Electrochemically controlled solid phase microextraction based on a conductive polyaniline-graphene oxide nanocomposite for extraction of tetracyclines in milk and water.

BACKGROUND: Tetracycline antibiotics are employed for human and animal health and for speeding up growth rates. However, their presence in food products and environmental waters has been a concern for some years. Therefore, a variety of sample preparation methods have been developed for the analysis of tetracycline residues in these matrices. RESULTS: An electrochemically controlled solid phase microextraction based on a modified copper electrode with polyaniline/graphene oxide (PANI/GO) conductive nanocomposite was developed for the extraction of oxytetracycline, tetracycline and doxycycline before high-performance liquid chromatography-UV analysis. PANI/GO was synthesized by in situ chemical oxidative polymerization, characterized by scanning electron microscopy and Fourier-transform infrared spectroscopy, and bound on the electrode using high purity conductive double-sided adhesive carbon glue. The significant factors affecting the performance of microextraction were investigated and optimized. Under the optimized conditions [sample, 15 mL; sorbent, 10 mg; pH, 3.0; electroextraction voltage, -0.9 V; electroextraction time, 20 min; eluent (MeOH/NH3 ), 500 µL; and desorption time, 5 min], the limits of detection for target analytes were in the ranges 0.32-1.01 and 2.42-7.59 µg L-1 in water and milk samples, respectively. The linear ranges were 1.06-750 µg L-1 for water and 8.05-750 µg L-1 for milk samples. The intra-day and inter-day precisions were 2.32-3.80 and 3.29-4.25, respectively. The method was applied to the determination of analytes in milk and water samples with different fat contents, and the recoveries were obtained in the range 71-104%. CONCLUSION: The developed electro-microextraction method provides a facile, rapid, cost-effective, sensitive and efficient promising procedure for the extraction of antibiotics in complex matrices. © 2020 Society of Chemical Industry.

Double surfactants-assisted electromembrane extraction of cyromazine and melamine in surface water, soil and cucumber samples followed by capillary electrophoresis with contactless conductivity detection.

BACKGROUND: Cyromazine (CYR) and its main degradation product melamine (MEL) are attracting wide attention due to their potential hazards to the environment and humans. In this work, double surfactants-assisted electromembrane extraction (DS-EME) by Tween 20 and alkylated phosphate was firstly used for purification and extraction of CYR and MEL, and the extract was directly analyzed by capillary electrophoresis with capacitively coupled contactless conductivity detection. RESULTS: Under the optimum conditions, two targets could be well separated from the main interferences, including common biogenic amines and inorganic cations within 14 min. This developed method was successfully applied to the analyses of surface water, soil and cucumber samples, and the average recoveries were in the range 93.3-112%. DS-EME provided a synergistic purification and enrichment effect for CYR and MEL by adding Tween 20 and alkylated phosphate into donor phase and supporting liquid membrane, respectively. Satisfactory limits of detection [0.2-1.5 ng mL-1 , signal-to-noise ratio (S/N) = 3] could be obtained in the tested sample matrices, and the corresponding enrichment factors were up to 115∼123 times. CONCLUSION: This developed method provides an alternative for the simultaneous analysis of CYR and MEL in complex real-world samples. © 2019 Society of Chemical Industry.

Biosorption-based dispersive liquid-liquid microextraction combined with polypyrrole-coated magnetic nanoparticles as an effective sorbent for the extraction of ibuprofen from water samples using magnetic solid-phase extraction.

In this paper, biosorption-based dispersive liquid-liquid microextraction (BioDLLME) in combination with magnetic solid-phase extraction (MSPE) has been developed as a sample pretreatment method with high enrichment factor for the sensitive determination of ibuprofen in water samples. At first, magnetic Fe3 O4 /polypyrrole nanoparticles were synthesized and employed as sorbent for the MSPE of ibuprofen. After the elution of the desired compound from the sorbent by using methanol, BioDLLME technique was performed on the obtained solution. After MSPE, the eluent of MSPE was used as the disperser solvent for BioDLLME, so that the extra preconcentration factor could be achieved. The properties of the prepared magnetic sorbent were characterized using field emission scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction methods. Experimental parameters affecting the extraction efficiency were studied and optimized. Under optimum conditions, the enrichment factor was 274. The linear dynamic range and limit of detection are 0.25-80 and 0.083 µg/L, respectively. The relative standard deviations for six replicate measurements are 3.82%.

Treatment of the terephthalic acid-containing wastewater using a biological-aerated filter.

In this paper, the biological-aerated filter (BAF) was employed to treat the wastewater containing terephthalic acid (TA). Factors that affected the efficiency of TA and CODCr removal were evaluated experimetally, including pH, hydraulic loading, hydraulic retention time (HRT) and TA volume loading. At pH 7-8, hydraulic loading rate 0.067-0.48 m3/(m2 h), HRT more than 3.5h and TA loading 0.04-0.15g/(m3 d), the TA and CODCr removal efficiency was more than 93% and 87%, respectively. The mathematical model of matrix (TA) was obtained by Monod's relation and the experimental parameters of the model were 1.972 g/(m2d) and 9.782 mg/L.

Mechanisms of MS2 bacteriophage removal by fouled ultrafiltration membrane subjected to different cleaning methods.

An ultrafiltration unit with a polyvinylidene fluoride (PVDF) membrane of 40 nm nominal pore size was used to study bacteriophage MS2 removal under different membrane conditions: pristine membrane, membrane fouled by soluble microbial product (SMP) extracted from membrane bioreactor (MBR) feedwater, backwashed membrane, and chemically cleaned membrane. The order of MS2 removal by these membranes was as follows: fouled membrane > backwashed membrane > chemically cleaned membrane ≈ pristine membrane. A linear correlation between membrane relative permeability and MS2 removal was found. Mass balance analysis showed a high percentage of MS2 in the concentrate for the fouled membrane as compared with the pristine membrane. Quartz crystal microbalance (QCM) results showed faster kinetics of MS2 adhesion to the pristine membrane than to the SMP-fouled membrane. In agreement with QCM results, an attractive force between MS2 and the pristine membrane was detected using an atomic force microscope (AFM), whereas a repulsive force was detected for the interaction between MS2 and the fouled membrane. The presence of SMP on the membrane surface led to higher rejection of MS2 due to both pore blocking and repulsion between MS2 and the SMP layer. Chemical cleaning removed most of the SMP foulant and as a result led to a lower MS2 removal.

Combination of microalgae cultivation with membrane processes for the treatment of municipal wastewater.

The treatment of wastewater by microalgae cultivation has attracted more and more attention. However, the way to harvest microalgae cells from the wastewater and the treatment of the large quantity of residual solution have become critical issues. In this work, a new approach for the treatment of municipal wastewater is presented. The combination of flocculation for removing mainly microalgae and thereafter membrane filtration for chemical oxygen demand (COD) and conductivity reduction of the residual solution after flocculation is discussed. The COD concentration of the wastewater decreased from 260 to 84 mg/L after flocculation by chitosan. Five ultrafiltration (UF) membranes and two nanofiltration (NF) membranes were used for filtration to find a suitable membrane for COD and conductivity reduction. Among the five UF membranes, GR82PE showed the best performance, whose permeate flux and COD retention at 4 bar were 189.66 L/(m(2)·h) and 43.03%, respectively. NF membranes showed higher COD and conductivity retentions than UF membranes. The COD retention of Desal5-DK reached 98.3% at 20 bar. Lastly, the flux recovery after the filtration test of each membrane is also discussed.

Treatment of waste thermal waters by ozonation and nanofiltration.

After their use for heating, e.g. in greenhouses, waste thermal waters may cause environmental problems due to their high contents of ions, and in some cases organic matter (associated with an oxygen demand) or toxic compounds. The aims of this work were to decrease the high organic content of waste thermal water by a combination of ozone treatment and membrane separation, and to investigate the accompanying membrane fouling. The results demonstrated that the chemical oxygen demand and the total organic content can be effectively decreased by a combination of ozone pretreatment and membrane filtration. Ozone treatment is more effective for phenol elimination than nanofiltration alone: with a combination of the two processes, 100% elimination efficiency can be achieved. The fouling index b proved to correlate well with the fouling and polarization layer resistances.

A high-flux isopore micro-fabricated membrane for effective concentration and recovering of waterborne pathogens.

A high-flux metallic micro/nano-filtration membrane has been fabricated and validated for isolation of waterborne pathogens from drinking water. Obtained membrane with smooth surface and perfectly ordered pores was achieved by a high yield and cost effective multilevel lithography and electroplating technique. The micro-fabricated membrane was also strengthened with an integrated back-support, which can withstand a high pressure during filtration. The results of microfiltration tests with model particles revealed the superior performance of the micro-fabricated filter than current commercial filters in sample throughput, recovery ratio, and reusability. This study highlighted the potential application of micro-fabricated filer in rapid filtration and recovery of C. parvum oocysts for downstream analysis.

A polymer microfluidic chip for quantitative detection of multiple water- and foodborne pathogens using real-time fluorogenic loop-mediated isothermal amplification.

Inexpensive, portable, and easy-to-use devices for rapid detection of microbial pathogens are needed to ensure safety of water and food. In this study, a disposable polymer microfluidic chip for quantitative detection of multiple pathogens using isothermal nucleic acid amplification was developed. The chip contains an array of 15 interconnected reaction wells with dehydrated primers for loop-mediated isothermal amplification (LAMP), and requires only a single pipetting step for dispensing of sample. To improve robustness of loading and amplification, hydrophobic air vents and microvalves were monolithically integrated in the multi-layered structure of the chip using an inexpensive knife plotter. For quantification, LAMP was performed with a highly fluorescent DNA binding dye (SYTO-82) and the reactions monitored in real-time using a low-cost fluorescence imaging system previously developed by our group (Ahmad et al., Biomed. Microdevices 13(5), 929-937). Starting from genomic DNA mixtures, the chip was successfully evaluated for rapid analysis of multiple virulence and marker genes of Salmonella, Campylobacter jejuni, Shigella, and Vibrio cholerae, enabling detection and quantification of 10-100 genomes per µl in less than 20 min. It is anticipated that the microfluidic chip, along with the real-time imaging system, may be a key enabling technology for developing inexpensive and portable systems for on-site screening of multiple pathogens relevant to food and water safety.

Effect of disinfectant, water age, and pipe material on occurrence and persistence of Legionella, mycobacteria, Pseudomonas aeruginosa, and two amoebas.

Opportunistic pathogens represent a unique challenge because they establish and grow within drinking water systems, yet the factors stimulating their proliferation are largely unknown. The purpose of this study was to examine the influence of pipe materials, disinfectant type, and water age on occurrence and persistence of three opportunistic pathogens (Legionella pneumophila, Mycobacterium avium, and Pseudomonas aeruginosa), broader genera (Legionella and mycobacteria), and two amoeba hosts (Acanthamoeba spp. and Hartmanella vermiformis). Triplicate simulated distribution systems (SDSs) compared iron, cement, and PVC pipe materials fed either chlorinated or chloraminated tap water and were sampled at water ages ranging from 1 day to 5.7 days. Quantitative polymerase chain reaction quantified gene copies of target microorganisms in both biofilm and bulk water. Legionella, mycobacteria, P. aeruginosa, and both amoebas naturally colonized the six SDSs, but L. pneumophila and M. avium were not detected. Disinfectant type and dose was observed to have the strongest influence on the microbiota. Disinfectant decay was noted with water age, particularly in chloraminated SDSs (due to nitrification), generally resulting in increased microbial detection frequencies and densities with water age. The influence of pipe material became apparent at water ages corresponding to low disinfectant residual. Each target microbe appeared to display a distinct response to disinfectant type, pipe materials, water age, and their interactions. Differences between the first and the second samplings (e.g., appearance of Legionella, reduction in P. aeruginosa and Acanthamoeba) suggest a temporally dynamic drinking water microbial community.

The use of clay-polymer nanocomposites in wastewater pretreatment.

Some agricultural effluents are unsuitable for discharge into standard sewage-treatment plants: their pretreatment is necessary to avoid clogging of the filtering devices by colloidal matter. The colloidal stability of the effluents is mainly due to mutual repulsive forces that keep charged particles in suspension. Pretreatment processes are based on two separate stages: (a) neutralization of the charges ("coagulation") and (b) bridging between several small particles to form larger aggregates that sink, leaving clarified effluent ("flocculation"). The consequent destabilization of the colloidal suspension lowers total suspended solids (TSSs), turbidity, and other environmental quality parameters, making the treatments that follow more efficient. Clay-based materials have been widely used for effluent pretreatment and pollutant removal. This study presents the use of nanocomposites, comprised of an anchoring particle and a polymer, as "coagoflocculants" for the efficient and rapid reduction of TSS and turbidity in wastewater with a high organic load. The use of such particles combines the advantages of coagulant and flocculant by neutralizing the charge of the suspended particles while bridging between them and anchoring them to a denser particle (the clay mineral), enhancing their precipitation. Very rapid and efficient pretreatment is achieved in one single treatment step.

Impact of bottled water storage duration and location on bacteriological quality.

An investigation studying the effects of storage duration and location on the persistence of heterotrophic microorganisms in oligotrophic bottled water environments has been completed. One-gallon high-density polyethylene water containers stored for up to 16 weeks at temperatures ranging from 2°C to >49°C in a refrigerator, indoor cabinet, covered porch, and car trunk were evaluated for microbiological quality. Heterotrophic plate counts (HPCs) of up to 4 × 10(3) cfu/mL were detected in containers stored on a porch and car trunk; whereas, HPCs were found not to exceed 400 cfu/mL and 100 cfu/mL for bottles stored in indoor cabinets and refrigerators, respectively. Containers stored on an enclosed porch for up to seven years contained HPC of up to 4 × 10(4) cfu/mL. Logistic and Gompertz growth models predicted microbial growth rates for bottled water stored on a protected porch environment for long (R(2) 0.99) and short-term (R(2) 0.86) durations.

Micropollutants removal in an anaerobic membrane bioreactor and in an aerobic conventional treatment plant.

The paper expresses an attempt to tackle the problem due to the presence of micropollutants in wastewater which may be able to disrupt the endocrine system of some organisms. These kinds of compounds are ubiquitously present in municipal wastewater treatment plant (WWTP) effluents. The aim of this paper is to compare the fate of the alkylphenols-APs (4-(tert-octyl)) phenol, t-nonylphenol and 4-p-nonylphenol and the hormones (estrone, 17ß-estradiol and 17α-ethinylestradiol) in a submerged anaerobic membrane bioreactor (SAMBR) pilot plant and in a conventional activated sludge wastewater treatment plant (CTP). The obtained results are also compared with the results obtained in a previous study carried out in an aerobic MBR pilot plant. The results showed that the APs soluble concentrations in the SAMBR effluent were always significantly higher than the CTP ones. Moreover, the analyses of the suspended fraction revealed that the AP concentrations in the SAMBR reactor were usually higher than in the CTP reactor, indicating that under anaerobic conditions the APs were accumulated in the digested sludge. The aerobic conditions maintained both in the CTP system and in the aerobic MBR favoured the APs and hormones degradation, and gave rise to lower concentrations in the effluent and in the reactor of these systems. Furthermore, the results also indicated that the degradation of APs under aerobic conditions was enhanced working at high solid retention time (SRT) and hydraulic retention time (HRT) values.

Occurrence and removal of microbial indicators from municipal wastewaters by nine different MBR systems.

Nine different membrane bioreactor (MBR) systems with different process configurations (submerged and external), membrane geometries (hollow-fiber, flat-sheet, and tubular), membrane materials (polyethersulfone (PES), polyvinylidene fluoride (PVDF), and polytetrafluoroethylene (PTFE)) and membrane nominal pore sizes (0.03-0.2 µm) were evaluated to assess the impact of influent microbial concentration, membrane pore size and membrane material and geometries on removal of microbial indicators by MBR technology. The log removal values (LRVs) for microbial indicators increased as the influent concentrations increased. Among the wide range of MBR systems evaluated, the total and fecal coliform bacteria and indigenous MS-2 coliphage were detected in 32, 9 and 15% of the samples, respectively; the 50th percentile LRVs were measured at 6.6, 5.9 and 4.5 logs, respectively. The nominal pore sizes of the membranes, membrane materials and geometries did not show a strong correlation with the LRVs.

Performance evaluation and modelling studies of gravel--coir fibre--sand multimedia stormwater filter.

A horizontal flow multimedia stormwater filter was developed and tested for hydraulic efficiency and pollutant removal efficiency. Gravel, coconut (Cocos nucifera) fibre and sand were selected as the media and filled in 1:1:1 proportion. A fabric screen made up of woven sisal hemp was used to separate the media. The adsorption behaviour of coir fibre was determined in a series of column and batch studies and the corresponding isotherms were developed. The hydraulic efficiency of the filter showed a diminishing trend as the sediment level in inflow increased. The filter exhibited 100% sediment removal at lower sediment concentrations in inflow water (>6 g L(-1)). The filter could remove NO3(-), SO4(2-) and total solids (TS) effectively. Removal percentages of Mg(2+) and Na(+) were also found to be good. Similar results were obtained from a field evaluation study. Studies were also conducted to determine the pattern of silt and sediment deposition inside the filter body. The effects of residence time and rate of flow on removal percentages of NO3(-) and TS were also investigated out. In addition, a multiple regression equation that mathematically represents the filtration process was developed. Based on estimated annual costs and returns, all financial viability criteria (internal rate of return, net present value and benefit-cost ratio) were found favourable and affordable to farmers for investment in the developed filtration system. The model MUSIC was calibrated and validated for field conditions with respect to the developed stormwater filter.

Effects of coconut granular activated carbon pretreatment on membrane filtration in a gravitational driven process to improve drinking water quality.

This study evaluates the performance of a polymeric microfiltration membrane, as well as its combination with a coconut granular activated carbon (GAC) pretreatment, in a gravitational filtration module, to improve the quality of water destined to human consumption. The proposed membrane and adsorbent were thoroughly characterized using instrumental techniques, such as contact angle, Brunauer-Emmett-Teller) and Fourier transform infrared spectroscopy analyses. The applied processes (membrane and GAC + membrane) were evaluated regarding permeate flux, fouling percentage, pH and removal of Escherichia coli, colour, turbidity and free chlorine. The obtained results for filtrations with and without GAC pretreatment were similar in terms of water quality. GAC pretreatment ensured higher chlorine removals, as well as higher initial permeate fluxes. This system, applying GAC as a pretreatment and a gravitational driven membrane filtration, could be considered as an alternative point-of-use treatment for water destined for human consumption.

Characterization and effect of biofouling on polyamide reverse osmosis and nanofiltration membrane surfaces.

Biofouling is a major reason for flux decline in the performance of membrane-based water and wastewater treatment plants. Initial biochemical characterization of biofilm formation potential and biofouling on two commercially available membrane surfaces from FilmTec Corporation were investigated without filtration in laboratory rotating disc reactor systems. These surfaces were polyamide aromatic thin-film reverse osmosis (RO) (BW30) and semi-aromatic nanofiltration (NF270) membranes. Membrane swatches were fixed on removable coupons and exposed to water with indigenous microorganisms supplemented with 1.5 mg l(-1) organic carbon under continuous flow. After biofilms formed, the membrane swatches were removed for analyses. Staining and epifluorescence microscopy revealed more cells on the RO than on the NF surface. Based on image analyses of 5-µm thick cryo-sections, the accumulation of hydrated biofoulants on the RO and NF surfaces exceeded 0.74 and 0.64 µm day(-1), respectively. As determined by contact angle the biofoulants increased the hydrophobicity up to 30° for RO and 4° for NF surfaces. The initial difference between virgin RO and NO hydrophobicities was ∼5°, which increased up to 25° after biofoulant formation. The initial roughness of RO and NF virgin surfaces (75.3 nm and 8.2 nm, respectively) increased to 48 nm and 39 nm after fouling. A wide range of changes of the chemical element mass percentages on membrane surfaces was observed with X-ray photoelectron spectroscopy. The initial chemical signature on the NF surface was better restored after cleaning than the RO membrane. All the data suggest that the semi-aromatic NF surface was more biofilm resistant than the aromatic RO surface. The morphology of the biofilm and the location of active and dead cell zones could be related to the membrane surface properties and general biofouling accumulation was associated with changes in the surface chemistry of the membranes, suggesting the validity of the combination of these novel approaches for initial assessment of membrane performance.

Ten persistent myths and the realities of membrane bioreactor technology for municipal applications.

Twelve years after the first full scale municipal application in Europe of membrane bioreactor (MBR) technology, the process is now accepted as a technology of choice for wastewater treatment, and the market is showing sustained growth. However early misconceptions about the technology are persistent and false statements are commonly encountered in articles and conferences, generating unnecessary research efforts or even fuelling either fascination or scepticism with regards to the technology, which is ultimately detrimental to the perception of the process by water professionals. We try to provide some factual and rational clarifications on ten issues which are often wrongly reported about MBR technology.

Limiting the emissions of micro-pollutants: what efficiency can we expect from wastewater treatment plants?

The next challenge of wastewater treatment is to reliably remove micro-pollutants at the microgram per litre range in order to meet the environmental quality standards set by new regulations like the Water Framework Directive. The present work assessed the efficiency of different types of primary, secondary and tertiary processes for the removal of more than 100 priority substances and other relevant emerging pollutants through on-site mass balances over 19 municipal wastewater treatment lines. Secondary biological processes proved to be in average 30% more efficient than primary settling processes. The activated sludge (AS) process led to a significant reduction of pollution loads (more than 50% removal for 70% of the substances detected). Biofilm processes led to equivalent removal efficiencies compared to AS, except for some pharmaceuticals. The membrane bioreactor (MBR) process allowed to upgrade removal efficiencies of some substances only partially degraded during conventional AS processes. Preliminary tertiary processes like tertiary settling and sand filtration could achieve significant removal for adsorbable substances. Advanced tertiary processes, like ozonation, activated carbon and reverse osmosis were all very efficient (close to 100%) to complete the removal of polar pesticides and pharmaceuticals; less polar substances being better retained by reverse osmosis.