聚合氯化铁的制备及其絮凝效果

以赤铁矿和工业盐酸为原料,采用盐酸酸浸和加碱聚合等方法制取聚合氯化铁絮凝剂(PFC),将其用来处理造纸废水,并与市售聚合氯化铁和碱式氯化铝絮凝剂进行比较.结果表明,在碱化度为2∶1、聚合温度为40℃、陈化时间为24h时,自制聚合氯化铁絮凝剂对造纸废水具有较好的处理效果;投加量为1.4mL/L时,造纸废水的浊度降低了99%,化学需氧量(COD)降低了69.55%,优于市售絮凝剂对造纸废水的处理效果;且三种絮凝剂用量相同时,自制的聚合氯化铁絮凝剂形成絮体的速率和沉降速率都较快.     

Modelling of submerged membrane bioreactor: Conceptual study about link between activated slugde biokinetics,aeration and fouling process

A mathematical model was developed to simulate filtration process and aeration influence on submerged membrane bioreactor (SMBR) in aerobic conditions. The biological kinetics and the dynamic effect of the sludge attachment and detachment from the membrane, in relation to the filtration and a strong intermittent aeration, were included in the model. The model was established considering soluble microbial products (SMP) formation-degradation. The fouling components responsible of pore clogging, sludge cake growth, and temporal sludge film coverage were considered during calculation of the total membrane fouling resistance. The influence of SMP, transmembrane pressure, and mixed liquor suspended solids on specific filtration resistance of the sludge cake was also included. With this model, the membrane fouling under different SMBR operational conditions can be simulated. The influence of a larger number of very important process variables on fouling development can be well quantified. The model was developed for evaluating the influence on fouling control of an intermittent aeration of bubbles synchronized or not with the filtration cycles, taking into account the effects of shear intensity on sludge cake removal.     

Determination of fluoroquinolone antibiotics in hospital and municipal wastewaters in Coimbra by liquid chromatography with a monolithic column and fluorescence detection

The main goal of this work was determination of residues of the antibiotics ofloxacin (OFLO), norfloxacin (NOR), ciprofloxacin (CIPRO), and enrofloxacin (ENRO) in wastewater samples. The samples, after acidification to pH 4.5 and addition of EDTA, were extracted on an anion-exchange cartridge in tandem with an Oasis HLB cartridge. The LC–FD method, developed in previous studies, was based on application of a monolithic C₁₈ column. The limit of quantification (LOQ) of the method was 250 ng L⁻¹ for OFLO, 25 ng L⁻¹ for NOR and CIPRO, and 50 ng L⁻¹ for ENRO. Mean recovery ranged between 75 and 121% for OFLO, NOR, CIPRO, and ENRO. A total of 14 wastewater samples were analyzed; these were collected from four hospitals and from influent and effluent from a wastewater-treatment plant in Coimbra, Portugal, during spring and autumn. CIPRO was present in all the samples, NOR was detected second most often, followed by OFLO. ENRO was found at concentrations under the LOQ in five hospital samples, and the highest level was found in influent from the WWTP.     

Application of sulfur microparticles for solid-phase extraction of polycyclic aromatic hydrocarbons from sea water and wastewater samples

The application of sulfur microparticles as efficient adsorbents for the solid-phase extraction (SPE) and determination of trace amounts of 10 polycyclic aromatic hydrocarbons (PAHs) was investigated in sea water and wastewater samples using high performance liquid chromatography coupled with an ultraviolet detector (HPLC–UV). Parameters influencing the preconcentration of PAHs such as the amount of sulfur, solution flow rate and volume, elution solvent, type and concentration of organic modifier, and salt effect were examined. The results showed that at a flow rate of 10 mL min⁻¹ for the sample solutions (100 mL), the PAHs could be adsorbed on the sulfur microparticles and then eluted by 2.0 mL of acetonitrile. For HPLC–UV analysis of extracted PAHs, the calibration curves were linear in the range of 0.05–80.0 μg L⁻¹; the coefficients of determinations (r²) were between 0.9934 and 0.9995. The relative standard deviations (RSDs) for eight replicates at two concentration levels (0.5 and 4.0 μg L⁻¹) of PAHs were lower than 7.3%, under optimized conditions. The limits of detection (LODs, <!-- no-mfc -->S/N<!-- /no-mfc --> = 3) of the proposed method for the studied PAHs were 0.007–0.048 μg L⁻¹. The recoveries of spiked PAHs (0.5 and 4 μg L⁻¹) in the wastewater and sea water samples ranged from 78% to 108%. The simplicity of experimental procedure, high extraction efficiency, short sample analysis, and using of low cost sorbent demonstrate the potential of this approach for routine trace PAH analysis in water and wastewater samples.     

Evaluation of the suitability of low hazard surfactants for the separation of phenols and carotenoids from red‐flesh orange juice and olive mill wastewater using cloud point extraction

Natural antioxidants derived from plant sources attract considerable scientific interest. While classic extraction methods consume high volumes of toxic organic solvents, cloud point extraction requires surfactant not exceeding 15% of the waste volume. In preliminary tests, the suitability of various low hazard surfactants (Span 20, PEG 400, Tween 80 and 20) was explored for separation of phenols and carotenoids from olive mill wastewater and red‐flesh orange juice. Tween 80 showed the highest recovery and further applied to the next experiments. The most appropriate surfactant concentrations were 5% (for olive mill wastewater) and 7% (for orange juice) as indicated by recovery % and the rest cloud point extraction parameters (analyte concentration, concentration factor, and phase volume ratio). A double step CPE with 5% + 5% of Tween 80 recovered up to 94.4% of the total phenols from olive mill wastewater, while a 7% + 7% of Tween 80 recovered up to 72.4% of the total carotenoids from orange juice. Evaluation of the final effects and extraction efficiency of single and double step cloud point extraction shows that double step scheme seems to be preferable in both cases. Finally, phenols and carotenoids recovered by Tween 80 maintained high antiradical activity (DPPH test).     

Textile Dye Biodecolorization by Manganese Peroxidase: A Review

Wastewater emissions from textile factories cause serious environmental problems. Manganese peroxidase (MnP) is an oxidoreductase with ligninolytic activity and is a promising biocatalyst for the biodegradation of hazardous environmental contaminants, and especially for dye wastewater decolorization. This article first summarizes the origin, crystal structure, and catalytic cycle of MnP, and then reviews the recent literature on its application to dye wastewater decolorization. In addition, the application of new technologies such as enzyme immobilization and genetic engineering that could improve the stability, durability, adaptability, and operating costs of the enzyme are highlighted. Finally, we discuss and propose future strategies to improve the performance of MnP-assisted dye decolorization in industrial applications.     

Polycyclic aromatic hydrocarbons in the centralized wastewater treatment plant of a chemical industry zone: Removal, mass balance and source analysis

Increased attention has been given to the fate of pollutants such as polycyclic aromatic hydrocarbons (PAHs) introduced to the wastewater treatment plants.Dissolved and adsorbed PAHs were detected in the centralized wastewater treatment plant of a chemical industry zone in Zhejiang Province,China.The most abundant PAHs were the low molecular weight PAHs (e.g.,Acy,Ace,Flu and Phe),accounting for more than 80% of the total 16 PAHs in each treatment stage.Phase partitioning suggested that the removal of PAHs in every treatment stage was influenced greater by the sorption of particles or microorganisms.The removal efficiencies of individual PAHs ranged between 4% and 87% in the primary sedimentation stage,between 1% and 42% in anaerobic hydrolysis stage,between <1% and 70% in aerobic bio-process stage,between 1.5% and 80% in high-density clarifier stage,and between 44% and 97% in the whole treatment process.Mass balance calculations in primary stage showed significant losses for low molecular weight PAHs and relatively good agreements for high molecular weight PAHs as well as in anaerobic hydrolysis,high-density clarifier stage and sludge stream for most PAHs.Great gains of 60%-150% were obtained for high molecular weight PAHs in aerobic bio-process stage due to biosorption and bioaccumulation.Our investigations found that PAHs entering the wastewater treatment plant (WWTP) could be derived from the dyeing chemical processes as the byproducts,and the contribution supported by the largest dyeing chemical group was up to 48%.     

抑制荧光光谱法测定模拟废水中痕量汞

基于在pH 8.00磷酸氢二钠-柠檬酸缓冲介质中,血红蛋白对过氧化氢氧化对甲酚反应具有强的催化作用,汞(Ⅱ)对上述指示反应具有灵敏的抑制作用,从而提出了抑制荧光光谱法测定模拟废水中汞含量的方法。优化的试验条件如下:①血红蛋白的浓度为2.00×10-7 mol·L-1;②对甲酚的浓度为1.60×10-3 mol·L-1;③过氧化氢的浓度为1.11×10-3 mol·L-1;④反应时间为80min。在激发波长318nm、发射波长405nm处,反应体系的ΔF(即F0与F值之差)与汞(Ⅱ)的浓度在2.00×10-8～1.00×10-5 mol·L-1范围内呈线性关系。方法用于模拟废水的分析,测得加标回收率在94.0%～105%之间,相对标准偏差(n=8)在2.5%～3.3%之间。     

氢化物-原子吸收光谱法测定冶金企业废水中的砷

采用HNO3/HClO4(体积比10∶1)消解冶金废水样品,经6mol.L-1 HCl溶液酸化后,加入碘化钾(3%)、抗坏血酸(1%)及硫脲(1%)混合溶液进行还原,用氢化物-原子吸收光谱法(HG-AAS)测定了样品中的As含量.结果表明,该方法的检出限为0.297μg/L,相对标准偏差RSD为5.463%,样品加标回收率为93%～108%;其操作方便、选择性好、灵敏度高、干扰少,适合于复杂废水中微量和痕量As的测定.     

Development of a multi-residue analytical methodology based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters

This paper describes development, optimization and validation of a method for the simultaneous determination of 29 multi-class pharmaceuticals using off line solid phase extraction (SPE) followed by liquid chromatography-triple quadrupole mass spectrometry (LC-MS-MS). Target compounds include analgesics and non-steroidal anti-inflammatories (NSAIDs), lipid regulators, psychiatric drugs, anti-histaminics, anti-ulcer agent, antibiotics and β-blockers. Recoveries obtained were generally higher than 60% for both surface and wastewaters, with exception of several compounds that yielded lower, but still acceptable recoveries: ranitidine (50%), sotalol (50%), famotidine (50%) and mevastatin (34%). The overall variability of the method was below 15%, for all compounds and all tested matrices. Method detection limits (MDL) varied between 1 and 30 ng/L and from 3 to 160 ng/L for surface and wastewaters, respectively. The precision of the method, calculated as relative standard deviation (R.S.D.), ranged from 0.2 to 6% and from 1 to 11% for inter and intra-day analysis, respectively. A detailed study of matrix effects was performed in order to evaluate the suitability of different calibration approaches (matrix-matched external calibration, internal calibration, extract dilution) to reduce analyte suppression or enhancement during instrumental analysis. The main advantages and drawbacks of each approach are demonstrated, justifying the selection of internal standard calibration as the most suitable approach for our study. The developed analytical method was successfully applied to the analysis of pharmaceutical residues in WWTP influents and effluents, as well as in river water. For both, river and wastewaters, the most ubiquitous compounds belonged to the group of anti-inflammatories and analgesics, antibiotics, the lipid regulators being acetaminophen, trimethoprim, ibuprofen, ketoprofen, atenolol, propranolol, mevastatin, carbamazepine and ranitidine the most frequently detected compounds.