Adsorption of phosphate from aqueous solution using electrochemically modified biochar calcium-alginate beads: Batch and fixed-bed column performance.

Batch and continuous fixed-bed column studies were investigated using electrochemically modified biochar calcium-alginate beads (EMB-CABs) as an adsorbent for the removal of phosphate from aqueous solutions. Batch experiments revealed that the phosphate adsorption behavior of EMB-CABs and its structural characteristics were highly dependent on pH condition. Also, kinetics and equilibrium isotherms studies demonstrated that the experimental data correlated well with the pseudo-second-order and Sips isotherm models, respectively. The effects of different operating parameters such as bed height, initial phosphate concentration, and flow rate were investigated in a continuous fixed-bed column, and the experimental data were fitted to three different breakthrough models, the Adams-Bohart, Thomas, and Yoon-Nelson models. The results suggested that the Yoon-Nelson model showed better agreement with the breakthrough curves than other models. Lastly, the design parameters for a large-scale column were calculated via the scale-up approach using the breakthrough parameters obtained from lab-scale column tests.

Facile synthesis of magnetic biochar/Fe3O4 nanocomposites using electro-magnetization technique and its application on the removal of acid orange 7 from aqueous media.

This study introduces a new methodology to synthesize magnetic biochar/Fe3O4 nanocomposites (M-BC) from marine macroalgae using a facile electro-magnetization technique. M-BC was prepared by stainless steel electrode-based electrochemical system, followed by pyrolysis. Physical and chemical analyses revealed that the porosity and magnetic properties were simultaneously improved via the electro-magnetization process, which enabled not only higher adsorption performance, but also easier separation/recovery from aqueous media at post-adsorption stage using a bar magnet. The adsorption equilibrium studies reveal that the Sips model satisfactorily predicts the adsorption capacity, which found to be 190, 297, and 382mgg(-1) at 10, 20, and 30°C, respectively. The overall findings indicate that one-step electro-magnetization technique can be effectively utilized for the fabrication of biochar with concurrent acquisition of porosity and magnetism, which can bring about new directions in the practical use of adsorption process in environment remediation and mitigate crises originating from it.

Fabrication of granular activated carbons derived from spent coffee grounds by entrapment in calcium alginate beads for adsorption of acid orange 7 and methylene blue.

Biomass-based granular activated carbon was successfully prepared by entrapping activated carbon powder derived from spent coffee grounds into calcium-alginate beads (SCG-GAC) for the removal of acid orange 7 (AO7) and methylene blue (MB) from aqueous media. The dye adsorption process is highly pH-dependent and essentially independent of ionic effects. The adsorption kinetics was satisfactorily described by the pore diffusion model, which revealed that pore diffusion was the rate-limiting step during the adsorption process. The equilibrium isotherm and isosteric heat of adsorption indicate that SCG-GAC possesses an energetically heterogeneous surface and operates via endothermic process in nature. The maximum adsorption capacities of SCG-GAC for AO7 (pH 3.0) and MB (pH 11.0) adsorption were found to be 665.9 and 986.8mg/g at 30°C, respectively. Lastly, regeneration tests further confirmed that SCG-GAC has promising potential in its reusability, showing removal efficiency of more than 80% even after seven consecutive cycles.

Comprehensive reuse of drinking water treatment residuals in coagulation and adsorption processes.

While drinking water treatment residuals (DWTRs) inevitably lead to serious problems due to their huge amount of generation and limitation of landfill sites, their unique properties of containing Al or Fe contents make it possible to reuse them as a beneficial material for coagulant recovery and adsorbent. Hence, in the present study, to comprehensively handle and recycle DWTRs, coagulant recovery from DWTRs and reuse of coagulant recovered residuals (CRs) were investigated. In the first step, coagulant recovery from DWTRs was conducted using response surface methodology (RSM) for statistical optimization of independent variables (pH, solid content, and reaction time) on response variable (Al recovery). As a result, a highly acceptable Al recovery of 97.5 ± 0.4% was recorded, which corresponds to 99.5% of the predicted Al recovery. Comparison study of recovered and commercial coagulant from textile wastewater treatment indicated that recovered coagulant has reasonable potential for use in wastewater treatment, in which the performance efficiencies were 68.5 ± 2.1% COD, 97.2 ± 1.9% turbidity, and 64.3 ± 1.0% color removals at 50 mg Al/L. Subsequently, in a similar manner, RSM was also applied to optimize coagulation conditions (Al dosage, initial pH, and reaction time) for the maximization of real cotton textile wastewater treatment in terms of COD, turbidity, and color removal. Overall performance revealed that the initial pH had a remarkable effect on the removal performance compared to the effects of other independent variables. This is mainly due to the transformation of metal species form with increasing or decreasing pH conditions. Finally, a feasibility test of CRs as adsorbent for phosphate adsorption from aqueous solution was conducted. Adsorption equilibrium of phosphate at different temperatures (10-30 °C) and initial levels of pH (3-11) indicated that the main mechanisms of phosphate adsorption onto CRs are endothermic and chemical precipitation; the surfaces are energetically heterogeneous for adsorbing phosphate.

Preparation of modified-biochar from Laminaria japonica: Simultaneous optimization of aluminum electrode-based electro-modification and pyrolysis processes and its application for phosphate removal.

The preparation conditions of electro-modification (current density) and pyrolysis (pyrolysis temperature and heating rate) processes were simultaneously optimized using response surface methodology with the quadratic regression model associated with Box-Behnken design. By numerical optimization, the phosphate adsorption capacity of 245.06mg/g was achieved, corresponding to 99.9% of the predicted values under statistically optimized conditions (current density: 38.78mA/cm(2), pyrolysis temperature: 584.1°C, heating rate: 6.91°C/min). By considering R(2) and three error functions values, the experimental results of adsorption kinetics, and the equilibrium isotherms at different temperatures (10-30°C) showed that predictive pseudo-second-order and Sips isotherm models could adequately interpret the phosphate adsorption process for 'statistically optimized electrically modified'-biochar (SOEM-biochar). The maximum phosphate adsorption capacities of SOEM-biochar were found to be 273.9, 345.1, and 460.3mg/g at 10, 20, and 30°C, respectively, which are higher than that of other adsorbents reported in the literature.

Characteristics of biochar derived from marine macroalgae and fabrication of granular biochar by entrapment in calcium-alginate beads for phosphate removal from aqueous solution.

In this work, granular biochar, Laminaria japonica-derived biochar (LB)-calcium alginate beads (LB-CAB), was successfully prepared by dropping a mixture of powder biochar and alginate solution into a calcium chloride solution for phosphate adsorption. Among different marine macroalgae derived biochars, LB exhibited the best performance, showing a phosphate removal rate of 97.02%, which was attributed to its high Ca/P and Mg/P ratios. With increasing pyrolysis temperature up to 600°C, the physicochemical properties of LB became suitable for adsorbing phosphate. Experimental results of kinetics and equilibrium isotherms at different temperatures (10-30°C) showed that the phosphate adsorption process is endothermic and is mainly controlled by external mass transfer and the intraparticle diffusion rate. The maximum adsorption capacity was found to be 157.7mgg(-1) at 30°C, as fitted by the Langmuir-Freundlich model, which is higher than capacities of other powder form of biochars.

Fabrication of porosity-enhanced MgO/biochar for removal of phosphate from aqueous solution: Application of a novel combined electrochemical modification method.

A novel combined electrochemical modification (CEM) method, using a graphite electrode-based electric field and MgCl2 as electrolyte, was newly developed to prepare porosity-enhanced biochar containing periclase (MgO) nanocomposites (PE-MgO/biochar). During the CEM method, the dried marine macroalgae was immersed in the MgCl2 solution, and a voltage of 20V was then applied for 10min prior to pyrolysis. Morphological and chemical analyses results showed that nano-sized MgO particles with a highly crystalline structure were dispersed and enriched on the surface of the PE-MgO/biochar, which enabled higher phosphate adsorption capability. In an adsorption equilibrium test, among various biochars, PE-MgO/biochar exhibited the highest phosphate adsorption capacity from aqueous solution with a Langmuir-Freundlich maximum adsorption capacity as high as 620mg-Pg(-1). It can be concluded that the newly introduced CEM method is a potent additional technique to effectively prepare modified-biochar in terms of a simple and time-saving modification method.

Dual purpose recovered coagulant from drinking water treatment residuals for adjustment of initial pH and coagulation aid in electrocoagulation process.

The present study is focused on the application of recovered coagulant (RC) by acidification from drinking water treatment residuals for both adjusting the initial pH and aiding coagulant in electrocoagulation. To do this, real cotton textile wastewater was used as a target pollutant, and decolorization and chemical oxygen demand (COD) removal efficiency were monitored. A preliminary test indicated that a stainless steel electrode combined with RC significantly accelerated decolorization and COD removal efficiencies, by about 52% and 56%, respectively, even at an operating time of 5 min. A single electrocoagulation system meanwhile requires at least 40 min to attain the similar removal performances. Subsequently, the interactive effect of three independent variables (applied voltage, initial pH, and reaction time) on the response variables (decolorization and COD removal) was evaluated, and these parameters were statistically optimized using the response surface methodology. Analysis of variance showed a high coefficient of determination values (decolorization, R(2) = 0.9925 and COD removal, R(2) = 0.9973) and satisfactory prediction second-order polynomial quadratic regression models. Average decolorization and COD removal of 89.52% and 94.14%, respectively, were achieved, corresponding to 97.8% and 98.1% of the predicted values under statistically optimized conditions. The results suggest that the RC effectively played a dual role of both adjusting the initial pH and aiding coagulant in the electrocoagulation process.

Influence of pyrolysis temperature on characteristics and phosphate adsorption capability of biochar derived from waste-marine macroalgae (Undaria pinnatifida roots).

The collected roots of Undaria pinnatifida, the main waste in farming sites, accounting for 40-60% of annual production, was pyrolyzed under temperature ranging from 200 to 800°C to evaluate the influence of pyrolysis temperature on biochar properties and phosphate adsorption capacity. It was confirmed that an increase in the pyrolysis temperature led to a decrease of the yield of biochar, while ash content remained almost due to carbonization followed by mineralization. Elemental analysis results indicated an increase in aromaticity and decreased polarity at a high pyrolysis temperature. When the pyrolysis temperature was increased up to 400°C, the phosphate adsorption capacity was enhanced, while a further increase in the pyrolysis temperature lowered the adsorption capacity due to blocked pores in the biochar during pyrolysis. Finally, a pot experiment revealed that biochar derived from waste-marine macroalgae is a potent and eco-friendly alternative material for fertilizer after phosphate adsorption.

Phosphate adsorption ability of biochar/Mg-Al assembled nanocomposites prepared by aluminum-electrode based electro-assisted modification method with MgCl2 as electrolyte.

In this work, the textural properties and phosphate adsorption capability of modified-biochar containing Mg-Al assembled nanocomposites prepared by an effective electro-assisted modification method with MgCl2 as an electrolyte have been determined. Structure and chemical analyses of the modified-biochar showed that nano-sized stonelike or flowerlike Mg-Al assembled composites, MgO, spinel MgAl2O4, AlOOH, and Al2O3, were densely grown and uniformly dispersed on the biochar surface. The adsorption isotherm and kinetics data suggested that the biochar/Mg-Al assembled nanocomposites have an energetically heterogeneous surface and that phosphate adsorption could be controlled by multiple processes. The maximum phosphate adsorption capacity was as high as 887 mg g(-1), as fitted by the Langmuir-Freundlich model, and is the highest value ever reported. It was concluded that this novel electro-assisted modification is a very attractive method and the biochar/Mg-Al assembled nanocomposites provide an excellent adsorbent that can effectively remove phosphate from aqueous solutions.

A novel approach for preparation of modified-biochar derived from marine macroalgae: Dual purpose electro-modification for improvement of surface area and metal impregnation.

In the present study, an aluminum electrode-based electrochemical process was newly adopted as a modification method for fabricating physically and chemically modified biochar derived from marine macroalgae. Specifically, a current density of 93.96 mA cm(-2) was applied for 5 min at pH 3.0. Subsequently, the mixture was stirred continuously for 30 min without electric field, and the dried sample was then pyrolyzed at 450 °C under a N2 environment for 2 h. SEM-EDS and XRD analyses clearly indicated that nano-sized aluminum crystals (beohemite, AlOOH) were uniformly present on the EM-biochar surface. Adsorption equilibrium tests showed that the phosphate adsorption onto EM-biochar agreed well with the Langmuir-Freundlich adsorption isotherm model, with a maximum adsorption capacity of 31.28 mg-P g(-1). These findings suggest that this novel and simple electro-modification method is a reasonable and effective option for simultaneously upgrading both the surface area and chemical properties of biochar.

Lead and copper removal from aqueous solutions using carbon foam derived from phenol resin.

Phenolic resin-based carbon foam was prepared as an adsorbent for removing heavy metals from aqueous solutions. The surface of the produced carbon foam had a well-developed open cell structure and the specific surface area according to the BET model was 458.59m(2)g(-1). Batch experiments showed that removal ratio increased in the order of copper (19.83%), zinc (34.35%), cadmium (59.82%), and lead (73.99%) in mixed solutions with the same initial concentration (50mgL(-1)). The results indicated that the Sips isotherm model was the most suitable for describing the experimental data of lead and copper. The maximum adsorption capacity of lead and copper determined to Sips model were 491mgg(-1) and 247mgg(-1). The obtained pore diffusion coefficients for lead and copper were found to be 1.02×10(-6) and 2.42×10(-7)m(2)s(-1), respectively. Post-sorption characteristics indicated that surface precipitation was the primary mechanism of lead and copper removal by the carbon foam, while the functional groups on the surface of the foam did not affect metal adsorption.

Decolorization of Acid Orange 7 by an electric field-assisted modified orifice plate hydrodynamic cavitation system: Optimization of operational parameters.

In this study, the decolorization of Acid Orange 7 (AO-7) with intensified performance was obtained using hydrodynamic cavitation (HC) combined with an electric field (graphite electrodes). As a preliminary step, various HC systems were compared in terms of decolorization, and, among them, the electric field-assisted modified orifice plate HC (EFM-HC) system exhibited perfect decolorization performance within 40 min of reaction time. Interestingly, when H2O2 was injected into the EFM-HC system as an additional oxidant, the reactor performance gradually decreased as the dosing ratio increased; thus, the remaining experiments were performed without H2O2. Subsequently, an optimization process was conducted using response surface methodology with a Box-Behnken design. The inlet pressure, initial pH, applied voltage, and reaction time were chosen as operational key factors, while decolorization was selected as the response variable. The overall performance revealed that the selected parameters were either slightly interdependent, or had significant interactive effects on the decolorization. In the verification test, complete decolorization was observed under statistically optimized conditions. This study suggests that EFM-HC is a useful method for pretreatment of dye wastewater with positive economic and commercial benefits.

Application and optimization of electric field-assisted ultrasonication for disintegration of waste activated sludge using response surface methodology with a Box-Behnken design.

In the present study, an electric field is applied in order to disintegrate waste activated sludge (WAS). As a preliminary step, feasibility tests are investigated using different applied voltages of 10-100V for 60min. As the applied voltage increases, the disintegration degrees (DD) are gradually enhanced, and thereby the soluble N, P, and carbohydrate concentrations increase simultaneously due to the WAS decomposition. Subsequently, an optimization process is conducted using a response surface methodology with a Box-Behnken design (BBD). The total solid concentration, applied voltage, and reaction time are selected as independent variables, while the DD is selected as the response variable. The overall results demonstrate that the BBD with an experimental design can be used effectively in the optimization of the electric field treatment of WAS. In the confirmation test, a DD of 10.26±0.14% is recorded, which corresponds to 99.1% of the predicted response value under the statistically optimized conditions. Finally, the statistic optimization of the combined treatment (electric field+ultrasonication) demonstrated that even though this method is limited to highly disintegrated WAS when it is applied individually, a high DD of 47.28±0.20% was recorded where the TS concentration was 6780mg/l, the strength of ultrasonication was 8.0W, the applied voltage was 68.4V, and the reaction time was 44min. E-SEM images clearly revealed that the application of the electric field is a significant alternative method for the combined treatment of WAS. This study was the first attempt to increase disintegration using the electric field for a combined treatment with ultrasonication.

Development of a novel electric field-assisted modified hydrodynamic cavitation system for disintegration of waste activated sludge.

In this current study, we present a modified hydrodynamic cavitation device that combines an electric field to substitute for the chemical addition. A modified HC system is basically an orifice plate and crisscross pipe assembly, in which the crisscross pipe imparts some turbulence, which creates collision events. This study shows that for maximizing disintegration, combining HC system, which called electric field-assisted modified orifice plate hydrodynamic cavitation (EFM-HC) in this study, with an electric field is important. Various HC systems were compared in terms of disintegration of WAS, and, among them, the EFM-HC system exhibited the best performance with the highest disintegration efficiency of 47.0±2.0% as well as the destruction of WAS morphological characteristics. The experimental results clearly show that a conventional HC system was successfully modified. In addition, electric field has a great potential for efficient disintegration of WAS for as a additional option in a combination treatment. This study suggests continued research in this field may lead to an appropriate design for commercial use.

Characteristics of flux and gel layer on microfilter and non-woven fabric filter surface based on anoxic-aerobic MBRs.

Non-woven fabric filter- (NWFF) and microfilter-MBR modules were made using 100 µm polypropylene and 0.25 µm polyethylene materials, respectively. The performances and mechanisms of the two processes were investigated, including additional batch filtration tests to find the function of the dynamic gel layer on the membrane surface. The HRT of both MBRs was 9 h and the operating permeate flux was 13 L/m(2)/h. The two MBRs consisted of an anoxic and aerobic reactor. The NWFF or microfilter (MF) was submerged in each of the aerobic reactors. The two MBRs showed similar performances for the removal of organic matters, suspended solids and nitrogen. Cake formation on the NWFF contributed to major resistance, while the gel layer on the microfilter or internal fouling of the pores played a key role in the fouling of the membrane surface. The amount of soluble extracellular polymer substances (EPS) (13 mg/L) of the attached sludge on the NWFF surface was larger than that (11 mg/L) of that suspended sludge. Consequently, the functional gel layer for the coarse and microfilter is established based on the relationship among the EPS, transmembrane pressure and MLSS.

The effects of antecedent dry days on the nitrogen removal in layered soil infiltration systems for storm run-off control.

The effects of antecedent dry days (ADD) on nitrogen removal efficiency were investigated in soil infiltration systems, with three distinguishable layers: mulch layer (ML), coarse soil layer (CSL) and fine soil layer (FSL). Two sets of lab-scale columns with loamy CSL (C1) and sandy CSL (C2) were dosed with synthetic run-off, carrying chemical oxygen demand of 100 mg L(-1) and total nitrogen of 13 mg L(-1). The intermittent dosing cycle was stepwise adjusted for 5, 10 and 20 days. The influent ammonium and organic nitrogen were adsorbed to the entire depth in C1, while dominantly to the FSL in C2. In both columns, the effluent ammonium concentration increased while the organic nitrogen concentration decreased, as ADD increased from 5 to 20 days. The effluent of C1 always showed nitrate concentration exceeding influent, caused by nitrification, by increasing amounts as ADD increased. However, the wash-out of nitrate in C1 was not distinct in terms of mass since the effluent flow rate was only 25% of the influent. In contrast, efficient reduction (>95%) of nitrate loading was observed in C2 under ADD of 5 and 10 days, because of insignificant nitrification in the CSL and denitrification in the FSL. However, for the ADD of 20 days, a significant nitrate wash-out appeared in C2 as well, possibly because of the re-aeration by the decreasing water content in the FSL. Consequently, the total nitrogen load escaping with the effluent was always smaller in C2, supporting the effectiveness of sandy CSL over loamy FSL for nitrogen removal under various ADDs.

Removal of nitrogen by a layered soil infiltration system during intermittent storm events.

The fates of various nitrogen species were investigated in a layered biological infiltration system under an intermittently wetting regime. The layered system consisted of a mulch layer, coarse soil layer (CSL), and fine soil layer (FSL). The effects of soil texture were assessed focusing on the infiltration rate and the removal of inorganic nitrogen species. The infiltration rate drastically decreased when the uniformity coefficient was larger than four. The ammonium in the synthetic runoff was shown to be removed via adsorption during the stormwater dosing and nitrification during subsequent dry days. Stable ammonium adsorption was observed when the silt and clay content of CSL was greater than 3%. This study revealed that the nitrate leaching was caused by nitrification during dry days. Various patterns of nitrate flushing were observed depending on the soil configuration. The washout of nitrate was more severe as the silt/clay content of the CSL was greater. However, proper layering of soil proved to enhance the nitrate removal. Consequently, a strictly sandy CSL over FSL with a silt and clay content of 10% was the best configuration for the removal of ammonium and nitrate.

Effects of internal recycling time mode and hydraulic retention time on biological nitrogen and phosphorus removal in a sequencing anoxic/anaerobic membrane bioreactor process.

This study investigated the effects of internal recycling time mode and hydraulic retention time (HRT) on nutrient removal in the sequencing anoxic/anaerobic membrane bioreactor process. Denitrification and phosphorus release were reciprocally dependent on the anoxic/anaerobic time ratio (Ax/An). As Ax/An increased, nitrogen removal rate increased but phosphorus removal rate decreased. The increasing Ax/An provided the longer denitrification period so that the organic substrate were consumed more for denitrification rather than phosphorus release in the limited condition of readily biodegradable substrate. Decreasing HRT increased both nitrogen and phosphorus removal efficiency because as HRT decreased, food-to-microorganism loading ratio increased and thus enhanced the biological capacity and activity of denitrifying bacteria. This could be verified from the observation mixed liquor suspended solids concentration and specific denitrification rate. The change of Ax/An and HRT affected phosphorus removal more than nitrogen removal due to the limitation of favourable carbon source for phosphorus accumulating organisms.

Contribution of microfiltration on phosphorus removal in the sequencing anoxic/anaerobic membrane bioreactor.

This study investigated the contribution of microfiltration to phosphorus removal in the sequencing anoxic/anaerobic membrane bioreactor. The phosphorus content in activated sludge was fractionated by the Schmidt-Thannhauser-Schneider method. The size distribution of phosphorus in the influent was analyzed to estimate the portion of particulate phosphorus rejected physically by the 0.2 mum microfiltration. The result was that along with the high removal of phosphorus (83%) the phosphorus content of activated sludge was measured as 58.66 mgP/gVSS corresponding to 5.87% on dry weight basis. About 9% of total phosphorus was chemically precipitated phosphates while 56% was stored inside the microbial cell by activity of PAOs, and 35% was the sum of minor intracellular compositions and the particulate residuals, which could be rejected completely by the microfiltration. The biological activity is the dominant way of phosphorus removal in the process. However, the microfiltration also contributed significantly to phosphorus removal by retaining the particulate phosphorus inside the system.