Thallium adsorption onto phyllosilicate minerals

The adsorption of thallium (Tl) onto phyllosilicate minerals plays a critical role in the retention of Tl in soils and sediments and the potential transfer of Tl into plants and groundwater. Especially micaceous minerals are thought to strongly bind monovalent Tl(i), in analogy to their strong binding of Cs. To advance the understanding of Tl(i) adsorption onto phyllosilicate minerals, we studied the adsorption of Tl(i) onto Na- and K-saturated illite and Na-saturated smectite, two muscovites, two vermiculites and a naturally Tl-enriched soil clay mineral fraction. Macroscopic adsorption isotherms were combined with the characterization of the adsorbed Tl by X-ray absorption spectroscopy (XAS). In combination, the results suggest that the adsorption of Tl(i) onto phyllosilicate minerals can be interpreted in terms of three major uptake paths: (i) highest-affinity inner-sphere adsorption of dehydrated Tl(+) on a very low number of adsorption sites at the wedge of frayed particle edges of illite and around collapsed zones in vermiculite interlayers through complexation between two siloxane cavities, (ii) intermediate-affinity inner-sphere adsorption of partially dehydrated Tl(+) on the planar surfaces of illite and muscovite through complexation onto siloxane cavities, (iii) low-affinity adsorption of hydrated Tl(+), especially in the hydrated interlayers of smectite and expanded vermiculite. At the frayed edges of illite particles and in the vermiculite interlayer, Tl uptake can lead to the formation of new wedge sites that enable further adsorption of dehydrated Tl(+). On the soil clay fraction, a shift in Tl(i) uptake from frayed edge sites (on illite) to planar sites (on illite and muscovite) was observed with increasing Tl(i) loading. The results from this study show that the adsorption of Tl(i) onto phyllosilicate minerals follows the same trends as reported for Cs and Rb and thus suggests that concepts to describe the retention of (radio)cesium by different types of phyllosilicate minerals in soils, sediments and rocks are also applicable to Tl(i)

Enhancing adsorption of heavy metal ions onto biobased nanofibers from waste pulp residues for application in wastewater treatment

Biobased nanofibers are increasingly considered in purification technologies due to their high mechanical properties, high specific surface area, versatile surface chemistry and natural abundance. In this work, cellulose and chitin nanofibers functionalized with carboxylate entities have been prepared from pulp residue (i.e., a waste product from the pulp and paper production) and crab shells, respectively, by chemically modifying the initial raw materials with the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated oxidation reaction followed by mechanical disintegration. A thorough investigation has first been carried out in order to evaluate the copper(II) adsorption capacity of the oxidized nanofibers. UV spectrophotometry, X-ray photoelectron spectroscopy and wavelength dispersive X-rays analysis have been employed as characterization tools for this purpose. Pristine nanofibers presented a relatively low content of negative charges on their surface thus adsorbing a low amount of copper(II). The copper adsorption capacity of the nanofibers was enhanced due to the oxidation treatment since the carboxylate groups introduced on the nanofibers surface constituted negative sites for electrostatic attraction of copper ions (Cu2+). The increase in copper adsorption on the nanofibers correlated both with the pH and carboxylate content and reached maximum values of 135 and 55mgg−1 for highly oxidized cellulose and chitin nanofibers, respectively. Furthermore, the metal ions could be easily removed from the contaminated nanofibers through a washing procedure in acidic water. Finally, the adsorption capacity of oxidized cellulose nanofibers for other metal ions, such as nickel(II), chromium(III) and zinc(II), was also demonstrated. We conclude that TEMPO oxidized biobased nanofibers from waste resources represent an inexpensive and efficient alternative to classical sorbents for heavy metal ions removal from contaminated water

Community-Based Monitoring Detects Sources and Risks of Mining-Related Water Pollution in Zimbabwe

Although mining and mineral processing are vital for many economies in the Global South, they are associated with enormous challenges of managing potentially devastating environmental impacts. In contexts where environmental oversight agencies often lack financial and personal capacities to fulfill their role, community-based monitoring might be a valid alternative to monitor potential environmental impacts. In this study, we present the setup and the implementation of a citizen science project to monitor water quality parameters in a river downstream of a coal mining area in Hwange, Western Zimbabwe. In a joint effort over 1.5 years, community monitors and scientists took close to 800 water samples in the Deka River and effluent channels. The data allowed identifying sources of pollution and relating these to past and present mining activities. The primary source of acid mine drainage came from abandoned underground mine sites. Illegal mine water dumping from active mine sites accentuated the problem and resulted in fish kills and food risks for the local population. Concentrations of manganese, nickel and arsenic were exceeding national fresh water guidelines and international drinking water standards. Manganese concentrations exceeded guidelines by a factor of 70 resulting in a public health risk. In this study, we showed that community-based monitoring offers a promising approach to establish a high-quality dataset for assessing mining-related risks if the implementation of sampling protocols is followed tightly. The monitoring scheme significantly improves the collection and interpretation of water quality data in challenging contexts where governmental institutions and industrial players are not enforcing environmental standards.ISSN:2296-665

Kinetics & Mechanism of Oxidation of Tellurium(IV) by Thallium(III) in Perchloric Acid Medium

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Enhancing adsorption of heavy metal ions onto biobased nanofibers from waste pulp residues for application in wastewater treatment

Biobased nanofibers are increasingly considered in purification technologies due to their high mechanical properties, high specific surface area, versatile surface chemistry and natural abundance. In this work, cellulose and chitin nanofibers functionalized with carboxylate entities have been prepared from pulp residue (i.e., a waste product from the pulp and paper production) and crab shells, respectively, by chemically modifying the initial raw materials with the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated oxidation reaction followed by mechanical disintegration. A thorough investigation has first been carried out in order to evaluate the copper(II) adsorption capacity of the oxidized nanofibers. UV spectrophotometry, X-ray photoelectron spectroscopy and wavelength dispersive X-rays analysis have been employed as characterization tools for this purpose. Pristine nanofibers presented a relatively low content of negative charges on their surface thus adsorbing a low amount of copper(II). The copper adsorption capacity of the nanofibers was enhanced due to the oxidation treatment since the carboxylate groups introduced on the nanofibers surface constituted negative sites for electrostatic attraction of copper ions (Cu2+). The increase in copper adsorption on the nanofibers correlated both with the pH and carboxylate content and reached maximum values of 135 and 55 mg g−1 for highly oxidized cellulose and chitin nanofibers, respectively. Furthermore, the metal ions could be easily removed from the contaminated nanofibers through a washing procedure in acidic water. Finally, the adsorption capacity of oxidized cellulose nanofibers for other metal ions, such as nickel(II), chromium(III) and zinc(II), was also demonstrated. We conclude that TEMPO oxidized biobased nanofibers from waste resources represent an inexpensive and efficient alternative to classical sorbents for heavy metal ions removal from contaminated water.ISSN:1572-882XISSN:0969-023

Thallium Speciation and Extractability in a Thallium- and Arsenic-Rich Soil Developed from Mineralized Carbonate Rock

We investigated the speciation and extractability of Tl in soil developed from mineralized carbonate rock. Total Tl concentrations in topsoil (0–20 cm) of 100–1000 mg/kg are observed in the most affected area, subsoil concentrations of up to 6000 mg/kg Tl in soil horizons containing weathered ore fragments. Using synchrotron-based microfocused X-ray fluorescence spectrometry (μ-XRF) and X-ray absorption spectroscopy (μ-XAS) at the Tl L₃-edge, partly Tl­(I)-substituted jarosite and avicennite (Tl₂O₃) were identified as Tl-bearing secondary minerals formed by the weathering of a Tl–As–Fe-sulfide mineralization hosted in the carbonate rock from which the soil developed. Further evidence was found for the sequestration of Tl­(III) into Mn-oxides and the uptake of Tl­(I) by illite. Quantification of the fractions of Tl­(III), Tl­(I)-jarosite and Tl­(I)-illite in bulk samples based on XAS indicated that Tl­(I) uptake by illite was the dominant retention mechanism in topsoil materials. Oxidative Tl­(III)­uptake into Mn-oxides was less relevant, probably because the Tl loadings of the soil exceeded the capacity of this uptake mechanism. The concentrations of Tl in 10 mM CaCl₂-extracts increased with increasing soil Tl contents and decreasing soil pH, but did not exhibit drastic variations as a function of Tl speciation. With respect to Tl in contaminated soils, this study provides first direct spectroscopic evidence for Tl­(I) uptake by illite and indicates the need for further studies on the sorption of Tl to clay minerals and Mn-oxides and its impact on Tl solubility in soils