Involvements of chloride ion in decolorization of Acid Orange 7 by activated peroxydisulfate or peroxymonosulfate oxidation

The effects of Cl^- on the decolorization of AO7 by SO₄^·- based-peroxydisulfate or peroxymonosulfate oxidation under various activated conditions were different.     

Chronic toxicity and cytotoxicity of synthetic pyrethroid insecticide cis-bifenthrin

With the increasing use of synthetic pyrethroids (SPs), the significance of ecological safety and health risk is an emerging concern. In this study, we evaluated the chronic aquatic toxicity of cis-bifenthrin (cis-BF) in Daphnia magna and its cytotoxicity in Chinese hamster ovary (CHO) cells as well as human cervical carcinoma (Hela) cells. Chronic aquatic toxicity tests showed that cis-BF could significantly affect the reproduction of D. magna. The lowest observed effective concentration and the non-observed effective concentration of cis-BF to D. magna were 0.02 and 0.01 μg/L, respectively, and the chronic value was 0.014 μg/L. The intrinsic rate of natural increase was significantly decreased (p < 0.05) to 0.02 μg/L. The cytotoxicity assay demonstrated that cis-BF decreased cell viability in CHO and Hela cells in a concentration-and time-dependent manner. The IC₅₀ values for Hela and CHO cells were 4.0 × 10⁻⁵ and 3.2 × 10⁻⁵ mol/L, respectively. Together, these results indicated that cis-BF induced chronic toxicity in both aquatic invertebrate animals and mammalian cells. These findings assist in understanding the impact of SPs on health and environmental safety. Considering the wide spectrum of SPs, a more comprehensive understanding of the negative effects is indispensible for planning future application and regulation of these pesticides.     

Determination of paraquat in water samples using a sensitive fluorescent probe titration method

Paraquat (PQ), a nonselective herbicide, is non-fluorescent in aqueous solutions. Thus, its determination through direct fluorescent methods is not feasible. The supramolecular inclusion interaction of PQ with cucurbit[7]uril was studied by a fluorescent probe titration method. Significant quenching of the fluorescence intensity of the cucurbit[7]uril-coptisine fluorescent probe was observed with the addition of PQ. A new fluorescent probe titration method with high selectivity and sensitivity at the ng/mL level was developed to determine PQ in aqueous solutions with good precision and accuracy based on the significant quenching of the supramolecular complex fluorescence intensity. The proposed method was successfully used in the determination of PQ in lake water, tap water, well water, and ditch water in an agricultural area, with recoveries of 96.73% to 105.77%. The fluorescence quenching values (ΔF) showed a good linear relationship with PQ concentrations from 1.0×10^-8 to 1.2× 10^-5 mol/L with a detection limit of 3.35×10^-9 mol/L. In addition, the interaction models of the supramolecular complexes formed between the host and the guest were established using theoretical calculations. The interaction mechanism between the cucurbit[7]uril and PQ was confirmed by ¹H NMR spectroscopy.     

Effects of nitrogen and phosphorus concentrations on the bioaccumulation of polybrominated diphenyl ethers by Prorocentrum donghaiense

The growth, cellular total lipids, bioaccumulation amount, and bioaccumulation factors (BAFs) of 2,4,4 ′ -tribromodiphenyl ether (BDE28), 2,2 ′ ,4,4 ′ -tetrabromodiphenyl ether (BDE47), and 2,2 ′ ,4,4 ′ ,5-pentabromodiphenyl ether (BDE99) in a semi-continuous culture of Prorocentrum donghaiense were studied in relation to nitrate (0, 128, and 512 μmol/L) and phosphate (0, 8, and 32 μmol/L) concentrations. The BDE28, BDE47, and BDE99 content per cell under 0 μmol N/L were 3.77 × 10 6 , 3.95 × 10 6 , and 4.32 × 10 6 ng/cell, respectively, which were significantly higher than those under 128 and 512 μmol N/L. A nearly 5-fold increase in polybrominated diphenyl ether (PBDE) content per algal cell was found between 0 and 8 μmol P/L and between 8 and 32 μmol P/L. With increasing N and P concentrations, the PBDE content per volume of algal culture and the accumulation percentage of available PBDEs declined slightly. The BAFs for the PBDEs based on lipids showed that the logBAF lip under 0 μmol N/L was higher than those under 128 and 512 μmol N/L. The logBAF lip under 0 μmol P/L was higher than that under 8 μmol P/L but lower than that under 32 μmol P/L. Correlation analysis indicated a significant negative correlation between nutrient concentration and cellular total lipids, as well as the PBDE content per cell. The results indicate that different N and P concentrations change the total lipids content of P. donghaiense, thereby resulting in varying PBDE accumulation.     

Preparation, characterization and application of CuCrO2/ZnO photocatalysts for the reduction of Cr(VI)

The delafossite CuCrO₂ elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstructure is fairly homogenous with a mean crystallite size of ca. 2 μm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of -0.26 V_SCE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO₂/ZnO (1/1). CuCrO₂ is photoactivated by visible light and the electrons in the conduction band (-1.34 V_SCE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25℃, 5×10^-4 mol/L) because of the HCrO₄^- dark adsorption onto ZnO (4HCrO₄^- + 3C₇H₆O₃ + 18O₂ + 16H⁺ → 4Cr³⁺ + 21CO₂ + 19H₂O, ΔG⁰ = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 μmol/(hr·g).     

双酚-A和17β-雌二醇对人乳腺癌细胞生长的影响

通过MTT-细胞增殖活性测定法和双参数流式细胞光度术研究了双酚-A和17b-雌二醇对人乳腺癌细胞株MCF-7增殖、细胞周期以及核酸和蛋白合成的影响.结果表明,在310^-16～310^-8mol/L范围内,双酚-A和17b-雌二醇都能促进细胞增殖;在310^-14mol/L时,细胞增殖活性达到最高值.当作用浓度为310^-14mol/L时,细胞周期的S期比例增加,细胞总蛋白表达量明显增加.统计结果表明,双酚-A和17b-雌二醇对MCF-7细胞生长特性的雌激素效应非常相似.     

Efficient visible light photo-Fenton-like degradation of organic pollutants using in situ surface-modified BiFeO3 as a catalyst

The visible light photo-Fenton-like catalytic performance of BiFeO₃ nanoparticles was investigated using Methyl Violet (MV), Rhodamine B (RhB) and phenol as probes. Under optimum conditions, the pseudo first-order rate constant (k) was determined to be 2.21×10^-2, 5.56×10^-2 and 2.01×10^-2 min^-1 for the degradation of MV (30 μmol/L), RhB (10 μmol/L) and phenol (3 mmol/L), respectively, in the BiFeO₃-H₂O₂-visible light (Vis) system. The introduction of visible light irradiation increased the k values of MV, RhB and phenol degradation 3.47, 1.95 and 2.07 times in comparison with those in dark. Generally, the k values in the BiFeO₃-H₂O₂-Vis system were accelerated by increasing BiFeO₃ load and H₂O₂ concentration, but decreased with increasing initial pollutant concentration. To further enhance the degradation of pollutants at high concentrations, BiFeO₃ was modified with the addition of surface modifiers. The addition of ethylenediamineteraacetic acid (EDTA, 0.4 mmol/L) increased the k value of MV degradation (60 μmol/L) from 1.01×10^-2 min^-1 in the BiFeO₃-H₂O₂-Vis system to 1.30 min^-1 in the EDTA-BiFeO₃-H₂O₂-Vis system by a factor of 128. This suggests that in situ surface modification can enable BiFeO₃ nano-particles to be a promising visible light photo-Fenton-like catalyst for the degradation of organic pollutants.     

An improved GC-ECD method for measuring atmospheric N2O

Gas chromatography equipped with an electron capture detector (GC-ECD) has been widely used for measuring atmospheric N2O,but nonlinear response and the influence of atmospheric CO2 have been recognized as defects for quantification.An original GCECD method using N 2 as carrier gas was improved by introducing a small flow rate of CO2 makeup gas into the ECD,which could well remedy the above defects.The N2O signal of the improved method was 4-fold higher than that of the original method and the relative standard deviation was reduced from > 1% to 0.31%.N2O concentrations with different CO2 concentrations (172.2×10-6-1722×10-6mol/mol) measured by the improved GC-ECD method were in line with the actual N2O concentrations.However,the N2O concentrations detected by the original method were largely biased with a variation range of-4.5%～7%.The N2O fluxes between an agricultural field and the atmosphere measured by the original method were greatly overestimated in comparison with those measured by the improved method.Good linear correlation (R2=0.9996) between the response of the improved ECD and N2O concentrations (93×10-9-1966×10-9mol/mol) indicated that atmospheric N2O could be accurately quantified via a single standard gas.Atmospheric N2O concentrations comparatively measured by the improved method and a high precision GC-ECD method were in good agreement.     

Perchlorate removal using granular activated carbon supported iron compounds: Synthesis, characterization and reactivity

Synthesis and use of the iron compounds supported on granular activated carbon (ICs/GAC) have shown significant environmental implications for perchlorate (ClO 4 ) removal. ICs/GAC was synthesized via hydrolyzing FeSO 4 ·7H 2 O on GAC, reduced by NaBH 4 solution in polyethylene glycol 6000 and ethanol solution, dried in vacuum condition and exposed to air. Synthesized ICs/GAC was characterized using transmission electron micrograph (TEM), Brunauer-Emmett-Teller, X-ray photoelectron spectroscopy (XPS). ICs/GAC was determined to be containing a large amount of FeOHSO 4 , Fe 2 O 3 and a small amount of zero-valent iron (ZVI) nanoparticles according to TEM and XPS measurements. Batch static kinetic tests showed that 97% of ClO 4 was removed within 10 hr at 90°C and 86% of ClO 4 was removed within 12 hr at 25°C, at ICs/GAC dosage of 20 g/L. The experimental results also showed that FeOHSO 4 and Fe 2 O 3 nanoparticles have the function of perchlorate adsorption and play important roles in ClO 4 removal. The activation energy (E a ) was determined to be 9.56 kJ/mol.     

Effect of chlorine content of chlorophenols on their adsorption by mesoporous SBA-15

Studies on the effect of the chlorine content of chlorophenols (CPs) on their adsorption from aqueous solution by mesoporous SBA-15 are important in understanding the mechanisms of CP adsorption. In this study, three CPs with different degrees of chlorine content (i.e., 2-chlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol) were investigated. The effects of parameters such as temperature and solution pH were studied. The results showed that CP adsorption by SBA-15 increased with increasing number of chlorine substituents and depended strongly on the temperature and solution pH. Thermodynamic parameters such as Gibbs free energy change (ΔG⁰), enthalpy change (ΔH⁰) and entropy change (ΔS⁰) were also calculated. By comparison of the adsorption coefficient of CPs with varying physical-chemical properties (size, hydrophobicity and electron density), we propose that hydrophobic interactions between CPs and the SBA-15 surface, as well as electron donor-acceptor (EDA) complexes between oxygen of the siloxane surface of SBA-15 (e^--donor) and the πup-system of the CPs (e^--acceptor), were dominant adsorption mechanisms.     

Sensitive voltammetric and amperometric responses of respiratory toxins at hemin-adsorbed carbon-felt

A hemin [iron-Fe(III) protoporphyrin IX chloride] was adsorbed onto a carbon-felt (CF), which is a microelectrode ensemble of micro carbon fiber (ca. 7 μm diameter). The resulting hemin-adsorbed-CF (hemin-CF) showed a well-defined redox wave based on the hemin-Fe(III)/Fe(II) redox process with the formal potential of -0.225 V vs. Ag/AgCl in deoxygenated phosphate/citrate buffer solution (0.1 mol/L, pH 5.0). The apparent heterogenous electron transfer rate constant was estimated to be 8.6 sec^-1. In air-saturated electrolyte solution, the hemin-CF exhibited an excellent electrocatalytic activity for the reduction of dioxygen (O₂). This activity was reversibly inhibited by respiratory toxins such as cyanide and azide, which bind sixth coordination position of iron active center of hemin. The electrocatalytic O₂ reduction current at the hemin-CF was modulated by the toxins in a concentration-depending manner. Based on the relationship between the inhibition and the toxin concentration, apparent inhibition constants of cyanide and azide were evaluated to be 4.52 and 1.98 μmol/L, respectively. When the hemin-CF was used as a working electrode unit of the CF-based electrochemical flow-through detector with air-saturated carrier, the injection of the azide induced peak-shape current responses, which allowed rapid and continuous flow-amperometric determination of azide with high sensitivity.     

Investigation of potential interferences on the measurement of dissolved reactive phosphate using zirconium oxide-based DGT technique

A diffusive gradients in thin films (DGT) technique based on hydrous zirconium oxide (Zr-oxide) has been recently developed for the measurement of dissolved reactive phosphate (DRP). In this study, the detailed performance of the DGT technique is reported. Spiking experiments revealed that several orthophosphate monoester compounds contributed to the Zr-oxide DGT measurements of DRP. However, such a phenomenon is unlikely to occur during field conditions due to the low concentration of organic P in typical natural waters. The presence of Cl- (up to 106 g/L), SO42- (up to 16 g/L), HCO3- (up to 817 g/L), and AsO2- and AsO 3 4 (both up to 1 mg As/L) in solutions had negligible effects on the measurement of DRP. The threshold concentrations of Cl-, SO42- and HCO3- have been increased from previous reports for the measurements of DRP using other adsorbent-based DGT techniques. The capacity for DGT measurements of DRP decreased with increasing solution pH (4.2-9.2). The lowest capacity (95 μg P/m2 at pH 9.2) was still greater than that of other DGT techniques that are usually used for the measurement of DRP (2-12 μg P/cm2 ). The Zr-oxide binding gel could be stored for up to 2 years without any aging effect. This period of validity was considerably longer than the ferrihydrite binding gel that is commonly used in present DGT devices (6 months). The field application revealed that the concentrations of DRP measured in three fresh water samples using the Zr-oxide DGT technique were in agreement with those of the traditional colorimetric method.     

松花江及哈尔滨市饮用水雌激素活性的调查与分析

利用固相萃取/酵母双杂交法调查了哈尔滨市饮用水及周边松花江水的雌激素活性.结果表明,松花江哈尔滨段江水在夏秋两季的雌激素活性［以雌二醇当量（EEQs）计］为528～965 pg·L^-1,其中上游水源地水雌激素活性水平较高.自来水厂对雌激素活性的去除率为34.6%～50.5%,整个水处理工艺并不能有效去除源水中的雌激素类物质,致使出厂水仍具有298～718 pg·L^-1的雌激素活性;自来水厂所采用的3种净水工艺中以混凝沉淀工艺对雌激素活性的去除最为稳定,去除率为11.4%～26.1%,占总去除的32.9%～69.0%,而砂滤与氯消毒工艺出水不稳定,雌激素活性有时较进水有升高现象发生.此外,由于管网配送过程中产生了二次污染,致使管网水雌激素活性较出厂水最高可升高44.9%.7次取样测得哈尔滨市管网水的雌激素活性为347～1 362 pg·L^-1,均值为738 pg·L^-1.     

Ru(III) catalyzed permanganate oxidation of aniline at environmentally relevant pH

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.     

重组基因酵母法研究酞酸酯类化合物的类雌激素作用

为了检测五种酞酸酯类化合物的类雌激素活性,采用重组人雌激受体α、相关效应元件以及β-半乳糖苷酶报告基因酵母分别测定17β-雌二醇(E)2、邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二辛酯(DOP)、邻苯二甲酸丁苄酯(BBP)单独作用时诱导酶活并计算其EC50。通过各化合物与E2的EC50的比以及最大β-半乳糖苷酶活性来比较酞酸酯类化合物的类雌激素活性。五种酞酸酯类化合物的实验浓度范围为1.0×10-3~1.0×10-11 mol/L。结果表明,DEP(1×10-7~1×10-9 mol/L)、DBP(1×10-6~1×10-9 mol/L)、BBP(1×10-3~1×10-6 mol/L)具有明显的类雌激素活性,诱导的最大酶活分别为:1.515、0.832 2、1.669,而DMP和DOP并未检出明显的类雌激素活性。DEP、DBP、BBP与E2的EC50的比分别为8.85×10-2、2.54×10-2、8.82×10-6。说明DEP、DBP在低浓度就表现出类雌激素活性,而BBP在较高浓度才表现出类雌激素活性。     

Size distributions of aerosol and water-soluble ions in Nanjing during a crop residual burning event

To investigate the impact on urban air pollution by crop residual burning outside Nanjing, aerosol concentration, pollution gas concentration, mass concentration, and water-soluble ion size distribution were observed during one event of November 4-9, 2010. Results show that the size distribution of aerosol concentration is bimodal on pollution days and normal days, with peak values at 60-70 and 200-300 nm, respectively. Aerosol concentration is 10⁴ cm^-3. nm^-1 on pollution days. The peak value of spectrum distribution of aerosol concentration on pollution days is 1.5-3.3 times higher than that on a normal day. Crop residual burning has a great impact on the concentration of fine particles. Diurnal variation of aerosol concentration is trimodal on pollution days and normal days, with peak values at 03:00, 09:00 and 19:00 local standard time. The first peak is impacted by meteorological elements, while the second and third peaks are due to human activities, such as rush hour traffic. Crop residual burning has the greatest impact on SO₂ concentration, followed by NO₂, O₃ is hardly affected. The impact of crop residual burning on fine particles (< 2.1 μm) is larger than on coarse particles (> 2.1 μm), thus ion concentration in fine particles is higher than that in coarse particles. Crop residual burning leads to similar increase in all ion components, thus it has a small impact on the water-soluble ions order. Crop residual burning has a strong impact on the size distribution of K⁺, Cl^-, Na⁺, and F^- and has a weak impact on the size distributions of NH₄⁺, Ca²⁺, NO₃^- and SO₄^2-.     

Determination of photochemically-generated reactive oxygen species in natural water

Reactive oxygen species(ROS) can be produced by interactions between sunlight and light-absorbing substances in natural water environment.ROS may participate in the indirect photolysis of trace organic pollutants,therefore resulting in changes in their environmental fates and ecological risks in natural water systems.Bisphenol A(BPA),an endocrine-disrupting chemical,exits widely in natural waters.The photodegradation of BPA promoted by ROS(.OH,1O2,HO2./O2·-),which were produced on the excitation of ubiquito...     

一种新的阴离子表面活性剂电极的研制及应用

研制出一种新的阴离子表面活性电极,电极膜最佳组成：ＴＨＤＡ－ＤＢＳ５ｍｇ,ＤＢＰ０４ｍｌ,ＮＢ０．３ｍｌ,ＰＶＣ粉０．２ｇ,电极线性范围１×１０＾－３－８．１×１０＾－７ｍｏｌ／Ｌ,级差５８ｍＶ／ｄｅｃ,对ＤＢＳ和ＳＤＳ检测分别为５．６×１０＾－７ｍｏｌ／Ｌ和７．４×１０＾－７ｍｏｌ／Ｌ。     

MCF-7细胞评价老龄渗滤液经IME-Fenton处理后酚类提取物的雌激素效应

成分复杂的垃圾渗滤液经处理后,研究其中残留的极低浓度的酚类环境内分泌干扰物的雌激素效应及其对生态环境的毒性作用具有非常重要的实际价值.本文选择对雌激素敏感的MCF-7人类乳腺癌细胞进行体外培养,将老龄渗滤液原液、经过内部微电解(IME)和内部微电解结合芬顿试剂(IME-Fenton)处理后的渗滤液酚类提取液稀释10~107倍,采用MTT法测定MCF-7细胞的增殖和细胞划痕损伤实验评价渗滤液中酚类物质的雌激素效应,并探讨了活性炭在反应中对酚类物质的去除效果.结果表明,渗滤液中酚类提取物对MCF-7细胞增殖在浸染72 h后达到最大;与渗滤液原液相比,渗滤液经IME和IME-Fenton处理后,最大增殖效应分别下降了85%和110%,酚类提取物减缓了MCF-7细胞的迁移速度;活性炭对渗滤液中酚的吸附主要发生在反应前30 min,渗滤液经活性炭吸附后的酚类提取物稀释10~107倍仍表现出细胞毒性.渗滤液经IME-Fenton处理后降低了酚类物质进入环境引起的危害,MCF-7细胞增殖和细胞划痕也为检测浓度低至10-15g·L-1的酚类雌激素提供新方法.     

Removal of bromate ion using powdered activated carbon

Bromate ion (BrO 3) removal from drinking water by powdered activated carbons (PAC S) in bath mode was evaluated under various operational conditions.Six kinds of PACs,including wood-based carbon,fruit-based carbon,coal-based carbon,and these three carbons thermally deoxidized in a nitrogen atmosphere,were selected to investigate their capacity on BrO 3 removal.With the highest zeta potential value and being richly mesoporous,coal-based carbon had a high and an excellent BrO 3 adsorption efficiency.The removal content of BrO 3 by per gram of coal-based carbon was 0.45 mg within 5 hr in 100 μg/L bromate solution.The surface characteristics of PACs and bromide formation revealed that both physical and chemical PACs properties simultaneously affected the adsorptionreduction process.Under acidic conditions,PAC S possessed high zeta value and adequate basic groups and exhibited neutral or positive charges,promoting BrO 3 adsorption-reduction on the carbon surface.Interestingly,the PAC S thermally deoxidized in N 2 atmosphere optimized their properties,e.g.increasing their zeta values and decreasing the oxygen content which accelerated the BrO 3 removal rate.The maximum adsorption capacity of fruit-based carbon was the highest among all tested carbons (99.6 mg/g),possibly due to its highest pore volume.Remarkably,the thermal regeneration of PACs in N 2 atmosphere could completely recover the adsorption capacity of PACs.The kinetic data obtained from carbons was analyzed using pseudo second-order and intraparticle diffusion models,with results showing that the intraparticle diffusion was the more applicable model to describe adsorption of BrO 3 onto PACs.