Characterization of cation-pi interactions in aqueous solution using deuterium nuclear magnetic resonance spectroscopy

Chemical interactions of aromatic organic contaminants control their fate, transport, and toxicity in the environment. Recent molecular modeling studies have suggested that strong interactions can occur between the pi electrons of aromatic molecules and metal cations in aqueous solutions and/or on mineral surfaces, and that such interactions may be important in some environmental systems. However, spectroscopic evidence for these so-called cation-pi interactions has been extremely limited to date. In this paper, cation-pi interactions in aqueous salt solutions were characterized via 2H nuclear magnetic resonance (NMR) spin-lattice relaxation times (T1) and calculations of molecular correlation times (tau(c)) for a series of perdeuterated (d6-benzene) benzene-cation complexes. The T1 values for d6-benzene decreased with increasing concentrations of LiCl, NaCl, KCl, RbCl, CsCl, and AgNO3, with the largest effects observed in the AgNO3 and CsCl solutions. Upon normalizing tau(c) values by solution viscosity effects, an overall affinity trend of Ag+ > Cs+ > K+ > Rb+ > Na+ > Li+ was derived for the d6-benzene-cation complexes. The ability of Ag+ to complex d6-benzene was significantly reduced upon addition of NH3, which strongly coordinates Ag+ at high pH. Results with d6-benzene, d8-naphthalene, d2-dichloromethane, and d12-cyclohexane in 0.1 M methanolic salt solutions confirmed that spin-lattice relaxation rates are characterizing cation-pi interactions. The relatively strong cation-pi bonding observed between Ag+ and aromatic hydrocarbons probably results from covalent interactions between the aromatic pi electrons and the d orbitals of Ag+, in addition to the normal electrostatic interaction.     

Structural and sorption characteristics of adsorbed humic acid on clay minerals

Clay-humic complexes are commonly distributed in natural environments. They play very important roles in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study examined the structural changes of humic acid (HA) after adsorption by clay minerals and determined phenanthrene sorption by clay-humic complexes. Solid- and liquid-state 13C nuclear magnetic resonance (NMR), for the first time, provided direct evidence for HA fractionation during adsorption on mineral surfaces, that is, aliphatic fractions were preferentially adsorbed by clay minerals while aromatic fractions were left in the solution. The ratio of UV absorbance of HA at 465 and 665 nm (E4 to E6 ratio), which is related to aromaticity, corroborated with the NMR results. For both montmorillonite and kaolinite, adsorbed HA fractions had higher sorption linearity (N) and affinity (K(oc)) than the source HA. The K(oc) of adsorbed HA for the clay-humic complexes could be up to several times higher than that of the source HA. This large increase may be contributed by the low polarity of the bound HA. Moreover, for each mineral, the N values of adsorbed HA increased with increasing HA loading. It is believed that HA may develop a more condensed structure on mineral surface at lower HA loading level due to the stronger interactions between HA and mineral surface as a result of close contacts.     

Effect of cobalt sorption on metal fractionation in anaerobic granular sludge

A sequential extraction procedure was applied to two anaerobic methanogenic sludges (Eerbeek and Nedalco) to examine the speciation of micro- and macronutrients in the sludges after cobalt sorption by exposing the sludge to a 1 mM Co solution for 4 d at pH 7 and 30 degrees C. The effect of different physicochemical conditions on cobalt sorption was studied as well: effect of pH (6-8), effect of competition by a second trace element (Ni or Fe), modification of the granular matrix by glutaraldehyde or heat treatment, and EDTA (ethylenediaminetetraacetic acid) addition. Sorbed Co was found to distribute between the carbonates, organic matter + sulfides, and residual fractions. Cobalt adsorption resulted in an antagonistic interaction with other metals present in the granular matrix, evidenced by the solubilization of other trace elements (e.g., Ni, Cu, and Zn) as well as macronutrients (especially Ca and Fe). Modification of the sludge matrix by glutaraldehyde or heat treatment, or exposure to EDTA, led to serious modifications of the Co sorption capacity and strong interactions with multivalent cations (i.e., Ca(2+) and Fe(2+)).     

Sorption of aromatic compounds to clay mineral and model humic substance-clay complex: effects of solute structure and exchangeable cation

Clay minerals and humic substance (HS)-clay complexes are widely distributed in soil environments. Improved predictions on the uptake of organic pollutants by soil require a better understanding of fundamental mechanisms that control the relative contribution from organic and inorganic constituents. Five selected aromatic compounds varying in electronic structure, including nonpolar phenanthrene (PHEN), 1,2,4,5-tetrachlorobenzene (TeCB), polar 1,3-dinitrobenzene (DNB), 2,6-dichlorobenzonitrile (dichlobenil [DNL]), and 1-naphthalenyl methylcarbamate (carbaryl [CBL]), were sorbed separately from aqueous solution to Na(+)-, K(+)-, Cs(+)-, and Ca(2+)-saturated montmorillonites with and without the presence of dissolved HS at pH about 6. Upon normalizing for hydrophobic effects by solute aqueous solubility, the overall trend of sorptive affinity to HS-free K(+)-clay is DNB > DNL, CBL > PHEN, TeCB, indicating preferential adsorption of the polar solutes. With the presence of HS, sorption of PHEN, TeCB, and CBL increases by several times compared with the pure clay, attributed to HS-facilitated hydrophobic partition (PHEN and TeCB) or H-bonding (CBL). The enhanced sorption of PHEN by HS is cation dependent, where Cs(+) shows the strongest facilitative effect. Coadsorption of HS does not affect sorption of DNB and DNL to clays except that of DNB to Ca(2+)-clay because cation-dipole interactions between the polar group (NO(2) or CN) of solute and weakly hydrated exchangeable cations dominate the overall sorption.     

Sorption and stability of the polycyclic nitramine explosive CL-20 in soil

The polycyclic nitramine CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) is being considered for use as a munition, but its environmental fate and impact are unknown. The present study consisted of two main elements. First, sorption-desorption data were measured with soils and minerals to evaluate the respective contributions of organic matter and minerals to CL-20 immobilization. Second, since CL-20 hydrolyzes at a pH of >7, the effect of sorption on CL-20 degradation was examined in alkaline soils. Sorption-desorption isotherms measured using five slightly acidic soils (5.1 < pH < 6.9) containing various amounts of total organic carbon (TOC) revealed a nonlinear sorption that increased with TOC [K(d) (0.33% TOC) = 2.4 L kg(-1); K(d) (20% TOC) = 311 L kg(-1)]. Sorption to minerals (Fe(2)O(3), silica, kaolinite, montmorillonite, illite) was very low (0 < K(d) < 0.6 L kg(-1)), suggesting that mineral phases do not contribute significantly to CL-20 sorption. Degradation of CL-20 in sterile soils having different pH values increased as follows: sandy agricultural topsoil from Varennes, QC, Canada (VT) (pH = 5.6; K(d) = 15 L kg(-1); 8% loss) < clay soil from St. Sulpice, QC, Canada (CSS) (pH = 8.1; K(d) = 1 L kg(-1); 82% loss) < sandy soil provided by Agriculture Canada (SAC) (pH = 8.1, K(d) = approximately 0 L kg(-1); 100% loss). The faster degradation in SAC soil compared with CSS soil was attributed to the absence of sorption in the former. In summary, CL-20 is highly immobilized by soils rich in organic matter. Although sorption retards abiotic degradation, CL-20 still decomposes in soils where pH is >7.5, suggesting that it will not persist in even slightly alkaline soils.     

Can assessing for potential contribution of soil organic and inorganic components for butachlor sorption be improved?

Sorption of butachlor to various types of common soil components was investigated. Six pure minerals (montmorillonite [Mont], kaolinite [Kaol], Ca homoionic montmorillonite [Ca-Mont] and kaolinite [Ca-Kaol], amorphous hydrated Al and Fe oxides [AHOs-Al, AHOs-Fe]), four soil alkali-extractable pure humic acids (HAs), and the four corresponding HAs originated real unmodified and HO-treated soils were selected as the representative sorbents. Results showed that the HAs played a crucial role, and clay minerals (especially Mont) also showed an important effect in butachlor sorption. The AHOs may likely influence only in a mediator way by enhancing the availability of sorption domains of HAs. By removing 78% (on average) of the total organic carbon (TOC) from the soils with HO, the content ratio of clay to TOC (RCO) increased by an average of 367% and became >60. This change simultaneously decreased the sorption capacity of soils (40%, on average). Considering that the surface sorption domain on clay minerals may be highly exposed and more competitive after the partial removal of soil organic matter (SOM), this reaffirmed the potential contribution from clay minerals. It can thus be inferred that in the real soil where SOM and clay minerals are associated, the coating of clay minerals may have weakened the partition function of SOM or blocked some sorption domain within SOM, resulting in a decreased sorption of butachlor. Therefore, clay minerals, especially 2:1 type expanding minerals, may play a dual function vs. SOM content for the sorption of butachlor in soil.     

Adsorption of nutrients and cadmium by different minerals: experimental studies and modelling

This work analyses cadmium sorption by natural vermiculite, zeolite, and pumice, which have been recently considered for their potential use in remediation of contaminated soils. Batch experiments were performed to investigate the interactions between the mineral surfaces and the main nutritive cations of Hoagland solution. In addition to their ameliorative effect of reducing metal mobility, these minerals are able to interact to different extents with various components of the nutrient solution and can change the availability of essential nutrients in solution. Therefore, the minerals were also exposed to a range of cadmium doses to compare their different affinities for this element and to analyse the cadmium–nutrient interactions. The results showed that the nutrient solution composition was significantly modified by contact with zeolite and vermiculite, and to a minor extent with pumice. The ionic equilibrium between the solid and aqueous phases was attained at several time points depending on the cation. Ammonium and potassium ions were almost entirely absorbed by zeolite, while in vermiculite endogenous magnesium ions were exchanged with the liquid phase calcium ions. The amount of cadmium adsorbed on mineral surfaces equilibrated with the nutrient solution showed the following sequence zeolite>vermiculite>pumice, and the cation concentrations of the fluid phase were sensitive to cadmium addition.     

Effects of mineral surfaces on pyrene partitioning to well-characterized humic substances

Mineral surfaces can alter the ability of humic substances (HS) to bind hydrophobic organic contaminants. In this study, complete adsorption (i.e., to avoid HS adsorptive fractionation effects) of a small subset of well-characterized terrestrial and aquatic HS on kaolinite and hematite significantly changed their subsequent organic carbon-normalized partition coefficients K(ads)(oc) for pyrene relative to their original respective dissolved organic carbon-normalized partition coefficients K(dis)(oc). Parallel experiments with ultrafiltration (UF) fractions obtained from purified Aldrich humic acid (PAHA) (Aldrich Chemical, Milwaukee, WI) gave similar results. The heterogeneity among the PAHA UF fractions was examined via their mineral surface adsorption characteristics and their subsequent ability to bind pyrene. As expected, variations in maximum adsorption densities (q(max)), Langmuir adsorption constants (K(q)), and pyrene K(ads)(oc) values were observed among the PAHA UF fractions. However, general trends of q(max), K(q), and pyrene log K(ads)(oc) values for the PAHA UF fractions versus the logarithm of their weight-average molecular weights (MW(w)) did not typically match the corresponding trends obtained with the four aquatic and terrestrial HS. In general, an ideal mixture competitive adsorption model gave reasonable predictions for PAHA sorption to kaolinite and hematite based on their corresponding UF isotherm parameters. Ideal mixture predictions of pyrene partitioning to adsorbed PAHA from the corresponding UF fraction results were better for kaolinite versus hematite, indicating that the underlying mineral surface can alter the effects of HS heterogeneity on hydrophobic organic contaminant sorption.     

Cadmium adsorption on vermiculite, zeolite and pumice: batch experimental studies

Batch experiments were performed to evaluate the combined effects of ionic activity, pH, and contact time on the cadmium sorption in three different minerals, vermiculite, zeolite, and pumice, commonly employed as substrata in nurseries and recently considered for their potential use in remediation methods. The extent of cadmium sorption was vermiculite>zeolite>pumice, as shown by the Langmuir and Freundlich parameters, and it was highly dependent on mineral characteristics. The percentage of cadmium sorption in zeolite and vermiculite did not depend on cadmium concentration, while in pumice this percentage was positively correlated to the initial cadmium concentration. At low cadmium concentrations (30-120 microM), the metal sorbed on zeolite was mainly present in the nonexchangeable form (70%) at levels much higher than those found for vermiculite and pumice. The primary variable responsible for determination of cadmium mobility in these minerals was confirmed to be pH. The ionic concentrations of Hoagland nutrient solution were significantly modified by both pH and mineral composition, while the presence of cadmium caused no changes. With vermiculite and zeolite, the time-course of cadmium sorption was related to mineral composition to a greater extent than to cadmium concentration. While with pumice, the percentage of cadmium sorbed after 6 weeks was lower than with the other two minerals, and it was inversely correlated to the initial cadmium concentration.     

Adsorption of pesticides onto quartz, calcite, kaolinite, and alpha-alumina

The fate of pesticides in aquifers is influenced by the small but not insignificant adsorption of pesticides to mineral surfaces. Batch experiments with five pesticides and four minerals were conducted to quantify the contributions to adsorption from different mineral surfaces and compare adsorption characteristics of selected pesticides. Investigated mineral phases included quartz, calcite, kaolinite, and alpha-alumina. Selected pesticides comprised atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea)], mecoprop [(RS)-2-(4-chloro-2-methylphenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2-dioxide]. Specific surface area and mineral surface charge proved to be important for the adsorption of these pesticides. Detectable adsorption of the anionic pesticides (mecoprop, 2,4-D, and bentazone) was only measured when positive sites were present on the mineral surface. However, when CaCl2 was added as an electrolyte, a detectable adsorption of mecoprop and 2,4-D was also measured on kaolinite (which exhibits a negative surface charge), probably due to formation of Ca-pesticide--surface complexes. Adsorption of the uncharged pesticides (atrazine and isoproturon) was detected only on kaolinite. The lack of adsorption on alpha-alumina indicates that the uncharged pesticides have a greater affinity for the silanol surface sites (=SiOH) than for the aluminol surface sites (=AlOH) in kaolinite. No measurable effect of ionic strength was found for the uncharged pesticides. The results indicate that quartz and calcite play a smaller role than clay minerals.     

Binding of heavy metal contaminants onto chitosans--an evaluation for remediation of metal contaminated soil and water

The binding efficiency of chitosan samples for Ag(+), Cd(2+), Cu(2+), Pb(2+) and Zn(2+) has been evaluated in order to consider their application to remediate metal contaminated soil and water. The sorption behaviour of metal ions was assessed using a batch technique at different contact time and initial metal concentration with different background electrolytes. The kinetics followed a pseudo-second-order model, while the equilibrium data correlated well with the Freundlich and Langmuir isotherm models. For example, the maximum sorption capacity (Q) for chitosan was estimated as 1.93 mmol/g for Ag(+), 1.61 mmol/g for Cu(2+), 0.94 mmol/g for Zn(2+), 0.72 mmol/g for Cd(2+) and 0.64 mmol/g for Pb(2+). Covalent interaction between metal ions and functional groups (amino and hydroxyl) of the chitosans was the main binding mechanism. Ion exchange is not an important process. Chitosan and cross-linked chitosans were able to bind metal ions in the presence of K(+), Cl(-) and NO(3)(-). The nature of Cl(-) and NO(3)(-) ions did not affect Zn(2+) binding by the chitosans. Even at 11x dilution, the chitosans were able to retain metal ions on their surfaces.     

Molecular-level investigation of monoaromatic compound sorption to suspended soil particles by deuterium nuclear magnetic resonance

Molecular-level sorption behavior of monoaromatic compounds in suspensions of water-dispersable clay components was studied by measuring 2H nuclear magnetic resonance (NMR) spin-spin relaxation times (T2). In general, decreased T2 values indicate stronger solute-sorbent interactions and increased sorption of the solute. A decreasing trend for T2 values in the order benzene > fluorobenzene > toluene (-C6D5 moiety) was observed, which was probably caused by the hydrophobic effect. The T2 values for benzene and the -C6D5 moiety of toluene increased with increasing pH, whereas the trend with pH was much weaker and less consistent for fluorobenzene and the methyl group of toluene. Conversely, no clear relationship was found between T2 values and pH for dichloromethane. These contrasting results cannot be explained by the pH-dependent self-assembly and hydrophobicity of humics. Instead, directed specific forces, including hydrogen bonding, cation-pi interactions, and aromatic-aromatic interactions, are proposed between the benzene ring of monoaromatic solutes and soil organic matter (SOM). Substituents of benzene affect these interactions by varying the pi electron density. When the soil fraction was treated with NaOH to remove humic and fulvic acids, T2 values for the different monoaromatic solutes were surprisingly lower compared with those for the untreated soil fraction. This result is probably caused by the increased ratio of solutes adsorbed to "hard" or "glassy" SOM components, which leads to less mobile sorbed solute molecules, after removing NaOH-extractable humics that contain more "soft" or "rubbery" SOM components.     

The desorption of antimony(V) from sediments, hydrous oxides, and clay minerals by carbonate, phosphate, sulfate, nitrate, and chloride

The desorption of antimony, Sb(V), from two sediment samples by phosphate, carbonate, sulfate, chloride, and nitrate at pH 8 was examined. One highly contaminated sediment sample was taken from an Sb mine (Goesdorf, Luxembourg); the other sample was the certified reference material PACS-2 (marine sediment). Phosphate was found to have a strong mobilizing ability, whereas that of carbonate was in general weaker. For comparison, and to understand better the possible importance of individual components of the sediments, desorption experiments were performed on pure phases (i.e., hydrous oxides of Fe, Mn, and Al) and the clay minerals kaolinite and montmorillonite. In the cases of hydrous metal oxides, Sb(V) was most effectively desorbed by phosphate, followed by carbonate. Phosphate also desorbed Sb(V) from the clay minerals, whereas carbonate had no effect. The pH dependence of adsorption of Sb(V) in the absence and presence of carbonate revealed that adsorption densities were higher (except in the case of montmorillonite) in the absence of carbonate, suggesting a competition between carbonate and [Sb(OH)] for surface sites generally and a lowering of surface charge in the case of hydrous aluminum oxide. The observations are unlikely to be due to ionic strength effects because activity coefficients in the blank and spiked solutions differ by <4%. Desorption experiments on sediments with varying concentrations of phosphate and carbonate demonstrated that at environmentally relevant concentrations, desorption by phosphate is negligible, whereas the effect of carbonate is not. Sulfate, chloride, and nitrate generally had little effect. The proportion of Sb desorbed in blank experiments coincides with that mobilized in the first fraction of the Bureau Communautaire de Référence (BCR) sequential extraction (easily exchangeable and carbonate-bound fraction).     

Contamination time effect on lead and cadmium fractionation in a tropical coastal clay

The capability of a tropical coastal clay to immobilize lead (Pb) and cadmium (Cd) was investigated in laboratory batch sorption tests conducted under acidic, neutral, and slightly alkaline conditions. The contact time was extended to 65 d. The distribution of Pb and Cd among various sorbed phases was examined using a sequential extraction technique. The sorbed phases were fractionated into the exchangeable, carbonate, reducible, organic, and residual fractions. There were only small changes in the total Pb and Cd sorption beyond a 1-d sorption period. The metal fractionation results show that the amount of Pb and Cd in various fractions changed with sorption time, and the changes were pH-dependent. These changes could be attributed to mineral dissolution and transformation or redistribution of the sorbed phases. Transformation of the sorbed phases resulted in increasing Pb and Cd retention in the more persistent fractions with time, at the expense of reductions in the loosely bound fractions. Nevertheless, Pb and Cd fractionation in the solid phase appeared to reach equilibrium within the 65-d sorption period. These Pb and Cd fractionation results reflect the effect of contamination time on the heavy metal lability and bioavailability in the subsurface environment.     

Prediction of metal-adsorption behaviour in the remediation of water contamination using indigenous microorganisms

In recent years, the adsorption of heavy metal cations onto bacterial surfaces has been studied extensively. This paper reports the findings of a study conducted on the heavy metal ions found in mine effluents from a mining plant where Co²⁺ and Ni²⁺ bearing minerals are processed. Heavy metal ions are reported to be occasionally present in these mine effluents, and the proposed microbial sorption technique offers an acceptable solution for the removal of these heavy metals. The sorption affinity of microorganisms for metal ions can be used to select a suitable microbial sorbent for any particular bioremediation process. Interactions of heavy metal ions (Co²⁺ and Ni²⁺) and light metal ions (Mg²⁺ and Ca²⁺) with indigenous microbial cells (Brevundimonas spp., Bacillaceae bacteria and Pseudomonas aeruginosa) were investigated using the Langmuir adsorption isotherm, pseudo second-order reaction kinetics model and a binary-metal system. Equilibrium constants and adsorption capacities derived from these models allowed delineation of the effect of binding affinity and metal concentration ratios on the overall adsorption behaviour of microbial sorbents, as well as prediction of performance in bioremediation systems. Although microbial sorbents used in this study preferentially bind to heavy metal ions, it was observed that higher concentrations (>90 mg/?) of light metal ions in multi-metal solutions inhibit the adsorption of heavy metal ions to the bacterial cell wall. However, the microbial sorbents reduced Ni²⁺ levels in the mine-water used (93–100% Ni²⁺ removal) to below the maximum acceptable limit of 350 μg/?, established by the South African Bureau of Standards. Competition among metal ions for binding sites on the biomaterial surface can occur during the bioremediation process, but microbial sorption affinity for heavy metal ions can enhance their remediation in dilute (<5 mg/? heavy metal) wastewaters.     

Sorption of MS2 bacteriophage to layered double hydroxides: effects of reaction time, pH, and competing anions

Batch sorption and column breakthrough studies were conducted to investigate the potential of layered double hydroxides (LDHs) to remove bacteriophage MS2 from contaminated waters. All four of the LDHs evaluated in this study had very high retention capacities for MS2. Sorption results showed that MS2 could be completely removed from 5.2 x 10(2) plaque-forming units (pfu)/mL solution by Mg-Al LDH 2 (i.e., 2:1 Mg to Al ratio LDH), with the highest sorption capacity observed in this study of 1.51 x 10(10) pfu/g. Attachment of MS2 to LDHs was a rapid process and reached quasi-equilibrium after a 1-h reaction time. Within the pH range studied (pH 4-9), Mg-Al LDH 2 showed high sorption potential for MS2 at all pH values but sorption decreased slightly with increasing solution pH. Background solution anions influenced virus sorption, with SO4(2-) and HPO4(2-) decreasing sorption significantly whereas the presence of NO3- had little effect on the attachment of MS2 to Mg-Al LDH 2. The addition of another virus (phiX174) only caused a slight decrease in the retention of MS2 by Mg-Al LDH 2, suggesting that there was insignificant competitive sorption between MS2 and phiX174 on LDH surfaces. Results from column experiments indicate that there was no MS2 breakthrough from columns packed with Mg-Al LDH 2-coated sand, suggesting complete MS2 retention at the virus concentration tested. The high mass recovery by beef extract solution revealed that the removal of viruses by the LDH was due to sorption of MS2 to LDH surfaces, rather than inactivation.     

Amelioration of physical strength in waste foundry green sands for reuse as a soil amendment

To avoid increasing costs of landfill disposal, it has become increasingly important for U.S. foundries to identify beneficial reuses for the 8 to 12 million tons of waste foundry sand (WFS) generated annually. A major drawback to the reuse of some WFSs as a soil amendment is their high soil strength, under dry conditions, where root growth may be limited. Fifteen WFSs were analyzed for strength to rupture using lab-formed clods, exchangeable cations (Na, Mg, Ca), metal oxide concentration (Fe, Mn, Al, Si), cation exchange capacity (CEC), and % clay. Several WFS samples from gray iron foundries demonstrated high strength to rupture values (> 1.5 MPa), and could potentially restrict root growth in amended soils. The percentage of Na-bentonite exhibited a positive correlation (R(2) = 0.84) with strength to rupture values. When WFSs containing more Na-bentonite were saturated with 1 mol L(-1) Ca ions, strength values decreased by approximately 70%. Waste foundry sands containing less Na-bentonite were saturated with 1 mol L(-1) Na ions and exhibited a threefold increase in strength. Additions of gypsum (up to 9.6 g kg(-1) sand) to high strength waste foundry sands also caused decreases in strength. These results indicate that high strength WFSs have properties similar to hardsetting soils which are caused by high Na(+) clay content and can be ameliorated by the addition of Ca(2+).     

Extra-framework cation release from heulandite-type rich tuffs on exchange with NH(4)(+)

The outgoing cations of Greek heulandite-rich tuff samples (heulandite type-III, 91wt.%, mica 4wt.%, feldspar 5wt. %, CEC 2.22meq/g) were analysed upon exchange with ammonium acetate using atomic absorption spectrometry (AAS). The kinetic curves of each cation were investigated over a total time of contact of 720h with sampling at frequent intervals. The materials were examined by powder X-ray diffraction, SEM-EDS, and AAS. The sorption ability was measured using the ammonium acetate saturation method. It was found that Ca(2+) presents an unexpected extra-framework release and a surprisingly high degree of exchange (90%). The exchange of Mg (57%) is also worthy of note whereas the behavior of K(+) showed an expected rapid initial release. The behavior of Na(+) must be similar. However, its lower concentration in the zeolitic material minimizes its overall significance somewhat. On the other hand, Ca(2+) and Mg(2+) release is kinetically much slower, compared to that of alkali metal ions, and this phenomenon indicates that different exchange energies are needed till final equilibrium.     

Sorption and mobility of ivermectin in different soils

Avermectins are widely used to treat livestock for parasite infections. Ivermectin, which belongs to the group of avermectins, is particularly hazardous to the environment, especially to crustaceans and to soil-dwelling organisms. Sorption is one of the key factors controlling transport and bioavailability. Therefore, batch studies have been conducted to characterize the sorption and desorption behavior of ivermectin in three European soils (Madrid, York, and artificial soil). The solid-water distribution coefficient (K(d)) for ivermectin sorption to the tested soils were between 57 and 396 L kg(-1) (determined at 0.1 microg g(-1)), while the organic carbon-normalized sorption coefficients (K(oc)) ranged from 4.00 x 10(3) to 2.58 x 10(4) L kg(-1). The Freundlich sorption coefficient (K(F)) was 396 (after 48 h) for the artificial soil over a concentration range of 0.1 to 50 microg g(-1), with regression constants indicating a concentration-dependent sorption. The obtained data and data in the literature are inconclusive with regard to whether hydrophobic partitioning or more specific interactions are involved in sorption of avermectins. For abamectin, hydrophobic partitioning seems to be one of the dominant types of binding, while hydrophobicity is less important for ivermectin, which is probably due to the lower lipophilicity of the molecule. Furthermore, the presence of cations such as Ca(2+) leads to decreasing sorption. Thus, it is presumed that ivermectin binds to soil by formation of complexes with immobile, inorganic soil matter. In contrast to abamectin, hysteresis could be excluded for ivermectin in the studied soils for the evaluation of sorption and desorption. The sorption mechanism is highly dependent on physicochemical properties of the avermectin.     

Imazaquin adsorbed on pillared clay and crystal violet-montmorillonite complexes for reduced leaching in soil

Ground water pollution due to herbicide leaching has become a serious environmental problem. Imazaquin [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid] is an herbicide used to control broadleaf weeds in legume crops. Imazaquin is negatively charged at the basic pH of calcareous soils and exhibits high leaching potential in soils. Our aim was to design formulation of imazaquin to reduce herbicide leaching. Imazaquin sorption on pillared clay (PC) and crystal violet (CV)-montmorillonite complexes was studied. The CV-montmorillonite complexes become positively charged with adsorption of CV above the cation exchange capacity (CEC) of montmorillonite, and thus can sorb imazaquin. The Langmuir equation provides a good fit to isotherms of imazaquin sorption on PC and CV-montmorillonite complexes, but for charged complexes an equation that combines electrostatics with specific binding was preferred. Maximal imazaquin sorption was 17.3 mmol kg-1 for PC and 22.2 mmol kg-1 for CV-montmorillonite complexes. The extents of imazaquin desorption into water were 21% for PC and 5% for CV-clay complexes. The presence of anions decreased imazaquin sorption on both sorbents in the sequence phosphate > acetate > sulfate. Reduction of imazaquin sorption by the anions and the extent of its desorption in electrolyte solutions were higher for PC than for CV-clay complexes. Leaching of imazaquin from CV-montmorillonite formulations through soil (Rhodoxeralf) columns was two times less than from PC formulations and four times less than that of technical imazaquin. The CV-montmorillonite complexes at a loading above the CEC appear to be suitable for preparation of organo-clay-imazaquin formulations that may reduce herbicide leaching significantly.