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Metal partitioning in soils is a key process controlling metal bioavailability and mobility and is greatly influenced by the solid/liquid ratio. However, metal partitioning is difficult to describe either by a simple partition coefficient or by isotherm adsorption equations. This study investigated the solubility of Ni(II) and Cd(II) in 19 soils as a function of three extraction reagents (water, 0.01 M NaNO 3 , and 0.01 M CaCl 2 ), five solid/liquid ratios (5–400 g/L) and field condition extracted by Rhizon samplers. Thermodynamically based multi-surface models (MSMs) that included generic parameters were used to describe metal partitioning under the studied conditions. The results showed that Ni/Cd solubility depended on the soil type, extraction reagent, and solid/liquid ratio. Soil major background cations (especially Ca 2+ , Mg 2+ , Fe 3+ and Al 3+ ) had a significant effect on the model's prediction ability. The MSM was able to predict the extractable metal in 0.01 M CaCl 2 in various soils at different solid/liquid ratios when soil background cations were included in the calculation; without the background cations, the model was able to predict metal partitioning only at solid/liquid ratios of <100 g/L. In addition, the model failed to predict water-extracted and 0.01 M-NaNO 3 -extracted Ni/Cd if background cations were not included, but could reasonably do so if they were included. More importantly, after the background cations were included, MSMs relatively well predicted the Ni/Cd content in soil pore water under 80% field capacity conditions with water as the solution matrix. [ABSTRACT FROM AUTHOR]

The adsorption of glufosinate (GLU), a widely used herbicide similar to glyphosate (GLY), onto goethite was investigated as a function of the pH, ionic strength, background cations and anions, heavy metal ions and fulvic acids (FAs) by using batch adsorption experiments. In situ ATR-FTIR spectroscopy and density functional theory (DFT) calculations were carried out to characterize the molecular interactions between GLU and goethite surfaces. The macroscopic results indicated that an increasing pH exerted an adverse effect on GLU adsorption because of the electrostatic repulsion, and the adsorption was not sensitive to ionic strengths or background cation types, indicating that an inner-sphere surface complex was involved. GLU adsorption can be considerably depressed by PO 4 3 − , SO 4 2 − , and a high level of FA because of the competitive effect, while being enhanced by Cu 2 + with a maximum adsorption at approximately pH 5 because of the metal ion bridging effect. Other examined divalent metal cations (Cd 2 + , Zn 2 + , and Pb 2 + ) showed almost no effect on GLU adsorption, indicating weak interaction between them. ATR-FTIR spectra and the DFT calculations further proved that GLU was bonded to goethite surfaces through the formation of a monodentate mononuclear inner-sphere complex between the phosphinic moiety and surface Fe(III) centers under an acidic condition. The results showed that GLU had a similar adsorption mechanism to that of GLY onto goethite, but with a lower adsorption affinity, possibly exerting higher mobility and risk in soils. [ABSTRACT FROM AUTHOR]

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) 2 CitMe and (≡FeOH) 2 MeCit2−, 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. [Display omitted] - Citric acid(CA) enhances Cd(II) binding on goethite by acting as a bridge ligand. - Ni(II) adsorption is enhanced at low CA but inhibited at high CA levels. - Cd-CA has a weaker but faster adsorption on goethite than Ni-CA. - A surface complexation model coupled with multi-rate kinetic model is proposed. - The model describes both thermodynamic and kinetic behaviors of the ternary system. [ABSTRACT FROM AUTHOR]

The mobility of toxic metals in soils or sediments is of great concern to scientists and environmentalists since it directly affects the bioavailability of metals and their movement to surface and ground waters. In this study, a multi-surface soil speciation model for Cd (II) and Pb (II) was developed to predict the partition of metals on various soil solid components (e.g. soil organic matter (SOM), oxide mineral, and clay mineral). In previous study, the sorption of metal cations on SOM and oxide minerals has been evaluated by thermodynamically based surface complexation model. However, metal binding to soil clay fractions was normally treated in a simplistic manner: only cation exchange reactions were considered and exchange coefficient was assumed unity. In this study, the binding of metals onto clays was described by a two-site surface sorption model (a basal surface site and an edge site). The model was checked by predicting the adsorption behavior of Cd (II) and Pb (II) onto three selected Chinese soils as a function of pH and ionic strengths. Results showed that the proposed model more accurately predicted the metal adsorption on soils under studied condition, especially in low ionic strength condition, suggesting that adsorption of metals to soil clay fractions need to be considered more carefully when modeling the partition of trace elements in soils. The developed soil speciation model will be useful when evaluating the movement and bioavailability of toxic metals in soil environment. [ABSTRACT FROM AUTHOR]

Abstract: The adsorption of tetracycline (TC) on a Na-montmorillonite was studied as a function of five background electrolyte cations (Li+, Na+, K+, Mg2+ and Ca2+), one transitional metal cation (Cu2+) and humic acid (HA) over a pH range from 3 to 9 using batch experiments combined with XRD and FTIR measurement. Results showed that pH had great effect on the TC adsorption and acidic condition is more favored. Monovalent (Li+, Na+ and K+) and divalent (Mg2+, Ca2+ and Cu2+) cations showed very different effects on the TC adsorption onto montmorillonite. In the presence of monovalent cations, the adsorption edge curves were little affected by the types of cations. They presented a great decrease at pH<6, then an increase to a local maximum at about pH 8, followed by a gradual decrease (8Mg2+, which might be due to the capability of “bridge” effect of divalent cations. The difference of enhancing TC adsorption in the presence of Ca2+ and Mg2+ might be a result of different ionic radii and different interacting groups in TC molecular. XRD results showed that TC was intercalated into interlayers of montmorillonite since the interlayer expansion was observed. The band changes of amide carbonyl and amino groups in tricarbonyl methane group and the carbonyl group in phenolic deketone group in the FTIR spectra of TC equilibrated with montmorillonite confirmed that TC was adsorbed to the clay via cation exchange and surface complexation. It was also found that the effect of HA on the TC adsorption was pH-dependent and the presence of HA significantly reduced the mobility of TC in solution especially under acidic condition due to the complexation between cationic or zwitterionic TC species and the deprotonated sites on HA (mainly carboxylic groups) via electrostatic attraction. These results suggested that coexistence of divalent cations and HA would reduce TC''s mobility in soil environment, especially at acidic condition. [Copyright &y& Elsevier]

Abstract: Illite samples from Fithian, IL were purified and saturated with Na+ ions. The acid–base surface chemistry of the Na-saturated illite was studied by potentiometric titration experiments with 0.1, 0.01, and 0.001 M NaNO3 solutions as the background electrolyte. Results showed that the titration curves obtained at different ionic strengths did not intersect in the studied pH range. The adsorption of Cd(II), Cu(II), Ni(II), Pb(II), and Zn(II) onto illite was investigated as a function of pH and ionic strength by batch adsorption experiments. Two distinct mechanisms of metal adsorption were found from the experimental results: nonspecific ion-exchange reactions at lower pH values on the basal surfaces and ‘frayed edges’ and specific adsorption at higher pH values on the mineral edges. Ionic strength had a greater effect on the ion-exchange reactions. The binding constants for the five heavy metals onto illite were determined using the least-square fitting computer program FITEQL. Linear free energy relationships were found between the surface binding constants and the first hydrolysis constants of the metals. [Copyright &y& Elsevier]

Arsenic pollution poses severe threat to human health, therefore dealing with the problem of arsenic contamination in water bodies is extremely important. The adsorption behaviors of different arsenic species, such as arsenate (As(V)), p-arsanilic acid (p-ASA), roxarsone (ROX), dimethylarsenate (DMA) from water using mesoporous bimetal oxide magnetic manganese ferrite nanoparticles (MnFe 2 O 4 ) have been detailedly investigated. The adsorbent was synthesized via a facile co-precipitation approach and recovered conveniently owing to its strong magnetic properties. The obtained MnFe 2 O 4 with large surface area and abundant hydroxyly functional groups exhibited excellent adsorption performance for As(V) and p-ASA, in contrast to ROX and DMA with the maximum adsorption capacities of As(V), p-ASA, ROX and DMA of 68.25 mg g −1 , 59.45 mg g −1 , 51.49 mg g −1 , and 35.77 mg g −1 , respectively. The Langmuir model and the pseudo-second-order kinetic model correlated satisfactorily with the adsorption thermodynamics and kinetics, and thermodynamic parameters depicted the spontaneous endothermic nature for the adsorption of different arsenic species. The adsorption mechanism of different arsenic species onto MnFe 2 O 4 nanoparticles at various pH values could be explained by surface complexation and molecular structural variations. Attenuated Total internal Reflectance Fourier Transform Infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) further proved that arsenic species were bonded to the surface of MnFe 2 O 4 through the formation of an inner-sphere complex between the arsenic acid moiety and surface metal centers. The results would help to know the interaction of arsenic species with iron-manganese minerals and the mobility of arsenic species in natural environments. [ABSTRACT FROM AUTHOR]

Abstract: The surface adsorption behavior of tetracycline (TC), a zwitterionic antibiotic, to goethite was investigated as a function of pH, ionic strength and TC concentration using batch adsorption experiments and structural information was derived from attenuated total reflectance Fourier transform infrared spectrum observations. The spectroscopic results suggested that the tricarbonylamide group and the phenolic diketone group of the TC molecule were involved in interacting with the goethite surface depending on the pH level. A charge distribution surface complexation model was developed to describe the macroscopic adsorption trends. Two inner-sphere surface complexation species could successfully describe observed adsorption trends: under acidic condition TC may interact with the surface of goethite, forming a monodentate complex through the tricarbonylamide group, while under alkaline condition forming a more stable bidentate complex via the tricarbonylamide and phenolic diketone groups. The model could well predict the adsorption behavior of TC under a relatively wide range of pH, ionic strength and surface coverage. However, since the model did not fully consider the molecular size of TC, the model might overestimate the adsorption when TC surface coverage is higher than 1.42μmolm−2. [Copyright &y& Elsevier]

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. [Display omitted] • White polyethylene (PE) mulch film was the most susceptible to aging. • Soil-surface aging produced greater deterioration in PE films than soil-burial aging. • Soil-surface aging increased triclosan and Pb adsorption capacities of microplastics. • Aging decreased desorption rates of chemicals in simulated gastrointestinal fluids. • Exposure patterns played a central role in pollutant bioavailability. [ABSTRACT FROM AUTHOR]

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. • Sorption of antibiotics on two polar microplastics mediated by Cu and Cd was studied. • Detailed calculation of chemical species in various composite systems was involved. • Cu substantially enhanced antibiotic sorption due to dominant complexation mechanism. • Cd improved or inhibited sorption due to cationic bridging or competitive sorption. • Role of complexation in sorption basically relied on complexation ability of metals. [ABSTRACT FROM AUTHOR]

Abstract: Adsorption of tetracycline, one of the most widely used antibiotics, onto goethite was studied as a function of pH, metal cations, and humic acid (HA) over a pH range 3–10. Five background electrolyte cations (Li+, Na+, K+, Ca2+, and Mg2+) with a concentration of 0.01M showed little effect on the tetracycline adsorption at the studied pH range. While the divalent heavy metal cation, Cu2+, could significantly enhance the adsorption and higher concentration of Cu2+, stronger adsorption was found. The results indicated that different adsorption mechanisms might be involved for the two types of cations. Background electrolyte cations hardly interfere with the interaction between tetracycline and goethite surfaces because they only form weak outer-sphere surface complexes. On the contrary, Cu2+ could enhance the adsorption via acting as a bridge ion to form goethite–Cu2+–tetracycline surface complex because Cu2+ could form strong and specific inner-sphere surface complexes. HA showed different effect on the tetracycline sorption under different pH condition. The presence of HA increased tetracycline sorption dramatically under acidic condition. Results indicated that heavy metal cations and soil organic matters have great effects on the tetracycline mobility in the soil environment and eventually affect its exposure concentration and toxicity to organisms. [Copyright &y& Elsevier]

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. [Display omitted] • The adsorption of Ni(II), Co(II), Cr(VI), and P(V) on goethite was investigated. • An integrated thermodynamic-kinetic model was developed. • The model is suitable for various pH, loading concentrations and ionic strength. • The binary competitive adsorption was predicted by model derived from single-ion. [ABSTRACT FROM AUTHOR]

Birnessite is one of the most common manganese oxides in the environment and an important scavenger of trace metals. This study investigated the adsorption of seven divalent metal cations (Cd2+, Co2+, Cu2+, Mn2+, Ni2+, Pb2+ and Zn2+) on birnessite at different pH conditions, ionic strengths and initial concentrations. The adsorption data were used to formulate a self-consistent, two-site surface complexation model consisting of a triple-corner-sharing (TCS) complex at interlayer vacancies and a double-corner-sharing (DCS) complex at mineral edge sites. Unlike the other metals, Ni2+ had a relatively low adsorption capacity on birnessite, attributable to its tendency to incorporate within Mn vacancies (INC); hence a two-site model with INC and DCS complexes was used to describe Ni2+ adsorption on birnessite. The model well described all the adsorption data and was verified by data from the literature. In addition, a linear free energy relationship (LFER) was developed between the TCS binding constants and metal electronegativity and hydrous ionic radii, which can be used to estimate the binding constants of other trace metals. The proposed model contributes to a better understanding of the adsorption mechanisms of trace metals by manganese oxides. Furthermore, the data set can be included in geochemical assemblage models to predict the dissolution and mobility of metals in the environment. Unlabelled Image • The adsorption of Cd, Co, Cu, Mn, Ni, Pb and Zn on birnessite was investigated. • A two-site surface complexation model was developed to describe the adsorption. • The model included a TCS complex at vacancies and a DCS complex at edge sites. • The model is self-consistent and was verified using data from the literature. [ABSTRACT FROM AUTHOR]