Optimisation of an in-tube solid phase microextraction method coupled with HPLC for determination of some oestrogens in environmental liquid samples using different capillary columns

A simple on-line method for simultaneous determination of some oestrogens including oestriol (E3), norethisterone (NORE), ethynylestradiol (EE2), D-norgestrel (NORG) and bisphenol A (BPA), in environmental liquid samples was developed by coupling in-tube solid phase microextraction (in-tube SPME) to high-performance liquid chromatography with diode array (DAD) and fluorescence (FLD) detectors. Two capillary chromatographic columns (Supel-Q? and Carboxen? 1006 porous layer open tubular) were selected to develop this method. To achieve optimum extraction performance, several parameters were investigated including number of draw/eject cycles and the sample volume for each of the columns. Reproducibility was satisfactory for inter- and intra-day precision, yielding % RSDs of less than 10% and 7.6%, respectively. Limits of detection (LODs) and quantification (LOQs) for the proposed method using a DAD detector were achieved in the ranges of 0.04–0.63?ng?mL^?1 and 0.12–1.9?ng?mL^?1, depending of the capillary column used. Fluorescence detection improved these parameters for E3, BPA and EE2, obtaining LODs of 0.005–0.03?ng?mL^?1 and LOQs of 0.015–0.08?ng?mL^?1 using Supel-Q and LODs of 0.01–0.015?ng?mL^?1 and LOQs of 0.025–0.04?ng?mL^?1 using Carboxen. The proposed method was successfully applied to spiked environmental waters obtaining recoveries greater than 80%.     

Treatment of CNC industry wastewater by electrocoagulation technology: an application through response surface methodology

ABSTRACT

Removal of COD, and several toxic heavy metals (Cu²⁺ and Ni²⁺) from CNC (metalworking fluid) wastewater was investigated using electrocoagulation method (EC) with Fe and Al electrodes. The interaction effects of the current density, reaction time and initial pH were analyzed and were correlated to assess the removal efficiencies for COD, copper, and nickel. Coefficient of determination (R²) and adjusted R² was found to be higher than 96.81% and 92.77; 99.01% and 89.94 for all responses at Fe and Al electrodes, respectively. Removal efficiencies were determined to be 95.72%, 96.03%, 95.22% and 97.11%, 98.51%, 92.49% for COD, copper and nickel at iron and aluminum electrodes, respectively under optimum operating conditions. The operational cost of the EC process for COD, copper, and nickel removal, were found to be 2.54, 3.36, 2.50 €/m³ for iron electrode and 7.16, 8.95, 8.50 €/m³ for aluminum electrode at optimum conditions, respectively. The results provide that The EC process seems to be an effective treatment method for removing COD and several trace heavy metals from the CNC machine (metalworking fluid) wastewater.     

Preconcentration and Determination of Chlorophenols in Wastewater with Dispersive Liquid–Liquid Microextraction Using Hydrophobic Deep Eutectic Solvents

Abstract

Hydrophobic deep eutectic solvents (DESs) were synthesized and developed for the preconcentration of three chlorophenols from wastewater by dispersive liquid–liquid microextraction (DLLME). The analyte concentrations were determined by high-performance liquid chromatography (HPLC). The hydrophobic DESs were prepared with the combination of hydrogen bond donors of decanoic acid or octanoic acid with different hydrogen bond acceptors of quaternary ammonium salts of tetrabutylammonium chloride, tetraoctylammonium chloride, methyltrioctylammonium chloride, and tetraheptylammonium chloride). Following the study of the stability and characterization by Fourier transform infrared spectroscopy, the hydrophobic DESs were developed as extractants and employed for the removal of 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) from wastewater. Using hydrophobic DESs as the microextraction solvents, several key parameters were optimized, including the type and volume of the hydrophobic DES, pH, and time of the extraction procedure. Under the optimized conditions, good recoveries from 90.8% to 93.0% were obtained for the three chlorophenols. The limits of detection were less than 0.05?µg/mL with relative standard deviations between 1.8% and 3.1%. The method was applied for the isolation and determination of synthetic chlorophenols in wastewater.     

Application of electron beam irradiation combined to conventional treatment to treat industrial effluents

A preliminary study to combine electron beam irradiation process with biological treatment was carried out. Experiments were conducted using samples from a governmental wastewater treatment plant (WTP) that receives about 20% of industrial wastewater, with the objective of destroying the refractory organic pollutants and to obtain a better performance of this plant. Samples from five different steps of WTP were collected and irradiated in the electron beam accelerator in a batch system with 5.0, 10.0 and 20.0 kGy doses. The main results showed a removal of 99% of all organic compound analysed in the industrial receiver unit (IRU) effluent and in the coarse bar screen (CBS) effluent with a 20 kGy dose, and for the medium bar screen (MBS) and primary sedimentation (PS) effluent a 10 kGy dose was sufficient. In the case of final effluent (FE), a dose of 5 kGy removed the remaining organic compounds and dyes present after biological treatment.     

共沉淀法制备Ag3PO4/MWCNTs复合光催化材料及其表征与降解染料废水

通过简单的共沉淀法制备掺杂不同碳管含量的Ag₃PO₄/MWCNTs复合光催化材料,并对样品进行XRD、SEM、FT-IR、UV-vis等表征。以300 W氙灯模拟太阳光,通过光催化材料对甲基橙的降解来评价光催化材料对印染废水的催化效果。结果表明：PVP的存在使得制备的Ag₃PO₄颗粒表面光滑、结晶性好、尺寸较小（200~300 nm）;经过混酸改性后增加了大量的带有羧基基团的碳管,均匀地分布在Ag₃PO₄颗粒表面,与其形成了很好的复合;合成的复合材料较纯Ag₃PO₄具有更加优异的光催化活性,当碳管质量分数为3.6%时催化效果最好。最后,对所制备材料的光催化机理进行了分析。     

Non-linear model parameter estimation–estimating a feasible parameter set with respect to model use

This article deals with non-linear model parameter estimation from experimental data. As for non-linear models a rigorous identifiability analysis is difficult to perform, parameter estimation is performed in such a way that uncertainty in the estimated parameter values is represented by the range of model use results when the model is used for a certain purpose. Using this approach, the article presents a simulation study where the objective is to discover whether the estimation of model parameters can be improved, so that a small enough range of model use results is obtained. The results of the study indicate that from plant measurements available for the estimation of model parameters, it is possible to extract data that are important for the estimation of model parameters relative to a certain model use. If these data are improved by a proper measurement campaign (e.g. proper choice of measured variables, better accuracy, higher measurement frequency) it is to be expected that a valid model for a certain model use will be obtained. The simulation study is performed for an activated sludge model from wastewater treatment, while the estimation of model parameters is done by Monte Carlo simulation.     

Process Optimization and Modeling of Phenol Adsorption onto Sludge-Based Activated Carbon Intercalated MgAlFe Ternary Layered Double Hydroxide Composite

A sewage sludge-based activated carbon (SBAC) intercalated MgAlFe ternary layered double hydroxide (SBAC-MgAlFe-LDH) composite was synthesized via the coprecipitation method. The adsorptive performance of the composite for phenol uptake from the aqueous phase was evaluated via the response surface methodology (RSM) modeling technique. The SBAC-MgAlFe-LDH phenol uptake capacity data were well-fitted to reduced RSM cubic model (R² = 0.995, R²-adjusted = 0.993, R²-predicted = 0.959 and p-values < 0.05). The optimum phenol adsorption onto the SBAC-MgAlFe-LDH was achieved at 35 °C, 125 mg/L phenol, and pH 6. Under the optimal phenol uptake conditions, pseudo-first-order and Avrami fractional-order models provided a better representation of the phenol uptake kinetic data, while the equilibrium data models’ fitting follows the order; Liu > Langmuir > Redlich–Peterson > Freundlich > Temkin. The phenol uptake mechanism was endothermic in nature and predominantly via a physisorption process (ΔG° = −5.33 to −5.77 kJ/mol) with the involvement of π–π interactions between the phenol molecules and the functionalities on the SBAC-LDH surface. The maximum uptake capacity (216.76 mg/g) of SBAC-MgAlFe-LDH was much higher than many other SBAC-based adsorbents. The improved uptake capacity of SBAC-LDH was attributed to the effective synergetic influence of SBAC-MgAlFe-LDH, which yielded abundant functionalized surface groups that favored higher aqueous phase uptake of phenol molecules. This study showcases the potential of SBAC-MgAlFe-LDH as an effective adsorbent material for remediation of phenolic wastewater     

国内外厌氧消化模型研究进展

 厌氧生物法是一种适用于处理高浓度有机废水的高效低能耗的处理工艺,厌氧消化模型是表述兼性细菌和厌氧细菌将可生物降解的有机物分解成二氧化碳、甲烷和水的过程模型。它是一个具有分解和水解、产酸、产乙酸和产甲烷等过程的复杂的结构化模型。本文主要介绍了国内外污泥厌氧消化模型的研究现状及其进展,模型包括厌氧消化1号模型(ADM1)、好氧活性污泥-厌氧消化模型(ASM1-ADM1)、单相中温-厌氧消化模型(SPMT-ADM1)、单相高温-厌氧消化模型(SPHT-ADM1)、两相-厌氧消化模型(TP-ADM1)、厌氧消化-活性污泥复合模型(ADM1-ASMs)、硫酸盐还原-厌氧消化模型(SR-ADM1)、硝酸盐还原-厌氧消化模型(NR-ADM1)、产气-厌氧消化模型(GPAE-ADM1)、沉淀池-厌氧消化模型(ST-ADM1)和抑制因子-厌氧消化模型(IK-ADM1)。对这些模型进行了综述,根据目前存在的不足对今后的研究方向提出了建议。     

国内外活性污泥模型研究进展

 活性污泥模型(ASM)是表述废水中各种污染物质与废水处理系统中微生物之间的复杂生物化学反应过程的数学模型。本文主要介绍了国内外活性污泥数学模型的研究现状及进展,包括活性污泥1号模型(ASM1)、BSM1模型、ASM-SST模型、ASM-ASS模型、活性污泥2号模型(ASM2)、活性污泥2d模型(ASM2d)、活性污泥3号模型(ASM3)、FCASM3模型等。对这些模型做了评价和比较,并对今后的研究方向提出了建议：需要在活性污泥法机理、模型参数的确定和相关软件方面开发上多做研究,在水处理工艺设计以及水质监测方面多进行应用。     

含氮杂环化合物冲击负荷对厌氧滤池-曝气生物滤池工艺处理焦化废水的影响

采用生物强化及未生物强化厌氧滤池(AF)–曝气生物滤池(BAF)两套反应器处理焦化废水, 并研究外加杂环化合物咔唑、喹啉和吡啶对工艺处理效果的影响。结果表明: 未添加杂环化合物, 两套AF-BAF反应器系统厌氧段COD的去除率均为35%, 厌氧出水可生化性从进水的0.33上升为0.59; 添加100 mg/L咔唑后, 生物强化反应器厌氧段COD去除率仍维持在35%, 出水可生化性变为 0.53, 未生物强化反应器厌氧段COD去除率降为23%, 出水可生化性降为 0.45; 同时添加100 mg/L喹啉和50 mg/L吡啶, 生物强化反应器厌氧段COD的去除率降为27%, 出水可生化性降为0.48, 未生物强化反应器厌氧段COD去除率降为12%, 出水可生化性降为0.38。生物强化有效地提高了反应器对高浓度杂环化合物的耐冲击能力。高效液相色谱结果显示, 外加的咔唑、喹啉和吡啶在生物强化反应器厌氧段的去除率可达83%, 91%和88%, 而在未生物强化反应器厌氧段的去除率仅为57%, 66%和55%。气相色谱–质谱分析表明, 外加杂环化合物导致生物强化反应器厌氧出水烷烃与含苯环酯类物质种类的增加。研究结果揭示了高浓度杂环化合物咔唑、喹啉和吡啶负荷对A/O工艺处理焦化废水效果的影响。