Iron-containing nanominerals for sustainable phosphate management: A comprehensive review and future perspectives.

Adsorption, which is a quick and effective method for phosphate management, can effectively address the crisis of phosphorus mineral resources and control eutrophication. Phosphate management systems typically use iron-containing nanominerals (ICNs) with large surface areas and high activity, as well as modified ICNs (mICNs). This paper comprehensively reviews phosphate management by ICNs and mICNs in different water environments. mICNs have a higher affinity for phosphates than ICNs. Phosphate adsorption on ICNs and mICNs occurs through mechanisms such as surface complexation, surface precipitation, electrostatic ligand exchange, and electrostatic attraction. Ionic strength influences phosphate adsorption by changing the surface potential and isoelectric point of ICNs and mICNs. Anions exhibit inhibitory effects on ICNs and mICNs in phosphate adsorption, while cations display a promoting effect. More importantly, high concentrations and molecular weights of natural organic matter can inhibit phosphate adsorption by ICNs and mICNs. Sodium hydroxide has high regeneration capability for ICNs and mICNs. Compared to ICNs with high crystallinity, those with low crystallinity are less likely to desorb. ICNs and mICNs can effectively manage municipal wastewater, eutrophic seawater, and eutrophic lakes. Adsorption of ICNs and mICNs saturated with phosphate can be used as fertilizers in agricultural production. Notably, mICNs and ICNs have positive and negative effects on microorganisms and aquatic organisms in soil. Finally, this study introduces the following: trends and prospects of machine learning-guided mICN design, novel methods for modified ICNs, mICN regeneration, development of mICNs with high adsorption capacity and selectivity for phosphate, investigation of competing ions in different water environments by mICNs, and trends and prospects of in-depth research on the adsorption mechanism of phosphate by weakly crystalline ferrihydrite. This comprehensive review can provide novel insights into the research on high-performance mICNs for phosphate management in the future.

Electroplating wastewater treatment by in-situ formation of organic anions and inorganic anions intercalated layered double hydroxides.

The electroplating wastewater containing various metal ions was treated by adding sodium dodecyl benzene sulfonate (SDBS) and regulating pH value, and the resulting precipitates were characterized by X-ray diffraction (XRD). The results showed that organic anions intercalated layered double hydroxides (OLDHs) and inorganic anions intercalated layered double hydroxides (ILDHs) were in-situ formed to remove heavy metals during the treatment process. In order to reveal the formation mechanism of the precipitates, SDB- intercalated Ni-Fe OLDHs, NO3- intercalated Ni-Fe ILDHs and Fe3+-DBS complexes were synthsized by co-precipitation at various pH values for comparison. These samples were characterized by XRD, Fourier Transform infrared (FTIR), element analysis as well as the aqueous residual concentrations of Ni2+ and Fe3+ were detected. The results showed that OLDHs with good crystal structures can be formed as pH≤7, while ILDHs began to form at pH = 8. When pH < 7, complexes of Fe3+ and organic anions with the ordered layered structure were formed firstly, and then with increase in pH value, Ni2+ inserted into the solid complex and the OLDHs began to form. However, Ni-Fe ILDHs were not formed when pH ≤ 7. The Ksp (Solubility Product Constant) of OLDHs was calculated to be 3.24 × 10-19 and that of ILDHs was 2.98 × 10-18 at pH = 8, which suggested that OLDHs might be easier to form than ILDHs. The formation process of ILDHs and OLDHs were also simulated through MINTEQ software, and the simulation output verified that OLDHs could be easier to form than ILDHs at pH ≤ 7. Information from this study provides a theoretical basis for effective in-situ formation of OLDHs in wastewater treatment.

Environmental implication of geochemical record in the Arctic Ny-Ålesund glacial sediment, Svalbard (Norway).

Glacial sediments as an important end member of the global dust system, could indicate changes in global climate, aerosols sources, ocean elements, and productivity. With global warming, ice caps shrinking and glaciers retreat at high latitudes have attracted concern. To understand the response of glacier to environment and climate in modern high latitude ice-marginal environments, this paper investigated glacial sediments in the Ny-Ålesund region of the Arctic and clarified the response of polar environmental to global changes through geochemical characteristics of glacial sediments. The results showed that: 1) main factors affecting the elements distribution of the Ny-Ålesund glacial sediments were thought as soil formation, bedrock and weathering, and biological activity; 2) variations of SiO2/Al2O3 and SiO2/Al2O3 + Fe2O3, indicating low weathering of the soil. The ratio of Na2O/K2O indicating a weak chemical weathering, was negatively correlated to the CIA. With the average CIA of Ny-Ålesund glacial sediments for main minerals of quartz, feldspar, and muscovite as well as dolomite and calcite 50.13, which implied glacial sediments at the early stage of chemical weathering and depletion of Ca and Na; 3) the separating effect of stones and soils by stone circle formation due to thermal conductivity and frost heave makes sediments in stone circle have lower chemical weathering with only two main minerals, albite and quartz; 4) changes of carbonate content in sediments with glacier front retreating in different period implied that weathering rate of calcite averagely reached an estimate of 0.0792%wt/year in glacier A. The succession of vegetation made biological weathering become an important driving force for carbonate leaching from glacial sediments. These results and data provide scientifically significant archive for future global change studies.

Adsorption characteristics of assembled and unassembled Ni/Cr layered double hydroxides towards methyl orange.

The lamella aggregation state of layered double hydroxides (LDHs) may affect their sorption capacity for organic compounds. The dried LDH samples (Ni/Cr LDH-FA-D and Ni/Cr LDH-H2O-D) and the undried samples (Ni/Cr LDH-FA-W and Ni/Cr LDH-H2O-W) were flexibly prepared by a co-precipitation method in formamide (FA) and water, respectively. The results of X-ray diffraction (XRD) and transmission electron microscope (TEM) showed that the undried LDHs were unassembled, which had no the stacking layers but had a pseudohexagonal nanosheet lamella structure. And the unassembled LDH layers can be assembled again during the dry process. Ni/Cr LDH-FA-W and Ni/Cr LDH-H2O-W showed much greater adsorption capacities towards methyl orange (MO) than Ni/Cr LDH-FA-D and Ni/Cr LDH-H2O-D, as well as shorter time to reach equilibrium. The maximum adsorption capacity of MO could be calculated to 806 mg/g and 740 mg/g for Ni/Cr LDH-FA-W and Ni/Cr LDH-H2O-W by Langmuir-type simulation. The greater adsorption capacities of unassembled LDH could be attributed to the loosen structure and much more exposed adsorption sites. It could be concluded that unassembled LDHs were an effective and conducive preparation pathway for the exploration of the adsorption sites of LDHs.

Bentonite-supported nano zero-valent iron composite as a green catalyst for bisphenol A degradation: Preparation, performance, and mechanism of action.

Bisphenol A (BPA) is a toxic environmental pollutant commonly found in wastewater. Using non-toxic materials and eco-friendly technology to remove this pollutant from wastewater presents multiple advantages. Treatment of wastewater with clay minerals has received growing interest because of the environment friendliness of these materials. Bentonite is a 2:1 layered phyllosilicate clay mineral that can support nano-metal catalysts. It can prevent the agglomeration of nano-metal catalysts and improve their activity. In this article, a green catalytic nano zero-valent iron/bentonite composite material (NZVI@bentonite) was synthesized via liquid-phase reduction. The average size of NZVI was approximately 40-50 nm. Good dispersion and low aggregation were observed when NZVI was loaded on the surface or embedded into the nanosheets of bentonite. Degradation of BPA, a harmful contaminant widely found in wastewater at relatively high levels, by NZVI@bentonite was then investigated and compared with that by pristine NZVI through batch Fenton-like reaction experiments. Compared with pristine NZVI and bentonite alone, the NZVI@bentonite showed a higher BPA degradation ratio and offered highly effective BPA degradation up to 450 mg/g in wastewater under optimum operating conditions. Adsorption coupled with the Fenton-like reaction was responsible for BPA degradation by NZVI@bentonite. This work extends the application of NZVI@bentonite as an effective green catalyst for BPA degradation in aqueous environments.

Use of autoclaved aerated concrete particles for simultaneous removal of nitrogen and phosphorus as filter media from domestic wastewater.

ABSTRACT In this study, autoclaved aerated concrete particles (AACPs) from construction waste were used to simultaneously remove phosphorus and nitrogen in biological aerated filters (BAFs). The effects of air/water (A/W) ratio on the removal performance of phosphorus (PO4 3-), total organic carbon, total nitrogen (TN), and ammonia nitrogen were investigated. Results showed that AACP BAF was more efficient than commercially available ceramsite (CAC) BAF. For example, the removal rates of TN with AACP and CAC were 45.96% and 15.64%, respectively, and those of PO4 3- with AACP and CAC were 72.45% and 33.97%, respectively, at the A/W ratio of 3:1. Different characterization methods were utilized to evaluate the surface shape, elemental compostion, and internal and surface structure of AACP. The interconnectivity and uniformity of pores and the rough surface of AACP were found to be suitable for the growth of microbial biofilm. In addition, the growth of internal pores in AACP promoted the removal of phosphorus and nitrogen. The surface of used AACP contained a small amount of irregular crystals and was covered with a layer of aggregates, which were characterized as hydroxyapatite [HAP, Ca5(OH)(PO4)3]. The formation of HAP as a final byproduct confirmed the successful removal of phosphorus. Therefore, construction wastes, such as AACPs, could be recycled and utilized as a promising biofilter media for excellent wastewater treatment.

Investigation of mineralogical and bacteria diversity in Nanxi River affected by acid mine drainage from the closed coal mine: Implications for characterizing natural attenuation process.

Due to the supply-side reform and environmental protection in China, many small coal mines have been closed since 2015. However, acid mine drainage from these coal mines are continuously discharging into many rural creeks, which requires the systematical investigation on the variations of geochemical and environmental biological aspects in these water systems. In this study, from a classic acid mine drainage (AMD) from a closed coal mine of Hunan, China, various sediments and water samples in different sections were collected and analyzed. According to the corresponding Mineralogical and simple bacterial characteristics analysis (16S rRNA gene sequencing), the main findings were: 1) Secondary iron-containing minerals gradually transited from Gr(CO32-) (green rust), Sh (schwertmannite) to Akg (Akaganeite) and more stable Gt (Goethite); 2) compared to the pristine sediment, these minerals decreased the acid-neutralizing capacity and cation exchange capacity (CEC) of sediments; 3) Proteobacteria and Firmicutes were the dominant phyla and the obvious variation of Firmicutes species was observed in the creek affected by AMD, which probably could been a biological index to diagnose the natural attenuation of AMD. These results could be greatly significant to understand typical variations of creek attenuation and bacterial community in the presence of high metal and sulfate concentration.

Formation, characteristics, and applications of environmentally persistent free radicals in biochars: A review.

Due to abundant biomass and eco-friendliness, biochar is exemplified as one of the most promising candidates to mediate the degradation of environmental contaminants. Recently, environmentally persistent free radicals (EPFRs) have been detected in biochars, which can activate S2O82- or H2O2 to generate reactive oxygen species for effective degradation of organic and inorganic contaminants. Comprehending the formation mechanisms of EPFRs in biochars and their interactions with contaminants is indispensable to further develop their environmental applications, e.g., direct and indirect EPFR-mediated removal of organics/inorganics by biochars. With reference to the information of EPFRs in environmental matrices, this article critically reviews the formation mechanisms, characteristics, interactions, and environmental applications of EPFRs in biochars. Synthesis conditions and loading of metals/organics are considered as key parameters controlling their concentrations, types, and activities. This review provides new and important insights into the fate and emerging applications of surface-bound EPFRs in biochars.

Transformation of functional groups and environmentally persistent free radicals in hydrothermal carbonisation of lignin.

In this study, lignin was selected as the main component of waste biomass to synthesise carbonaceous adsorbents with environmentally persistent free radicals (EPFRs) through hydrothermal carbonisation (HTC) under different conditions. The HTC method with Fe(III) doping was superior for promoting dehydration and decarboxylation of lignin hydrochar than that with HTC Cu(II) doping. The deconstruction of oxygen-containing groups of lignin was reduced while esterification was enhanced by Fe(III). The Fe(III) addition was conducive to the formation of EPFRs as carbon-centred radicals with an adjacent oxygen atom and oxygen-centred radicals. A comparison of lignin with cellulose and d-xylose suggests that the formed EPFRs on lignin hydrochar were derived from their phenolic hydroxyl groups. A high removal efficiency of bisphenol A by lignin hydrochar was observed owing to oxygen-centred radicals, which activated H2O2 to produce OH. These results will facilitate the design and application of novel hydrochar materials with EPFRs.

Multivariate linear regression model for source apportionment and health risk assessment of heavy metals from different environmental media.

The study evaluated source apportionment of heavy metals in vegetable samples from the potential sources of fertilizer, water and soil samples collected along the Changjiang River delta in China. The results showed that 25.72% of vegetable samples (Brassica chinensis L.) containing Pb, and Cd, Cu, Hg and Zn at relatively serious levels were from soil. Combined with principle component analysis (PCA) and cluster analysis (CA), the results of the spatial distribution of heavy metals in different environmental media indicated that fertilizer, water and soil were the main sources of heavy metals in vegetables. The results of multivariate linear regression (MLR) using partition indexes (P) showed that fertilizer contributed to 38.5%, 40.56%, 46.01%, 53.34% and 65.25% of As, Cd, Cu, Pb and Zn contents in vegetables, respectively. In contrast, 44.58% of As, 32.57% of Hg and 32.83% of Pb in vegetables came from soil and 42.78% of Cd and 66.97% of Hg contents in vegetables came from the irrigation water. The results of PCA and CA verified that MLR using P was suitable for determining source apportionment in a vegetable. A health risk assessment was performed; As, Cd and Pb contributed to more than 75% of the total hazard quotient (THQ) values and total carcinogenic risk values (Risktotal) for adults and children through oral ingestion. More than 70% of the estimated THQ and Risktotal is contributed by water and fertilizer. Therefore, it is necessary to increase efforts in screening limits/levels of heavy metals in fertilizer and irrigation water and prioritize appropriate pollution management strategies.

Cadmium transfer from contaminated soils to the human body through rice consumption in southern Jiangsu Province, China.

Consumption of crops grown in cadmium-contaminated soils is an important Cd exposure route to humans. The present study utilizes statistical analysis and in vitro digestion experiments to uncover the transfer processes of Cd from soils to the human body through rice consumption. Here, a model was created to predict the levels of bioaccessible Cd in rice grains using phytoavailable Cd quantities in the soil. During the in vitro digestion, a relatively constant ratio between the total and bioaccessible Cd in rice was observed. About 14.89% of Cd in soils was found to be transferred into rice grains and up to 3.19% could be transferred from rice grains to the human body. This model was able to sufficiently predict rice grain cadmium concentrations based on CaCl2 extracted zinc and cadmium concentrations in soils (R2 = 0.862). The bioaccessible Cd concentration in rice grains was also able to be predicted using CaCl2 extracted cadmium from soil (R2 = 0.892). The models established in this study demonstrated that CaCl2 is a suitable indicator of total rice Cd concentrations and bioaccessible rice grain Cd concentrations. The chain model approach proposed in this study can be used for the fast and accurate evaluation of human Cd exposure through rice consumption based on the soil conditions in contaminated regions.

Sorption of iodide (I-) from aqueous solution using Mg/Al layered double hydroxides.

In this article, the authors report the adsorption of iodide by Mg/Al LDHs and thermally activated LDH materials in laboratory scale batch experiments. The optimal Mg/Al cation ratio was 3:1while the percentage iodide uptake increased with increasing adsorbent dose up to 1g/20mL of solution. The effect of initial iodide concentration was investigated using the Langmuir and Freundlich adsorption isotherm models, while the pseudo second order kinetic model appeared to provide the best fit for the experimental data. High iodide uptake of over 80% could be achieved without completely eliminating dissolved or atmospheric carbonate and leaching of 131I from LDHs did not appear to be a significant problem over the period of 28days investigated. These results demonstrate that LDHs, which are already commercially available in large quantities, are a technology that shows considerable promise for the removal of radioiodine from aqueous solution.

Visible and near-infrared spectroscopic comparison of five phyllosilicate mineral samples.

Portable visible and near-infrared (vis/NIR) spectroscopy was used to characterize and differentiate the five phyllosilicate minerals and relate the bands to the mineral structure. The feature band at 2160-2170nm (4600-4630cm-1) has been assigned to the high presence of Al-OH and is described as typical of dioctahedral phyllosilicate with OH groups coordinated around Al, and the feature occurred near 2322nm is considered to be due to a combination of the OH stretch with the MgOH deformation mode, which is a typical of trioctahedral phyllosilicates. The presence of the bands 1400 and 1900nm in vis/NIR spectrum indicated that some water is present in this sample. The absence of a 1900nm band but the presence of a 1400nm band indicates that only OH is present. Moreover, the significant differences between these five minerals were observed by the portable vis/NIR spectroscopy. The results show a potential for the application of vis/NIR spectroscopy in the identification and quantification of these minerals in the field. Further, such analysis can also provide important constraints on the nature of putative global and local-scale mineralogical transitions on Mars.

Infrared and Raman spectroscopic characterizations on new Fe sulphoarsenate hilarionite (Fe2((III))(SO4)(AsO4)(OH)·6H2O): Implications for arsenic mineralogy in supergene environment of mine area.

Hilarionite (Fe2 (SO4)(AsO4)(OH)·6H2O) is a new Fe sulphoarsenates mineral, which recently is found in the famous Lavrion ore district, Atliki Prefecture, Greece. The spectroscopic study of hilarionite enriches the data of arsenic mineralogy in supergene environment of a mine area. The infrared and Raman means are used to characterize the molecular structure of this mineral. The IR bands at 875 and 905cm(-1) are assigned to the antisymmetric stretching vibrations of AsO4(3-). The IR bands at 1021, 1086 and 1136cm(-1) correspond to the possible antisymmetric and symmetric stretching vibrations of SO4(2-). The Raman bands at 807, 843 and 875cm(-1) clearly show that arsenate components in the mineral structure, which are assigned to the symmetric stretching vibrations (ν1) of AsO4(3-) (807 and 843cm(-1)) and the antisymmetric vibration (ν3) (875cm(-1)). IR bands provide more sulfate information than Raman, which can be used as the basis to distinguish hilarionite from kankite. The powder XRD data shows that hilarionite has obvious differences with the mineral structure of kankite. The thermoanalysis and SEM-EDX results show that hilarionite has more sulfate than arsenate.

Remediation of Cr (VI) by inorganic-organic clay.

Application of inorganic-organic clays (IOCs) for the remediation of hexavalent chromium (Cr (VI)) and the effect of bisphenol-A (BPA) were investigated. IOCs were better adsorbents for the removal of Cr (VI) than organoclay. Solution pH significantly affected the surface charge of IOCs and speciation of Cr in the solution; hence, the adsorption of Cr onto IOCs. Pseudo-second order model and Langmuir model were the best fit for the kinetics and equilibrium data, indicating chemisorption and formation of monolayer on homogenous adsorption sites, respectively. Cr (VI) adsorption by IOCs was driven by electrostatic interactions between positively charged IOC surfaces and HCrO4- anions. The IOC adsorption capacity for Cr (VI) correlates with the amount of loosely held ODTMA on the external surface of the clay. Involvement of an anion-exchange reaction was suggested in which the counter halide ions of the cationic surfactants were replaced by HCrO4- anions. Cr (VI) adsorption was not affected by the presence of BPA in the medium and two mechanisms for the adsorption of BPA and Cr (VI) were suggested. Partial reduction of Cr (VI) to Cr (III) was observed on the surface of IOC and the reducing agent responsible was suggested to be the Fe (II) in montmorillonite.

Leaching of iodide (I(-)) and iodate (IO3(-)) anions from synthetic layered double hydroxide materials.

Several studies have previously demonstrated that layered double hydroxides (LDHs) show considerable potential for the adsorption of radioiodine from aqueous solution; however, few studies have demonstrated that these materials are able to store radioactive (131)I for an acceptable period. The leaching of iodide (I(-)) and iodate (IO3(-)) form Mg/Al LDHs has been carried out. Contact time appeared to be a more significant variable for the leaching of iodate (IO3(-)) compared to that of iodide (I(-)). Experimental results are fitted to the pseudo second order model, suggesting that diffusion is likely to be the rate-limiting step. The presence of carbonate in the leaching solution appeared to significantly increase the leaching of iodide (I(-)) as did the presence of chloride to a lesser extent. The maximum amount of iodate (IO3(-)) leached using ultrapure water as the leaching solution was 21% of the iodate (IO3(-)) originally present. The corresponding result for iodide (I(-)) was even lower at 3%.

Environmental applications of inorganic-organic clays for recalcitrant organic pollutants removal: Bisphenol A.

Bisphenol-A (BPA) adsorption onto inorganic-organic clays (IOCs) was investigated. For this purpose, IOCs synthesised using octadecyltrimethylammonium bromide (ODTMA, organic modifier) and hydroxy aluminium (Al13, inorganic modifier) were used. Three intercalation methods were employed with varying ODTMA concentration in the synthesis of IOCs. Molecular interactions of clay surfaces with ODTMA and Al13 and their arrangements within the interlayers were determined using Fourier transform infrared spectroscopy (FTIR). Surface area and porous structure of IOCs were determined by applying Brunauer, Emmett, and Teller (BET) method to N2 adsorption-desorption isotherms. Surface area decreased upon ODTMA intercalation while it increased with Al13 pillaring. As a result, BET specific surface area of IOCs was considerably higher than those of organoclays. Initial concentration of BPA, contact time and adsorbent dose significantly affected BPA adsorption into IOCs. Pseudo-second order kinetics model is the best fit for BPA adsorption into IOCs. Both Langmuir and Freundlich adsorption isotherms were applicable for BPA adsorption (R(2)>0.91) for IOCs. Langmuir maximum adsorption capacity for IOCs was as high as 109.89mgg(-1) and it was closely related to the loaded ODTMA amount into the clay. Hydrophobic interactions between long alkyl chains of ODTMA and BPA are responsible for BPA adsorption into IOCs.

Vibrational spectroscopic characterization of mudstones in a hydrocarbon-bearing depression, South China Sea: Implications for thermal maturity evaluation.

A better understanding of mineral transformations in sedimentary rocks and the controls on thermal maturity have become essential in the petroleum exploration industry in recent years. The Fushan Depression is an important hydrocarbon-bearing depression in South China Sea, which can be subdivided into three structural zones: the western, central and eastern zones. In this study, a series of mudstone samples selected from 13 drilling cores with depths ranging from 2100 to 3800 m were studied using infrared reflectance spectroscopy and X-Ray Powder Diffraction (XRD) methods. And another 10 samples have been chosen for vitrinite reflectance measurement so as to investigate the ability of using infrared spectroscopy for thermal maturity evaluations. The infrared spectra results show that quartz and silicates (e.g. illite, kaolinite, smectite) are the dominant minerals in all samples. The semi-quantitative XRD analysis reveals a clear trend in illite content as the eastern zone (mean 80.81%)>the western zone (mean 73.52%)>the central zone (mean 55.04%) as well as a contrary trend in kaolinite content. This study documents that the peak height and position of Si-O antisymmetric stretching bands at ~1025 cm(-1) and ~1000 cm(-1) have a significant correlation with the degree of kaolinite illitization, suggesting that the utility of infrared spectroscopy is a valuable tool for the study of thermal maturity in sedimentary basins. The infrared spectra and XRD results together with vitrinite reflectance data indicate that the thermal maturity in the eastern zone is anomalously high, followed by the western zone, and that in the central zone is lowest. The igneous intrusion in the eastern zone has a significant impact on thermal maturation, resulting in high degree of kaolinite illitization. By contrast, the abundance in kaolinite in the central zone represents relatively low degree of kaolinite illitization, which should be attributed to shallow burial depth.

Structural and thermal properties of inorganic-organic montmorillonite: Implications for their potential environmental applications.

Inorganic-organic clays (IOCs), clays intercalated with both organic cations such as cationic surfactants and inorganic cations such as metal hydroxy polycations have the properties of both organic and pillared clays, and thereby the ability to remove both inorganic and organic contaminants from water simultaneously. In this study, IOCs were synthesised using three different methods with different surfactant concentrations. Octadecyltrimethylammonium bromide (ODTMA) and hydroxy aluminium ([Al13O4(OH)24(H2O)12](7+) or Al13) are used as the organic and inorganic modifiers (intercalation agents). According to the results, the interlayer distance, the surfactant loading amount and the Al/Si ratio of IOCs strictly depend on the intercalation method and the intercalation agent ratio. Interlayers of IOCs synthesised by intercalating ODTMA before Al13 and IOCs synthesised by simultaneous intercalation of ODTMA and Al13 were increased with increasing the ODTMA concentration used in the synthesis procedure and comparatively high loading amounts could be observed in them. In contrast, Al/Si decreased with increasing ODTMA concentration in these two types of IOCs. The results suggest that Al-pillars can be fixed within the interlayers by calcination and any increment in the amount of ODTMA used in the synthesis procedure did not affect the interlayer distance of the IOCs. Overall the study provides valuable insights into the structure and properties of the IOCs and their potential environmental applications.

Combined (1)H NMR and LSER study for the compound-specific interactions between organic contaminants and organobentonites.

The compound-specific mechanisms for the sorption of organic contaminants onto cetyltrimethylammonium-saturated bentonite (i.e., CTMA-Bentonite) in water were evaluated by (1)H NMR study and Linear Solvation Energy Relationship (LSER) approach. In (1)H NMR study, comparing with pure CTMAB, the up-field shifts of hydrogen peaks for CH2N(+) and CH3N(+) of CTMA(+) in CTMAB-aromatics (1-naphtylamine, aniline and phenol) mixtures are much greater than that in CTMAB-aliphatics (cyclohexanone and cyclohexanol) mixtures. Meanwhile, the peak position of hydrogen on amino- and hydroxyl-groups of aromatic compounds also changes greatly. (1)H NMR data demonstrated the strong molecular interaction between the positive ammonium group of CTMA(+) and the delocalized π-systems of aromatic solutes, whereas the interactions of CTMA(+) with aliphatic compounds having electron-donating groups (such as cyclohexanol and cyclohexanone) or aromatic ring substituted by electron-withdrawing groups (i.e., nitrobenzene) or nonpolar aromatic compounds with single phenyl ring (i.e., toluene) are weak. The derived LSER equation was obtained by a multiple regression of the solid-water sorption coefficients (Kd) of 16 probe solutes upon their solvation parameters, and demonstrates aromatics sorption onto CTMA-Bentonite is concurrently governed by the π-/n-electron pair donor-accepter interaction and the cavity/dispersion interaction, while the predominant mechanism for aliphatic compounds is the cavity/dispersion interaction, consisting with the (1)H NMR results.