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1.
李阳  许玻珲  邓琳  罗伟 《环境科学》2022,43(9):4597-4607
以抗新型冠状肺炎药物——磷酸氯喹(CQP)为研究对象,考察其在紫外活化过硫酸盐体系(UV/PS)中的降解效果.通过竞争动力学实验,确定了CQP与羟基自由基(HO·)和硫酸根自由基(SO4-·)的二级反应速率常数,同时考察了PS浓度、pH和常见无机阴离子对UV/PS体系中CQP降解的影响,并通过建立动力学模型预测CQP浓度和主要自由基浓度以探究其影响机制.结果表明,UV/PS体系对CQP的降解效果显著优于单一UV、单一太阳光或单一PS体系,在10 min内可降解91.3%的CQP;在pH为6.9的条件下,CQP与HO·和SO4-·的二级反应速率常数分别为8.9×109 L·(mol·s)-1和1.4×1010 L·(mol·s)-1,其中SO4-·是主要活性物种;CQP的降解速率随PS浓度增加而增大,HCO3-和Cl-的加入对UV/PS体系中CQP的去除起到抑制作用,碱性较强的条件不利于CQP的转化.经LC-MS分析,发现CQP在UV/PS体系中主要经过N-脱乙基化、C—N键断裂和抽氢等反应被逐步降解为其他有机中间产物.加大PS浓度和pH可提高其矿化率.此研究可为抗新冠肺炎医药废水的处理提供帮助.  相似文献   

2.
党璞  赵亚娟  谢会东  王康康  赵儒霞 《环境科学》2023,44(10):5587-5598
采用水热法成功合成了CuNiFe LDHs/BiO2-x复合光催化剂,并在可见光照射下用于活化过硫酸盐(PMS)降解环丙沙星(CIP).由于光催化和PMS活化的协同作用,CIP的去除率高达88.3%.利用XRD、FT-IR、SEM、XPS和UV-Vis DRS等方法对制备的光催化剂进行了表征.确定了CuNiFe LDHs的最佳负载量,并考察了PMS用量、初始pH值和无机阴离子(Cl-、CO32-和NO3-)对降解的影响.电子顺磁共振和自由基捕获实验表明·OH和h+是CIP降解的主要活性物种,并提出了该体系可能的降解机制.  相似文献   

3.
李鑫  尹华  罗昊昱  欧阳晓芳  刘航  祝铭韩 《环境科学》2021,42(10):4798-4806
环境中的多溴联苯醚(PBDEs)对人类健康和生态环境存在潜在危害,开发高效、经济和环保的高级氧化体系对其进行有效降解具有重要意义.利用水热法合成的磁性生物炭负载二氧化锰复合材料(α-MnO2/MWB)作为催化剂,有效活化过一硫酸盐(PMS)降解2,2'',4,4''-四溴联苯醚(BDE-47),通过SEM、XRD、FT-IR和BET等手段对材料进行表征分析,同时探究了材料对PMS的催化活化能力.结果表明,α-MnO2/MWB具有最佳的催化性能,在α-MnO2/MWB负载质量比为1:2、催化剂投加量为0.05 g·L-1、PMS浓度为5 mmol·L-1的条件下,对1 mg·L-1 BDE-47的降解率达到94%.溶液初始pH对体系的影响较小,氯离子(Cl-)和腐殖酸(HA)对BDE-47的降解有抑制作用,随其浓度升高抑制作用增强,硝酸根离子(NO3-)和碳酸氢根离子(HCO3-)对降解几乎无影响.通过自由基淬灭实验证明SO4-·和·OH是该体系降解BDE-47的两种关键自由基,其中SO4-·占主导地位.反应前后材料的XPS表征分析表明,Mn和Fe元素的价态转化是活化PMS的主要原因.α-MnO2/MWB经重复利用4次,仍保持着高效的催化性能.  相似文献   

4.
通过搭建超声复合铁碳活化过硫酸盐耦合系统(US/PS/Fe-C),用于处理三苯甲烷衍生物结晶紫(CV).结果表明US/PS/Fe-C三元体系具有良好的耦合效果.对商品铁碳和自制的不同工艺铁碳活化剂,分别采用X-射线衍射仪和扫描电子显微镜对活化剂的结构和表面形貌进行分析.使用商品铁碳作为活化剂研究不同因素对US/PS/Fe-C三元耦合体系降解CV的影响,其最优条件为:PDS浓度2 mmol ·L-1,铁碳活化剂1 g ·L-1,pH未调,30 min后对质量浓度为15 mg ·L-1CV的去除率达90%.探究阴阳离子对于体系的影响,发现Mg2+和NO3-对体系处理几乎没有影响,Mn2+、Cl-和CO32-对于体系的处理有一定的抑制作用,Fe2+在低浓度时可以促进反应,在高浓度时会抑制反应.通过加入不同的淬灭剂,得出在该体系中主要含有1O2、SO4- ·、·O2-和·OH这4种活性物质.  相似文献   

5.
Fe2+可激活过二硫酸盐(PDS)快速产生硫酸根自由基(SO4-·),但Fe2+会快速转化为低活性的Fe3+,且Fe2+的投加量普遍较大,限制了该体系的广泛应用.采用亚硫酸氢盐(BS)强化微量Fe2+-PDS体系降解水中的扑热息痛(APAP).结果表明,投加BS可促进Fe2+-Fe3+的循环,明显改善Fe2+-PDS体系对APAP的降解效果,在最优条件下(PDS=0.6 mmol·L-1;BS=0.4 mmol·L-1;Fe2+=10 μmol·L-1;pH=4)下,APAP (4 μmol·L-1)可在180 s内被完全降解.同时,APAP的降解速率随BS (0~0.6 mmol·L-1)和PDS (0.2~1.5 mmol·L-1)浓度的增大而升高,适量提高Fe2+浓度可促进APAP的降解,但增加BS的投加次数对降解速率影响不大.HCO3-与HPO42-明显抑制了体系降解APAP的效率,Cl-和NO3-有轻微抑制作用,腐殖酸(HA)则影响不大.通过淬灭实验和电子顺磁共振波谱检测,证实了体系中SO4-·、·OH和单线态氧的产生,其中SO4-·是降解APAP的主要活性物种.利用三维荧光光谱技术对APAP降解过程进行了表征,表明APAP降解产物具有荧光特性.此外,还鉴定出5种中间产物,并提出了3种可能的降解途径.体系在实际水体中的效能低于超纯水中的表现,但延长反应时间可明显增强降解效果,表明BS-Fe2+-PDS体系是一种有前景的有机污染物降解方法.  相似文献   

6.
分别以Zn(CH3COO)2·2H2O、Mn(CH3COO)3·2H2O和Co(CH3COO)2·4H2O为锌源、锰源和钴源,采用溶胶-凝胶自燃烧法成功制备了ZnMnxCo2-xO4x=0~2)复合物,并用X射线衍射和X射线光电子能谱对其进行表征.同时,还研究了Mn/Co物质的量比、催化剂用量及PMS用量对目标污染物降解的影响.结果表明,该复合物可催化活化过一硫酸钾(PMS)降解有机污染物,当催化剂中x=0.8,催化剂投加量为0.2 g·L-1,PMS用量为0.4 mmol·L-1(0.25 g·L-1)时,20 μmol·L-1(10 mg·L-1)罗丹明B(RhB)可在15 min内完全降解.ZnMn0.8Co1.2O4的高催化活性主要归功于Mn3+和Co2+的协同效应.将ZnMnxCo2-xO4-PMS体系用于亚甲基蓝、结晶紫、金橙、双酚A、4-氯酚等其他污染物的降解,也取得了较好的效果.基于电子自旋共振ESR和自由基猝灭实验的结果,可以推测该反应体系中活性物种为硫酸根自由基和羟基自由基.  相似文献   

7.
以脱水干化污泥为原料,经450℃热解制成污泥生物炭(BC),活化过一硫酸盐(PMS),构建BC/PMS体系,降解环丙沙星(CIP).采用扫描电子显微镜(SEM)、X射线能谱(EDS)、傅里叶变换红外吸收光谱(FTIR)、X射线衍射(XRD)、Zeta电位分析仪和电子自旋共振(EPR)分析了BC的理化性质;考察了BC投加量、PMS投加量、初始pH值和无机阴离子对BC/PMS体系降解CIP效果的影响;通过自由基淬灭实验和X射线光电子能谱(XPS)分析,深入探讨了BC/PMS体系对CIP降解机制.结果表明,CIP降解率随BC投加量和PMS投加量增大而升高,随溶液初始pH增大而降低,在BC 1.0 g·L-1、PMS 3.0 mmol·L-1、初始pH 6.0、CIP 20 mg·L-1和反应时间120 min时,CIP降解率为49.09%;SO42-和NO3-对BC/PMS体系降解效果无显著影响,HCO3-和Cl-具有明显抑制作用;BC/PMS体系降解CIP是自由基途径(·OH和SO4-·)和非自由基途径(1O2)共同作用的结果,降解路径主要包括哌嗪环开环和羟基化反应.  相似文献   

8.
通过简易的高温煅烧和共沉淀方法成功制备出pg-C3N4/BiOBr/Ag复合材料,通过XRD、SEM、TEM、XPS、UV-Vis、BET和光电流等检测手段对其进行表征,并探究了该复合材料在模拟可见光照射下对10 mg·L-1磺胺甲唑的降解效果.结果表明,当银单质的负载比例为5%时,pg-C3N4/BiOBr/Ag复合材料对磺胺甲唑的降解效果最佳.与pg-C3N4、BiOBr单体和二元复合材料pg-C3N4/BiOBr相比,pg-C3N4/BiOBr/Ag(5%)光催化降解磺胺甲唑的效果显著提升,在30 min内降解率几乎接近100%,反应速率常数(0.2101 min-1)是pg-C3N4/BiOBr的13.15倍.通过自由基猝灭实验,证明在光催化降解过程中,起主要作用的活性物质是空穴(h+)、超氧自由基(·O2-)和单线态氧(1O2),其中,超氧自由基(·O2-)贡献最大.对pg-C3N4/BiOBr/Ag进行多次循环实验,证明合成的材料具有良好的循环稳定性能,应用前景良好.  相似文献   

9.
林涛  苑宇杰 《环境科学》2024,45(3):1553-1560
研究了紫外光活化亚硫酸盐高级氧化工艺降解水中典型新污染物——卡马西平(CBZ)的效能和降解机制.探究了不同溶解氧浓度[ρ(DO)]对紫外光活化亚硫酸盐降解CBZ的影响,并在模拟自然水体环境控制初始ρ(DO)为(8.0±0.2) mg·L-1条件下,考察了不同工艺参数(亚硫酸盐投加量、反应pH)与水环境要素(碳酸氢根离子、氯离子、腐殖酸)对CBZ降解效能的影响.结果表明,紫外光活化亚硫酸盐工艺可在30 min内降解85.3%的CBZ,降解过程遵循拟一级动力学,动力学常数为0.055 7 min-1.并采用电子顺磁共振波谱技术、活性物质淬灭实验和竞争反应动力学实验发现,CBZ的降解主要来自紫外光活化亚硫酸盐工艺中硫酸根自由基(SO4-·)与羟基自由基(·OH)等活性物质,且降解贡献率分别为43.9%和56.1%.而且CBZ降解率随HCO3-浓度升高而降低,但Cl-浓度变化对CBZ降解率影响不大,水中存在的腐殖酸可显著抑制CBZ的降解.反应过程中硫酸盐的积累量显著低于《生活饮用水卫生标准》(GB 5749-2022)限值,且亚硫酸盐消耗速率(0.004 4 min-1)显著低于CBZ的降解速率,说明亚硫酸盐可被紫外光高效活化用于降解水中存在的CBZ.  相似文献   

10.
基于硫酸根自由基(SO4·-)的高级氧化技术被广泛应用于土壤和地下水污染修复.本研究系统地考察了三氯生在热活化过硫酸盐高级氧化过程中的动力学、中间产物和降解途径.结果表明,提高反应温度或增加过硫酸盐的浓度,可加快三氯生的降解.三氯生的降解符合假一级反应动力学规律,反应活化能(Ea)为142 kJ·mol-1.水中的腐殖酸显著抑制了三氯生的降解,而氯离子(Cl-)对三氯生降解的影响比较复杂.当Cl-浓度为5 μmol·L-1时,三氯生的降解受到了轻微的促进;但是当Cl-的浓度增加至10 μmol·L-1甚至更高时,三氯生的降解反而受到了抑制.通过质谱分析发现三氯生降解过程中生成了4-氯-邻苯二酚、2,4-二氯苯酚和2-氯-5-(2,4-二氯-6-羟基苯氧基)-1,4-苯醌等6种主要中间产物,并由此推测醚键的断裂和酚环羟基化是三氯生的可能降解途径.本研究为基于SO4·-的高级氧化技术去除水中三氯生的应用可行性提供了依据.  相似文献   

11.
Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis (DGGE) and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity (both in gene richness and diversity index values) and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor (50 mg/kg) recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos (150 mg/kg) caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos (250 mg/kg) produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes (bands) responded differently to the impact of agrochemicals: four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.  相似文献   

12.
The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.  相似文献   

13.
Several main metabolites of benzo[a]pyrene (BaP) formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone (BP 1,6- quinone), trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene (BP 7,8-diol), 3-hydroxybenzo[a]pyrene (3-OHBP), were identified by high-performance liquid chromatography (HPLC). The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that (1) the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; (2) the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; (3) the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% (w/v), concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.  相似文献   

14.
Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.  相似文献   

15.
In this study an effort has been made to use plant polyphenol oxidases; potato (Solanum tuberosum) and brinjal (Solanum melongena), for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.  相似文献   

16.
The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.  相似文献   

17.
A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p < 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.  相似文献   

18.
RemovalofheavymetalsfromsewagesludgebylowcostingchemicalmethodandrecyclinginagricultureWuQitang,NyirandegePascasie,MoCehuiF...  相似文献   

19.
A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several (halo)aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no (chloro)catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.  相似文献   

20.
Single and joint effects of pesticides and mercury on soil urease   总被引:3,自引:3,他引:3  
The influence of two pesticides including chlorimuron-ethyl and furadan and mercury (Hg) on urease activity in 4 soils (meadow burozem and phaeozem) was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase (up to 13%-21%) in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship (P〈0.05) between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose (ED50) values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.  相似文献   

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