Inhibition of phosphorus removal performance in activated sludge by Fe(III) exposure: transitions in dominant metabolic pathways.

Introduction: Simultaneous chemical phosphorus removal process using iron salts (Fe(III)) has been widely utilized in wastewater treatment to meet increasingly stringent discharge standards. However, the inhibitory effect of Fe(III) on the biological phosphorus removal system remains a topic of debate, with its precise mechanism yet to be fully understood. Methods: Batch and long-term exposure experiments were conducted in six sequencing batch reactors (SBRs) operating for 155 days. Synthetic wastewater containing various Fe/P ratios (i.e., Fe/P = 1, 1.2, 1.5, 1.8, and 2) was slowly poured into the SBRs during the experimental period to assess the effects of acute and chronic Fe(III) exposure on polyphosphate-accumulating organism (PAO) growth and phosphorus metabolism. Results: Experimental results revealed that prolonged Fe(III) exposure induced a transition in the dominant phosphorus removal mechanism within activated sludge, resulting in a diminished availability of phosphorus for bio-metabolism. In Fe(III)-treated groups, intracellular phosphorus storage ranged from 3.11 to 7.67 mg/g VSS, representing only 26.01 to 64.13% of the control. Although the abundance of widely reported PAOs (Candidatus Accumulibacter) was 30.15% in the experimental group, phosphorus release and uptake were strongly inhibited by high dosage of Fe(III). Furthermore, the abundance of functional genes associated with key enzymes in the glycogen metabolism pathway increased while those related to the polyphosphate metabolism pathway decreased under chronic Fe(III) stress. Discussion: These findings collectively suggest that the energy generated from polyhydroxyalkanoates oxidation in PAOs primarily facilitated glycogen metabolism rather than promoting phosphorus uptake. Consequently, the dominant metabolic pathway of communities shifted from polyphosphate-accumulating metabolism to glycogen-accumulating metabolism as the major contributor to the decreased biological phosphorus removal performance.

Machine learning for predicting halogen radical reactivity toward aqueous organic chemicals.

Rapid advances in machine learning (ML) provide fast, accurate, and widely applicable methods for predicting free radical-mediated organic pollutant reactivity. In this study, the rate constants (logk) of four halogen radicals were predicted using Morgan fingerprint (MF) and Mordred descriptor (MD) in combination with a series of ML models. The findings highlighted that making accurate predictions for various datasets depended on an effective combination of descriptors and algorithms. To further alleviate the challenge of limited sample size, we introduced a data combination strategy that improved prediction accuracy and mitigated overfitting by combining different datasets. The Light Gradient Boosting Machine (LightGBM) with MF and Random Forest (RF) with MD models based on the unified dataset were finally selected as the optimal models. The SHapley Additive exPlanations revealed insights: the MF-LightGBM model successfully captured the influence of electron-withdrawing/donating groups, while autocorrelation, walk count and information content descriptors in the MD-RF model were identified as key features. Furthermore, the important contribution of pH was emphasized. The results of the applicability domain analysis further supported that the developed model can make reliable predictions for query compounds across a broader range. Finally, a practical web application for logk calculations was built.

The determination of thallium in the environment: A review of conventional and advanced techniques and applications.

Thallium (Tl) is a potential toxicity element that poses significant ecological and environmental risks. Recently, a substantial amount of Tl has been released into the environment through natural and human activities, which attracts increasing attention. The determination of this hazardous and trace element is crucial for controlling its pollution. This article summarizes the advancement and progress in optimizing Tl detection techniques, including atomic absorption spectroscopy (AAS), voltammetry, inductively coupled plasma (ICP)-based methods, spectrophotometry, and X-ray-based methods. Additionally, it introduces sampling and pretreatment methods such as diffusive gradients in thin films (DGT), liquid-liquid extraction, solid phase extraction, and cloud point extraction. Among these techniques, ICP-mass spectrometry (MS) is the preferred choice for Tl detection due to its high precision in determining Tl as well as its species and isotopic composition. Meanwhile, some new materials and agents are employed in detection. The application of novel work electrode materials and chromogenic agents is discussed. Emphasis is placed on reducing solvent consumption and utilizing pretreatment techniques such as ultrasound-assisted processes and functionalized magnetic particles. Most detection is performed in aqueous matrices, while X-ray-based methods applied to solid phases are summarized which provide non-destructive analysis. This work improves the understanding of Tl determination technology while serving as a valuable resource for researchers seeking appropriate analytical techniques.

Cotransport of aged biochar colloids and thallium(I) in water-saturated porous media: Impact of the ionic strength, pH and aging degree.

Biochar colloids entering the soil undergo aging over time and exhibit strong capabilities in adsorbing and transporting pollutants. Therefore, investigating the cotransport of aged biochar colloids and thallium (Tl(I)) in quartz sand media is crucial for understanding Tl(I) migration in underground environments. This study investigated the migration of biochar colloids with two different aging degrees and Tl(I) in quartz sand media at various pH and ionic strengths (ISs). The results revealed that under all ISs and pH, 30%AWB (biochar aged with 30 % (w/w) HNO3) inhibited Tl(I) migration in media. This inhibition primarily arose from the introduction of hydroxyl and carboxyl groups during aging, which significantly enhanced colloid adsorption onto Tl(I). At lower ISs, 30%AWB colloids exhibited greater inhibition of Tl(I) migration due to their increased adsorption capacity. Additionally, aging promoted the migration of biochar colloids in the media. Greater biochar aging notably enhanced this promotion, potentially owing to reduced colloidal particle size and the formation of biochar derivatives. Moreover, 50%AWB (biochar aged with 50 % (w/w) HNO3) inhibited Tl(I) migration under low ISs but had almost no impact under high ISs. Nonetheless, at high pH, 50%AWB colloids facilitated Tl(I) migration. This phenomenon might be attributed to the inhibitory effect of aged biochar colloids on Tl(I) adsorption onto media at a high pH, as well as the stable binding between Tl(I) and aged biochar colloids. This study discusses the cotransport of biochar with various degrees of aging and Tl(I) in media, providing insights into remediating soils contaminated with Tl.

The application of machine learning methods for prediction of heavy metal by activated carbons, biochars, and carbon nanotubes.

Carbonaceous materials are commonly used as adsorbents for heavy metals. The determination of the adsorption capacity needs time and energy, and the key factors affecting the adsorption capacity have not been determined. Therefore, a new and efficient method is needed to predict the adsorption capacity and explore the decisive factors in the adsorption process. In this study, three tree-based machine learning models (i.e., random forest, gradient boosting decision tree, and extreme gradient boosting) were developed to predict the adsorption capacity of eight heavy metals (i.e., As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) on activated carbons, biochars, and carbon nanotubes using 3674 data points extracted from 151 journal articles. After a comprehensive comparison, the gradient boosting decision tree had the best performance for a combined model based on all data (R2 = 0.9707, RMSE = 0.1420). Moreover, independent models were developed for three datasets classified by the adsorbent and eight datasets classified by the heavy metals. In addition, a graphical user interface was built to predict the adsorption capacity of heavy metals. This study provides a novel strategy and convenient tool for the removal of heavy metals and can help to improve the removal efficiency of heavy metals to build a healthier world.

Photochemical transformation and immobilization of thallium in the presence of iron and arsenic: Mechanistic insights from the coupled formation of arsenate complexes.

Despite the occurrence of thallium (Tl) in the acidic mining-affected areas being highly positively correlated with iron (Fe) and arsenic (As), the effects of the two accompanying elements on Tl redox transformation and immobilization remain largely unknown. Here, we investigated the photochemical redox kinetics and immobilization efficiency of Tl for a wide range of As/Fe and As/Tl ratios under acidic conditions. We provided the first experimental confirmation of the complexation of Tl(III) with As(V) by the spectrophotometric method and revealed the role of Tl(III)-As(V) complexes in decreasing the photoreduction rate of Tl(III) under sunlight. Additionally, the negative impact of colloidal Fe(III)-As(V) and Fe(III)-As(III) complexes formation on decreasing photoactive Fe(III) speciation and thus the apparent quantum yield of •OH was highlighted, which consequently hindered the oxidative conversion of Tl(I) to Tl(III). We rationalize the kinetics results by developing the model which quantitatively describes the photochemistry of Tl. Furthermore, we demonstrated the colloid-facilitated immobilization of Tl(III) through the formation of Tl(III)-As(V) clusters and surface adsorption onto the complexes. This study broadens the mechanistic understanding of redox transformation and immobilization potential of Tl and aids in assessing Tl speciation as well as its coupled transformation with Fe and As species in the sunlit water environment.

Prediction of antibiotic sorption in soil with machine learning and analysis of global antibiotic resistance risk.

Although the sorption of antibiotics in soil has been extensively studied, their spatial distribution patterns and sorption mechanisms still need to be clarified, which hinders the assessment of antibiotic resistance risk. In this study, machine learning was employed to develop the models for predicting the soil sorption behavior of three classes of antibiotics (sulfonamides, tetracyclines, and fluoroquinolones) in 255 soils with 2203 data points. The optimal independent models obtained an accurate predictive performance with R2 of 0.942 to 0.977 and RMSE of 0.051 to 0.210 on test sets compared to combined models. Besides, a global map of the antibiotic sorption capacity of soil predicted with the optimal models revealed that the sorption potential of fluoroquinolones was the highest, followed by tetracyclines and sulfonamides. Additionally, 14.3% of regions had higher antibiotic sorption potential, mainly in East and South Asia, Central Siberia, Western Europe, South America, and Central North America. Moreover, a risk index calculated with the antibiotic sorption capacity of soil and population density indicated that about 3.6% of soils worldwide have a high risk of resistance, especially in South and East Asia with high population densities. This work has significant implications for assessing the antibiotic contamination potential and resistance risk.

Removal of thallium by MnOx coated limestone sand filter through regeneration of KMnO4: Combination of physiochemical and biochemical actions.

Treatment of industrial thallium(Tl)-containing wastewater is crucial for mitigating environmental risks and health threats associated with this toxic metal. The incorporation of Mn oxides (MnOx) into the filtration system is a promising solution for efficient Tl(I) removal. However, further research is needed to elucidate the underlying mechanism behind MnOx-enhanced filtration and the rules of its stable operation. In this study, limestone, a cost-effective material, was selected as the filter media. Raw water with Mn(II), Tl(I), and other pollutants was prepared after a thorough investigation of actual industrial wastewater conditions. KMnO4 was added to induce the formation of MnO2 on limestone surfaces, while long-term operation led to enrichment of manganese oxidizing microorganisms (MnOM). Results revealed a dual mechanism. Firstly, most Mn(II) were oxidized by KMnO4 to form MnO2 attaching to limestone sands, and both Tl(I) and residual Mn(II) were adsorbed onto the newly formed MnO2. Subsequently, enzymes secreted by MnOM facilitated oxidation of remaining Mn(II), resulting in the generation of biogenic manganese oxides (BioMnOx) with numerous vacancies during long-term operation. The generated BioMnOx not only adsorbed Mn(II) and Tl(I) but also promoted their oxidation process. This approach offers an effective and sustainable method for removing both Mn(II) and Tl(I) from industrial wastewater, thereby addressing the challenges posed by thallium-contaminated effluents.

Preparing for the Next Pandemic: Predicting UV Inactivation of Coronaviruses with Machine Learning.

The epidemic of coronaviruses has posed significant public health concerns in the last two decades. An effective disinfection scheme is critical to preventing ambient virus infections and controlling the spread of further outbreaks. Ultraviolet (UV) irradiation has been a widely used approach to inactivating pathogenic viruses. However, no viable framework or model can accurately predict the UV inactivation of coronaviruses in aqueous solutions or on environmental surfaces, where viruses are commonly found and spread in public places. By conducting a systematic literature review to collect data covering a wide range of UV wavelengths and various subtypes of coronaviruses, including severe acute respiratory syndrome 2 (SARS-CoV-2), we developed machine learning models for predicting the UV inactivation effects of coronaviruses in aqueous solutions and on environmental surfaces, for which the optimal test performance was obtained with R2 = 0.927, RMSE = 0.565 and R2 = 0.888, RMSE = 0.439, respectively. Besides, the required UV doses at different wavelengths to inactivate the SARS-CoV-2 to 1 Log TCID50/mL titer from different initial titers were predicted for inactivation in protein-free water, saliva on the environmental surface, or the N95 respirator. Our models are instructive for eliminating the ongoing pandemic and controlling the spread of an emerging and unknown coronavirus outbreak.

Improving mesophilic anaerobic digestion of food waste by side-stream thermophilic reactor: Activation of methanogenic, key enzymes and metabolism.

Anaerobic digestion (AD) is a favorable way to convert organic pollutants, such as food waste (FW), into clean energy through microbial action. This work adopted a side-stream thermophilic anaerobic digestion (STA) strategy to improve a digestive system's efficiency and stability. Results showed that the STA strategy brought higher methane production as well as higher system stability. It quickly adapted to thermal stimulation and increased the specific methane production from 359 mL CH4/g·VS to 439 mL CH4/g·VS, which was also higher than 317 mL CH4/g·VS from single-stage thermophilic anaerobic digestion. Further exploration of the mechanism of STA using metagenomic and metaproteomic analysis revealed enhanced activity of key enzymes. The main metabolic pathway was up-regulated, while the dominant bacteria were concentrated, and the multifunctional Methanosarcina was enriched. These results indicate that STA optimized organic metabolism patterns, comprehensively promoted methane production pathways, and formed various energy conservation mechanisms. Further, the system's limited heating avoided adverse effects from thermal stimulation, and activated enzyme activity and heat shock proteins through circulating slurries, which improved the metabolic process, showing great application potential.

Sunlight-Mediated Reductive Transformation of Thallium(III) in Acidic Natural Organic Matter Solutions: Mechanisms and Kinetic Modeling.

Thallium (Tl) redox state determines its speciation and fate in aqueous environments. Despite the high potential of natural organic matter (NOM) providing the reactive groups to complex and reduce Tl(III), the kinetics and mechanisms by which NOM influences the Tl redox transformation have remained insufficiently understood. Here, we studied the reduction kinetics of Tl(III) in acidic Suwannee River fulvic acid (SRFA) solutions under dark and solar-irradiated conditions. Our results show that the thermal Tl(III) reduction occurs by the reactive organic moieties in SRFA, with the electron-donating capacities of SRFA increased with pH and decreased with [SRFA]/[Tl(III)] ratios. Solar irradiation promoted Tl(III) reduction in SRFA solutions as a result of ligand-to-metal charge transfer (LMCT) within the photoactive Tl(III) species as well as an additional reduction process mediated by a photogenerated superoxide. We demonstrated that the formation of Tl(III)-SRFA complexes decreased the reducibility of Tl(III), with the kinetics dependent on the nature of the binding component and SRFA concentrations. A "three ligand class" kinetics model has been developed and satisfactorily describes Tl(III) reduction kinetics over a range of experimental conditions. The insights presented here should assist in understanding and predicting the NOM-mediated speciation and redox cycle of Tl in a sunlit environment.

Dynamic retention of thallium(I) on humic acid: Novel insights into the heterogeneous complexation ability and responsiveness.

Widely distributed soil humic acid (HA) would significantly affect the environmental migration behavior of Tl(I), but a quantitative and mechanistic understanding of the dynamic Tl(I) retention process on HA is limited. A unified kinetic model was established by coupling the humic ion-binding model with a stirred-flow kinetic model, which quantified the complexation constants and responsiveness coefficients during dynamic Tl(I)-HA complexation. Furthermore, the heterogeneous complexation mechanism of HA and Tl(I) was revealed by batch adsorption experiments, stirred-flow migration experiments, and 2D-FTIR-COS analysis. An increase in pH significantly improved the responsiveness of HA organic binding sites, promoting Tl(I) dynamic retention. Monodentate carboxyl groups induced rapid Tl(I) complexation (kd = 1.9 min-1) in strongly acidic environments. Under weakly acidic conditions, Tl(I) retention on HA was mainly attributed to the synergistic complexation effect of carboxyl and amide groups. Among the groups, multidentate carboxyl-phenolic hydroxyl sites could achieve sustained Tl(I) retention due to their stable complexing properties (logK = 4.48∼7.46) and slow response (kd = 1.1 × 10-3 min-1). These findings are crucial for a comprehensive understanding of the environmental interactions of Tl(I) with humic substances in swamp environments.

Sequestration and oxidation of heavy metals mediated by Mn(II) oxidizing microorganisms in the aquatic environment.

Microorganisms can oxidize Mn(II) to biogenic Mn oxides (BioMnOx), through enzyme-mediated processes and non-enzyme-mediated processes, which are generally considered as the source and sink of heavy metals due to highly reactive to sequestrate and oxidize heavy metals. Hence, the summary of interactions between Mn(II) oxidizing microorganisms (MnOM) and heavy metals is benefit for further work on microbial-mediated self-purification of water bodies. This review comprehensively summarizes the interactions between MnOM and heavy metals. The processes of BioMnOx production by MnOM has been firstly discussed. Moreover, the interactions between BioMnOx and various heavy metals are critically discussed. On the one hand, modes for heavy metals adsorbed on BioMnOx are summarized, such as electrostatic attraction, oxidative precipitation, ion exchange, surface complexation, and autocatalytic oxidation. On the other hand, adsorption and oxidation of representative heavy metals based on BioMnOx/Mn(II) are also discussed. Thirdly, the interactions between MnOM and heavy metals are also focused on. Finally, several perspectives which will contribute to future research are proposed. This review provides insight into the sequestration and oxidation of heavy metals mediated by Mn(II) oxidizing microorganisms. It might be helpful to understand the geochemical fate of heavy metals in the aquatic environment and the process of microbial-mediated water self-purification.

Conductive materials enhance microbial salt-tolerance in anaerobic digestion of food waste: Microbial response and metagenomics analysis.

Previous studies have shown that high salinity environments can inhibit anaerobic digestion (AD) of food waste (FW). Finding ways to alleviate salt inhibition is important for the disposal of the growing amount of FW. We selected three common conductive materials (powdered activated carbon, magnetite, and graphite) to understand their performance and individual mechanisms that relieve salinity inhibition. Digester performances and related enzyme parameters were compared. Our data revealed that under normal and low salinity stress conditions, the anaerobic digester ran steady without significant inhibitions. Further, the presence of conductive materials promoted conversion rate of methanogenesis. This promotion effect was highest from magnetite > powdered activated carbon (PAC) > graphite. At 1.5% salinity, PAC and magnetite are beneficial in maintaining high methane production efficiency while control and the graphite added digester acidified and failed rapidly. Additionally, metagenomics and binning were used to analyze the metabolic capacity of the microorganisms. Some species enriched by PAC and magnetite possessed higher cation transport capacities and were to accumulate compatible solutes. PAC and magnetite promoted direct interspecies electron transference (DIET) and syntrophic oxidation of butyrate and propionate. Also, the microorganisms had more energy available to cope with salt inhibition in the PAC and magnetite added digesters. Our data imply that the promotion of Na+/H+ antiporter, K+ uptake, and osmoprotectant synthesis or transport by conductive materials may be crucial for their proliferation in highly stressful environments. These findings will help to understand the mechanisms of alleviate salt inhibition by conductive materials and help to recover methane from high-salinity FW.

Highly inhibited transport of dissolved thallium(I) in manganese oxide-coated sand: Chemical condition effects and retention mechanisms.

Thallium contamination in water can cause great danger to the environment. In this study, we synthesized manganese oxide-coated sand (MOCS) and investigated the transport and retention behaviors of Tl(I) in MOCS under different conditions. Characterization methods combined with a two-site nonequilibrium transport model were applied to explore the retention mechanisms. The results showed that Tl(I) mobility was strongly inhibited in MOCS media, and the retention capacity calculated from the fitted model was 510.41 mg/g under neutral conditions. The retention process included adsorption and oxidative precipitation by the manganese oxides coated on the sand surface. Cotransport with the same concentration of Mn(II) led to halving Tl(I) retention due to competition for reactive sites. Enhanced Tl(I) retention was observed under alkaline conditions, as increasing pH promoted electronegativity on the media surface. Moreover, the competitive cation Ca2+ significantly weakened Tl(I) retention by occupying adsorption sites. These findings provide new insights into understanding Tl(I) transport behavior in water-saturated porous media and suggest that manganese oxide-coated sand can be a cost-effective filter media for treating Tl-contaminated water.

Enhanced phosphorus release from waste activated sludge using ascorbic acid reduction and acid dissolution.

Due to the widespread application of various iron (Fe)-derived substances used in phosphorus (P) removal during wastewater treatment, Fe-P species generated in this process constitute an important part of P speciation in non-digested sludge. SEM-EDS and sequential extraction methods were utilized to analyze the speciation, distribution, and spatial variation of P contained in the sludge. Inorganic P accounted for 91.3% of the total P, and Fe(III)-P represented the greatest percentage (68.5%) in the inorganic P fraction. Ascorbic acid, also known as vitamin C (VC), performed well in releasing P from sludge, especially in combination with subsequent pH adjustment to 3.0 using HCl. Fe(III)-P in sludge was first reduced to Fe(II)-P by VC, then dissolved in acidic conditions to release Fe2+ and PO43-. Other metal-P compounds were also partially dissolved and released. VC disrupted the sludge floc structure, releasing organic P via organic efflux. There was a positive correlation (R2>0.97, p<0.05) between the amount of released P and the amount of reductant (VC). There was a synergistic effect between 120 mmol/L VC and acidity, producing the greatest P release of 67.1% of total sludge P. The P release efficiency achieved in this study was higher than other reported methods. Additionally, VC provides a more sustainable option due to its natural biodegradability. Released P and Fe2+ can be recovered as vivianite with recovery rates of 88% and 99%, respectively. This finding provides a new direction for effective, sustainable sludge P recovery and utilization.

Impact of biochar colloids on thallium(I) transport in water-saturated porous media: Effects of pH and ionic strength.

Understanding the migration behavior of thallium (TI) in subsurface environments is essential for Tl pollution prevention. With the wide production and utilization of biochar, the notable ability of biochar colloids to carry environmental contaminants may make these colloids important for Tl(I) mobility. This study systematically investigated the impact of wood-derived biochar (WB) and corn straw-derived biochar (CB) colloids on Tl(I) transport in water-saturated porous media under different pH (5, 7 and 10) and ionic strengths (ISs) (1, 5 and 50 mM NaNO3). WB colloids improved Tl(I) transport under all IS conditions at pH 7 due to the adsorption capacity of biochar and competition for adsorption sites on the sand surface. However, at IS 50 mM, CB colloids slightly impeded Tl(I) mobility due to the straining. In addition, both WB and CB colloids accelerated Tl(I) mobility under all pH conditions at IS 5 mM. At pH 10, the promotion effect was more obvious due to the deprotonation of O-containing functional groups and higher fluidity of biochar colloids. Furthermore, the two-site nonequilibrium model and two-site kinetic attachment/detachment model suitably described the breakthrough curves (BTCs) of Tl(I) and biochar colloids, respectively. The colloid-facilitated solute transport model could also describe Tl(I) transport influenced by biochar colloids reasonably well. This study provides insight into the migration and fate of Tl(I) in the presence of biochar colloids.

Chronic high-dose silver nanoparticle exposure stimulates N2O emissions by constructing anaerobic micro-environment.

Silver nanoparticles (Ag-NPs) were found to be responsible for nitrous oxide (N2O) generation; however, the mechanism of Ag-NP induced N2O production remains controversial and needs to be elucidated. In this study, chronic Ag-NP exposure experiments were conducted in five independent sequencing batch biofilm reactors to systematically assess the effects of Ag-NPs on N2O emission. The results indicated that a low dose of Ag-NPs (< 1 mg/L) slightly suppressed N2O generation by less than 22.99% compared with the no-Ag-NP control method. In contrast, a high dose (5 mg/L) of Ag-NPs stimulated N2O emission by 67.54%. ICP-MS and SEM-EDS together revealed that high Ag-NP content accumulated on the biofilm surface when exposed to 5 mg/L Ag-NPs. N2O and DO microelectrodes, as well as N2O isotopic composition analyses, further demonstrated that the accumulated Ag-NPs construct the anaerobic zone in the biofilm, which is the primary factor for the stimulation of the nitrite reduction pathway to release N2O. A metagenomic analysis further attributed the higher N2O emissions under exposure to a high dose of Ag-NPs to the higher relative abundance of narB and nirK genes (i.e. 1.52- and 1.29-fold higher, respectively). These findings collectively suggest that chronic exposure to high doses of Ag-NPs could enhance N2O emissions by forming anaerobic micro-environments in biofilms.

Retention of thallium(I) on goethite, hematite, and manganite: Quantitative insights and mechanistic study.

The reversibility of monovalent thallium (Tl) absorption on widely distributed iron/manganese secondary minerals may affect environmental Tl migration and global cycling. Nevertheless, quantitative and mechanistic studies on the interfacial retention and release reactions involving Tl(I) are limited. In this study, batch and stirred-flow experiments, unified kinetics modeling, spectral detection, and theoretical calculations were used to elucidate the retention behaviors of Tl(I) on goethite, hematite, and manganite with different solution pH values and Tl loading concentrations. Sustained Tl(I) retention (kd, MeOHTl=0.005∼0.018 min-1) was induced by hydration of the surface hydroxyl groups. Rapid Tl(I) retention (kd,MeOTlOH=1.232∼2.917 min-1) was enhanced by the abundant hydroxide ions and deprotonated hydroxyl groups, which increased the Tl(I) binding ability. Compared to the ambient Tl concentration, pH had a more substantial effect on the formation and distribution of surface Tl(I) binding species. In alkaline environments, the large adsorption energy for Tl(I) binding to surface species (Eads=-6.14 eV) induced fast Tl(I) binding response on the surfaces of iron/manganese secondary minerals. This study provides new insights into the heterogeneous surface complexation and retention behaviors of Tl(I) and contributes to an in-depth understanding of the environmental fate of Tl and the remediation of Tl contamination.

Light- and H2O2-Mediated Redox Transformation of Thallium in Acidic Solutions Containing Iron: Kinetics and Mechanistic Insights.

The redox transformation between the oxidation states of thallium (Tl(I) and Tl(III)) is the key to influencing its toxicity, reactivity, and mobility. Dissolved iron (Fe) is widely distributed in the environment and coexists at a high level with Tl in acidic mine drainages (AMDs). While ultraviolet (UV) light and H2O2 can directly (by inducing Tl(III) reduction) and indirectly (by inducing Fe(III) to form reactive intermediates) impact the redox cycles of Tl in Fe(III)-containing solutions, the kinetics and mechanism remain largely unclear. This study is the first to investigate the UV light- and H2O2-mediated Tl redox kinetics in acidic Fe(III) solutions. The results demonstrate that UV light and H2O2 could directly reduce Tl(III) to Tl(I), with the extent of reduction dependent on the presence of Fe(III) and the solution pH. At pH 3.0, Tl(I) was completely oxidized to Tl(III), which can be ascribed to the generation of hydroxyl radicals (•OH) from the Fe(III) photoreduction or Fe(III) reaction with H2O2. The kinetics of Tl(I) oxidation were strongly affected by the Fe(III) concentration, pH, light source, and water matrix. Kinetic models incorporating Tl redox kinetics with Fe redox kinetics were developed and satisfactorily interpreted Tl(III) reduction and Tl(I) oxidation under the examined conditions. These findings emphasize the roles of the UV light- and H2O2-driven Fe cycles in influencing the redox state of Tl, with implications for determining its mobility and fate in the environment.