Adsorption of imidazolinone herbicides on ferrihydrite-humic acid associations.

Adsorption of the imidazolinone herbicides imazapyr, imazethapyr and imazaquin was studied on two binary systems (ferrihydrite-humic acid) prepared by treating ferrihydrite (Fh) immediately after its precipitation with a soil humic acid (HA) at different loadings (4% and 8% HA content), and on a blank ferrihydrite sample prepared in the same way, but without HA addition. Imidazolinone adsorption on pure Fh and on the 4% Fh-HA decreased with increasing of the herbicide hydrophobicity (imazaquin相似文献   

Abiotic degradation (photodegradation and hydrolysis) of imidazolinone herbicides

The abiotic degradation of the imidazolinone herbicides imazapyr, imazethapyr and imazaquin was investigated under controlled conditions. Hydrolysis, where it occurred, and photodegradation both followed first-order kinetics for all herbicides. There was no hydrolysis of any of the herbicides in buffer solutions at pH 3 or pH 7; however, slow hydrolysis occurred at pH 9. Estimated half-lives for the three herbicides in solution in the dark were 6.5, 9.2 and 9.6 months for imazaquin, imazethapyr and imazapyr, respectively. Degradation of the herbicides in the light was considerably more rapid than in the dark with half lives for the three herbicides of 1.8, 9.8 and 9.1 days for imazaquin, imazethapyr and imazapyr, respectively. The presence of humic acids in the solution reduced the rate of photodegradation for all three herbicides, with higher concentrations of humic acids generally having greater effect. Photodegradation of imazethapyr was the least sensitive to humic acids. The enantioselectivity of photodegradation was investigated using imazaquin, with photodegradation occurring at the same rate for both enantiomers. Abiotic degradation of imidazolinone herbicides on the soil surface only occurred in the presence of light. The rate of degradation for all herbicides was slower than in solution, with half-lives of 15.3, 24.6 and 30.9 days for imazaquin, imazethapyr and imazapyr, respectively. Abiotic degradation of these herbicides is likely to be slow in the environment and is only likely to occur in clear water or on the soil surface.     

Abiotic degradation (photodegradation and hydrolysis) of imidazolinone herbicides

The abiotic degradation of the imidazolinone herbicides imazapyr, imazethapyr and imazaquin was investigated under controlled conditions. Hydrolysis, where it occurred, and photodegradation both followed first-order kinetics for all herbicides. There was no hydrolysis of any of the herbicides in buffer solutions at pH 3 or pH 7; however, slow hydrolysis occurred at pH 9. Estimated half-lives for the three herbicides in solution in the dark were 6.5, 9.2 and 9.6 months for imazaquin, imazethapyr and imazapyr, respectively. Degradation of the herbicides in the light was considerably more rapid than in the dark with half lives for the three herbicides of 1.8, 9.8 and 9.1 days for imazaquin, imazethapyr and imazapyr, respectively. The presence of humic acids in the solution reduced the rate of photodegradation for all three herbicides, with higher concentrations of humic acids generally having greater effect. Photodegradation of imazethapyr was the least sensitive to humic acids. The enantioselectivity of photodegradation was investigated using imazaquin, with photodegradation occurring at the same rate for both enantiomers. Abiotic degradation of imidazolinone herbicides on the soil surface only occurred in the presence of light. The rate of degradation for all herbicides was slower than in solution, with half-lives of 15.3, 24.6 and 30.9 days for imazaquin, imazethapyr and imazapyr, respectively. Abiotic degradation of these herbicides is likely to be slow in the environment and is only likely to occur in clear water or on the soil surface.     

Utilization and degradation of imazaquin by a naturally occurring isolate of Arthrobacter crystallopoietes

A species of bacteria that is capable of utilizing imazaquin as the sole carbon source was isolated from soil with repeated imazaquin applications, and was identified as Arthrobacter crystallopoietes (designated as strain “WWX-1”). This isolate degrades imazaquin as high as 200 μg ml⁻¹, and the estimated dissipation half-lives increased from 1.51 d for the treatment at 50 μg ml⁻¹ to 4.75 d for 200 μg ml⁻¹. Optimal growth of WWX-1 in mineral salt medium with 50 μg ml⁻¹ imazaquin was obtained at 35 °C and a pH of 5.0. Growth of WWX-1 was also observed in mineral salt medium with the addition of other imidazolinone herbicides such as imazethapyr and imazapyr, but not with different classes of herbicides such as metsulfuron-methyl. Two imazaquin metabolites were detected, and spectral analysis with HPLC–MS, ¹H NMR, and IR revealed one metabolite with a molecular weight (MW) of 199 as quinoline-2,3-dicarboxylic anhydride. We propose that A. crystallopoietes (WWX-1) could serve as an efficient biodegradation system for remediation of water and soils that are heavily contaminated with imazaquin or other structurally similar chemicals.     

Sorption-desorption behavior of metsulfuron-methyl and sulfosulfuron in soils

Sorption of metsulfuron-methyl and sulfosulfuron were studied in five Indian soils using batch sorption method. Freundlich adsorption equation described the sorption of herbicides with K(f) (adsorption coefficient) values ranging between 0.21 and 1.88 (metsulfuron-methyl) and 0.37 and 1.17 (sulfosulfuron). Adsorption isotherms were L-type suggesting that the herbicides sorption decreased with increase in the initial concentration of the herbicide in the solution. The K(f) for metsulfuron-methyl showed good positive correlation with silt content (significant at p = 0.01) and strong negative correlation with the soil pH (significant at p = 0.05) while sorption of sulfosulfuron did not correlate with any of the soil parameter. Desorption of herbicides was concentration dependent and, in general, sulfosulfuron showed higher desorption than the metsulfuron-methyl. The study indicates that these herbicides are poorly sorbed in the Indian soil types and there may be a possibility of their leaching to lower soil profiles.     

Sorption-desorption behavior of metsulfuron-methyl and sulfosulfuron in soils

Sorption of metsulfuron-methyl and sulfosulfuron were studied in five Indian soils using batch sorption method. Freundlich adsorption equation described the sorption of herbicides with K_f (adsorption coefficient) values ranging between 0.21 and 1.88 (metsulfuron-methyl) and 0.37 and 1.17 (sulfosulfuron). Adsorption isotherms were L-type suggesting that the herbicides sorption decreased with increase in the initial concentration of the herbicide in the solution. The K_f for metsulfuron-methyl showed good positive correlation with silt content (significant at p = 0.01) and strong negative correlation with the soil pH (significant at p = 0.05) while sorption of sulfosulfuron did not correlate with any of the soil parameter. Desorption of herbicides was concentration dependent and, in general, sulfosulfuron showed higher desorption than the metsulfuron-methyl. The study indicates that these herbicides are poorly sorbed in the Indian soil types and there may be a possibility of their leaching to lower soil profiles.     

Montmorillonite-Cu(II)/Fe(III) oxides magnetic material as adsorbent for removal of humic acid and its thermal regeneration

In this work, the adsorption features of montmorillonite and the magnetic properties of Cu(II)/Fe(III) oxides were combined in a material to produce magnetic adsorbent, which can be separated from the medium by a simple magnetic process after adsorption. The magnetic material is effective for the removal of humic acid. At pH 6.1, 96% removal was observed from 4.4 mg l(-1) humic acid solution containing 0.02 M NaCl. The adsorption is pH and ionic strength dependent. Adsorption is favored at lower pH values and dissolved NaCl can enhance the adsorption. The adsorption mechanism of humic acid to the magnetic material was suggested to be the ligand exchange reaction between carboxylic groups of humic acid molecules and the magnetic material surface. The magnetic material can be thermally regenerated. The temperature and time required to achieve good regeneration efficiency were determined to be 300 degrees C and 3 h, respectively. The regenerated adsorbent is still magnetic and approximately has as high specific saturation magnetization and good adsorption capacities as the as-prepared adsorbent.     

Surface charge and adsorption from water onto quartz sand of humic acid

The surface charge of humic acid under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)) was determined by a titration method using a cationic polyelectrolyte as titrant. Adsorption isotherms in batch experiments of the polymer from water onto quartz sand were determined at 20 degrees C, 40 degrees C, and 60 degrees C and under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)). The data indicate significant decrease of humic acid surface charge by decreasing the pH value from 10.0 to 4.1. Similar decrease of humic acid surface charge was observed by increasing either the ionic strength or the affinity of the divalent cation toward the humic acid. At ambient temperature the adsorption of humic acid on the quartz sand seems to be controlled mainly by electrical interaction between the organic particle and the solid substrate. A correlation is found between the surface charge and the adsorbed amount of the polymer, the adsorbed amount increases when the surface charge of humic acid decreases. The increase of the adsorbed amount with the temperature suggests that adsorption process is endothermic.     

Reduced adsorption of ametryn in clay, humic acid, and soil by interaction with ferric ion under Fenton treatment conditions

Previous work in our laboratory indicated a weak interaction between ferric ion and several triazine/triazinone herbicides during a Fenton treatment process, and the intensity of the interaction was calculated. To further support the existence of this weak interaction, the adsorption of ametryn, a triazine herbicide, was investigated in kaolinite clay, humic acid, and soil under pseudo-Fenton conditions. At a low addition rate of ferric ion, the adsorption of ametryn in clay, humic acid, and soil was enhanced due to the decreased pH resulting from the hydrolysis of ferric ion. But the pH effect was totally neutralized and the adsorption of ametryn was significantly reduced by further addition of ferric ion, demonstrating the existence of the weak interaction between ametryn and ferric acid. Further study showed that the adsorption-reduction effect of ferric ion existed not only with ametryn but also with several other triazine/triazinone herbicides. This weak interaction may accelerate the desorption process during the remediation of triazine/triazinone herbicide-contaminated soil using a Fenton/Fenton-like treatment, but it may also impede the degradation of these herbicides.     

Abiotic degradation of imazethapyr in aqueous solution

The photodegradation of imazethapyr [2-(4,5-dihydro-4-méthyl-4-(1-méthylethyl)-5-oxo-1H-imidazol-2-yl)-5-ethyl-3-pyridinecarboxylic acid] in aqueous solution in the presence of titranium dioxide (TiO2) and humic acids (HA) at different ratios of herbicide/TiO2 and herbicide/humic acids was studied at pH 7.0. Irradiation was carried out with polychromatic light using Heraeus apparatus equipped with xenon lamp to simulate sunlight having a spectral energy distribution similar to solar irradiation (>290 nm). The concentration of remaining herbicide was followed using a High Pressure Liquid Chromatograph (HPLC) equipped with UV detector at 230 nm. In pure aqueous solution imazethapyr degrades slowly and the photodegradation leads to the formation of two metabolites labelled A and B. The presence of TiO2 caused enhancement of the degradation rate. The presence of HA induced an increase of the photodegradation of the pesticide with respect to pure aqueous solution.     

Reduced Adsorption of Ametryn in Clay,Humic Acid,and Soil by Interaction with Ferric Ion Under Fenton Treatment Conditions

Previous work in our laboratory indicated a weak interaction between ferric ion and several triazine/triazinone herbicides during a Fenton treatment process, and the intensity of the interaction was calculated. To further support the existence of this weak interaction, the adsorption of ametryn, a triazine herbicide, was investigated in kaolinite clay, humic acid, and soil under pseudo-Fenton conditions. At a low addition rate of ferric ion, the adsorption of ametryn in clay, humic acid, and soil was enhanced due to the decreased pH resulting from the hydrolysis of ferric ion. But the pH effect was totally neutralized and the adsorption of ametryn was significantly reduced by further addition of ferric ion, demonstrating the existence of the weak interaction between ametryn and ferric acid. Further study showed that the adsorption-reduction effect of ferric ion existed not only with ametryn but also with several other triazine/triazinone herbicides. This weak interaction may accelerate the desorption process during the remediation of triazine/triazinone herbicide-contaminated soil using a Fenton/Fenton-like treatment, but it may also impede the degradation of these herbicides.     

Sorption of naphthalene and phenanthrene by soil humic acids

Humic acids are a major fraction of soil organic matter (SOM), and sorption of hydrophobic organic chemicals by humic acids influences their behavior and fate in soil. A clear understanding of the sorption of organic chemicals by humic acids will help to determine their sorptive mechanisms in SOM and soil. In this paper, we determined the sorption of two hydrophobic organic compounds, naphthalene and phenanthrene by six pedogenetically related humic acids. These humic acids were extracted from different depths of a single soil profile and characterized by solid-state CP/MAS 13C nuclear magnetic resonance (NMR). Aromaticity of the humic acids increased with soil depth. Similarly, atomic ratios of C/H and C/O also increased with depth (from organic to mineral horizons). All isotherms were nonlinear. Freundlich exponents (N) ranged from 0.87 to 0.95 for naphthalene and from 0.86 to 0.92 for phenanthrene. The N values of phenanthrene were consistently lower than naphthalene for a given humic acid. For both compounds, N values decreased with increasing aromaticity of the humic acids, such an inverse relationship was never reported before. These results support the dual-mode sorption model where partitioning occurs in both expanded (flexible) and condensed (rigid) domains while nonlinear sorption only in condensed domains of SOM. Sorption in the condensed domains may be a cause for slow desorption, and reduced availability and toxicity with aging.     

Sorption and desorption of the herbicide alachlor on humic acid fractions from two vermicomposts.

The present study focuses on the analysis of two vermicomposts, that have been used as alternative sources of restitution of soil organic matter, as well as sources of nutrient replacements. For this purpose, two samples of vermicomposts from different Brazilian regions (S?o Carlos-SP and Londrina-PR) were characterized according to their humic acid content. Both samples had a pH value near 7.0, and the humic acids present showed high cationic exchange capacities and low values for the C/N ratios. The infrared spectra showed bands that suggested the presence of aliphatic and aromatic components bound to phenolic, carboxylic and amide groups. The effect of vermicompost added to soil on the application of alachlor was evaluated. Alachlor sorption, Freundlich isotherms and alachlor desorption curves in the soil matrix and the vermicompost/soil mixture matrix were determined.     

Complexation of the antibiotic tetracycline with humic acid

The effect of solution chemistry and sorbate-to-sorbent ratio on the interaction of the antibiotic tetracycline with Elliott soil humic acid (ESHA) was investigated using equilibrium dialysis and FITEQL modeling. Tetracycline speciation strongly influenced its sorption to ESHA. Sorption was strongly pH-dependent with a maximum around pH 4.3, and competition with H+ and electrolyte cation (Na+) was evident. The pH-dependent trend was consistent with complexation between the cationic/zwitterionic tetracycline species and deprotonated sites in ESHA (mainly carboxylic functional groups). Modification of ESHA by Ca2+ addition increased tetracycline sorption suggesting that ternary complex formation (ESHA-metal-tetracycline) may be important at higher concentrations of multivalent metal cations. The macroscopic data (pH-envelope and sorption isotherms) were successfully modeled using a discrete logK function with the FITEQL 4.0 chemical equilibrium program indicating that ESHA-tetracycline interaction could be reasonably represented as complex formation of a monoacid with discrete sites in humic acid. Sorption-desorption hysteresis was observed; both sorption and desorption isotherms were well described by the Freundlich equation.     

Kinetics and mechanisms of interaction of simazine with humic acids

Abstract

The adsorption of simazine on two fractions of hu‐mic acids of different molecular size was investigated at a pH range of 2.5 to 6.2. The amounts of the herbicide adsorbed decreased with increasing pH for both of the two humic acids fractions used and no adsorption was observed at pH 5.5. The adsorption capacity of fraction I (M_v >100,000) exceeded that of fraction IV (M_v < 4,000) over the entire pH region used. No appreciable changes in the adsorbed amounts were observed after 24 hours.

Continuous flow dialysis techniques were used to determine the extent of binding between simazine and dissolved humic acids. It was observed that 50% and 60% of simazine added were thus removed from the dialysis bags containing humic acids fractions I and IV,respectively. Higher amounts of simazine were adsorbed by the high molecular weight humic fraction. The adsorption processes involve ionic bonds between simazine and humic acids. In addition it is likely that hydrogen bonds and physical forces are also involved in the adsorption of simazine by humic acids.     

Theoretical aspects and experimental evidence of the capacity of humic substances to bind herbicides by charge-transfer mechanisms (electron donor-acceptor processes)

Theoretical aspects of the possible occurrence of electron donor-acceptor processes involving free radical intermediates and leading to stable charge-transfer complexes between electron donor herbicides and acceptor quinone-like units of humic acids have been discussed on the basis of similar mechanisms occurring on biological scale in the chloroplasts. Experimental evidence of the former hypotheses was given by the analyses of infrared and electron spin resonance data obtained from interaction complexes of a number of s-triazines and substituted ureas (photosynthesis inhibitor herbicides) with soil humic acids. In the case of s-triazines it was shown that with decrease of the capacity of humic molecules to form ionic and hydrogen bonds, the tendency to act as electron acceptor increased, as shown by the higher free radical generation observed after the interaction process. The existence of correlations between the bioactivity of substituted ureas - expressed as inhibitory potency in the Hill reaction (pI₅₀ indexes) - and free radical concentrations in the humic acid - herbicide complexes was also demonstrated.     

Sorption behavior of a new acidic herbicide in soils

The sorptive behavior of the experimental herbicide quinmerac (7-chloro-3-methyl-quinoline-8-carboxylic acid) was investigated in soils of different organic carbon content. Distribution coefficients are low (K_d = 0.03 - 12 mL g⁻¹) and are mainly determined by the soil organic carbon content. The adsorption mechanism operating in neutral to slightly acid agricultural soils is supposed to be cation bridging with the anionic form of quinmerac. Under acid conditions (pH 5.2) the predominating sorption mechanism is hydrophobic interaction. Therefore soil pH and cationic composition are also major factors determining the sorptive capacity of soils for quinmerac.

Adsorption kinetics, equilibrium adsorption and desorption isotherms were determined in batch experiments. Sorption kinetics were investigated at various times from 15 min to 96 hours. A two-step sorption behavior with time was found for the anionic form indicating two types of sorption mechanisms or sorption sites. Equilibrium for the first type was reached at a time-scale of minutes and for the second type after 24 hours. Adsorption isotherms were determined for two soil/solution ratios 1/5 and 1/3. Alteration of the adsorbent concentration exerted a strong influence on the adsorption isotherms. An increase of sorption was found with increasing adsorbent concentration. Under natural soil conditions sorption is therefore expected to be higher compared to the batch experiments. Desorption isotherms were obtained using the consecutive desorption method. Desorption hysteresis was not observed which indicates weak interactions. Implications of the results for the movement of quinmerac under field conditions and for models describing transport are discussed.     

Glyphosate adsorption in soils compared to herbicides replaced with the introduction of glyphosate resistant crops

Use of glyphosate resistant crops was helpful in addressing observed increases in environmental contamination by herbicides. Glyphosate is a broad-spectrum herbicide, and its behaviour-as well as that of other herbicides-in soils is an important consideration for the overall environmental evaluation of genetically resistant crop introduction. However, few data have been published comparing glyphosate behaviour in soil to that of the herbicides that would be replaced by introduction of glyphosate resistant crops. This work compares glyphosate adsorption in soil with that of other herbicides frequently used in rape (trifluralin and metazachlor), sugarbeet (metamitron) and corn (sulcotrione). Herbicide adsorption was characterised in surface soils and in the complete soils profiles through kinetics and isotherms using batch equilibration methods. Pedological and molecular structure factors controlling the adsorption of all five herbicides were investigated. Glyphosate was the most strongly adsorbed herbicide, thus having the weakest potential for mobility in soils. Glyphosate adsorption was dependent on its ionisable structure in relation to soil pH, and on soil copper, amorphous iron and phosphate content. Trifluralin adsorption was almost equivalent to glyphosate adsorption, whereas metazachlor, metamitron and sulcotrione adsorption were lower. Trifluralin, metazachlor and metamitron adsorption increased with soil organic carbon content. Sulcotrione was the least adsorbed herbicide in alkaline soils, but its adsorption increased when pH decreased. Ranking the adsorption properties among the five herbicides, glyphosate and trifluralin have the lowest availability and mobility in soils, but the former has the broadest spectrum for weed control.     

Effects of organic acids on adsorption of lead onto montmorillonite,goethite and humic acid

Adsorption isotherms for Pb onto six soil components (quartz, feldspar, kaolinite, montmorillonite, goethite and humic acid) were studied. The influence of pH, EDTA and citric acid on the adsorption of Pb onto montmorillonite, goethite and humic acid were considered. Results indicate that the experimental data fit the Langmuir Adsorption Isotherm. The adsorption capacity for Pb at pH 6 was found to be in the order: humic acid (22.7 mg g(-1)) > goethite (11.04 mg g(-1)) > montmorillonite (10.4 mg g(-1)) > kaolinite (0.91 mg g(-1)) > feldspar (0.503 mg g(-1)) > quartz (0.148 mg g(-1)). Generally, the amount of Pb adsorbed onto montmorillonite, goethite and humic acid decreased with increasing concentrations of EDTA and citric acid and with increases in alkality. However, there were two exceptions: (1) addition of citric acid increased the amount of Pb adsorbed onto humic acid; and (2) the amount of Pb adsorbed onto goethite decreased with increasing pH in the presence of EDTA. Some mechanisms involved in the adsorption reactions are discussed.