The role of magnesium ion in the interactions between humic acid and tetracycline in solution.

Coexisting tetracycline (TC), dissolved organic matter (DOM), and metal cations in aqueous environments might form complexes and consequently affect the environmental fate of TC. In this study, the interactions among coexisting humic acid (HA), TC, and Mg(II) in solutions were investigated by equilibrium dialysis batch experiments and nuclear magnetic resonance hydrogen spectroscopy (1H NMR) characterization. In the binary systems, the dimethylamine (4Me2NH+) functional group on the A-ring of TC bound to the oxygen-containing functional groups of HA via hydrogen bond. The solution pH affected the agglomeration morphology and dissociation of the oxygen-containing functional groups of HA as well as protonation and spatial conformation of TC, which in turn affected the HA-TC interactions. The complexation sites and ratio of Mg(II) on TC affect the binding mode in the ternary system. When the TC-Mg(II) complexation ratio is 1:1, the B, C, and D rings of TC preferentially complex with Mg(II), resulting in the change of TC from an extended to a twisted conformation. At this time, Mg(II) had a weaker inhibitory effect on binding affinity between HA and TC. When the complexation ratio was 1:2, the second Mg(II) complexation deactivated the 4Me2NH + on the A ring and further stabilized TC twisted conformation, resulting in a stronger inhibitory effect on the binding of TC to HA. Under acidic conditions, the solution pH mainly caused the difficulty in forming TC-Mg(II) complexes. The inhibitory effect of Mg(II) on the binding between HA and TC is weaker than that under alkaline conditions.

Control mechanism of trichloroethylene back diffusion by microstructure in a low permeability zone.

The trailing effect caused by the back diffusion (BD) of contaminants in low-permeability zones (LPZs), which prolongs remediation time and increases remediation costs, has caused widespread concern. In this study, the BD of trichloroethylene (TCE) from the LPZ to the high-permeability zone (HPZ) was determined using flow cell experiments. The anomalous variance in the BD flux of the TCE-spanning 2-4 times the deviation under identical experimental conditions, attracted our attention. To determine the cause of this aberrant behavior, a micro computed tomography (micro-CT) characterization of the flow cell was conducted, which revealed significant microstructural disparities in the LPZ. The study found that the pore connectivity of LPZs determines the efficiency of BD and that LPZs with different porosities have different sensitivities to connectivity. The pore shape complexity indicates the possibility of BD retardation, and remediation is more difficult for these types of LPZs. Changing the structure of LPZs to improve their remediation efficiency may be a new research topic. Notably, correcting the model parameters through microstructural characterization significantly refined the prediction accuracy.

Influencing mechanisms of tartaric acid on adsorption and degradation of tetracycline on goethite: insight from solid and liquid aspects.

The interactions between organic pollutants and iron minerals play an important role in their environmental fate. In this study, the effects of low-molecular-weight organic acids (LMWOAs) on the adsorption and degradation of tetracycline (TC) on goethite were investigated. Tartaric acid (TA) was taken as the representative of LMWOAs to study the influencing mechanism through batch experiments and microscale characterization. In addition, the properties of TC-TA clusters under different pHs were determined by density functional theory (DFT) calculations. The results showed that all five LMWOAs inhibited TC adsorption and degradation. The preferential adsorption of TA on goethite changed TC adsorption from inner spherical to outer spherical complexation and mainly inhibited TC adsorption and degradation of the singly coordinated hydroxyl group. TC degradation rate decreased from 0.0287 to 0 h-1 in the first stage. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy results showed that TA could influence the interactions of amide groups, C = O on the A-ring, and dimethylamino group of TC with goethite, and the formation of ≡Fe(II) was inhibited. In addition to competing for the effective sites, the effects of complexation between TA and TC in solution should be considered. According to DFT calculations, hydrogen bonds could be formed between the carboxyl group of TA and the H atom of TC at different pH. These findings can provide evidence for estimating the contribution of adsorption and degradation to TC removal by iron oxides with the coexistence of LMWOAs in a soil-water environment.

Effect of endogenetic dissolved organic matter on tetracycline adsorption by biochar.

The endogenetic biochar-derived dissolved organic matter (BDOM) might interact with pollutants in the environment. In this study, tetracycline (TC) was selected as the representative pollutant, and corn straw biochar (pyrolyzed at 300 °C) was used as the adsorbent. Through batch experiments and microscopic characterization, the releasing kinetics of BDOM and its effect on TC adsorption on biochar were investigated. The results showed that BDOM with weaker aromaticity and higher molecular weight was preferentially released. BDOM release led to the decrease of specific surface area (from 4.02 to 1.83 m2/g), mesopore number, and aromaticity of biochar (H/C increased from 0.80 to 0.91) and consequently weakened the pore filling of TC on biochar, hydrophobic interaction, and π-π EDA (electron donor receptor) interaction between biochar and TC. In addition, the released BDOM could form a complex with TC in solution to prevent TC adsorption on biochar. Overall, the change in the structural properties of biochar caused by BDOM release had a greater impact on the inhibition of TC adsorption than that of BDOM and TC complexation in this study. Through EEM-PRARFAC, BDOM contained about 63% humic acid-like fluorescent component and 37% tryptophan-like fluorescent component; the former (logKb values were 7.31 and 6.48, respectively) had a stronger binding strength with TC than the latter (logKb was 6.45). The findings of this study could provide some useful evidence for the removal of organic pollutants in soil and water environments and biochar application in pollution remediation.

Active binding sites for ofloxacin resulted from adsorptive fractionation of humic acid on kaolinite.

The adsorptive fractionation of humic acid (HA) at the interface between minerals and water can significantly affect the fate of pollutants in water-soil environment. However, the adsorptive fractionation behavior of HA on kaolinite and its effect on the migration of fluoroquinolones (FQs) have not been fully understood. In this study, fluorescence and infrared spectroscopy, combined with two-dimensional correlation analyses, were used to explore the adsorptive fractionation of humic acid (HA) and its effects on ofloxacin adsorption on kaolinite. The results indicated that humic-like, rather than reduced quinone-like and tyrosine-like, was the main adsorptive fractionation component and preferentially bound to the Al-O sites of kaolinite. The adsorption mechanisms of humic-like and tyrosine-like mainly include hydrogen bonds between acidic functional groups and the Si-O or Al-O groups of kaolinite, n-π electron donor-acceptor interaction and electrostatic attraction. At pH 7.0, with addition of 4.0 and 16.0 mg C/L HA in solution, the adsorptive fractionation of HA on kaolinite led to increases in ofloxacin (in zwitterionic form) adsorption capacity by 1.46 and 3.35 mg/g, respectively. The interactions between ofloxacin and the humic-like were mainly hydrogen bonds and electrostatic attraction. Therefore, the influence of adsorptive fractionation of dissolved organic matter on minerals should be considered in estimating FQs environmental behaviors.

Typical Sulfonamide Antibiotics Removal by Biochar-Amended River Coarse Sand during Groundwater Recharge.

The high porosity of medium-coarse sand (MCS) layers in groundwater recharge areas presents a high environmental risk. Sulfamethoxazole (SMX) and trimethoprim (TMP) are two common sulfonamide antibiotics in surface water that have a high propensity to migrate into groundwater. In this study, four biochars were prepared and biochar-amended soil aquifer treatment (SAT) columns were constructed to remove SMX and TMP. Batch experiments demonstrated that the sorption isotherms conformed to the Freundlich model. The maximum adsorptions of biochars prepared at 700 °C were 54.73 and 67.62 mg/g for SMX and 59.3 and 73.38 mg/g for TMP. Electrostatic interaction may be one of the primary mechanisms of adsorption. The column experiments showed that the SMX and TMP removal rate of the biochar-amended SAT was as high as 96%, while that of the MCS SAT was less than 5%. The addition of biochar greatly improved the retention capacity of the pollutants in the MCS layer in the groundwater recharge area and effectively reduced environmental risk.

Transport and retention of nano emulsified vegetable oil in porous media: Effect of pore straining, roughness wedging, and interfacial effects.

Emulsified vegetable oil (EVO), as one of the novel green substrates, has been widely used in subsurface remediation. In these applications, the retention behavior of EVO presents a challenge to remediation efficiency as mechanism insights into the retention of EVO is limited. Herein, Brinell funnels experiments with X-ray microtomography (XMT) were conducted to examine the drainage and retention of nanoscale EVO in porous media, with a specific focus on investigating the impact of pore straining, grain surface roughness, and interfacial effects on Nano-EVO (NEVO) retention. This study demonstrated that the retention of NEVO in porous media is the synergistic result of pore straining, roughness wedging, and interface attachment. With the action of these effects, three residual states of NEVO, incorporating retention at porous ganglia, grain-grain contacts, and grain surface, were identified by XMT in porous media. After multiple periods of drainage and imbibition, the NEVO arrived at stable retention proportions of 46.3%, 72.2%, and 85.9% in three independent systems with coarse, medium, and fine sand as porous media, respectively. The interfacial effects, including the attachment of solid-phase and air-liquid interface, are confirmed as the dominant factors for the retention of NEVO in porous media, which contributed 35.63-47.33% of total retention for the conditions employed. Correspondingly, the contributions of pore straining and roughness wedging only ranged 3.78-24.06% and 3.87-9.94%, respectively. The consistency of the contributions between the actual measurement of XMT and computational evaluation further confirmed the rationality and reliability of the results. In such the dominant factor, interfacial tension, contact angle, and capillary radius play an essential role in NEVO retention, which could be reflected by capillary rise height. These findings advance our understanding on NEVO retention caused by substrate-media interaction and also offer a promising direction for subsurface remediation.

Cotransport of nano-hydroxyapatite and different Cd(II) forms influenced by fulvic acid and montmorillonite colloids.

Soil colloids can affect the cotransport of nanoparticles and pollutants. In this study, the influencing mechanisms of organic fulvic acid (FA) and inorganic montmorillonite colloid (MONT) on the cotransport of nHAP and Cd(II) were investigated. Column experiments combined with Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, attachment efficiency calculation and two-site kinetic retention model were applied to study the mechanisms. Results showed that the co-existence of FA or MONT made the transport of nHAP improved by 58-75% and 33-59%, respectively. Both of them could improve the stability of nHAP particles and enhance electrostatic repulsion between nHAP particles and sand. Retention of nHAP in the sand was mainly caused by secondary energy minimum and physical straining. The co-existence of FA or MONT changed the amount of adsorbed species of Cd(II) and decreased the retardation effect of nHAP on Cd(II) transport. With increasing FA concentration, soluble FA·Cd and suspended nHAP·FA·Cd complexes in the system increased. Transport of soluble Cd(II) and total Cd(II) were strengthened due to the concentration effect of FA and the improved stability of nHAP particles. With increasing MONT concentration, the amount of soluble Cd(II) decreased, but that of colloidal Cd(II) (nHAP·Cd and MONT·Cd) increased. Due to the stronger effect of colloidal Cd(II) change than that of the soluble Cd(II) change, the transport of total Cd(II) was improved by 34-57%. The findings of this study can help to understand the fate of nanoparticles and Cd(II) in natural water and soil.

Coupling of multi-hydrochemical and statistical methods for identifying apparent background levels of major components and anthropogenic anomalous activities in shallow groundwater of the Liujiang Basin, China.

Natural background levels (NBLs) is a prerequisite for distinguishing anthropogenic groundwater pollution and judging the evolution of groundwater quality. However, due to regional differences of hydrogeochemitry and water-rock interaction, coupled with long-term anthropogenic activities, it is no longer accurate to assess NBLs with only statistical methods or without considering human impact. Herein, multi-hydrochemical and statistical methods were examined to identify apparent background levels and anthropogenic anomalous activities of shallow groundwater by selecting Liujiang Basin as a study area. The results showed that the differences in hydrochemical characteristics among each hydrogeological unit (HU) fully illustrated the necessity of rationally dividing HU for background value identification. The application of the concept of apparent background levels (ABLs), that is, incorporating normal human activities into the background levels, efficiently solved the problem of being unable to obtain pristine NBLs due to long-term human activities. The coupling of Hydrochemistry and Grubbs' test (Hydro-Grubbs) was confirmed as the optimal method in identifying and eliminating anthropogenic groundwater anomalies, performing sufficiently superiority when compared with purely statistical methods. It is mainly because the Hydro-Grubbs method not only considers the discreteness of the data itself, but also considers the internal connection and evolution process of the hydrochemical compositions. For the eliminated abnormal points, 91.0-93.6% of which have been effectively explained by pollution percentage index and the impact of coal mining, industrial activities, residents, agricultural activities, and septic tanks leakage, proving the rationality and reliability of Hydro-Grubbs method and ABLs evaluation result. This finding will assist in accurately identifying anthropogenic pollution on a regional scale and guiding future efforts to protect groundwater resources.

Selenium distribution in cultivated Argosols and Gleyosols of dry and paddy lands: A case study in Sanjiang Plain, Northeast China.

Distribution pattern of selenium (Se) fractions in soil could influence Se content in crops and thereby intake of Se in human body. In order to investigate the effects of soil types and farming conditions on Se distribution in small-scaled cultivated land developed under the same conditions of climate, topography and parent materials, two types of soils (i.e., Argosols and Gleyosols) from paddy and dry lands in the Sanjiang Plain of Northeast China were selected. Total Se (T-Se) content in Argosols was influenced by organic carbon (Org C) content and pH of bulk topsoil. In Gleyosols, it was mainly affected by Org C content in dry land and pH in paddy land, respectively. In rice root associated topsoil, organic matter associated Se (OM-Se) accounted for 70% of T-Se. Compared with pH (median 6.10) and OM weakly bound Se (OW-Se) (0.14 ± 0.04 mg kg-1) of Argosols, the higher pH (median 6.77) resulted in less OW-Se (0.10 ± 0.04 mg kg-1) of Gleyosols. Vertical distribution of Se in borehole cores within the depth of 0-900 cm was mainly affected by the soil type. Se accumulated mainly within 0-150 cm depth (horizon A, E and B) in Argosols and above 40 cm depth (horizon H), existing prominently as OM strongly bound Se (OS-Se), in Gleyosols. Within the depth of 0-150 cm, various Se fractions for both soils were probably controlled by reductive fixation and complexation of Org C; In the alkaline paddy land, DOM-complexed Se was the main composition of A-Se. The findings of this study could help in understanding the mechanisms of Se distribution and enrichment in soils developed under different formation processes and farming conditions.

Effects of Al substitution on sorption of diclofenac to Fe(III) (hydr)oxides: roles of phase transition and sorption mechanisms.

Fe(III) (hydr)oxides commonly contained many metal impurities such as Al. The incorporation of Al might change the properties of minerals and consequently affect sorption behaviors of pollutants with polar functional groups (e.g., diclofenac (DCF)). In this study, batch experiments and microscale characterization were conducted to investigate the DCF sorption mechanisms to goethite and Al-substituted minerals. Goethite and Al-substituted products (including Al-goethite, Al-goethite-hematite, and Al-hematite) were synthesized with different Al contents (i.e., 0%, 5%, 10%, and 15% (in mol)) by co-precipitation method. Due to difference of ionic radius between Al and Fe and formation of excessive -OH, Al substitution resulted in deviation of cell parameters from the Vegard line. Al substitution caused increasing -OH in Al-goethite and phase transformation caused decreasing -OH in Al-hematite. The total -OH in minerals was positively related to DCF sorption capacity. In the lower initial concentration range (0.4-9 mg/L), the sorption distribution coefficient (Kd) values of goethite, Al-goethite, and Al-hematite were 21.98, 22.25, and 21.18 L/kg, respectively. Desorption characteristics and ion strength effects indicated that DCF sorption to minerals occurred mainly through outer-sphere complexation. Fourier transform infrared analyses revealed that H-bonds could be formed through -OH of minerals and -COOH of DCF, and the H-bond strength on Al-hematite was stronger than that on goethite/Al-goethite. In the normal environmental pH (e.g., 6.0 to 8.0), Kd values of DCF decreased linearly with increasing pH. These findings are helpful for understanding of DCF migration in environment involving Al-substituted minerals.

Different binding characteristics of ciprofloxacin to iron mineral surfaces: Thermodynamic evidence and site energy distribution analysis.

Iron minerals in soil play an important role in controlling the migration of fluoroquinolones. In this study, batch experiments were carried out to investigate interactions in ciprofloxacin (CIP) adsorption to goethite, hematite, and magnetite at pH 6.0. Thermodynamics and the site energy distribution theory (SEDT) were adopted to clarify the complexation types. Using the adsorption results, pH-dependent interactions were qualitatively elucidated. The thermodynamic data revealed the difference in adsorption mechanisms. With increasing sorbate loading, CIP adsorption to hematite and magnetite was endothermic, and both enthalpy change and entropy change decreased; however, CIP sorption to goethite showed opposite characteristics. The higher adsorption capacity and affinity of CIP to hematite and magnetite than those to goethite were caused by their higher site energy of the highest occurring frequency (E0 * ) and the temperature-dependent average site energy, respectively. The E0 * on the surface of goethite was about 17-19 kJ mol-1 , where E0 * values of hematite and magnetite were 20-26 kJ mol-1 . When temperature increased from 289.15 to 308.15 K, the high- and low-energy site densities for three iron minerals changed by -32 to 167% and by -36 to 223%, respectively. The different thermodynamic and SEDT results indicated that CIP adsorption mechanisms to goethite and hematite/magnetite were mainly outer- and inner-sphere complexation, respectively. The findings of this study reveal the adsorption mechanisms and are helpful in evaluating the transport of antibiotics in soils containing typical iron minerals.

Effects of endogenous and exogenous dissolved organic matter on sorption behaviors of bisphenol A onto soils.

The transport of organic contaminants in groundwater might be greatly affected by coexistence of dissolved organic matter (DOM) from different sources. In this study, the effects of endogenous and exogenous DOMs (referred to as DOMen and DOMex, respectively) on sorption behavior of bisphenol A (BPA) onto two reference soils were investigated by batch experiments and microscopic characterization. The results showed that BPA sorption onto soils was dominated by soil organic matter content and affected by DOM properties. The effect of DOMen on BPA sorption was also related to the inorganic components of the two soils. The decrease of organic matter content reduced the sorption capacity of fluvo-aquic soil. However, because the content of available inorganic components in black soil was high, after removing DOMen, more inorganic sites were exposed to increase the sorption capacity. In addition, DOMen could form complexes with BPA in solution, thus the removal of DOMen promoted BPA sorption onto black soil. Under the experimental conditions, contribution of DOMex to the total sorption of BPA onto both soils was not more than 30%. Results of dialysis experiments and soil sorption experiments indicated that effects of coexisting DOMex on BPA sorption was related to the affinity of DOMex to soils and complexation of BPA and DOMex. Since the affinity of DOMex to fluvo-aquic soil was relatively low, the complex of BPA and DOMex in solution was the main inhibition mechanism for BPA sorption. For black soil, higher complexation proportion of BPA with DOMex adsorbed onto soil which promoted BPA sorption onto soil. The findings are of significance for understanding the co-migration of DOM with BPA through soils.

Synergistic Effects of Micronano Structures on Porosity and the Permeability of Shale Under Varying Effective Stresses and Temperatures: A Case Study of Fresh Outcrops from Lower Silurian Longmaxi Formation Shale in the Southern Sichuan Basin, China.

To study the changes in porosity-permeability and the characteristics of the pore structure of shale under stress and high temperature, the Lower Silurian Longmaxi Formation shale in the southern Sichuan Basin, China, was investigated under conditions of continuous pressurization and heating. In addition, the pore compression coefficients and permeability stress sensitivity coefficients were analyzed and quantified. The mineral composition of these black shales was analyzed using scanning electron microscopy (SEM) and nuclear magnetic resonance (NMR). Our results reveal that the porosity and permeability of the shales exponentially decreases with increasing stress, reflecting that microfracture development during increasing stress causes the pores in these shale samples to enlarge. However, the pore compressibility and stress sensitivity coefficient vary for each sample, and the quantitative results indicate an overall decrease with increasing stress, suggesting that the shale deformation is nonlinear during stress release. Based on the mineral composition analyses and SEM measurements, we conclude that the nonuniform changes during stress release are related to the complexity of the shale mineral compositions and the different intercrystalline/ interlaminar pores of the different minerals, which are affected in different ways by pressure. The NMR measurements reveal that the mesopores are most developed in the shale samples, the pore volumes of the micro- and macropores are small, and the nanoscale pores are mainly from 1-60 nm in diameter. The different types of pore sizes decrease with increasing stress, indicating that the porosities measured experimentally reflect the synergistic effects of the different pore sizes on porosity. As the temperature increases, the permeability of the shale decreases significantly, which is primarily caused by the thermal expansion effect. The high clay mineral content of the shales also causes their permeabilities to be sensitive to temperature.

Pore-scale identification of residual morphology and genetic mechanisms of nano emulsified vegetable oil in porous media using 3D X-ray microtomography.

The application of emulsified vegetable oil (EVO) has attracted widespread attention in environmental remediation. Residual morphology is an important factor affecting its migration and mass transfer. However, proper identification of the EVO residual morphology at pore-scale has still remained a challenging task. Hence, this study aimed to identify the residual morphology of nanoscale EVO (NEVO) through developing a method combining natural breaks with 3D X-ray microtomography, then further explore the genetic mechanism of each residual morphology to verify the rationality of this method. The results showed that the natural breaks method can effectively classify the residual morphology of NEVO. Four morphologies including cluster, throat, corner, and membrane state were obtained from coarse, medium, and fine sands with a total proportion of 18.3%, 26.2%, and 30.8%. The cluster state was the main residual morphology, accounting for 10.0- 16.2%, then followed by corner-throat state and membrane state. Pore radius, throat radius, and length were confirmed providing sufficient evidences for cluster residues, because these factors determined the connectivity of porous media for the trapping of droplets. Comparison of the theoretical and actual results implied that capillarity coupling pore-throat shape jointly controlled corner and throat residues. Grain surface roughness and specific surface area were the main factors of membrane residue. The different residual morphologies of NEVO identified by the natural breaks method can reasonably explain their magnitude and controlling mechanisms, which in turn confirms the rationality of this method. Although the proportions of each form are related to the experimental conditions, the classification method and mechanism are of great significance for understanding NEVO residues.

[Simulation of Water Quality Response of Guishui River Wetland Plants and Water Diversion].

A two-dimensional model MIKE21 coupled with a modified EcoLab module was applied to model the water quality of surface flow wetlands. In the model, vegetation effects, oxygen production, nutrient consumption by microorganisms and vegetation were set in the solutions of hydrodynamic, chemical, and biological processes. Based on the field investigation and measurements in the Guishui River wetland, the model was established for the downstream reaches of the Guishui River and the Sanli River. The model calculated the hydrodynamics and water quality changes by vegetation type and distribution. The model parameters were calibrated and results were validated using the measurements. The concentrations of ammonia nitrogen, phosphate, and total nitrogen at outflow decreased by 14.29%, 33.33%, and 20.00% in the presence of wetland vegetation compared to no wetland vegetation. During water circulation, the flow rate increased by 0.4 m3 ·s-1 at the inlet of Guishui and Sanli rivers, increasing the water level and velocity in some parts of the rivers. The water areas with vegetation in Sanli and Guishui rivers increased by 144.44% and 13.16%, respectively. The concentrations of ammonia nitrogen, phosphate, and total nitrogen at outflow decreased by 35.71%, 50.00%, and 46.67% compared to no wetlands and no circulation. The circulation strengthened the wetland purification function. The wetland vegetation distribution was organically integrated into the model for water quality calculation, which provides the technical support for the water quality response research under comprehensive measures such as river and lake wetland ecological restoration and water conservancy regulation.

The impacts of Cu(II) complexation on gatifloxacin adsorption onto goethite and hematite.

Gatifloxacin (GAT) is a new generation fluoroquinolone antibiotic and its adsorption onto iron minerals influenced by coexisting trace elements [e.g., Cu(II)] has not been well investigated. To evaluate the adsorption behavior of GAT and Cu(II) onto goethite and hematite, the complexation constants of GAT with Cu(II) were determined using potentiometric titration, and the effects of Cu(II) concentration and solution pH on GAT adsorption were investigated using batch experiments. It was observed that GAT adsorption was negatively correlated with molar concentration ratio of Cu(II) to GAT. In our experimental pH range (i.e., 3.0-10.8), the calculated main species involved in GAT adsorption were Cu(GAT± )2+ and Cu(GAT± )2 2+ under acidic to neutral conditions, and formation of Cu(GAT- )2 (s) facilitated the removal of GAT from solution under alkaline condition. The adsorption data were well fitted by the Freundlich model and showed high nonlinearity. In adsorption onto goethite, the primary interactions shifted from electrostatic repulsion to formation of goethite-Cu(II)-GAT ternary surface complexes with increase of GAT concentration. For hematite, electrostatic repulsion was the main inhibiting mechanism and became stronger with increase of Cu(II) concentration. Our findings suggest that it is necessary to consider the complexation between GAT and coexisting metal cations in evaluating its transport in soils rich in different iron minerals.

Roles of dissolved humic acid and tannic acid in sorption of benzotriazole to a sandy loam soil.

To clarify the role of dissolved organic matter (DOM) in sorption of organic pollutants, batch experiments on effects of two representatives of DOM (dissolved humic acid (HA) and tannic acid (TA)) on sorption of benzotriazole (BTA) to a sandy loam soil were conducted. Both HA and TA promoted BTA sorption to soil. Strong positive correlation between sorbed amount of BTA and DOM confirmed the contribution of cumulative sorption by HA or TA in enhancing BTA binding. TA promoted BTA sorption more obviously than HA by providing more sites. For HA with complex structure composed of heterogeneous fractions, its high molecular weight (>3200 Da) fraction could be preferentially sorbed by soil, and it can enhance BTA sorption more obviously than the low molecular weight fraction. The promoting effect of HA on BTA sorption decreased with pH increasing from 6.5 to 10.5 due to reduced sites and electrostatic repulsion between anionic BTA, HA and soil. Sorption of neutral BTA to soil affected by DOM could be well predicted by a modified Freundlich model with Kd (L kg-1) deviations less than 0.2 log unit.

Effects of fulvic acid and montmorillonite colloids at different concentrations on Cd(II) sorption onto nano-hydroxyapatite.

Natural colloids can influence the binding mechanisms between nano-hydroxyapatite (nHAP) and Cd(II). In this study, the effects of organic and inorganic natural colloids on Cd(II) sorption onto nHAP were compared. Different experimental approaches combined with the additivity model and the Extended-Derjaguin-Landau-Verwey-Overbeek model were used to quantify the distribution of Cd(II) in the systems of nHAP and natural colloid, and the interaction energy between particles. The results showed that both fulvic acid (FA) and montmorillonite colloid (MONT) had the promotion and inhibition effects on Cd(II) sorption onto nHAP. Coexistence of FA or MONT could stabilize nHAP particles. FA could adsorb onto nHAP particle surface via carboxylic and phenolic groups, which increased nHAP electronegativity and formed steric resistance effect. Coexistence of MONT mainly increased nHAP electronegativity. These effects prevented the reduction of the specific surface area of nHAP particles and increased the Cd(II) sorption onto nHAP. However, the inhibition effect on Cd(II) sorption was enhanced with increasing concentration of FA or MONT because more soluble FA-Cd or suspended MONT-Cd complexes formed in the system. In nHAP-FA-Cd systems, the Cd(II) sorption onto FA was well predicted but that onto solid phase was underestimated by the additivity model. In nHAP-MONT-Cd systems, Cd(II) sorbed onto mixtures of nHAP and MONT was well described by the additive model. The findings of this study can help to understand the fate of Cd(II) in natural water and soil.

Sorption of ionic and neutral species of pharmaceuticals to loessial soil amended with biochars.

To clarify the impact of biochar amendment on soil sorption for coexisting pharmaceuticals, wheat straw-derived biochars pyrolyzed at 300 and 700 °C (labeled as WS300 and WS700, respectively) were prepared. Batch experiments on ketoprofen (KTP), atenolol (ATL) and carbamazepine (CBZ) sorption to biochars, loessial soil and biochar-amended soils were conducted. The results indicated that sorption affinity of different species of pharmaceuticals to WS300 and WS700 was in the order of cationic ATL > neutral CBZ > anionic KTP. Cationic ATL had the highest sorption to biochars due to electrostatic attraction. Coexisting ATL, CBZ and KTP competed for the shared adsorption sites on carbonized phase of biochars, and π-π interactions were proposed to be the main sorption mechanism. Sorption coefficients (Kd) and nonlinearity of ATL, CBZ and KTP to soil increased when biochar was added (5% by weight), especially for WS700 with higher specific surface area. Kd values of the three pharmaceuticals to WS700-amended soil in either single solute or bisolute system were one to two orders of magnitude higher than those to soil, indicating the promoting role of WS700 in sorption of coexisting pharmaceuticals in soil. The study demonstrated the enhanced and competitive sorption of ionic and neutral species of pharmaceuticals to soil amended with biochars, which is helpful in designing biochar as effective sorbents for immobilization of pharmaceuticals in soil remediation.