戊唑醇在土壤中的光降解行为动力学研究

以高压汞灯为光源, 研究了戊唑醇在土壤中的光化学降解行为及各种因素对光降解的影响。结果表明, 戊唑醇在高压汞灯下的光降解符合化学反应一级动力学方程。戊唑醇在不同类型土壤中的光解速度为砂姜黑土〉河潮土〉红壤〉棕壤〉紫泥土, 这与土壤有机质和黏粒含量有关;随土壤含水量增加, 戊唑醇的光解速率加快, 主要是因为水分增加了农药分子在土壤中的移动性;中性环境较酸或碱性环境更有利于戊唑醇的光解;当土壤中戊唑醇的浓度为20~100 mg·kg-1时, 其光解速率与浓度呈负相关关系;表面活性剂十二烷基苯磺酸钠和十六烷基三甲基溴化铵对戊唑醇的降解均具有光猝灭作用;不同添加剂量的尿素对戊唑醇的光解几乎均表现出光猝灭作用, 氯化钾则表现为敏化作用。高压汞灯下, 戊唑醇在土壤中降解半衰期为10~22 min。     

戊唑醇在土壤中的光降解行为动力学研究

以高压汞灯为光源, 研究了戊唑醇在土壤中的光化学降解行为及各种因素对光降解的影响.结果表明, 戊唑醇在高压汞灯下的光降解符合化学反应一级动力学方程.戊唑醇在不同类型土壤中的光解速度为砂姜黑土>河潮土>红壤>棕壤>紫泥土, 这与土壤有机质和黏粒含量有关;随土壤含水量增加, 戊唑醇的光解速率加快, 主要是因为水分增加了农药分子在土壤中的移动性;中性环境较酸或碱性环境更有利于戊唑醇的光解;当土壤中戊唑醇的浓度为20～100 mg·kg-1时, 其光解速率与浓度呈负相关关系;表面活性剂十二烷基苯磺酸钠和十六烷基三甲基溴化铵对戊唑醇的降解均具有光猝灭作用;不同添加剂量的尿素对戊唑醇的光解几乎均表现出光猝灭作用, 氯化钾则表现为敏化作用.高压汞灯下, 戊唑醇在土壤中降解半衰期为10～22 min.     

TBHQ对阿维菌素光解的影响及对灰飞虱的增效作用

为延缓阿维菌素的光解,研究了不同浓度抗氧化剂TBHQ对阿维菌素光解的影响,并通过稻茎浸渍法测定其与阿维菌素混用后对灰飞虱的毒力。结果表明:阿维菌素的光解行为符合化学反应一级动力学方程,阿维菌素在太阳光下的光解速率小于紫外光下的光解速率;在TBHQ抑制阿维菌素光解试验中,其与阿维菌素比值为1︰1时,阿维菌素的光解速率最小,光解半衰期为11.81h,比不添加TBHQ在紫外光下的光解半衰期延长167.19%。室内生物测定结果表明,TBHQ与阿维菌素混用后对灰飞虱表现为增效作用;经太阳光和紫外光光照3h后,加入TBHQ的阿维菌素对灰飞虱的毒力均显著高于未添加TBHQ的处理,增效比分别为2.00和2.63。     

阿特拉津在土表的紫外光降解行为研究

本文研究了阿特拉津在土壤表面的紫外光光解的动力学,并研究了各种因素对光解的影响。实验表明,土壤粒度、湿度、pH值、有机质、腐殖酸和表面活性剂都影响阿特拉津在土壤中的降解。在紫外光辐射下,阿特拉津在土壤表面降解速率常数为(0.09~0.17)/min,光解深度为0.1~0.3mm,半衰期为4~8min。     

阿维菌素3种剂型的光解研究

以太阳光为光源,利用玻片药膜法和高效液相色谱法研究浓度、水质硬度、pH和共存离子等因子对阿维菌素乳油、水乳剂和微乳剂3种液体剂型光解的影响。结果表明：3种阿维菌素液体剂型光解率随光照时间延长而逐渐增大。在试验初始浓度范围内,3种阿维菌素制剂光解均符合一级动力学方程,且与药液浓度呈负相关。在不同浓度、pH、共存离子条件下,阿维菌素的光解速率均表现为乳油〉水乳剂〉微乳剂,pH对单一剂型光解有较大影响,而共存离子对其影响作用较小。在不同浓度硬水条件下则表现为随水质硬度增加,微乳剂半衰期减少,水乳剂和乳油略微增大,在蒸馏水下的半衰期为微乳剂〉水乳剂〉乳油,而在684mg·L-1硬水时半衰期为水乳剂〉微乳剂≈乳油。相比于乳油,微乳剂和水乳剂光解速率较慢,可以有效延长阿维菌素持效期,进一步提高阿维菌素在田间的应用效果。     

碘甲磺隆钠盐在水溶液中的光解研究

为了解碘甲磺隆钠盐在水溶液中的光降解特性,评价其环境安全性,以太阳光和高压汞灯为光源,进行光解试验,研究了碘甲磺隆钠盐在不同水溶液中的光解行为及水体pH值对其光解的影响。结果表明,碘甲磺隆钠盐在所有试验水体中的降解均符合一级动力学方程,不同水体中碘甲磺隆钠盐的半衰期分别为14.29～21.26h（太阳光）与2.29～3.76min（高压汞灯）,两种光源下碘甲磺隆钠盐在各自然水体中的降解速率依次为井水〉河水〉池塘水〉稻田水。不同pH值水体中的光解实验表明,碘甲磺隆钠盐在酸性介质中的光解比在碱性介质中快,顺序为pH5〉pH7〉pH9〉pH11。     

阿特拉津在土表的光解行为动力学研究

研究了阿特拉津在土壤表面的光解行为的动力学,并研究了各种因素对光解的影响。实验表明,土壤粒度、湿度、pH值、有机质、腐殖酸和表面活性剂都影响阿特拉津在土壤中的降解。在太阳光辐射下,阿特拉津在土壤表面降解速率常数为0. 08~0. 17d-1,光解深度为0. 3mm以内,半衰期为4~8d。     

纳米TiO2催化下表层土壤中BaP的紫外光降解

采用光解试验,研究了紫外照射与纳米TiO2联合作用下,土壤表层中苯并[a]芘（BaP）的降解动力学;同时考察了催化剂的浓度、土壤pH、腐植酸和光质对BaP的光催化降解的影响。结果表明,土壤中BaP的光催化降解表现为准一级动力学。催化剂TiO2可以明显地促进土壤中BaP的光降解,较少量的催化剂（0．5％）使光解的半衰期从363．22h减少到103．26h。H^＋和OH^-离子对BaP的催化光解起促进作用,在酸性和碱性土壤中BaP光催化降解高于中性土壤,酸性土壤中的降解速率最快。腐殖质吸收紫外光照射时,产生的活性氧中间产物能够攻击BaP,添加腐植酸能增加土壤表层中BaP的光催化降解。BaP的光解半衰期从无外加腐植酸的89．34h,减少到添加浓度分别为5、10、20和40mg·kg^-1的29．37、32．69、35．73和38．51h。BaP的催化降解随波长的增加而降低,在波长254、310和365nm下,BaP降解的一级动力学常数分别为0．0078h^-1、0．0061h。和0．005h^-1。     

双草醚在稻田土壤中的降解及其影响因子的研究

采用了实验室模拟方法研究了双草醚在不同土壤中的降解动态。结果表明,在未灭菌的土壤中,双草醚三种浓度(2.0、10.0、50.0mg kg-1)处理的半衰期为7.6~10.3d,远远小于在灭菌土壤中3种添加浓度处理的半衰期(43.3~61.9 d);双草醚在偏酸土壤中降解较快,随着土壤含水量的增加和环境温度的增高,双草醚降解速度加快。4种试验因子中土壤微生物是影响双草醚降解的主要因素,有利于土壤中微生物生长的环境因素,如偏酸的土壤、较高的温度和土壤湿度等,也能促进土壤中双草醚的降解。     

氰戊菊酯在土壤中的降解及其影响因子研究

研究了氰戊菊酯在青紫泥、乌栅土以及黄泥土3种不同类型土壤中的降解,并探讨了土壤理化性质、外界环境条件等对其降解的影响。结果表明:氰戊菊酯在3种土壤中的降解半衰期分别为25.3、19.4、17.7d,降解速率常数分别为0.0274、0.0357、0.0392,即在青紫泥中降解最慢,黄泥土中降解最快。而经过灭菌后的土壤,其降解明显减缓,半衰期延长。由此可见,土壤中降解过程主要是微生物的作用。影响降解的最主要因素是有机质含量,其次为土壤酸碱度,即有机质含量越高,土壤碱性越强,则其半衰期越短,降解速度越快。除此之外,外界环境条件对氰戊菊酯的降解影响也较大,温度越高,湿度越大,降解越快;另外,药剂的添加浓度对降解也有重要的影响,添加浓度越高,降解速率越慢。     

More toxic and photoresistant products from photodegradation of fenoxaprop-p-ethyl

The photodegradation pathway of the commonly used herbicide fenoxaprop-p-ethyl (FE) was elucidated, and the effects of the photodegradation on its toxicity evolution were investigated. Under solar irradiation, FE could undergo photodegradation, and acetone enhanced the photolysis rates significantly. The same photoproducts formed under the irradiation of lambda > 200 nm and lambda > 290 nm through rearrangement, loss of ethanol after rearrangement, de-esterification, dechlorination, photohydrolysis, and the breakdown of the ether linkages. One of the main transformation products, 4-[(6-chloro-2-benzoxazolyl)oxy] phenol (CBOP), was resistant to photodegradation under the irradiation of lambda > 290 nm, and its photolysis rate was seven times slower than the parent under the irradiation of lambda > 200 nm. Among the metabolites, CBOP (48 h EC50 of 1.49-1.64 mg/L) and hydroquinone (48 h EC50 of 0.25-0.28 mg/L) were more toxic to Daphnia magna than the parent FE (48 h EC50 of 4.2-6.9 mg/L). Thus, more toxic and photoresistant products were generated from photolysis of the herbicide. Ecotoxicological effects of phototransformed products from pesticides should be emphasized for the ecological risk assessment of these anthropogenic pollutants.     

苯噻草胺光催化和直接光解影响因素和降解途径研究

采用微波辅助光催化降解和直接光解实验方法,研究了苯噻草胺在光催化和直接光解两种体系下的降解情况,并考察了初始pH值、腐植酸浓度以及阿特拉津对其光催化降解和直接光解的影响。结果表明,在光照4min内,苯噻草胺直接光解效率为93．3％,较光催化降解效率高出28．9％;初始pH值从1．88增加至10．28时,苯噻草胺光催化和光解速率常数分别提高了250％和58．6％;添加腐植酸对苯噻草胺的直接光解和光催化均具有抑制效应,并且抑制效应随着腐植酸浓度的增加而增加,当腐植酸浓度增加至40mg·L^-1时,直接光解和光催化降解速率分别降低了51．8％和47．5％;10mg·L^-1的阿特拉津抑制了苯噻草胺的前期降解,整体直接光解速率降低了46．3％,但整体光催化降解速率没有减小。此外,采用GC—MS对苯噻草胺两种降解体系下的主要中间产物进行鉴定,并提出了主要的光降解途径。     

Photodegradation of rotenone in soils under environmental conditions

An environmental fate study was performed to analyze the effects of soil components on the photochemical behavior of rotenone. Photodegradation experiments were carried out on three types of soil collected in southern Italy, Valenzano (VAL), Turi (TUR), and Conversano (CON), from April to June 2006. Soil thin-layer plates (1 mm thick) were spiked with 1.5 mg/kg of rotenone and exposed under natural conditions of sunlight and temperature. The plates were removed from the sunlight at predetermined intervals of continuous irradiation. Other soil samples, control and sterilized, were kept in the dark to evaluate possible effects of chemical and microbiological degradation during the irradiation experiment. The time for 50% loss of the initially applied rotenone varied from 5 to 7 h, following the order TUR < CON < VAL. In environmental studies, changes in temperature and/or moisture affected the degradation rate and caused deviations from first-order kinetics. The photolysis reaction fit the two compartment or the multiple compartment model pathways better. A fast initial decrease during the first 5 h of rotenone irradiation was followed by a much slower decline, which clearly indicates the rather complex chemical process of rotenone photodegradation on soil surfaces. Also, the degradation was shown to be directly related to the soil concentration of clay and organic matter. Rotenolone (12abeta-hydroxyrotenone) was detected by HPLC/DAD/MS analysis as the only photodegradation byproduct of rotenone in soil thin layers. Results provide additional insights on the rates and the mechanisms of rotenone degradation, aiming to describe more clearly the degradation performance of chemical residues in the environment.     

Metolachlor photodegradation study in aqueous media under natural and simulated solar irradiation

To elucidate the photochemical behavior of pesticide metolachlor, degradation was carried out in aqueous media of different compositions such as sea, river, lake, and distilled water under natural and simulated solar irradiation. In addition, the effect of important constituents of natural water such as dissolved organic matter (DOM, isolated from Pamvotis Lake) and nitrate ions was also examined. It was found that photodegradation proceeds via a pseudo-first-order reaction in all cases. The presence of DOM inhibits the photolysis reaction with half-lives ranging from 87 to 693 h whereas the degradation rate was accelerated up to 11 times in the presence of NO(3)(-). In addition, the toxicity of the degradation products formed (generally through hydroxylation, dealkylation, and cyclization reactions) was also performed using the marine luminescent bacterium Vibrio fisheri. Our results indicated a toxicity increase of the irradiated solution showing that photoproducts of higher acute toxic effects were formed.     

Soil photolysis in a moisture- and temperature-controlled environment. 2. Insecticides

The photolytic degradations of imidacloprid, carbofuran, diazinon, chlorpyrifos, pyridaben, propoxur, and esfenvalerate were independently compared in both moist (75% field moisture capacity at 0.33 bar) and air-dry microbially viable soils at 5 microg/g. All compounds were applied to sandy soil except for propoxur, which was applied to sandy loam soil. Diazinon was applied to both sandy soil and sandy loam soil. The samples were exposed for up to 360 h, depending on the half-life of the compound. Moisture and temperature were maintained through the use of a specially designed soil photolysis apparatus. Corresponding dark control studies were performed concurrently. With the exception of esfenvalerate, the other compounds exhibited significantly shorter half-lives in moist soils, attributed to the increased hydrolysis and microbial activity of the moist soil. The esfenvalerate metabolism was not first order due to limited mobility in the soil because of its very low water solubility. The overall half-life for esfenvalerate was 740 h, as the percent remaining did not drop below 60%. The imidacloprid half-life in irradiated moist soil was 1.8 times shorter than in air-dry soils. However, on dry soil the photodegradation showed poor first-order kinetics after 24 h of exposure. The metabolism of carbofuran and diazinon was highly dependent on soil moisture. Carbofuran exhibited 2.2 times longer half-lives when less moisture was available in the soil. Diazinon in moist sandy soil degraded rapidly, but slowed significantly in irradiated and dark control air-dry sandy soil. Diazinon photolysis on sandy loam soil was not first order, as it attained a constant concentration of 54.9%, attributed to decreased mobility in this soil. Chlorpyrifos photolysis was 30% shorter on moist sand than on air-dry sand. Pyridaben photolyzed rapidly throughout the first 72 h of irradiation but maintained 48% through 168 h. Propoxur metabolism in moist sandy loam soil was not first order and did not degrade below 50% after 360 h of exposure, but the overall half-life was still nearly half of that on irradiated air-dry soil. Three of the compounds showed differences in metabolism patterns during exposure on moist or air-dry soil. Typically, the moist soils produced a more linear decline than that seen in the dry soils, corresponding to the susceptibility of the particular chemical to hydrolysis and/or biodegradation. Four of the eight experiments had shorter half-lives in dark control moist soils than in irradiated dry soils.     

Phototransformation of propiconazole in aqueous media.

The photolysis of propiconazole in pure water, in water containing humic substances, and in natural water was investigated. The reaction rates were determined, and the main photoproducts were identified with the help of HPLC-mass spectrometry and by NMR. The quantum yield for direct photolysis was 0.11 +/- 0.01 at the maximum of absorption (269 nm). Photocyclization after HCl elimination and photohydrolysis of the cyclized intermediate were the main reaction pathways at 254 nm. By contrast, oxidation prevailed over dechlorination in simulated or natural solar light. Humic substances (10 mg x L(-)(1)) and naturally occurring chromophores contained in natural water enhanced the rate of propiconazole photodegradation in solar light. Half-life in June in Clermont-Ferrand (latitude 46 degrees N) was found to be 85 +/- 10 h in pure water and 60 +/- 10 h in natural water; showing that photodegradation of propiconazole in natural waters involves both direct photolysis and photoinduced reactions.     

林丹环境安全性评价研究

为了评价林丹在环境介质中的持久性,对林丹的土壤降解、水解、光解与快速生物降解性进行了试验研究。结果表明,林丹的土壤降解半衰期为36．9～68．6d,水解半衰期为8．94～2310d,对光反应稳定,难以快速生物降解。林丹对斑马鱼的96h—LC50为4．22μg·L^-1,对环境生物具有极高的毒性;林丹在金鱼体内的生物富集系数BCF〉1000,具有较高的生物富集性。根据试验结果推断,林丹在环境介质中具有极强的稳定性,很容易在食物链中发生生物积累。