Sorption of the antibiotic tetracycline to humic-mineral complexes

Humic substances, by altering the surface properties and/or competing for available reaction sites, can either suppress or promote sorption of organic compounds to mineral surfaces. Limited literature evidence points to the reduction in sorption of the antibiotic tetracycline to clay minerals in the presence of humic substances. We investigated the surface interaction of Elliott soil humic acid (ESHA) with hydrous Al oxide (HAO) and the effect of this association on tetracycline sorption. Strong interaction between ESHA and HAO led to ESHA-promoted dissolution of HAO and surface charge reversal. The ESHA-HAO sorption-desorption isotherms were successfully described using a modified Langmuir model that accounted for the heterogeneity of HAO surface and ESHA. Ligand exchange was proposed as the major interaction mechanism, and the edge Al atoms on HAO surface were considered as the sorption sites for ESHA macromolecules. ESHA was coated onto HAO to achieve two different organic content (foc) levels of 0.81 and 1.52%. Sorption results were compared for the binary ESHA-tetracycline and HAO-tetracycline systems, and the ternary ESHA-HAO-tetracycline system. The coating of ESHA on HAO significantly suppressed tetracycline sorption levels, attributable to altered HAO surface charge characteristics and/or direct competition between ESHA and tetracycline for potential sorption sites. Higher foc level, besides increasing the extent of sorption suppression, also resulted in greater ionic strength dependence and increased nonlinearity of sorption behavior. It, therefore, appears that the presence of humic substances, in both dissolved and mineral-bound forms, is likely to increase the environmental mobility of tetracycline compounds.     

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.     

土壤环境汞形态及吸附解吸研究进展

汞污染一直是全球备受关注的问题,由于土壤是环境汞的源和汇,因此已经开展了大量相关的研究工作。本论文系统总结了土壤环境汞形态及吸附解吸特征的研究现状,综述了不同类型土壤汞的背景含量,以及汞在土壤中的赋存形态,分析了土壤汞吸附特征及几种典型的土壤吸附剂（粘土矿物、铁锰氧化物、硫化物和土壤有机质）对汞吸附的作用机制。     

Adsorption and transport of arsenic(V) in experimental subsurface systems

The adsorption and transport of As(V) in a heterogeneous, iron oxide-containing soil was investigated in batch and column laboratory experiments. The As(V) adsorbed rapidly to the soil over the first 48 h, but continued to adsorb slowly over the next several weeks, clearly indicating the potential for rate-limited transport. The equilibrium As(V) adsorption isotherm was markedly nonlinear, further indicating the potential for nonideal transport. A model developed for the adsorption of As(V) to hydrous ferric oxide (HFO) was able to predict the pH-dependent adsorption of As(V) to the soil in batch experiments within 0.116 to 0.726 root mean square error (RMSE). Arsenic(V) was significantly retarded in column transport experiments. The column transport experiments were modeled using the one-dimensional advection-dispersion equation, considering both linear and nonlinear adsorption equilibrium. Although the nonlinear local equilibrium model (NLLE, RMSE = 0.273) predicted the data better than the linear local equilibrium model (LLE, RMSE = 0.317), As(V) breakthrough occurred more rapidly than predicted by either model due to adsorption nonequilibrium. However, due to the presence of an irreversible or slowly desorbing fraction, the peak aqueous As(V) concentration (0.624 mg L(-1)) and the total amount of As(V) recovered (44%) was lower than predicted based on the two equilibrium models (NLLE and LLE). For the conditions used in this study [1 mg L(-1) As(V), pH 4.5 and 9,0-0.25 mM PO4, 0.53-1.6 cm min(-1) pore water velocity], the effect on As(V) mobility and recovery increased in the order pH < pore water velocity < PO4.     

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).     

A method for determining the phosphorus sorption capacity and amorphous aluminum of aluminum-based drinking water treatment residuals

A high amorphous aluminum or iron oxide content in drinking water treatment residuals (WTRs) can result in a high phosphorus (P) sorption capacity. Therefore, WTR may be used beneficially to adsorb P and reduce P loss to surface or ground water. The strong relationship between acid ammonium oxalate-extractable aluminum (Al(ox)) and Langmuir phosphorus adsorption maximum (P(max)) in WTR could provide a useful tool for determining P(max) without the onus of the multipoint batch equilibrations necessary for the Langmuir model. The objectives of this study were to evaluate and/or modify an acid ammonium oxalate extraction of Al(ox) and the experimental conditions used to generate P adsorption isotherms to strengthen the relationship between Al(ox) and P(max). The oxalate extraction solution to WTR ratio varied from 40:1, 100:1, and 200:1. Batch equilibration conditions were also varied. The WTR particle size was reduced from <2 mm to <150 microm, and batch equilibration was extended from 17 h to 6 d. Increasing the solution to WTR ratio to 100:1 extracted significantly greater Al(ox) at levels of >50 mg Al kg(-1). No additional increase was found at 200:1. Reducing WTR particle size from <2 mm to <150 microm increased P(max) 2.46-fold. Extending the equilibration time from 17 h to 6 d increased P(max) by a mean of 5.83-fold. The resulting empirical regression equation between the optimized Al(ox) and P(max) (r(2) = 0.91, significant at the 0.001 probability level) may provide a tool to estimate the P(max) of Al-based WTR simply by measuring Al(ox). The accurate determination of WTR P(max) and Al(ox) is essential in using WTR effectively to reduce P loss in runoff or to reduce the solubility of P in agricultural soils or organic waste materials (biosolids, manure).     

Adsorption and clay-catalyzed degradation of erythromycin A on homoionic clays

Erythromycin has been widely used in food-producing animals and in humans, and is frequently detected as an organic pollutant in U.S. streams. In batch experiments with homoionic clays, the Freundlich isotherms were determined at 10 and 25 degrees C. The adsorption of erythromycin A was strongly influenced by clay type, exchanged cations, the pH of the bulk solutions, and the acidity of clay surfaces. The formation of clay-erythromycin A complexes was thermodynamically favorable except for K+- and Fe3+-exchanged montmorillonites, since the reactions were exothermic (deltaH(o) > 0) and the systems became stable (deltaS(o) > 0). Clays catalyzed the erythromycin A degradation by the hydrolysis of the neutral sugar and the multiple dehydrations. The surface acidity of clay surface enhanced the rate of clay-catalyzed degradation of erythromycin A. In addition, the Fe3+-exchanged clay minerals seemed to have an electrostatic interaction with the erythromycin A molecule, by which the hydrolysis of the neutral sugar was influenced.     

Atrazine, isoproturon, mecoprop, 2,4-D, and bentazone adsorption onto iron oxides

Iron oxides are important components influencing the adsorption of various inorganic and organic compounds in soils and sediments. In this study the adsorption on iron oxides of nonionic and ionic pesticides was determined as a function of solution pH, ionic strength, and pesticide concentration. The investigated iron oxides included two-line ferrihydrite, goethite, and lepidocrocite. 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]. The adsorption of the nonionic pesticides (atrazine and isoproturon) was insignificant, whereas the adsorption of the acidic pesticides (mecoprop, 2,4-D, and bentazone) was significant on all investigated iron oxides. The adsorption capacity increased with decreasing pH, with maximum adsorption reached close to the pKa values. The addition of CaCl2 in concentrations from 0.0025 to 0.01 M caused the adsorption capacity to diminish. The adsorption of bentazone was significantly lower than the adsorption of mecoprop and 2,4-D, illustrating the importance of a carboxyl group in the pesticide structure. The adsorption capacity on the iron oxides increased in the order: lepidocrocite < goethite < two-line ferrihydrite. The maximum adsorption capacities of meco-prop and 2,4-D on goethite were found to be equivalent to the site density of singly coordinated hydroxyl groups on the faces of the dominant (110) form, suggesting that singly coordinated hydroxyl groups are responsible for adsorption. Differences in adsorption capacities between iron oxides can be explained by differences in the surface site density of singly coordinated hydroxyl groups. The maximum measured adsorption capacity of mecoprop on two-line ferrihydrite was equivalent to 0.2 mol/mol Fe.     

Effects of impurities on the removal of heavy metals by natural limestones in aqueous systems

Effects of impurities on the removal of heavy metals by natural limestones in aqueous solutions were studied by evaluating various factors including limestone concentration, pH, contact time and temperature. Solutions of Pb(II), Cd(II), Cu(II) and Zn(II), prepared from chloride reagents at a concentration of 10 mg/L, were studied in a batch method. Four natural limestone samples, collected from the Campanian-Maastrichtian limestone beds in Tunisia, were used as adsorbents. Sorption experiments indicated that high removal efficiencies could be achieved. Limestone samples containing impurities, such as silica, iron/aluminum oxides and different kinds of clay minerals, demonstrated enhanced sorption capacity, nearing 100% removal in some cases. Kinetic experiments showed that the sorption of metal ions occurred rapidly at a low coverage stage, and that solutions were nearly at equilibrium after 60 min. Data trends generally fit pseudo-second order kinetic, and intra-particle diffusion, models. The following conditions were found to promote optimum, or near-optimum, sorption of heavy metals: 1) contact time of more than 60 min, 2) pH = 5, 3) >3 g/L limestone concentration and 4) T = 35 °C. The results of this study suggest that the limestones from northern Tunisia, that contain higher amounts of silica and iron/aluminum oxides, are promising adsorbents for the effective removal of toxic heavy metals from wastewaters.     

Adsorption of 2,4-dichlorophenoxyacetic acid by an Andosol

To identify the important soil components involved in 2,4-dichlorophenoxyacetic acid (2,4-D) adsorption on Andosols, 2,4-D adsorption on a surface horizon of an Andosol was compared with that on hydrogen peroxide (H2O2)-treated (soil organic matter [SOM] was removed), acid-oxalate (OX)-treated (active metal hydroxides and SOM were removed), and dithionite-citrate-bicarbonate (DCB)-treated (free and active metal [hydr]oxides and SOM were removed) soil samples at equilibrium pHs ranging from 4 to 8. Although the untreated soil contained a large amount of organic C (71.9 g kg-1), removal of SOM had little effect on 2,4-D adsorption. Active surface hydroxyls, which were attached to the active and free metal (hydr)oxides and metal SOM complexes, were identified as the most important soil functional group for 2,4-D adsorption. The dominant mechanism of the 2,4-D adsorption was a ligand exchange reaction in which the carboxylic group of 2,4-D displaced the active surface hydroxyl associated with metals and formed a strong coordination bond between the 2,4-D molecule and soil solid phase. The ligand exchange reaction reasonably accounted for the selective adsorption of 2,4-D over Cl-, competitive adsorption of phosphate over 2,4-D, reduction in plant-growth-inhibitory activity of soil-adsorbed 2,4-D, and the high 2,4-D adsorption ability of Andosols. Although a humic acid purified from the soil did not adsorb 2,4-D, the presence of the humic acid increased 2,4-D adsorption on Al and Fe, probably by inhibiting the hydrolysis and polymerization of Al and Fe resulting in the preservation of available adsorption sites on these metals. The adsorption behavior of 2,4-D on soils could be a good index for predicting the adsorption behavior of other organic acids in soils.     

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.     

Molecular analysis of carbon dioxide adsorption processes on steel slag oxides

This review presents a summary of the main interactions that occur during the carbon dioxide (CO₂) adsorption at the surface of steel slags with basic (CaO, MgO), amphoteric (Al₂O₃, Cr₂O₃, TiO₂, MnO, iron oxides) and acidic (SiO₂) oxides. The high content of metal oxides in steel slags gives them a great potential to adsorb CO₂, reaching a saturation value of about 0.25 kg of CO₂/kg of slag. CO₂ is physisorbed and chemisorbed on the most of metal oxide types. Generally, the CO₂ physisorption on the basic and amphoteric metal oxides involves an electrostatic interaction between the CO₂ and the cation from the oxides while the CO₂ chemisorption rather implicates the basic sites that acts as the electron donor, and which are associated with O^2? ions localized at surface defects. These interactions result in the formation of carbonates (monodentates or unidentates and bidentates). The affinity of oxides for the CO₂ and the carbonate formation principally depend of the strength and number of basic sites at their surface and varies as following: basic oxides > amphoteric oxides > acidic oxides. The basic metal oxides generally represent the best electron donors and thus the best CO₂ adsorbents due to the high basicity and their great number of reaction sites. Hence, it appears that the surface structure of basic and amphoteric metal oxides which may favour their interaction with the CO₂, as well as their basicity is the determinant factor contributing to the formation of carbonate species. The molecular analysis of CO₂ adsorption on steel slag metal oxides will provide useful data to identify rate-controlling mechanisms and should be considered for the development of new effective methods for the capture of atmospheric CO₂ emissions released from industries.     

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.     

Interactions of chlorpyrifos with colloidal materials in aqueous systems

An understanding of sorptive processes is key to describing the fate of chlorpyrifos [O,O-diethyl-O-(3, 5, 6-trichloro-2-pyridyl) phosphorothioate] in aquatic environments. The objectives of this study were to evaluate isotherms for adsorption and desorption of chlorpyrifos on colloidal materials and to advance understanding of interaction mechanisms between chlorpyrifos and colloidal materials. Six Ca-saturated reference smectites, one Ca-saturated humic acid (Ca-humate), and one suspended sediment sample, collected from the Upper Cedar River, Iowa, were studied. A batch equilibration technique was employed to quantify adsorption and desorption isotherms for chlorpyrifos over the 0 to 100 microg L(-1) concentration range in a 0.01 M CaCl(2) background. Large differences in sorption affinity and variation in desorption hysteresis were found among the smectites. Neither chlorpyrifos adsorption nor its desorption were correlated with cation exchange capacity, surface area, or surface charge density of the smectites. The evidence suggests that physical interaction between chlorpyrifos and smectites is the dominant mechanism for adsorption of chlorpyrifos in aqueous systems. Chlorpyrifos was very strongly sorbed on Ca-humate and was not desorbed from the Ca-humate back into the aqueous solution. Chlorpyrifos was moderately sorbed on river sediment, and a large adsorption-desorption hysteresis was also found. The study implies that the nature of both organic and inorganic materials in suspended sediment can influence the adsorption-desorption behavior of chlorpyrifos in aqueous systems.     

Metolachlor dechlorination by zerovalent iron during unsaturated transport

Permeable zerovalent iron (Fe0) barriers have become an established technology for remediating contaminated ground water. This same technology may be applicable for treating pesticides amenable to dehalogenation as they move downward in the vadose zone. By conducting miscible displacement experiments in the laboratory with metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide; a chloroacetanilide herbicide] under unsaturated flow, we provide proof-of-concept for such an approach. Transport experiments were conducted in repacked, unsaturated soil columns attached to vacuum chambers and run under constant matrix potential (-30 kPa) and Darcy flux (approximately 2 cm d(-1)). Treatments included soil columns equipped with and without a permeable reactive barrier (PRB) consisting of a Fe0-sand (50:50) mixture supplemented with Al2(SO4)3. A continuous pulse of 14C-labeled metolachlor (1.45 mM) and tritiated water (3H2O) was applied to top of the columns for 10 d. Results indicated complete (100%) metolachlor destruction, with the dehalogenated product observed as the primary degradate in the leachate. Similar results were obtained with a 25:75 Fe0-sand barrier but metolachlor destruction was not as efficient when unannealed iron was used or Al2(SO4)3 was omitted from the barrier. A second set of transport experiments used metolachlor-contaminated soil in lieu of a 14C-metolachlor pulse. Under these conditions, the iron barrier decreased metolachlor concentration in the leachate by approximately 50%. These results provide initial evidence that permeable iron barriers can effectively reduce metolachlor leaching under unsaturated flow.     

Adsorption of cadmium on biosolids-amended soils

Debate exists over the biosolid phase (organic or inorganic) responsible for the reduction in phytoavailable Cd in soils amended with biosolids as compared with soils amended with inorganic salts. To test the importance of these two phases, adsorption isotherms were developed for soil samples (nine biosolids-amended soils and their five companion controls) and two biosolids samples from five experimental sites with documented histories of biosolids application. Subsamples were treated with 0.7 M NaClO to remove organic carbon. Cadmium nitrate was added to both moist soil samples and their soil inorganic fractions (SIF) in a 0.01 M Ca(NO3)2 solution at three pH levels (6.5, 5.5, and 4.5), and equilibrated at 22 +/- 1 degrees C for at least 48 h. Isotherms of Cd adsorption for biosolids-amended soil were intermediate to the control soil and biosolids. Decreasing pH did not remove the difference between these isotherms, although adsorption of Cd decreased with decreasing pH level. Organic matter removal reduced Cd adsorption on all soils but had little influence on the observed difference between biosolids-amended and control soils. Thus, increased adsorption associated with biosolids application was not limited to the organic matter addition from biosolids; rather, the biosolids application also altered the adsorptive properties of the SIF. The greater affinity of the inorganic fraction of biosolids-amended soils to adsorb Cd suggests that the increased retention of Cd on biosolids-amended soils is independent of the added organic matter and of a persistent nature.     

Factors controlling phosphate interaction with iron oxides

Factors such as pH, solution ion composition, and the presence of natural organic matter (NOM) play a crucial role in the effectiveness of phosphorous adsorption by iron oxides. The interplay between these factors shows a complicated pattern and can sometimes lead to controversial results. With the help of mechanistic modeling and adsorption experiments, the net macroscopic effect of single and combined factors can be better understood and predicted. In the present work, the relative importance of the above-mentioned factors in the adsorption of phosphate was analyzed using modeling and comparison between the model prediction and experimental data. The results show that, under normal soil conditions, pH, concentration of Ca, and the presence of NOM are the most important factors that control adsorption of phosphate to iron oxides. The presence of Ca not only enhances the amount of phosphate adsorbed but also changes the pH dependency of the adsorption. An increase of dissolved organic carbon from 0.5 to 50 mg L can lead to a >50% decrease in the amount of phosphate adsorbed. Silicic acid may decrease phosphate adsorption, but this effect is only important at a very low phosphate concentration, in particular at high pH.     

Enhanced desorption of herbicides sorbed on soils by addition of Triton X-100

A study of the desorption of atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine) and linuron [1-methoxy-1-methyl-3-(3,4-dichlorophenyl)urea] adsorbed on soils with different organic matter (OM) and clay contents was conducted in water and in the presence of the non-ionic surfactant Triton X-100 at different concentrations. The aim was to gain insight into soil characteristics in surfactant-enhanced desorption of herbicides from soils. Adsorption and desorption isotherms in water, in all Triton X-100 solutions for atrazine, and in solutions of 0.75 times the critical micelle concentration (cmc) and 1.50cmc for linuron fit the Freundlich equation. All desorption isotherms showed hysteresis. Hysteresis coefficients decreased for linuron and increased or decreased for atrazine in Triton X-100 solutions. These variations were dependent on surfactant concentration and soil OM and clay contents. In the soil-water-surfactant system desorption of linuron from all soils was always greater than in the soil-water system but for atrazine this only occurred at concentrations higher than 50cmc. For the highest Triton X-100 concentration (100cmc), the desorption of the most hydrophobic herbicide (linuron) was increased more than 18-fold with respect to water in soil with an OM content of 10.3% while the atrazine desorption was increased 3-fold. The effect of Triton X-100 on the desorption of both herbicides was very low in soil with a high clay content. The results indicate the potential use of Triton X-100 to facilitate the desorption of these herbicides from soil to the water-surfactant system. They also contribute to better understanding of the interactions of different molecules and surfaces in the complex soil-herbicide-water surfactant system.     

Kinetics of chromate adsorption on goethite in the presence of sorbed silicic acid

The adsorption of chromate on mineral surfaces has received much attention due to its toxicity in natural systems. Spectroscopic studies have demonstrated that chromate forms inner-sphere complexes on variable-charge surfaces. However, in natural systems chromate has been observed to be fairly mobile, which has been explained by the presence of naturally occurring ligands competing with chromate for mineral surface sites. Silicic acid is a ubiquitous ligand in soil and water environments and also sorbs strongly to variable-charge surfaces. Yet little research has examined its influence on chromate adsorption to variable-charge surfaces such as goethite. This study examined the influence of silicic acid (0.10 and 1.0 mM) on the adsorption kinetics of chromate (0.05 and 0.10 mM) on goethite over a range of common soil pH values (4, 6, and 8). The rate and total quantity of chromate adsorption decreased in all the experiments except at a pH value of 4 and a chromate concentration of 0.05 mM. The inhibition of chromate adsorption ranged from 3.1% (pH = 4, Si = 0.10 mM, chromate = 0.10 mM) to 83.3% (pH = 8, Si = 1.0 mM, chromate = 0.05 mM). The rate of chromate adsorption decreased with an increase in pH and silicic acid concentration. This was attributed to a reduction in the surface potential of goethite on silicic acid adsorption as well as a competition for surface sites. The presence of naturally occurring ligands such as silicic acid may be responsible for the enhanced mobility of chromate in natural systems and demonstrates the importance of competitive adsorption for evaluating the mobility of trace elements.     

Sorption-desorption of carbamazepine from irrigated soils

Th anti-seizure medication carbamazepine is often found in treated sewage effluent and environmental samples. Carbamazepine has been shown to be very persistent in sewage treatment, as well as ground water. Due to environmental persistence, irrigation with sewage effluent could result in carbamazepine contamination of surface and ground water. To determine the potential for leaching of carbamazepine, a series of adsorption and desorption batch equilibrium experiments were conducted on irrigated soils. It was found that carbamazepine adsorption to biosolid-amended (T) soils had a KD of 19.8 vs. 12.6 for unamended soil. Based on adsorption, carbamazepine leaching potential would be categorized as low. During desorption significant hysteresis was observed and KD increased for both soils. Desorption isotherms also indicate a potential for irreversibly bound carbamazepine in the T soil. Results indicate that initial removal of carbamazepine via adsorption from irrigation water is significant and that desorption characteristics would further limit the mobility of carbamazepine through the soil profile indicating that carbamazepine found in sewage effluent used for irrigation has a low leaching potential.