Thallium isotopic fractionation in soils from a historic HgTl mining area: New insights on thallium geochemistry.

Thallium (Tl), a highly toxic heavy metal, which may pose significant environmental threats due to extensive discharge from anthropogenic activities. It is crucial to understand geochemical behavior of Tl in soils for initiating proper measures for Tl pollution control. For this purpose, transport behavior of Tl and its dominant factors in soils collected from a typically Tl-enriched depth profile, surrounding a historical tailing dump near an independent HgTl mine area in China, were investigated by using Tl isotope compositions. Results showed that an overall enrichment of Tl (48.68-375.21 mg/kg) was accompanied with As elevation (135.00-619.00 mg/kg) in the whole depth profile, and Tl and As exhibited co-migration behavior with Fe, S, K, and Rb. Geochemical fractionation of Tl unveiled by sequential extraction further indicated that Mn-/Fe-bearing minerals and clay minerals act as main hosts of Tl in the studied soils. Thallium isotopic composition and its fractionation pattern further revealed that the major contributors to high Tl levels in the depth profile were tailing and lorandite minerals, with mean contribution rate of 51.99% and 42.47%, respectively. These findings facilitate the understanding of Tl transport behavior in highly contaminated environment, providing valuable insights for developing new technologies in mining waste treatment and historical mine reclamation.

Applying thallium isotopic compositions as novel and sensitive proxy for Tl(I)/Tl(III) transformation and source apportionment.

Thallium is a rare metal known for its highly toxic nature. Recent research has indicated that the precise determination of Tl isotopic compositions using Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP MS) provides new opportunities for understanding Tl geochemical behavior. While isotopic fractionation of Tl derived from anthropogenic activities (e.g., mining, smelting) have been reported, there is limited information regarding Tl influenced by both natural weathering processes and anthropogenic origins. Herein, we investigated, for the first time, the Tl isotopic compositions in soils across a representative Tl-rich depth profile from the Lanmuchang (LMC) quicksilver mine (southwest China) in the low-temperature metallogenesis zone. The results showed significant variations in Tl isotope signatures (ε205Tl) among different soil layers, ranging from -0.23 to 3.79, with heavier isotope-205Tl enrichment observed in the bottom layers of the profile (ε205Tl = 2.18-3.79). This enrichment of 205Tl was not solely correlated with the degree of soil weathering but was also partially associated with oxidation of Tl(I) by Fe (hydr)oxide minerals. Quantitative calculation using ε205Tl vs. 1/Tl data further indicated that the Tl enrichment across the soil depth profile was predominantly derived from anthropogenic origins. All these findings highlight that the robustness and reliability of Tl isotopes as a proxy for identifying both anthropogenic and geogenic sources, as well as tracing chemical alterations and redox-controlled mineralogical processes of Tl in soils. The nascent application of Tl isotopes herein not only offers valuable insights into the behavior of Tl in surface environments, but also establishes a framework for source apportionment in soils under similar circumstances.

Effects and mechanisms of mineral amendment on thallium mobility in highly contaminated soils.

Thallium (Tl) is an extremely toxic element, whose toxicity is even higher than mercury, arsenic, and cadmium. It is of great significance to hinder the migration and transfer of Tl from soils to the plants. A synthetic mineral amendment (SMA), mainly composed of different silicates, was evaluated for its effects on the transformation and retention of Tl in two typical highly Tl-contaminated soils from Southwest China. The results indicated that the addition of mineral amendment increased the soil of the pH by 0.46-2.13 units and distinctly reduced the content of active thallium in the soils. The extent of Tl reduction was related to the morphological characteristics of the original soil In particular, the application of the mineral amendment transformed 25.8-52.5% of the active Tl fractions in the soils to the residual fraction at 60 d. Adding mineral amendment to the soils can provide conditions to facilitate Tl to enter the silicate crystal lattice. The results of XPS evidenced that the proportion of Tl(I) in the soil was greatly reduced after adding the mineral amendment.

Geochemical fractionation of thallium in contaminated soils near a large-scale Hg-Tl mineralised area.

Enriched levels of thallium (Tl) in the environment are not only derived from anthropogenic sources but also have potential natural origins owing to Tl-rich sulphide mineralization. However, little is known regarding the geochemical fractionations of Tl in contaminated soils from geogenic sources. This study aims to reveal the Tl geochemical fractionations in different types of soils from a large-scale independent Tl mine in southwestern China, via a modified Institute for Reference Materials and Measurement (IRMM) sequential extraction (four-step) scheme. The results revealed that a large percentage of Tl was related to the labile portions (including reducible, weak-acid-exchangeable, and oxidizable fraction) of the soils (68.8-367 mg kg-1). Further analyses by Scanning Transmission Electron Microscopy-Energy Dispersive X-ray Spectrometer (STEM-EDS) found that Tl mainly existed in the Fe-containing minerals (such as jarosite and hematite) with fine particles (∼1 µm). These results highlight that, apart from the anthropogenically induced Tl pollution, the naturally occurring Tl contamination in soils may also pose significant risks to human health and ecological safety. Owing to the relatively high mobility and bioavailability of Tl in the labile fractions, it is important to understand geochemical fractionations of this element for alleviating Tl pollution and effective management of naturally occurring Tl contaminated soils.