摘要
吸附和降解是农药在土壤环境中行为和归宿的两个重要过程。农药在土壤粘土矿物上的吸附影响着农药在土壤中的迁移、转化和生物利用等过程。降解作用是农药消失的主要途径,是土壤净化功能的重要表现。了解农药在土壤中的吸附/解吸与生物降解规律,对于预测和评价农药对土壤、地下水存在的潜在危害性、开展土壤的化学修复和生物修复等都具有十分重要的意义。本文以蒙脱石、高岭石和针铁矿三种土壤粘粒矿物为吸附材料,研究了甲基对硫磷、西维因及其降解菌在矿物表面的吸附/解吸特征,探讨了固定态甲基对硫磷和西维因的降解动力学以及粘粒矿物对细菌活性的影响,主要内容如下:
1.运用吸附-解吸等化学方法和傅立叶变换红外光谱(FTIR)技术,讨论了甲基对硫磷和西维因在蒙脱石、高岭石和针铁矿表面的吸附-解吸特征,基本揭示了两种农药在不同粘粒矿物表面的结合机制。甲基对硫磷在三种矿物表面的吸附较好地符合Freundlich方程,而西维因在矿物表面的吸附更好地符合Langmuir方程;蒙脱石对两种农药的吸附量均大于针铁矿和高岭石;用动力学方程对这两种农药的吸附过程进行拟合,Elovich方程为最佳模型,相关系数在0.93～0.98之间,说明该吸附过程为非均相扩散过程;两种农药的粘附量均随初始pH的升高先减小后增大;三种矿物对农药的亲和力大小为:蒙脱石＞高岭石＞针铁矿;两种农药可通过氢键、静电引力与矿物发生结合。
2.首次研究了粘粒矿物固定甲基对硫磷的生物降解特性,用微量热仪测定了甲基对硫磷降解菌在不同粘粒矿物存在下的代谢活性,以及该菌利用游离与固定态甲基对硫磷进行生长代谢的热动力学特征。甲基对硫磷的生物降解明显受到农药浓度和矿物类型的影响。对于游离态甲基对硫磷,低浓度时开始具有较大的降解率,而高浓度时降解相对平缓。在降解初期(前7h),固定态甲基对硫磷的降解速率高于所有游离态。随着时间延长,固定态甲基对硫磷降解速率减慢,明显低于游离态。固定在不同矿物上的甲基对硫磷,其降解行为也存在明显差异。蒙脱石固定的甲基对硫磷,其降解百分数最大,高岭石次之,针铁矿最低。蒙脱石和高岭石对细菌第一次指数生长期有抑制作用,但促进了细菌的二次生长,且蒙脱石的促进作用大于高岭石,针铁矿则对细菌的代谢活性一直有抑制作用。矿物的存在显著影响了细菌活性,进而成为影响固定态甲基对硫磷生物降解的主要因素,矿物对甲基对硫磷的吸附作用则可能是次要的影响因素。
3.运用吸附-解吸等化学方法研究了甲基对硫磷降解菌在不同粘粒矿物表面的吸附/解吸特征,结合FTIR技术探讨了其结合机制,研究了该固定菌对甲基对硫磷的降解动力学,并首次用微量热仪测定了不同粘粒矿物固定菌利用甲基对硫磷生长代谢的热动力学特征。甲基对硫磷降解菌在矿物表面的吸附量大小和结合强度均为:针铁矿＞高岭石＞蒙脱石。在pH等于或接近蒙脱石和高岭石的等电点时,细菌在这两种矿物表面的吸附量最大。细菌与粘粒矿物之间有多种作用力,包括范德华力、静电力、配体交换、氢键等,这些作用力对吸附的贡献大小也不一样。细菌与蒙脱石之间可能是范德华力占主导地位,与高岭石之间可能是非静电力(如氢键)起主要作用,与针铁矿之间则可能是配体交换、静电力发挥主要作用。细菌被粘粒矿物固定后,其降解甲基对硫磷的能力与游离菌明显不同。在低浓度农药下,游离菌的降解能力比固定菌要强。而在高浓度下,矿物的存在起初(前12h)有利于农药的降解,随着时间延长,固定菌对甲基对硫磷的降解程度渐渐低于游离菌。不同矿物固定菌的降解能力为:蒙脱石＞高岭石＞针铁矿。从吸附强度看,蒙脱石对甲基对硫磷降解菌的亲和力最弱,但它对细菌的代谢活性起到促进作用,有利于农药的生物降解;而针铁矿与细菌之间的键合强度最大,细菌活性因此受到抑制,不利于农药的生物降解。
4.首次研究了粘粒矿物固定西维因的降解动力学,用微量热仪测定了不同矿物对西维因降解菌代谢活性的影响,结合前面的吸附实验分析了固定态西维因生物降解的影响因素。固定态西维因的降解速率和程度明显受矿物的影响,其影响程度随时间的延长而变化。在降解初期(前20h),固定态西维因的降解速率高于游离态,随着时间延长,其降解速率渐渐低于游离态。固定在不同矿物上的西维因,其降解率大小为:蒙脱石＞高岭石＞针铁矿,这与矿物对西维因键合强度的顺序一致。蒙脱石和高岭石可以强化西维因降解菌的代谢活性,有利于西维因的降解,而针铁矿对细菌的活性有抑制作用,不利用农药降解。固定态西维因的生物降解主要受到微生物活性的控制,矿物与西维因之间的吸附机制可能是次要的影响因素。
Sorption and degradation are the two important processes governing the fate of pesticides in soil system.Sorption on minerals is shown to control the transport, transformation and biological processes of pesticides in the subsurface.Biodegradation is a fundamental attenuation process for pesticides and an important performance of soil purification.It is meaningful to investigate the sorption-desorption and biodegradation of pesticides for evaluating the potential effects on soil and groundwater and developing the soil chemical remediation and bioremediation.In this study,montmorillonite,kaolinite and goethite were selected as model minerals.The adsorption and desorption characteristics of methyl parathion(MP),carbaryl and their degrading cells on clay minerals were obtained.Batch experiments were applied to determine the biodegradation kinetics of the immobilized pesticides.Microbial activities in the absence and presence of montmorillonite,kaolinite or goethite were monitored by microcalorimetry.The main contents were outlined as follow:
1.Chemical adsorption-desorption and Fourier transform infrared spectra(FTIR) were employed to investigate the adsorption characteristics of MP and carbaryl on soil clay minerals.The results showed that the adsorption of MP on clay minerals fitted Freundlich equation very well,and the adsorption of carbaryl more fitted Langmuir equation.Montmorillonite had a greater adsorption capacity for the two pesticides than goethite and kaolinite.Elovich equation was the optimum model for their adsorption kenitics,of which the coefficients(R~2) ranged between 0.93 and 0.98,indicating that the adsorption was a non-homogeneous diffusion process.In addition,the adsorption amounts of pesticides first decreased then increased with the increasing of the pH value. The binding strength of pesticides on minerals followed the sequence:montmorillonite＞kaolinite＞goethite.The FTIR spectra demonstrated that hydrogen bond and electrostatic bond could be formed in the adsorption process.
2.The biodegradation kinetics of mineral-sorbed MP was determined.The metabolic activities of MP-degrading cells in the presence of various clay minerals or using free/immobilized MP were monitored by microcalorimetry.The biodegradation of MP was significantly impacted by the concentration of pesticide and the nature of minerals.For the free MP,the pesticide with a low concentration was degraded more rapidly than that with a high concentration.The degradation of sorbed MP proceeded at a rate faster than free pesticide over the initial 7 h of incubation.However,the percent degradation of free MP was obviously higher than that of immobilized pesticides afterwards.The differences of biodegradation were also observed when MP was sorbed on various minerals.The percent degradation of sorbed MP followed the sequence: montmorillonite＞kaolinite＞goethite,which was in accordance with the binding strength of MP on minerals.The presence of montmorillonite or kaolinite depressed the first exponential growth of MP-degrading cells but stimulated their second growth. However,goethite displayed inhibitory effect on bacterial activity at all times.The biodegradation of sorbed MP may be dominantly controlled by the activities of the MP-degrading microorganisms.The sorption characteristics of methyl parathion on minerals could be the secondary factors.
3.Chemical adsorption-desorption and FTIR were employed to investigate the adsorption characteristics and mechanisms of MP-degrading cells on soil clay minerals. The kinetics of MP biodegradation by the immobilized cells were investigated.The metabolism curves of free/immobilized cells using MP were monitored by microcalorimetry.The adsorption amounts and the binding strength of MP-degrading cells on minerals examined followed the sequence:montmorillonite＞kaolinite＞goethite.The maximum adsorption of cells adsorption on montmorillonite and kaolinite occurred at pHs equivalent or close to the zero point charge of the two clay minerels. There were a variety of forces such as Van der Waals forces,electrostatic interactions, ligand exchange and hydrogen bonding in the process of MP-degrading cells adsorbed on minerals.The Van der Waals forces could dominated cells adsorption on montmorillonite, and the cells were adsorbed on kaolinite predominantly by non-electrostatic forces(e.g. hydrogen bond).The ligand exchange and electrostatic force were considered to be the main forces controlling the sorption of cells on goethite.Compared to free cells,the metabolism abilities of immobilized cells significantly weaken in the low MP concentration system.The presence of minerals enhanced the MP degradation in the high pesticide concentration system at the first 12h.Afterwards,the percent degradation of MP by immobilized cells was lower than that by free cells.The percent degradation of MP were different when cells sorbed on various minerals,which followed the sequence of montmorillonite＞kaolinite＞goethite.Montmorillonite presented a lower affinity for cells as compared to goethite and kaolinite,but it could enhance the activity of MP-degrading cells and further stimulated the bioavailability of pesticide.However, goethite displayed an inhibitory effect on the bacterial activity because of the tight attachment of bacterial cells and hindered the substrate biodegradation.
4.The biodegradation kinetics of mineral-sorbed carbaryl was determined and the metabolic activities of carbaryl-degrading cells in the presence of various clay minerals were assessed by microcalorimetric technique for the first time.The impact on sorbed carbaryl bioavailability were illustrated by microbial activity and previous sorption experiments.The results showed that both degradation efficiency and rate of sorbed carbaryl were significantly impacted by the presence of minerals.The degradation of mineral-sorbed carbaryl proceeded at a rate faster than free pesticide over the initial 20 h of incubation.However,the percent degradation of aqueous carbaryl was obviously higher than that of immobilized pesticides afterwards.The differences of biodegradation were also observed when carbaryl was sorbed on various minerals.The percent degradation of sorbed carbaryl followed the sequence:montmorillonite＞kaolinite＞goethite,which is in accordance with the binding strength of carbaryl on minerals.The presence of montmorillonite or kaolinite enhanced the bacterial activity and further stimulated the bioavailability of carbaryl.However,goethite displayed inhibitory effect on bacterial activity and reduced the substrate degradation.The biodegradation of mineral-sorbed carbaryl may be dominantly controlled by the activities of the carbaryl-degrading cells.The sorption characteristics of carbaryl on minerals were considered to be the secondary factors.
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