Search Results (18)

Adsorption studies of ciprofloxacine (CPX) and lidocaine (LID) emerging contaminants were performed on two fibrous Mg clays from the Madrid basin and Senegal. The samples were characterized by X-ray diffraction, ICP major element analysis, infrared spectroscopy, thermal analysis, optical petrography, scanning and transmission electron microscopy, cation exchange capacity (CEC), and N₂-BET analysis. Two mineral assemblages were established. Assemblage 1 mainly consists of sepiolite and minor trioctahedral smectite, while assemblage 2 is mostly composed of palygorskite, which is associated with dioctahedral smectite. The sorption was fast and reached equilibrium in 2 h. Fibrous Mg clays showed a higher adsorption capacity for CPX than for LID in the conditions studied. CPX adsorption on sepiolite and palygorskite can be the result of the combination of various mechanisms: ion exchange with permanently charged sites, electrostatic attractions with external surfaces, and an inner sphere complex with broken edges. LID adsorption mainly occurs by ion exchange and electrostatic interaction with the external surfaces of the clays. Dioctahedral smectite, as an associated phase, contributed to a higher removal percentage in palygorskite samples. By contrast, the trioctahedral smectite did not play a significant role in the adsorption of the samples with sepiolite. The mesoporous structure, high surface area, and moderate cation exchange of fibrous clays play a key role in the sorption process of CPX and LID. Full article

Aflatoxin B1 (AFB1) can impair the growth of chickens and reduce the quality of eggs and meat, resulting in significant economic losses. The inclusion of mycotoxin detoxifying agents (MyDA) with binding properties in the diet is an efficient tool to reduce their absorption rate in the gastrointestinal tract. Our aim was to investigate the ability of two innovative MyDA (SeOX, a feed additive featuring a tri-octahedral smectite mixed with lignocellulose, and CHS, a di-octahedral smectite functionalized with an organic non-toxic modifier) in both reducing the bio-accessibility and mitigating the adverse effects of AFB1 in broilers exposed for 10 days to concentrations approaching the European Union maximum limits in feed (0.02 mg/kg). The amount of AFB1 in the excreta of birds, collected over four consecutive days (starting on day 7), was significantly lower (p < 0.001) in the group exposed to AFB1 alone compared to the groups treated with either SeOX or CHS. The calculated bio-accessibility was decreased by nearly 30% with both MyDA. This positive effect was reflected by a significant reduction (p < 0.001) in the oxidative stress (measured as serum antioxidant capacity and hepatic lipid peroxidation) induced by AFB1. Although antioxidant enzyme activities and glutathione levels were unaffected by any treatment, AFB1 significantly induced (p < 0.001) the upregulation of CYP2A6 and the downregulation of Nrf2; the latter was reverted by each MyDA. Overall, these results demonstrate that the selected MyDA are effective in limiting the AFB1 absorption rate, thereby mitigating or even reverting the oxidative stress induced by AFB1 in broilers. Full article

The identification of minerals, particularly clay minerals, using visible, near-infrared, and short-wave infrared (VNIR-SWIR) spectroscopy has gained prominence due to its efficiency and the advancement of remote hyperspectral sensors. However, identifying minerals in polymineralic samples remains challenging due to overlapping absorption features. This study prepared systematic binary mixtures of two smectites (dioctahedral and trioctahedral) with common non-clay minerals (calcite, dolomite, gypsum, quartz, and feldspar). Spectra from these mixtures were obtained using the ASD FieldSpec 4 Hi-Res spectroradiometer and analyzed with continuum removal and second derivative preprocessing to define detection limits. These limits indicate the minimum percentage of each mineral required for clear identification in various smectite–non-clay combinations. After continuum removal, smectites are identified at ≥5%–10% in mixtures with carbonates, quartz, and feldspar, but ≥70% is needed for gypsum. Non-clay minerals have detection limits of ≥70% for calcite and 20% for gypsum in the presence of smectites, while dolomite remains undetectable. The second derivative improves these limits, enabling smectite identification at 5% in carbonate mixtures and 5%–15% in gypsum mixtures. Calcite detection limits are 65%, and dolomite can be identified at ≥65% and ≥85% with dioctahedral and trioctahedral smectites, respectively. Gypsum detection limits are reduced to 10%, while quartz and feldspar cannot be identified due to lacking absorption features. Full article

The Ni-laterite deposit at the San Felipe plateau, located 30 km northwest of Camagüey, in central Cuba, is the best example of a clay-type deposit in the Caribbean region. San Felipe resulted from the weathering of mantle peridotites of the Cretaceous Camagüey ophiolites. In this study, a geochemical and mineralogical characterization of two profiles (83 and 84) from the San Felipe deposit has been performed by XRF, ICP-MS, quantitative XRPD, oriented aggregate mount XRD, SEM, FE-SEM, and EMPA. Core 83, with a length of 23 m and drilled in the central part of the plateau, presents a notable concentration of cryptocrystalline quartz fragments and a rather poor content of NiO, averaging 0.87 wt.%. Core 84, which is 12 m long and drilled at the border of the plateau, lacks silica fragments and presents a higher NiO content, averaging 1.79 wt.%. The smectite structural formulae reveal that they evolve from trioctahedral to dioctahedral towards the top of the laterite profiles. Quantitative XRD analyses indicate that smectite is a dominant Ni-bearing phase, accompanied by serpentine and minor chlorite. Serpentine, as smectite, is enriched in the less soluble elements Fe³⁺, Al, and Ni towards the top of the profiles. Core 83 seems to have been affected by collapses and replenishments, whereas core 84 may have remained undisturbed. Full article

This study focuses on hydrothermal alteration, and more specifically clays, in the geothermal reservoir of Cerro Pabellón in Andean Cordillera, Northern Chile. Although it is the first commercial geothermal power plant in South America with 48 MWe installed and an additional 33 MWe during 2022, the alteration mineralogy of the deep reservoir remains poorly investigated. Cuttings from two deep wells drilled between 500 and 3000 m depth were sampled. The fine-grained clay fraction was analyzed using X-ray diffraction to observe the mineral distribution and variations of crystal structure of the clays. Scanning electron microscopy coupled with energy dispersive spectroscopy allowed us to perform microanalysis of the clays. The results suggest a high heterogeneity of the reservoir in term of alteration: a pervasive alteration dominated by trioctahedral clays was observed in all the samples, whereas a fracture-controlled alteration was only observed locally, dominated by dioctahedral clays. Illite-smectite mixed layers with more than 90% illite typically occur in permeable fracture and fault as a typical clay signature. This study completed an integrated conceptual model of the high enthalpy reservoir (>250 °C). Circulations of a neutral pH Na-K-Cl fluid occur in a wide fracture system connected to highly dipping and NW-striking faults and could extend beyond the Pabelloncito graben. Full article

Lithofacies belonging to mud-flat and palustrine deposits (lake margin) in the Miocene of the Madrid Basin (Spain) have been studied. Four lithofacies corresponding to mud flat (1 and 3) and palustrine (2 and 4) deposits have been differentiated. Units 1 and 3 consist mainly of mudstones and carbonates (calcretes and diolocretes). The clay fraction is dominated by trioctahedral smectite (up to 79%) with illite and kaolinite as minor components. The d(060) spacing value shows reflections at 1.52 and 1.50 Å indicating also the presence of dioctahedral phyllosilicates. Unit 2 consists predominantly of lutites (claystones), locally with carbonate and chert nodules. The clay fraction is dominated by sepiolite (up to 96%) with variable contents of smectite and subordinate illite. The d(060) spacing value shows reflections at 1.51 and 1.52 Å indicating trioctahedral clay minerals. Unit 4 consists mostly of carbonates (limestones) with mudstone and lutite inserts. The clay fraction shows different contents of sepiolite, palygorskite and dioctahedral smectite. The analysis of a selection of trace elements (Cr, Co, Th, La, Sc) has allowed us to determine the characteristics of the source area as dioritic, somewhat different from those of the nearby materials from the Batallones sector. Sepiolite shows FWHM values ranging between 0.68 and 1.10 (2θ), indicating “low crystallinity sepiolite”. Differences in the conditions of formation of magnesian smectite and palygorskite have been observed in the mud-flat and palustrine deposits. The formation of sepiolite mainly by neoformation in palustrine deposits with different hydrochemistry is remarkable, leading to differences in fibre size and crystallinity of the fibrous clay mineral. Authigenic transformation processes from previous Al-rich phases would be responsible for the formation of saponite and palygorskite in mud flat and palustrine environments, with different pH conditions. Full article

Simultaneous removal of mycotoxins has been poorly addressed, and a limited number of studies have reported the efficacy of feed additives in sequestering a large spectrum of mycotoxins. In this study, a new mycotoxin-adsorbing agent was obtained by properly mixing a tri-octahedral smectite with a lignocellulose-based material. At a dosage of 1 mg mL⁻¹, these materials simultaneously adsorbed frequently occurring mycotoxins and did not exert a cytotoxic effect on intestinal cells. Chyme samples obtained by a simulated GI digestion did not affect the viability of Caco-2TC7 cells as measured by the MTT test. In addition, the chyme of the lignocellulose showed a high content of polyphenols (210 mg mL⁻¹ catechin equivalent) and good antioxidant activity. The properties of the individual constituents were maintained in the final composite, and were unaffected by their combination. When tested with a pool of seven mycotoxins at 1 µg mL⁻¹ each and pH 5, the composite (5 mg mL⁻¹) simultaneously sequestered AFB₁ (95%), FB₁ (99%), ZEA (93%), OTA (80%), T-2 (63%), and DON (22%). HT-2 adsorption did not occur. Mycotoxin adsorption increased exponentially as dosage increased, and occurred at physiological pH values. AFB₁, ZEA and T-2 adsorption was not affected by pH in the range 3–9, whereas OTA and FB₁ were adsorbed at pH values of 3–5. The adsorbed amount of AFB₁, ZEA and T-2 was not released when pH rose from 3 to 7. FB₁ and OTA desorption was less than 38%. Langmuir adsorption isotherms revealed high capacity and affinity for adsorption of the target mycotoxins. Results of this study are promising and show the potential of the new composite to remove mycotoxins in practical scenarios where several mycotoxins can co-occur. Full article

This paper revisits the clay mineralogy of the “smectite” alteration zone in the Krafla geo-thermal field via the study of an exploratory well in which temperatures range from 40 °C to 215 °C. The clay alteration consists of several mineral assemblages superimposed in time and space, resulting from different stages of water-rock interaction. Trioctahedral clay minerals (chlorite, corrensite and smectite) are observed throughout the studied section. These minerals can form in nearly closed systems as replacements of groundmass minerals/glass after interactions with resident and nearly stagnant fluids not far from chemical equilibrium (neutral to basic pH conditions) or from direct precipitation from geothermal fluids. They are locally superimposed by Al clay phases (smectite, illite/smectite and kaolinite), which result from intense leaching of the host rocks due to their interaction with low pH fluids under strong W/R ratios. The absence of mineralogical zoning is explained by the fact that hydrothermal alteration is strongly dependent on very recent hydrodynamics. The current fluid circulation generates trioctahedral clays at depth that cannot be distinguished from pervasive earlier alteration. The only easily detectable signature of current activity and the most relevant signature for geothermal exploration is the presence of Al dioctahedral phases since it indicates leaching and intense hydrothermal activity. Full article

A mineralogical characterization of a group of bentonite samples was done by X-ray diffraction (XRD), chemical analysis by inductively coupled plasma mass spectroscopy (ICP-MS), and visible-near infrared and short-wave infrared spectroscopy (VNIR-SWIR). As tested by XRD, all samples are very pure, composed mainly of smectites with very small amounts of impurities, such as quartz and feldspar. The results of the chemical analysis show high contents of Al₂O₃ in all the samples except for COU(V), which has high contents of Fe₂O₃ and R4, which is a trioctahedral smectite. Within VNIR-SWIR spectra, absorption feature characteristics of the smectites due to the presence of Fe are observed at lowest wavenumber while, at the SWIR region, the absorptions are related to the M-OH bonds and there are differences among the samples according to their octahedral content. Full article

Saponite is a trioctahedral 2:1 smectite with the ideal composition M_xMg₃Al_xSi_4−xO₁₀(OH,F)₂.nH₂O (M = interlayer cation). Both the success of the saponite synthesis and the determination of its applications depends on robust knowledge of the structure and composition of saponite. Among the routine characterization techniques, spectroscopic methods are the most common. This review, thus, provides an overview of various spectroscopic methods to characterize natural and synthetic saponites with focus on the extensive work by one of the authors (JTK). The Infrared (IR) and Raman spectra of natural and synthetic saponites are discussed in detail including the assignment of the observed bands. The crystallization of saponite is discussed based on the changes in the IR and Raman spectra and a possible crystallization model is provided. Infrared emission spectroscopy has been used to study the thermal changes of saponite in situ including the dehydration and (partial) dehydroxylation up to 750 °C. ²⁷Al and ²⁹Si magic-angle-spinning nuclear magnetic resonance spectroscopy is discussed (as well as ¹¹B and ⁷¹Ga for B- and Ga-Si substitution) with respect to, in particular, Al(IV)/Al(VI) and Si/Al(IV) ratios. X-ray photoelectron spectroscopy provides chemical information as well as some information related to the local environments of the different elements in the saponite structure as reflected by their binding energies. Full article

Ochratoxin A (OTA) is a mycotoxin which represents an emerging problem for both animal and human health, due to its high presence in feed and foods. Exposure to OTA is associated with oxidative stress-induced nephrotoxicity. Therefore, the identification of new antioxidant or adsorbent substances with protective action constitutes one of the main challenges to reduce the negative effects induced by mycotoxins. For this purpose, we investigated the effect of two innovative feed additives, a bio-organoclay (CHS) and a mixture of a tri-octahedral Na-smectite with a ligno-cellulose based material (MIX) alone or in combination with OTA in kidneys of treated chickens. Real-Time PCR analyses for NADPH oxidase 4 (NOX) and p47-phox were performed to evaluate oxidative stress. Our results demonstrated an increase in NOX and p47-phox levels in OTA-treated chickens. Moreover, CHS, more than MIX, was able to reduce OTA-induced toxicity, restoring NOX levels. Taken together, these findings highlight the potential beneficial role of CHS in reverting OTA-induced nephrotoxicity in chickens and could lead to the production of healthier foods with beneficial consequences for human and animal health. Full article

Aflatoxin B1 (AFB1), the mainly Aspergillus fungi derived mycotoxin, is well known for its carcinogenic effects on liver, and frequently occurs in food supplies, leading to fatal consequences in both farm animals and humans. Poultry, one of the most important segments of agro-industry, has been demonstrated to be extremely sensitive to AFB1 intake, which results in chickens’ low performance, decreased quality of both eggs and meat and a negative economic feedback. Oxidative stress caused by AFB1 plays a crucial role in chickens’ kidney damage by generating lipid peroxidation accompanied by a concomitant increase in the antioxidant enzymes involved in ROS metabolism (NADPH oxidase isoform 4 (NOX4) and its regulatory subunit p47-phox). The aim of the present work was to investigate the benefits of dietary supplementation, in chickens affected by AFB1 mycotoxicosis, using a new Feed additive (FA) containing a mixture of a tri-octahedral Na-smectite with a ligno-cellulose-based material an antioxidant adjuvant. Exposure of AFB1-treated chickens to the feed additive induced a significant down-regulation of both NOX4 and p47-phox genes expression levels. This trend was confirmed by their protein expression, demonstrating the great potential of the FA to counteract oxidative stress. To conclude, these results could open new perspectives in the methods of feeding chickens, using eco-friendly dietary supplements able to reduce AFB1-induced mycotoxicosis and to ameliorate poultry performances. Full article

Mg clay minerals are usually associated with carbonates in alkaline-saline environments, precipitated from solution and/or transformation from other minerals. The aim of this research is to identify the mineralogy and geochemistry of clay minerals in different alkaline lakes in the Nhecolândia region, the southernmost region of the Pantanal wetland (Brazil). Sediment samples were analyzed by X-ray diffraction, X-ray fluorescence, scanning electron microscopy and transmission electron microscopy. Water samples were analyzed, determining their main cations and anions, in order to understand their relationship with the clays. The analyses allowed classifying the water bodies as saline, oligosaline and freshwater lakes. The sediments are composed mainly of quartz and a fine-clay fraction, dominated by illite, kaolinite and smectite. The XRD results showed illite and smectite mixed-layered in the saline lakes at Barranco Alto farm, whereas at Nhumirim farm, trioctahedral smectite was only observed in one lake. The smectite minerals were normally identified coupled with calcite at the top of the sequences, associated with exopolymeric substances (EPS) in the lakes, suggesting that these minerals are precipitating due to the physical-chemical and biological conditions of the water bodies. Full article

Smectite is a common clay mineral in nature. Due to its tendency to swell and its strong cation exchange capacity (CEC), smectite is prevalently used in industrial and technological applications. Numerous scholars have explored smectite synthesis, which usually involves autoclaving under high pressure. However, this approach requires an array of expensive equipment, and the process consumes time and energy. This study adopted self-developed equipment to synthesize zinc saponite (Zn-saponite), a type of trioctahedral smectite, using a microwave circulating reflux method under atmospheric pressure. Compared with the conventional hydrothermal methods, the proposed method entails fewer constraints regarding the synthesis environment and can be more easily applied to large-scale synthesis. The phase purity of the synthetic product was examined using X-ray diffraction and the CEC of the product was tested. The results revealed that the microwave circulating reflux method could synthesize Zn-saponite in 16 h under atmospheric pressure, and the CEC of the product reached 120 cmol(+)/kg. In addition, the product exhibited larger basal spacing and a 32% increase in CEC compared with Zn-saponite synthesized using a hot-plate under atmospheric pressure. Full article

A review and a synthesis of the geological, mineralogical, and crystal chemical data available in the literature on active Spanish bentonitic exploitations were done, and at the same time, new data are provided from a set of representative samples from these deposits. They were located in three different areas with different geological origins: (1) Miocene sedimentary deposits from the Tajo Basin (Madrid–Toledo provinces) in the center of the Iberian Peninsula, where bentonites appear in two different units named for their colors (Green Clays and Pink Clays); (2) samples from Tamame de Sayago (Zamora province) originating from the hydrothermal alteration of granitic Variscan rocks; and 3) Miocene deposits originating from the hydrothermal alteration of volcanic or subvolcanic rocks from the Cabo de Gata volcanic area (Almería Province) in the southern part of Spain, where the three main deposits (Cortijo de Archidona, Los Trancos, and Morrón de Mateo) were studied. The bentonites from the Tajo Basin were formed mainly by trioctahedral smectites, and there were significant mineralogical differences between the Green and Pink Clays, both in terms of the contents of impurities and in terms of smectite crystallochemistry and crystallinity. The smectites from Tamame de Sayago were dioctahedral (montmorillonite–beidellite series), and they appeared with kaolinite, quartz, and mica in all possible proportions, from almost pure bentonite to kaolin. Finally, the compositions of the bentonites from the three studied deposits in Cabo de Gata were quite similar, and zeolites and plagioclases were the main impurities. The structural formulae of the smectites from Cortijo de Archidona and Los Trancos showed a continuous compositional variation in beidellite–montmorillonite, while in Morrón de Mateo, the smectites were mainly montmorillonite, although there was continuous compositional variation from Al montmorillonites to Fe–Mg-rich saponites. The variation in the smectite composition is due to the intrusion of a volcanic dome, which brings new fluids that alter the initial composition of the smectites. Full article