Sorption and catalytic hydrolysis of diethatyl-ethyl on homoionic clays

Sorption and catalytic hydrolysis of the herbicide diethatyl-ethyl [N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester] on homoionic Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite clays were studied in aqueous media. The Freundlich sorption coefficient, K(f), measured from isotherms on clay followed the order of Na(+) approximately K(+) > Mg(2+) approximately Ca (2+). Analysis of FT-IR spectra of diethatyl-ethyl sorbed on clay suggests probable bonding at the carboxyl and amide carbonyl groups of the herbicide. The rate of herbicide hydrolysis in homoionic clay suspensions followed the same order as that for sorption, indicating that sorption may have preceded and thus caused hydrolysis. Preliminary product identification showed that hydrolysis occurred via nucleophilic substitution at the carboxyl carbon, causing cleavage of the ester bond and formation of diethatyl and its dechlorinated derivative, and at the amide carbon, yielding an ethyl ester derivative and its acid. These pathways also suggest that hydrolysis of diethatyl-ethyl was catalyzed by sorption on the clay surface.     

对硝基氯苯在土壤和腐殖酸上的长期吸附与多步解吸的研究

采用批量平衡实验法研究了对硝基氯苯（p-NCB）在土壤和腐殖酸上的长期吸附和多步解吸,比较了连续的多步解吸与一步解吸的差异。结果表明,随着吸附时间的增加吸附量均会有所增加,随吸附时间增加吸附等温线的非线性增强。p-NCB在液相和固相上的初始浓度对吸附速率有一定影响,低浓度比高浓度时达到平衡的速率要低。对于两种受试土壤,两次解吸得到的等温线均无法与吸附等温线重合,表现出很强的吸附不可逆性。而尽管p-NCB在腐殖酸上表现出明显的非线性吸附（n = 0.794）,但4次解吸后所得到的平衡位点与吸附所得的平衡位点基本落在同一条直线上,对数坐标下进行线性拟合的相关系数（R2）可达0.988,说明吸附过程是完全可逆的。     

Interactive Sorption of Metal Ions and Humic Acids onto Mineral Particles

The sorption of metal ions (Pb2+, Zn2+ and Cu2+) and soil humic acids (HA) from aqueous solutions onto mineral particles (sand, calcite and clay) was investigated using a batch equilibrium system. The sorption reactions in two- component systems (heavy metals-mineral particles and humic acids- mineral particles), as well as interactions in three-component system (heavy metals-humic acids-mineral particles) were examined. Results showed that the presence of humic acids, dissolved or bound onto mineral surfaces, considerably influenced the fixation of heavy metals. The various effects, depending on mineral type, humic concentration and specific metal-ion, were observed in three- component system. Sorption of Cu2+-ions on all minerals studied rapidly increased as the concentration of dissolved HA increased. The amount of Pb2+-ions sorbed on sand slightly decreased, while on kaolin increased between 15 and 20%. Sorption of Zn2+-ions on all minerals studied decreased at pH 4. At pH 5.5 the sorption of Zn2+-ions onto calcite decreased, while on kaolin and sand increased as a function of the humic acid concentration giving the curve with maximum at c(HA) = 2.5 mmol C L-1. At pH 6.5 sorption onto kaolin and sand increased. This effect occurs as a result of the conditional stability constant of Zn-HA complexes increasing at higher pH which in turn promotes the chelation of Zn2+-ions to mineral- bound humic substances. The enhanced sorption of metal ions from the aqueous phase in three-component systems is not only the result of mineral sorption of free metals but also the result of chelation with HA sorbed on the mineral surface.     

Caesium sorption—desorption in clay—humic acid systems

Soaking for 7 d with 0.05 M NaCl resulted in less caesium being sorbed by bentonite and kaolinite, but more by illite, compared to soaking for 2 d prior to addition of Cs. Overall the amount of Cs sorbed by the three clays was in the order bentonite > illite > kaolinite. Addition of humic acid to the clays depressed the sorption of Cs by all three clays, with illite showing the greatest effect. Desorption of added Cs was not totally reversible. The presence of humic acid resulted in an enhanced desorption of Cs from bentonite and to a lesser extent kaolinite. This enhanced desorption in the presence of humic acid was not seen for illite. The order of Cs retention following desorption for both clay and clay/ humic-acid mixtures was illite > bentonite > kaolinite. A single K_d value could not describe the whole isotherm, but individual values were calculated at different Cs concentrations to cover the range of the isotherm. K_d values for desorption were higher than the corresponding K_d for sorption. For both sorption and desorption, the presence of humic acid resulted in lower K_d values than in its absence.     

Sorption and desorption of endosulfan sulfate and diuron to composted cotton gin trash

This paper investigates the potential use of composted cotton gin trash (CCGT) as a pesticide sorption medium in remediation of contaminated tailwater. CCGT was found to contain a large organic matter fraction (25.22%). Sorption of endosulfan sulfate and diuron, using the batch equilibrium method, was rapid but not limited for the range of applied concentrations, with diuron failing to reach equilibrium after two days. The partition K d and organic carbon partition K(OC) coefficients determined diuron ( Kd = 78; K(OC) = 526) and endosulfan sulfate ( Kd = 1500; K(OC) = 10,111) to reside in the solid phase. Limited desorption of diuron and higher range concentrations of endosulfan sulfate (50-100 microg L(-1)) were quantified. Sorption and desorption resulted from hydrophobic and hydrophilic interactions with the humic components of the compost. CCGT was concluded to have a superior sorption capacity to other sorbents reported in the literature, an assessment that requires field substantiation.     

Influence of herbicide structure,clay acidity,and humic acid coating on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite was studied by coupling batch equilibration and FT-IR analysis. Adsorption decreased in the order metolachlor > acetochlor > alachlor > propachlor on Ca(2+)- or Mg(2+)-saturated clays and in the order metolachlor > alachlor > acetachlor > propachlor on Al(3+)- or Fe(3+)-saturated clays. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in bonding. For the same herbicide, adsorption of alachlor, acetachlor, and metolachlor on clay followed the order Ca(2+) approximately Mg(2+) < Al(3+) < or = Fe(3+), which coincided with the increasing acidity of homoionic clays. Adsorption of propachlor, however, showed an opposite dependence, suggesting a different governing interaction. In clay and humic acid mixtures, herbicide adsorption was less than that expected from independent additive adsorption by the individual constituents, and the deviation was dependent on the clay-to-humic acid ratio, with the greatest deviation consistently occurring at a 60:40 clay-to-humic acid ratio.     

Sorption-desorption of aminocyclopyrachlor in selected Brazilian soils

Aminocyclopyrachlor sorption/desorption was investigated in 14 soils from Brazil, representing a range of pH, and organic carbon (OC) and clay contents. The Freundlich equation adequately described behavior of aminocyclopyrachlor in soil. Freundlich sorption coefficient (K(f)) values ranged from 0.06 to 1.64 and 1/n values for ranged from 0.9 to 1.0. Sorption was correlated to OC (K(f,oc) ranged from 11 to 64) and clay contents. The lowest sorption was found for soils with very low OC contents (0.50-0.65%) and loamy-sand to sand textures. The 1/n values for desorption were lower than those observed for sorption, suggesting that aminocyclopyrachlor sorption by soil was not reversible; hysteresis coefficients ranged from 0.13 to 0.74. The results suggest that although aminocyclopyrachlor would be very mobile based on its sorption coefficients, its potential depth of leaching may be overestimated due to the hysteretic desorption.     

Applications of the continuous-flow stirred-cell (CFSC) technique: II. The adsorption behaviour of Na, Cs, Sr, Cu, Ni and Pb on humic acids

The first part of this paper deals with the sorption of Na, Cs, Sr, Ni, Cu and Pb on two humic fractions derived from a soil. The sorption data for individual elements were obtained using the continuous-flow stirred-cell (CFSC) technique, in which the metal sorptive solution is pumped through a cell containing a known mass of the humic acid retained by a filter and the solution emerging from the cell was analysed by either atomic absorption spectrometry (Cu, Ni and Pb) or by the combined use of radioisotope dilution and gamma-ray spectroscopy (Na, Cs and Sr). Sorption isotherms were determined at two flow rates. It was found that, in general, the sorption isotherms for all the metals studied could be described by the Langmuir equation and parameters derived from the fitted line provided information on the metal-humate binding strengths and the maximum amount of metal sorbed per unit mass of humic acid. Caesium showed anomalous behaviour at certain flow rates in both its sorption and desorption behaviour. In the second part of the paper we discuss the sequential sorption and desorption of one metal by another on the same humic fraction, using Na, Cs, Zn and Cd. The aim was to elucidate the nature of the binding process when several metals were competing simultaneously for the functional groups on the humic acids. In addition, at the end of the experiment, the humic material was isolated and analysed by gamma-ray spectroscopy to determine the metals still bound in this fraction. Some tentative conclusions concerning the nature of the metal-humate complexes are made on the basis of these data.     

Effects of Oxalate and Humic Acid on Arsenate Sorption by and Desorption from a Chinese Red Soil

Studies on arsenate (As(V)) sorption and desorption have been mainly limited to soil minerals and sorption and desorption reactions in whole soils are poorly understood. In this study the sorption of As(V) by and phosphate-induced desorption from a Chinese red soil were studied in the presence of oxalate and humic acid (HA). Arsenate was strongly sorbed mainly through ligand exchange reactions on the soil. Arsenate sorption decreased in the presence of oxalate or HA. Oxalate and HA influenced As(V) sorption mainly by competing for sorption sites and reducing sorption sites, and oxalate could also decrease sorption through dissolving clay minerals. Oxalate and HA could also facilitate As(V) desorption from the soil. Both sorption and desorption kinetics were two stage processes. Sorption kinetics conducted from 0.2–840 h showed that As(V) sorption increased with increasing residence time. Sorption equilibrium was retarded and the maximum sorption decreased in the presence of oxalate or HA. Phosphate-induced desorption kinetics conducted on the soil with 24 h and 840 h of sorption equilibrium time showed a significant effect of equilibrium time on As(V) desorption. The presence of oxalate or HA during the sorption process resulted in more As(V) desorption. Due to the degradation of oxalate, soil treated with oxalate and with a sorption equilibrium time of 840 h showed no significant difference in desorption kinetics from untreated soil.     

Sorption and desorption of triadimefon by soils and model soil colloids

Sorption-desorption of the azole fungicide triadimefon [1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2, 4-triazol-1-yl)-2-butanone] on eight soils and a series of single, binary, and ternary model soil colloids was determined using the batch equilibration technique. Regression analysis between Freundlich sorption coefficients (K(f)) and soil properties suggested that both clay and organic C (OC) were important in triadimefon sorption by soils, with increasing importance of clay for soils with high clay and relatively low OC contents. Triadimefon sorption coefficients on soil were not significantly affected by the concentration of electrolyte or the presence of soluble soil material in solution, but they were highly dependent on the soil:solution ratio due to the nonlinearity of triadimefon sorption on soil. Freundlich sorption isotherms slopes were very similar for all soils (0.75 +/- 0.02). Desorption did not greatly depend on the concentration at which it was determined and showed higher hysteresis for more sorptive soils. Results of triadimefon sorption on model sorbents supported that both humic acid and montmorillonite-type clay constituents contribute to triadimefon retention by soil colloids.     

Phenanthrene sorption by compost humic acids

Nonlinear isotherms were observed for sorption of polycyclic aromatic hydrocarbons (PAHs) to humic materials, but the exact sorption mechanism is not clearly understood. This study aimed to investigate the sorption of PAHs by compost humic materials. Humic acids (HAs) were progressively extracted from two compost samples by a 0.1-M sodium pyrophosphate solution. Sorption of phenanthrene by the extracted HAs was studied with a batch equilibration technique. Competitive sorption between pyrene and phenanthrene in the HAs was also examined. Elemental analysis and solid-state ¹³C NMR were used to characterize HAs. All sorption isotherms were nonlinear although these samples contained little black carbons if any. Isotherm linearity increased with increasing number of extractions. Isotherm nonlinearity was negatively related to HA aliphaticity. Addition of pyrene to the phenanthrene-HA system increased isotherm linearity. Competition between phenanthrene and pyrene sorption was more pronounced in the first fraction of HAs with a higher content of aromatic moieties. This study showed that humic materials alone could lead to nonideal sorption for PAHs.     

Competitive Effect of Copper,Zinc, Cadmium and Nickel on Ion Adsorption and Desorption by Soil Clays

This study evaluated the effect of competing copper, zinc, cadmium and nickel ions in 0.01 M Ca(NO₃)₂ on heavy metal sorption and desorption by soil clay fractions. Initial Cu addition levels varied from 99 mg kg^-1 to 900 mg kg^-1 and Zn, Cd and Ni levels were 94, 131 and 99 mg kg^-1, respectively. Sorption of Cu conformed to a Freundlich equation. The amounts of metals not displaced by successive 48 h desorption cycles with 0.01 M Ca(NO₃)₂ were considered ‘specifically adsorbed’. Total sorption of Zn and Cd generally decreased in the order: Vertisol > Gleyic Acrisol > Planosol clay. More than 70% of the copper was specifically sorbed. Specific sorption of Zn was depressed by competition with Cu in the three clays investigated. At surface coverages higher than 200 mg Cu per kg of soil clay, zinc sorption in the Planosol and Gleyic Acrisol clays took place at low affinity sites. The exchangeable component of sorbed cadmium accounted for >:60% of the sorption in the Vertisol clay, >70% in the Gleyic Acrisol clay and was almost 100% in the Planosol clay. Nickel was not retained by the Planosol and Gleyic Acrisol clays and was ionexchangeably adsorbed by the Vertisol clay. At the conditions studied, Ni and Cd remain a ready source of pollution hazard.     

风化煤腐殖酸对氮、磷、钾的吸附和解吸特性

研究了风化煤腐殖酸在不同pH值条件下对氮、磷、钾的吸附和解吸特性。结果表明,1)在pH.4～8条件下,随着氮、磷、钾初始处理浓度的增加,腐殖酸对其吸附量和解吸量均呈上升趋势,但解吸率均呈下降趋势;2)在不同pH值的介质溶液中,腐殖酸对氮、磷、钾的吸附和解吸特性不尽相同,其中,在碱性条件下,腐殖酸对氮的吸附和解吸作用较强,在酸性条件下,腐殖酸对磷的吸附和解吸作用较强,而腐殖酸对钾的的吸附和解吸作用在中性条件下更易发生;3)腐殖酸对氮、磷、钾的等温吸附可用Linear、Langmuir和Freundlich三个吸附方程来拟合,相关性达显著或极显著水平,但以Freundlich方程为最优。     

Molecular structures of gellan gum imaged with atomic force microscopy in relation to the rheological behavior in aqueous systems in the presence or absence of various cations

Aqueous solutions of gellan gum with comparable molecular masses but with different acyl contents were investigated by atomic force microscopy and rheological measurements in the presence or absence of various cations. For a high-acyl sample, no continuous network structures were identified microscopically, except in the presence of Ca (2+), where structural inhomogeneity was the highest in terms of the height distribution of molecular assemblies. Rheological thermal hysteresis between sol-gel transitions was detected in the presence of K (+) and Ca (2+), particularly Ca (2+). The storage modulus at 20 degrees C was larger in the order Na (+) < Ca (2+) < K (+). For a low-acyl sample, continuous network structures were identified in the presence of each cation, involving greater thermal hysteresis than the corresponding data for the high-acyl sample. Structural homogeneity was the highest in the presence of K (+). Thermal hysteresis and elasticity of the system were discussed in terms of continuousness and homogeneity of network structures.     

Sorption behavior of prochloraz in different soils.

The sorption behavior of the imidazole fungicide prochloraz [PCZ; N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide] was studied in batch experiments with different soils. The soil organic matter content was found to control the amount sorbed by different soils. K(d) values ranged from 56 +/- 0 to 552 +/- 10 (mean = 221 +/- 5) and K(OC) values from 7273 +/- 0 to 16250 +/- 1300 (mean = 11829 +/- 303). As calculated from a linear regression of K(d) versus %OC, K(OC) was 12900 +/- 1300. Additionally, the pH value of the soil had considerable influence on the sorption of the weakly basic PCZ (pK(a) = 3.8), giving rise to stronger sorption at lower pH. K(d) values determined on pH-modified soils confirmed the pH dependency. Sorption isotherms on two soils were recorded, initial concentrations ranging from 0.09 to 5.71 mg L(-)(1). The Freundlich isotherm was fitted to the values measured. The Freundlich exponents calculated were significantly smaller than unity, indicating nonlinear sorption. Sorption experiments with two metabolites of PCZ (PCZ-formylurea and PCZ-urea) revealed K(d) values one-fourth to one-third those for PCZ on two soils.     

毒死蜱有毒代谢物3,5,6-TCP在土壤中的吸附-解吸研究

应用OECD106批平衡方法,研究了毒死蜱的有毒代谢物3,5,6-TCP在6种典型土壤中的吸附-解吸行为。结果表明：Elovich方程、双常数方程和抛物线扩散方程能较好地拟合3,5,6-TCP在第四纪红土、黑土、黄壤和褐土中的吸附动力学过程,而对紫色土和潮沙土的拟合度较低（拟合相关系数小于0.85）;应用Freundlich方程和线性方程拟合第四纪红土、黑土、黄壤和褐土的经验常数nfads均小于1（非线性吸附）,而紫色土和潮沙土的nfads值则接近于1（线性吸附）;3,5,6-TCP在6种土壤中解吸的滞后系数H值均大于1,即解吸速率大于吸附速率。6种土壤对3,5,6-TCP的吸附常数Kfads从1.37-6.74μg1-n·fmLn·fg^-1,吸附系数Kd值从0.50-1.30mL·g^-1,其中第四纪红土和黑土对其吸持力较强（Kd〉1）,因而更应注意环境安全;其他4种土壤的Kd值则均小于1,淋溶风险较大。     

Adsorption and desorption of cadmium by synthetic and natural organo-clay complexes

Tracer levels of ¹⁰⁹Cd were used to study the adsorption and desorption of Cd by synthetic and natural organo—clay complexes. Synthetic organo—clay complexes were made by adsorbing humic acid extracted from soil to various forms of < 2 μm diameter montmorillonite (Na, Ca, Al, and Fe saturated and Ca-montmorillonite coated with Al or Fe hydroxide). Natural organo—clay complexes were fractionated from the clay fraction of a Captina silt loam by density-gradient centrifugation in a large-scale zonal rotor.To evaluate the influence of humic acid on adsorption of Cd, Cd was adsorbed to the various forms of montmorillonite before and after humic acid adsorption. No appreciable difference in Cd adsorption was noted except in the case where montmorillonite was coated with Al or Fe hydroxides. Cadmium was found to be strongly bonded to clays coated with Al or Fe hydroxides; however, Cd adsorption to these clays after humic acid adsorption was considerably less. Data indicated Cd and humic acid adsorption sites on Al or Fe coated clays were either identical or prior adsorption of humic acid simply covered available Cd sites.Cadmium adsorption to clay density fractions showed that greatest adsorption was to fractions containing high quantities of organic matter or sesquioxides. Desorption of Cd with 0.01 M Ca (NO₃)₂ showed that Cd was adsorbed more tenaciously to the sesquioxides than organo—clay fractions.     

Adsorption and desorption of triasulfuron by soil

The adsorption and desorption of the herbicide triasulfuron [2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide] by three soils, soil organic matter (H(+) and Ca(2+)-saturated), and an amorphous iron oxide were studied. Adsorption isotherms conformed to the Freundlich equation. It was found that pH is the main factor influencing the adsorption in all of the systems. Indeed, the adsorption on soils was negatively correlated with pH. The highest level of adsorption was measured on soils with low pH and high organic carbon content. Moreover, it was found that humic acid is more effective in the adsorption compared with calcium humate (the pH values of the suspensions being 3.5 and 6, respectively). Experiments on amorphous iron oxide confirmed the pH dependence. Desorption was hysteretic on soils having high organic carbon content.     

Sorption of humic acid on Fe oxides,bacteria, and Fe oxide-bacteria composites

Purpose

Sorption of humic substances on other soil components plays an important role in controlling their function and fate in soil. Sorption of humic substances by individual soil components has been studied extensively. However, few studies reported the sorption characteristic of humic substances on composites of soil components. This study aimed to investigate the sorption characteristics of humic acid on Fe oxide-bacteria composites and improve the understanding on the interaction among humic substance Fe oxide bacteria in soil.

Materials and methods

Humic acid was purchased from Sigma-Aldrich and was purified. Hematite and ferrihydrite were synthesized in the lab. Bacillus subtilis and Pseudomonas putida were cultivated in Luria-Broth medium and harvested at stationary growth phase. Batch sorption experiments were carried out at pH 5.0. Various amounts of humic acid were mixed with 20 mg of Fe oxide, bacteria, or Fe oxide-bacteria composite (oxide to bacteria of 1:1) in 10 mL of KCl (0.02 mol L^?1) to construct sorption isotherms. The effects of phosphate concentration and addition order among humic acid, Fe oxide, bacteria on the sorption of humic acid were also studied. The sorption of humic acid was calculated by the difference between the amount of humic acid added initially and that remained in the supernatant.

Results and discussion

The maximum sorption of humic acid on hematite, ferrihydrite, B. subtilis and P. putida was 73.2, 153.5, 69.1, and 56.7 mg C g^?1, respectively. The maximum sorption of humic acid on examined Fe oxide-bacteria composite was 28.2–57.2 % less than the predicted values, implying that the sorption of humic acid was reduced by the interaction between Fe oxides and bacteria. The presence of phosphate exerted negligible influence on the sorption of humic acid on bacteria while it inhibited the sorption of humic acid on Fe oxides. On Fe oxide-bacteria composites, inhibiting influences followed by promoting or weak inhibiting effects of phosphate with increasing concentration on the sorption of humic acid were found.

Conclusions

The interaction between Fe oxides and bacteria reduced the sorption of humic acid; moreover, the reduction was greater by the interaction of bacteria with ferrihydrite than that with hematite. Phosphate exerted negligible and inhibiting influence on the sorption of humic acid by bacteria and Fe oxides, respectively. On Fe oxide-bacteria composites, humic acid sorption was initially inhibited and then promoted or weakly inhibited by phosphate with increasing concentration.     

Zinc sorption–desorption by two Andepts: effect of pH and support medium

Laboratory experiments were carried out to evaluate the effect of pH, ionic strength and electrolyte composition on zinc sorption–desorption by two Andepts from the Canary Islands (Spain). At the natural soil pH, the soils exhibited little net negative surface charge and small Zn sorption capacities. More than 75% of the sorbed Zn was apparently strongly bonded. The pH greatly influenced the sorption–desorption reactions. Sorption increased with increasing pH, and retention increased abruptly at pH > 6.0. Sorption also occurred at pH values below the point of zero charge (PZC) of the soils, when most of the surface sites are positively charged. Desorption decreased continuously with rising pH and became a trace at pH > 6.0. An increase in the ionic strength of the background electrolyte decreased Zn sorption and enhanced the amount of sorbed metal that could be subsequently released. In the two soils, Zn sorption diminished somewhat in the K and Ca electrolytes as compared with the Na electrolyte. However, this did not happen at small Zn loadings. Desorption was not affected by the type of electrolyte and cation used. The results are consistent with chemisorption being responsible for most of the sorption. The results also suggested a strong affinity sorption or even precipitation at high pHs.