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 ametryn and imazethapyr in twenty-five soils from Pakistan and Australia.

Sorption of ametryn and imazethapyr in 25 soils from Pakistan and Australia was investigated using the batch method. The soils varied widely in their intrinsic capacities to sorb these herbicides as shown by the sorption coefficients, Kd, which ranged from 0.59 to 47.6 for ametryn and 0.02 to 6.94 for imazethapyr. Generally the alkaline soils of Pakistan had much lower Kd values of both herbicides than the soils of Australia. Both soil pH and soil organic carbon (SOC) were correlated significantly with the sorption of ametryn, whereas only soil pH was strongly correlated with imazethapyr sorption. No correlation was found between Kd values of the herbicides and the clay contents of the soils. Multiple regression analysis showed that Kd values were better correlated (r2=0.94 and 0.89 for ametryn and imazethapyr, respectively) if SOC and pH were simultaneously taken into account. The study indicated that sorption of these herbicides in the alkaline soils of Pakistan was low and consequently there is considerable risk of groundwater contamination.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption-desorption processes. Four soils from Melozal (35° 43' S; 71° 41' W), Parral (36° 08' S; 71° 52' W), San Carlos (36° 24' S; 71° 57' W), and Panimavida (35° 44' S; 71° 24' W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g?1) and were related to soil pH. Molinate showed K(d) values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g?1 and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K(d) values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g?1. MCPA K(d) ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Adsorption and thermodynamic parameters of chlorantraniliprole and dinotefuran on clay loam soil with difference in particle size and pH

The behavior of chlorantraniliprole (CAP) and dinotefuran (DNF) insecticides was investigated in clay loam soil, a common type of the Egyptian soil. Effect of temperature, pH and particle size of the soil on the adsorption process was studied. Adsorption isotherm by bulk soil and its constituents; humic acid (HA), clay, silt and sand fractions was measured using batch equilibration technique. The results showed that the adsorption of the insecticides tested was significantly affected by the temperature and was a spontaneous interfacial process in the soil. Freundlich model accurately predicted the adsorption behavior of both insecticides. The interaction between soil and insecticides was endothermic and the highest adsorption for CAP and DNF was obtained at pH 9. However, the effect of pH on the adsorption of DNF was lower than that of CAP. Sorption of CAP and DNF on HA fraction was significantly greater than on clay fraction and bulk soil. In addition, the adsorption was significantly increased with particle size decrease. It could be inferred that the adsorption of CAP and DNF on clay loam soil was physical in nature and greatly influenced by the soil components, pH and temperature.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption–desorption processes. Four soils from Melozal (35° 43′ S; 71° 41′ W), Parral (36° 08′ S; 71° 52′ W), San Carlos (36° 24′ S; 71° 57′ W), and Panimavida (35° 44′ S; 71° 24′ W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g^?1) and were related to soil pH. Molinate showed K_d values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g^?1and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K_d values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g^?1. MCPA K_d ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g^?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Effect of humic matter on metal adsorption onto clay materials: Testing the linear additive model

Migration of contaminants with low affinity for the aqueous phase is essentially governed by interaction with mobile carriers such as humic colloids. Their impact is, however, not sufficiently described by interaction constants alone since the humic carriers themselves are subject to a solid–liquid distribution that depends on geochemical parameters.In our study, co-adsorption of the REE terbium (as an analogue of trivalent actinides) and humic acid onto three clay materials (illite, montmorillonite, Opalinus clay) was investigated as a function of pH. ¹⁶⁰Tb(III) and ¹³¹I-labelled humic acid were employed as radiotracers, allowing experiments at very low concentrations to mimic probable conditions in the far-field of a nuclear waste repository. Humate complexation of Tb was examined by anion and cation exchange techniques, also considering competitive effects of metals leached from the clay materials.The results revealed that desorption of metals from clay barriers, occurring in consequence of acidification processes, is generally counteracted in the presence of humic matter. For all clay materials under study, adsorption of Tb was found to be enhanced in neutral and acidic systems with humic acid, which is explained by additional adsorption of humic-bound Tb.A commonly used composite approach (linear additive model) was tested for suitability in reconstructing the solid–liquid distribution of Tb in ternary systems (Tb/humic acid/clay) on the basis of data determined for binary subsystems. The model can qualitatively explain the influence of humic acid as a function of pH, but it failed to reproduce our experimental data quantitatively. It appears that the elementary processes (metal adsorption, metal–humate complexation, humic acid adsorption) cannot be considered to be independent of each other. Possible reasons are discussed.     

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   

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.     

Comparison of hydrolysis/coagulation behavior of polymeric and monomeric iron coagulants in humic acid solution

Fluorescence quenching is commonly used to study the extent of metal binding to humic acid or fulvic acid. By studying this phenomenon, the hydrolysis and precipitation behaviors of polymeric and monomeric iron coagulants in the coagulation of humic acid were evaluated. Combined measurements of fluorescence intensity and dissolved organic carbon were performed to distinguish the hydrolysis and organic matter binding of polymeric and monomeric iron salts in coagulating high molecular weight organic compounds. Experimental results showed that ferric chloride had lower fluorescence quenching than polyferric sulfate (PFS), indicating more rapid hydrolysis of the monomeric ferric ion in the coagulation and dilution process. The less fluorescence quenching was caused by the lower residual concentration of Fe-humic acid complexes in the filtrate. There was no clear difference in adsorption ability and fluorescence quenching, which indicated that the physical and chemical properties of Fe(OH)3 flocs formed from PFS and FeCl3 coagulation were similar. From the pH study, we found that sludge formed from PFS coagulation was more stable than that from FeCl3 coagulation.     

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.     

凹凸棒土对腐殖酸的低温吸附性能研究

首次研究凹凸棒土对饮用水中腐殖酸的低温吸附性能,考察5℃条件下,吸附时间与腐殖酸初始浓度、吸附剂投加量、pH对凹凸棒土吸附腐殖酸的影响,确定吸附剂的吸附等温线、吸附动力学和热力学等相关理论参数,研究凹凸棒土对腐殖酸的吸附性能与机理。结果表明,江苏盱眙凹凸棒土在温度5℃、pH=4、水中腐殖酸初始浓度为5 mg/L,投加量为15 g/L的条件下,吸附180 min后对腐殖酸的去除率可达97.26%。凹凸棒土对腐殖酸的吸附符合二级吸附动力学方程与Freundlich吸附等温式,吸附过程由孔隙内扩散过程控制,吸附为自发的吸热过程,包括物理吸附与化学吸附。根据Fre-undlich吸附等温式拟合计算,5℃、pH=7时理论最大吸附量为9 mg/g,说明凹凸棒土对于低温饮用水中腐殖酸具有良好的吸附效果。     

腐殖酸树脂处理含Pb2+、CU2+、Ni2+废水的研究

利用泥炭为原料制备腐殖酸树脂.在动态条件下,研究了腐殖酸树脂对重金属离子Pb2+、Cu2+和Ni2+的吸附效果及吸附条件.同时探讨了腐殖酸树脂对重金属离子Pb2+、Cu2+和Ni2+的吸附与解吸再生机理,吸附机理研究表明,腐殖酸树脂对重金属离子Pb2+、Cu2+和Ni2+的主要吸附形式为离子交换吸附和络合吸附.结果表明,在废水pH值为5.0～7.0,Pb2+、Cu2+和Ni2+浓度分别为50 mg/L,经腐殖酸树脂处理,Pb2+、Cu2+和Ni2+去除率可达98%以上,且处理后废水近中性.含Pb2+、Cu2+和Ni2+电镀废水经腐殖酸树脂处理后,废水中Pb2+、Cu2+和Ni2+含量显著低于国家排放标准.     

Sorptive behavior of the phenylamide fungicides,mefenoxam and metalaxyl,and their acid metabolite in typical Cameroonian and German soils

Laboratory soil sorption experiments were conducted on mefenoxam, formulated metalaxyl (F-metalaxyl), pure metalaxyl (P-metalaxyl) and metalaxyl acid metabolite to elucidate differences in their sorptive behaviour on typical Cameroonian forest soil (sand clay loam, pH 4.8 and 3.01% OC) and German soil (sandy loam, pH 7.2, 1.69% OC) using a batch equilibrium method. The data obtained on all test chemicals conformed to linear and Freundlich adsorption isotherms. The Langmuir equation failed to describe the sorption of the substances tested. All substances were adsorbed to a greater extent by the Cameroonian soil. The average percentage adsorptions for mefenoxam, F-metalaxyl, P-metalaxyl and the acid metabolite on the Cameroonian soil were 27.8%, 28.3%, 31.8% and 46.8% respectively while for the German soil they were 21.7%, 21.5%, 24.7% and 9.8% respectively. The KD and KF parameters and the Freundlich exponential term (1/n) were low, indicating that the interactions between soil particles and the fungicides were weak. The sorption parameters were lower in the German soil. P-metalaxyl exhibited a higher adsorption capacity than F-metalaxyl in both soils. Mefenoxam and F-metalaxyl exhibited similar sorption parameters in soils, whereas those of P-metalaxyl and acid metabolite differed. Differences observed in the adsorption between the two soils could be attributed to their properties. Desorption studies revealed that the adsorbed fungicides were not firmly retained by soil particles and their adsorption was reversible. Desorption of adsorbed mefenoxam, P-metalaxyl and of the acid metabolite from German soil was almost completely reversible with percentage desorption rates of more than 91.0%, whereas the rate for F-metalaxyl was 74.1%. All compounds exhibited some resistance to desorption from the Cameroonian soil, with percentage desorption rates less than 77.0%. Therefore if degradation in the soil is slow the fungicides described have a potential to leach to lower soil horizons.     

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.     

Interactions of sodium azide with triazine herbicides: effect on sorption to soils

Sodium azide (NaN(3)) is one of the biocides commonly used to inhibit microbial growth during sorption experiments. However, a few reports have suggested that NaN(3) can react with the analyte of interest. In this study, the interactions of NaN(3) with triazine herbicides were investigated and the effect of atrazine transformation on its sorption to soil was evaluated. The concentration of atrazine in the presence of NaN(3) decreased significantly over period of time. After 14 days, only 38% of the initial atrazine concentration (10 mg l(-1)) was detected in a solution containing 1,000 mg l(-1) NaN(3) at pH 5.5. The magnitude and the rate of atrazine transformation increased with increase in NaN(3) load and with decrease in pH. In contrast to atrazine behavior, the concentrations of prometon and ametryn did not change during the experiment. GC/MS analysis indicated that the chlorine atom of atrazine is replaced by the azide group yielding 2-azido-4-(ethylamino)-6-(isopropylamino)-s-triazine. Atrazine transformation by NaN(3) significantly affected sorption of herbicide to soil. The presence of NaN(3) affects indirectly the sorption of atrazine due to competitive effect of its derivative. Our results demonstrated that the application of NaN(3) as a biocide in sorption-desorption experiments must be carefully evaluated. This issue is vital for sorption experiments conducted over long periods of time or/and with concentration of NaN(3) higher than 100 mg l(-1).     

Sorption–desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions

Sorption–desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption–desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd_ads, varied according to its initial concentration and was ranged 40–84 for HA, 14–58 for clay and 1.85–4.15 for bulk soil. Freundlich sorption coefficient, Kf_ads, values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ～800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n_ads values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.     

Effect of various cyclodextrins on photodegradation of a hydrophobic herbicide in aqueous suspensions of different soil colloidal components

This paper investigated the photochemical behaviour of the herbicide norflurazon (NFL) in the presence of different soil colloidal components and several cyclodextrins (CDs). The interaction of NFL with CDs yielded the formation of inclusion complexes at 1:1 stoichiometric ratio in solution, with an increase of the herbicide solubility. The irradiation of NFL aqueous solutions in the presence of CDs showed that the higher the formation constant of NFL-CD complexes (Kc) and their solubility, the higher their photocatalytic effects, following the CDs in the order: RAMEB>HPBCD>beta-CD>alpha-CD>gamma-CD. The presence of the different soil colloidal components in aqueous suspension provoked the reduction of the NFL photodegradation rate, due to a screening effect, especially when goethite and humic acids were present. No disappearance of NFL was detected in parallel studies carried out in the dark, except in the case of humic acids, where a 5% adsorption of the initial amount of NFL was adsorbed in the dark control. The presence of the different CDs in such systems showed an inductive photodegradation effect on the herbicide. This could be largely explained by the inclusion effects of CDs in catalyzing interactions between NFL and certain reactive radicals generated by the different colloidal components. Although this work was carried out at laboratory scale and therefore, has limited applications, it reveals that cyclodextrins increase solubilization of hydrophobic herbicides and could lead to their increased photodegradation. This could be a promising method for pesticide-contaminated water remediation. However, it is important to consider the effect of the soil colloidal components in the different aquatic systems and their concentrations, since they can alter the photodegradative effects of the cyclodextrins.