Large Cation Exchange Capacity Research Articles

Fundamentals of copper(II) adsorption on phyllosilicate minerals relevant to crud formation in solvent extraction from heap leach liquors

Because of the common presence of different silicate minerals, like kaolinite, montmorillonite and muscovite as gangue minerals in the beneficiation of copper oxide ores, the interaction between copper(II) ions in solution and each of these minerals is a field of strong interest, considering their implications on the aggregation of these minerals in the extreme pH conditions typical of hydrometallurgical unit operations for copper production. After copper adsorption isotherms determination at pH 2 and 4, specific adsorption data were fitted to both Langmuir and Freundlich models. It was found that adsorption is systematically larger at pH 4, and that montmorillonite is the mineral that displays a larger adsorption capacity, as in principle expected by its larger cation exchange capacity, CEC. A good fitting to the Langmuir model was obtained for the three samples, and montmorillonite also appears to conform to Freundlich isotherm predictions, as the tested concentrations of copper(II) do not allow to reach saturation. Furthermore, some desorption is measured for kaolinite and muscovite at the highest copper concentrations, probably because of significant interactions between the adsorbed ions. No such desorption was detected in montmorillonite samples. An XPS analysis of the surfaces of the three minerals suggests that copper adsorption in kaolinite is not associated to a cation exchange process but rather to electrostatic interactions between silica-like faces of the clay. In contrast, ionic exchange of structural calcium (for montmorillonite) or potassium (in the case of muscovite) seems to be the predominant mechanism of Cu(II) adsorption in the other two samples. Electrophoretic mobility determinations agree with this hypothesis: the mobility (always negative, with no traces of charge inversion) decreases in absolute value when kaolinite particles are in contact with solutions of increasing copper concentration at pH 2 or pH 4. On the other hand, the electrophoretic mobility values of muscovite and montmorillonite showed a weak pH and copper concentration dependence, a result that matches well with the ion exchange processes detected in the XPS measurements.

Unlocking the potential of V/Ti-AAC: a promising eco-friendly catalyst for cyclohexene epoxidation

Abstract Bentonite is an abundant natural resource in the Maghnia region of Algeria that may have potential value in catalysis, but heretofore has been considered of low value for this purpose due to its low acidity and low catalytic activity. Low cost is one of the main criteria for choosing a suitable material for catalysis. Because bentonite is abundant and low-cost, its use as a starting material for the preparation of catalysts deserves reconsideration. The present study was undertaken, therefore, to optimize the performance of bentonite as a catalyst in one of the most promising reactions in organic synthesis, namely, cyclohexene epoxidation. The bentonite was subjected to adjustment of its structure by means of a number of laboratory treatments based on its large cation exchange capacity. These modifications aimed to achieve an environmentally friendly catalytic process by incorporating transition metals, specifically titanium and vanadium, into the modified bentonite structure through acid activation. Redox properties were enhanced and Lewis and Brønsted acidities were introduced. The vanadium oxide, supported on titania-pillared, acid-activated bentonite (5V/Ti-AAC), was characterized comprehensively using various techniques, including diffuse-reflectance UV-visible spectroscopy (DR UV-Vis), Fourier-transform infrared spectroscopy (FTIR) for surface acidity analysis, X-ray diffraction (XRD), nitrogen adsorption-desorption isotherms, and scanning electron microscopy (SEM) coupled with energy-dispersive X-ray elemental analysis (EDX). The catalytic activity was investigated in response to certain variables, such as catalyst mass, nature of the solvent, amount of oxidant, and reaction temperature. A kinetic study was conducted to understand the reaction behavior. The experimental results demonstrated intriguing catalytic activity, achieving a 42% conversion rate with ~68% selectivity toward the epoxide product when employing tert-butyl hydroperoxide (TBHP) as the oxidant and heptane as the solvent. This study highlights the potential of 5V/Ti-AAC as an environmentally friendly catalyst applied in the epoxidation of cyclohexene.

Hydrothermally synthesized smectite as a thickener with favorable rheological and tribological properties over a wide temperature range

Lubricating grease is essential for many applications. Although smectite grease is an important type of lubricating grease, its properties can be inconsistent due to variations in the properties of natural smectite. In this work, pure smectite was synthesized from an H2O/NH4F/Mg(CH3COO)2/Al(NO3)3/tetraethoxysilane/NaOH system by a one-step hydrothermal method. Compared with natural smectite, synthetic smectite has a larger cation exchange capacity (CEC), smaller particle size, and fluffier morphology. The pure smectite grease showed higher energy storage modulus and better thixotropy than natural smectite grease at the same thickener content. Synthetic smectite grease showed more stable tribological behavior, maintaining better anti-wear and anti-friction properties at different test temperatures. These improvements can be mainly ascribed to its fixed elemental composition, larger CEC, good rheological properties, and absence of impurities. Due to the convenient synthetic method and superior rheological and tribological performances, synthetic smectite as a grease thickener has promising potential for use in demanding advanced precision instruments, as well as pharmaceuticals, food, and other industrial fields.

Effects of biochar produced from distiller grains on agronomic performances of sorghum (Sorghum bicolor L.) and greenhouse gas emissions from soil

Aromatic liquor breweries produce massive distiller grains containing a high percentage of rice husks that necessitate harmless treatment and resource utilization. These husk-rich distiller grains can be pyrolyzed in the Ni-based catalyst system at a relatively low temperature (480 °C) into combustible gas, which is used in liquor distillation, and biochar (BDG) with high mineral nutrients and good surface properties. A 3-year field experiment (2018–2020) was established to understand the effects of BDG on sorghum agronomic performances and greenhouse gas emissions from the soil. The results showed that BDG had higher mineral nutrient (N, P, K, and S) contents, larger cation exchange capacity, and better surface structure than those prepared using the traditional method at 400 and 600 °C. Compared with sole chemical fertilizer (CF), the combination of CF and BDG (CF+BDG) increased sorghum nutrient (N, P, and K) uptake, yield, fertilizer use efficiency, and economic benefit. Cumulative CO2 emission from the soil changed little between with and without BDG, indicating the microbial stability of BDG. The effective adsorption of NH3 or NH4+ by BDG upon N application may reduce N loss through NH3 and N2O emissions and increase the efficiency of fertilizer N use. Cumulative CH4 emission ranged from 32.45 to 44.86 g ha-1, which could be overlooked as a greenhouse gas in the sorghum field. Moreover, CF+BDG significantly decreased NH3 and N2O emissions for the production of each unit of sorghum grains and the CO2 emission from the land for the production of a certain amount of sorghum grains. Therefore, CF+BDG exhibited better agronomic and environmental performances in sorghum cultivation.

Vermibiochar: A Novel Approach for Reducing the Environmental Impact of Heavy Metals Contamination in Agricultural Land

Environmental pollution has become a pressing concern worldwide due to the accumulation of pollutants from industries and agricultural sectors in soil and water environments. Heavy metals pose severe hazards to the environment, plants, and human health. Consequently, an eco-friendly technique is needed to combat environmental pollutants. Vermibiochar, a product prepared through the combined action of earthworms and biochar, demonstrates great potential in reducing heavy metal concentrations in contaminated soil. Its large surface area and high cation exchange capacity enhance the sorption of contaminants onto the vermibiochar surface, reducing their bioavailability. This review highlights the roles played by earthworms and biochar in heavy metal detoxification and immobilization. It discusses the current methods of remediation, vermibiochar production, its effects on soil properties and plant growth, and biochar’s impact on earthworm growth and reproduction. The studies reviewed suggest that vermibiochar is a novel strategy for addressing heavy metal contamination.

Physicochemical Variation of Clay Minerals and Enrichment of Rare Earth Elements in Regolith-hosted Deposits: Exemplification from The Bankeng Deposit in South China

AbstractThe wide application of rare earth elements (REEs) in the development of a carbon–neutral society has urged resource exploration worldwide in recent years. Regolith-hosted REE deposits are a major source of global REE supply and are hosted mostly in clay minerals. Nonetheless, the ways in which changes in the physicochemical properties of clay minerals during weathering affect the concentrations of REEs in the regolith are not well known. In the current study, a world-class regolith-hosted REE deposit (Bankeng, South China) has been studied to illustrate further the effect of clay minerals on sorption and fractionation of REEs during weathering to form economic deposits. In the weathering profile, halloysite and illite are abundant in the saprolite due to weathering of feldspars and biotite from the bedrock. During weathering, halloysite and illite transform gradually to kaolinite and vermiculite. The large specific surface area, pore volume, and cation exchange capacity of the clay mineral assemblages are favorable to the sorption of REEs, probably because of the formation of vermiculite. The abundance of vermiculite could explain the enrichment of REEs in the upper part of the lower pedolith. For the saprolite-pedolith interface, halloysite is probably the main sorbent for the REEs, as indicated by the distinctive appearance of pore sizes of 2.4–2.8 nm characteristic of halloysite. The progressive transformation of halloysite to kaolinite reduces the pores and desorbs the REEs, causing REE depletion in the shallower soils. As a result, REEs were mobilized downward and re-sorbed in the lower pedolith-upper saprolite causing gradual enrichment and formation of these regolith-hosted deposits.

Aluminum mobilization as influenced by soil organic matter during soil and mineral acidification: A constant pH study

Soil acidification is an increasing challenge to food security due to the production of free aluminum ion (Al3+) that is toxic to crops. The production of exchangeable Al3+ in soils during acidification is a complex process and its specific mechanism is not clear. In this study, kaolinite, montmorillonite, and three acidic soils (two Ultisols and one Alfisol) were used to investigate the changes in exchangeable and soluble Al with pH using a constant pH automatic potentiometric titrator. The effect of soil organic matter (SOM) on soil pH and Al change was also investigated. The results showed that montmorillonite consumed more acid than kaolinite under the same conditions, which were consistent with the larger cation exchange capacity (CEC) of montmorillonite than kaolinite. When the pH was adjusted from 4.8 to 4.3, the exchangeable Al of montmorillonite was significantly higher than that of kaolinite. This was consistent with their CEC and indicated that montmorillonite adsorbed more H+ than kaolinite at the same pH, resulting in more exchangeable Al on its surface. Besides CEC, SOM shows a significant effect on acid buffering capacity and Al activation of acid soils. When acidified to the same pH, the content of exchangeable Al in Alfisol was larger than that in Ultisols. This observation was consistent with the larger CEC and smaller organic matter content of Alfisol. The presence of more organic matter in the Ultisols not only improved their acid buffering performance, but also inhibited the production of exchangeable and soluble Al. In conclusion, CEC of soils and minerals play an important role in soil acid buffering performance. While, SOM not only improves soil acid buffering performance, but also inhibits the mobilization of soil Al.

Effects of biochar application on soil nitrogen transformation and N 2 O emissions: a review

The sustainability and uncertainty of global climate warming have a profound impact on the sustainable development of human society. The continuous increase of atmospheric N2O concentration is one of the major contributions to the global climate warming. Soil is an important site of nitrogen transformation and a biochemical reaction reservoir of the nitrogen cycle, and also an important source of N2O emissions. Therefore, changes in soil N2O emission rate will significantly affect atmospheric N2O concentration. Biochar refers to the aromatic chemicals prepared by pyrolysis of biomass under the condition of complete or partial hypoxia. Biochar has the characteristics of porosity, strong adsorption, chemical stability, high pH and large cation exchange capacity. After it is applied to soils, biochar will directly or indirectly affect the transformation process of soil nitrogen and significantly affect the soil N2O emissions. This article reviewed the research progress of biochar effects on nitrogen transformation and N2O emission in the soil ecosystem, elaborated the effects of biochar input on the dynamic changes of soil inorganic nitrogen, nitrification, denitrification and N2O emission. Futher, in terms of biochar’s absorption and reduction of nitrogen leaching, effects on soil physicochemical properties, abundance and diversity of soil ammonia oxidizing bacterial, along with functional genes of denitrifying bacteria, the machamnisms influencing the processes above-mentioned are specifically elucidated in details. The future research of biochar in increasing soil sinks, reducing emissions and mitigating the greenhouse effect, as well as the related technology promotion, have been prospected. [Ch, 109 ref.]

Induced Polarization as a Tool to Assess Alteration in Geothermal Systems: A Review

The mineral alteration patterns in high- to low-temperature geothermal fields affect the induced polarization (electrical conductivity and chargeability) properties of volcanic rocks. Indeed, these properties are sensitive to the cation exchange capacity and the porosity of the rock, which are both dependent on the alteration path, temperature, and depth of burial. Therefore induced polarization tomography appears as a powerful non-intrusive geophysical method to investigate alteration patterns in geothermal fields. Among clay minerals, the production of smectite through prograde reactions occurs progressively in volcanic rocks up to 220 °C. The presence of smectite dominates the induced polarization response of the volcanic rocks because of its very large cation exchange capacity. It follows that induced polarization can be used as a non-intrusive temperature proxy up to 220 °C for both active and inactive geothermal fields, recording the highest temperatures reached in the past. The influence of magnetite and pyrite, two semi-conductors, also has a strong influence regarding the induced polarization properties of volcanic rocks. Various field examples are discussed to show how induced polarization can be used to image volcanic conduits and smectite-rich clay caps in volcanic areas for both stratovolcanoes and shield volcanoes.

Interactions between Cationic Dye Toluidine Blue and Fibrous Clay Minerals

Interactions between cationic dyes and negatively charged mineral surfaces have long attracted great attention from clay mineralogists, environmental scientists, and chemical engineers. In this study, the interactions between a cationic dye toluidine blue (TB) and palygorskite and sepiolite were investigated under different experimental conditions. The results showed that in addition to cation exchange, the specific surface area (SSA) of the minerals, particularly the formation of dimer molecules on the surface of both minerals, also accounted for the much higher TB uptake in comparison to their cation exchange capacities (CEC). The TB molecules were sorbed to the external surfaces, as no d-spacing expansion was observed in X-ray diffraction analyses. FTIR analyses showed strong interactions between the C=N or N-(CH3)2 group and the mineral surfaces, suggesting net electrostatic interactions if either of these functional groups bears a positive charge. Results from molecular dynamic simulations suggested dense monolayer TB formation on palygorskite because of its limited SSA and large CEC values. In comparison, a loosely dimeric formation was revealed on sepiolite for its large SSA and limited CEC values. Therefore, palygorskite is a better carrier for the sorption of cationic dyes, as evidenced by Maya blue paintings.

Effect of Low Zeolite Doses on Plants and Soil Physicochemical Properties.

Thousands of tons of zeolitic materials are used yearly as soil conditioners and components of slow-release fertilizers. A positive influence of application of zeolites on plant growth has been frequently observed. Because zeolites have extremely large cation exchange capacity, surface area, porosity and water holding capacity, a paradigm has aroused that increasing plant growth is caused by a long-lasting improvement of soil physicochemical properties by zeolites. In the first year of our field experiment performed on a poor soil with zeolite rates from 1 to 8 t/ha and N fertilization, an increase in spring wheat yield was observed. Any effect on soil cation exchange capacity (CEC), surface area (S), pH-dependent surface charge (Qv), mesoporosity, water holding capacity and plant available water (PAW) was noted. This positive effect of zeolite on plants could be due to extra nutrients supplied by the mineral (primarily potassium—1 ton of the studied zeolite contained around 15 kg of exchangeable potassium). In the second year of the experiment (NPK treatment on previously zeolitized soil), the zeolite presence did not impact plant yield. No long-term effect of the zeolite on plants was observed in the third year after soil zeolitization, when, as in the first year, only N fertilization was applied. That there were no significant changes in the above-mentioned physicochemical properties of the field soil after the addition of zeolite was most likely due to high dilution of the mineral in the soil (8 t/ha zeolite is only ~0.35% of the soil mass in the root zone). To determine how much zeolite is needed to improve soil physicochemical properties, much higher zeolite rates than those applied in the field were studied in the laboratory. The latter studies showed that CEC and S increased proportionally to the zeolite percentage in the soil. The Qv of the zeolite was lower than that of the soil, so a decrease in soil variable charge was observed due to zeolite addition. Surprisingly, a slight increase in PAW, even at the largest zeolite dose (from 9.5% for the control soil to 13% for a mixture of 40 g zeolite and 100 g soil), was observed. It resulted from small alterations of the soil macrostructure: although the input of small zeolite pores was seen in pore size distributions, the larger pores responsible for the storage of PAW were almost not affected by the zeolite addition.

Microbial biomodification of clay minerals.

Clay minerals are important reactive centers in the soil system. Their interactions with microorganisms are ubiquitous and wide-ranging, affecting growth and function, interactions with other organisms, including plants, biogeochemical processes and the fate of organic and inorganic pollutants. Clay minerals have a large specific surface area and cation exchange capacity (CEC) per unit mass, and are abundant in many soil systems, especially those of agricultural significance. They can adsorb microbial cells, exudates, and enzymes, organic and inorganic chemical species, nutrients, and contaminants, and stabilize soil organic matter. Bacterial modification of clays appears to be primarily due to biochemical mechanisms, while fungi can exhibit both biochemical and biomechanical mechanisms, the latter aided by their exploratory filamentous growth habit. Such interactions between microorganisms and clays regulate many critical environmental processes, such as soil development and transformation, the formation of soil aggregates, and the global cycling of multiple elements. Applications of biomodified clay minerals are of relevance to the fields of both agricultural management and environmental remediation. This review provides an overview of the interactions between bacteria, fungi and clay minerals, considers some important gaps in current knowledge, and indicates perspectives for future research.

Experimental features of cation exchange capacity determination in organic-rich mudstones

To the petroleum industry, the cation exchange capacity (CEC) is one of the critical petrophysical parameters of the rock-gas-fluid system and the response of well logging tools. The widely used laboratory protocols for CEC determination (wet chemistry methods) came mainly from soil science, but with slight or even without modifications are being applied to organic-rich mudstones (shales). However, using such laboratory practice leads to large CEC errors in the presence of carbonate and gypsum minerals, high-salinity pore water, etc.The paper attempts to find optimal in terms of accuracy and reliability methods for measuring both CEC and exchangeable cations concentrations of organic-rich mudstones, along with sample treatment procedures including drying, extraction, and fraction size due to crushing. The paper presents a CEC data set obtained using both hexaamminecobalt(III) chloride (CoHex) and modified (NH4Cl)Alc methods for a representative collection of core samples of the Bazhenov shale formation (West Siberia, Russian Federation). The results show a) CEC growth inversely versus fraction size, and b) stable CEC measurements within fraction size 0.25–1.0 mm. The BET specific surface area (SSA) spans in the range of 0.25–6 m2/g. SSA follows the CEC trend in terms of fraction size with a growth ratio up to 3 times. The modified (NH4Cl)Alc method outperforms the CoHex method and reliably determines the concentrations of the exchangeable cations for a carbonate content of more than 5 wt%. Both direct [Co(NH3)6]3+ measurements in the CoHex method and the sum of exchangeable cation concentrations in the modified (NH4Cl)Alc method provide a fair estimate of the total CEC. Careful sample preparation, including drying or solvent extraction, is required for accurate CEC determinations. The measured CEC for the target rock samples varies from 2.87 to 6.43 cmol/kg and driven by the total clay content.

Sorptive Removal of Color Dye Safranin O by Fibrous Clay Minerals and Zeolites

The increased use of color dyes in industry imposes a great threat to the environment. As such, developing cost‐effective techniques for dye removal from wastewater attracted great attention. Earth materials, particularly those with large specific surface area (SSA) and high cation exchange capacity (CEC), were evaluated for their potential use for wastewater treatment. In this study, palygorskite, sepiolite, and clinoptilolite were evaluated for their removal of cationic dyes using safranin O (SO+) as a model compound. The CEC values of the materials played a key role in SO+ removal while other physicochemical conditions, such as temperature, equilibrium solution pH, and ionic strength, had less influence on SO+ removal. Sorbed SO+ cations were limited to the external surfaces of the minerals, as their channel sizes are less than the size of SO+ cation. Molecular dynamic simulations showed dense monolayer SO+ uptake on palygorskite due to its relatively large CEC value. In contrast, loosely packed monomer SO+ uptake was adopted on sepiolite for its large SSA and low CEC. Dense multilayers or admicelles of SO+ formed on zeolite surfaces. As such, for the best SO removal, palygorskite is better than sepiolite, though both are fibrous clay minerals.

Multivariate analysis of native forest species in relation to chemical and texture attributes of soil in the region of Cotriguaçu – Mato Grosso State

This paper aimed to classify the forest species related to the demands on soil fertility and to identify groups with similar characteristics using multivariate statistical techniques. To do so, we analyzed soil samples for the texture and for chemical attributes and we carried out a phytosociological survey of the region. In the principal component analysis, the relations of the complex soil were summarized into four components, which together explained 80% of data variance, with most signifcant relationships between the sum of bases, base saturation, total cation exchange capacity, aluminum saturation, Ca + Mg, Al and clay, with correlation coeffcient greater than 90%. In hierarchical cluster analysis, 70% is similar to soil attributes; three distinct groups of forest species were formed. Multivariate analysis was effective in reducing the original variables, separation and classifcation of groups and identifcation of soil chemical properties most required by forest species. Groups 1 and 2 contain species more demanding in fertility, with preferences for medium textured soils and rich in calcium and magnesium bases. While Group 3 seems to be less demanding, with a predominance in sandy and acidic soils, with large cation exchange capacity and high aluminum saturation. Therefore, the species of the latter group can be indicated for the recovery of the degraded areas. The species Copaifera sp . and Goupia glabra deserve more studies about the mechanisms of adaptation to low soil fertility conditions.

Análise multivariada de espécies florestais nativas em relação aos atributos químicos e texturais do solo na região de Cotriguaçu – MT

Objetivou-se neste trabalho classificar as espécies florestais quanto às exigências em fertilidade do solo, bem como identificar grupos com características semelhantes utilizando técnicas da estatística multivariada. Para isso, foram analisadas amostras de solo quanto à textura e aos atributos químicos e realizado um levantamento fitossociológico da região. Na análise de componentes principais, as relações do complexo solo foram resumidas em quatro componentes que juntos explicaram 80% da variância dos dados, com relações mais significativas entre a soma de bases, saturação por bases, capacidade de troca catiônica efetiva, saturação por alumínio, Ca+Mg, Al e argila, com coeficiente de correlação maior que 90%. Na análise de agrupamento hierárquico, com 70% de similaridade quanto aos atributos do solo, formaram-se três grupos distintos de espécies florestais. A análise multivariada foi eficiente na redução das variáveis originais, separação e classificação dos grupos e identificação dos atributos químicos do solo mais requeridos pelas espécies florestais. Os Grupos 1 e 2 contêm espécies mais exigentes em fertilidade, com preferências por solos de textura média ricos em bases de cálcio e magnésio, enquanto o Grupo 3 parece ser menos exigente, prevalecendo em solos mais arenosos e mais ácidos, com grande capacidade de troca de cátions e elevada saturação por alumínio; podendo, as espécies desse último grupo, ser indicadas para recuperação de áreas degradadas. As espécies Copaifera sp. e Goupia glabra merecem mais estudos quanto aos mecanismos de adaptação às condições de baixa fertilidade do solo.

Enhanced Phototransformation of Tetracycline at Smectite Clay Surfaces under Simulated Sunlight via a Lewis-Base Catalyzed Alkalization Mechanism.

As an important class of soil minerals and a key constituent of colloidal particles in surface aquifers, smectite clays can strongly retain tetracyclines due to their large surface areas and high cation exchange capacities. However, the research on phototransformation of tetracyclines at smectite clay surfaces is rarely studied. Here, the phototransformation kinetics of tetracycline preadsorbed on two model smectite clays (hectorite and montmorillonite) exchanged with Na+, K+, or Ca2+ suspended in aqueous solution under simulated sunlight was compared with that of tetracycline dissolved in water using batch experiments. Adsorption on clays accelerated tetracycline phototransformation (half-lives shortened by 1.1-5.3 times), with the most significant effects observed for Na+-exchanged clays. Regardless of the presence or absence of clay, the phototransformation of tetracycline was facilitated by increasing pH from 4 to 7. Inhibition or enhancement of photolysis-induced reactive species combined with their measurement using scavenger/probe chemicals indicate that the facilitated production of self-photosensitized singlet oxygen (1O2) was the key factor contributing to the clay-enhanced phototransformation of tetracycline. As evidenced by the red shifts and the increased molar absorptivity in the UV-vis absorption spectra, the complexation of tetracycline with the negatively charged (Lewis base) sites on clay siloxane surfaces led to formation of the alkalized form, which has larger light absorption rate and is more readily to be oxidized compared to tetracycline in aqueous solution at equivalent pH. Our findings indicate a previously unrecognized, important phototransformation mechanism of tetracyclines catalyzed by smectite clays.

Sorption of atenolol, sulfamethoxazole and carbamazepine onto soil aggregates from the illuvial horizon of the Haplic Luvisol on loess

The leakage of pharmaceuticals present in soils towards groundwater is largely controlled by sorption of those compounds in soils. In some soils, soil aggregates are covered by coatings, which may have considerably different composition in comparison to that in an inner part of the aggregates. The aim of this study was to evaluate the sorption of three pharmaceuticals, which were applied in single or all compounds solutions, onto soil samples taken from the Bt horizon of a Haplic Luvisol. Analyses were performed on three types of disturbed soil samples: (1) entire aggregates, (2) aggregates from which coatings were removed, and (3) clay-organic coatings. Sorption of atenolol onto material from coatings was slightly higher than that onto material from the inner parts of the aggregates. On the other hand, sorption of sulfamethoxazole onto material from the coatings was lower than that from the aggregate interior. Both associates with a dominant fraction of clay particles (that are mostly negatively charged) in the coatings in comparison to soil composition in interiors and thus larger cation exchange capacity, which increased sorption of the positively charged atenolol and decreased sorption of the negatively charged sulfamethoxazole. Sorption of carbamazepine, which was in neutral form, did not substantially differ. The sorption of all three compounds did not decrease due to the competition between these compounds for the same sorption sites when applied simultaneously. Atenolol sorption was similar for both applications. Sorption of sulfamethoxazole increased when applied in solution with the other two compounds in comparison to its negligible sorption measured for the single compound solution likely due to sorption of the positively charged molecules of atenolol onto the negatively charged surface of soil components and reduction of repulsion between the soil components and the negatively charged molecules of sulfamethoxazole. Carbamazepine sorption also increased probably due to ionization of molecules due to dipole - induced dipole interaction between non-polar and polar molecules in solution.

Intercalated theophylline-smectite hybrid for pH-mediated delivery

On the basis of their large specific surface areas, high adsorption and cation exchange capacities, swelling potential and low toxicity, natural smectite clays are attractive substrates for the gastric protection of neutral and cationic drugs. Theophylline is an amphoteric xanthine derivative that is widely used as a bronchodilator in the treatment of asthma and chronic obstructive pulmonary disease. This study considers the in vitro uptake and release characteristics of the binary theophylline-smectite system. The cationic form of theophylline was readily ion exchanged into smectite clay at pH 1.2 with a maximum uptake of 67 ± 2 mg g−1. Characterisation of the drug-clay hybrid system by powder X-ray diffraction analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy confirmed that the theophylline had been exclusively intercalated into the clay system in an amorphous form. The drug remained bound within the clay under simulated gastric conditions at pH 1.2; and the prolonged release of approximately 40% of the drug was observed in simulated intestinal fluid at pH 6.8 and 7.4 within a 2-h timeframe. The incomplete reversibility of the intercalation process was attributed to chemisorption of the drug within the clay lattice. These findings indicate that smectite clay is a potentially suitable vehicle for the safe passage of theophylline into the duodenum. Protection from absorption in the stomach and subsequent prolonged release in the small intestine are advantageous in reducing fluctuations in serum concentration which may impact therapeutic effect and toxicity.

Evaluation of the long‐term effect of biochar on properties of temperate agricultural soil at pre‐industrial charcoal kiln sites in Wallonia, Belgium

Research on biochar has increased, but its long‐term effect on the fertility of temperate agricultural soil remains unclear. In Wallonia, Belgium, pre‐industrial charcoal production affected former forested areas that were cleared for cultivation in the nineteenth century. The sites of traditional charcoal kilns, largely enriched in charcoal residues, are similar to soil amended with hardwood biochar more than 150 years ago. We sampled 17 charcoal kiln sites to characterize their effect on soil properties compared with adjacent reference soils. Charcoal‐C content was estimated by differential scanning calorimetry. The kiln soil contains from 1.8 to 33.1 g kg−1 of charcoal‐C, which markedly increases organic C:N and C:P ratios. It also contains slightly more uncharred soil organic carbon (SOC) than the reference soil, which accords with larger total N content. We measured a small increase in nitrates in the kiln soil that might relate to greater mineralization and nitrification of organic N. Frequent application of lime raised the pH to values close to neutral, which offset the residual effect of charcoal production on soil acidity. A cation exchange capacity (CEC) of 414 cmolc kg−1 was estimated for charcoal‐C, whereas that of uncharred SOC was 213 cmolc kg−1. Despite the large CEC of the kiln soil, exchangeable K+ content was no different from the adjacent soil, whereas exchangeable Ca2+ and Mg2+ contents were considerably larger. Charcoal enrichment has little effect on available, inorganic and total P, but it can form strong complexes with Cu, which reduces the availability of the metal. Biochar is very persistent in soil; therefore, long‐term implications should not be overlooked.HighlightsCharcoal kiln soil contains from 1.8 to 33.1 g kg−1 of charcoal‐C, which raises C:N and C:P ratios. Charcoal‐C content was estimated by differential scanning calorimetry. We estimated a CEC of 414 cmolc kg−1 for charcoal‐C and 213 cmolc kg−1 for uncharred SOC. Retention of exchangeable K+ remained unaffected by charcoal but that of Ca2+ and Mg2+ increased.