Universal Langmuir and Fractal Analysis of High-Resolution Adsorption Isotherms of Argon and Nitrogen on Macroporous Silica.

High-resolution isotherms of argon and nitrogen adsorption on macroporous silica have been simulated with universal Langmuir and fractal models. A four-parameter, fractal universal Langmuir equation is a good fit to the data at low pressures. Standard Gibbs energy changes calculated from equilibrium adsorption coefficients show a series of broad peaks that indicate adsorbate structural transformations as a function of pressure and coverage. The Freundlich equation or mean fractal model is also a good fit to isotherms at low pressures. Pressure-varying fractals are accurate fits to the data. Fractal exponents provide information on adsorbate coverage and surface access. Broad peaks in pressure-varying exponents are indicators of adsorbate structure. From adsorptive gas amounts, mean and pressure-varying fractal exponents provide details of adsorbate fractal dimensions and surface roughness. Both Ar and N2 adsorption cause increases in mean surface roughness when compared with pure silica. Surface roughness fluctuations from pressure-dependent adsorptive gas fractal dimensions are associated with adsorbate structure. At one trough, the surface is smooth and is linked to close-packed Ar or N2. For Ar adsorption at 87 K, this structure is a complete monolayer (1.00(4)), while for Ar (77 K), 1.15(4) layers and for N2 (87 K), 2.02(10) layers. The universal Langmuir specific area of the silica is 10.1(4) m2 g-1. Pressure- and coverage-dependent adsorbate structures range from filling defects and holes on the surface to cluster formation to adsorbed Ar or N2 evenly distributed or packed across the surface. The Ar (87 K) isotherm is most sensitive to adsorbate structural transformations.

Pressure-varying Langmuir parameters and stepped nitrogen adsorption on alumina and silica.

Insights into surface structures and thermodynamics are provided for nitrogen adsorption on two nonporous alumina adsorbents and two macroporous silica adsorbents by modelling high-resolution data using the simple Langmuir isotherm equation combined with pressure-varying flexible least squares. The fitted parameters, maximum adsorption capacity and standard Gibbs energy change for each adsorbent show multiple steps that are assumed to be indicative of transitions to different complete monolayer and multilayer structures. Pressure-varying N2 cross-sectional areas for three of the adsorbents are calculated by assuming that one of the steps is the Brunauer-Emmett-Teller monolayer with molecular area 16.2 Å2. The silica with added octyldimethylsilyl groups has pressure-varying parameter profiles that differ from the other adsorbents and here the N2 cross-sectional area is assumed to be 21.3 Å2 to ensure consistency with the literature surface area. Seven monolayers and multilayers are identified across the four adsorbents, and corresponding molecular areas compare favourably with reported values. At low pressures, adsorption occurs at the strongest sites, and is localised and dependent on surface heterogeneity and topography. Up to five complete, two-dimensional lattice structures are apparent in the mid-pressure ranges. At high pressures, multilayers and liquefaction points are observed and are independent of surface composition and heterogeneity.

Sequential extraction of labile and recalcitrant fractions of soil organic matter: A case study focusing on antimony (Sb) in humic acids, fulvic acids and humin fractions of long-term aged contaminated soils.

Soil organic matter (SOM) plays a key role in environmental chemistry of macro and micro nutrients as well as heavy metal (loids). In this research, a modified sequential extraction scheme was used to isolate labile and recalcitrant SOM from organic rich soils after 18 months of ageing with antimony. Humic substances were extracted with a mixture of 0.5 M sodium hydroxide +0.1 M sodium pyrophosphate solution from soils. Then soils deprived of humic substances were sequentially subjected to extraction with glycerol, citric acid, pre-treated with acid and extracted with boiling alkali mixture. The humic acids (HA) and fulvic acids (FA) of isolated SOM fractions were separated and HAs been characterized using FTIR, 1H NMR, and UV-VIS. Acid-alkali treatment of the most recalcitrant SOM fraction (A1-ROM) led to the extraction of sparingly soluble, highly aromatic compound with considerable amounts of N (44% of the extractable N), possibly due to the breakdown of bounds between aromatic rings and amine functional groups. Nevertheless, the highest content of C and TOC was associated with the glycerol extractable SOM. Substantial amounts of Fe and Al were extracted with glycerol, resulting in a dramatic rise of Sb in SOM extracts. The largest increase (60%) in Sb concentrations was observed after the removal of Fe with citric acid. The humic substances (HS) were responsible for 63% of extractable Sb, whereas even after exhaustive alkali extractions 22% of the total Sb remained in the residual humin fraction. Within the HS fraction, 95% of antimony was associated with the low molecular weight FAs. Antimony concentrations in organic fractions correlated significantly with TOC and N contents, possibly due to the role of amine functional groups in Sb complexation. The results of this research highlight the importance of Fe-Al-SOM bridging and humin fraction in sequestration of Sb in recalcitrant SOM pools.

The influence of different antimony (Sb) compounds and ageing on bioavailability and fractionation of antimony in two dissimilar soils.

Assessing the bioavailability of various Sb substances plays a crucial role in human health and the ecological risk assessment of contaminated soils. However, fate, behaviour and bioavailability of different Sb compounds in soils are insufficiently known. Therefore, in this present study, the effects of soil properties and ageing on bioavailability of four different Sb compounds (C8H4K2O12Sb2, Sb2S3, Sb2O3 and Sb2O3 nanoparticles) were evaluated during 120 days ageing time. A black soil (BS) with approximately 12% organic matter (OM) and a red soil (RS) with less than 1% OM were amended with 1000 mg Sb kg-1 of different Sb compounds and subjected to single extractions with distilled (DI) water, 2M HNO3, Simplified Bioaccessibility Extraction Test (SBET) and a modified Community Bureau of Reference (BCR) sequential extraction method. The results revealed that there are substantial variations in dissolution rate of various Sb sources, depending upon soil type and Sb compound. The amounts of DI water extractability of Sb during the incubation time varied between <1% and 2%, whereas HNO3 extractable fractions and Sb bioaccessibility at the end of ageing time ranged between about 1%-3% and <1%-9% of the total Sb, with maximum bioaccessibility observed in BS contaminated with C8H4K2O12Sb2. The residual and labile fractions accounted for 77-93% and 0.1-4% of the total Sb, respectively, indicating that Sb is mostly associated with recalcitrant fractions of the soils. The results of single and sequential extraction studies revealed that source of Sb, ageing time and soil properties can greatly affect the bioavailability of Sb in soils. The findings of this research provide a deeper understanding of the potential risks associated with Sb compounds and highlights the role of site-specific considerations for improving the robustness of toxicity guidelines and long-term management of Sb contaminated sites.

Charge density analysis of two polymorphs of antimony(III) oxide.

High-resolution X-ray diffraction data have been collected on the cubic polymorph of antimony(III) oxide (senarmontite) to determine the charge distribution in the crystal. The results are in quantitative agreement with crystal Hartree-Fock calculations for this polymorph, and have been compared with theoretical calculations on the orthorhombic polymorph (valentinite). Information about the nature of bonding and relative bond strengths in the two polymorphs has been extracted in a straightforward manner via topological analysis of the electron density. All the close contacts in both polymorphs are found to be similar in nature based on the value of the Laplacian, the magnitude of the electron density and the local energy density at the bond critical points, and these characterise the observed interactions as substantially polar covalent, similar to molecular calculation results on Si-O and Ge-O. Electrostatic potential isosurfaces reveal the octopolar nature of this function for senarmontite, and shed light on the observed packing arrangement of Sb4O6 molecules in the crystal.