Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

Fenton法氧化处理水中土霉素的研究

为了评价Fenton法预处理抗生素生产废水中残留的高浓度土霉素的可行性,对Fenton试剂(Fe2 -H2O2)法催化氧化降解水溶液中的土霉素进行了研究.探讨了H2O2与Fe2 投加比例、投加量以及起始pH值对降解效果的影响,同时考察了土霉素废水中大量共存的草酸根离子对氧化过程的影响.结果表明,当H2O2与Fe2 按照5:1的比例投加时降解效率最高,最佳初始pH值在3.0-4.0之间.在最佳投加比例下,H2O2投加量为0.9 mmol/L,100 mg/L的土霉素可在10 min内得到完全降解.最佳反应条件下经过处理后土霉素水溶液TOC的去除率达40%左右,可生化性(BOD5/COD)也得到明显的改善.水中共存的草酸根离子对氧化效率具有明显的影响,但通过增加亚铁离子的量可以消除草酸的影响.     

Dissipation of oxytetracycline in soils under different redox conditions

This study investigated the dissipation kinetics of oxytetracycline in soils under aerobic and anoxic conditions. Laboratory experiments showed that the dissipation of oxytetracycline in soil followed first-order reaction kinetics and its dissipation rates decreased with increasing concentration. Oxytetracycline dissipated faster in soil under aerobic conditions than under anoxic conditions. The half-lives for oxytetracycline in soil under aerobic conditions ranged between 29 and 56 days for non-sterile treatments and 99-120 days for sterile treatments, while under anoxic conditions the half-lives of oxytetracycline ranged between 43 and 62 days in the non-sterile soil and between 69 and 104 days in the sterile soil. This suggests microbes can degrade oxytetracycline in agricultural soil. Abiotic factors such as strong sorption onto soil components also played a role in the dissipation of oxytetracycline in soil.     

Degradation of diuron in aqueous solution by ozonation

Degradation of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] in aqueous solution and the proposed degradation mechanism of diuron by ozonation were investigated. The factors that affect the degradation efficiency of diuron were examined. The generated inorganic ions and organic acids during the ozonation process were detected. Total organic carbon removal rate and the amount of the released Cl^? increased with increasing ozonation time, but only 80.0% of the maximum theoretical concentration of Cl^? at total mineralization was detected when initial diuron concentration was 13.8 mg L^?1. For N species, the final concentrations of NO₃ ^? and NH₄ ⁺ after 60 min of reaction time were 0.28 and 0.19 mg L^?1, respectively. The generated acetic acid, formic acid and oxalic acid were detected during the reaction process. The main degradation pathway of diuron by ozonation involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes, leading to small organic species and inorganic species. The degradation efficiency of diuron increased with decreasing initial diuron concentration. Higher pH value, more ozone dosage, additive Na₂CO₃, additive NaHCO₃ and additive H₂O₂ were all advantageous to improve the degradation efficiency of diuron.     

磺胺二甲嘧啶在纯水和污水厂二级出水中的光解差异及机制

以磺胺二甲嘧啶（SM2）为目标污染物,研究了高压汞灯和紫外灯两种光源和初始浓度对SM2光解的影响以及SM2在二级出水中光解的主要影响因素,并通过自由基猝灭实验确定SM2光解过程中的主要活性物质。结果表明：SM2在紫外灯下的光解速率是高压汞灯的2.6倍;SM2光解速率随其初始浓度的增加而减慢。SM2在二级出水中的光解速率是纯水中的2.5倍,溶解性有机质（DOM）能显著促进SM2的光解。SM2在纯水中光解主要是激发三重态SM2（3SM2*）参与的直接光解过程,其自敏化光解不利于SM2的光解;含有DOM的溶液中,激发三重态DOM（3DOM*）参与的敏化光解是促进SM2光解的主要原因。     

UV及UV/US降解对二氯苯水溶液的研究

使用紫外光（UV）和超声波（US）降解水溶液中的对二氯苯（p-DCB）。考察了p-DCB初始浓度,初始pH、腐殖酸和H2O2的存在对p-DCB光解的影响。结果表明,较低的初始浓度或弱酸性pH有利于p-DCB降解。溶液中存在20 mg/L的腐殖酸可使p-DCB的反应速率常数提高32.6%。加入氧化剂H2O20=0.1 mmol/L,［H2O20=0.1 mmol/L,pH0=5.8,反应180 min条件下,p-DCB的降解率为95.5%。超声波对p-DCB的降解速率（14.6×10-3/min）大约是紫外光（4.3×10-3/min）的3.4倍,紫外光 超声波耦合时的降解速率（20.6×10-3/min）大于两者单独降解速率的加合。在各种实验条件下,p-DCB的降解均遵循表观一级动力学。     

Characteristics of oxytetracycline sorption and potential bioavailability in soils with various physical-chemical properties

Veterinary antibiotics are widely used for disease treatment, prevention and animal growth promoting. Frequent detection of veterinary antibiotics in environments, caused by land application of untreated or even treated antibiotics-containing animal wastes, has posed the growing concern of their adverse effect on natural ecosystems. Oxytetracycline (OTC) is one of the most widely-used veterinary antibiotics in livestock industry. OTC present as a cation, zwitterions, or net negatively charged ion in soils complicates predicting its sorption characteristics and potential bioavailability and toxicity. This study was to identify soil properties influencing OTC sorption and its subsequent bioavailability in five soils with various physical-chemical properties. A solution used to determine bioavailable analytes in soils and sediments, 1 M MgCl₂ (pH 8.5), was chosen to desorb the potentially bioavailable fraction of OTC sorbed onto soils. Our results demonstrated that soils with higher illite content and permanent cation exchange capacity have higher OTC sorption capacity, but increase the availability of sorbed OTC indicated by higher release of sorbed OTC from soils into aqueous phase in 1 M MgCl₂ (pH 8.5). Reversely, soil organic matter (SOM), clay, kaolinite, variable cation exchange capacity, DCB-Fe and -Al have lower OTC sorption capacity, but decrease the release of sorbed OTC from soils into 1 M MgCl₂. These findings indicate that SOM and clay greatly influence OTC adsorption and potential availability. This study contributes significantly to our understanding of the potential bioavailability of sorbed OTC and the effects of soil properties on OTC sorption behaviors in soils.     

高压脉冲放电等离子体对水中土霉素的降解

采用针-板式高压脉冲放电等离子体降解水中土霉素,考察了放电输出功率、空气流量、电极间距、溶液初始浓度、初始pH、初始电导率和添加Fe2+的量对土霉素去除率的影响。实验结果表明,高压脉冲放电等离子体对水中土霉素有较好的去除效率,在初始浓度200 mg/L,放电功率64 W,电极间距8 mm,空气流速0.05 m3/h,初始pH为2.6,初始电导率1.083 mS/cm条件下,反应12 min后,土霉素的去除率可达97%。向溶液中添加Fe2+,可提高土霉素的去除率。TOC随着反应时间的延长逐渐减小,反应12 min时,TOC去除率可达57%,说明大分子物质被降解为小分子物质,部分被完全矿化为CO2和H2O。     

Destruction of phenol aqueous solution by photocatalysis or direct photolysis

The photodegradation of phenol has been investigated under a high-pressure mercury lamp with a kind of jacket (glass or quartz) depending on used UV light range and a variety of experimental conditions: UV (lambda > 200 nm) with oxygen or with TiO2 and oxygen or with N2; UV (lambda > 330 nm) with oxygen or with TiO2 and oxygen or with N2. Photocatalysis and direct photolysis of phenol have different reaction pathways. Direct photolysis of phenol yielded a brown-yellow complex organic polymer in both aerobic and anaerobic environments. The polymer cannot be mineralized in an anaerobic environment. The effects of catalyst amount and oxygen concentration in the reaction atmosphere on the destruction of phenol were studied. The results prove that an appropriate catalyst amount can avoid direct photolysis and increase the mineralization rate of phenol.     

超声波降解四环素类抗生素废水

采用超声波降解模拟废水中四环素类抗生素(TCs):土霉素(OTC)、四环素(TC)和金霉素(CTC),考查废水初始浓度、初始pH、超声波输入功率密度、曝气量和自由基清除剂(正丁醇)对降解效率的影响。结果表明,超声波可以快速高效地降解废水中的TCs,CTC最易被降解,TC和OTC次之;在OTC、TC和CTC初始浓度0.25 mg/L,初始pH=8.2,声功率密度1.2 W/mL,气水体积比30∶1的条件下,超声波辐照20 min后去除率分别达到76.8%、84.0%和94.4%。在实验研究条件下,TCs去除率均随初始浓度(0.25~2.00 mg/L)的增大而降低,但总去除浓度升高;碱性条件有利于TCs降解,去除率随初始pH(6~11)升高而升高;功率密度(0.24~1.96 W/mL)越高,TCs去除率也越高;曝气后TCs的去除率明显升高,随着气水比(10∶1~60∶1)的增大,去除率逐渐上升;正丁醇有效抑制TCs超声波降解,可推断TCs主要降解途径为自由基氧化。TCs超声波降解过程符合伪一级动力学反应特征。     

Photolytic degradation of fluoroquinolone carboxylic acids in aqueous solution

Subsequent to irradiation with a xenon lamp simulating sunlight, fluoroquinolone carboxylic acids in aqueous solution form polar pyridone dicarboxylic and tricarboxylic acids. After liquid/liquid partition with chloroform/water these substances can be isolated by ion exchange chromatography of the aqueous phase. They can be regarded as intermediate compounds on the route to a complete photomineralization. The structural elucidation is performed by such mass spectroscopic methods as MS, GC/MS and HPLC/MS, whereby HPLC/MS shows the highest reliability. Additionally¹H- and¹³C-NMR measurements confirm the structure of the main polar degradation product.     

水中四环素类化合物在不同光源下的光降解

研究了模拟太阳光和实际室外太阳光下四环素类化合物在水溶液中的光降解。结果表明,四环素类化合物(TCs)在模拟太阳光照射下均能发生直接光降解,且其降解速率随pH不同变化很大。四环素(TC)、土霉素(OTC)、金霉素(CTC)和多西环素(DTC)的光降解速率随溶液pH升高明显加快,而米诺环素(MTC)在水中的光降解速率随溶液pH升高略有下降。天然水体pH范围内,模拟太阳光照下四环素类化合物表观光降解速率常数在0.004～0.026 min-1范围内,降解半衰期在26～136 min范围内。在室外实际太阳光照下,四环素类化合物光降解反应速率与太阳光强成正比例关系。晴朗无云天气下,四环素类化合物降解半衰期在春冬季节较长、夏季节较短;四环素在东江实际水体中表观光降解速率很快,在冬季晴天天气下,其平均半衰期仅为8.2 min。     

γ-射线辐照降解水中阿莫西林

研究了60Coγ-射线辐照条件下水中阿莫西林(AMX)的辐照降解,考察了AMX初始浓度、辐照剂量、p H、H2O2、自由基消除剂(碳酸氢钠和正丁醇)以及溶解氧等因素对AMX辐照降解的影响。结果表明,γ辐照可有效降解水中AMX,当AMX初始浓度为10.0 mg/L,辐照剂量为15 k Gy时,降解率达100%,随着AMX浓度增大,其降解率降低。碱性条件有利于AMX的降解,当p H为11,且辐照剂量大于10 k Gy时,AMX的降解率在90%以上。同时,加入H2O2可以促进AMX的降解;·OH自由基消除剂的存在和缺氧条件会明显抑制γ-射线对AMX的辐照降解,分析表明,AMX的降解主要是基于·OH自由基的氧化。     

水中盐酸环丙沙星的超声降解

为研究超声波降解水中盐酸环丙沙星的机理,在不同超声波功率、不同盐酸环丙沙星初始浓度以及不同添加剂条件下,对盐酸环丙沙星进行超声降解研究.在实验条件下,当功率从180 W增至1 000 W时,10 mg/L盐酸环丙沙星降解率从55.2%提高到75.3%; 当功率为360 W,超声2 h时,未加添加剂时其降解率为62.5%,而加入FeSO4、NaCl、H2O2、CCl4、CuSO4、KI和N2后其降解率分别为85.3%、65.7%、70.1%、98.8%、43.6%、8.1%和51.2%.研究结果表明,FeSO4、NaCl、H2O2及CCl4的添加能促进盐酸环丙沙星的超声降解,而CuSO4、KI和N2却显著压抑其降解.盐酸环丙沙星的超声降解主要归因于·OH等活性自由基的氧化作用.     

紫外辐射加速磺胺嘧啶生物降解的机理

采用紫外光解与生物降解耦合的方法可以明显提高磺胺嘧啶(SD)的生物降解速率。经过分析,发现SD在紫外光解过程中首先生成对氨基苯磺酸(p-aminobenzenesulfonic acid, ABS)和2-氨基嘧啶(2-aminopyrimidine, 2-AP),而ABS很快分解为苯胺(aniline, An)和SO42-。其中2-AP不能加速苯胺的生物降解,反而具有一定的生物抑制。而苯胺可以提高其生物降解速率。按比例同时将2-AP和An加入到SD溶液中,其生物降解速率与紫外光解耦合生物降解时相近,是单独生物降解速率的2倍。这是因为苯胺在生物氧化过程中,可以提供足够的电子并通过共基质作用加速SD的初始单加氧反应。     

Degradation kinetics of tebufenozide in model aquatic systems under controlled laboratory conditions

Abstract

The hydrolysis of the insecticide tebufenozide was studied in the dark at 20 to 40°C in buffered (pH 4 to 10) distilled water, and at 20°C in unbuffered, sterilized and unsterilized stream water. Tebufenozide was very stable in acidic and neutral buffers at 20°C and the corresponding pseudo‐first‐order rate constants (k_obsd) and half‐lives (T_1/2) were 5.946 × 10^‐4 and 13.10 × 10^‐4 d^‐1, and 1166 and 529 d, respectively. The hydrolytic degradation was dependent on pH and temperature. At pH 10 and at 20,30 and 40°C, the k_obsd (10^‐4 d^‐1) and T_1/2 (d) values were 34.22, 66.72 and 130.0; and 203, 104 and 53.3, respectively. The energy of activation (E_a) values for the hydrolysis of tebufenozide at pH 4, 7 and 10, calculated from the Arrhenius plots, were 83.50, 66.71 and 50.87 kJ/mol, respectively. Tebufenozide was stable in sterilized stream water in the dark (T_1/2 = 734 d) but it degraded fairly rapidly in unsterilized stream water (T_1/2 = 181 d). Sunlight photodegradation of the chemical was slower (T_1/2 = 83.0 h) than the photolysis by ultraviolet radiations (T_1/2 values at 254 and 365 nm were 9.92 and 27.6 h, respectively); nevertheless, it was still appreciable during the summer months at 46°31’ N latitude. The differences in degradation rates between the unsterilized and sterilized stream water and the degradation of the chemical in the sterile, distilled water in sunlight, suggests that microbial processes and photolysis are the two main degradative routes for tebufenozide in natural aquatic systems.     

Electrospray Ionization Mass Spectrometry (ESI-MS) monitoring of the photolysis of diazinon in aqueous solution: Degradation route and toxicity of by-products against Artemia salina

The photolytic degradation of diazinon, an organophosphorus pesticide, in aqueous medium under assorted pH values was continuously monitored by direct infusion electrospray ionization mass spectrometry (ESI-MS). The results indicated that the UV radiation was quite efficient in promoting the pesticide degradation at the three pH levels evaluated (5, 7 and 8). The m/z of the most abundant ions observed in the mass spectra (MS), in conjunction with the fragmentation patterns of such ionic species (MS/MS data), made possible the proposition of chemical structures for the main by-products formed. As a result, routes for the photodegradation of diazinon in aqueous solution could thus be suggested. In the assays using Artemia salina (brine shrimp) it was verified that the photodegradation products exhibited much lower toxicity than the primary substrate. Aiming at mimicking the conditions ordinarily found in water treatment plants, an additional series of tests was conducted with a solution containing sodium hypochlorite and diazinon. This solution, when not exposed to UV radiation, exhibited high toxicity against the microorganisms. Under the influence of UV radiation, however, the toxicity rates decreased dramatically. This result is relevant because it points toward the confident application of UV radiation to neutralize the deleterious effects caused by diazinon (and perhaps other organophosphorus pesticides) as well as sodium hypochlorite to the environment.     

Phototransformation of ibuprofen and ketoprofen in aqueous solutions

The UV (254 nm) and UV/VUV (254/185 nm) photolysis of two anti-inflammatory drugs, ibuprofen and ketoprofen, have been studied in aqueous solutions as a possible process for the removal of non-biodegradable compounds.We have examined the effects of dissolved oxygen and initial target concentration. Upon irradiation at 254 nm, the decomposition rate of ketoprofen is almost forty times higher as it of ibuprofen whilst VUV irradiation only increased the ibuprofen decomposition rate. The presence of dissolved oxygen accelerated the photodegradation of ibuprofen, whereas no effect was observed on the degradation of ketoprofen. The maximum quantum yield for the phototransformation was 0.2. The rate of mineralization in both cases was ∼60%, even after 1 h of treatment and this suggests the formation of stable by-products which were identified using GC-MS and HPLC-MS, respectively.     

芬顿氧化法处理水中酸性品红的研究

研究了酸性品红在Fenton体系中的降解过程,反应30 min后,在[Fe2+]0=0.06 mmol/L、[H2O2]0=0.3 mmol/L、pH=3、T=30℃的条件下,初始浓度为20 mg/L的酸性品红的去除率达到97%以上。升高反应温度,有利于Fenton体系中酸性品红的降解,但影响并不显著。根据不同温度下的速率常数,并结合Arrhenius方程求出了Fenton试剂降解酸性品红的反应活化能,仅为11.63 kJ/mol。C1?的存在对酸性品红在Fenton体系中的降解表现出明显的阻碍作用,并且随着C1?浓度的增加,抑制作用越来越大;SO24-和NO3-的存在也降低了Fenton试剂的氧化性能。     

Fenton试剂氧化降解水中的盐酸四环素

利用Fenton试剂对水中盐酸四环素（TC）氧化降解,考察H2O2/Fe2+（摩尔比）、Fenton试剂投加量、溶液pH值对盐酸四环素去除的影响,研究了盐酸四环素降解过程及动力学特征。研究结果表明：对于初始浓度为0.10 mmol·L-1的盐酸四环素,最优反应条件为pH值3.0,H2O2/Fe2+=10：1（物质的量之比）,H2O2施加量1.58 mmol·L-1。在该条件下反应60 min,盐酸四环素降解率达88.47%,对应TOC去除率为18.48%;紫外可见光谱扫描结果表明氧化过程中盐酸四环素的共轭结构被首先破坏;分别采用一级和二级动力学方程拟合降解过程,结果表明反应过程遵循二级动力学模型。