有机磷农药生物降解研究进展

有机磷农药是目前我国使用量最大的农药 ,对农业的发展有重要的作用 ,但同时造成了严重的环境污染 .利用微生物或微生物源酶制剂来降解农药是近年来的一个主要努力方向 .至今 ,已经陆续分离到许多有机磷降解菌 ,并对其相应的降解酶的生化性质进行了鉴定 ,相关的基因也被克隆、鉴定和改造 .另外 ,基因工程及生物技术方面的进展为开发微生物或酶制品奠定了基础 .本文综述了有机磷农药降解菌、降解酶以及有机磷农药生物降解技术等方面的研究现状 .表 1参 6 1     

有机磷农药污染土壤降解修复研究进展

有机磷农药的大量生产和使用,导致其在土壤环境中累积,从而危害人类健康.通常,有机磷农药会在环境中发生光解、水解、生物降解等自然降解反应,但对于较高浓度的有机磷农药污染,其自然降解程度远远不足,无法在短时间内实现污染土壤的安全利用,因此发展了多种人工强化修复有机磷农药技术.本文在解析有机磷农药自然降解机理的基础上,综述了其主流的人工强化修复技术的原理与研究现状,并对未来研究方向提出建议,为有机磷农药降解人工强化技术的研究与工程应用提供技术支撑.     

海藻多糖稀土配合物对蔬菜有机磷农药残留的降解作用

以小白菜、甘蓝、芹菜为试验材料,采用大田试验研究了海藻多糖稀土配合物对蔬菜中有机磷农药残留的影响.试验结果表明,叶面喷施海藻多糖稀土配合物对小白菜、甘蓝、芹菜中毒死蜱、氧化乐果、敌敌畏等有机磷农药残留具有明显的降解作用;对甘蓝中毒死蜱和氧化乐果的降解效果优于小白菜,但对芹菜中毒死蜱的降解效果远不及甘蓝和小白菜,表现出一定的作物选择性.叶面喷施海藻多糖稀土配合物对敌敌畏等磷酸酯类有机磷农药的降解作用比毒死蜱、氧化乐果等硫代磷酸酯类有机磷农药的降解强烈,表现出一定的农药选择性;另外,喷水对叶片表面残存农药具有一定的冲洗作用,可减少叶面农药的残留量;叶面喷施海藻多糖稀土配合物对甘蓝和小白菜中有机磷农药的降解率远高于叶面喷水.以上结果表明海藻多糖稀土配合物确实具有降解有机磷农药残留的作用.在蔬菜生产中将海藻多糖稀土配合物作为农药残留降解制剂是可行的,有利于蔬菜安全生产和提高蔬菜产品的食用安全性。     

高铁酸钾对菠菜中3种有机磷农药残留降解的影响

菠菜(Spinaciao leracea L.)是我国出口的重要蔬菜品种之一,其农药残留是制约我国菠菜出口的重要"技术壁垒".在露地栽培条件下,研究了叶面喷施高铁酸钾水溶液对菠菜中有机磷农药的降解作用,并探讨了高铁酸钾对菠菜相关酶活、MDA含量及品质指标的影响.结果表明,叶面喷施不同浓度的高铁酸钾(200、400、600mg·L-1)可有效降低菠菜中敌敌畏、毒死蜱和乐果等有机磷农药的残留量.随着高铁酸钾喷施浓度的增大,菠菜中敌敌畏、毒死蜱和乐果残留量显著降低;试验浓度下以600mg·L-1高铁酸钾处理的降解效果最好,可使菠菜中敌敌畏、毒死蜱和乐果的降解率达到72.43%、87.15%和75.45%.叶面喷施高铁酸钾对菠菜过氧化物酶(POD)、过氧化氢酶(CAT)活性、MDA含量以及品质指标没有明显影响.试验表明高铁酸钾具有降解有机磷农药残留的作用,在菠菜生产中将高铁酸钾作为有机磷农药残留降解制剂是可行的.     

固相合成钛酸钙的光催化性能

采用CaCO3和TiO2作为原料,在1400℃、2h条件下烧结得到CaTiO3.应用X射线衍射(XRD)、扫描电子显微镜(SEM)对高温处理后的混合物料进行了表征.以亚甲基蓝为降解物,研究了光照时间、pH值、溶液初始浓度、催化剂投加量对CaTiO3光催化性能的影响.实验结果表明,光照时间延长,亚甲基蓝降解率增加,但是亚甲基蓝被降解速率降低;碱性条件有利于CaTiO3对亚甲基蓝的光催化降解;CaTiO3对低浓度的亚甲基蓝溶液具有较高的光催化降解率;随着CaTiO3投加量增加,亚甲基蓝降解率增大,但是当CaTiO3投加量大于0.1g时,随着CaTiO3投加量的增加,亚甲基蓝的降解率几乎不变,甚至有所降低.     

甲胺磷农药降解菌HS-A32的分离鉴定及降解特性

从长期受有机磷农药污染的土壤中分离到一株降解菌HS-A32,能以甲胺磷作为唯一的碳源和氮源生长.HS-A32菌降解甲胺磷的最适温度为30℃,最适pH值为7.0,甲胺磷的最适降解浓度为1 000 mg/L,降解率达82%.聚酰胺薄层色谱(TLC)可检测到降解产物中有NH4 生成.HS-A32菌能以多种碳、氮源生长,外加可利用的碳源和氮源能促进甲胺磷的降解.通过16S rDNA扩增、测序,运用BLAST检索分析,构建系统进化树.结合生理生化鉴定,初步确定HS-A32为不动杆菌属(Acinetobacter).HS-A32菌还能降解甲基对硫磷等多种有机磷农药.图6表1参14     

31P NMR与HPLC联用筛选高效有机磷降解细菌

从有机磷农药污染地区分离到14株具有高效甲胺磷降解活力的细菌,并用HPLC对其降解效率进行分析,发现一周内降解率最高达74％．采用^31 PNMR对其降解产物进行了同步监测,发现其降解产物不同,其中有三株可以把甲胺磷代谢成磷酸．这三株降解细菌可以从环境中有效的清除有机磷的污染．     

有机磷农药降解菌的紫外诱变育种

有机磷农药降解菌地衣芽孢杆菌（ Ｂａｃｉｌｌｕｓｌｉｃｈｅｎｉｆｏｒｍｉｓ） 经紫外线诱变后,筛选出突变菌株Ｐ１２ ．在θ＝３０℃,溶解氧ρ（Ｏ２） ＝２ ．５ ｍｇ Ｌ－１ 的培养条件下,３ ｄ 内对甲胺磷的降解率为８０ ．１％ ,比出发菌株提高了将近１０％的降解率．农药斜面连续传代１０ 次,降解活力保持稳定．     

蜡状芽孢杆菌不同菌株降解有机磷农药的特性分析

筛选分离降解微生物解决有机磷农药残留给水体和土壤环境带来的污染问题是一项可行的生物修复技术。采用富集培养和定时取样分析有机磷农药残留的方法,分离驯化出三株能够降解有机磷农药的细菌,研究了其形态特征和生理生化特性并对其16SrDNA序列进行了分析,同时比较了三菌株对甲基对硫磷（Methyl－parathion）、毒死蜱（Chlorpyrifos）和_二唑磷（Triazophos）的降解特性。结果表明：通过富集培养得到10菌株具有降解甲基对硫磷和毒死蜱的能力,比较确定HY-1、HY-2和HY-4三菌株作为研究对象,经鉴定为蜡状芽孢杆菌（Bacilluscereus）的不同菌株,三菌株在Genbank上的登录号分别为：eu915687、eu915686和eu915688。在甲基对硫磷质量浓度为50mg·L-1时,三菌株72h的降解率分别为91．7％、87．7％与92．4％．降解率无显著性差异（P〉0．05）,当甲基对硫磷质量浓度增加到100mg·L-1时,三菌株对甲基对硫磷的降解率有所下降,其中HY-2对甲基对硫磷的降解率下降最大达23％,且和其他两菌株有显著性差异（P〈0．05o三菌株72h对100mg·L-1毒死蜱的降解率分别达到64．8％、53．7％和56．5％,在不同的毒死蜱初始质量浓度下,HY-1和HY-4两菌株对毒死蜱的降解率无显著性差异（P〉0．05）,HY-2与HY-1、HY-4两菌株有显著性差异（P〈0．05o三菌株对三唑磷的降解率均较低,其中HY-2对初始质量浓度为100mg·L-1三唑磷的降解率最高仅为20．7％,其余两菌株对三唑磷的降解率比HY-2低且无显著性差异（P〉0．05o可以得出本研究分离得到的蜡状芽孢杆菌不同菌株对有机磷农药的降解存在多态性。     

手性有机磷农药在土壤中对映体选择性降解特征

马拉硫磷和丙溴磷是2种常用的有机磷杀虫剂,均有一个手性中心存在2个对映体.采用室内避光培养的方法,在对映体水平上研究了马拉硫磷和丙溴磷在2种土壤中的降解情况.结果表明,2种农药在土壤中的降解均较快,马拉硫磷和丙溴磷的降解半衰期分别为:黄土中3.5 h和21.5 h,红土中4.3 h和29.4 h.进一步的手性测定表明2种农药的降解均存在一定的对映体差异,丙溴磷对映体的选择性明显高于马拉硫磷,在2种土壤中马拉硫磷的左旋对映体降解快于右旋对映体,丙溴磷的右旋体降解快于左旋体.研究有助于深入认识2种有机磷农药在环境中的归趋,并对其生态风险性进行更合理的评估.     

南京市夏季青菜中有机磷农药残留量调查

１９９４年夏季调查和测定了南京市市售青菜中甲胺磷、乐果、甲基－１６０５等５种有机磷农药残留量。结果表明，夏季青菜（包括青菜秧）中有机磷农药残留量有超标现象，其中甲胺磷在青菜中的平均残留量为０．０６３ｍｇ／ｋｇ，超标率为１１．５％，其余４种有机磷农药在青菜中未检出。     

Photocatalytic degradation of the diuron pesticide

The occurrence of chlorinated pesticides in wellwaters is a major problem of public health in Ivory Coast and other African countries. Here, we studied the photocatalytic degradation of the pesticide diuron in aqueous solution in presence of two commercial TiO₂ catalysts, P25 and PC500. The capacity of diuron adsorption at the TiO₂ surface is lower for both photocatalysts. The efficiency of photocatalytic degradation of diuron, it is higher using P25 Degussa than PC500 Millenium TiO₂ catalyst.     

Photocatalytic degradation of polybrominated diphenyl ethers in pure water system

Due to the low water solubility of polybrominated diphenyl ethers, organic solvent is usually added into the oxidation system to enhance the removal efficiency. In this study the photocatalytic degradation of decabromodiphenyl ether (BDE209), a type of polybrominated diphenyl ether used throughout the world, in pure water without the addition of organic solvent was investigated. In the pure water system, BDE209 was not dissolved but dispersed as nano-scale particles with a mean diameter of 166 nm. Most of BDE209 (>98%) were removed within 4 h and the final debromination ratio was greater than 80%. Although the addition of organic solvent (tetrahydrofuran, THF) could lead to a relatively high BDE209 degradation rate, the final debromination ratio (<50%) was much lower than that in pure water system. Major oxidation intermediates of tetrahydrofuran, including tetrahydro-2-furanol and γ-butyrolactone, were detected indicating the engagement of THF in the BDE209 degradation process. The photocatalytic degradation of BDE209 in the pure water system followed first-order kinetics. The BDE209 degradation rate constant increased from 0.0011 to 0.0023 min⁻¹ as the pH increased from 3 to 9.     

Photocatalytic degradation of phosphamidon using Ag-doped ZnO nanorods

The photocatalytic degradation of the organo-phosphorous pesticide phosphamidon at low concentration in aqueous solution on Ag-doped ZnO nanorods was investigated. Nanosized Ag-doped ZnO rods were synthesized by using a microwave assisted aqueous method. High molecular weight polyvinyl alcohol was used as a stabilizing agent. Composition and structure were investigated using energy-dispersive X-ray spectroscopy (EDAX) and X-ray diffraction (XRD). The XRD pattern reveals that ZnO nanorods are of hexagonal wurtzite structure. The average crystallite size calculated from Scherrer's relation was found to be 30?nm. The effects of catalyst loading, pH value, and initial concentration of phosphamidon on the photocatalytic degradation efficiency using Ag-doped ZnO nanorods as a photocatalyst have been discussed. The results revealed that Ag-doped ZnO nanorods with a diameter of 30?nm showed highest photocatalytic activity at a surface density of 1?g?dm^?3. The catalyst doped with 0.2?mol% Ag is effective for the degradation of phosphamidon with visible light. This opens a new possibility to decompose pesticides that are present in wastewater.     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO<Subscript>2</Subscript> composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

Preparation of effective TiO<Subscript>2</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> photocatalysts for water treatment

Photocatalytic oxidation using semiconductors is one of the advanced oxidation processes for degradation of organic pollutants in water and air. TiO₂ is an excellent photocatalyst that can mineralize a large range of organic pollutants such as pesticides and dyes. The main challenge is to improve the efficiency of the TiO₂ photocatalyst and to extend TiO₂ light absorption spectra to the visible region. A potential solution is to couple TiO₂ with a narrow band gap semiconductor possessing a higher conduction band such as bismuth oxide. Therefore, here we prepared Bi₂O₃/TiO₂ heterojunctions by the impregnation method with different Bi/Ti ratio. The prepared composites have been characterized by UV–Vis diffused reflectance spectra and X-ray diffraction. The photocatalytic activity of the heterojunction has been determined from the degradation of orange II under visible and UV light. Results show that Bi₂O₃/TiO₂ heterojunctions are more effective than pure TiO₂-anatase under UV-A irradiation, with an optimum for the Bi/Ti ratio of 5 %, for the photocatalytic degradation of Orange II. However, the photocatalytic activity under irradiation at λ higher than 420 nm is not much improved. Under UV–visible radiation, the two semiconductors are activated. We propose a mechanism explaining why our products are more effective under UV–visible irradiation. In this case the charge separation is enhanced because a part of photogenerated electrons from the conduction band of TiO₂ will go to the conduction band of bismuth oxide. In this composite, titanium dioxide is the main photocatalyst, while bismuth oxide acts as adsorbent photosensitizer under visible light.     

Methylobacterium sp. YAL-2对乙酰甲胺磷的降解特性

从有机磷生产厂家的下水道污泥中分离出一株对高浓度和低浓度乙酰甲胺磷都具有高效降解能力的寡营养菌YAL-2,根据形态、生理生化和16S rRNA基因系统发育分析,将菌株YAL-2鉴定为Methylobacterium sp.降解特性实验表明,菌株YAL-2能利用乙酰甲胺磷为唯一碳源生长和降解;在添加了甲醇的无机盐培养基中,84 h可完全降解300mg L-1乙酰甲胺磷,24 h将50 mg L-1和10 mg L-1乙酰甲胺磷降至非检测水平;4 d能完全去除100 mg L-1甲胺磷,5 d分别降解58.4%和40.6%的100 mg L-1乐果、敌敌畏.小青菜农药残留去除实验显示,菌株YAL-2可在7 d内将乙酰甲胺磷和甲胺磷将至限量水平.结果表明,将菌株YAL-2应用于保证果蔬等食品的食用安全是可行的.     

Photocatalytic degradation of phenol with mesoporous TiO2?xBx

We report a facile approach for preparing mesoporous boron-doped TiO₂ materials by combining the sol?Cgel process with the dehydration of glucose. Specifically a high surface carbon material was formed by dehydration of glucose, then used as template. This material and the TiO₂ dry gel were calcinated to produce porous TiO₂. The as-synthesized boron-doped TiO₂ was in pure anatase crystallite phase with high surface area. X-ray photoelectron spectroscopy (XPS) results showed that boron was incorporated into the anatase TiO₂ lattice to form TiO_2?xB_x. The absorption spectra of TiO_2?xB_x extended into the visible region to 460?nm. The TiO_2?xB_x exhibited much higher photocatalytic activity on phenol degradation than pure TiO₂. It showed that the phenol degradation by-products of TiO_2?xB_x were different from that of pure TiO₂. Mechanism of the photocatalytic degradation of phenol at TiO_2?xB_x was also proposed.     

Organophosphate Residues in Grasshoppers from Sprayed Rangelands

Grasshoppers (Orthoptera) were collected in pastures that had been sprayed with malathion and acephate to estimate the secondary exposure of insectivorous birds to those pesticides. Residues of malathion were below 3 ppm at 30 and 54 hours after spraying and no malaoxon was detected. In contrast, acephate was found at 8 and 9 ppm 4 hours after spray; 3-5 ppm of the toxic metabolite methamidophos were also detected at that time. By 53 hours postspray, acephate levels declined to 2 ppm and methamidophos to less than 1 ppm. These results suggest that although malathion may not be a hazard to insectivorous species, acephate may be hazardous through metabolic transformation to methamidophos.