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。     

纳米TiO2暴露对水中四环素类抗生素光降解行为的影响

本文研究了纳米二氧化钛(TiO₂)暴露对水中土霉素(OTC)、金霉素(CTC)光降解行为的影响。结果表明：纳米TiO₂暴露下OTC、CTC在模拟太阳光下的降解遵循准一级反应动力学模型,光降解效率随纳米TiO₂投加量的增大、粒径的减小和初始pH的升高而逐渐提高。当纳米TiO₂投加量为50.0 mg·L^-1、粒径为5 nm,体系初始pH为6.0时,经360 min反应后OTC、CTC光降解率分别为95.93%、97.13%。溶液中共存的HCO₃^-对光降解过程起促进作用,而C^l-起抑制作用。自由基捕获实验证明·O₂^-是OTC、CTC光降解过程中起主导作用的活性物种,光降解贡献率分别为91.01%、87.35%。通过毒性实验证明纳米TiO2长期暴露下可降低OTC、CTC的急性毒性和遗传毒性。     

超声波/零价铁降解对氯苯胺性能及机理研究

在超声波/零价铁体系中考察了溶液初始pH值、浓度对对氯苯胺降解的影响.在pH值为3～11范围内最佳条件为pH=9;初始浓度为0.1、0.2和0.4 mmol/L时的降解率(180 min)分别为83.2%、63.5%和36.1%.对氯苯胺在单纯铁粉、单纯超声波和超声波/零价铁3种体系中降解符合拟一级反应动力学规律,速率常数分别为6.83×10-4、3.95×10-3和1.01×10-2 min-1,增强因子为218%,表明铁粉与超声波对对氯苯胺降解有明显的协同效应.在体系中加入自由基捕捉剂正丁醇能抑制对氯苯胺的降解,证实对氯苯胺降解主要是依靠羟基自由基的氧化作用.     

高铁酸钾降解苯胺废水的机制研究

研究了高铁酸钾投加量、初始pH及苯胺初始浓度对苯胺降解效果的影响.结果表明.苯胺废水的COD去除事随高铁酸钾投加量和苯胺初始浓度的增大而升高,而初始pH对COD去除率影响不明显.对高铁酸钾降解苯胺废水后的产物进行了气相色谱/质谱(GCIMS)分析.在此基础上详细探讨了高铁酸钾降解苯胺的机制.     

CuO/ZnO复合光催化剂降解海水养殖废水中盐酸四环素

为降解海水养殖废水中盐酸四环素,采用沉淀法自制CuO/ZnO复合光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外—可见漫反射(UV-Vis DRS)等表征手段对其进行表征,得到CuO/ZnO复合光催化剂的粒径、外貌特征以及光吸收范围。可见光照射下,考察了CuO/ZnO复合光催化剂投加量、煅烧温度、掺杂比(ZnO和CuO摩尔比)、过氧化氢浓度、反应时间以及盐酸四环素初始浓度6项因素对光催化降解海水养殖废水中盐酸四环素的影响。通过正交试验得到CuO/ZnO复合光催化剂降解盐酸四环素的优化反应条件为:海水养殖废水中含有的盐酸四环素初始质量浓度为0.025g/L,过氧化氢质量浓度为0.5g/L,掺杂比为10∶1,煅烧温度为550℃,CuO/ZnO复合光催化剂投加量为0.15g/L,可见光下反应3.5h。在此条件下海水养殖废水中盐酸四环素的平均去除率可达93.01%。     

活性污泥对甲醛废水的净化性能

采用微生物法处理低浓度甲醛废水达标排放是比较经济的方法之一.在研究中采用序批式活性污泥法(SBR)工艺,考察了曝气时间、进水甲醛浓度、进水 pH 和水温对微生物净化低浓度甲醛废水的影响.结果表明,随着曝气时间的延长,活性污泥对甲醛的去除率增大.进水甲醛浓度在 40～120 mg/L 范围内,随着浓度升高甲醛污泥负荷增加,微生物对甲醛的降解速率增加,但对甲醛的去除率降低.活性污泥在 pH 为 5～7 的中性和弱酸性环境中对甲醛的降解速率较高.在15～35℃范围内,污泥对废水中甲醛的去除率随温度升高而上升,微生物对甲醛的降解速率随温度升高呈指数递增趋势.     

紫外光降解硝酸盐体系中四环素

为了考察紫外光照射下四环素(tetracycline,TC)在硝酸盐(NO_3~-)体系中的降解过程,研究了初始pH、TC初始浓度、NO_3~-浓度、腐殖酸以及磷酸盐等环境因子对TC光降解的影响,利用ESR检测和自由基猝灭实验,量化分析体系中不同氧化途径对TC去除的贡献率。结果表明:TC在NO_3~-体系中的光降解受pH影响显著;腐殖酸和磷酸盐对TC的降解表现出不同程度的抑制作用;TC通过直接光解、HO·、~1O_2和O_2~(·-)氧化4种途径降解,当TC浓度为10.0 mg·L~(-1),NO_3~-浓度为1.0 mmol·L~(-1),pH为7.0时光照150 min后,不同途径的贡献率分别为60.4%、25.6%、8.9%和5.1%。结果有助于了解TC的环境化学行为,为TC治理提供参考。     

Fe~(2+)/过硫酸钠体系降解盐酸四环素的研究

采用Fe~(2+)/过硫酸钠体系降解水溶液中的盐酸四环素,探讨了盐酸四环素初始浓度、Fe~(2+)浓度、过硫酸钠浓度、温度、pH等因素对降解效果的影响。单因素实验结果表明,盐酸四环素去除率随着盐酸四环素的初始浓度、过硫酸钠浓度、温度的增大而增大;随着Fe~(2+)浓度的增加,盐酸四环素去除率先增大后减小;酸性条件有利于Fe~(2+)/过硫酸钠体系对盐酸四环素的降解。当盐酸四环素初始质量浓度为50mg/L、Fe~(2+)摩尔浓度为0.10mmol/L、过硫酸钠摩尔浓度为2.0mmol/L、反应温度为30℃、pH=3.0时,反应90min后盐酸四环素去除率可达87.6%。Fe~(2+)/过硫酸钠体系对盐酸四环素的降解用一级反应动力学方程进行拟合,得到该反应体系下盐酸四环素降解的活化能为5.173kJ/mol。     

改性碳纤维阴极电Fenton法处理电镀废水中的有机物

采用改性碳纤维(ACF)阴极电Fenton法处理电镀废水中的有机物,研究pH、Fe2+浓度、电流密度和曝气量对电镀废水COD去除率的影响。结果表明,改性ACF电Fenton法对电镀废水COD去除效果明显,在最佳反应条件(pH为3.0,Fe2+初始摩尔浓度为2.0mmol/L,电流密度为3.0mA/cm2,曝气量为0.9L/min)下反应90min,COD去除率为90.7%。     

双频超声辐射协同H_2O_2降解偶氮染料废水的研究

采用双频超声协同H2O2降解酸性绿20染料废水,考察超声功率密度、染料初始浓度和pH、饱和气体及H2O2投加量等因素对酸性绿20降解效果的影响,结果表明,在给定实验条件下,双频降解效果优于单频超声波,且降解率随超声功率密度的增大而增大。酸性条件有利于酸性绿20的降解,当染料废水初始pH=4可取得最佳的降解效果;酸性绿20的降解效率随染料初始浓度的增大而降低,其优化初始浓度为40 mg/L。在反应体系中通入空气并投加H2O2,可取得最佳的降解效果。在优化实验条件下,采用双频超声协同H2O2降解5 h,酸性绿20的色度和TOC去除率分别为94.6%和36.3%;分析降解前后的紫外-可见光谱图可知,酸性绿20并非完全被降解为CO2和H2O,而是生成一些小分子有机中间体。     

New insights into the characterization of the binding of tetracycline analogues with lysozyme: a biophysical study

Tetracycline (TC), chlortetracycline (CTC) and oxytetracycline (OTC) are the most common members of the widely used veterinary drug tetracyclines, the residue of which in the environment can enter human body, being potentially harmful. Lysozyme is a monomeric protein widely distributed in the nature including human beings, having many physiological and pharmaceutical functions. The aim of this study was to examine the interaction of lysozyme with the three tetracyclines (TC, CTC and OTC) through spectroscopic and molecular modeling methods. The experimental results revealed that all the three tetracyclines (TCs) can interact with lysozyme with one binding site to form TCs-lysozyme complex, mainly through electrostatic forces with the affinity order: CTC > TC > OTC. The binding of TCs can cause conformational and some microenvironmental changes of lysozyme. Furthermore, molecular docking was applied to define the specific binding sites, the results of which show that all the three TCs can bind into lysozyme cleft and interact with the key active-site residues Glu 35 or Asp 52, resulting in competitive inhibition of lysozyme activity. The accurate and full basic data in the work is beneficial to clarifying the binding mechanism of TCs with lysozyme in vivo.     

US/UV联用降解荧光增白剂CBW的研究

对超声波、紫外联用技术降解荧光增白剂的反应进行研究，考察了辐射时间、超声功率、pH、H2O2投加量等因素对降解效率的影响。结果表明：荧光增白剂的降解效率受辐射时间影响较大，降解过程符合拟一级反应I提高超声波的功率可提高荧光增白剂的降解率；H2O2的添加，可使溶液中的氢氧自由基的浓度增加，从而提高了荧光增白剂的降解率。在初始浓度为40mg／L，超声功率为500w、pH为9、H2O2的添加量为30mL／L、反应120min的条件下，荧光增白剂的降解率可达95％。     

Dissipation of oxytetracycline, chlortetracycline, tetracycline and doxycycline using HPLC-UV and LC/MS/MS under aquatic semi-field microcosm conditions

A mixture of four tetracyclines; oxytetracycline (OTC), chlortetracycline (CTC), tetracycline (TC), and doxycycline (DC) was applied in fifteen 12000l outdoor microcosms at four treatment levels plus controls each with three replicates (n = 3). The dissipation times of parent compounds were monitored and half-lives (DT50) of 1-4 days, depending on treatment level were recorded. This is in accordance with half-lives from previous findings in bench-top experiments. Parent compound DT50, were determined using HPLC-UV. Furthermore, the samples were analyzed for ten different tetracycline products using LC/MS/MS. Two products were found for chlortetracycline; 4-epi-anh-chlortetracyline and the iso-chlortetracycline. Iso-forms were only found for CTC and only at the highest treatment (300 microg l(-1)). The half-lives, trajectories, and relative amounts of the products were analogous for all four tetracyclines. DT50 for products were less than 1.2 days. Formation of 4-epi-anh-tetracyclines, occurred at neutral to weak alkaline conditions.     

紫外光协助高锰酸钾降解四环素的研究

高锰酸钾氧化法在实际水处理中得到了一定的应用,但对有机污染物的去除和降解能力相对有限,为此提出了以外加紫外光照射协助高锰酸钾氧化的方法。以四环素作为模型污染物,考察了四环素浓度、高锰酸钾浓度、反应时间、初始pH条件和不同紫外光照射等的影响。结果表明,高锰酸钾能够氧化并去除四环素,紫外光照射明显提高了高锰酸钾对四环素的降解效果,并且254 nm紫外光照射对降解的促进作用远大于365 nm紫外光。在所考察的pH范围内,无论紫外光照射与否,高锰酸钾在酸性条件下的降解效率最高,中性条件较高,碱性条件次之。     

Anaerobic digestion of livestock and poultry manures spiked with tetracycline antibiotics

Abstract

We investigated the anaerobic degradation of tetracycline antibiotics (tetracycline [TC], oxytetracycline [OTC] and chlortetracycline [CTC]) in swine, cattle, and poultry manures. The manures were anaerobically digested inside polyvinyl chloride batch reactors for 64?days at room temperature. The degradation rate constants and half-lives of the parent tetracyclines were determined following first-order kinetics. For CTC the fastest degradation rate was observed in swine manure (k?=?0.016?±?0.001 d^?1; half-life = 42.8?days), while the slowest degradation rate was observed in poultry litter (k?=?0.0043?±?0.001 d^?1; half-life = 161?days). The half-lives of OTC ranged between 88.9 (cattle manure) and 99.0?days (poultry litter), while TC persisted the longest of the tetracycline antibiotics studied with half-lives ranging from 92.4?days (cattle manure) to 330?days (swine manure). In general, the tetracyclines were found to degrade faster in cattle manure, which had the lowest concentrations of organic matter and metals as compared to swine and poultry manures. Our results demonstrate that tetracycline antibiotics persist in the animal manure after anaerobic digestion, which can potentially lead to emergence and persistence of antibiotic resistant bacteria in the environment when anaerobic digestion byproducts are land applied for crop production.     

微波强化Fenton/活性炭工艺处理制药废水的影响因素

为了研究微波强化Fenton/活性炭工艺处理高浓度制药废水的影响因素,以阜新某集团公司生产制药原料排出的废水为研究对象,利用静态实验,采用混凝-微波强化Fenton/活性炭工艺对高浓度制药废水进行实验。实验用水为100 mL、COD为576~1 440 mg/L的制药废水,当活性炭投加量为2 g,H2O2投加量为3/4Qth,pH值为5,微波辐照功率和时间分别为500 W和7 min时,COD去除率可达到92.6%,出水COD在42.6~106.6 mg/L范围内。实验结果表明,活性炭的投加量、H2O2的投加量、pH值、微波辐照功率和辐照时间对微波强化Fenton/活性炭工艺的处理效果影响都较显著。     

The influence of light exposure,water quality and vegetation on the removal of sulfonamides and tetracyclines: A laboratory-scale study

The effect of aquatic vegetation (Spyrogira sp. and Zannichellia palustris), light exposure and water quality (secondary-treated wastewater vs. ultrapure water) on the removal efficiency of six antibiotics (sulfonamides and tetracyclines) is studied in laboratory-scale reactors. After 20 d of treatment, 3–59% of sulfonamides were eliminated in the reactors exposed to light. Removal was about 10% in unplanted reactors in darkness. The elimination of tetracycline (TC) and oxytetracycline (OTC) ranged between 83% and 97% in both planted and unplanted reactors. However, in dark unplanted reactors, OTC was largely removed (88%) while only 15% of TC was eliminated. These results suggest that TC was mainly removed by photodegradation whereas biodegradation or hydrolysis process seems to be significant processes for OTC. Sulfonamides were mainly eliminated by biodegradation or indirect photodegradation processes. Pseudo-first order kinetics removal rates ranged from 0.003 and 0.007 d^?1 for Sulfamethazine and TC in the covered control reactors to 0.13 and 0.21 d^?1 for TC and OTC in the uncovered control reactors, with half-lives from 3 to 350 d. A TC photodegradation product was tentatively identified in uncovered reactors. This study highlights the important role played by light exposure in the elimination of antibiotics in polishing ponds.     

阴极液及底物浓度对AFB-MFC同步废水处理及产电性能影响

为了提高厌氧流化床微生物燃料电池（AFB-MFC）的性能,并为双室MFC寻找价廉、易得、无污染的阴极液,在曝气量16～24 L/h、温度（35±2）℃、回流量10.2 L/h、阴极底边距阴极室内底部17.3 cm、外电阻250 Ω、水力停留时间（HRT）14.0～14.9 h以及进水pH 7.81～8.37下,研究了阴极液及底物浓度对系统产电及废水处理性能的影响。结果表明,使用缓冲溶液、阳极室出水和自来水作阴极液时,自来水的产电性能最佳,阴极液种类不影响系统有机基质的去除。以自来水为阴极液时,阴极液pH及电导率随运行时间增加而增加,COD去除率为80.11%～89.29%,输出电压及功率密度开始随运行时间增加而增加,之后稳定在440～452 mV和48.40～51.08 mW/m²之间。增加底物浓度对COD去除率影响不大,而输出电压及功率密度随底物浓度增加而下降;底物COD浓度由3 307.09 mg/L增至9 520 mg/L时,COD去除率在85.77%～94.44%之间,输出电压及功率密度则分别由449 mV和50.40 mW/m²下降至406 mV和41.21 mW/m²。自来水作阴极液可避免二次污染及阴极液对阳极室微生物的影响,并得到高的产电能力。     

Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO₂ at mild conditions (pH 4-9 and 22 °C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg²⁺ or Ca²⁺. Experimental results of TTC indicate that MnO₂ promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO₂ generate little iso-OTC, but occur mainly at the A ring’s dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO₂, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines.