Effects of nZVI on the migration and availability of Cr(VI) in soils under simulated acid rain leaching conditions.

Hexavalent chromium, Cr(VI), is a ubiquitous toxic metal that can be reduced to Cr(III) by nano-zero-valent iron (nZVI). Finding out effects of continuous rainfall leaching on the Cr(VI) release and availability remains a problem, needing to be addressed. Whether the Cr(VI) reduction by nZVI and continuous rainfall leaching lead to localized heterogeneity in soil is unclear. Therefore, two in situ high-resolution (HR) techniques of the diffusive gradients in thin-films (DGT) and planar optode were combined with ex situ sampling experiments here. Results demonstrate that nZVI decreased Cr(VI) leaching by 5.60-8.50 % compared to control soils. DGT-measured concentrations of Cr(VI), CDGT-Cr(VI), ranged from 7.31 to 19.4 µg L-1 in the control soils, increasing with depth while CDGT-Cr(VI) in nZVI-treated soils (2.41-6.18 µg L-1) decreased or remained stable with depth. However, simulated acid-rain leaching increases CDGT-Cr(VI) by 1.61-fold in nZVI-treated soils, negatively affecting the remediation. DGT measurements in bulk soils using disc devices are better at capturing the change of Cr(VI) availability at different conditions, whereas 2D-HR DGT mappings did not characterize significant mobilization of Cr(VI) at the micro-scale. These findings emphasize the importance of monitoring Cr(VI) release and availability in remediated soil under acid-rain leaching conditions for effective environment management.

Antimony and arsenic migration in a heterogeneous subsurface at an abandoned antimony smelter under rainfall.

While antimony (Sb) and arsenic (As) co-contamination in subsurface soil systems due to the legacy of Sb smelting wastes has been documented, the role of inherent heterogeneity on pollutant migration is largely overlooked. Herein this study investigated Sb and As migration in a slag impacted, vertically stratified subsurface at an abandoned Sb smelter. A 2-dimensional flume was assembled as a lab-scale analogue of the site and subject to rainfall and stop-rain events. Reactive transport modeling was then performed by matching the experimental observations to verify the key factors and processes controlling pollutant migration. Results showed that rainfall caused Sb and As release from the shallow slag layer and promoted their downward movement. Nevertheless, the less permeable deeper layers limited physical flow and transport, which led to Sb and As accumulation at the interface. The re-adsorption of Sb and As onto iron oxides in the deeper, more acidic layers further retarded their migration. Because of the large difference between Sb and As concentrations, Sb re-adsorption was much less effective, which led to higher mobility. Our findings overall highlight the necessity of understanding the degree and impacts of physicochemical heterogeneity for risk exposure assessment and remediation of abandoned Sb smelting sites.

Natural aging and adsorption/desorption behaviors of polyethylene mulch films: Roles of film types and exposure patterns.

Polyethylene (PE) mulch films are an important source of microplastics (MPs) in agricultural soils, which may further affect the bioavailability of coexisting pollutants. In this study, white (WM), black (BM), and silver-black (SM) PE mulch films were aged on the soil surface and under soil burial to simulate the two exposure patterns of abandoned mulch films in the field. Results indicated that the soil-surface exposure induced more pronounced aging characteristics, and WM seemed the most susceptible. Serious surface deterioration by aging led to a drastic decrease in the tensile properties of the films, suggesting the tendency to fragment. Oxygen-containing functional groups were generated on the film surfaces, with oxygen/carbon ratios increasing by up to 29 times, which contributed to the prominent increase in Pb adsorption on the film-derived MPs. Additionally, the film surface became more hydrophobic when exposed to the soil surface but more hydrophilic in the soil-burial exposure, which was in agreement with the change in triclosan adsorption, i.e., promotion and suppression, respectively. Aging generally decreased the desorption potential of the adsorbed pollutants in simulated gastrointestinal solutions due to increased interactions. By comparison, exposure patterns were revealed to be the critical factor for these changes, regardless of film types.

Comparison of the arsenic protective effects of four nanomaterials on pakchoi in an alkaline soil.

Accurately applying engineered nanoparticles (NPs) in farmland stress management is important for sustainable agriculture and food safety. We investigated the protective effects of four engineered NPs (SiO2, CeO2, ZnO, and S) on pakchoi under arsenic (As) stress using pot experiments. The results showed that CeO2, SiO2, and S NPs resulted in biomass reduction, while ZnO NPs (100 and 500 mg kg-1) significantly increased shoot height. Although 500 mg kg-1 S NPs rapidly dissolved to release SO42-, reducing soil pH and pore water As content and further reducing shoot As content by 21.6 %, the growth phenotype was inferior to that obtained with 100 mg kg-1 ZnO NPs, probably due to acid damage. The addition of 100 mg kg-1 ZnO NPs not only significantly reduced the total As content in pakchoi by 23.9 % compared to the As-alone treatment but also enhanced plant antioxidative activity by increasing superoxide dismutase (SOD) and peroxidase (POD) activities and decreasing malondialdehyde (MDA) content. ZnO NPs in soil might inhibit As uptake by roots by increasing the dissolved organic carbon (DOC) by 19.12 %. According to the DLVO theory, ZnO NPs were the most effective in preventing As in pore water from entering plant roots due to their smaller hydrated particle size. Redundancy analysis (RDA) further confirmed that DOC and SO42- were the primary factors controlling plant As uptake under the ZnO NP and S NP treatments, respectively. These findings provide an important basis for the safer and more sustainable application of NP-conjugated agrochemicals.

How Fe-bearing materials affect soil arsenic bioavailability to rice: A meta-analysis.

Arsenic (As) contamination is widespread in soil and poses a threat to agricultural products and human health due to its high susceptibility to absorption by rice. Fe-bearing materials (Fe-Mat) display significant potential for reducing As bioavailability in soil and bioaccumulation in rice. However, the remediation effect of various Fe-Mat is often inconsistent, and the response to diverse environmental factors is ambiguous. Here, we conducted a meta-analysis to quantitatively assess the effects of As in soils, rice roots, and grains based on 673, 321, and 305 individual observations from 67 peer-reviewed articles, respectively. On average, Fe-Mat reduced As bioavailability in soils, rice roots, and grains by 28.74 %, 33.48 %, and 44.61 %, respectively. According to the analysis of influencing factors, the remediation efficiency of Fe-Mat on As-contaminated soil was significantly enhanced with increasing Fe content in the material, in which the industry byproduct was the most effective in soils (-42.31 %) and rice roots (-44.57 %), while Fe-biochar was superior in rice grains (-54.62 %). The efficiency of Fe-Mat in minimizing soil As mobility was negatively correlated with soil Fe content, CEC, and pH. In addition, applying Fe-Mat in alkaline soils with higher silt, lower clay and available P was more effective in reducing As in rice grains. A higher efficiency of applying Fe-Mat under continuous flooding conditions (27.39 %) compared with alternate wetting and drying conditions (23.66 %) was also identified. Our results offer an important reference for the development of remediation strategies and methods for various As-contaminated paddy soils.

Porous pillararene-based polymer as adsorbent and solid disinfectant for water treatment.

Pillararene polymers have been widely used as excellent adsorbents for water treatment, but pillararene polymers with ultra-high specific surface area and versatility are still rarely reported. Herein, a quaternary ammonium salt modified pillar [5] arene polymer, QPBP [5], with specific surface area of 1844 m2 g-1 was successfully synthesized. Since QPBP [5] has abundant different adsorption sites, it exhibits excellent performance for the simultaneously removal of organic pollutants with different charges from water. The selected three model pollutants, Rhodamine B (RhB, positively charged), Sulfamethazine (SMT, electrically neutral) and Fulvic acid (FA, negatively charged), could be rapidly and efficiently removed from water by QPBP [5] within 10 min, which are much faster than them by most of the reported adsorbents. RhB and SMT are mainly adsorbed through hydrophobic interactions with the QPBP [5] surface, while FA is mainly removed through ion exchange. In addition, QPBP [5] also showed excellent reusability and adsorption performance for the environmentally relevant concentration of pollutants. Furthermore, the quaternary ammonium groups on QPBP [5] makes it a solid disinfectant with excellent antibacterial properties. In conclusion, QPBP [5] is a promising multifunctional adsorbent for the treatment of complex pollutants in water.

Delamination of multilayer Ti3C2Tx MXene alters its adsorpiton and reduction of heavy metals in water.

MXenes are considered as an emerging class of two-dimensional (2D) adsorbent for various environmental applications. In this work, two different morphologies of Ti3C2Tx MXene (multilayer (ML-Ti3C2Tx) and delaminated titanium carbide (DL-Ti3C2Tx)) were prepared through mild in situ HF etching and further delamination. The structural differences between the two were explored with a focus on their effects on the performance and mechanism of removing heavy metals from water. In comparison to ML-Ti3C2Tx, DL-Ti3C2Tx had more oxygen-containing functional groups, higher specific surface area (19.713 vs. 8.243 m2/g), larger pore volume (0.135 vs. 0.040 cm3/g), higher maximum Pb(II) adsorption capacity (77.0 vs. 56.68 mg/g), but lower maximum Cu(II) adsorption capacity (23.08 vs. 55.46 mg/g). Further investigation revealed that the removal of Pb(II) by the MXenes was mainly controlled through electrostatic attraction and surface complexation mechanisms, while Cu(II) was removed mainly through surface reduction by Ti-related groups. Because delamination of ML-Ti3C2Tx increased the surface area and surface functional groups, DL-Ti3C2Tx became a better sorbent for Pb(II) in water. During sonication, however, delamination inevitably led to partial oxidation of Ti3C2Tx nanosheets and thus weakened the reducing ability of DL-Ti3C2Tx for Cu(II) in water. Nevertheless, both ML- and DL-Ti3C2Tx not only exhibited excellent heavy metal adsorption capacity under different solution conditions, but also showed good reusability. Findings of this study indicate that Ti3C2Tx MXenes are promising adsorbents for treating heavy metal pollutants in water.

Reduced dietary Ca, Cu, Zn, Mn, and Mg bioavailability but increased Fe bioavailability with polyethylene microplastic ingestion in a mouse model: Changes in intestinal permeability and gut metabolites.

Microplastics emerge as a new environmental and human health crisis. Minimal research exists on effects of microplastic ingestion on the oral bioavailability of minerals (Fe, Ca, Cu, Zn, Mn, and Mg) in the gastrointestinal tract via impacting intestinal permeability, mineral transcellular transporters, and gut metabolites. Here, mice were exposed to polyethylene spheres of 30 and 200 µm (PE-30 and PE-200) in diet (2, 20, and 200 µg PE g-1) for 35 d to determine the microplastic effects on mineral oral bioavailability. Results showed that for mice fed diet amended with PE-30 and PE-200 at 2-200 µg g-1, Ca, Cu, Zn, Mn, and Mg concentrations in the small intestine tissue were 43.3-68.8 %, 28.6-52.4 %, 19.3-27.1 %, 12.9-29.9 %, and 10.2-22.4 % lower compared to control mice, suggesting hampered bioavailability of these minerals. In addition, Ca and Mg concentrations in mouse femur were 10.6 % and 11.0 % lower with PE-200 at 200 µg g-1. In contrast, Fe bioavailability was elevated, as suggested by significantly (p < 0.05) higher Fe concentration in the intestine tissue of mice exposed to PE-200 than control mice (157-180 vs. 115 ± 7.58 µg Fe g-1) and significantly (p < 0.05) higher Fe concentrations in liver and kidney with PE-30 and PE-200 at 200 µg g-1. Following PE-200 exposure at 200 µg g-1, genes coding for duodenal expression of tight junction proteins (e.g., claudin 4, occludin, zona occludins 1, and cingulin) were significantly up-regulated, possibility weakening intestinal permeability to Ca, Cu, Zn, Mn, and Mg ions. The elevated Fe bioavailability was possibly related to microplastic-induced greater abundances of small peptides in the intestinal tract, which inhibited Fe precipitation and elevated Fe solubility. Results showed that microplastic ingestion may cause Ca, Cu, Zn, Mn, and Mg deficiency but Fe overload via altering intestinal permeability and gut metabolites, posing a threat to human nutrition health.

Prediction heavy metals accumulation risk in rice using machine learning and mapping pollution risk.

Rapid and accurate prediction of metal bioaccumulation in crops are important for assessing metal environmental risks. We aimed to incorporate machine learning modeling methods to predict heavy metal contents in rice crops and identify influencing factors. We conducted a field study in Jiangsu province, China, collecting 2123 pairs of soil-rice samples in a uniform measurement and using 10 machine learning algorithms to predict the uptake of Cd, Hg, As, and Pb in rice grain. The Extremely Randomized Tree model exhibited the best performance for rice-Cd and rice-Hg (Cd: R2 = 0.824; Hg: R2 = 0.626), while the Random Forest model performed best for As and Pb (As: R2 = 0.389; Pb: R2 = 0.325). The feature importance analysis showed that soil-Cd and pH had the highest impact on rice-Cd risk, which is in line with previous studies; while temperature and soil organic carbon were more important to rice-Hg than soil-Hg. Then, based on another set of 1867 uniformly distributed paddy soil samples in Jiangsu province, the Cd and Hg risks of soil and rice were visualized using the established models. Mapping result revealed an inconsistent pattern of hotspot distribution between soil-Hg and rice-Hg, i.e., a higher rice-Hg risk in the northern area, while higher soil-Hg in south. Our findings highlight the importance of temperature on Hg bioaccumulation risk to crops, which has often been overlooked in previous risk assessment processes.

A molecular level understanding of antimony immobilization mechanism on goethite by the combination of X-ray absorption spectroscopy and density functional theory calculations.

A molecular level understanding of antimony (Sb) immobilization mechanism on Fe oxides is required to clarify the fate of Sb in the soil. In this study, macroscopic sorption experiments, combined with extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT), were utilized to explore the interaction between Sb and goethite. The ion strength has no effect on Sb sorption on goethite, indicating the inner-sphere complex Sb formed on goethite. Goethite has the higher sorption potential to Sb(III) than Sb(V), consistent with the higher thermodynamic stability of the geometry for Sb(III) formed on goethite than Sb(V) revealed by DFT calculations. By comparing the Sb-Fe distances obtained by EXAFS spectroscopy and DFT, eight kinds of Sb(III) surface complexes and nine kinds of Sb(V) surface complexes were considered to be the possible geometries Sb formed on different crystal planes of goethite, including monodentate mononuclear, bidentate mononuclear, bidentate binuclear, tridentate mononuclear, tridentate binuclear, tridentate four-nuclear complexes. The structural and energetic details of these filtered geometries provide comprehensive information on Sb immobilization mechanism on goethite, helpful in clarifying the fate of Sb in soils.

Heavy metal-mediated adsorption of antibiotic tetracycline and ciprofloxacin on two microplastics: Insights into the role of complexation.

Microplastics (MPs) have recently become an emerging environmental concern. Nevertheless, limited information is known about the adsorption of MPs for organic contaminants under combined heavy metals pollution, with an emphasis on the role of complexation. Thus, this study aims to comprehensively compare and investigate the adsorption performance of antibiotic tetracycline (TC) and ciprofloxacin (CIP) on two polar MPs (polyamide (PA) and polyvinyl chloride (PVC)) affected by Cu(II) and Cd(II) with contrasting complexation abilities. Batch adsorption experiments were used in combination with speciation calculation, zeta potential determination, FTIR spectroscopy characterization and investigation of the affinity of MPs for heavy metals. Results showed that the sorption kinetics and isotherms of TC and CIP on PA and PVC could be well fitted to pseudo-second-order and Langmuir models, respectively, both in the absence and presence of Cu and Cd, suggesting that multiple interactions and monolayer adsorption played an important role in the adsorption process. The presence of Cu substantially improved TC and CIP adsorption and obviously changed the pH dependence of their adsorption onto both MPs, which may result from the Cu-induced strong complexation with TC and CIP. The presence of Cd slightly enhanced TC adsorption on both MPs while reduced CIP adsorption especially on PVC, which may be ascribed to the Cd-induced cationic bridging effects in TC adsorption and the competitive adsorption of Cd in CIP adsorption. Therefore, the heavy metal-mediated complexation effects may play a dominant role in antibiotic adsorption by MPs only in the presence of heavy metals with strong complexation ability while the adsorption performance in the presence of heavy metals with negligible complexation capacity may be influenced by effects other than complexation. This study helps further understand the heavy metal-mediated adsorption behavior of organic contaminants on polar MPs and the role of complexation reactions therein.

Prediction of Cd Accumulation in Wheat (Triticum aestivum L.) and Simulation Calculation of Lime or Zn Fertilizer Remediated Soil.

Soil Cd contamination to wheat raise wide concerns over food safety. It is essential to find the key factors affecting Cd accumulation in wheat and to establish a predictive model. The effects of pH, Zn, Ca, and DOM on the accumulation of Cd in wheat were investigated using hydroponic experiments. The results showed that Zn was the most important factor inhibiting Cd uptake in wheat. Models were developed to predict the Cd contents in wheat tissues based on the ion concentration. Meanwhile, the available Cd contents in soil were predicted using a geochemical multi-surface model (MSM) which is suitable for various soils and conditions. The combination of the hydroponic accumulation model and MSM exhibits good predictions of wheat-Cd (R2 = 0.822-0.862, RMSE = 0.317-0.533). The results of this study can quantitatively predict the accumulation of Cd in wheat and provide a reference for soil remediation and safe wheat production.

Synthesis and adsorption performance of three-dimensional gels assembled by carbon nanomaterials for heavy metal removal from water: A review.

This review focuses on the removal of heavy metals from water by three-dimensional gels with carbon nanomaterials as the main building units. It highlights the fundamental knowledge, most recent advances, and future prospects of carbon nanomaterial-assembled gels (CNAGs) as effective adsorbents for heavy metals in water. Various synthesis methods of CNAGs including template-assisted, self-assembly and other methods are systematically summarized and evaluated. Adsorption performances of CNAGs to typical cationic and anionic heavy metals, especially lead, cadmium, mercury, chromium, and arsenic, are thoroughly examined and discussed in detail. These analyses bring out that composite CNAGs constructed from carbon nanomaterials with polymers or other engineered nanoparticles are the most promising adsorbents for heavy metal removal from water. Current challenges and future research directions that are critical to the applications of CNAGs in the removal of heavy metals from contaminated water are outlined at the end of the review.

Thermodynamic and kinetic modeling the interaction of goethite-ligand-metal ternary system.

Low-molecular-weight organic acids may significantly influence the mobility of metal in environment, but the kinetics are not fully understood and have not been quantified. In this study, the thermodynamic and kinetic effects of citric acid (CA) on the adsorption of Cd(II) and Ni(II) on goethite were investigated using batch-adsorption and stirred-flow experiments. A charge distribution and multisite complexation model (CD-MUSIC) and a thermodynamically based multi-rate kinetic model were employed to describe the adsorption behaviors. Two ternary surface complexes, (≡FeO)2CitMe and (≡FeOH)2MeCit2-, were involved in the adsorption. In addition, CA differed in its effects on Cd(II) and Ni(II) adsorption, enhancing Cd(II) adsorption but inhibiting Ni(II) adsorption at high levels. Kinetically, in the presence of CA, the adsorption of Cd(II) was faster than that of Ni(II). Increasing CA concentration led to faster Cd(II) adsorption, but resulted in the dissolution of the adsorbed Ni(II), possibly due to the much higher complexation constants of Ni-CA than of Cd-CA in aqueous phase. This finding implied that, in the rhizosphere, high level of CA may lead to more dissolution of Ni(II) than Cd(II); while in acidic ferrosol, CA may alleviate Cd(II) mobility and toxicity. The proposed mechanistic model sheds light on ion partition in the soil environment and may improve predictions thereof.

Flooding and drainage induced abiotic reactions control metal solubility in soil of a contaminated industrial site.

Intense industrialization has led to the increasing leaching risk of metals into groundwater at heavily polluted industrial sites. However, metal dissolution in polluted industrial soils has been neither fully investigated nor quantified before. In this study, the dissolution of Zn, Ni, and Cu in soil from a heavily contaminated industrial site during a flooding-drainage period was investigated by sequential extraction, geochemical modelling, and X-ray absorption near edge structure spectroscopy. The results showed a steady decrease in metal solubility during both reduction and oxidation stages. During reduction, with limited decrease in Eh (>100 mV), formation of carbonate precipitates rather than sulfide precipitates and adsorption on soil solids was responsible for Zn and Ni dissolution, whereas bound to soil organic matter (SOM) and iron oxides dominated Cu dissolution, due to its lower concentration and higher affinity to SOM and iron oxides compared to Zn and Ni. During oxidation, the acidity caused by ferrous oxidation was buffered by calcite dissolution, while metal precipitation ceased and adsorption on soil surface controlled metal solubility. The metal solubility and speciation during the flooding-drainage process were quantitatively predicted by geochemical model. The findings demonstrate that due to high metal concentrations and weak microbial effect in the industrial soil, metal release was largely regulated by abiotic reactions rather than biotic reactions, which is somehow different from that of the wetland or rice field soils.

Treatment technologies for selenium contaminated water: A critical review.

Selenium is an indispensable trace element for humans and other organisms; however, excessive selenium in water can jeopardize the aquatic environment. Investigations on the biogeochemical cycle of selenium have shown that anthropogenic activities such as mining, refinery, and coal combustion mainly contribute to aquatic selenium pollution, imposing tremendous risks on ecosystems and human beings. Various technologies thus have been developed recently to treat selenium contaminated water to reduce its environmental impacts. This work provides a critical review on the applications, characteristics, and latest developments of current treatment technologies for selenium polluted water. It first outlines the present status of the characteristics, sources, and toxicity of selenium in water. Selenium treatment technologies are then classified into three categories: 1) physicochemical separation including membrane filtration, adsorption, coagulation/precipitation, 2) redox decontamination including chemical reduction and catalysis, and 3) biological transformation including microbial treatment and constructed wetland. Details of these methods including their overall efficiencies, applicability, advantages and drawbacks, and latest developments are systematically analyzed and compared. Although all these methods are promising in treating selenium in water, further studies are still needed to develop sustainable strategies based on existing and new technologies. Perspectives on future research directions are laid out at the end.

MIL series of metal organic frameworks (MOFs) as novel adsorbents for heavy metals in water: A review.

With large specific surface area, abundant adsorption sites, flexible pore structure, and good water stability, Materials of Institute Lavoisier frameworks (MILs) have attracted increasing attention as effective environmental adsorbents. This review systematically analyzes and recapitulates recent progress in the synthesis and application of MIL-based adsorbents for the removal of aqueous heavy metal ions. Commonly used solvothermal, microwave, electrochemical, ultrasonic, and mechanochemical syntheses of MILs are first summarized and compared. Instead of focusing on adsorption process parameters, adsorption performances and governing mechanisms of virgin MILs, functional MILs, MIL-based composites, and carbonized MILs to representative metal(loid) ions (chromium, arsenic, lead, cadmium, and mercury) in water under various conditions are then systematically reviewed and discussed. In the end, this work also outlines prospects and future directions to promote the applications of MILs in treating heavy metal contaminated water.

Passive sampling of chlorophenols in water and soils using diffusive gradients in thin films based on ß-cyclodextrin polymers.

Chlorophenols (CPs) have been listed as priority control pollutants because of their high toxicity and wide range. An In-situ monitoring technique using diffusive gradients in thin films based on porous ß-cyclodextrin polymers as binding materials (CDP-DGT), was established to monitor four typical CPs, namely, 4-Chlorophenol (4-CP), 2,4-Dichlorophenol (2,4-DCP), 2,4,5-Trichlorophenol (2,4,5-TCP), 2,4,6-Trichlorophenol (2,4,6-TCP) in water and soils. The performance of CDP-DGT are stable under the conditions of pH 3.5-9.3, ionic strength 0.001-0.500 mol L-1 and dissolved organic matter concentration 0-20 mol L-1. The adsorption capacities of CDP-DGT for 4-CP, 2,4-DCP, 2,4,5-TCP, 2,4,6-TCP were 57.80 µg cm-2, 98.82 µg cm-2, 95.69 µg cm-2 and 98.91 µg cm-2, respectively. The time-average weighted concentrations of four CPs determined by CDP-DGT at Sanjiangkou wharf (Yangtze river, China) were consistent with the results of grab sampling, indicating the feasibility of CDP-DGT application in actual water. In addition, the distribution of CPs in the red soil of Kunming and paddy soil of Yixing were also studied by CDP-DGT, and the desorption kinetics in the two soils were analyzed with the DIFS model. The higher the soil organic matter content is, the more CPs are distributed in the soil solid phase. CPs in both soils can be partially resupplied to soil solution from the soil solid phase and the higher the partition coefficient for labile CPs is, the stronger the supplement capacity is.

Competitive kinetics of Ni(II)/Co(II) and Cr(VI)/P(V) adsorption and desorption on goethite: A unified thermodynamically based model.

Predicting the dynamic behavior of coexisting ions on mineral interface is essential to understanding their lability in soil matrix, but a mechanical kinetic model for predicting competitive adsorption is lacking. In this study, the thermodynamic and kinetic adsorption behaviors of Ni(II), Co(II), Cr(VI), and P(V) on goethite under various condition were investigated by batch and stirred-flow experiments, respectively. The equilibrium model CD-MUSIC was developed to describe their equilibrium behavior, followed by the development of a multi-rate kinetic model constrained by the equilibrium model to describe their kinetic behavior. Ni(II) and Co(II) exhibit similar adsorption affinities, while the adsorption of P(V) was stronger and faster than that of Cr(VI). The two surface species of Cr(VI) and P(V) differed in dynamic features, a finding confirmed by in-situ ATR-FTIR spectroscopy. The kinetic model was successfully used to predict the binary competitive adsorption of Ni(II)-Co(II) and Cr(VI)-P(V), and especially the overshooting of Cr(VI) induced by P(V). Our results showed that an integrated thermodynamic-kinetic model obtained from a single-ion experiment can be extended to describe complex multi-ion interactions, indicating the robustness and scalability of the model's parameters. This approach can be used to construct more comprehensive equilibrium and dynamic models of the actual soil environment.