A novel application of thallium isotopes in tracing metal(loid)s migration and related sources in contaminated paddy soils.

Thallium (Tl) is a highly toxic heavy metal, which is harmful to plants and animals even in trace amounts. Migration behaviors of Tl in paddy soils system remain largely unknown. Herein, Tl isotopic compositions have been employed for the first time to explore Tl transfer and pathway in paddy soil system. The results showed considerably large Tl isotopic variations (ε205Tl = -0.99 ± 0.45 ~ 24.57 ± 0.27), which may result from interconversion between Tl(I) and Tl(III) under alternative redox conditions in the paddy system. Overall higher ε205Tl values of paddy soils in the deeper layers were probably attributed to abundant presence of Fe/Mn (hydr)oxides and occasionally extreme redox conditions during alternative dry-wet process which oxidized Tl(I) to Tl(III). A ternary mixing model using Tl isotopic compositions further disclosed that industrial waste contributed predominantly to Tl contamination in the studied soil, with an average contribution rate of 73.23%. All these findings indicate that Tl isotopes can be used as an efficient tracer for fingerprinting Tl pathway in complicated scenarios even under varied redox conditions, providing significant prospect in diverse environmental applications.

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.

Thallium isotopic compositions as tracers in environmental studies: A review.

Thallium is a highly poisonous heavy metal. Since Tl pollution control has been neglected worldwide until the present, countless Tl pollutants have been discharged into the environment, endangering the safety of drinking water, farmland soil, and food chain, and eventually posing a great threat to human health. However, the source, occurrence, pathway and fate of Tl in the environment remains understudied. As Tl in non-contaminated systems and from anthropogenic origin exhibits generally different isotopic signatures, which can provide fingerprint information and a novel way for tracing the anthropogenic Tl sources and understanding the environmental processes. This review summarizes: (i) the state-of-the-art development in highly-precise determination analytical method of Tl isotopic compositions, (ii) Tl isotopic fractionation induced by the low-temperature surface biogeochemical process, (iii) Tl isotopic signature of pollutants derived from anthropogenic activities and isotopic fractionation mechanism of Tl related to the high-temperature industrial activities, and (iv) application of Tl isotopic composition as a new tracer emerging tracer for source apportionment of Tl pollution. Finally, the limitations and possible future research about Tl isotopic application in environmental contamination is also proposed: (1) Tl fractionation mechanism in different environmental geochemistry processes and industrial activities should be further probed comprehensively; (2) Tl isotopes for source apportionment should be further applied in other different high Tl-contaminated scenarios (e.g., agricultural systems, water/sediment, and atmosphere).

Uranium re-adsorption on uranium mill tailings and environmental implications.

Uranium mill tailings (UMTs) are one critical source of environmental U pollution. Leaching test has been extensively used to reveal U release capacity and mechanism from UMTs, while little attention has been paid to the effects of re-adsorption process on U release. In this study, the role of U re-adsorption behaviors during leaching test with UMTs was comprehensively investigated. Through paired data on mineralogical composition and aqueous U speciation, the influence of environmentally relevant factors on U re-absorption capacity and mechanism on UMTs with different particle sizes was revealed. Significant amounts of U re-adsorption were observed and primarily attributed to the adsorption on chlorite, albite and muscovite as well as combined reduction-sequestration by muscovite. Uranium re-adsorption predominantly occurred via inner-sphere complexation and surface precipitation depending on leachant pH. Coexisting sulfate or phosphate could further enhance U re-adsorption. The enhanced re-adsorption from sulfate occurred when inner-sphere complexation governed the re-adsorption process. These findings suggest that the environmental hazards and ecological risks of the U containing (waste) solids might have been underestimated due to the ignorance of the re-adsorption process, since the re-adsorbed U could be easily re-mobilized. The insights from this study are also helpful in developing effective in-situ remediation strategies.

Geochemical and U-Th isotopic insights on uranium enrichment in reservoir sediments.

Uranium (U) geochemistry and its isotopic compositions of reservoir sediments in U mine area were poorly understood. Herein, U and Th isotopic compositions were employed to investigate source apportionment and geochemical behavior of U in 41 reservoir sediments from a U mining area, Guangdong, China. The remarkably high contents of both total U (207.3-1117.7 mg/kg) and acid-leachable U (90.3-638.5 mg/kg) in the sediments exhibit a severe U contamination and mobilization-release risk. The U/Th activity ratios (ARs) indicate that all sediments have been contaminated apparently by U as a result of discharge of U containing wastewater, especially uranium mill tailings (UMT) leachate, while the variations of U/Th ARs are dominated by U geochemical behaviors (mainly redox process and adsorption). The U isotopic compositions (δ238U) showed a large variance through the sediment profile, varying from - 0.62 to - 0.04‰. The relation between δ238U and acid-leachable U fraction demonstrates that the U isotopic fractionation in sediments can be controlled by bedrock weathering (natural activity), UMT leachate (anthropogenic activity) and subsequent biogeochemical processes. The findings suggest that U-Th isotopes are a powerful tool to better understand U geochemical processes and enrichment mechanism in sediments that were affected by combined sources and driving forces.

Cadmium isotopic fractionation in lead-zinc smelting process and signatures in fluvial sediments.

Cadmium (Cd) is a toxic heavy metal pollutant. Various industrial activities, especially metal smelting, are the main sources of Cd pollution. Cd isotopes have exhibited the ability to be excellent source tracers and can be used to assess the pollution contributions from different sources. Herein, in a typical lead-zinc smelter, Shaoguan, China, significant Cd isotopic fractionation was found during the high temperature smelting process and followed a Rayleigh distillation model. The heavier Cd isotopes were concentrated in the slag, while the lighter Cd isotopes were concentrated in the dust. In the downstream sediment profile of the smelter, sediments have extremely high Cd concentrations that far exceed the Chinese background sediment, indicating severe pollution levels. The ε114/110Cd of the sediment core, ranged from - 0.62 ± 0.5-1.73 ± 0.5, are found between slag (ε114/110Cd=10.42) and dust (ε114/110Cd=-5.68). The binary mixture model suggests that 88-93% of the Cd in sediment profile was derived from the slag, and 7-12% from the deposition of dust. The findings demonstrate the great potential to apply Cd isotopes as a new geochemical tool to distinguish anthropogenic sources and quantify the contribution from various sources in the environment.

Cadmium isotopes as tracers in environmental studies: A review.

Cadmium isotopic compositions in non-contaminated systems and anthropogenic sources of Cd generally have different isotopic signatures. Cadmium isotopes, as a novel tracer, can be useful for fingerprinting the anthropogenic Cd sources, providing a promising source tracing technique in environmental studies. This review presents: (i) analytical techniques for Cd isotopic composition; (ii) isotopic signatures of Cd derived from anthropogenic activities; (iii) isotopic compositions of Cd in the industrial-impacted environmental samples; (iv) cadmium isotopic fractionation induced by geochemical process. Finally, the perspectives of using Cd isotopic compositions in environmental studies are also briefly discussed.

High Efficiency Mesoscopic Solar Cells Using CsPbI3 Perovskite Quantum Dots Enabled by Chemical Interface Engineering.

All-inorganic α-CsPbI3 perovskite quantum dots (QDs) are attracting great interest as solar cell absorbers due to their appealing light harvesting properties and enhanced stability due to the absence of volatile organic constituents. Moreover, ex situ synthesized QDs significantly reduce the variability of the perovskite layer deposition process. However, the incorporation of α-CsPbI3 QDs into mesoporous TiO2 (m-TiO2) is highly challenging, but these constitute the best performing electron transport materials in state-of-the-art perovskite solar cells. Herein, the m-TiO2 surface is engineered using an electron-rich cesium-ion containing methyl acetate solution. As one effect of this treatment, the solid-liquid interfacial tension at the TiO2 surface is reduced and the wettability is improved, facilitating the migration of the QDs into m-TiO2. As a second effect, Cs+ ions passivate the QD surface and promote the charge transfer at the m-TiO2/QD interface, leading to an enhancement of the electron injection rate by a factor of 3. In combination with an ethanol-environment smoothing route that significantly reduces the surface roughness of the m-TiO2/QD layer, optimized devices exhibit highly reproducible power conversion efficiencies exceeding 13%. The best cell with an efficiency of 14.32% (reverse scan) reaches a short-circuit current density of 17.77 mA cm-2, which is an outstanding value for QD-based perovskite solar cells.

Adsorption of thallium(I) on rutile nano-titanium dioxide and environmental implications.

Rutile nano-titanium dioxide (RNTD) characterized by loose particles with diameter in 20-50 nm has a very large surface area for adsorption of Tl, a typical trace metal that has severe toxicity. The increasing application of RNTD and widespread discharge of Tl-bearing effluents from various industrial activities would increase the risk of their co-exposure in aquatic environments. The adsorption behavior of Tl(I) (a prevalent form of Tl in nature) on RNTD was studied as a function of solution pH, temperature, and ion strength. Adsorption isotherms, kinetics, and thermodynamics for Tl(I) were also investigated. The adsorption of Tl(I) on RNTD started at very low pH values and increased abruptly, then maintained at high level with increasing pH >9. Uptake of Tl(I) was very fast on RNTD in the first 15 min then slowed down. The adsorption of Tl(I) on RNTD was an exothermic process; and the adsorption isotherm of Tl(I) followed the Langmuir model, with the maximum adsorption amount of 51.2 mg/g at room temperature. The kinetics of Tl adsorption can be described by a pseudo-second-order equation. FT-IR spectroscopy revealed that -OH and -TiOO-H play an important role in the adsorption. All these results indicate that RNTD has a fast adsorption rate and excellent adsorption amount for Tl(I), which can thus alter the transport, bioavailability and fate of Tl(I) in aqueous environment.

Growth kinetics and mechanisms of multinary copper-based metal sulfide nanocrystals.

Multinary copper-based metal sulfide (Cu-M-S) nanocrystals (NCs) usually have high absorption coefficients and near-optimum direct band gaps, which have been considered as novel photo-absorption materials for quantum dot-sensitized solar cells (QDSCs) and hole-transport materials for perovskite solar cells (PSCs). However, the formation and phase transformation mechanisms of Cu-M-S NCs during the solution-based preparing approaches are complicated. Herein, Cu-M-S NCs, including Cu2ZnSnS4 (CZTS), Cu2SnS3 (CTS), CuInS2 (CIS), and CuSbS2 (CAS), have been synthesized through solution-based hot-injection methods. Their formation and phase transformation mechanisms have been studied in terms of the growth kinetics. An effective method has been proposed to investigate the formation mechanisms of Cu-M-S NCs. The results suggest that CZTS, CTS, and CIS NCs are formed through an inter-reaction between metal sulfides rather than the classical cation exchange reactions, and CAS NCs are formed based on the CuxS structure; these findings provide new insights into the formation of Cu-M-S NCs. In addition, the anisotropic or isotropic growth processes during the growth stage have been found to be the key issues in the formation of a zinc blende or wurtzite structure NCs, respectively, which can be controlled by tuning the relative reactivity of metal precursors.