Application of comprehensive two-dimensional gas chromatography with mass spectrometric detection for the analysis of selected drug residues in wastewater and surface water

Pharmaceutical residues have become tightly controlled environmental contaminants in recent years, due to their increasing concentration in environmental components. This is mainly caused by their high level of production and everyday consumption. Therefore there is a need to apply new and sufficiently sensitive analytical methods, which can detect the presence of these contaminants even in very low concentrations. This study is focused on the application of a reliable analytical method for the analysis of 10 selected drug residues, mainly from the group of non-steroidal anti-inflammatory drugs (salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen, and dicofenac), in wastewaters and surface waters. This analytical method is based on solid phase extraction, derivatization by N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and finally analysis by comprehensive two-dimensional gas chromatography with Time-of-Flight mass spectrometric detection (GC×GC- TOF MS). Detection limits ranged from 0.18 to 5 ng/L depending on the compound and selected matrix. The method was successfully applied for detection of the presence of selected pharmaceuticals in the Svratka River and in wastewater from the wastewater treatment plant in Brno-Modrice, Czech Republic. The concentration of pharmaceuticals varied from one to several hundreds of ng/L in surface water and from one to several tens of μg/L in wastewater.     

Cost-performance analysis of nutrient removal in a full-scale oxidation ditch process based on kinetic modeling

A full-scale oxidation ditch process for treating sewage was simulated with the ASM2d model and optimized for minimal cost with acceptable performance in terms of ammonium and phosphorus removal. A unified index was introduced by integrating operational costs (aeration energy and sludge production) with effluent violations for performance evaluation. Scenario analysis showed that,in comparison with the baseline (all of the 9 aerators activated), the strategy of activating 5 aerators could save aeration energy significantly with an ammonium violation below 10%. Sludge discharge scenario analysis showed that a sludge discharge flow of 250–300 m3/day (solid retention time (SRT), 13–15 days) was appropriate for the enhancement of phosphorus removal without excessive sludge production. The proposed optimal control strategy was: activating 5 rotating disks operated with a mode of "111100100" ( "1"represents activation and "0" represents inactivation) for aeration and sludge discharge flow of 200 m3/day (SRT, 19 days). Compared with the baseline, this strategy could achieve ammonium violation below 10% and TP violation below 30% with substantial reduction of aeration energy cost (46%) and minimal increment of sludge production (< 2%). This study provides a useful approach for the optimization of process operation and control.     

含铬废水的处理技术及机理简述

介绍了废水中六价铬的来源及存在形态,以及处理含铬废水的物理、物化、化学及生物等各种工艺,并对各种工艺的机理和优缺点进行分析,展望含铬废水的治理前景。     

A pilot-scale study of cryolite precipitation from high fluoride-containing wastewater in a reaction-separation integrated reactor

Fluoride removal by traditional precipitation generates huge amounts of a water-rich sludge with low quality, which has no commercial or industrial value. The present study evaluated the feasibility of recovering fluoride as low water content cryolite from industrial fluoride-containing wastewater. A novel pilot-scale reaction-separation integrated reactor was designed. The results showed that the seed retention time in the reactor was prolonged to strengthen the induced crystallization process. The particle size of cryolite increased with increasing seed retention time, which decreased the water content. The recovery rate of cryolite was above 75% under an influent fluoride concentration of 3500 mg/L, a reaction temperature of 50℃, and an influent flow of 40 L/hr. The cryolite products that precipitated from the reactor were small in volume, large in particle size, low in water content, high in crystal purity, and recyclable.     

Biodegradation of 2-methylquinoline by Enterobacter aerogenes TJ-D isolated from activated sludge

Bacterial strain Enterobacter aerogenes TJ-D capable of utilizing 2-methylquinoline as the sole carbon and energy source was isolated from acclimated activated sludge under denitrifying conditions. The ability to degrade 2-methylquinoline by E. aerogenes TJ-D was investigated under denitrifying conditions. Under optimal conditions of temperature (35℃) and initial pH 7, 2-methylquinoline of 100 mg/L was degraded within 176 hr. The degradation of 2-methylquinoline by E. aerogenes TJ-D could be well described by the Haldane model (R² > 0.91). During the degradation period of 2-methylquinoline (initial concentration 100 mg/L), nitrate was almost completely consumed (the removal efficiency was 98.5%), while nitrite remained at low concentration (< 0.62 mg/L) during the whole denitrification period. 1,2,3,4-Tetrahydro-2-methylquinoline, 4-ethyl-benzenamine, N-butyl-benzenamine, N-ethyl-benzenamine and 2,6-diethyl-benzenamine were metabolites produced during the degradation. The degradation pathway of 2-methylquinoline by E. aerogenes TJ-D was proposed. 2-Methylquinoline is initially hydroxylated at C-4 to form 2-methyl-4-hydroxy-quinoline, and then forms 2-methyl-4-quinolinol as a result of tautomerism. Hydrogenation of the heterocyclic ring at positions 2 and 3 produces 2,3-dihydro-2-methyl-4-quinolinol. The carbon-carbon bond at position 2 and 3 in the heterocyclic ring may cleave and form 2-ethyl-N-ethyl-benzenamine. Tautomerism may result in the formation of 2,6-diethyl-benzenamine and N-butyl-benzenamine. 4-Ethyl-benzenamine and N-ethyl-benzenamine were produced as a result of losing one ethyl group from the above molecules.     

Ethyl thiosemicarbazide intercalated organophilic calcined hydrotalcite as a potential sorbent for the removal of uranium(VI) and thorium(IV) ions from aqueous solutions

This work was conducted to determine the practicability of using a new adsorbent 4-ethyl thiosemicarbazide intercalated,organophilic calcined hydrotalcite(ETSC-OHTC) for the removal of uranium(U(VI)),and thorium(Th(IV)) from water and wastewater.The FTIR analysis helped in realizing the involvement of nitrogen and sulphur atoms of ETSC in binding the metal ions through complex formation.Parameters like adsorbent dosage,solution pH,initial metal ions concentration,contact time and ionic strength,that influence adsorption phenomenon,were studied.The optimum pH for maximum adsorption of U(VI) and Th(IV) was found to be in the range 4.0-6.0.The contact time required for reaching equilibrium was 4 hr.The pseudo second-order kinetic model was the best fit to represent the kinetic data.Analysis of the equilibrium adsorption data using Langmuir,Freundlich and Sips models showed that the Freundlich model was well suited to describe the metal ions adsorption.The K F values were 25.43 and 29.11mg/g for U(VI) and Th(IV),respectively,at 30°C.The adsorbent can be regenerated effectively from U(VI) and Th(IV) loaded ones using 0.01mol/L HCl.The new adsorbent was quite stable for many cycles,without much reduction in its adsorption capacity towards the metals.     

不同Fe(Ⅲ)对活性污泥异化铁还原及除磷影响研究

以SBBR反应器活性污泥作为铁还原菌菌种来源,采用兼性厌氧/严格厌氧恒温培养试验,投加不同Fe(Ⅲ)考察各条件下的异化铁还原能力同时比较对磷的去除效果.结果表明:2种条件下Fe(Ⅲ)还原能力具有较好的一致性,依次为:Fe(OH)3＞氧化铁皮＞青矿＞红矿,其中严格厌氧条件下较好.同时,除磷效果与其呈正相关,富集培养至7d,Fe(OH)3及氧化铁皮体系出水磷浓度均达到2mg/L以下,之后继续降低,最终达到0.5mg/L以下.结合异化铁还原除磷机理,可以证明,不同Fe(Ⅲ)表面吸附作用对TP的去除贡献较小,其主要作用为铁还原菌驱动下的化学沉淀去除.     

三槽氧化沟内底推位置与积泥厚度的分析研究

氧化沟工艺由于进水中含有大量的无机颗粒,无机颗粒的沉淀导致沟内积泥较厚。为了不影响正常生产,依据经验数据,依次对1号、2号氧化沟安装底推。对沟内积泥情况及影响因素进行分析比较,得出氧化沟的积泥主要由进水中密度较大的无机颗粒造成,且积泥规律与底推安装位置和运行情况相关。     

Differences in rheological and fractal properties of conditioned and raw sewage sludge

Rheological tests for raw and conditioned activated sludge(AS) or anaerobic digested sludge(ADS) show that power-law relationships can be used to describe the evolution of several rheological parameters,i.e.,limiting viscosity(η∞),yield stress(τy),cohesion energy of the sludge network(Ec),and storage modulus(G’),with total suspended solid(TSS) content in raw and conditioned sludge.A gel-like structure that behaves similar to weak-link flocs/aggregates was observed in AS and ADS.As derived from the double-logarithmic plots of G’-TSS content,the mass fractal dimensions of the raw and conditioned AS or ADS flocs/aggregates were 2.70 and 2.53 or 2.85 and 2.79,respectively.The rheological tests also indicate that both polymer conditioning and increased TSS content led to improved elastic behavior,cohesion energy,and yield stress of the sludge network,as well as expanded the corresponding linear viscoelastic range.The porosity of AS or ADS flocs/aggregates will be improved by polymer conditioning.     

Biodegradation by bioaugmentation of dairy wastewater by fungal consortium on a bioreactor lab-scale and on a pilot-scale

A fungal consortium including Aspergillus niger, Mucor hiemalis and Galactomyces geotrichum was tested for the treatment of dairy wastewater. The bio-augmentation method was tested at lab-scale (4 L), at pilot scale (110 L) and at an industrial scale in Wastewater Treatment Plants (WWTP). The positive impact of fungal addition was confirmed when fungi was beforehand accelerated by pre-culture on whey (5 g/L lactose) or on the dairy effluent. Indeed, chemical oxygen demand (COD) removal yields increased from 55% to 75% for model medium, diluted milk. While after inoculation of an industrial biological tank from a dairy factory with the fungal consortium accelerated by pre-cultivation in a 1000 L pilot plant, the outlet COD values decreased from values above the standard one (100 mg/L) to values in the range of 50-70 mg/L. In addition, there was a clear impact of fungal addition on the ’hard’ or non-biodegradable COD owing to the significant reduction of the increase of the COD on BOD 5 ratio between the inlet and the outlet of the biological tank of WWTP. It was in the range of 451%-1111% before adding fungal consortium, and in the range of 257%-153% after bio-augmentation with fungi. An inoculated bioreactor with fungal consortium was developed at lab-scale and demonstrated successfully at pilot scale in WWTP.