Potential contributions of smectite clays and organic matter to pesticide retention in soils.

Soil organic matter (SOM) is often considered the dominant sorptive phase for organic contaminants and pesticides in soil-water systems. This is evidenced by the widespread use of organic-matter-normalized sorption coefficients (K(OM)) to predict soil-water distribution of pesticides, an approach that ignores the potential contribution of soil minerals to sorption. To gain additional perspective on the potential contributions of clays and SOM to pesticide retention in soils, we measured sorption of seven pesticides by a K-saturated reference smectite clay (SWy-2) and SOM (represented by a muck soil). In addition, we measured the adsorption of atrazine by five different K-saturated smectites and Ca-saturated SWy-2. On a unit mass basis, the K-SWy-2 clay was a more effective sorbent than SOM for 4,6-dinitro-o-cresol (DNOC), dichlobenil, and carbaryl of the seven pesticides evaluated, of which, DNOC was sorbed to the greatest extent. Atrazine was sorbed to a similar extent by K-SWy-2 and SOM. Parathion, diuron, and biphenyl were sorbed to a greater extent by SOM than by K-SWy-2. Atrazine was adsorbed by Ca-SWy-2 to a much lesser extent than by K-SWy-2. This appears to be related to the larger hydration sphere of Ca(2+) (compared to that of K(+)) which shrinks the effective size of the adsorption domains between exchangeable cations, and which expands the clay layers beyond the apparently optimal spacing of approximately 12.2 A for sorption of aromatic pesticide structures. Although a simple relation between atrazine adsorption by different K-smectites and charge properties of clay was not observed, the highest charge clay was the least effective sorbent; a higher charge density would result in a loss of adsorption domains. These results indicate that for certain pesticides, expandable soil clays have the potential to be an equal or dominant sorptive phase when compared to SOM for pesticide retention in soil.     

除草剂咪草烟在土壤上吸附-脱附过程及作用机理

本文研究了咪唑啉酮类除草剂咪草烟在不同土壤固－液相间的分配及与土壤组分作用的定量相关性。结论指出：咪草烟在土壤固－液相的分配主要受土壤粘粒,有机质及土壤ｐＨ的影响。它们在土壤上的吸附－脱除均可用Ｆｒｅｕｎｄｌｉｃｈ方程描述;通过运用红外及Ｘ－衍射技术,从分子水平研究了咪草烟与蒙脱石的作用机理,发现咪草烟与蒙脱的作用不仅发生在表面,而且咪草烟还能进入蒙脱石内层与其层间阳离子形成配合物。     

Effect of soil composition on adsorption of lead as reflected by a study on a natural forest soil profile

The adsorption characteristics of lead on each genetic horizon of a natural brown forest soil profile were studied to recognize the possible immobilizing effect of a mineralogical diverse soil profile in the case of a possible lead contamination. Lead adsorption experiments were carried out on whole soil samples, soil clay fractions, as well as on their carbonate and organic matter free variant. TEM-EDS analyses were performed to characterize the adsorption capacity of individual mineral phases. The most important lead adsorbents in order of importance are the organic matter, the clay minerals, and the iron oxides. The most significant process is the ion exchange of calcium by lead with the respect to adsorption. The organic matter adsorbs more lead than clay minerals, and clay fractions adsorb more lead as compared to the whole soil samples. Among mixed layer clay minerals, those containing swelling component have the highest lead adsorption capacity, but the exact distinguishing of the individual clay mineral particles with the respect to their adsorption capacity is not possible. The calcite influences the lead adsorption through its buffering capacity: high calcite content results in lead precipitation. Soils characterized by high amount of organic matter, swelling clay mineral accumulation horizon and calcareous subsoil are suitable medium to immobilize a significant lead pollution.     

Adsorption and mobility of linuron in soils as influenced by soil properties, organic amendments, and surfactants

Adsorption and mobility of the herbicide linuron (3-3, 4-dichlorophenyl-1-methoxy-1-methylurea) in 35 irrigated soils with organic matter (OM) contents in the 0.43-2.59% range and in four natural soils with OM contents in the 4.16-11.69% range were studied using the batch equilibration technique. The adsorption isotherms were found to conform to the Freundlich adsorption equation. The Freundlich constant, K, and the distribution coefficient, K(d), were seen to be highly significantly correlated (p < 0.001) with the OM content when all soils or only those with an OM content above 2% were considered. There was also a significant correlation of K and K(d) with the OM content (p < 0.05) and of K(d) with the clay and silt plus clay contents (p < 0.1) when the soils with a OM content below 2% were considered. On the basis of the R(f)() values obtained by soil TLC, the pesticide was found to be slightly mobile in 77% and moderately mobile in 23% of the soils studied. The results of the leaching of linuron in soil columns unmodified and modified with two organic agricultural amendments, a city refuse compost, and two surfactants (one of them cationic and the other anionic) revealed that the leaching rate and the mass transfer of the herbicide to water were affected, increasing or decreasing according to the characteristics of the amendments and the doses added. These results also point to the usefulness of selected organic materials and surfactants in the development of physicochemical methods for preventing the pollution of soils, sediments and aquifers by hydrophobic pesticides.     

Structural influences in relative sorptivity of chloroacetanilide herbicides on soil

Adsorption of the chloroacetanilide herbicides acetochlor, alachlor, metolachlor, and propachlor was determined on soils and soil components, and their structural differences were used to explain their sorptivity orders. On all soils and soil humic acids, adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca(2+)-saturated montmorillonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR differential spectra of herbicide-clay or herbicide-humic acid-clay showed possible formation of hydrogen bonds and charge-transfer bonds between herbicides and adsorbents. The different substitutions and their spatial arrangement in the herbicide molecule were found to affect the relative sorptivity of these herbicides by influencing the reactivity of functional groups participating in these bond interactions. It was further suggested that structural characteristics of pesticides from the same class could be used to improve prediction of pesticide adsorption on soil.     

Selective modification of clay minerals for the adsorption of herbicides widely used in olive groves

Ground and surface water contamination by herbicides applied to olive groves in Spain and other Mediterranean countries is demanding strategies to prevent and remediate the environmental problems repeatedly caused by such herbicides. In this study, six different organic cations (L-carnitine, spermine, hexadimethrine, tyramine, phenyltrimethylammonium, and hexadecyltrimethylammonium) were incorporated into Na-rich Wyoming montmorillonite (SWy-2) and Ca-rich Arizona montmorillonite (SAz-1) at two different loadings (50% and 100% of the cation exchange capacity of the clays) as a strategy to enhance the affinity of the clay minerals for three herbicides widely used in olive groves: terbuthylazine, diuron, and MCPA. The modified montmorillonites were characterized and tested as adsorbents of the herbicides through batch adsorption tests. At the experimental conditions used, some of the modified montmorillonites removed more than 95% of the herbicide initially present in aqueous solution, whereas the unmodified clays removed less than 15%. All three herbicides displayed very strong affinities for SAz-1 exchanged with hexadecyltrimethylammonium cations, particularly when these were incorporated at 100% of the cation exchange capacity of the clay mineral. Terbuthylazine and diuron also displayed very strong affinities for SWy-2 exchanged with L-carnitine and spermine, respectively. The chemical characteristics of the organic cation greatly influenced the adsorptive properties of the resultant organoclay. The herbicides were in general reversibly adsorbed by the modified clays. The results indicate that some of the tested modified clays could be suitable for the removal of the assayed herbicides from contaminated water and also as possible supports for the design of slow release formulations of such herbicides to attenuate their environmental impact when used in high-risk scenarios such as olive groves.     

Adsorption effect on the degradation of carbaryl, mecoprop, and paraquat by anodic fenton treatment in an SWy-2 montmorillonite clay slurry

The Fenton reaction-based anodic Fenton treatment (AFT) was applied to three widely used organic agrochemicals, carbaryl, mecoprop, and paraquat, in a clay slurry. The adsorption and degradation behaviors of these neutral (carbaryl), anionic (mecoprop), and cationic (paraquat) agrochemicals were studied in a slurry of SWy-2 Na(+)-montmorillonite clay, and adsorption isotherms were obtained at given experimental conditions. The d spacing (d 001) of the clay layer before and after adsorption or degradation was measured by X-ray diffraction (XRD). On the basis of the change of d spacing, molecular disposition at the clay interlayer was inferred: both mecoprop and paraquat form a monolayer sitting flat and parallel to the clay siloxane surfaces. Results show that, due to different adsorption mechanisms, the adsorption effect on chemical degradation by AFT varies with pesticide: strong and tight adsorption of paraquat at the clay interlayer protects paraquat from being attacked by hydroxyl radicals; loosely adsorbed carbaryl or mecoprop is readily degraded. XRD analysis clearly indicates that AFT is capable of effectively degrading interlayer noncationic organic chemicals that are not usually available for biodegradation.     

POTASSIUM-CALCIUM EXCHANGE EQUILIBRIA IN SOILS: THE LOCATION OF NON-SPECIFIC (GAPON) AND SPECIFIC EXCHANGE SITES

Several studies (e.g. Bolt et al., 1963; Beckett, 1964a) of the exchange equilibria between K and Ca on soil colloids or pure clay minerals have drawn attention to the presence of sites with different affinities for K. There is so far no evidence to indicate the location of sites with the highest affinity, though several workers (e.g. van Schouwenburg and Schuffelen, 1963) have assumed that they lie on the edge-faces of stacks of clay plates, or in the spaces between the expanded leaves of partially weathered stacks of clay plates. Earlier work has resolved the K: Ca exchange isotherms of soils and clays into a curved part at low values of aK/√aCa, attributed to exchange at sites with a high specific affinity for K, and an upper linear part commonly described by the Gapon equation and attributed to non-specific sites. The present work on soil clays and clay minerals shows that Na hexametaphosphate or changes in pH affect the curved but not the linear part; cetyl trimethyl ammonium bromide and changes in the amount or charge of exchangeable Al affect the linear but not the curved part of the isotherms. At low pH, the linear but not the curved part of the kaolinite isotherm obeys Schofield's Ratio Law. Grinding has more effect on the curved than on the linear part. So the specific sites are attributed to the edges or peripheral interstices of stacks of clay plates, and the non-specific sites to their planar surfaces. The specific sites take up K more slowly from solution than the non-specific sites. The isotherms of completely dispersed bentonites have no curved part. The specific sites are attributed to the wedge-shaped interstices opened between clay plates by weathering, from which exchange is diffusion-controlled. Added organic cations reduce the numbers of both kinds of site; peroxide treatment increases them. This paper confirms that the exchange sites with highest affinity for K are indeed associated with the edges, rather than the faces, of stacks of clay plates.     

硅酸盐黏土矿物的表面酸性研究进展

表面酸性是硅酸盐黏土矿物的重要表面化学性质之一。本文综述了硅酸盐黏土矿物表面酸性的主要测定方法,讨论了黏土矿物表面酸性的发生源及其影响因素,并论述了黏土矿物表面酸性与有机碱化合物吸附固定行为之间的关系。     

Heavy Metal Release from Some Industrial Wastes: Influence of Organic and Inorganic Acids, Clay Minerals, and Nanoparticles

Knowledge about heavy metal release from industrial solid wastes(ISWs) is crucial for better management of their environmental risks. This study was conducted to investigate the effect of organic and inorganic acids, clay minerals, and nanoparticles(NPs) on the release of heavy metals from sugar factory waste, ceramic factory waste, leather factory waste, and stone cutting waste. The influence of the extractants on heavy metal release from these ISWs was in the following descending order: citric acid oxalic acid nitric acid≥ sulfuric acid Ca Cl2. Addition of clay minerals and NPs as adsorbents decreased heavy metal release, which was significantly lower in NP-treated wastes than in the clay mineral-treated wastes. On the other hand, the presence of organic and inorganic acids increased heavy metal adsorption by NPs and clay minerals. These results suggest that NPs can be applied successfully in waste remediation,and organic and inorganic acids play an important role in the removal of heavy metals from the studied adsorbents.     

Sorption-desorption of imidacloprid and its metabolites in soil and vadose zone materials

Sorption-desorption is one of the most important processes affecting the leaching of pesticides through soil because it controls the amount of pesticide available for transport. Subsurface soil properties can significantly affect pesticide transport and the potential for groundwater contamination. This research characterized the sorption-desorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) and three of its metabolites, 1-[(6-chloro-3-pyridinyl)methyl]-2-imidazolidinone (imidacloprid-urea), 1-[(6-chloro-3-pyridinyl)methyl]-4,5-dihydro-1H-imidazol-2-amine (imidacloprid-guanidine), and 1-[(6-chloro-3-pyridinyl)methyl]-1H-imidazol-2-amine (imidacloprid-guanidine-olefin), as a function of changing soil properties with depth in two profiles extending from the surface to a depth of 1.8 or 8 m. Sorption of each compound was highly variable and hysteretic in all cases. Normalizing the sorption coefficients (K(f)) to the organic carbon or the clay content of the soil did not reduce the variability in sorption coefficients for any compound. These results illustrate the importance of evaluation of the sorption data used to predict potential mobility. Understanding the variability of soil properties and processes as a function of depth is necessary for accurate prediction of pesticide dissipation.     

Removal of carbaryl, linuron, and permethrin by Lupinus angustifolius under hydroponic conditions

The metabolism of organic pollutants by plants normally requires contaminant direct uptake by cells. Factors affecting this uptake and the later distribution of chemicals within the plant include the physicochemical properties of the compounds (concentration, structure, solubility, log k(ow), diffusion rate) and the biochemical characteristics of the plant. This paper reports the tolerance, uptake, and effects of the pesticides carbaryl, linuron, and permethrin on Lupinus angustifolius germination and growth as well as contaminant intraplant distribution and possible degradation. Lupine plants were grown in hydroponic culture containing either 1 or 5 mg of the individual pesticides, or combinations of these (1, 5, or 10 mg of each), in 100 mL nutrient and water solutions. Analysis of the remaining solutions 8 days post-germination showed the water solutions to have higher remaining pesticide concentrations than nutrient solutions. Furthermore, in the presence of pesticides, germination was more frequent in the water solutions. After 16 days of growth, the plants were harvested, and their tissues were microwaved digested and analyzed by reversed-phase liquid chromatography. Although only minor quantities of each pesticide were detected in plant tissues, their amount in the roots was higher than in the stems. No accumulation was noted in the cotyledons, and only 2% of linuron was detected in the leaves. Mass recovery at the end of the experiment showed that 57, 53, and 55% of carbaryl, linuron, and permethrin, respectively, were degraded and/or bound in an irreversible manner to plant material. The results suggest that L. angustifolius could be useful for the cleaning/remediation of pesticide-contaminated water.     

Effects of organic matter and calcium on soil structural stability

The cationic bridging effect of the calcium ion (Ca²⁺) and the flocculating ability of clay and organic matter are crucial in the formation and stability of soil aggregates. They are therefore likely to influence the soil's saturated hydraulic conductivity ( K _s). We tested the individual effects of these factors on aggregate stability and related hydraulic properties, and studied the influence of clay mineralogy also. Samples from the surface (0–10 cm) of three contrasting soils in Trinidad were used. The soils were treated with three levels of Ca²⁺ and three levels of organic matter in a 3 × 3 × 3 factorial design and incubated for 14 days. Both aggregate stability and saturated hydraulic conductivity were influenced by all factor combinations. Interactions between soil type and Ca²⁺ revealed the importance of polyvalent cations in aggregate stability of soils with low activity minerals. The influence of organic matter varied with quantity; the more there was, the more stable the soil became, particularly in the soil containing little clay. Clay dispersion and slaking of expanding minerals occurred even with large additions of Ca²⁺ and organic matter, emphasizing the overall influence of mineralogy in determining the response of soils to stability treatments.     

Sorption-desorption of alachlor and linuron in a semiarid soil as influenced by organic matter properties after 16 years of periodic inputs

The effect of management practices on soil potential for regulating the residual concentration of pesticides was examined in samples from a Calcic Haploxeralf in Toledo (central Spain). Sorption-desorption of alachlor and linuron was found to depend on inputs of lignocelullosic wastes or cattle manure for the past 16 years. For a given herbicide, the soil sorption capacity (K(f)) follows the order control < crop residues < manure, which is consistent with the organic C content in the soil samples. Some structural characteristics of the soil humic acid as revealed by visible and infrared spectroscopies and analytical pyrolysis were useful to forecast the sorption-desorption intensity. Simple and multiple linear correlation analyses illustrate enhanced sorption of alachlor and linuron in soil plots where slightly altered soil organic matter accumulated (positive correlations with the intensity of infrared lignin signature band and with the methoxyphenol yields after pyrolysis of the humic acids and negative correlation with the aromaticity as pointed out by the optical density at 465 nm). Linuron showed a preference for soils with humic acids of low molecular weight and low degree of internal cross-linking, as inferred from the positive correlation with the ratio between optical densities at 465 and 665 nm. Under the conditions of the present experiment, agricultural practices including organic amendments seem to have a beneficial effect in the control of leaching and sorption of pesticides.     

Pesticide adsorptivity of aged particulate matter arising from crop residue burns

Particulates (ashes) arising from the burning of crop residues are potentially effective adsorbents for pesticides in agricultural soils. To determine the long-term adsorptive sustainability of ashes, a wheat (Triticum aestivum L.) ash was aged under environmentally relevant conditions (in CaCl(2) solution at room temperature and pH 7) in soil extract for 1 month and in a soil (1% ash) for a period of up to 12 months. The aged ash and ash-amended soil were used to sorb diuron from water. The diuron sorption was also measured in the presence of atrazine as a competing pesticide. There was no observed microbial impact on the stability of the wheat ash in soil. All isotherms with the ash were nonlinear type-I curves, suggestive of the surface adsorption. On a unit mass basis, the ash in soil extract was 600-10000 times more effective than the soil in sorbing diuron. Adsorption of dissolved soil organic matter (DOM) during aging on the ash surfaces reduced the diuron adsorption by 50-60%. Surface competition from the atrazine adsorption also reduced the ash adsorption of diuron by 10-30%. A total of 55-67% reduction in diuron sorption by the ash-amended soil was observed. Due to its high initial adsorptivity, the ash fraction of the aged ash-amended soil contributed >50% to the total diuron sorption. Thus, the wheat ash aged in the soil remained highly effective in adsorbing diuron. As crop residues are frequently burned in the field, pesticides in agricultural soils may be highly immobilized due to the presence of ashes.     

Degradation of the fungicide metalaxyl and its non-extractable residue formation in soil clay and silt fractions

The proportion of organic matter and mineral composition are important factors determining the formation and type of non-extractable residues (NERs) of pesticides in soil. In this study, we investigated the enantioselectivity in degradation and NER formation of the chiral fungicide metalaxyl in soil particle size fractions (silt and clay). Microbial and extracellular enzyme activities during these processes were monitored in incubation of silt and clay samples isolated from sterilized and non-sterilized soil samples collected from a long-term agricultural field experimental site in Ultuna, Sweden. The temporal influence on the fate of the fungicide was noted by short-term (10-d) and long-term (92-d) incubations. Besides the acquisition of quantitative data with gas chromatography-mass spectrometry (GC/MS), stereoselective analyses were performed with chiral GC/MS. Quantitative results pointed to a higher metabolism rate of the pesticide through microbial activity than through extracellular enzyme activity. This was also confirmed by the enantioselective depletion of R-metalaxyl and the subsequent formation of R-metalaxyl acid in microbially active samples from non-sterilized soil. The silt fraction containing a high amount of organic matter exhibited a significant hydrolyzable proportion of metalaxyl NERs that was releasable under alkaline conditions. On the contrary, the clay fraction showed an enhanced affinity for covalently bound residues. Based on our results, we recommend differentiating between reversibly and irreversibly bound proportions of pesticides in persistence and environmental risk assessment because the reversible fraction contained potentially bioavailable amounts of residues that may be released under natural conditions.     

Montmorillonite-phenyltrimethylammonium yields environmentally improved formulations of hydrophobic herbicides

This study aimed to design formulations of hydrophobic herbicides, alachlor and metolachlor, by adsorbing them on the clay mineral montmorillonite preadsorbed by the small organic cation phenyltrimethylammonium (PTMA). An adsorption model that considers electrostatics and specific binding and the possibility of cation adsorption above the cation exchange capacity (CEC) could explain and yield predictions for PTMA adsorption in the presence of NaCl concentrations from 0 to 500 mM. Adsorption of alachlor and metolachlor from aqueous solution on a clay mineral preadsorbed by PTMA was determined by GC and modeled by Langmuir equation. Herbicide interactions with the organoclay were studied by Fourier transform infrared spectroscopy. Leaching of herbicides was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of alachlor and metolachlor on montmorillonite preadsorbed by PTMA at a loading of 0. 5 mol/kg (Mont-PTMA0.5) were higher than at a loading up to the CEC, that is, 0.8 mol/kg, and were higher than those obtained by using several other organic cations. Herbicide formulations based on Mont-PTMA0.5 yielded the largest shifts of the infrared peaks of the herbicides. These formulations based on Mont-PTMA0.5 gave slower release and showed improved weed control in comparison with formulations based on other organoclays. These formulations maintained herbicidal activity in the topsoil and yielded the most significant reduction in herbicide leaching.     

土壤镉吸附的研究进展

综述了土壤镉吸附的机理和土壤pH、有机质含量、粘粒矿物类型及含量、土壤溶液中竞争性阳离子、共存阴离子、土壤温度等土壤性质对土壤镉吸附的影响；总结了土壤镉的吸附量随土壤pH增加、温度升高及有机质、铁锰氧化物和粘土矿物含量增加而增加的机理；竞争性阳离子的存在抑制镉的吸附，土壤溶液中共存阴离子对镉吸附的影响取决于阴离子种类和土壤类型。     

有机酸对高岭石, 针铁矿和水铝英石吸附镉的影响

Effects of organic acids （oxalic, acetic, and citric） on adsorption characteristics of Cadmium （Cd） on soil clay minerals （kaolinite, goethite, and bayerite） were studied under different concentrations and different pH values. Although the types of organic acids and minerals were different, the effects of the organic acids on the adsorption of Cd on the minerals were similar, i.e., the amount of adsorbed Cd with an initial solution pH of 5.0 and initial Cd concentration of 35 mg L^-1 increased with increasing concentration of the organic acid in solution at lower concentrations, and decreased at higher concentrations. The percentage of Cd adsorbed on the minerals in the presence of the organic acids increased considerably with increasing pH of the solution. Meanwhile, different Cd adsorption in the presence of the organic acids, due to different properties on both organic acids and clay minerals, on kaolinite, goethite, or bayerite for different pHs or organic acid concentrations was found.     

THE ADSORPTION OF COPPER BY SOIL MATERIALS AT LOW EQUILIBRIUM SOLUTION CONCENTRATIONS

The adsorption of copper by individual soil components (organic matter fractions, oxides and clay minerals) was examined at equilibrium solution concentrations of copper within the range found in natural soils, the distribution of copper between solution and solid phases being measured by means of labelling with radioactive ⁶⁴Cu. At these low solution concentrations it was found that the copper adsorption isotherms were essentially linear. The oxides and organic materials adsorbed the greatest amounts of copper. The concentration of copper in natural soil solutions will be controlled by these materials to a far greater extent than by the clay minerals, the influence of which may be negligible in some soils. Solution concentrations of copper are relatively unaffected by both the background concentration of major cations and by changes in pH within the ionic strength and pH range found in normal agricultural soils. Copper adsorption studies with humic and fulvic acids showed that total solution copper concentrations could be greatly enhanced above the equilibrium levels for ionic copper by the presence of soluble organic complexes. The importance of taking into account the presence of such copper complexes in soil copper studies is emphasised.