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1.
Chlorine dioxide (ClO2), an alternative disinfectant to chlorine, has a superior ability to inactivate microorganisms, in which protein damage has been considered as the main inactivation mechanism. However, the reactivity of ClO2 with amino acid residues in oligopeptides and proteins remains poorly investigated. In this research, we studied the reaction rate constants of ClO2 with tryptophan residues in five heptapeptides and four proteins using stopped-flow or competition kinetic method. Each heptapeptide and protein contain only one tryptophan residue and the reactivity of tryptophan residue with ClO2 was lower than that of free tryptophan (3.88 × 104 (mol/L)?1sec?1 at pH 7.0). The neighboring amino acid residues affected the reaction rates through promoting inter-peptide aggregation, changing electron density, shifting pKa values or inducing electron transfer via redox reactions. A single amino acid residue difference in oligopeptides can make the reaction rate constants differ by over 60% (e.g. 3.01 × 104 (mol/L)?1sec?1 for DDDWNDD and 1.85 × 104 (mol/L)?1sec?1 for DDDWDDD at pH 7.0 (D: aspartic acid, W: tryptophan, N: asparagine)). The reaction rates of tryptophan-containing oligopeptides were also highly pH-dependent with higher reactivity for deprotonated tryptophan than the neutral specie. Tryptophan residues in proteins spanned a 4-fold range reactivity toward ClO2 (i.e. 0.84 × 104 (mol/L)?1sec?1 for ribonuclease T1 and 3.21 × 104 (mol/L)?1sec?1 for melittin at pH 7.0) with accessibility to the oxidant as the determinating factor. The local environment surrounding the tryptophan residue in proteins can also accelerate the reaction rates by increasing the electron density of the indole ring of tryptophan or inhibit the reaction rates by inducing electron transfer reactions. The results are of significance in advancing understanding of ClO2 oxidative reactions with proteins and microbial inactivation mechanisms.  相似文献   

2.
Low-density polyethylene (LDPE) has been widely used as a sorbent for passive sampling of hydrophobic organic contaminants (HOCs) in aquatic environments. However, it has seen only limited application in passive sampling for measurement of freely dissolved concentrations of parent and substituted PAHs (SPAHs), which are known to be toxic, mutagenic and carcinogenic. Here, the 16 priority PAHs and some typical PAHs were selected as target compounds and were simultaneously determined by gas chromatography–mass spectrometer (GC–MS). Some batch experiments were conducted in the laboratory to explore the adsorption kinetics of the target compounds in LDPE membranes. The results showed that both PAHs and SPAHs could reach equilibrium status within 19–38?days in sorption kinetic experiments. The coefficients of partitioning between LDPE film (50?μm thickness) and water (KLDPE) for the 16 priority PAHs were in good agreement with previously reported values, and the values of KLDPE for the 9 SPAHs are reported in this study for the first time. Significant linear relationships were observed, i.e., log KLDPE?=?0.705?×?log KOW?+?1.534 for PAHs (R2?=?0.8361, p?<?0.001) and log KLDPE?=?0.458?×?log KOW?+?3.092 for SPAHs (R2?=?0.5609, p?=?0.0077). The selected LDPE film was also proven to meet the condition of “zero sink” for the selected target compounds. These results could provide basic support for the configuration and in situ application of passive samplers.  相似文献   

3.
As an active metabolite of venlafaxine and emerging antidepressant, O-desmethylvenlafaxine (ODVEN) was widely detected in different water bodies, which caused potential harm to human health and environmental safety. In this study, the comparative work on the ODVEN degradation by UV (254 nm) and UV-LED (275 nm) activated sodium percarbonate (SPC) systems was systematically performed. The higher removal rate of ODVEN can be achieved under UV-LED direct photolysis (14.99%) than UV direct photolysis (4.57%) due to the higher values of photolysis coefficient at the wavelength 275 nm. Significant synergistic effects were observed in the UV/SPC (80.38%) and UV-LED/SPC (53.57%) systems and the former exhibited better performance for the elimination of ODVEN. The degradation of ODVEN all followed the pseudo-first-order kinetics well in these processes, and the pseudo-first-order rate constant (kobs) increased with increasing SPC concentration. Radicals quenching experiments demonstrated that both ·OH and CO3· were involved in the degradation of ODVEN and the second-order rate constant of ODVEN with CO3· (1.58 × 108 (mol/L)−1 sec−1) was reported for the first time based on competitive kinetic method. The introduction of HA, Cl, NO3 and HCO3 inhibited the ODVEN degradation to varying degrees in the both processes. According to quantum chemical calculation, radical addition at the ortho-position of the phenolic hydroxyl group was confirmed to be the main reaction pathways for the oxidation of ODVEN by ·OH. In addition, the oxidation of ODVEN may involve the demethylation, H-abstraction, OH-addition and C-N bond cleavage. Eventually, the UV-LED/SPC process was considered to be more cost-effective compared to the UV/SPC process, although the UV/SPC process possessed a higher removal rate of ODVEN.  相似文献   

4.
In this study, carbamazepine (CBZ) decay in solution has been studied by coupling electrocoagulation with electro-Fenton (EC-EF) with a novel P-rGO/carbon felt (CF) cathode, aiming to accelerate the in-situ generation of •OH, instead of adding Fe2+ and H2O2. Firstly, the fabricated P-rGO and its derived cathode were characterized by XRD, SEM, AFM, XPS and electrochemical test (EIS, CV and LSV). Secondly, it was confirmed that the performance in removal efficiency and electric energy consumption (EEC) by EC-EF (kobs=0.124 min−1, EEC=43.98 kWh/kg CBZ) was better than EF (kobs=0.069 min−1, EEC=61.04 kWh/kg CBZ). Then, P-rGO/CF (kobs=0.248 min−1, EEC=29.47 kWh/kg CBZ, CE=61.04%) showed the best performance in EC-EF, among all studied heteroatom-doped graphene/CF. This superior performance may be associated with its largest layer spacing and richest C=C, which can promote the electron transfer rate and conductivity of the cathode. Thus, more H2O2 and •OH could be produced to degrade CBZ, and almost 100% CBZ was removed with kobs being 0.337 min−1 and the EEC was only 24.18 kWh/kg CBZ, under the optimal conditions (P-rGO loading was 6.0 mg/cm2, the current density was 10.0 mA/cm2, the gap between electrode was 2.0 cm). Additionally, no matter the influent is acidic, neutral or alkaline, no additional pH adjustment is required for the effluent of EC-EF. At last, an inconsecutive empirical kinetic model was firstly established to predict the effect of operating parameters on CBZ removal.  相似文献   

5.
Herein, Na+ and Ca2+ are introduced to MnO2 through cation-exchange method. The presence of Na+ and Ca2+ significantly enhance the catalytic activity of MnO2 in toluene oxidation. Among them, the Ca-MnO2 catalyst exhibits the best catalytic activity (T50 = 194°C, T90 = 215°C, Ea = 57.2 kJ/mol, reaction rate 8.40 × 10?10 mol/(sec?m2) at 210°C. T50 and T90: the temperature of 50% and 90% toluene conversion; Ea: apparent activation energy) and possess high tolerance against 2.0 vol.% water vapor. Results reveal that the increased acidic sites of the MnO2 sample can enhance the adsorption of gaseous toluene, and the mobility of oxygen species and the content of reactive oxygen species in the catalyst are significantly improved due to the formed oxygen vacancy. Thus these two factors result in excellent catalytic performance for toluene oxidation combining with the weak CO2 adsorption ability.  相似文献   

6.
Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H2O2 oxidation process. The removal rate of TCEP in the UV/H2O2 system was 89.1% with the production of Cl? and PO43? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H2O2 system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min?1 (R2=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H2O and the oxidation reaction with H2O2 were found during the degradation pathway of 5 mg/L TCEP in the UV/H2O2 system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H2O2 system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.  相似文献   

7.
The preparation of highly active supported noble metal catalysts with a low noble metal loading has always been the ultimate goal of researchers working on catalysis. Hydrothermally treated Pt/Al2O3 (Pt/Al2O3-H) exhibits better catalytic activity than that (Pt/Al2O3-C) treated via the conventional calcination approach. At the high space velocity of 100,000 mL/(g∙hr), the temperature that correspond to 50% toluene conversion (T50) of Pt/Al2O3-H is 115°C lower than that of Pt/Al2O3-C, and the turnover frequency (TOF) value can reach 0.0756 sec−1. The mechanism by which the hydrothermal approach enhances Pt/Al2O3 activity has been investigated. The structure associated with the high catalytic activity of Pt nanoparticles (NPs) can be retained via hydrothermal treatment. Furthermore, the support is transformed to AlO(OH) with numerous surface hydroxyl groups, which in turn can facilitate the adsorption of toluene. And the synergistic effects of Pt NPs and AlO(OH) increases the contents of Pt in oxidation state and active oxygen, which are beneficial for toluene oxidation.  相似文献   

8.
Phosphine (PH3) is an important factor driving the outbreak of cyanobacterial blooms that produce toxic microcystin threating human health. To clarify the physiological and biochemical responses of cyanobacteria to PH3 under elevated CO2 concentration, Microcystis aeruginosa was used in the coupling treatment of 1000 ppmv CO2 and PH3 at different concentrations respectively. The chlorophyll a (Chl-a), carotenoid, net photosynthetic rate and total protein of M. aeruginosa exhibited evidently increasing tendency under the coupling treatment of 1000 ppmv CO2 and PH3 at different concentrations (7.51 × 10?3, 2.48 × 10?2, 7.51 × 10?2 mg/L). The coupling treatments resulted in the higher concentrations of Chl-a and carotenoid of M. aeruginosa, compared to those in the control and the treatment with CO2 alone, and their enhancement increased with the increase in PH3 concentrations. The total antioxidant capacity (T-AOC) in the coupling treatment with CO2 and PH3 of 2.48 × 10?2 mg/L and 7.51 × 10?3 mg/L showed increasing tendency, compared to the treatment with PH3 alone. Additionally, the coupling treatment with 1000 ppmv CO2 and PH3 also altered the pH and DO level in the culture medium. In this regard, the coupling treatment with CO2 and PH3 at an appropriate concentration can enhance the resistance of M. aeruginosa to PH3 toxicity and is beneficial to the reproduction of M. aeruginosa, presumably resulting in potential for the outbreak of cyanobacteria bloom. Given the concern about global warming and the increase in atmospheric CO2 level, our research laid a foundation for the scientific understanding of the correlation between PH3 and cyanobacteria blooms.  相似文献   

9.
Nitrate (NO3?) is known to be actively involved in the processes of mineralization and heavy metal transformation; however, it is unclear whether and how it affects the bioavailability of antimony (Sb) in paddy soils and subsequent Sb accumulation in rice. Here, the effects of NO3? on Sb transformation in soil-rice system were investigated with pot experiments over the entire growth period. Results demonstrated that NO3? reduced Sb accumulation in brown rice by 15.6% compared to that in the control. After amendment with NO3?, the Sb content in rice plants increased initially and then gradually decreased (in roots by 46.1%). During the first 15 days, the soil pH increased, the oxidation of Sb(III) and sulfides was promoted, but the reduction of iron oxide minerals was inhibited, resulting in the release of adsorbed and organic-bound Sb from soil. The microbial arsenite-oxidizing marker gene aoxB played an important role in Sb(III) oxidation. From days 15 to 45, after NO3? was partially consumed, the soil pH decreased, and the reductive dissolution of Fe(III)-bearing minerals was enhanced; consequently, iron oxide-bound Sb was transformed into adsorbed and dissolved Sb species. After day 45, NO3? was completely reduced, Sb(V) was evidently reduced to Sb(III), and green rust was generated gradually. Thus, the available Sb decreased due to its enhanced affinity for iron oxides. Moreover, NO3? inhibited the reductive dissolution of iron minerals, which ultimately caused low Sb availability. Therefore, NO3? can chemically and biologically reduce the Sb availability in paddy soils and alleviate Sb accumulation in rice. This study provides a potential strategy for decreasing Sb accumulation in rice in the Sb-contaminated sites.  相似文献   

10.
Atmospheric visibility can directly reflect the air quality. In this study, we measured water-soluble ions (WSIs), organic and element carbon (OC and EC) in PM2.5 from September 2017 to August 2018 in Urumqi, NW China. The results show that SO42?, NO3? and NH4+ were the major WSIs, together accounting for 7.32%–84.12% of PM2.5 mass. Total carbon (TC=OC+EC) accounted for 12.12% of PM2.5 mass on average. And OC/EC > 2 indicated the formation of secondary organic carbon (SOC). The levels of SO42?, NO3? and NH4+ in low visibility days were much higher than those in high visibility days. Relative humidity (RH) played a key role in affecting visibility. The extinction coefficient (bext) that estimated via Koschmieder formula with visibility was the highest in winter (1441.05 ± 739.95 Mm?1), and the lowest in summer (128.58 ± 58.00 Mm?1). The bext that estimated via IMPROVE formula with PM2.5 chemical component was mainly contributed by (NH4)2SO4 and NH4NO3. The bext values calculated by both approaches presented a good correlation with each other (R2 = 0.87). Multiple linear regression (MLR) method was further employed to reconstruct the empirical regression model of visibility as a function of PM2.5 chemical components, NO2 and RH. The results of source apportionment by Positive Matrix Factorization (PMF) model showed that residential coal combustion and vehicle emissions were the major sources of bext.  相似文献   

11.
Ru(Ⅲ) was employed as catalyst for aniline oxidation by permanganate at environmentally relevant pH for the first time. Ru(Ⅲ) could significantly improve the oxidation rate of aniline by 5-24 times with its concentration increasing from 2.5 to 15 μmol/L. The reaction of Ru(Ⅲ) catalyzed permanganate oxidation of aniline was first-order with respect to aniline, permanganate and Ru(Ⅲ), respectively. Thus the oxidation kinetics can be described by a third-order rate law. Aniline degradation by Ru(Ⅲ) catalyzed permanganate oxidation was markedly influenced by pH, and the second-order rate constant (ktapp) decreased from 643.20 to 2.67 (mol/L)^-1 sec^-1 with increasing pH from 4.0 to 9.0, which was possibly due to the decrease of permanganate oxidation potential with increasing pH. In both the uncatalytic and catalytic permanganate oxidation, six byproducts of aniline were identified in UPLC-MS/MS analysis. Ru(Ⅲ), as an electron shuttle, was oxidized by permanganate to Ru(Ⅵ) and Ru(Ⅶ), which acted the co-oxidants for decomposition of aniline. Although Ru(Ⅲ) could catalyze permanganate oxidation of aniline effectively, dosing homogeneous Ru(Ⅲ) into water would lead to a second pollution. Therefore, efforts would be made to investigate the catalytic performance of supported Ru(Ⅲ) toward permanganate oxidation in our future study.  相似文献   

12.
As a green oxidant, permanganate has received considerable attention for the removal of micropollutants in drinking water treatment. To provide a better understanding of the oxidation of organic micropollutants with permanganate, the oxidation kinetics of 32 micropollutants were compiled. The pollutants include algal toxins, endocrine disrupting chemicals (EDCs), and pharmaceuticals. The oxidation kinetics of micropollutants by permanganate were found to be first order with respect to both contaminant and permanganate concentrations from which second-order rate constants (k″) were obtained. Permanganate oxidized the heterocyclic aromatics with vinyl moiety (i.e., microcystins, carbamazepine, and dichlorvos) by the addition of double bonds. For the polycyclic aromatic hydrocarbons (PAHs) with alkyl groups, permanganate attacked the benzylic C-H through abstraction of hydrogen. The mechanism for the oxidation of phenolic EDCs by permanganate was a single electron transfer and aromatic ring cleavage. The presence of background matrices could enhance the oxidation of some phenolic EDCs by permanganate, including phenol, chlorinated phenols, bisphenol A, and trichlosan. The toxicity of dichlorvos solution increased after permanganate oxidation, and the estrogenic activity of bisphnol A/estrone increased significantly at the beginning of permanganate oxidation. Therefore, the toxicity of degradation products or intermediates should be determined in the permanganate oxidation processes to better evaluate the applicability of permanganate. The influence of background ions on the permanganate oxidation process is far from clear and should be elucidated in the future studies to better predict the performance of permanganate oxidation of micropollutants. Moreover, methods should be employed to catalyze the permanganate oxidation process to achieve better removal of micropollutants.  相似文献   

13.
纳米金/碳纳米管修饰石墨电极测定邻苯二酚   总被引:1,自引:0,他引:1       下载免费PDF全文
采用自沉积方法将HAuCl4直接还原成纳米金颗粒并修饰在碳纳米管表面,所制备的纳米金(Au-CNTs/C)修饰电极对邻苯二酚(CAT)具有高的电催化氧化作用.采用循环伏安法考察CAT在Au-CNTs/C电极上的电化学行为,发现CAT在该修饰电极上发生可逆的氧化还原反应,在0.25V有明显的氧化峰.在磷酸盐缓冲溶液PBS(pH7.4)中,CAT的响应电流与浓度在5.0×10-7~5.0×10-3mol/L范围内呈线性关系,相关系数为0.9992,检出限为3.3×10-7mol/L.  相似文献   

14.
MnO_2催化KMnO_4氧化降解酚类化合物   总被引:2,自引:1,他引:1  
庞素艳  江进  马军  欧阳峰 《环境科学》2010,31(10):2331-2335
研究了MnO2强化KMnO4氧化降解酚类化合物的效能与机制.在假一级动力学实验条件下(KMnO4初始浓度是目标有机物初始浓度的10倍),考察了KMnO4对酚类化合物(2-氯酚和4-氯酚)的氧化降解规律.发现在KMnO4氧化降解酚类化合物过程中存在着明显的自催化现象,即原位产生的胶体MnO2可以促进KMnO4对有机物的氧化降解.实验进一步考察了MnO2浓度、粒径大小和溶液pH对MnO2催化KMnO4氧化降解酚类化合物的影响.结果表明,外加胶体MnO2和颗粒MnO2都可以催化KMnO4氧化降解酚类化合物,而且假一级动力学常数(K)随着MnO2浓度(30~180μmol·L-1)的增加呈线性增加;与胶体MnO2相比,颗粒MnO2的催化能力较弱;随着溶液pH的增加,MnO2催化能力逐渐减弱.实验中还发现外加MnO2能够催化KMnO4氧化降解2-硝基酚(单独MnO2和KMnO4均不能将其氧化),但对于二甲基亚砜(其不具有与金属离子络合配位的能力)则没有催化作用.由此推测MnO2催化KMnO4氧化降解有机物的作用机制可能为表面吸附络合催化,即吸附在MnO2表面形成的络合物比存在于溶液中的有机物本身更易被KMnO4氧化.  相似文献   

15.
文章将纳米金与钴氢氧化物膜的催化作用有效结合,制备了GNPs/CoOOH复合修饰电极,该修饰电极在碱性条件下对邻苯二酚和对苯二酚具有较强的电催化活性。考察了支持电解质酸度及纳米金沉积时间对邻苯二酚和对苯二酚电化学响应的影响,选取0.1 mol/L PBS(pH 10.0)作为支持电解质,纳米金的最佳沉积时间为4 min。在优化的实验条件下,利用差示脉冲伏安法(DPV)对邻苯二酚和对苯二酚进行选择性检测:当两者浓度同时改变时,对苯二酚和邻苯二酚的氧化峰电流与其浓度分别在7~100μmol/L和6~100μmol/L范围内呈良好的线性关系,对应的检出限分别为0.9、0.8μmol/L(S/N=3)。该复合修饰电极具有较好的重现性、稳定性及较强的抗干扰能力。  相似文献   

16.
本文报导用导数示波极谱法直接测定农药中微量三氯乙醛的方法。实验结果表明,三氯乙醛在0.010mol/L NH_4Cl、5.00×10~(-4)mol/L EDTA和2.00×10~(-6)mol/L四乙基溴化铵组成的底液中,于滴汞电极上产生灵敏的峰电流。峰电位为-1.55V(Vs·S·C·E·)。检测下限为3.00×10~(-7)mol/L;浓度在3.00×10~(-7)~1.00×10~(-3)mol/L范围内与峰电流呈良好的线性关系。  相似文献   

17.
选用高锰酸钾为氧化剂从动力学的角度研究高锰酸钾初始浓度,pH值和温度对沙拉沙星氧化反应速率的影响,并比较高锰酸钾氧化其他氟喹诺酮类药物(恩诺沙星,氧氟沙星,环丙沙星,诺氟沙星)的动力学参数,旨在为沙拉沙星污染治理提供科学依据和建议.研究得出:氧化过程符合二级反应动力学规律,随着高锰酸钾浓度和环境温度的升高,反应速率增加;相对于中性条件和碱性条件[K=30~47L/(mol·min)],酸性条件(pH=4~5)下其反应速率[K=66~91.28L/(mol·min)]要明显更快.高锰酸钾氧化沙拉沙星的动力学参数与环丙沙星的类似,在相关研究中可以适当参考环丙沙星的处理参数.  相似文献   

18.
文章以金属钴为基体,在其表面形成对磷酸二氢盐有良好电化学响应的氧化钴敏感膜,成功的制备了磷酸盐离子选择性电极。详细讨论了不同活化时间和不同活化溶液对磷酸盐检测的线性响应范围、响应斜率及检测限的影响。实验结果表明:该基于钴的磷酸盐离子选择性电极在0.025 mol/L邻苯二甲酸氢钾的底液中,对磷酸二氢盐在10-4~10-1mol/L浓度范围内呈线性响应,其响应斜率为-48.27 mV/dec,检测限为2.27×10-5mol/L,相关系数R2为0.99。该电极具有良好的稳定性和重现性。已成功用于实际自来水样中磷酸二氢盐的检测,结果满意。  相似文献   

19.
不同氧化剂降低膜污染效果的研究   总被引:1,自引:0,他引:1       下载免费PDF全文
采用不同的氧化剂预处理黄浦江原水后进行微滤膜(MF)膜过滤试验,考察预氧化对有机物的去除作用,及其对MF膜过滤特性的影响.结果表明,3种不同氧化剂对有机物的去除效果存在较大差别.臭氧投量在0.5~3.0mg/L范围内,臭氧对DOC和UV254的去除率最高分别为10%和71%;而氯和高锰酸钾对有机物的去除效果则较差.臭氧可将大分子有机物转变成小分子有机物,将大部分疏水性有机物氧化成亲水性有机物.这种有机物组成结构的改变对膜过滤特性产生影响,明显降低了膜污染,膜污染下降率最高可达到22.7%.氯和高锰酸钾的氧化性相对较弱,仅能去除少部分疏水性有机物,对膜污染有较小减缓作用,膜污染下降率最高分别为9%和8.5%.  相似文献   

20.
徐睿  杨威  杨哲  成倩兰  顾丽婷  郭盛 《环境工程》2020,38(2):48-54,47
通过浸渍加焙烧制备出膨胀石墨(EG)负载CuO复合材料(CuO/EG),并通过X射线衍射和扫描电镜对催化剂的晶体结构和表面形貌进行表征分析。将复合材料用于活化过硫酸盐(过氧单磺酸钾,PMS)降解盐酸四环素(TC),在焙烧温度为500℃,负载量为1:4,催化剂投加量为0.2 g/L,PMS投加量为0.2 g/L的条件下,CuO/EG/PMS体系在20 min内即可将TC完全降解。同时,研究发现该复合催化体系在较广pH范围(3~9)内,以及无机阴离子共存的条件下均保持高效的催化性能。催化剂循环使用5次后,仍具有较高的催化活性。捕获实验表明,催化降解体系中起主要作用的是SO4-·。此外,CuO/EG/PMS体系对于染料罗丹明B和酸性红G同样具有优异的降解效果,表明催化剂具有较好的普遍适用性。  相似文献   

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