Dissolved organic matter sorption by mineral constituents of subsoil clay fractions

The retention of dissolved organic matter in soils is mainly attributed to interactions with the clay fraction. Yet, it is unclear to which extent certain clay‐sized soil constituents contribute to the sorption of dissolved organic matter. In order to identify the mineral constituents controlling the sorption of dissolved organic matter, we carried out experiments on bulk samples and differently pretreated clay‐size separates (untreated, organic matter oxidation with H₂O₂, and organic matter oxidation with H₂O₂ + extraction of Al and Fe oxides) from subsoil horizons of four Inceptisols and one Alfisol. The untreated clay separates of the subsoils sorbed 85 to 95% of the dissolved organic matter the whole soil sorbed. The sorption of the clay fraction increased when indigenous organic matter was oxidized by H₂O₂. Subsequent extraction of Al and Fe oxides/hydroxides caused a sharp decrease of the sorption of dissolved organic matter. This indicated that these oxides/hydroxides in the clay fraction were the main sorbents of dissolved organic matter of the investigated soils. Moreover, the coverage of these sorbents with organic matter reduced the amount of binding sites available for further sorption. The non‐expandable layer silicates, which dominated the investigated clay fractions, exhibited a weak sorption of dissolved organic matter. Whole soils and untreated clay fractions favored the sorption of ”︁hydrophobic” dissolved organic matter. The removal of oxides/hydroxides reduced the sorption of the lignin‐derived ”︁hydrophobic” dissolved organic matter onto the remaining layer silicates stronger than that of ”︁hydrophilic” dissolved organic matter.     

Adsorption of the Bacillus thuringiensis toxin (Cry1Ab) on Na‐montmorillonite and on the clay fractions of different soils

The adsorption of the toxin from Bacillus thuringiensis (Bt‐toxin), which is synthesized in genetically modified maize, on sterilized Na‐montmorillonite and on H₂O₂‐treated and untreated clay fractions of three soils from different sites were studied. All adsorption isotherms can be described by a linear isotherm. Although all clay fractions from the different soils show nearly the same mineralogical composition, we found different affinities ranging from k = 47.7 to k = 366.7 of the adsorbates for the Bt‐toxin. The H₂O₂‐treated clay fractions show no correlation between the adsorption affinity and the amount of soil organic matter. On the other hand, there is a correlation between the content of organic carbon and the adsorption affinity of the untreated clay fractions. This can be explained by the fact that due to the coatings of soil organic matter on aggregates, the Bt‐toxin polymers are not able to adsorb within the clay aggregates.     

Retention of cobalt by an oxisol in relation to the content of iron and manganese oxides

Abstract

The study aims at determining the cobalt retention properties of various soil components. Therefore, cobalt (Co) sorptions and extractions were carried out using an Oxisol sample before (untreated) and after successive removal of organic matter and active manganese (Mn) oxides (H₂O₂‐treated) and iron (Fe) oxides (H₂O₂+CBD‐treated). A synthetic goethite was included for comparison. Sorption of the four sorbents was determined over a range of Co concentrations (initially 10^‐8 M to 10^‐4 M), pH values (3 to 8) and reaction times (2 hours to 504 hours). The Co species sorbed was Co(ll), since oxygen exclusion during sorption had no effect on the amount sorbed. The pH‐dependent sorption curve (sorption edge) was shifted to lower pH at decreasing initial Co concentration and increasing reaction time. The displacements, in particular of the sorption edges corresponding to the lowest initial Co concentrations, to successively higher pH following removal of Mn oxides, organic matter and Fe oxides could be attributed to sorption onto sites of decreasing Co affinity [Mn oxides (and organic matter) > Fe oxides > kaolinite]. Extractions of sorbed Co at pH 5.5–7.5 with 2 M HCI showed that the extractability decreased with increasing sorption time and decreasing initial Co concentration. The untreated and H₂O₂‐treated soil samples retained sorbed Co at least as firmly as the synthetic goethite, whereas the H₂O₂+CBD‐treated sample (kaolinite) was clearly less effective. The results emphasized the importance of the soil Mn and Fe oxides for Co retention in soils but also the necessity of taken interior sorption sites into consideration.     

Molybdenum Determination in Mehlich‐1 and Mehlich‐3 Soil Test Extracts and Molybdenum Adsorption in Brazilian Soils

Abstract

The extractant Mehlich‐1 is routinely used in Brazil for determination of soil nutrients, whereas Mehlich‐3 has been suggested as a promising extractor for soil fertility evaluation. Both were used for extraction of molybdenum (Mo) in Brazilian soils with Mo dosage by the KI+H₂O₂ method. The Langmuir and Freundlich isotherms were used to study soil Mo adsorption. Mehlich‐1 extracted more Mo than Mehlich‐3 in soils with high contents of organic matter, clay, and iron (Fe) oxides. Mehlich‐3 and Mehlich‐1 extractions correlated positively and significantly with amorphous Fe oxides, crystalline Fe oxides, and organic matter. Molybdenum recovering rates correlated to crystalline Fe oxides and clay contents but not to organic matter, pH, and Mo adsorption capacity. Amorphous and crystalline Fe oxides, clay, and organic matter were responsible for most of the Mo adsorption. The Langmuir isotherm described better the Mo adsorption to soil amorphous Fe oxides and organic matter than the Freundlich isotherm.     

Copper and lead adsorption as influenced by organic matter in soils from a tropical toposequence with different chemical and mineralogical attributes

The aim of this work was to investigate the influence of the organic matter on copper and lead adsorption in soils with different physiochemical and mineralogical attributes. Suspensions (pH 6.0) of a Latosol, a Neosol and a Vertisol containing increasing amounts of copper or lead were used to obtain sorption isotherms while identical experiments were carried out with the soils previously treated with H₂O₂ to remove organic matter (OM). For the undisturbed soils, L-type and H-type isotherms were predominant for copper and lead respectively, showing that lead interacts more strongly with adsorption sites. For both metals, the non-linear Freundlich adsorption model revealed higher concentration of adsorption sites for Vertisol due to 2:1 clays. For the OM-removed soils, C-type isotherms were observed for copper with the permanence of less stable and more homogeneous sites. For this metal, a high correlation (R² = 0.997) was observed between the decrease of adsorbent sites and the loss of organic carbon, evidencing the central role of organic matter on copper complexation, while lead may be able to interact efficiently with both organic matter and soil minerals.     

Effect of organic matter on the parameters of the selective sorption of cobalt and zinc by soils and their clay fractions

The sorption and ion-exchange behavior of Co(II) and Zn in the soil-equilibrium solution system was studied for different types and varieties of native soils and their clay fractions before and after mild oxidation with H₂O₂ to remove the organic carbon. The parameters of the ion-exchange adsorption and the selectivity coefficients of the (Co(II), Zn)/Ca ion exchange were determined using different models for describing the relationship between the dissolved and sorbed forms of the metals. These were the empirical Langmuir and Freundlich adsorption isotherms and the model of the ion-exchange adsorption based on the acting mass law. It was found that the soil organic matter played an important role in the selectivity of the ion-exchange adsorption of Co(II) and Zn by the soils and their clay fractions. This was confirmed by an abrupt decrease (to almost 1) of the selectivity coefficients of the Co²⁺/Ca²⁺ and Zn²⁺/Ca²⁺ exchange after the treatment of the clay fraction with hydrogen peroxide.     

Adsorption and Desorption of Copper in Pasture Soils

Abstract

Copper (Cu) is bound strongly to organic matter, oxides of iron (Fe) and manganese (Mn), and clay minerals in soils. To investigate the relative contribution of different soil components in the sorption of Cu, sorption was measured after the removal of various other soil components; organic matter and aluminum (Al) and Fe oxides are important in Cu adsorption. Both adsorption and desorption of Cu at various pH values were also measured by using diverse pasture soils. The differences in the sorption of Cu between the soils are attributed to the differences in the chemical characteristics of the soils. Copper sorption, as measured by the Freundlich equation sorption constants [potassium (K) and nitrogen (N)], was strongly correlated with soil properties, such as silt content, organic carbon, and soil pH. The relative importance of organic matter and oxides on Cu adsorption decreased and increased, respectively, with increasing solution Cu concentrations. In all soils, Cu sorption increased with increasing pH, but the solution Cu concentration decreased with increasing soil pH. The cumulative amounts of native and added soil Cu desorbed from two contrasting soils (Manawatu and Ngamoka) during desorption periods showed that the differences in the desorbability of Cu were a result of differences in the physico‐chemical properties of the soil matrix. This finding suggests that soil organic matter complexes of Cu added through fertilizer, resulted in decreased desorption. The proportions of added Cu desorbed during 10 desorption periods were low, ranging from 2.5% in the 24‐h to 6% in the 2‐h desorption periods. The desorption of Cu decreased with increasing soil pH. The irreversible retention of Cu might be the result of complex formation with Cu at high pH.     

Selenite adsorption by a variety of oxides

Abstract

Selenite adsorption by a variety of oxides consisting of iron (Fe), aluminum (Al), titanium (Ti), manganes (Mn), and silicon (Si), and by two humic acids were investigated in order to grasp selenite behavior and fixation mechanisms in soil. It was found that selenite was apparently adsorbed even by the Mn oxides on which surface negative charge was dominant in normal pH range (pH <4). No selenite adsorption was observed in the silicon dioxide (SiO₂) and the two humic acids. A sequential extraction of adsorbed selenite with competitive anions showed the differences of binding force or stability of adsorbed selenite among the minerals. While the goethite fixed selenite strongly, selenite adsorbed on the Mn oxide was easily released to the liquid phase with other anions, such as phosphate. Each mineral had its inherent characteristic in ligand exchange reactions accompanied with selenite sorption. Selenite sorption by the Mn and the Ti oxides resulted in large increase of surface negative charge, while only a little increase in the Fe and Al oxides. Proton consumption with selenite sorption was extremely smaller for the Mn oxide than for the others.     

Soil hydrophobicity: a contribution of diuron sorption experiments

Retention processes play a major role in the fate and impact of organic contaminants in soils. The main goal of this study was to determine the influence of soil hydrophobic properties on the retention of diuron by using plots of a long‐term experiment in Versailles. We selected seven plots with pH 3.4 to 8.2 and low organic content. Sorption isotherms were obtained on soil slurries and kinetic measurements of diuron sorption were performed on undisturbed soil samples. The results showed that the Freundlich coefficient k_f decreased as pH increased and that the K_oc coefficient, k_f/TOC, was linearly related to the contact angle measured on the clay fraction over a wide range of pH. A low initial adsorption rate and low adsorption equilibrium were observed for the plot treated with NaNO₃. In this case, the structure in micro‐aggregates was assumed to limit the accessibility of adsorption sites. The CaCO₃ and CaO treated plots had similar organic matter contents, pHs, CECs and bulk densities, although their < 2 μm:C ratio differed. The higher retention of diuron in the CaCO₃ plot is attributed to the higher hydrophobicity of the < 2 μm fraction, probably masking part of the permanent clay negative charges. Thus, in addition to the different treatments, organic matter composition and distribution should also be included as specific soil properties. We conclude that the sorption properties of pesticides such as diuron can be a good tool to obtain greater understanding of soil properties and the degree of soil hydrophobicity/hydrophilicity in particular.     

Effects of Organic Matter-Rich Amendments on Selenium Mobility in Soils

Soil organic matter (SOM) plays an important role in the Se dynamics in soil. The potential effects of vermicompost and digestate as important sources of SOM on selenium (Se) mobility were assessed in this study. Three soils differing in their physicochemical parameters, fluvisol, chernozem, and luvisol, were chosen, and three types of vermicomposts based on various bio-waste materials as digestate (vermicompost 1), kitchen waste with woodchips (vermicompost 2), and garden bio-waste (vermicompost 3) were used due to their high organic matter content. Additionally, digestate samples alone were applied. To evaluate the potential effect of vermicompost application on sorption characteristics of soils, batch sorption experiments were performed. The results showed a predominant effect on Se species in the soils, where selenite sorbed more intensively compared to selenate, regardless of the soil and ameliorative material applied. In the control, the soil sorption ability of selenite tended to decrease in the order:fluvisol > luvisol > chernozem. However, these differences were not significant. Moreover, the effects of the ameliorative materials depended on both soil and amendment used. In fluvisol, all the amendment applications resulted in a decrease in distribution coefficient (K_d values) of Se, whereas in chernozem, this effect was observed only for the digestate-based vermicompost 1. Increasing K_d levels were reported in luvisol treated with digestate; the application of garden bio-waste-based vermicompost 3 tended to decrease the K_d values. Further studies are required on long-term effects of these amendments on Se mobility in soils and the role of individual organic matter fractions in this context.     

Role of Different Soil Fractions in Copper Sorption by Soils

Abstract

To evaluate contributions of organic matter, oxides, and clay fraction to copper (Cu) adsorption in six characterized soils, adsorption isotherms and distribution coefficients were obtained by a batch experimental method. Copper adsorption isotherms from untreated soil, organic matter removed from samples, and organic‐matter‐ and oxide‐removed samples were compared with curve patterns and correlated to Langmuir and Freundlich models. Copper sorption data on untreated soils described L or H‐curves, whereas in soils deprived of any component, their curves were S‐type. Distribution coefficients allowed knowing Cu adsorption capacity of untreated soil and of organic matter, oxides, and clay fraction. Soil organic matter is the main component that affects Cu adsorption as long as soil pH is near neutrality. At acid pH, oxides are the main component that affects Cu adsorption, although to a much smaller extent than organic matter near neutral conditions. Soil pH is the main soil factor that determines Cu adsorption.     

Copper retention by Danish Spodosols in relation to contents of organic matter and aluminum,iron, and manganese oxides

Abstract

The importance of various soil components on copper (Cu) retention by Spodosois was investigated. Copper sorption and extraction were conducted on samples from the B horizon from six Danish Spodosois. The investigation was conducted on untreated samples, on hydrogen peroxide‐treated samples (to remove organic matter), on oxalate‐treated samples [to remove amorphous to poorly crystalline aluminum (Al) and iron (Fe) oxides], on hydroxylamine‐treated samples [to remove manganese (Mn) oxides]. Subfractions treated with hydrogen peroxide (H₂O₂) were further treated with oxalate and citrate‐bicarbonate‐dithionite (CBD). Sorption of Cu from an initial 10^‐6 M solution after 48 hours was determined in the pH range 3 to 7 using 0.1M sodium nitrate (NaNO₃) as the background electrolyte. The pH‐dependent sorption curve (sorption edge) was shifted to a higher pH with decreasing Al oxide content in the soils, and for the treated sample after removal of organic matter and Al and Fe oxides. A negligible effect was seen after removal of the Mn oxides because of their low abundance. Extraction of sorbed Cu at pH 4 to 6 with 0.1M nitric acid (HNO₃) for 24 hours confirmed the sorption results, in inasmuch as removal of the Al (and Fe) oxides increased Cu extractability. Therefore, it was concluded that in the soils investigated, Cu retention is mainly determined by the oxalate‐extractable Al fraction with a minor contribution due to crystalline Fe oxides.     

Effect of Soil Organic Matter on Adsorption and Insecticidal Activity of Toxins from Bacillus thuringiensis

With the large-scale cultivation of transgenic crops expressing Bacillus thuringiensis (Bt) insecticidal toxin in the world, the problem of environmental safety caused by these Bt crops has received extensive attention. The effects of soil organic matter (SOM) on the adsorption and insecticidal activity of Bt toxin in variable- and constant-charge soils (red and brown soils, respectively) were studied. Organic carbon in the soils was removed using hydrogen peroxide (H_2O_2). After H_2O_2 treatment, the SOM in the red and brown soils decreased by 71.26% and 82.82%, respectively. Mineral composition of the H_2O_2-treated soils showed no significant changes,but soil texture showed a slight change. After SOM removal, the cation exchange capacity (CEC) and pH decreased, while the specific surface area (SSA), point of zero charge (PZC), and zeta potential increased. The adsorption isotherm experiment showed that the Bt toxin adsorption on the natural and H_2O_2-treated soils fitted both the Langmuir model (R~2≥ 0.985 7) and the Freundlich model (R~2≥ 0.984 1), and the amount of toxin adsorbed on the H_2O_2-treated soils was higher than that on the natural soils. There was a high correlation between the maximum adsorption of Bt toxin and the PZC of soils (R~2= 0.935 7); thus, Bt toxin adsorption was not only influenced by SOM content, but also by soil texture, as well as the SSA, CEC, PZC, and zeta potential. The LC_(50) (lethal concentration required to kill 50% of the larvae) values for Bt toxin in the H_2O_2-treated soils were slightly lower than those in the natural soils, suggesting that the environmental risk from Bt toxin may increase if SOM decreases. As the measurement of insecticidal activity using insects is expensive and time consuming, a rapid and convenient in vitro method of enzyme-linked immunosorbent assays is recommended for evaluating Bt toxin degradation in soils in future studies.     

Cadmium sorption by two acid soils as affected by clearing and cultivation

Abstract

The objective of this study was to determine the effect of clearing and cultivation on the sorption of cadmium (Cd) by two acid soils from Zimbabwe with differing cultivation stories. In their original state, not cleared‐not cultivated (virgin soils), the two soils exhibited noticeable and similar capacities to sorb Cd. The Mazowe soil contains the highest level of organic matter (40 g kg^‐1) and a effective cation exchange capacity (ECEC) of 144 mmol_c kg^‐1. Yet, Bulawayo soil (23.5 g kg^‐1 organic matter and ECEC of 146 mmol_c kg^‐1) has higher pH and Mn and Fe oxide content and these characteristics seemed to counteract the effect of lower organic matter. After 50 years of cultivation, The Mazowe soil has lost 60% of its organic matter and ECEC, and consequently the ability of its soil matrix to bind Cd has proportionally decreased. In Bulawayo (cleared in 1983 and first ploughed in 1984), on the contrary, the organic matter and ECEC of the cultivated soil remains over 95% of the values on its virgin counterpart. In this soil, the retaining ability for Cd has not still been affected. In the two soils Cd sorption was highly pH‐dependent. The extent of sorption was minimal under acidic conditions and increased sharply as the pH was raised. The immediate reversibility of the sorption process proved to be very low. When sorption and desorption data were compared it was clear that soil characteristics like high organic matter and oxide content which showed to enhanced Cd sorption, contributed at the same time to slow down the backward reaction.     

Specific surface area and surface charges of some argentinian soils

The specific surface areas of nine argentinian soils obtained by adsorption followed the order N₂ < ethylene glycol < H₂O, attributed to the presence of smectites (verified by XRD analysis) and some organic coating. The H₂O₂ treatment of these soils modified the former order of surface area determined by different absorbents. This order was modified because the mineral surface was evidenced and an increase of cation adsorption was produced by organic matter removal. This fact was supported by the decrease of PZC values of soils after H₂O₂ treatment. The specific surface area of initial soils obtained by water and ethylene glycol adsorptions showed a good correlation with carbon content and CEC of untreated soils and with the PZC of protonated soils.     

Effects of soil organic matter on pH-dependent phosphate sorption by soils

Effects of soil organic matter (80M) on P sorption of soils still remain to be clarified because contradictory results have been reported in the literature. In the present study, pH-dependent P sorption on an allophanic Andisol and an alluvial soil was compared with that on hydrogen peroxide (H₂0₂)-treated, acid-oxalate (OX)-treated, and dithionite-citrate- bicarbonate (DCB)-treated soils. Removal of 80M increased or decreased P sorption depending on the equilibrium pH values and soil types. In the H₂O₂ OX-, and DCB-treated soils, P sorption was pH-dependent, but this trend was not conspicuous in the untreated soils. It is likely that 80M affects P sorption of soils through three factors, competitive sorption, inhibition of polymerization and crystallization of metals such as AI and Fe, and flexible structure of metal-80M complexes. As a result, the number of available sites for P sorption would remain relatively constant in the wide range of equilibrium pH values in the presence of 80M. The P sorption characteristics were analyzed at constant equilibrium pH values (4.0 to 7.0) using the Langmuir equation as a local isotherm. The maximum number of available sites for P sorption (Q _max) was pH-dependent in the H₂0₂-, OX-, and DCBtreated soils, while this trend was not conspicuous in the untreated soils. Affinity constants related to binding strength (K) were less affected by the equilibrium pH values, soil types, and soil treatments, and were almost constant (log K ≈ 4.5). These findings support the hypothesis that 80M plays a role in keeping the number of available sites for P sorption relatively constant but does not affect the P sorption affinity. By estimating the Q _max and K values as a function of equilibrium pH values, pH-dependent P sorption was well simulated with four or two adjustable parameters. This empirical model could be useful and convenient for a rough estimation of the pH-dependent P sorption of soils.     

Chemical forms and sorption of copper and zinc in soils of central Chile

Abstract

Soil samples from a field irrigated with untreated industrial and municipal wastewater for several decades and from a field not receiving wastewater (control) were analyzed for total copper (Cu) and zinc (Zn) and for the amount of these elements removed in sequential extractions with MgCl₂, NaOAc, NH₂OH#lbHCl, 6H₂O₂‐HNO₃‐NH₄OAc, and HNO₃‐HF‐HCl. Organically‐bound Cu forms predominated in the wastewater‐affected soil while in the control soil both residual and organic forms yielded the same proportion of Cu. Distribution of Zn was different in the diverse fractions, and in the polluted soil the reducible and the residual forms predominated while in the control soil the residual form accounted for the highest proportion of recovered Zn. Sequential extraction of Cu from a copper sulfate‐treated soil incubated for 32 days at constant temperature resulted in the same proportional distribution of Cu forms in the polluted soil. In the control soil the oxidizable form decreased and the residual one increased noticeably. The two‐surface Langmuir adsorption model was used to adjust data and to interpret Cu and Zn adsorption by soils excepting Cu sorption by the polluted soil, where the one‐surface model was applied.     

Organic matter effects on phosphorus sorption in sandy soils

Phosphorus (P) sorption processes in soils contribute to important problems in agriculture: a deficiency of this plant nutrient and eutrophication in aquatic systems. Soil organic matter (SOM) plays a major role in sorption processes, but its influence on P sorption remains unclear and needs to be elucidated to improve the ability to effectively manage soil P. The aim of this research was to investigate the influence of SOM on P sorption. The study was conducted in sandy soil profiles and in topsoils before and after removal of SOM with H₂O₂. The results were interpreted with the Langmuir and Freundlich isotherms. Our results indicated that SOM affected P sorption in sandy soils, but that P sorption also depended on specific soil properties (e.g. values of the degree of P saturation (DPS), P sorption capacity (PSC) and pH) often related to land use. Removal of SOM decreased PSC in most of the topsoils tested; other soil properties became important in controlling P sorption. An increase in P desorption observed after SOM removal indicated that SOM was potentially that soil constituent which increased P binding and limited P leaching from these sandy soils.     

Adsorption of “real” dissolved organic matter on the clay and fine silt fractions of a forested Stagnic Gleysol

Dissolved organic matter (DOM) in soils is partially adsorbed when passing through a soil profile. In most adsorption studies, water soluble organic matter extracted by water or dilute salt solutions is used instead of real DOM gained in situ by lysimeters or ceramic suction cups. We investigated the adsorption of DOM gained in situ from three compartments (forest floor leachate and soil solution from 20 cm (Bg horizon) and 60 cm depth (2Bg horizon)) on the corresponding clay and fine silt fractions (< 6.3 μm, separated together from the bulk soil) of the horizons Ah, Bg, and 2Bg of a forested Stagnic Gleysol by batch experiments. An aliquot of each clay and fine silt fraction was treated with H₂O₂ to destroy soil organic matter. Before and after the experiments, the solutions were characterized by ultra‐violet and fluorescence spectroscopy and analyzed for sulfate, chloride, nitrate, and fluoride. The highest affinity for DOM was found for the Ah samples, and the affinity decreased in the sequence Ah > Bg > 2Bg. Dissolved organic matter in the 2Bg horizon can be regarded as slightly reactive, because adsorption was low. Desorption of DOM from the subsoil samples was reflected more realistically with a non‐linear regression approach than with initial mass isotherms. The results show that the extent of DOM adsorption especially in subsoils is controlled by the composition and by the origin of the DOM used as adsorptive rather than by the mineralogical composition of the soil or by contents of soil organic matter. We recommend to use DOM gained in situ when investigating the fate of DOM in subsoils.