碘甲磺隆钠盐对土壤中过氧化氢酶活性及呼吸作用的影响

通过模拟实验研究了除草剂碘甲磺隆钠盐对土壤中过氧化氢酶活性和土壤呼吸作用的影响。结果表明,在施用量超过田间推荐用量7倍的浓度范围内,碘甲磺隆钠盐对土壤中过氧化氢酶活性的影响不明显;当其浓度为1mg/kg时,在不同培养时间下,碘甲磺隆钠盐施用后对土壤过氧化氢酶活性的影响呈现出轻微的抑制-激活-恢复的过程;在不同土壤类型中,碘甲磺隆钠盐对土壤过氧化氢酶的抑制性随土壤有机质的增加、pH值的降低而加强;碘甲磺隆钠盐对土壤呼吸作用有一定的影响,浓度愈大,土壤呼吸强度初期抑制愈强,随着时间的推移,逐步由抑制转为一定程度的刺激作用,到12天后施药土壤与对照组土壤的呼吸强度基本上趋于一致。实验结果表明,碘甲磺隆钠盐对土壤微生物影响较小,属于低毒或无实际危害的农药。     

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.     

水中2，4—二氯苯酚的光催化降解研究

以高压汞灯、紫外灯、氙灯和太阳光为光源，进行ZnO,ZnS,TiO2及纳米TiO2对2，4－二氯苯酚溶液的光催化降解研究。结果表明，ZnO,ZnS,TiO2及纳米TiO2对2，4－二氯苯酚均有较强的光催化效果；在相同催化剂浓度下，以ZnO的催化效果最好，其次是TiO2；4种光源中以高压汞灯下的光解最快，太阳光次之；纳米TiO2对2，4－二氯苯酚的光催化降解属于一级动力学反应；曝气能加快2，4－二氯苯酚的光催化降解。     

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。     

土壤中14C-甲磺隆存在形态的动态研究

利用同位素示踪技术 ,在实验室条件下研究了1 4 C -甲磺隆在 1 5种不同土壤中存在形态的动态变化。结果表明 ,土壤pH值与甲磺隆1 4 C残留物的降解半衰期、残留量及可提取态残留量呈显著的正相关 ,而与结合态残留量呈显著负相关 ;土壤微生物的活性越强 ,甲磺隆降解速率越快 ,但结合态残留量也越高 ;土壤中各腐殖质组分和粘粒的含量也影响甲磺隆在土壤中的降解速率和存在形态。土壤中甲磺隆的残留符合一级反应动力学指数方程C =C0 e-kt,拟合方程的复相关系数达到极显著水平。甲磺隆残留与土壤性质之间经逐步回归分析可得到拟合效果较好的方程 ,由各自变量的决定系数可知 ,土壤pH值、微生物生物量碳和有机碳中富啡酸碳所占的比例是影响甲磺隆在土壤中残留的主要因素     

光催化降解沼液中四环素类抗生素效果及反应动力学研究

该文采用光催化降解途径探究沼液中四环素类抗生素降解的最佳光源、pH值以及光催化对不同初始质量浓度抗生素的降解效果,同时进行不同初始浓度、pH值条件下抗生素光催化降解动力学研究。结果表明:不同光源对四环素类抗生素的降解效果为:高压汞灯紫外消毒灯长弧氙灯无光。高压汞灯催化2 h后,四环素、土霉素、金霉素的降解率分别达到91.68%、85.58%、81.18%。四环素类抗生素的初始质量浓度越低,光催化效果越好。四环素、土霉素、金霉素初始质量浓度为5 mg/L时,其降解率最高可达94.80%、88.35%和95.39%,沼液初始pH值对四环素、金霉素的降解率影响存在显著性差异(P0.05)。当pH值为6时,四环素的降解率最大为96.16%,反应速率常数为1.5971h-1,半衰期为0.355 3 h;当pH值为10时,金霉素的降解率最大为90.47%,反应速率常数为1.084 4 h-1,半衰期为0.338 3 h。沼液初始pH值对土霉素的降解率影响无显著差异(P0.05)。当pH值为10时,3种抗生素的平均降解率最大为89.88%。采用高压汞灯在沼液初始pH值为10时,催化降解5 mg/L四环素类抗生素效果最佳。     

甲磺隆降解菌FLDA的分离鉴定及其降解特性研究

从生产甲磺隆的农药厂内采取污泥，经驯化富集后筛选到一株能高效降解甲磺隆的细菌FLDA，根据表型特征、生理生化特性及16S rDNA序列同源性分析，将FLDA初步鉴定为假单胞菌（Pseudomonas sp）。该菌能在含甲磺隆（30mgL^-1）的基础盐液体培养基中降解甲磺隆，5d降解率达72．6％，该菌降解甲磺隆的最适pH为7．0，最适温度为30℃，该菌降解甲磺隆的速率和起始接种量呈正相关。酶的定域实验表明，该菌中甲磺隆水解酶为胞内酶。FLDA投加土壤，可提高土壤中甲磺隆的降解速率。     

降解菌S113对甲磺隆污染土壤生物修复作用的研究

在室内条件下,研究了降解菌S113(Methylopila sp.)对甲磺隆污染土壤的修复作用。S113能够以甲磺隆为唯一碳源生长,72h对50mgL-1甲磺隆的降解率达98.38%。投加降解菌S113可显著提高土壤中甲磺隆的降解速率。当甲磺隆浓度为10mgkg-1干土,S113接种量为108个g-1土时,第30天土壤中甲磺隆降解率为76.9%,对照土壤中甲磺隆降解率仅为11.9%。S113降解甲磺隆的速率和接种量呈正相关,当接种量减少为105个g-1干土时,降解菌对甲磺隆的降解作用微弱。在土壤中甲磺隆浓度较低的条件下,S113的降解效果显著,而当土壤中甲磺隆浓度达到50mgkg-1时,甲磺隆降解率仅为39.6%。S113降解土壤中甲磺隆的最适温度为30℃,第30天的降解率可达75.9%。当温度为25℃、20℃时,第30天甲磺隆降解率仅为53.5%和23.9%。S113菌剂灌根,能不同程度地缓解土壤中浓度为40、80μgkg-1的甲磺隆对玉米生长的抑制作用,但当甲磺隆浓度增加到120μgkg-1时,接种S113对药害解除作用不显著。结果表明,人工接种降解菌S113,能有效去除土壤中甲磺隆残留。     

新农药甲硫嘧磺隆的醇解动力学及机理研究

甲硫嘧磺隆,试验代号为HNPC-C9908,化学名称为2-（4-甲氧基-6-甲硫基嘧啶-2-基）氨基甲酰基氨基磺酰基苯甲酸甲酯,是我国具有自主知识产权的新型磺酰脲类除草剂,主要用于麦田杂草的防除。采用HPLC和LC/MS研究了甲硫嘧磺隆的醇解动力学及其机理。结果表明,甲硫嘧磺隆在甲醇和乙醇中可发生快速的醇解反应,并可用一级动力学方程很好描述,其醇解半衰期分别为10.6和11.6 d,说明醇解反应可能是磺酰脲类化合物的普遍特征之一。甲硫嘧磺隆的醇解反应因温度、pH值、甲醇含量以及有效成分浓度而异。甲硫嘧磺隆的醇解速率随温度升高而加快,其在15、25、35和45 ℃等4个温度下的醇解半衰期分别为41.0 d、10.6 d、3.8 d和13.0 h,温度效应系数为28.06;甲硫嘧磺隆醇解反应的活化能和活化焓与温度之间无明显相关性,其平均活化能和活化焓分别为186.28和183.71 kJ·mol^-1,而活化熵绝对值则随温度升高而增加,表现出良好的相关性,其平均活化熵为－11.28 kJ·mol^-1·K^-1,说明甲硫嘧磺隆的醇解主要为双分子亲核取代反应;甲硫嘧磺隆在酸性醇液中的降解速率明显快于中性和碱性醇溶液中的降解速率,其在pH5、7和9的甲醇液中的醇解半衰期分别为6.8、172.2和109.5 d;当甲醇含量为40%、50%、60%、70％、80％、90％和100％时,甲硫嘧磺隆的降解半衰期为27．8、30．7、30．1、43．3、42．5、43．9和10．6d,而在纯水中的半衰期为29．4d;在浓度较低（5mg·L^-1）时,甲硫嘧磺隆的醇解速率较慢,其醇解半衰期为32．2d,而当增加到10和20mg·L^-1时,对甲硫嘧磺隆的醇解速率影响不大。甲硫嘧磺隆醇解的主要途径是分子中脲桥裂解生成2-苯甲酸甲酯基磺酰基氨基甲酸酯和2-氨基-4-甲氧基-6-甲硫基嘧啶。     

Water Remediation by Columns Filled with Micelle–Vermiculite Systems

Photodegradation of four pharmaceuticals (i.e. carbamazepine, ibuprofen, ketoprofen and 17α-ethinylestradiol) in aqueous media was studied using a solar light simulator (Xe lamp irradiation) and sunlight experiments. These experiments were carried out in river and seawater and compared to distilled water. The latter was used to evaluate the direct photodegradation pathways. Irradiation time was up to 400 min and 24 days for the solar light simulator and sunlight assays, respectively. Pharmaceutical photodegradation followed a first-order kinetics and their half-lives calculated in every aqueous matrix. Moreover, the sensitizing effect of DOC was evaluated by comparison with the kinetics obtained in distilled waters. Ketoprofen was rapidly transformed via direct photolysis in all the waters under both sunlight (t _1/2?=?2.4 min) and simulated solar light simulator test (t _1/2?=?0.54 min). Under xenon lamp radiation, ibuprofen and 17α-ethinylestradiol were photodegraded at moderate rate with half-lives from 1 to 5 h. Finally, carbamazepine had the lowest photodegradation rate (t _1/2?=?8–39 h) attributable to indirect photodegradation. Indeed, its elimination was strongly dependent on the DOC concentration present in solution. Finally, several ketoprofen photoproducts were identified and plotted against solar light simulator irradiation time. Accordingly, the photodegradation pathway of ketoprofen was postulated.     

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.     

Photolytic degradation of florasulam on soil and in water

The rate and pathway of degradation in the presence of light for the triazolopyrimidine herbicide florasulam was determined on soil and in aqueous systems. Florasulam was exposed to natural sunlight for up to 32 days; solar irradiance was measured with either chemical actinometers or by radiometry. The quantum yield for direct photodegradation in a sterile, buffered aqueous solution was determined to be 0.096; an analogous quantum yield for the sum of direct and indirect photodegradation on soil was 0.245. The quantum yields were used to estimate half-lives due to photodegradation as a function of season and temperature. Estimated half-lives due to photodegradation in summer at 40 degrees N latitude were 14 days on soil and 36 days in sterile, buffered water. Photodegradation was much faster in a natural water system, with a measured half-life of 3.3 days in summer at 51.5 degrees N latitude, indicating that indirect photolytic processes will be important contributors to photodegradation of florasulam in aqueous environments.     

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.     

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.     

TiO2-Assisted Photodegradation of Direct Blue 78 in Aqueous Solution in Sunlight

The photodegradation of azo dyes aqueous solution has been investigated using TiO₂ as catalyst in sunlight. The effect of amount of catalyst, concentration of dye, and pH value on the degradation of Direct Blue 78 was observed. A complete degradation of 100 mg/L Direct Blue 78 solution under solar irradiation was achieved in 6 h at pH?3.0, dosage of TiO₂ 1.0 g/L. A possible pathway for the photodegradation of Direct Blue 78 in sunlight was proposed.     

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.     

八氯二丙醚在土壤表面的紫外光解动力学研究

以紫外灯为光源,研究了八氯二丙醚在土壤表面的光化学降解动态以及不同因子对其光解的影响。结果表明,八氯二丙醚在土壤表面的光解动态符合化学反应一级动力学方程。八氯二丙醚在不同类型土壤中的光解速率为红壤〉潮土〉水稻土,光解半衰期分别为11.44、14.00h和20.63h。八氯二丙醚在中性土壤中光解速率最快,在偏酸或偏碱性土壤中光解半衰期均明显延长。土壤含水量增加,有利于八氯二丙醚的光解,干燥土壤（含水量为2%）中八氯二丙醚的光解半衰期是潮湿土壤的1.3~2.6倍。当土壤中八氯二丙醚添加浓度为0.2~10mg·kg-1时,其光解速率与添加浓度呈负相关关系;不同添加剂量的催化剂TiO2对八氯二丙醚的光解均表现出明显的光敏化作用,光解速率常数提高1.6~2.4倍。研究结果将为明确八氯二丙醚在土壤中的环境行为及其环境安全性评价提供科学依据。     

Structural elucidation of phototransformation products of azimsulfuron in water

The photodegradation of the sulfonylurea herbicide azimsulfuron, N-[[(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide (AZS), was studied in water at different wavelengths and in the presence of photocatalysts. AZS was rapidly degraded by UV light, affording three photoproducts. The main product, accounting for about 70% of photodegraded herbicide, was identified as 6-amino-5-[(4,6-dimethoxypyrimidin-2-yl)methylamino]-1,5,6,8-tetrahydro-7-oxa-8lambda(6)-tia-1,2,5,6-tetraza-azulen-4-one (ADTA) by single-crystal X-ray diffraction. With simulated sunlight irradiation, the reaction was slower and 2-amino-4,6-dimethoxypyrimidine (DPA) and 1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide (MPS), arising from a photohydrolytic cleavage of the sulfonylurea bridge, were the only byproducts observed. The reactions followed first-order kinetics. The addition of dissolved organic matter (DOM) did not modify significantly the AZS photodegradation rate. The presence of Fe2O3 accelerated more than twice the reaction rate affording two major products, DPA and MPS, together with minor amounts of N-[[(5-hydroxy-4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide (AZS-OH). The greatest degradation rate was detected in the presence of TiO2. Only the photohydroxylation product AZS-OH was observed, which was transformed rapidly into oxalic acid.