Synthesis of novel adsorbent by intercalation of biopolymer in LDH for the removal of arsenic from synthetic and natural water.

This study focuses on the synthesis of nanocomposites named CCA and CZA that were prepared by the incorporation of cellulose (CL) in the Ca/Al and Zn/Al layered double hydroxide (LDH), respectively. These materials were then used for the uptake of As(III) and As(V) from aqueous medium. Characterization of both nanocomposites (CCA and CZA) was done using FTIR and Raman analysis to identify the functional groups, N2 adsorption-desorption isotherms to determine the specific surface area and pore geometry and XPS analysis to obtain the surface atomic composition. Some other characters were investigated using simultaneous TGA and DTA and elemental chemical analysis (CHNS/O). The crystallinity of the prepared nanocomposites was displayed by XRD patterns. Furthermore, the sheet-like structure of the LDHs and the irregularity of surface morphology with porous structure were observed by TEM and SEM microphotographs. Optimization of maximum adsorption capacity was adjusted using different parameters including pH, contact time and adsorbent dosage. The pseudo-second-order model was in good fitting with kinetics results. The adsorption isotherm results showed that CZA exhibits better adsorption capacity for As(III) than CCA and the Langmuir isotherm model described the data well for both nanocomposites. Thermodynamic studies illustrated the endothermic nature of CCA and exothermic nature on CZA, as well as the fact that the adsorption process is spontaneous. A real water sample collected from well located in Gabes (Tunisia), has also been treated. The obtained experimental results were confirmed that these sorbents are efficient for the treatment of hazardous toxic species such as.

Removal and fate of emerging organic micropollutants (EOMs) in municipal wastewater by a pilot-scale membrane bioreactor (MBR) treatment under varying solid retention times.

This study investigates the removal and fate of 23 emerging organic micropollutants (EOMs) including a wide range of pharmaceuticals (antibiotics, ß-blockers, analgesics, diuretics, psychostimulants, antiepileptics, immunosuppressives, anticoagulants), and steroid hormones detected in municipal wastewater by a pilot-scale membrane bioreactor (MBR) plant at two different solid retention times (SRTs) of 60 and 21 days. Different removal efficiencies of the selected EOMs were observed and explained based on their physicochemical properties (such as distribution coefficient, log D; dissociation constant, pKa; solid-water distribution coefficients, and Kd) along with process operating parameters. The dominant removal mechanisms of EOMs were biotransformation and sorption onto the sludge, which were confirmed by the mass balance study. Moreover, changes in the sludge properties, as a consequence of different SRTs, were evaluated based on variations in soluble microbial products (SMP), extracellular polymeric substances (EPS), and capillary suction time (CST). Finally, the quality of the MBR effluent was compared with some established guidelines, which confirmed the fulfilment of water quality requirements for reuse purposes.

Intercomparison study on commonly used methods to determine microplastics in wastewater and sludge samples.

The harmonized procedures in terms of the sampling, sample treatment and identification of microplastics in different environmental samples are missing, which poses challenges to researchers to compare the results or to adopt 'the most effective' monitoring approach. Furthermore, in the related literature, the used procedures are rarely tested with spiked microplastics to predetermine their recovery rates. Without this knowledge, results should only be discussed as rough estimations of the real environmental concentrations of microplastics. In this study, six different methods previously used in microplastic studies of different media were tested with municipal wastewater and digested sludge samples, spiked with seven different types of plastic particles and fibres. Recovery rates, time consumption, advantages and disadvantages were assessed and most suitable treatment procedures (i.e. high recovery rates in short amount of time) were chosen for both wastewater and sludge. Suitability of staining with Rose Bengal was examined together with most efficient methods, but it did not improve the recovery of microplastics. In addition, the possible impacts of the treatments for identification with micro-Raman and FTIR microscope were assessed. Filtration with size fractioning was found to be the best method for both wastewater and sludge samples, with recovery rates of spiked microplastics around 91.4% and 92.9%, respectively.

Optimization of integrated ultrasonic-Fenton system for metal removal and dewatering of anaerobically digested sludge by Box-Behnken design.

This study reveals the optimization of ultrasonic-Fenton process for the treatment of sludge taken from a local municipal wastewater treatment plant after anaerobic digestion. Box-Behnken design (BBD), a common approach of response surface methodology (RSM), was applied to evaluate and optimize the individual and interactive effects of three process variables, namely Fe2+ dose, H2O2 amount and sonication time for Fenton-ultrasonication method. Five dependent parameters including total organic carbon (TOC), extracellular polymeric substances (EPS), as LB-EPS and TB-EPS, and metals such as Zn and Cu were considered as the responses to investigate. According to the results of analysis of variances (ANOVA), five modelling equations are proposed that can be used to operate the design space with high regression coefficient R2. Modelling results suggest that Fenton parameters, such as: H2O2 and Fe2+ dosage had the significant effects on the overall removal of TOC; whereas, sonication improved the metal removal from the sludge sample. Based on response surface methodology, best performance is achievable under the following conditions: 36 mM of Fe2+, 320 mM H2O2 with 30 min of sonication respectively for all of the responses.

Occurrence, identification and removal of microplastic particles and fibers in conventional activated sludge process and advanced MBR technology.

Wastewater treatment plants (WWTPs) are acting as routes of microplastics (MPs) to the environment, hence the urgent need to examine MPs in wastewaters and different types of sludge through sampling campaigns covering extended periods of time. In this study, the efficiency of a municipal WWTP to remove MPs from wastewater was studied by collecting wastewater and sludge samples once in every two weeks during a 3-month sampling campaign. The WWTP was operated based on the conventional activated sludge (CAS) process and a pilot-scale membrane bioreactor (MBR). The microplastic particles and fibers from both water and sludge samples were identified by using an optical microscope, Fourier Transform Infrared (FTIR) microscope and Raman microscope. Overall, the retention capacity of microplastics in the studied WWTP was found to be 98.3%. Most of the MP fraction was removed before the activated sludge process. The efficiency of an advanced membrane bioreactor (MBR) technology was also examined. The main related finding is that MBR permeate contained 0.4 MP/L in comparison with the final effluent of the CAS process (1.0 MP/L). According to this study, both microplastic fibers and particles are discharged from the WWTP to the aquatic environment.

Advanced oxidation processes for the removal of natural organic matter from drinking water sources: A comprehensive review.

Natural organic matter (NOM), a key component in aquatic environments, is a complex matrix of organic substances characterized by its fluctuating amounts in water and variable molecular and chemical properties, leading to various interaction schemes with the biogeosphere and hydrologic cycle. These factors, along with the increasing amounts of NOM in surface and ground waters, make the effort of removing naturally-occurring organics from drinking water supplies, and also from municipal wastewater effluents, a challenging task requiring the development of highly efficient and versatile water treatment technologies. Advanced oxidation processes (AOPs) received an increasing amount of attention from researchers around the world, especially during the last decade. The related processes were frequently reported to be among the most suitable water treatment technologies to remove NOM from drinking water supplies and mitigate the formation of disinfection by products (DBPs). Thus, the present work overviews recent research and development studies conducted on the application of AOPs to degrade NOM including UV and/or ozone-based applications, different Fenton processes and various heterogeneous catalytic and photocatalytic oxidative processes. Other non-conventional AOPs such as ultrasonication, ionizing radiation and plasma technologies were also reported. Furthermore, since AOPs are unlikely to achieve complete oxidation of NOM, integration schemes with other water treatment technologies were presented including membrane filtration, adsorption and others processes.

Removal of natural organic matter in drinking water treatment by coagulation: A comprehensive review.

Natural organic matter (NOM) is a complex matrix of organic substances produced in (or channeled to) aquatic ecosystems via various biological, geological and hydrological cycles. Such variability is posing a serious challenge to most water treatment technologies, especially the ones designed to treat drinking water supplies. Lately, in addition to the fluctuating composition of NOM, a substantial increase of its concentration in fresh waters, and also municipal wastewater effluents, has been reported worldwide, which justifies the urgent need to develop highly efficient and versatile water treatment processes. Coagulation is among the most applied processes for water and wastewater treatment. The application of coagulation to remove NOM from drinking water supplies has received a great deal of attention from researchers around the world because it was efficient and helped avoiding the formation of disinfection by products (DBPs). Nonetheless, with the increased fluctuation of NOM in water (concentration and composition), the efficiency of conventional coagulation was substantially reduced, hence the need to develop enhanced coagulation processes by optimizing the operating conditions (mainly the amount coagulants and pH), developing more efficient inorganic or organic coagulants, as well as coupling coagulation with other water treatment technologies. In the present review, recent research studies dealing with the application of coagulation for NOM removal from drinking water supplies are presented and compared. In addition, integration schemes combining coagulation and other water treatment processes are presented, including membrane filtration, oxidation, adsorption and others processes.

Optimized removal of oxytetracycline and cadmium from contaminated waters using chemically-activated and pyrolyzed biochars from forest and wood-processing residues.

In the present investigation, the adsorptive removal of the antibiotic drug oxytetracycline (OTC) and toxic heavy metal cadmium (Cd) from aqueous solution was carried out using forest and wood-processing residues. Numerous biochars were prepared using different chemical agents (H3PO4, H2SO4, NaOH and KOH) and pyrolysis times and temperatures. Several elemental, chemical and structural characterizations were performed. The optimum conditions for pyrolysis to enable the production of biochars with well-developed porosity was 600°C for 1h, for both residues. The adsorption process using selected activated biochars was optimized with respect to reaction time, pH, temperature and initial load of pollutants. Under optimized operating conditions, and based on equilibrium modelling data, the biochars which showed the highest removal efficiencies of OTC and cadmium were "5M H3PO4 forest" (263.8mg/g) and "1M NaOH forest" (79.30mg/g), respectively. Compared to adsorbents reported in the literature, the efficiencies of those biochars are highly competitive.

Assessing membrane fouling and the performance of pilot-scale membrane bioreactor (MBR) to treat real municipal wastewater during winter season in Nordic regions.

In this study, the performance of a pilot-scale membrane bioreactor (MBR) to treat real municipal wastewater was assessed at low temperatures (7 to 20°C) in Nordic regions. First, the effect of low temperatures on membrane fouling was evaluated by monitoring trans-membrane pressure. A significant membrane fouling was observed when the sludge temperature inside the MBR unit was below 10°C with a 75% permeability drop, thus indicating high deterioration of the membrane performance at low temperatures. Moreover, increasing values of sludge volume index (SVI) during low temperatures showed high deterioration of sludge settleability. As for the pollution removal, MBR achieved high performances primarily for pathogens and emerging micropollutants. The average log reductions of 1.82, 3.02, and 1.94 log units were achieved for norovirus GI, norovirus GII, and adenoviruses, respectively. Among the four trace organic compounds (TrOCs), the average removal efficiencies of bisoprolol, diclofenac and bisphenol A were 65%, 38%, and >97%, respectively. However, carbamazepine was not efficiently removed (-89% to 28%). Regarding trace metals, an average removal of >80% was achieved for Cd, Pb, and V. For the rest of the metals, the removal capacities were between 30 and 60%.

Optimized removal of antibiotic drugs from aqueous solutions using single, double and multi-walled carbon nanotubes.

In this study, experiments were carried out to investigate the use of as-synthesized single-walled (SWCNT), double-walled (DWCNT) and multi-walled carbon nanotubes (MWCNT) agglomerates for the removal of two antibiotics, Oxytetracycline (OXY) and Ciprofloxacin (CIP) from aqueous solution. The variations of key operating parameters on the removal process were assessed in order to find out the optimum conditions. It includes exposure time, solution pH, temperature, ultrasound assistance and desorption assays. The experimental results revealed that a moderate increase in adsorption was registered between pH 3 and 7 for both antibiotics. The application of ultrasound helped enhancing the removal capacities of OXY for all tested CNTs. For the case of MWCNTs, 1h of ultrasonication increased the adsorption capacity by 44.6%. As for CIP, the ultrasonic treatment did not enhance the overall adsorption, especially for the case of DWCNTS. The Brouers-Sotolongo equation was the best fitting isotherm model. The highest removal capacities were registered using SWCNTS for both antibiotics (724 mg/g for CIP and 554 mg/g for OXY). In addition, ethanol was the solvent that induced the highest desorption percent for the case of CIP (52% for MWCNTs). However, the desorption of OXY was negligible for all solvents (maximum 3.3% for DWCNTs using ethanol).

As-synthesized multi-walled carbon nanotubes for the removal of ionic and non-ionic surfactants.

This research deals with the application of untreated multi-walled carbon nanotubes (MWCNT) in their agglomerates form for the removal of non-ionic (TX-100), cationic (CTAB) and anionic (SDBS) surfactants from aqueous media. In order to optimize the removal process, the influence of several key parameters was investigated including contact time under different solid/liquid ratios, initial solution pH, temperature, along with ultrasonication assistance and desorption assays. Experimentations revealed that pH variation enhanced the removal capacities at optimum values of 6, 2 and 8 for TX-100, SDBS and CTAB, respectively, and that hydrophobic interaction is a major adsorption factor, especially for non-ionic surfactant with possible electrostatic interactions occurring for the ionic ones. As well, removal efficiencies peaked for an optimum temperature range between 35 and 45 °C. As for the ultrasonication assistance, it enhanced the overall removal capacities, especially that of the ionic surfactant, with an enhancement of 52% for the case of SDBS after 1h of treatment. The modeling results revealed that the pseudo-second order model provided the best correlation of the dynamic data and that the process was controlled by intraparticle diffusion phenomena. At equilibrium, and under optimized experimental conditions, untreated MWCNTs showed promising removal capacities with 359, 312 and 156 mg/g for TX-100, SDBS and CTAB, respectively.

Biosorption of methylene blue by chaetophora elegans algae: kinetics, equilibrium and thermodynamic studies.

Adsorptive removal capacities of renewable and highly available Chaetophora elegans algae have been investigated in this study. To assess the use of this soft water algae to remove organic pollutants from aqueous solution, Methylene blue (MB) dye was used as a model molecule. The effect of dye concentrations, pH, adsorbent mass, temperature, and particle size have been evaluated. The algal biomass showed quite interesting adsorption capacity under optimized operating conditions (333 mg of dye per gram of biomass at 30 °C). Pseudo-first and pseudo-second order kinetic models were applied to the adsorption dynamic data. Pseudo second order model was well in line with the experimental data, therefore suggesting a probable chemically-based adsorption process. Several isotherm models were investigated to monitor the adsorption behavior. The Langmuir-Freundlich isotherm model fitted the experimental data best. The adsorption thermodynamic parameters ΔG°, ΔH° and ΔS° were calculated. The maximum uptake is independent of temperature. From the values of the thermodynamic parameters, we concluded that the adsorption is exothermic, more ordered and spontaneous.

Applicability of some statistical tools to predict optimum adsorption isotherm after linear and non-linear regression analysis.

In any single component isotherm study, determining the best-fitting model is a key analysis to mathematically describe the involved sorption system and, therefore, to explore the related theoretical assumptions. Hence, several error calculation functions have been widely used to estimate the error deviations between experimental and theoretically predicted equilibrium adsorption values (Q(e,exp)vs.Q(e,theo) as X- and Y-axis, respectively), including the average relative error deviation, the Marquardt's percent standard error deviation, the hybrid fractional error function, the sum of the squares of the errors, the correlation coefficient and the residuals. In this study, five other statistical functions are analysed to investigate their applicability as suitable tools to evaluate isotherm model fitness, namely the Pearson correlation coefficient, the coefficient of determination, the Chi-square test, the F-test and the Student's T-test, using the commonly-used functions as references. The adsorption of textile dye onto Posidonia oceanica seagrass fibres was carried out, as study case, in batch mode at 20 degrees C. Besides, and in order to get an overall approach of the possible utilization of these statistical functions within the studied item, the examination was realized for both linear and non-linear regression analysis. The related results showed that, among the five studied statistical tools, the chi(2) and Student's T-tests were suitable to determine the best-fitting isotherm model for the case of linear modelling approach. On the other hand, dealing with the non-linear analysis, despite the Student's T-test, all the other functions gave satisfactorily results, by agreeing the commonly-used error functions calculation.

Investigation of the sorption mechanisms of metal-complexed dye onto Posidonia oceanica (L.) fibres through kinetic modelling analysis.

This research deals with the exploitation of highly available and renewable marine biomass, Posidonia oceanica (L.) fibres as low cost biosorbent for the removal of metal-complexed textile dyestuff from aqueous medium, and the investigation of the probably involved physiochemical mechanisms. Experiments were carried out in batch reactor. Firstly, the adsorption process was studied as a function of initial solution pH and contact time under different initial dye concentration. The results showed that the highest dye adsorption capacity was found at pH 2 under a constant temperature of 30 degrees C, and the equilibrium state was reached within 48 h of exposure time. Secondly, several adsorption kinetic models were applied to fit the experimental data, namely Lagergren irreversible first-order, Reversible first-order, Pseudo-second-order, Elovich, Ritchie and intraparticle diffusion models. The proposed explanations were deduced from the theoretical assumptions behind the most appropriate model(s), which could satisfactorily describe the present biosorption phenomenon. The interpretation of the related results have shown that, with R(2) of about 99%, the pseudo-second order model is the most suitable dynamic theory describing the biosorption of metal complex dye onto P. oceanica fibres, predicting therefore a chemisorption process.

Effects of aging on the extractability of naphthalene and phenanthrene from Mediterranean soils.

The effects of aging on the extractability of naphthalene and phenanthrene were investigated using laboratory batch assays. Experiments have been conducted with three soil matrices: a silty clay and two soils with different organic contents. Aging was conducted under abiotic conditions in water saturated and nonsaturated conditions, under a constant temperature (20 degrees C). The mobility of sorbed contaminants was evaluated through successive extractions in water, methanol, butanol and dichloromethane. Experimental results showed a reduction of the extractability of both naphthalene and phenanthrene with increasing aging times. The observed effects of aging might be related to slow diffusion of naphthalene and phenanthrene in sorbent microporosity and/or organic phases and possible evolutions of pollutant-sorbent interactions.

Kinetic and equilibrium studies of methylene blue biosorption by Posidonia oceanica (L.) fibres.

Batch biosorption experiments were carried out for the removal of methylene blue, a basic dye, from aqueous solution using raw Posidonia oceanica (L.) fibres, a marine lignocellulosic biomass. A series of assays were undertaken to assess the effect of the system variables, i.e. contact time, solution pH, biosorbent dosage and initial dye concentration. The results had showed that biosorption capacity was optimal using 6-9 solution pH range and by increasing the biosorbent concentration up to 1 g/L. The biosorption kinetics were analyzed using irreversible-first-order, reversible-first-order and pseudo-second-order and the sorption data were very well described by the pseudo-second-order model for the entire adsorption time with squared correlation coefficients equal to unity for all experimented initial dye concentrations. Besides, equilibrium data were very well represented by both Langmuir and Redlich-Peterson isotherm models followed by Freundlich, which confirm the monolayer coverage of methylene blue molecules onto P. oceanica fibres.