Assessing sorption of fluoroquinolone antibiotics in soils from a Kd compilation based on pure organic and mineral components.

The presence of fluoroquinolone (FQ) antibiotics in soils may cause a threat to human health due to overexposure and the generation of antibiotic resistance genes. Understanding their sorption behavior in soils is important to predict subsequent FQ (bio) availability. Here, FQ sorption in pure soil organic (i.e., humic substances) and mineral (i.e., metal oxides; phyllosilicates) components is evaluated through a solid-liquid distribution coefficient (Kd (FQ)) dataset consisting of 243 entries originated from 80 different studies, to elucidate their respective contribution to the overall Kd (FQ) in bulk soils. First, different factors affecting FQ sorption and desorption in each of these soil phases are critically discussed. The strong role of pH in Kd (FQ), due to the simultaneous effect on both FQ speciation and surface charge changes, encouraged the derivation of normalized sorption coefficients for the cationic, zwitterionic and anionic FQ species in humic substances and in different phyllosilicates. Kd (FQ) in metal oxides revealed a key role of metal nature and material specific surface area due to complexation sorption mechanisms at neutral pH. Cumulative distribution functions (CDF) were applied to each dataset to establish a sorption affinity range for each phase and to derive best estimate Kd (FQ) values for those materials where normalized sorption coefficients to FQ species were unavailable. The data analysis conducted in the different soil phases set the basis for a Kd (FQ) prediction model, which combined the respective sorption affinity of each phase for FQ and phase abundance in soil to estimate Kd (FQ) in bulk soils. The model was subsequently validated with sorption data in well characterized soils compiled from the literature.

The important role of surface hydroxyl groups in aluminum activation during phyllosilicate mineral acidification.

Phyllosilicate minerals are the important components in soils and an important source of activated aluminum (Al) during soil acidification. However, the mechanisms for Al activation in phyllosilicate minerals were not understood well. In this paper, the effect of phyllosilicate surface hydroxyl groups on Al activation during acidification was studied after the minerals were modified with inorganic and organic materials. After modification of kaolinite, montmorillonite, and illite with fulvic acid (FA-), iron oxide (Fe-), Fe combined with FA (Fe-FA-), and siloxane (Si-O-), the interlayer spaces were altered. For instance, when modified with Fe, Fe entered the interlayer spaces of kaolinite and montmorillonite and changed the interlayer spaces of both minerals but did not affect that of illite. Also, the other modification methods had significant effects on the interlayer space of montmorillonite but not on kaolinite and illite. It was observed that all the modification strategies inhibited Al activation during acidification by reducing the number of hydroxyl groups on the mineral surfaces and inhibiting protonation reactions between H+ and hydroxyl groups. Nevertheless, the inhibition effect varies with the type of phyllosilicate mineral. For kaolinite (Kao), the inhibition effect of the different modification methods on Al activation during acidification followed: Fe-FA-Kao > Fe-Kao > Si-O-Kao > FA-Kao. Additionally, for montmorillonite (Mon), the inhibition effect was in the order: Si-O-Mon > Fe-Mon > Fe-FA-Mon > FA-Mon, while for illite, it was: Fe-illite > Si-O-illite ≈ Fe-FA-illite > FA-illite. Thus, the hydroxyl groups on the surfaces and edges of phyllosilicate minerals play an important role in the activation of Al from the mineral structure. Also, the protonation of hydroxyl groups may be the first step during Al activation in these minerals. The results of this study can serve as a reference for the development of new technologies to inhibit soil acidification and Al activation.

Solid phase characterization and transformation of illite mineral with gas-phase ammonia treatment.

In situ remediation applications of ammonia (NH3) gas have potential for sequestration of subsurface contamination. Ammonia gas injections initially increase the pore water pH leading to mineral dissolution followed by formation of secondary precipitates as the pH is neutralized. However, there is a lack of understanding of fundamental alteration processes due to NH3 treatment. In these batch studies, phyllosilicate minerals (illite and montmorillonite) were exposed to NH3 gas with subsequent aeration to simulate in situ remediation. Following treatments, solids were characterized using a variety of techniques, including X-ray diffraction, N2 adsorption-desorption analysis for surface area, Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), and microscopy methods to investigate physicochemical transformations. Results indicate that, at high pH, the clays are altered as observed by differences in morphology and particle size via microscopy. However, the two clays interact differently with NH3. While montmorillonite interlayers collapsed due to intercalation, illite layers were unaffected as confirmed by FTIR analysis. Further, structural changes in silicate ([SiO4]n-) and aluminol (Al-OH) groups were identified by NMR and FTIR. This research showed that mineral alteration processes occur during and after NH3 gas treatment which may be used to remove radionuclides from the aqueous phase through sorption, co-precipitation, and coating with secondary phyllosilicate alteration products.

Phyllosilicate derived catalysts for efficient conversion of lignocellulosic derived biomass to biodiesel: A review.

The efforts have been made to review phyllosilicate derived (clay-based) heterogeneous catalysts for biodiesel production via lignocellulose derived feedstocks. These catalysts have many practical and potential applications in green catalysis. Phyllosilicate derived heterogeneous catalysts (modified via any of these approaches like acid activated clays, ion exchanged clays and layered double hydroxides) exhibits excellent catalytic activity for producing cost effective and high yield biodiesel. The combination of different protocols (intercalated catalysts, ion exchanged catalysts, acidic activated clay catalysts, clay-supported catalysts, composites and hybrids, pillared interlayer clay catalysts, and hierarchically structured catalysts) was implemented so as to achieve the synergetic effects (acidic-basic) in resultant material (catalyst) for efficient conversion of lignocellulose derived feedstock (non-edible oils) to biodiesel. Utilisation of these Phyllosilicate derived catalysts will pave path for future researchers to investigate the cost-effective, accessible and improved approaches in synthesising novel catalysts that could be used for converting lignocellulosic biomass to eco-friendly biodiesel.

Effect of the interaction of fulvic acid with Pb(II) on the distribution of Pb(II) between solid and liquid phases of four minerals.

Lead (Pb) is one of the top metal pollutants worldwide, and its distribution between liquid and solid phases of soils is strongly controlled by its adsorption on minerals, organic matter, and their composites. This paper presented the effect of fulvic acid (FA) coexistence on the distribution of Pb(II) at the solid-liquid interface of four minerals, which provided reference for how to use humic substances to remove toxic Pb(II) in soils. The free Pb2+ of suspensions, measured by Pb ion selective electrode, was used to characterize the complexation of FA with Pb2+ at various pH. The adsorption isotherms of Pb(II) by montmorillonite, kaolinite, goethite, and gibbsite with and without FA were studied with batch experiments. Results indicated that the free Pb2+ decreased and complexed Pb(II) increased with the increase of FA concentration in Pb(II)-FA solutions, whether the initial concentration of Pb(II) was 0.1 or 1 mM. Pb2+ hydrolysis was low and the free Pb2+ concentration in pure lead solution without FA was generally unchanged with increasing solution pH at pH < 6.0. But free Pb2+ decreased with the increase of pH in the presence of FA, suggesting that the complexation ability of FA with Pb2+ increased with the increase of solution pH. The adsorption of Pb(II) by the minerals without FA followed the order: montmorillonite > kaolinite ≈ goethite > gibbsite at pH5.0. The Pb(II) adsorption by montmorillonite and kaolinite significantly enhanced with 1 g/L FA, while significantly inhibited with 3 g/L FA at low initial Pb(II) concentration. However, the effect of FA on Pb(II) adsorption by montmorillonite was greater than that of kaolinite, which was mainly related to the crystal layer structure, adsorption area, and cation exchange capacity of the minerals. The Pb(II) adsorption by goethite and gibbsite was significantly enhanced by the addition of both 1 g/L and 3 g/L FA, and the enhancement was more evident in goethite system. The effect of FA on the distribution of Pb(II) between solid and liquid phases of the minerals was determined by the factors such as the initial concentration ratio of FA to Pb(II), the adsorption capacity of minerals for FA, and the number of soluble complexes of FA with Pb2+. Therefore, the distribution of FA between solid and liquid of four minerals affected the distribution of Pb(II) between solid and liquid phases of the minerals greatly. The results can provide an important reference for understanding the distribution of Pb(II) and the dynamics and mobility of active components in polluted soils.

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.