Thallium adsorption on three iron (hydr)oxides and Tl isotopic fractionation induced by adsorption on ferrihydrite.

Thallium (Tl) is an extraordinarily toxic metal, which is usually present with Tl(I) and highly mobile in aquatic environment. Limited knowledge is available on the adsorption and isotopic variations of Tl(I) to Fe-(hydr)oxides. Herein, the adsorption behavior and mechanism of Tl(I) on representative Fe-(hydr)oxides, i.e. goethite, hematite, and ferrihydrite, were comparatively investigated kineticly and isothermally, additional to crystal structure modelling and Tl isotope composition (205Tl/203Tl). The results showed that ferrihydrite exhibited overall higher Tl(I) adsorption capacity (1.11-10.86 mg/kg) than goethite (0.21-1.83 mg/kg) and hematite (0.14-2.35 mg/kg), and adsorption by the three prevalent Fe-minerals presented strong pH and ionic strength dependence. The magnitude of Tl isotopic fractionation during Tl(I) adsorption to ferrihydrite (αsolid-solution ≈ 1.00022-1.00037) was smaller than previously observed fractionation between Mn oxides and aqueous Tl(I) (αsolid-solution ≈ 1.0002-1.0015). The notable difference is likely that whether oxidation of Tl(I) occurred during Tl adsorption to the mineral surfaces. This study found a small but detectable Tl isotopic fractionation during Tl(I) adsorption to ferrihydrite and heavier Tl isotope was slightly preferentially adsorbed on surface of ferrihydrite, which was attributed to the formation of inner-sphere complex between Tl and ≡Fe-OH. The findings offer a new understanding of the migration and fate of 205Tl/203Tl during Tl(I) adsorption to Fe (hydr)oxides.

Perspective on Fe0-PS synergetic effect and reaction mechanism in the thallium(I) contaminated water treatment.

Due to extreme toxicity of the element of thallium (Tl), increasing aqueous Tl pollution incidents have aroused growing concerns. As the prevalent and stable form, i.e., monovalent Tl, the highly efficient removal methodologies of Tl(I) from (waste)water remains limited and challenging. In this study, an advanced oxidation method, the feasibility of using zero valent iron (Fe0) coupled with persulfate (PS) to treat Tl(I)-containing synthetic wastewater was investigated. Its influence parameters, including reaction time, initial Tl concentration, dosages of PS and Fe0, initial and coagulation pH, temperature, coexisting ions and organic matter (NO3-, SO42-, Cl- and HA) were examined. The results revealed that the system can be applied to a wide range of pH and temperature and the reaction equilibrium can be reached in about 30 min. Favorable Tl(I) removal rate (>98%) was observed in the synthetic wastewater with medium and relatively high Tl(I) concentration (≤0.250 mM). The analyses of characterization results including electron spin resonance spectrometer and X-ray photoelectron spectroscopy indicated that ·OH played a vital role in the removal of Tl(I), which was oxidized and removed by co-precipitation. Fe0 can be served as a stable source of Fe2+ to efficiently catalyze PS. The remaining Fe0 can be easily separated because of its magnetism, assuring the promising reusability of the reactant. The study aims to provide references for treatment of real Tl polluted wastewater.

Synergetic removal of thallium and antimony from wastewater with jacobsite-biochar-persulfate system.

Both of thallium (Tl) and antimony (Sb) are toxic elements in the natural environment. Emerging Tl and Sb pollution in water has gradually gained public concerns globally. However, limited technologies are available for co-removal of Tl and Sb from wastewater. Herein, an novel system was successfully fabricated to enhance the synergetic removal of both Tl and Sb in wastewater. In this study, MnFe2O4-biochar composite (MFBC) facilely synthesized by a one-pot hydrothermal method was used as adsorbent and persulfate (PS) activator for simultaneously removing Tl and Sb from wastewater. The optimal reaction conditions for best removal efficiency of Tl and Sb simultaneously were obtained by using the response surface design combined with Box-Behnken Design (BBD) model. Results unveiled that the average removal rates of Tl and Sb can achieve 98.33% and 89.14%, respectively under the optimal reaction conditions. Electron Spin Resonance (ESR), and radical quenching experiments showed that OH• and SO4•- play a critical role in the removal of Tl-Sb compound pollution. Via using different characterization, it is revealed that the mechanism of removing Tl-Sb containing wastewater by MFBC-1.4/PS system is oxidation, adsorption, complexation and ion exchange. All these results indicate that MFBC-1.4/PS technology is prospective in highly effective removal of Tl and Sb from wastewater simultaneously.

Thallium and potentially toxic elements distribution in pine needles, tree rings and soils around a pyrite mine and indication for environmental pollution.

In this study, the distributions of thallium (Tl), and other potential toxic elements, such as Cd, Co, Cu, Pb, Sr, As, Cr, Ni, Zn, and Mn in needles, tree rings and soils of pine trees in one of the largest pyrite mining areas in the world, i.e., Yunfu, China were investigated. The results showed that pseudo-total Tl concentration of the tree rings ranged from 0.41 to 2.03 mg/kg (average: 1.12 mg/kg) during the year of 1998 to 2011. This indicates an overall obvious enrichment of Tl. Further investigation of element level variations in the pine needles showed a negative correlation between Tl content and the distance from the mining area. The results of Principal Component Analysis additionally demonstrated that Tl in the tree rings was most likely derived from the pine needles. Notably, Tl contents in the tree rings exhibited generally similar distribution pattern to the annual production intensity of Yunfu pyrite mining activities. The findings suggest that metal(loid)s in particular of Tl in pine tree rings can be used as alternative proxies to approximatively reconstruct the chronological change of atmospheric environmental pollution induced by pyrite associated mining/smelting activities.

U(VI) adsorption by green and facilely modified Ficus microcarpa aerial roots: Behavior and mechanism investigation.

Uranium (U)-containing wastewater poses serious pressure to human health and environmental safety. The treatment of U-bearing wastewater using green and facilely fabricated materials is considered a promising alternative. Herein, the raw and modified aerial roots of Ficus microcarpa (RARF and MARF, respectively) were prepared and applied to the treatment of synthesized U-containing wastewater. The results showed that the adsorption process was spontaneous and chemically controlled, which was in good accordance with the pseudo-second-order kinetic and the Redlich-Peterson isotherm adsorption model. The adsorption mechanisms were proposed to be the complexation between U(VI) and oxygen/phosphorus-containing functional groups on MARF.

Highly efficient removal of thallium in wastewater by MnFe2O4-biochar composite.

Thallium (Tl), is a highly toxic trace metal in the natural environment. Emerging Tl pollution in waters has gradually become a global concern. However, limited removal technologies are available for Tl-containing wastewater. Herein, MnFe2O4-biochar composite (MFBC) was successfully fabricated via coprecipitation method as a novel and efficient adsorbent for treating Tl(I)-contaminated wastewater. It was found that the MFBC, with a specific surface area of 187.03 m2/g, exhibited high performance across a wide pH range of 4-11, with the superior Tl(I) removal capacity (170.55 mg/g) based on Langmuir model (pH 6.0, a dosage of 1 g/L). The removal mechanisms included physical and chemical adsorption, ion exchange, surface complexation, and oxidation. This investigation revealed that MFBC is a promising and environmentally friendly adsorbent with a low cost, large specific surface area, magnetic properties, and high efficiency for the removal of Tl(I) from wastewater.