201Tl Uptake Research Articles

Mitigation of thallium threat in paddy soil and rice plant by application of functional biochar

Thallium (Tl) is a highly toxic metal, and its contamination in soils entails high risks to human health via food chain. It remains largely unknown of the effects of applying biochar on Tl uptake in paddy systems despite that few studies have shown that biochar exhibits great potential for decreasing Tl bioavailability in soils. Herein, we examined the mitigating effects of the application of biochar (5 and 20 g/kg pristine biochar; 5 and 20 g/kg Fe/Mn-modified biochar) on Tl uptake in paddy soil and rice plant after an entire rice growth period. The results suggested that the application of Fe/Mn-modified biochar (FMBC) considerably mitigated the accumulation of Tl in different tissues of rice plants. Specifically, total Tl content in rice plants treated with FMBC-20 decreased by over 75% compared with control experiment. In addition, the amendment of FMBC in Tl-rich paddy soils can enhance the communities of microorganisms (Actinobacteria and Proteobacteria). Further analysis of the soil microbial symbiosis network revealed that FMBC promotes the living microorganisms to play modular synergistic interactions, which is crucial for FMBC-induced Tl stabilization in soils. All these findings indicated that FMBC is an efficient and environmentally friendly Tl-immobilization alternative material and can be potentially used in the remediation of Tl-contaminated paddy soils and/or cropland.

Mechanisms of Uptake and Translocation of Thallium in Brassica Vegetables: An X-ray Fluorescence Microspectroscopic Investigation.

Most nonoccupational human exposure to thallium (Tl) occurs via consumption of contaminated food crops. Brassica cultivars are common crops that can accumulate more than 500 μg Tl g-1. Knowledge of Tl uptake and translocation mechanisms in Brassica cultivars is fundamental to developing methods to inhibit Tl uptake or conversely for potential use in phytoremediation of polluted soils. Brassica cultivars (25 in total) were subjected to Tl dosing to screen for Tl accumulation. Seven high Tl-accumulating varieties were selected for follow-up Tl dosing experiments. The highest Tl accumulating Brassica cultivars were analyzed by synchrotron-based micro-X-ray fluorescence to investigate the Tl distribution and synchrotron-based X-ray absorption near-edge structure spectroscopy (XANES) to unravel Tl chemical speciation. The cultivars exhibited different Tl tolerance and accumulation patterns with some reaching up to 8300 μg Tl g-1. The translocation factors for all the cultivars were >1 with Brassica oleracea var. acephala (kale) having the highest translocation factor of 167. In this cultivar, Tl is preferentially localized in the venules toward the apex and along the foliar margins and in minute hot spots in the leaf blade. This study revealed through scanning electron microscopy and X-ray fluorescence analysis that highly Tl-enriched crystals occur in the stoma openings of the leaves. The finding is further validated by XANES spectra that show that Tl(I) dominates in the aqueous as well as in the solid form. The high accumulation of Tl in these Brassica crops has important implications for food safety and results of this study help to understand the mechanisms of Tl uptake and translocation in these crops.

Thallium content in vegetables and derivation of threshold for safe food production in soil: A meta-analysis

Soil thallium (Tl) pollution is a serious environmental problem, and vegetables are the primary pathway for human exposure to Tl. Therefore, it is important to investigate the characteristics of soil Tl uptake by vegetables. In this study, the meta-analysis approach was first applied to explore the relationship between Tl content in vegetables and soil environment, as well as key factors influencing soil physical–chemical properties, and to derive soil thresholds for Tl. The results indicated that various types of vegetables have different capabilities for Tl accumulation. Vegetables from contaminated areas showed high Tl accumulation, and the geomean Tl content in different types of vegetables was in the following order: leafy > root–stalk > solanaceous vegetables. Taro and kale had significantly higher capability to accumulate soil Tl among the 35 species studied, with Tl bioconcentration factor values of 0.060 and 0.133, respectively. Pearson correlation analysis and meta-analysis revealed that the Tl content in vegetables was significantly correlated with soil pH and Tl content in soil. The linear predictive model for Tl accumulation in vegetables based on soil Tl content described the data well, and the fitting coefficient R2 increased with soil pH value. According to potential dietary toxicity, the derived soil Tl thresholds for all, leafy and root–stalk vegetables increased with an increase in soil pH, and were in the range of 1.46–6.72, 1.74–5.26 and 0.92–6.06 mg/kg, respectively. The soil Tl thresholds for kale, lettuce and carrot were in the range of 0.24–4.89, 2.94–3.32 and 3.77–14.43 mg/kg, respectively. Ingestion of kale, beet, sweet potato, potato, taro, pepper, turnip, Chinese cabbage, eggplant and carrot poses potential health risks. The study provides scientific guidance for vegetable production in Tl-contaminated areas and can help with the selection of vegetable species suitable for avoiding the absorption of Tl from contaminated soil.

An eco-friendly composite hydrogel based on covalently crosslinked cellulose/poly (glycerol citrate) for thallium (Ι) removal from aqueous solutions

Cellulose/poly (glycerol citrate) reinforced with thiol-rich polyhedral oligomeric silsesquioxane and apple peel (POSS-SH@CAG-CEL/AP) was synthesized using gelation method in the presence of glutaraldehyde as a crosslinker agent and used as an efficient composite hydrogel for elimination of Tl(Ι) from aqueous solutions. This composite hydrogel and synthesized thiol-rich polyhedral oligomeric silsesquioxane were characterized by elemental analysis, FT-IR, NMR, TGA, and FE-SEM techniques. The effects of synthetic and environmental parameters on the adsorption capacity of the composite hydrogel were investigated and it was found that thiol-rich polyhedral oligomeric silsesquioxane has improved the hydrogel properties including the Tl(Ι) uptake and the thermal stability. The maximum adsorption capacity of 352.3 mg g−1 was obtained within 30 min under optimum reaction conditions. A typical Langmuir adsorption isotherm with was observed for adsorption of Tl(I) onto POSS-SH@CAG-CEL/AP and pseudo-second-order kinetic model provided the best correlation between experimental data. Thermodynamic studies showed that the Tl(I) adsorption was spontaneous process and exothermic. Also, the reusability tests confirmed that the POSS-SH@CAG-CEL/AP can be reused for four times without any remarkable change in its adsorption capacity. Thus, this reusable biobased composite hydrogel can be an ideal candidate for elimination of Tl(I) from aqueous solutions.

125I-labeled 2-[4-(2-iodophenyl)piperidino]cyclopentanol (125I-OI5V) imaging visualized augmented sigma-1 receptor expression according to the severity of myocardial ischemia

BackgroundWe aimed to explore how the severity of myocardial ischemia affects myocardial sigma-1 receptor (Sig-1R) expression using 125I-labeled 2-[4-(2-iodophenyl)piperidino]cyclopentanol (125I-OI5V) imaging. Methods and resultsThe left coronary artery was occluded for 30, 20, and 10 minute, to vary the severity of myocardial ischemia, followed by reperfusion. Dual-tracer autoradiography of the left ventricular short-axis slices was performed 3 and 7 days after reperfusion. 125I-OI5V was injected 30 minute before sacrifice and the area at risk (AAR) was evaluated by 99mTc-MIBI. Intense 125I-OI5V uptake was observed in the AAR and was significantly increased with increasing ischemia duration. To evaluate salvaged and nonsalvaged areas (preserved and decreased perfusion areas), triple-tracer autoradiography was performed 3 days after reperfusion. After dual-tracer autoradiography, 201Tl was injected 20 minute post 125I-OI5V injection. On triple-tracer autoradiography, the AAR/normally perfused area 125I-OI5V uptake ratio was positively correlated with the nonsalvaged area/whole left ventricular (LV) area ratio (P < .05). The AAR/normally perfused area 125I-OI5V uptake ratio was negatively correlated with the 201Tl uptake ratio of the AAR to normally perfused areas (P < .05). The comparison of the immunostaining distribution of 125I-OI5V and the macrophage marker CD68 revealed that 125I-OI5V was present mainly in, and immediately adjacent to the macrophage infiltration area. ConclusionsSignificant 125I-OI5V uptake in the AAR depends on the duration of ischemia and reduced 201Tl uptake; furthermore, 125I-OI5V was found in and around the macrophage infiltrate area. These results indicate that iodine-labeled OI5V is a promising tool for visualizing Sig-1R expression according to the ischemic burden.

Thallium isotope cycling between waters, particles, and sediments across a redox gradient

Thallium (Tl) isotopes are an emerging tool for tracking the history of molecular oxygen in seawater. Use of Tl isotopes in this manner requires a thorough understanding of the modern Tl isotope cycle, especially within the anoxic settings that typified Earth’s past oceans. To this end, we generated Tl concentration and isotope data for waters, particles, and sediments collected during three spring-summer-fall field seasons in Siders Pond, a salt-stratified and sulfide-rich (‘euxinic’) pond on Cape Cod (Massachusetts, USA). Over short timeframes (i.e., days to weeks), we observed a large degree of variability in the abundance (Tldiss = 9 pM–42 pM) and isotopic composition (ε205Tldiss = –3.9 ± 0.4; 2SD to –0.1 ± 0.7; 2SD) of dissolved Tl in pond surface waters. Thallium drawdown was common and favored removal of the lighter-mass Tl isotope. We surmise that biological Tl uptake plays a role in this phenomenon, but more work is warranted to confirm this hypothesis. Manganese oxides persisted in pond surface waters on many sampling days but had no obvious effect on Tldiss, only a slight effect on particulate ε205Tl values on the day of most prolific Mn oxide accumulation (driving ε205Tlpart as high as +0.9 ± 0.8; 2SD). In euxinic waters below the oxycline, rapid drawdown of dissolved Tl was observed on all sampling days together with a complimentary increase in particulate Tl (up to Tlpart = 21 pM). Strong associations between Tl and sulfide, and between Tl and other chalcophile metals (Mo and Cd), suggest that Tl is probably removed from euxinic waters in association with particulate sulfides, and seemingly with no resolvable isotopic fractionation effect despite non-quantitative Tl removal. The sediment data track the longer-term Tl cycle in the pond (i.e., across years) and reveal limited isotopic variability. Thallium isotope compositions leached from surface sediments match those predicted for contemporaneous waters, or nearly so, at all depths in the pond (above, within, and below the oxycline). Apparently, only a small fraction of the short-term Tl isotope variability found in the oxic surface waters of Siders Pond gets transferred to anoxic waters, and essentially none is transferred to sediments. Our results reaffirm the notion that Tl isotopes are uniquely capable of tracking long-term sedimentary Mn oxide burial – not mere Mn oxide formation. Our results also verify the ability of sediments formed under reducing conditions to capture the Tl isotope composition of contemporaneous waters. More broadly, the results of our investigation bolster our knowledge of the modern Tl isotope cycle and thereby permit more confident inferences of this cycle in Earth’s past.

Effect of montmorillonite biochar composite amendment on thallium bioavailability in contaminated agricultural soils and its mitigated health risk.

Little information is available on the effect of clay minerals and biochar composite on the remediation and bioavailability of thallium in agricultural soils. This study thus investigated the influence of montmorillonite biochar composite (Mnt-BC) amendment on the remediation of agricultural soil contaminated artificially by Tl and its potential health risks. Herein, bok choi was cultured to estimate the efficiency of soil Mnt-BC amendments through the bioavailability of Tl of the vegetable. Results showed that Tl bioavailability was significantly reduced in Mnt-BC-amended soils, mainly ascribed to the elevated soil pH and other improved soil properties of high functional groups (-OH, -COOH), negative charges, and exchangeable cations after amendment. Specifically, the highest immobilization efficiency of Tl in soils was observed in 2.5% treated soils with 79.11%, while in plant leaves the highest reduction of Tl was estimated to be 75.1% compared to the control treatment. Hence, the amendment dosage improved the immobilization of Tl in soil and subsequently reduced Tl uptake by the vegetable. Furthermore, from target hazard quotient (THQ) estimation, Mnt-BC amendment can lower the potential health risk while consuming such cultured bok choi in Tl-contaminated soils. Considering the environmental friendliness and high efficiency of Mnt-BC, it could be used as a potential soil amendment to remediate agricultural soils contaminated by Tl.

A graphite furnace-atomic absorption spectrometry-based rubidium efflux assay for screening activators of the Kv 7.2/3 channel.

For the characterization of Kv 7.2/3 channel activators, several analytical methods are available that vary in effort and cost. In addition to the technically elaborate patch-clamp method, which serves as a reference method, there exist several medium to high-throughput screening methods including a rubidium efflux flame-atomic absorption spectrometry (F-AAS) assay and a commercial thallium uptake fluorescence-based assay. In this study, the general suitability of a graphite furnace atomic absorption spectrometry (GF-AAS)-based rubidium efflux assay as a screening method for Kv 7.2/3 channel activators was demonstrated. With flupirtine serving as a reference compound, 16 newly synthesizedcompounds and the known Kv 7.2/3 activator retigabine were first classified as either active or inactive by using the GF-AAS-based rubidium (Rb) efflux assay. Then, the results were compared with a thallium (Tl) uptake fluorescence-based fluorometric imaging plate reader (FLIPR) potassium assay. Overall, 16 of 17 compounds were classified by the GF-AAS-based assay in agreement with their channel-activating properties determined by the more expensive Tl uptake, fluorescence-based assay. Thus, the performance of the GF-AAS-based Rb assay for primary drug screening of Kv 7.2/3-activating compounds was clearly demonstrated, as documented by the calculated Z'-factor of the GF-AAS-based method. Moreover, method development included optimization of the coating of the microtiter plates and the washing procedure, which extended the range of this assay to poorly adherent cells such as the HEK293 cells used in this study.

Global and Regional Reduction of Myocardial Perfusion in Patients with Transthyretin Type of Cardiac Amyloidosis: A Dual SPECT Study Using 99mTc Pyrophosphate and 201Thallium.

Purpose: We aimed to clarify the clinical characteristics of global and regional myocardial perfusion in patients with transthyretin type of cardiac amyloidosis (ATTR) using dual single-photon emission computed tomography (SPECT) with 99mTc pyrophosphate (PYP) and 201TL (TL). Methods: Consecutive 178 (mean age 78±12, male 79) patients known or suspect of ATTR who underwent PYP-TL dual SPECT were retrospectively enrolled. Patients were categorized according to the visual grading for planar PYP uptake using Perugini grading, and the patients with grade greater than or equal to 2 were analyzed. In planar analysis, the heart/contralateral ratio (H/CL) for PYP, and heart/lung ratio (H/L) for TL were obtained to evaluate global myocardial uptake. In TL-SPECT polar map analysis, the heterogeneity of myocardial uptake was evaluated using segmental mean %uptake. Cardiac function and left ventricular function and end-diastolic ventricular mass (LVmass) were measured by echocardiography. Results: Among 178 patients, 39 patients showed PYP uptake with grade 2 or 3 and H/CL >1.3 (81±5 ys, male 28). Of those, 4 patients showed significant perfusion defect in TL scan. Among 35 patients without perfusion defect, H/L showed a significant inverse correlation to H/CL, and LVmass (r=-0.3, p=0.02; r=-0.4, p=0.03. 95% confidence interval -0.4 to 0.2, and -0.7 to -0.04 for H/CL and LVmass). Polar map analysis demonstrated significantly lower mean %uptake for TL in septum compared to lateral (79.4±8.4 vs. 84.3±6.2, p=0.006 for TL in septum vs. lateral, respectively). Conclusion: In ATTR, TL uptake surrogated the reduction of global myocardial perfusion. A significant regional heterogeneity was observed with a notable reduction in septum despite the diffuse hypertrophy.

Calcium Enhances Thallium Uptake in Green Cabbage (Brassica oleracea var. capitata L.).

Thallium (Tl) is a nonessential and toxic trace metal that is detrimental to plants, but it can be highly up-taken in green cabbage (Brassica oleracea L. var. capitata L.). It has been proven that there is a significant positive correlation between Tl and Calcium (Ca) contents in plants. However, whether Ca presents a similar role for alleviating Tl toxicity in plants remains unclear, and little is known in terms of evidence for both Ca-enhanced uptake of Tl from soils to green cabbage and associated geochemical processes. In this study, we investigated the influence of Ca in soils on Tl uptake in green cabbage and the associated geochemical process. The pot experiments were conducted in 12 mg/kg Tl(I) and 8 mg/kg Tl(III) treatments with various Ca dosages. The results showed that Ca in soils could significantly enhance Tl uptake in green cabbage, increasing 210% in content over the control group. The soluble concentrations of Tl were largely increased by 210% and 150%, respectively, in 3.0 g/kg Ca treatment, compared with the corresponding treatment without Ca addition. This was attributed to the geochemical process in which the enhanced soluble Ca probably replaces Tl held on the soil particles, releasing more soluble Tl into the soil solution. More interestingly, the bioconcentration factor of the leaves and whole plant for the 2.0, 2.5, 3.0 g/kg Ca dosage group were greatly higher than for the non-Ca treatment, which could reach 207%, implying the addition of Ca can improve the ability of green cabbage to transfer Tl from the stems to the leaves. Furthermore, the pH values dropped with the increasing Ca concentration treatment, and the lower pH in soils also increased Tl mobilization, which resulted in Tl accumulation in green cabbage. Therefore, this work not only informs the improvement of agricultural safety management practices for the farming of crops in Tl-polluted and high-Ca-content areas, but also provides technical support for the exploitation of Ca-assisted phytoextraction technology.

Is Oxalic Acid Secretion A Detoxification Strategy for Rice Exposed to Tl(I) or Tl(III)?

Thallium (Tl) is a highly toxic element with two species, Tl(I) and Tl(III). We discovered the Tl uptake in rice exposed to Tl(III) hydroponic treatment was significantly lower than that to Tl(I) treatment, but the content of oxalic acid secreted from roots in Tl(III) treatment was higher than that in Tl(I). The physiological and molecular mechanisms underlying the difference between the two Tl species were studied using a hydroponic system. The results showed the reduction of oxalic acid content had no effect on the amount of Tl on the root surface, indicating oxalic acid might not immobilize Tl to affect the Tl uptake. Therefore, the secretion of oxalic acid from roots may not be a strategy for detoxifying Tl in rice. Notably, Tl(III) increased the expression of Oryza sativa H+-ATPase genes OsAs and the activity of H+-ATPase, and decreased potassium transport gene expression of OsKAT1.1 and OsHKT2;4, which indicated that the difference in Tl uptake of rice between the two Tl species mainly cause by the potassium transport system rather than oxalic acid.

Toward Bifunctional Chelators for Thallium-201 for Use in Nuclear Medicine.

Auger electron therapy exploits the cytotoxicity of low-energy electrons emitted during radioactive decay that travel very short distances (typically <1 μm). 201Tl, with a half-life of 73 h, emits ∼37 Auger and other secondary electrons per decay and can be tracked in vivo as its gamma emissions enable SPECT imaging. Despite the useful nuclear properties of 201Tl, satisfactory bifunctional chelators to incorporate it into bioconjugates for molecular targeting have not been developed. H4pypa, H5decapa, H4neunpa-NH2, and H4noneunpa are multidentate N- and O-donor chelators that have previously been shown to have high affinity for 111In, 177Lu, and 89Zr. Herein, we report the synthesis and serum stability of [nat/201Tl]Tl3+ complexes with H4pypa, H5decapa, H4neunpa-NH2, and H4noneunpa. All ligands quickly and efficiently formed complexes with [201Tl]Tl3+ that gave simple single-peak radiochromatograms and showed greatly improved serum stability compared to DOTA and DTPA. [natTl]Tl-pypa was further characterized using nuclear magnetic resonance spectroscopy (NMR), mass spectroscopy (MS), and X-ray crystallography, showing evidence of the proton-dependent presence of a nine-coordinate complex and an eight-coordinate complex with a pendant carboxylic acid group. A prostate-specific membrane antigen (PSMA)-targeting bioconjugate of H4pypa was synthesized and radiolabeled. The uptake of [201Tl]Tl-pypa-PSMA in DU145 PSMA-positive and PSMA-negative prostate cancer cells was evaluated in vitro and showed evidence of bioreductive release of 201Tl and cellular uptake characteristic of unchelated [201Tl]TlCl. SPECT/CT imaging was used to probe the in vivo biodistribution and stability of [201Tl]Tl-pypa-PSMA. In healthy animals, [201Tl]Tl-pypa-PSMA did not show the myocardial uptake that is characteristic of unchelated 201Tl. In mice bearing DU145 PSMA-positive and PSMA-negative prostate cancer xenografts, the uptake of [201Tl]Tl-pypa-PSMA in DU145 PSMA-positive tumors was higher than that in DU145 PSMA-negative tumors but insufficient for useful tumor targeting. We conclude that H4pypa and related ligands represent an advance compared to conventional radiometal chelators such as DOTA and DTPA for Tl3+ chelation but do not resist dissociation for long periods in the biological environment due to vulnerability to reduction of Tl3+ and subsequent release of Tl+. However, this is the first report describing the incorporation of [201Tl]Tl3+ into a chelator–peptide bioconjugate and represents a significant advance in the field of 201Tl-based radiopharmaceuticals. The design of the next generation of chelators must include features to mitigate this susceptibility to bioreduction, which does not arise for other trivalent heavy radiometals.

Comprehensive insights in thallium ecophysiology in the hyperaccumulator Biscutella laevigata

Biscutella laevigata is the strongest known thallium (Tl) hyperaccumulator plant species. However, little is known about the ecophysiological processes leading to root uptake and translocation of Tl in this species, and the interactions between Tl and its chemical analogue potassium (K). Biscutella laevigata was subjected to hydroponics experimentation in which it was exposed to Tl and K, and it was investigated in a rhizobox experiment. Laboratory-based micro-X-ray fluorescence spectroscopy (μ-XRF) was used to reveal the Tl distribution in the roots and leaves, while synchrotron-based μ-XRF was utilised to reveal elemental distribution in the seed. The results show that in the seed Tl was mainly localised in the endosperm and cotyledons. In mature plants, Tl was highest in the intermediate leaves (16,100 μg g−1), while it was one order of magnitude lower in the stem and roots. Potassium did not inhibit or enhance Tl uptake in B.laevigata. At the organ level, Tl was localised in the blade and margins of the leaves. Roots foraged for Tl and cycled Tl across roots growing in the control soils. Biscutella laevigata has ostensibly evolved specialised mechanisms to tolerate high Tl concentrations in its shoots. The lack of interactions and competition between Tl and K suggests that it is unlikely that Tl is taken up via K channels, but high affinity Tl transporters remain to be identified in this species. Thallium is not only highly toxic but also a valuable metal and Tl phytoextraction using B. laevigata should be explored.

Synergetic Tl and As retention in secondary minerals: An example of extreme arsenic and thallium pollution

Secondary minerals could be effective scavengers of toxic arsenic (As) and thallium (Tl). In environments polluted by mining, these elements are abundant both in acid rock/mine drainage scenarios, as well as in carbonate-buffered environments. In this study we have investigated the behavior of As and Tl during weathering in mine waste dumps and an associated technosol sample from the Crven Dol locality (Allchar Tl–As–Sb–Au deposit, North Macedonia) contaminated with up to 142 g kg−1 of As and 18 g kg−1 of Tl, making it an As- and Tl-extreme environment. We identified As and Tl reservoirs and discuss their difference from those observed in other naturally As- and Tl-rich environments. The pore waters show high concentrations of As (up to 196 mg L−1) and Tl (up to 660 μg L−1). Mild extractions mobilized up to 46% of the total Tl and 11% of the total As, indicating that a large amount of these toxic elements is weakly bound and can be easily mobilized into the environment. Apart from the recognition of Tl storage in several secondary phases (mainly as Tl(I) in members of the pharmacosiderite and jarosite groups, as well as Mn oxides, but also as very minor Tl(III) in other secondary phases), this study also provides the first evidence of Tl uptake by previously unknown thallium arsenate phases (with Tl:As ratios ∼ 2 and 4), detected in carbonate-buffered (near-neutral pH) As- and Tl-rich technosols and waste dumps. These results indicate the need for further studies on Tl speciation in extremely As- and Tl-rich environments.

Toxic effects of thallium acetate by acute exposure to the nematode C. elegans

BackgroundThallium (Tl) is a toxic metalloid and an emerging pollutant due to electronic devices and dispersal nearby base-metal mining. Therefore, Tl poses a threat to human health and especially the long-term impact on younger individuals exposed is still unknown. This study aimed to evaluate the toxic effects of thallium acetate in C. elegans in early larval stages, considering physiological and behavioral endpoints, as well as the Tl absorption and bioaccumulation. MethodsCaenorhabditis elegans (C. elegans) was exposed to Thallium acetate (50, 100, 150, 200, 250, 500, and 1000 μM) in the L1 larval stage, with the purpose to observe the toxic effects invoked until adulthood. Transgenic worms strains were transported GFP, reporters to DAF-16 and were used to verify the antioxidant response. ICP-MS quantified total Tl+ concentration to evidence Tl uptake and bioaccumulation. ResultsThallium acetate caused a significant reduction in the number of living worms (p < 0.0001 in 100–1000 μM), a delay in larval development (p < 0.01; p < 0.001 and p < 0.0001 in 100–1000 μM) through the larval stages, and egg production in the worm's uterus was reduced. Thallium acetate also induced behavioral changes. Additionally, thallium acetate activated antioxidant pathway responses in C. elegans by translocating the DAF-16 transcription factor and activation of SOD-3::GFP expression. The Tl+ quantification in worms showed its absorption in the L1 larval stage and bioaccumulation in the body after development. ConclusionsThallium acetate reduced survival, delayed development, caused behavioral changes, induced responses inherent to oxidative stress, and serious damage to the worm's reproduction. In addition, C. elegans absorbed and bioaccumulated Tl+. Together, our results highlight the impacts of Tl+ exposure in the early stages of life, even for a short period.

Transformation and fate of thallium and accompanying metal(loid)s in paddy soils and rice: A case study from a large-scale industrial area in China

Thallium (Tl) is an extremely toxic metal, while its occurrence and fate in paddy soil environment remain understudied. Herein, the enrichment and migration mechanisms and potential health risks of Tl and metal(loid)s were evaluated in paddy soils surrounding an industrial park utilizing Tl-bearing minerals. The results showed that Tl contamination was evident (0.63–3.16 mg/kg) in the paddy soils and Tl was generally enriched in root of rice (Oryza sativa L.) with a mean content of 1.27 mg/kg. A remarkably high level of Tl(III) (30–50%) was observed in the paddy soils. Further analyses by STEM-EDS and XPS indicated that Tl(I) in the paddy soils was jointly controlled by adsorption, oxidation, and precipitation of Fe/Mn(hydr)oxide (e.g. hematite and birnessite), which might act as important stabilization mechanisms for inhibiting potential Tl uptake by rice grains. The health quotient (HQ) values indicated a potentially high Tl risk for inhabitants via consumption of the rice grains. Therefore, it is critical to establish effective measures for controlling the discharge of Tl-containing waste and wastewater from different industrial activities to ensure food safety in the rice paddy soils.

In vitro proof of concept studies of radiotoxicity from Auger electron-emitter thallium-201

BackgroundAuger electron-emitting radionuclides have potential in targeted treatment of small tumors. Thallium-201 (201Tl), a gamma-emitting radionuclide used in myocardial perfusion scintigraphy, decays by electron capture, releasing around 37 Auger and Coster–Kronig electrons per decay. However, its therapeutic and toxic effects in cancer cells remain largely unexplored. Here, we assess 201Tl in vitro kinetics, radiotoxicity and potential for targeted molecular radionuclide therapy, and aim to test the hypothesis that 201Tl is radiotoxic only when internalized.MethodsBreast cancer MDA-MB-231 and prostate cancer DU145 cells were incubated with 200–8000 kBq/mL [201Tl]TlCl. Potassium concentration varied between 0 and 25 mM to modulate cellular uptake of 201Tl. Cell uptake and efflux rates of 201Tl were measured by gamma counting. Clonogenic assays were used to assess cell survival after 90 min incubation with 201Tl. Nuclear DNA damage was measured with γH2AX fluorescence imaging. Controls included untreated cells and cells treated with decayed [201Tl]TlCl.Results201Tl uptake in both cell lines reached equilibrium within 90 min and washed out exponentially (t1/2 15 min) after the radioactive medium was exchanged for fresh medium. Cellular uptake of 201Tl in DU145 cells ranged between 1.6 (25 mM potassium) and 25.9% (0 mM potassium). Colony formation by both cell lines decreased significantly as 201Tl activity in cells increased, whereas 201Tl excluded from cells by use of high potassium buffer caused no significant toxicity. Non-radioactive TlCl at comparable concentrations caused no toxicity. An estimated average 201Tl intracellular activity of 0.29 Bq/cell (DU145 cells) and 0.18 Bq/cell (MDA-MB-231 cells) during 90 min exposure time caused 90% reduction in clonogenicity. 201Tl at these levels caused on average 3.5–4.6 times more DNA damage per nucleus than control treatments.Conclusions201Tl reduces clonogenic survival and increases nuclear DNA damage only when internalized. These findings justify further development and evaluation of 201Tl therapeutic radiopharmaceuticals.

Thallium sorption by soil manganese oxides: Insights from synchrotron X-ray micro-analyses on a naturally thallium-rich soil

Thallium (Tl) is a highly toxic trace metal. It occurs mostly as soluble monovalent Tl(I) and less frequently as poorly soluble trivalent Tl(III). Laboratory studies have shown that vacancy-containing hexagonal birnessites can sorb Tl with a very high affinity via a mechanism that involves the oxidation of Tl(I) to Tl(III) and strong complexation of Tl(III), whereas other manganese (Mn) oxides bind Tl(I) non-oxidatively and with lower sorption affinity. Information on the mode of Tl uptake by natural Mn oxides in soils, on the other hand, is still limited. In this study, we characterized the association of Tl with Mn oxides and Tl (redox) speciation in a naturally Tl-rich soil using micro-focused synchrotron X-ray absorption near edge structure (XANES) spectroscopy and X-ray fluorescence (XRF) chemical imaging. The results show that most soil Tl was Tl(I) associated with micaceous clay minerals in the soil matrix. High levels of Tl in soil Mn concretions, on the other hand, were mostly identified as Tl(III), suggesting that oxidative Tl uptake by vacancy-containing hexagonal birnessite was the main process of Tl accumulation in soil Mn concretions. The spectroscopic results in combination with chemical extractions and published sorption isotherms for Tl on synthetic Mn oxides suggest that the formation and transformation of natural Mn oxides in soils and sorption competition of Tl with major and trace metal cations determine the extent and mode of Tl uptake by soil Mn oxides. Methodologically, this study compares classical micro-XRF element mapping combined with point XANES analyses for spatially-resolved element speciation with high-resolution chemical imaging of entire sample areas, which is of great interest for the geochemical community in light of diffraction-limited storage ring upgrades to many synchrotron lightsources.

Effects of MnO2 crystal structure on the sorption and oxidative reactivity toward thallium(I)

• Tl(I) uptake affinity decreased as: δ-MnO 2 > α-MnO 2 > γ-MnO 2 > β-MnO 2 > λ-MnO 2 . • α-MnO 2 exhibited the strongest oxidation ability for Tl(I). • Tl(I) was scarcely oxidized by β-MnO 2 over a wide range of pH values. • TlOH was involved in the redox process at alkaline pH conditions. Manganese dioxides (MnO 2 ) with a high affinity for thallium (Tl), strongly influence its fate and toxicity in aquatic environments. The crystal structure of MnO 2 plays a critical role in their activity for the uptake of heavy metals. However, few studies have examined the differences in interactions between Tl and various crystal structured MnO 2 . In this study, the fundamental data on the sorption and oxidative reactivity of Tl(I) by MnO 2 with five known crystal structures (δ-, α-, γ-, β-, λ-MnO 2 ) was obtained at different pH values (5, 7, 12). The results showed that the uptake of Tl followed the order of δ-MnO 2 > α-MnO 2 > γ-MnO 2 > β-MnO 2 > λ-MnO 2 , and increased with increasing pH for each MnO 2 . Moreover, α-MnO 2 exhibited the strongest oxidation ability for Tl(I) at all the tested pH values, while β-MnO 2 could scarcely oxidize aqueous Tl(I). However, for δ-MnO 2, γ-MnO 2 and λ-MnO 2 , the extent of Tl(I) oxidation was much larger at pH 12 than at pH 5 or 7, which was ascribed to the active species of TlOH involved in the redox process. Besides, the sorption of Tl(I) led to a decrease in crystallinity of δ-MnO 2 and α-MnO 2 but slightly impacted the structure of γ-MnO 2 , β-MnO 2 and λ-MnO 2 . These findings might contribute to understanding the immobilization processes of Tl by different crystal structured MnO 2 at various pH conditions.

Thallium isotopic fractionation in soil: the key controls

We studied the key geochemical and mineralogical factors that could affect the fractionation of stable thallium (Tl) isotopes in soil. A set of grassland soil samples enriched in geogenic Tl in combination with selected Tl-containing mineral materials from the Czech Republic (Kluky) were investigated for this purpose. The results demonstrate significant incorporation of Tl in pedogenic (specific) Mn-oxide, which led to a large accumulation of the heavy 205Tl isotope (∼+14 ε205Tl units), presumably resulting from oxidative Tl sorption. Consequently, we concluded that the Mn-oxide-controlled Tl uptake is the primary cause of the observed 205Tl enrichment in the middle profile zone, at the A/B soil horizon interface, with up to +4 of ε205Tl. Furthermore, our results displayed a clear relationship between the Tl isotopic fractionation degree and the Mn-oxide soil concentration (R2 = 0.6), as derived from the oxalate-extractable data. A combination of soil and mineralogical considerations suggests that 205Tl enrichment in respective soil samples is also partly due to the Tl present in micaceous clay minerals, mainly illite, which is the predominant pedogenic Tl host phase. In line with our previous results, this Tl behavior can be inferred from systematic Mn-oxide degradation and the associated Tl (enriched in 205Tl) cycling in the studied soils and thus, presumably in the redoximorphic soils in general.