment for rapid stabilisation of both metals and As compared to NM. Generally, low pH (∼ 4) and the presence of citrate complexes resulted in higher mobility of metals in the non- and NM-amended soil. In contrast, the presence of AMO in the soil accelerated the neutralisation reactions related to pH increase and (co-) precipitation of secondary Fe/Mn/Al oxyhydroxides. Mineralogical transformations of the AMO showed to be crucial for contaminant immobilisation.

Phytoextraction of Metals: Modeling Root Metal Uptake and Associated Processes

Because the efficiency of phytoextraction processes is still questionable, various mechanistic and empirical models are needed to better evaluate the suitability of the method. This chapter discusses different aspects of such modeling. First, models predicting the transport of metals and metalloids in the soils and in the roots are presented and discussed in accordance with well-known mechanisms of metal uptake. Because metal (and metalloid) uptake greatly depends on their speciation in the soil solution, several geochemical models providing such information are presented here. This chapter provides an in-depth overview of those models; however, their combination (geochemical, transport, empirical, etc.) will be crucial in order to obtain a robust and transferable model of metal/metalloid uptake and phytoextraction.

Engineered Nanomaterials for Phytoremediation of Metal/Metalloid-Contaminated Soils: Implications for Plant Physiology

Nanomaterials, including engineered nano-sized iron oxides, manganese oxides, cerium oxides, titanium oxides, or zinc oxides, provide specific affinity for metal/metalloids adsorption and their application is being rapidly extended for environmental management. Their significant surface area, high number of active surface sites, and high adsorption capacities make them very promising as cost-effective amendments for the remediation of contaminated soils. The alleviation of the toxicities of metal/metalloids by their immobilization in the soil stimulates the growth and development of plants during phytoremediation, but there is a body of evidence indicating that nanomaterials themselves can yield both beneficial and harmful effects in plant systems at the physiological, biochemical, nutritional, and genetic levels. Nanoecotoxicological studies are providing a good understanding of their interactions with plants, and an increasing number of publications have attempted to clarify and quantify their potential risks and consequences for plants. However, many results are contradictory and the safety of engineered nanomaterials still represents a barrier to their wide, innovative use in phytoremediation. Both their positive and negative effects on plants will have to be taken into account to evaluate their applicability, and the scientific community faces a challenge to understand deeply the factors which can determine their relevance in environmental science and technology.

Reliability of chemical microanalyses for solid waste materials

The investigation of solid speciation of metals and metalloids is required for accurate assessment of the hazardous properties of solid waste materials from high-temperature technologies (slag, bottom ash, fly ash, air-pollution-control residues). This paper deals with the problem of reliability of microanalyses using a combination of electron microprobe analysis (EPMA) and scanning electron microscopy (SEM) only. These methods do not permit to detect nanophases in host-crystals and lead to erroneous interpretation of analytical results, considering the elements of nanophases as belonging to the crystal structure of the main phase. More detailed analysis using transmission electron microscopy (TEM) on foils prepared by focused ion beam (FIB) can be used to solve this analytical problem. In this study, lamellar aggregates of potassium-rich clinopyroxenes were detected in copper smelting slags by a combination of SEM and EPMA. However, FIB-TEM indicated the presence of leucite inclusions (tens to hundreds nm in size) within the clinopyroxene lamellae. Based on examples from smelting slags and other solid waste materials, recommendations for standard SEM and EPMA applications and the need for methods with higher resolution for mineralogical investigation of waste materials are discussed.

Metal-contaminant leaching from lead smelter fly ash using pH-stat experiments

Abstract Fly ash from secondary Pb metallurgy was submitted to the pH-static leaching procedure according to the PrEN 14997 European leaching standard. The 48 h pH-static leaching experiments were performed on (1) fresh untreated fly ash and (2) previously washed fly ash with a cumulative wash step of 60 l kg−1. Greater release of metallic contaminants (Pb, Cd, Zn) was observed in the acidic pH range for both ashes. Washing significantly reduced the release of Cd and Zn, but greater concentrations of Pb were observed in leachates from washed fly ash due to the more important leaching of anglesite (PbSO4). The PHREEQC-2 speciation-solubility calculations showed that anglesite, phosgenite (PbCl2·PbCO3) and laurionite (Pb(OH)Cl) are the most important solubility-controlling phases for Pb, which is the most important contaminant.

Effect of nano zero-valent iron application on As, Cd, Pb, and Zn availability in the rhizosphere of metal(loid) contaminated soils

Characterisation of geochemical transformations and processes in soils with special focus on the rhizosphere is crucial for assessing metal(loid) bioavailability to plants during in situ immobilisation and phytostabilisation. In this study, the effects of nano zero-valent iron (nZVI) were investigated in terms of the immobilisation of As, Zn, Pb and Cd in two soil types and their potential uptake by plants using rhizobox experiments. Such system allowed monitoring the behaviour of trace elements in rooted and bulk soil compartments separately. Sunflower (Helianthus annuus L.) and ryegrass (Lolium perenne L.) were tested for As-rich (15.9 g As kg-1) and Zn-rich (4.1 g Zn kg-1) soil samples, respectively. The application of nZVI effectively lowered the uptake of all target risk elements into plant tissues. Efficient immobilisation of As was determined in the As-soil without a significant difference between plant and bulk soil compartments. Similarly, a significant decrease was determined for CaCl2-available fractions of Zn, Pb and Cd in nZVI-treated Zn-soil. The behaviour of As corresponded to changes in Eh, while Zn and Cd showed to be mainly pH-dependent. However, despite the observed stabilisation effect of nZVI, high amounts of As and Zn still remained available for plants. Furthermore, the accumulation of the target risk elements in roots and the overall effect of nZVI transformations in the rhizosphere were verified and visualised by SEM/EDS. The following immobilising mechanisms were suggested: (i) sorption onto both existing and newly formed Fe (hydr)oxides, (ii) formation of secondary Fe-As phases, and (iii) sorption onto Mn (hydr)oxides.

Stability and stabilizing efficiency of Mg-Fe layered double hydroxides and mixed oxides in aqueous solutions and soils with elevated As(V), Pb(II) and Zn(II) contents

Although the mechanisms of metal(loid) removal from aqueous solutions using LDHs (layered double hydroxides) and mixed oxides (thermally treated LDHs; CLDHs) have been studied, research dealing with their stability, stabilizing efficiency and remediation potential for contaminated soils remains scarce. We present a complex study investigating the stabilizing efficiency of Mg-Fe LDHs and CLDHs at different conditions, including aqueous solutions and real soils with highly elevated As(V), Pb(II) and Zn(II) concentrations. All studied materials showed excellent (ad)sorption efficiency for As(V), Pb(II) and Zn(II) in aqueous solutions. Additionally, the reconstruction ability of CLDHs at different conditions that could improve their adsorption properties was also evaluated, and the dependence on time, pH and the concentrations of metal(loid)s was shown. In general, CLDHs showed higher stability and stabilizing efficiency in aqueous and soil solutions; however, LDHs were more efficient in contaminated soils. Furthermore, solid state analyses coupled with geochemical modeling showed the formation of new phases corresponding to Mg‑carbonates/silicates on the surfaces of LDH/CLDH after their incubation in soils. Both LDHs and CLDHs significantly decreased the bioavailable/labile fraction of As(V) and Zn(II) in the studied soils. In general, our work shows Mg-Fe LDHs and CLDHs as prospective materials for water and soil remediation.