Smectite Clay Research Articles

Valorization of Different Clays Used in the Treatment of Oily Wastewater in the Development of Construction Products

AbstractThe aim of this research is to study the feasibility of using clays used in the decontamination of wastewater containing olive oil wastewater (OOW), new lubricating oil (NOW) or motor oil (MOW) in the manufacture of ceramic bricks. Three types of clays were used for filtration, kaolinite type clay (KT), smectite type clay (CT) both from Tunisia and illitic chloritic clay (CS) from Jaén (Spain). These clays containing different types of oils, as well as the control clays, were used in the manufacture of bricks fired at 900 °C. These bricks were characterized by physical, mechanical and thermal tests. The sintered microstructure’s evolution was followed by tracked through scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The results indicate that the specific type of clay used influences the technological characteristics of the bricks. The use of CT clay gives rise to increase bulk density, greater compressive strength, and reduced apparent porosity and water absorption. The use of clays used in the decontamination of water containing oils produced a decrease in bulk density, compressive strength and thermal conductivity and leads to an increase in apparent porosity and water absorption in the order OOW > NOW > MOW according to the total organic carbon content (TOC). Therefore, the use of clays used in the filtration of water that contain different oils can represent a promising way of valorizing this waste, which can alleviate the environmental impact and represents economic savings for the industry of construction materials with properties of thermal insulation, getting closer to a circular economy.

Olivine alteration and the loss of Mars' early atmospheric carbon.

The early Martian atmosphere had 0.25 to 4 bar of CO2 but thinned rapidly around 3.5 billion years ago. The fate of that carbon remains poorly constrained. The hydrothermal alteration of ultramafic rocks, rich in Fe(II) and Mg, forms both abiotic methane, serpentine, and high-surface-area smectite clays. Given the abundance of ultramafic rocks and smectite in the Martian upper crust and the growing evidence of organic carbon in Martian sedimentary rocks, we quantify the effects of ultramafic alteration on the carbon cycle of early Mars. We calculate the capacity of Noachian-age clays to store organic carbon. Up to 1.7 bar of CO2 can plausibly be adsorbed on clay surfaces. Coupling abiotic methanogenesis with best estimates of Mars' δ13C history predicts a reservoir of 0.6 to 1.3 bar of CO2 equivalent. Such a reservoir could be used as an energy source for long-term missions. Our results further illustrate the control of water-rock reactions on the atmospheric evolution of planets.

Electronic Structure Sensitivity to Hydration in Smectite Clays Unveiled by Near-Ambient Pressure X-ray Photoelectron Spectroscopy

Electronic Structure Sensitivity to Hydration in Smectite Clays Unveiled by Near-Ambient Pressure X-ray Photoelectron Spectroscopy

Insights into the formation and growth of authigenic chlorite in sandstone: Analysis of mineralogical and geochemical characteristics from Shaximiao Formation, Sichuan Basin, SW China

Chlorite is a widely distributed clay mineral in sandstone reservoirs, attracting significant attention due to its complex physicochemical properties and unique reservoir significance. The Shaximiao Formation in the Sichuan Basin, SW China, features abundant diagenetic chlorite, offering valuable insights into chlorite growth theories. Petrographic observations and electron probe analyses reveal that the formation of authigenic chlorite resembles a continuous, staged growth process, akin to tree growth. This process encompasses stages from depositional smectite clay (seeding) to inner-layer chlorite formation (germination), outer-layer chlorite development (branching), and pore-filling chlorite precipitation (blooming). During the initial burial, depositional smectite (seeds) transforms into low-Fe, low-Mg inner-layer chlorite (germination) under the influence of Fe and Mg ions in the original formation water. In the early diagenetic stage, volcanic detritus and biotite alteration release substantial Fe2+ and Mg2+, fostering the growth of outer-layer chlorite (branching) on the inner-layer chlorite. In the middle diagenetic stage, volcanic detritus releases Ca2+, Fe2+, and Mg2+ under the influence of organic acids, leading to supersaturation of Si4+, Al3+, Fe2+, and Mg2+ in pore water, which directly crystallizes into highly euhedral pore-filling chlorite (blooming). The presence of precursor smectite is fundamental to this process, while sufficient Fe and Mg sources are crucial for chlorite formation.

Rheology and Structure of Model Smectite Clay: Insights From Molecular Dynamics

AbstractThe low frictional strength of smectite minerals, such as montmorillonite, is thought to play a critical role in controlling the rheology and the stability of clay‐rich faults. In this study, we perform molecular dynamics simulations on a model clay system. Clay platelets are simplified as oblate ellipsoids interacting via the Gay‐Berne potential. We study the rheology and structural development during shear in this model system, which is sheared at constant strain rates for 10 strains after compression and equilibrium. We find that the system exhibits velocity‐strengthening behavior over a range of normal stresses from 1.68 to 56.18 MPa and a range of strain rates from 6.93 × 105 to 6.93 × 108/s. The relationship between shear stress and strain rate follows the Herschel‐Bulkley model. Shear localization is observed at lower strain rates despite the velocity‐strengthening friction, while homogeneous shear is realized at higher strain rates. The structure change due to shear is analyzed from various aspects: the porosity, particle orientation, velocity profile, and the parallel radial distribution function. We find that particle rearrangement and compaction dominate at the early stage of shear when the shear stress increases. The shear band starts to form in the later stage as the shear stress decreases and relaxes to a steady‐state value. The structural development at low strain rates is similar to previous experimental observations. The stacking structure is reduced during shear and restores logarithmically with time in the rest period.

An experimental study on the influence of pressure on permeability and seismic velocity in the Montserrat geothermal field (West Indies)

Volcanic regions are prime areas for harnessing geothermal energy. However, the geological complexity of these regimes can hinder the efficient exploitation of this renewable resource. As useful as geophysical surveys are in understanding the subsurface, models can be unconstrained due to the lack of realisitic data. Here, we present the results of a new laboratory study measuring permeability and P-wave velocity on altered lavas, volcaniclastic sediments and limestones samples obtained from three cores retrieved from the MON-3 well, drilled in the Montserrat geothermal field. By measuring these parameters at increasing effective pressure varying from 10 to 70 MPa, we found permeability stress senstivity factors varying from 0.006 to 0.122 MPa−1 and increases in P- wave velocity between 2 and 20 %. The highest permeability stress senstivity factor and largest increase in P-wave velocity found in altered lavas were interpreted to be as a result of the easy closure and deformation of slit shaped microfractures and smectite clays characteristic of low bulk modulus. Conversely, lowest permeability stress senstivity factors and smallest increases in P-wave velocity found in volcaniclastic sediments, were coincident with intergranular pore geometries and higher bulk modulus minerals such as quartz and illite-smectite that may enhance the rigidity of the rock. Additionally, by measuring permeability and P-wave velocity on samples cored perpendicular (vertical) and parallel (horizontal) to the axis of the core, we found higher permeability senstivity factors (0.001–0.05 MPa−1 higher) and P-wave velocity increases (1–4 % higher) on horizontal samples, which is consistent with the preferential closure of horizontally oriented pore spaces. From this experimental study, we provide implications for enhancing geothermal energy recovery in Montserrat. Overall, our findings can be utilized to help improve on geophysical and numerical models of volcanic geothermal regimes.

Mechanisms and Factors Influencing Adsorption of Nitroaromatic Compounds by Smectite Clays

Mechanisms and Factors Influencing Adsorption of Nitroaromatic Compounds by Smectite Clays

Insights on Adsorptive Property of Thermally Treated Smectite (Dioctahedral)

ABSTRACTThe use of clay in the field of mineral materials is directly impacted by its thermal stability and changes in microstructure and properties following heat and other treatments. Therefore, it is crucial to investigate how clay's composition and structure are changed with time or how its surface characteristics are changed because of heat treatment. In the current work, the effect of heat treatment on the adsorptive property of smectite clay under various conditions like initial polymer concentration and its molar mass, pH, and temperature variation has been investigated. Various techniques like X‐ray fluorescence spectrometry, thermal analysis, X‐ray diffraction, infrared spectroscopy, and scanning electron microscopy were used for the phase analysis and the structural features of the heat‐treated clay analysis. It was observed that the specific surface area of smectite gradually dropped as the preheating temperature was increased, and the phase composition and structure underwent significant changes. When clay is heated over 423 K, the adsorbed gases and water are forced off the surface, increasing the amount of free active sites, and smectite's adsorption potential was increased. By raising the polymer's initial concentration and molecular mass, the extent of adsorption was increased whereas it was decreased with the increase in pH. However, in the case of temperature, the adsorption was first increased and then decreased with the increase in temperature indicating a change in the chemical composition of the clay and hence the surface area.

Relevance of the Iron Distribution in Natural Smectite Clays for the Thermal Stability of PMMA-Clay Nanocomposites.

Polymer-clay nanocomposites have greater thermal stability compared to the pristine polymer matrix. This can be attributed to the physical barrier provided by the inclusion of 2D clay nanoparticles (especially of the smectite group), together with radical trapping related to the distribution of specific 3d atoms in the inorganic phase. To elucidate the relevance of the Fe3+ distribution in this synergic effect, the iron atoms present in octahedral sheets of natural nontronite clay (Non, 5.6 wt % Fe) or in maghemite (M) nanoparticles (γ-Fe2O3) were incorporated in a poly(methyl methacrylate) (PMMA) matrix. Na-laponite (Lap) clay was used to evaluate the contribution of the diffusion barrier effect to the increased thermal stability of a PMMA-Lap nanocomposite, as evidenced by the upshift of the thermogravimetric (TGA) curve compared to that for PMMA. The contribution of radical trapping to the thermal stability of the PMMA-Non nanocomposite was evidenced by a significant shift of the Fe K-edge rising edge position by -4.5 eV after iron reduction by heating in N2, while similar treatment of pristine nontronite did not lead to a significant rising edge shift in the X-ray absorption spectra (XAS). This downshift demonstrated the reduction of Fe3+ to Fe0, induced by the sequestration of radicals formed by PMMA depolymerization. Raman spectroscopy analysis evidenced the formation of graphitic char deposits above 400 °C, further improving the thermal stability of PMMA-Non by providing an additional physical barrier to mass transport. A fourth contribution of well-dispersed iron was the abstraction of carbon from the char by the iron carburization reaction, which hindered CO2 formation by oxidative coking. In contrast, no relevant contribution of graphitic layer deposition was observed for the PMMA-M-Lap nanocomposite, where its improved thermal stability was only due to the combined contributions of the gas diffusion barrier effect and radical trapping by iron atoms. The maghemite effectively captured the radicals confined by the clay sheets, resulting in significant stabilization of the nanocomposite, with a shift of the mass loss of the PMMA-M-Lap nanocomposite compared to PMMA-Lap.

Products from Photolysis Reactions of Tetracycline Mediated by Clay and Humic Substance Induce Contrasting Expressions of Target Resistance Genes.

Phototransformation is a key process affecting the fate of many antibiotics in the environment, but little is known about whether their photoproducts exert selective pressure on bacteria by inducing antibiotic resistance genes (ARGs). Here, we examined the expression of tetracycline resistance gene tet(M) of a fluorescent Escherichia coli whole-cell bioreporter influenced by the phototransformation of tetracycline. The presence of suspended smectite clay (montmorillonite or hectorite, 1.75 g/L) or dissolved humic substance (Pahokee Peat humic acid or Pahokee peat fulvic acid, 10 mg C/L) in aqueous solutions markedly facilitated the transformation of tetracycline (initially at 400 μg/L) with half-life shortened by 1.4-2.6 times. Despite the similar phototransformation ratios (80-90%) of the total loaded tetracycline after 60 min irradiation, the decreased ratios of cell fluorescence intensity (which was proportional to the expression amount of ARG tet(M)) were much higher with the two clays (94 and 93%) than with the two humic substances (44 and 69%) when compared to the respective dark controls. As illustrated by mass spectroscopic and chemical analyses, tetracycline was proposed to be mainly transformed to amide (ineffective in inducing ARGs) with the presence of clays by reaction with self-photosensitized singlet oxygen (1O2), while the humic substances might catalyze the production of another two demethylated and/or deaminated compounds (still effective in inducing ARGs) in addition to the amide compound via reaction with triplet excited state dissolved organic matter (3DOM*). As clay minerals and humic substances are important soil constituents and ubiquitously present in surface environments, the observed clay and humic-dependent photooxidation pathways of tetracycline and the differing selective pressures of the associated products highlight the need for monitoring the transformation compounds of antibiotics and provide critical insight into the development of antibiotic treatment protocols.

Laponite nanoclays for the sustained delivery of therapeutic proteins

Protein therapeutics hold immense promise for treating a wide array of diseases. However, their efficacy is often compromised by rapid degradation and clearance. The synthetic smectite clay Laponite emerges as a promising candidate for their sustained delivery. Despite its unique properties allow to load and release proteins mitigating burst release and extending their effects, precise control over Laponite-protein interactions remains challenging since it depends on a complex interplay of factors whose implication is not fully understood yet. The aim of this review article is to shed light on this issue, providing a comprehensive discussion of the factors influencing protein loading and release, including the physicochemical properties of the nanoclay and proteins, pH, dispersion buffer, clay/protein concentration and Laponite degradation. Furthermore, we thoroughly revise the array of bioactive proteins that have been delivered from formulations containing the nanoclay, highlighting Laponite-polymer nanocomposite hydrogels, a promising avenue currently under extensive investigation.

Smectite Clay Nanoparticles as a Sustained Release System for Cinnamom Essential Oil Targeting Candida albicans

Smectite Clay Nanoparticles as a Sustained Release System for Cinnamom Essential Oil Targeting Candida albicans

Application and efficacy of beidellite clay for the adsorption and detoxification of deoxynivalenol (vomitoxin)

The incidence of mycotoxin occurrence throughout the entire lifespan of some agricultural products could be due to climatic conditions and environmental factors (including high temperature, drought, and heavy rainfall) that enhance growth of fungi. Deoxynivalenol (DON) which is also referred to as vomitoxin is a mycotoxin produced from many Fusarium species. DON ranks high among the prominent mycotoxins in cereal products and is a ubiquitous toxin in livestock feeds. DON's adverse effects present major health challenges in both livestock and humans. The use of natural sorbents including smectite clays, is an economically feasible strategy to mitigate mycotoxin toxicities. Previous studies have demonstrated the potential of edible clays as protective components of human food and animal feed to alleviate toxicity associated with short-term exposure to mycotoxins including DON. Hence, this study was designed to investigate the sorption mechanisms of DON onto the binding surfaces of beidellite clay, assessing essential binding parameters such as enthalpy, free energy, binding capacity, affinity, and plateau surface density. These markers were used to predict availability of DON under the experimental conditions. Furthermore, the protection of beidellite clay against DON-induced toxicity was carried out using living organisms susceptible to DON toxicity, including Hydra vulgaris and Lemna minor. These studies investigated the dose-dependent detoxification of DON by 0.05–2 % inclusion of beidellite. Beidellite exhibited more than 75 % protection in Lemna minor and 53 % in Hydra vulgaris validating that this clay is effective in detoxifying DON. During emergencies, or after disasters, inclusion of edible clay like beidellite in food, water or capsules could reduce bioavailability of DON and halt potential exposures to humans and animals.

Montmorillonite restricts free fatty acid liberation and alters self-assembled structures formed during in vitro lipid digestion

The global rise in obesity necessitates innovative weight loss strategies. Naturally occurring smectite clays, such as montmorillonite (MMT), offer promise due to their unique properties that interfere with free fatty acid (FFA) liberation, reducing systemic uptake. However, the mechanisms of MMT-FFA interactions and their implications for weight management are undefined. This study investigates these interactions by adding MMT (10 % w/w) to in vitro lipolysis media containing medium chain triglycerides (MCTs), and monitoring FFA liberation using pH-stat titration. Nanoparticle tracking analysis (NTA) and synchrotron-based small-angle X-ray scattering (sSAXS) observed time-dependent structural changes, while electron microscopy examined clay morphology during digestion. A 35 % reduction in FFA liberation occurred after 25 min of digestion with MCT + MMT, with digestion kinetics following a biphasic model driven by calcium soap formation. NTA revealed a 17-fold decrease in vesicular structures with MCT + MMT, and sSAXS highlighted a rapid lamellar phase evolution linked to calcium soap formation. This acceleration is attributed to MMT's adsorption to unionized FFAs via hydrogen bonding, supported by TEM images showing a decrease in d-spacing, indicating FFA intercalation is not the main adsorption mechanism. These findings highlight MMT's potential as a novel intervention for reducing dietary lipid absorption in obesity and metabolic diseases.

HTO and selenate diffusion through compacted Na-, Na–Ca-, and Ca-montmorillonite

Radionuclide transport in smectite clay barrier systems used for nuclear waste disposal is controlled by diffusion, with adsorption significantly retarding transport rates. While a relatively minor component of spent nuclear fuel, 79Se is a major driver of the safety case for spent fuel disposal due to its long half-life (3.3 × 105 yr) and its low adsorption to clay (KD < 10 L/kg), thus a thorough understanding of Se diffusion through clay is critical for understanding the long-term safety of spent fuel disposal systems. Through-diffusion experiments with tritiated water (HTO, conservative tracer) and Se(VI) were conducted with a well-characterized, purified montmorillonite source clay (SWy-2) under a constant ionic strength (0.1 M) and three different electrolyte compositions: Na+, Ca2+, and a Na + -Ca2+ mixture at pH 6.5 in order to probe the effects of electrolyte composition and interlayer cation composition on clay microstructure, Se(VI) aqueous speciation, and ultimately diffusion. The results were modeled using a reactive transport modeling approach to determine values of porosity (ε), De (effective diffusion coefficient), and KD (distribution coefficient for adsorption). HTO diffusive flux was higher in Ca-montmorillonite (De = 1.68 × 10−10 m2 s−1) compared to Na-montmorillonite (De = 7.83 × 10−11 m2 s−1). This increase in flux is likely due to a greater degree of clay layer stacking in the presence of Ca2+ compared to Na+, which leads to larger inter-particle pores. Overall, the Se(VI) flux was much lower than the HTO flux due to anion exclusion, with Se(VI) flux following the order Ca (De = 1.03 × 10−11 m2 s−1) > Na–Ca (De = 2.12 × 10−12 m2 s−1) > Na (De = 1.28 × 10−12 m2 s−1). These differences in Se(VI) flux are due to a combination of factors, including (1) larger accessible porosity in Ca-montmorillonite due to clay layer stacking and smaller electrostatic effects compared to Na-montmorillonite, (2) larger accessible porosity for neutral-charge CaSeO4 species which makes up 32% of aqueous Se(VI) in the pure Ca system, and (3) possibly higher Se(VI) adsorption for Ca-montmorillonite. Through a combination of experimental and modeling work, this study highlights the compounding effects that electrolyte and counterion compositions can have on radionuclide transport through clay. Diffusion models that neglect these effects are not transferable from laboratory experimental conditions to in situ repository conditions.

Deciphering Mineralogical Composition and Clay Diagenesis in Exposed Shales of Jaintiapur, Surma Basin: Unveiling Insights into Burial Diagenesis

Mineralogical analysis of exposed shale samples in the Jaintiapur region was conducted utilizing X-ray diffraction (XRD) techniques. The studied shales are characterized by illite, chlorite, illite/ smectite mixed layer clay, and kaolinite as the predominant clay minerals, with a relatively lower proportion of smectite. Additionally, the non-clay fraction consists mainly of quartz, feldspar, dolomite, and trace amounts of pyrite. Notably, illite and chlorite exhibit prominent abundance within the clay portion, while quartz is the prevailing non-clay mineral. Furthermore, the investigation reveals a notable enrichment of illite and chlorite with the advancement from younger to older stratigraphic formations in the studied shale samples, indicating greater intensity in clay mineral diagenesis in deeper stratigraphic formations. The transition from smectite to illite minerals can release Si, Ca, Fe, and Mg ions, potentially entering nearby sandstones and leading to cementation with quartz, chlorite, and calcite. This process aids in retaining pore water in shales. In this context, overpressure development influenced by clay diagenesis is not primarily due to cementation while undergoing smectite to illite conversion but due to illite packet formation within smectite, reducing shale permeability. During this conversion, interlayer water shifts to free water, causing volume reduction compounded by the low permeability of shale, trapping fluids in the pores. This expansion of pore water, reduced velocity, and increased pore pressure suggest that mineral transformation with burial depth might contribute to overpressure development. However, the observed decline in smectite clays in sediments transitioning from younger to older, culminating in their absence in older shale-dominated formations, explains the presence of diagenetic illite and chlorite. This study underscores the progressive diagenetic transformation in clay mineralogical composition with progressive burial across the sedimentary succession. The Dhaka University Journal of Earth and Environmental Sciences, Vol. 12(2), 2023, P 69-82

Influence of Sol-Gel State in Smectite Aqueous Dispersions on Drying Patterns of Droplets.

The sol-gel state of smectite clay dispersions varies with the volume fraction of clay and electrolyte concentration. In this study, it was elucidated that the drying patterns of droplets from four types of smectite clay dispersions vary according to their sol-gel states. Droplets in the sol state exhibited a ring-shaped pattern, while those in the gel state showed a bump-shaped pattern. Near the boundary between the sol and gel states, patterns featuring both ring and bump structures were observed regardless of whether the droplets were on the sol or gel side. When guest particles or molecules were introduced into the clay dispersion, they dispersed uniformly within the system, and the drying pattern depended on the sol-gel state of the droplets. These findings suggest that the presence or absence of convection within the droplets during drying governs the drying pattern.

A synthetic and transparent clay removes Microcystis aeruginosa efficiently

Clay-algae flocculation is a promising method to remove harmful algal blooms (HABs) in aquatic ecosystems. Many HAB-generating species, such as Microcystis aeruginosa (M. aeruginosa), a common species in lakes, produce toxins and harm the environment, human health, and the economy. Natural clays, such as bentonite and kaolinite, and modification of these clays have been applied to mitigate HABs by forming large aggregates and settling down. In this study, we aim to examine the impact of laponite, a commercially available smectite clay that is synthetic, transparent, compatible with human tissues, and degradable, on removing HABs. We compare the cell removal efficiencies (RE) of laponite, two natural clays, and their polyaluminum chloride (PAC)-modified versions through clay-algae flocculation experiments. Our results show that the optimum concentrations of laponite, bentonite, kaolinite, PAC-modified bentonite, and PAC-modified kaolinite to remove 80 % of the M. aeruginosa cells from the water column are 0.05 g/L, 2 g/L, 4 g/L, 2 g/L and 0.3 g/L respectively. Therefore, to achieve the same cell removal efficiency, the amount of laponite needed is 40 to 80 times less than bentonite and kaolinite, and 6 times less than PAC-modified kaolinite. We demonstrate that the superior performance of laponite clay is because of its smaller particle size, which increases the encounter rate between cells and clay particles. Furthermore, experiments using water samples from Powderhorn Lake confirmed laponite's effectiveness in mitigating HABs. Our price analysis also suggests that this commercially-available clay, laponite, can be used in the field at a relatively low cost.

Diagenetic controls on the quality of shallow marine sandstones: An example from the Cambro-Ordovician Saq Formation, central Saudi Arabia

The Saq Formation is the most important Paleozoic aquifer in central and northern Saudi Arabia. However, owing to the continued depletion of the aquifers and the great depths to which the aquifers are buried in undrilled/underexplored regions, the aquifers porosity and permeability are increasingly becoming an issue of concern. Here, we employed thin-section petrography, petrophysical measurements, X-ray diffraction and scanning electron microscopic analyses, and fluid inclusion microthermometry to investigate the composition and diagenetic evolution of the Saq sandstones. The results of this study indicate that the sandstones are mainly quartz arenite in composition, mostly well sorted, and ranged in grain size from silt to coarse-grained sandstones. We observed three diagenetic stages (early, middle, and late) that impacted the porosity evolution of the Saq sandstones. Mechanical compaction, formation of authigenic kaolinite, and infiltration of smectitic clays occurred during early shallow burial diagenesis. The middle (deep-burial) diagenesis was dominated by mechanical and chemical compaction, formation of authigenic quartz overgrowths, transformation of kaolinite and smectite into illite, and precipitation of late calcite. The late (uplift-related) diagenesis resulted in the formation of authigenic kaolinite, dissolution of the late calcite, and the formation of predominantly pore-filling Fe-oxide (goethite) cement. Fluid inclusion results of this study show that quartz cement mostly formed at temperatures ranging between 151 °C and 175 °C and reached up to 272 °C, with, at least, two phases of overgrowth development. The overall high amounts of rigid grain contents (>65 %), low detrital matrix (<10 %), and coarser grain size have maintained the Saq sandstone quality (average permeability = 2100 mD) despite having been buried to great depths. The findings of this study provide useful insights into the diagenetic evolution of the Saq Formation, which has provided important input data for forward diagenetic modelling of their subsurface equivalent in Saudi Arabia and sandstones of similar depositional settings elsewhere.

Effects of humic acid and mineral Zn fertilizer on Zn uptake and maize yield in soils formed on limestone and marl parent materials

In this study, the effects of zinc (Zn) and humic acid (HA) applications on soils (12 Aridisol soil samples) formed on limestone and marl parent materials, which are very common in Türkiye, were tested by incubation, adsorption, and greenhouse experiments. Adsorption experiments were carried out using the batch sorption technique, and the Langmuir and Freundlich isotherm parameters were calculated. In the incubation, soils were incubated with control, HA, Zn, and HA+Zn, and the DTPA-Zn was tested in five different periods (1, 7, 15, 30, and 90th days). Maize was grown for eight weeks in pots in the greenhouse. The maximum Zn adsorption for all soils ranged between 3333 and 6250 mg kg-1 in marl soils and 1042 and 5263 mg kg-1 in limestone soils, which decreased to ranges between 2631 and 5555 mg kg-1 in marl soils and 1052 and 5000 mg kg-1 in limestone soils with HA appli-cation, respectively. The desorption rate (%) of adsorbed Zn increased as the initial Zn concentration increased in all soil series formed on marl (smectite clay mineral) and lime-stone (kaolinite clay mineral) parent materials. The effects of humic acid and Zn applica-tion on the fresh and dry weights of maize were found to be statistically significant at the 5% level for marl and limestone parent material. Humic acid application increased the fresh weight of maize compared with that of the control. The highest available Zn was determined in Başkuyu series (0.79 mg kg-1) formed on marl parent material, while the lowest available Zn was obtained in Saraççeşme series (0.60 mg kg-1) formed on limestone parent material. In the greenhouse, HA increased the fresh weight of maize in soils formed on both parent materials by 0.4 and 19.6%, respectively, compared to the control. Zn fertili-zation with HA further increased the fresh and dry yields, with 12 mg kg-1 performing bet-ter. Smax (maximum Zn adsorption of the soil) parameters of soils were negatively corre-lated with EC, Pav, Kav, organic matter, silt, clay, total N, and cation exchange capacity (CEC) of the samples. Although HA alone increases the availability of Zn in plants, HA + Zn appli-cations should be applied together to obtain higher yields.