Feasibility study of Aesculus turbinata fruit shell-derived biochar for ammonia removal in wastewater and its subsequent use as nitrogen fertilizer.

In the face of increasing nitrogen demand for crop cultivation driven by population growth, this study presents a sustainable solution to address both the heightened demand and the energy-intensive process of nitrogen removal from wastewater. Our approach involves the removal of nitrogen from wastewater and its subsequent return to the soil as a fertilizer. Using biochar derived from Aesculus turbinata fruit shells (ATFS), a by-product of post-medical use, we investigated the effect of pyrolysis temperature on the NH4-N adsorption capacity of ATFS biochar (ATFS-BC). Notably, the ATFS-BC pyrolyzed at 300 °C (ATFS-BC300) exhibited the highest NH4-N adsorption capacity of 15.61 mg/g. The superior performance of ATFS-BC300 was attributed to its higher number of oxygen functional groups and more negatively charged surface, which contributed to the enhanced NH4-N adsorption. The removal of NH4-N by ATFS-BC300 involved both physical diffusion and chemisorption, with NH4-N forming a robust multilayer adsorption on the biochar. Alkaline conditions favored NH4-N adsorption by ATFS-BC300; however, the presence of trivalent and divalent ions hindered this process. Rice plants were cultivated to assess the potential of NH4-N adsorbed ATFS-BC300 (NH4-ATFS-BC300) as a nitrogen fertilizer. Remarkably, medium doses of NH4-ATFS-BC300 (594.5 kg/ha) exhibited key agronomic traits similar to those of the commercial nitrogen fertilizer in rice seedlings. Furthermore, high doses of NH4-ATFS-BC300 demonstrated superior agronomic traits compared to the commercial fertilizer. This study establishes the viability of utilizing ATFS-BC300 as a dual-purpose solution for wastewater treatment and nitrogen fertilizer supply, presenting a promising avenue for addressing environmental challenges.

Algae development in rivers with artificially constructed weirs: Dominant influence of discharge over temperature.

Algal blooms contribute to water quality degradation, unpleasant odors, taste issues, and the presence of harmful substances in artificially constructed weirs. Mitigating these adverse effects through effective algal bloom management requires identifying the contributing factors and predicting algal concentrations. This study focused on the upstream region of the Seungchon Weir in Korea, which is characterized by elevated levels of total nitrogen and phosphorus due to a significant influx of water from a sewage treatment plant. We employed four distinct machine learning models to predict chlorophyll-a (Chl-a) concentrations and identified the influential variables linked to local algal bloom events. The gradient boosting model enabled an in-depth exploration of the intricate relationships between algal occurrence and water quality parameters, enabling accurate identification of the causal factors. The models identified the discharge flow rate (D-Flow) and water temperature as the primary determinants of Chl-a levels, with feature importance values of 0.236 and 0.212, respectively. Enhanced model precision was achieved by utilizing daily average D-Flow values, with model accuracy and significance of the D-Flow amplifying as the temporal span of daily averaging increased. Elevated Chl-a concentrations correlated with diminished D-Flow and temperature, highlighting the pivotal role of D-Flow in regulating Chl-a concentration. This trend can be attributed to the constrained discharge of the Seungchon Weir during winter. Calculating the requisite D-Flow to maintain a desirable Chl-a concentration of up to 20 mg/m3 across varying temperatures revealed an escalating demand for D-Flow with rising temperatures. Specific D-Flow ranges, corresponding to each season and temperature condition, were identified as particularly influential on Chl-a concentration. Thus, optimizing Chl-a reduction can be achieved by strategically increasing D-Flow within these specified ranges for each season and temperature variation. This study highlights the importance of maintaining sufficient D-Flow levels to mitigate algal proliferation within river systems featuring weirs.

Graphitic-carbon-nitride-hydrophilicity-dependent photocatalytic degradation of antibiotics with different log Kow.

The surface hydrophilicity of a photocatalyst is an important factor that directly influences its interactions with organic pollutants and significantly impacts its degradation. In this study, we investigated the impact of increased hydrophilicity of g-C3N4 (CN) by alkaline solvothermal treatment on the degradations of three antibiotics (oxytetracycline (OTC), oxolinic acid (OA), and sulfamethoxazole (SMX)) with different log Kow values. Scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), and Fourier-transform infrared (FT-IR) spectroscopy showed no significant differences in the morphology, crystalline structure, and surface functional groups of CN after alkaline solvothermal treatment (Nv-HPCN). However, contact angle analysis revealed that Nv-HPCN (31.8°) was more hydrophilic than CN (61.1°). To assess the hydrophilicity of the antibiotics, the log Kow values of SMX (0.77), OA (0.43), and OTC (-0.34) were measured. Nv-HPCN showed faster OTC degradation than CN, whereas the opposite pattern was observed for the degradation of OA. Scavenger tests showed that O2•- and h+ mainly contributed to the degradation of these antibiotics. Furthermore, the influences of NOM and coexisting anions on antibiotic degradation were investigated. This study thus offers perspectives on the impact of surface hydrophilicity of photocatalysts on the degradation of antibiotics.

Exploring the viability of a floating photocatalyst in a continuous stirred tank reactor system for continuous water treatment.

The use of photocatalysts in continuous stirred tank reactor (CSTR) systems allows for efficient and continuous water treatment, thus meeting the demand for scalable technology and comparative data in large-scale implementations. Hence, this study aims to explore the feasibility of a floating photocatalyst within a CSTR system for continuous water treatment. An expanded polystyrene (EPS)-TiO2 composite was synthesized following established methodologies, and their efficacy in removing the water pollutant methylene blue (MB) was compared for both batch and CSTR systems. A nonlinear first-order model was identified as the most suitable approach to accurately simulate MB degradation under experimental conditions, and the calculated pseudo-first-order degradation rate constant (k') for the CSTR system (0.0126-0.0172/min) was found to be superior to that observed for the batch system (0.0113/min). In addition, an increase in the flow rate reduced the retention time, leading to lower MB removal efficiency for the CSTR system. In addition, the EPS-TiO2/UV system with a CSTR configuration was found to efficiently use light and energy based on the calculated quantum yield (Φ = 2.86 × 10-4) and electrical energy per order (EEO = 857.46 kWh/m3/order). The findings of this study contribute to the development of sustainable and efficient water treatment strategies, offering valuable insight into the implementation of practical water treatment processes.

Use of thermally activated Fenton sludge for Cd removal in zinc smelter wastewater: Mechanism and feasibility of Cd removal.

Fenton sludge is a byproduct of the Fenton process that contains large amounts of Fe and Ca. Because of the secondary contamination generated during the disposal of this byproduct, ecofriendly treatment methods are needed. In this study, we used Fenton sludge to remove the Cd discharged from a zinc smelter factory, using thermal activation to enhance the Cd adsorption capacity. Among the various temperatures considered (300-900 °C), the Fenton sludge that was thermally activated at 900 °C (TA-FS-900) adsorbed the highest amount of Cd because of its high specific surface area and high Fe content. Cd was adsorbed onto TA-FS-900 via complexation with C-OH, C-COOH, FeO-, and FeOH and cation exchange with Ca2+. The maximum adsorption of TA-FS-900 was 260.2 mg/g, indicating that TA-FS-900 is an efficient adsorbent, comparable to those reported in the literature. The initial Cd concentration in the zinc smelter wastewater discharged was 105.7 mg/L, 98.4% of which was removed by applying TA-FS-900, suggesting the applicability of TA-FS-900 for real wastewater containing high concentrations of various cations and anions. The leaching of heavy metals from TA-FS-900 was within the EPA standard limits. We concluded that the environmental impact of Fenton sludge disposal can be reduced, and the use of Fenton sludge can add value to the treatment of industrial wastewater in terms of the circular economy and environment.

Cycling of phosphorus from wastewater to fertilizer using wood ash after energy production.

Quercus wood was used for thermal energy production, and wood bottom ash (WDBA) was used as a medium for water purification and soil fertilizer in accordance with the recently proposed food-water-energy nexus concept. The wood contained a gross calorific value of 14.83 MJ kg-1, and the gas generated during thermal energy production has the advantage of not requiring a desulfurization unit due to its low sulfur content. Wood-fired boilers emit less CO2 and SOX than coal boilers. The WDBA had a Ca content of 66.0%, and Ca existed in the forms of CaCO3 and Ca(OH)2. WDBA absorbed P by reacting with Ca in the form of Ca5(PO4)3OH. Kinetic and isotherm models revealed that the results of the experimental work were in good agreement with the pseudo-second-order and Langmuir models, respectively. The maximum P adsorption capacity of WDBA was 76.8 mg g-1, and 6.67 g L-1 of WDBA dose could completely remove P in water. The toxic units of WDBA tested using Daphnia magna were 6.1, and P adsorbed WDBA (P-WDBA) showed no toxicity. P-WDBA was used as an alternative P fertilizer for rice growth. P-WDBA application resulted in significantly greater rice growth in terms of all agronomic values compared to N and K treatments without P. This study proposed the utilization of WDBA, obtained from thermal energy production, to remove P from wastewater and replenish P in the soil for rice growth.

Value-added application of cattle manure bottom ash for phosphorus recovery from water and replenishment in soil.

This study addresses ways to circulate the flow of phosphorus (P) from water to soil to improve water quality and provide a sustainable supply of P into soil. Here, bottom ash (BA_CCM), the byproduct of the combustion of cattle manure, which is performed for obtaining energy, was used to remove P in wastewater. Next, the P-captured BA_CCM was used as P fertilizer for rice growth. BA_CCM was primarily composed of Ca (49.4%), C (24.0%), and P (9.9%), and the crystalline phases of Ca were calcium carbonate (CaCO3) and hydroxyapatite (Ca5(PO4)3OH). The mechanism of P removal by BA_CCM involves the formation of hydroxyapatite by reacting Ca2+ with PO43-. A reaction time of 3 h was required to achieve P adsorption to BA_CCM, and the maximum P adsorption capacity of BA_CCM was 45.46 mg/g. The increase in solution pH reduced P adsorption. However, at pH > 5, the P adsorption amount was maintained regardless of the pH increase. The presence of 10 mM SO42- and CO32- reduced P adsorption by 28.4% and 21.5%, respectively, and the impact of the presence of Cl- and NO3- was less than 10%. The feasibility of BA_CCM was tested using real wastewater, and 3.33 g/L of BA_CCM dose achieved a P removal ratio of 99.8% and a residual concentration of <0.02 mg/L. The toxicity unit of BA_CCM determined for Daphnia magna (D. magna) was 5.1; however, the BA_CCM after P adsorption (P-BA_CCM) did not show any toxicity to D. magna. BA_CCM after P adsorption was used as an alternative to commercial P fertilizer. Rice fertilized with a medium level of P-BA_CCM showed better agronomic values for most agronomic traits, except root length, than that seen with the commercial P fertilizer. This study suggests that BA_CCM can be used as a value-added product to address environmental issues.

Facile synthesis of N vacancy g-C3N4 using Mg-induced defect on the amine groups for enhanced photocatalytic •OH generation.

Photocatalysis offers opportunities to degrade recalcitrant organic pollutants without adding treatment chemicals. Nitrogen (N) vacancy is an effective point-defect engineering strategy to mitigate electron-hole recombination and facilitate hydroxyl radical (•OH) production via superoxide radical (O2•-) generation during photocatalytic application of graphitic carbon nitride (g-C3N4). Here, we report a novel strategy for fabrication of N-vacancy-rich g-C3N4 (NvrCN) via post-solvothermal treatment of Mg-doped g-C3N4. The addition of the Mg precursor during the polycondensation of urea created abundant amine sites in the g-C3N4 framework, which facilitates formation of N vacancies during post-solvothermal treatment. Elemental analysis and electron paramagnetic resonance spectra confirmed a higher abundance of N vacancies in the resultant NvrCN. Further optical and electronic analyses revealed the beneficial role of N vacancies in light-harvesting capacity, electron-hole separation, and charge transfer. N vacancies also provide specific reaction centers for O2 molecules, promoting oxygen reduction reaction (ORR). Therefore, •OH generation increased via enhanced formation of H2O2 under visible light irradiation, and NvrCN photocatalytically degraded oxytetracycline 4-fold faster with degradation rate constant of 1.85 × 10-2 min-1 (light intensity = 1.03 mW/cm2, catalyst concentration = 0.6 g/L, oxytetracycline concentration = 20 mg/L) than pristine g-C3N4. Overall, this study provides a facile method for synthesizing N-vacancy-rich g-C3N4 and elucidates the role of the defect structure in enhancing the photocatalytic activity of g-C3N4.

Efficient removal of dyes from aqueous solutions using short-length bimodal mesoporous carbon adsorbents.

Ordered mesoporous carbons (OMCs) with controlled mesopore lengths and volumes were synthesized and investigated to remove the model dye methylene blue (MB) from aqueous solutions. The pore size, specific surface area, pore volume, and pore length of OMCs (CMK-3, sCMK-3, and sCMK-5) were analyzed and benchmarked against commercial activated carbon (AC). CMK-3 and sCMK-3 had narrow pore size distributions (PSDs) centered at ∼4.4 nm, whereas the PSD of sCMK-5 was bimodal, derived from the same pores as CMK-3 (∼4.4 nm) and the inner diameter of the carbon nanotubes (∼5.8 nm). The pore length decreased from 743 nm for CMK-3 to 173 nm for sCMK-3 and 169 nm for sCMK-5, facilitating the MB accessibility and efficient utilization of internal mesopores. The MB adsorption on the prepared adsorbents was well described by a pseudo-second-order kinetic model (R2 > 0.999), and the initial adsorption rate (h) on sCMK-5 was 34.07-fold faster than that on commercial AC. The Langmuir model adequately explained the equilibrium adsorption data, and the increase in the Langmuir maximal adsorption capacity (qm) of the OMCs was proportional to the specific surface area. The MB adsorption on sCMK-5 was endothermic and spontaneous, and proceeded primarily through physical adsorption as well as chemisorption reacting with oxygen atoms in hydroxyl groups. The prepared adsorbents were also suitable for polishing textile wastewater containing color-causing substances along with the background organic matter. These OMCs are promising for treating wastewater as efficient adsorbents for large molecular pollutants such as dyes.

Effect of water filtration infrared-A (wIRA) sauna on inorganic ions excreted through sweat from the human body.

Sweat discharged as a result of exposure to sauna plays an important role in removing inorganic ions accumulated in the body, including heavy metals. In this study, inorganic ions (toxic and nutrient elements) excreted in the form of sweat from the body using a water-filtered infrared-A (wIRA) sauna were determined using inductively coupled plasma sector field mass spectrometry. The analyzed elements included eight toxic elements (Al, As, Be, Cd, Ni, Pb, Ti, and Hg) and 10 nutrient elements (Ca, Co, Cr, Cu, Fe, Mg, Mn, Se, V, and Zn), and their correlations were determined. Analysis of the sweat obtained from 22 people using the wIRA sauna showed a higher inorganic ion concentration than that obtained from conventional activities, such as exercise or the use of wet sauna, and the concentration of toxic elements in sweat was higher in females than in males. Correlation analysis of the ions revealed a correlation between the discharge of toxic elements, such as As, Be, Cd, and Ni, and discharge of Se and V, and Ni was only correlated with Mn. This study provides fundamental information on nutritional element supplementation when using wIRA sauna for detoxification.

Application of response surface methodology and artificial neural network for the preparation of Fe-loaded biochar for enhanced Cr(VI) adsorption and its physicochemical properties and Cr(VI) adsorption characteristics.

In this study, we optimized and explored the effect of the conditions for synthesizing Fe-loaded food waste biochar (Fe@FWB) for Cr(VI) removal using the response surface methodology (RSM) and artificial neural network (ANN). The pyrolysis time, temperature, and Fe concentration were selected as the independent variables, and the Cr(VI) adsorption capacity of Fe@FWB was maximized. RSM analysis showed that the p-values of pyrolysis temperature and Fe concentration were less than 0.05, indicating that those variables were statically significant, while pyrolysis time was less significant due to its high p-value (0.2830). However, the ANN model results showed that the effect of pyrolysis time was more significant on Cr(VI) adsorption capacity than Fe concentration. The optimal conditions, determined by the RSM analysis with a lower sum of squared error than ANN analysis, were used to synthesize the optimized Fe@FWB (Fe@FWB-OPT) for Cr(VI) removal. From the equilibrium model fitting, the Langmuir model showed a better fit than the Freundlich model, while the Redlich-Peterson isotherm model overlapped. The Cr(VI) sorption capacity of Fe@FWB-OPT calculated from the Langmuir model was 377.71 mg/g, high enough to be competitive to other adsorbents. The kinetic Cr(VI) adsorption was well described by the pseudo-second-order and Elovich models. The XPS results showed that Cr adsorbed on the surface of Fe-FWB-OPT was present not only as Cr(VI) but also as Cr(III) by the reduction of Cr(VI). The results of Cr(VI) adsorption by varying the pH indicate that electrostatic attraction is a key adsorption mechanism.

Application of calcium-rich mineral under nonwoven fabric mats and sand armor as cap layer for interrupting N and P release from river sediments.

This work investigates the applicability of thermally treated calcium-rich minerals (CRMs), such as sepiolite (SPL), attapulgite (ATT), and dolomite (DLM) to hinder the nitrogen (N) and phosphorus (P) release from river sediments. A non-woven fabric mat (NWFM) or a sand layer were also capped as armor layers, i.e., placed over CRMs to investigate the capping impact on the N/P release. The capping efficiency was evaluated in a cylindrical reactor, consisting of CRMs, armor layers, sediments, and sampled water. We monitored N/P concentrations, dissolved oxygen (DO), oxidation reduction potential, pH, and electric conductivity in overlying water over 70 days. The DO concentrations in the uncapped and capped conditions were preserved for 30 days and 70 days (until the end of experiment duration), respectively. ATT showed higher efficiency for NH4-N and T-N than the other two materials, and the capping efficiency of NH4-N was measured as 96.4%, 93.7%, and 61.6% when capped with 2-cm sand layer, 1-cm sand layer, and NWFM layer, respectively. DLM showed a superior rejection capability of PO4-P to ATT and SPL, reported as 97.2% when capped with 2-cm sand armor. The content of weakly adsorbed-P was lower in the uncapped condition than in the capping condition. It can be concluded that ATT and DLM can be used as capping agents to deactivate N and P, respectively, to reduce water contamination from sediments of the eutrophic river.

Phosphorus recovery from cattle manure bottom ash by extraction and precipitation methods.

Phosphorus, a limiting element, is essential for living organisms, but the total amount available is decreasing with its increasing use. This problem can be solved by studying the methods of phosphorus recovery from waste. Phosphorus (P2O5, 13.75%) is abundantly present in cattle manure bottom ash (CMBA), indicating its potential as a source for phosphorus recovery. Herein, phosphorus recovery from CMBA was investigated by acid extraction and precipitation methods. The optimum concentration of sulfuric acid for extraction was 1.4 M, which eluted approximately 90% of the phosphorus contained in CMBA. In the precipitation method, sodium hydroxide and calcium silicate hydrate (CSH, CaSiO3∙nH2O) were used to adjust the solution pH to 4 and 8, where more than 99% of the eluted phosphorus was recovered when the pH was adjusted to 8 using CSH alone. The chemical composition and crystal forms of the recovered precipitates were analyzed using X-ray fluorescence and an X-ray powder diffractometer. The results indicated monetite and brushite were the main crystal forms of precipitates at pH 4, and struvite, hydroxyapatite, and tricalcium phosphate were the main crystal forms at pH 8. The availability of phosphorus in the precipitates was also evaluated by quinoline gravimetric analysis using water and 2% citric acid, and the water-soluble precipitate was less than 35%, whereas it ranged from 65 to 97% in 2% citric acid. This study suggests that CMBA can be used as a promising source to recover phosphorus via acid extraction and precipitation processes.

Contamination of typical phthalate acid esters in surface water and sediment of the Pearl River, South China: Occurrence, distribution, and health risk assessment.

The occurrence and distribution of six phthalate acid esters (PAEs) in surface water and sediment of the Pearl River were investigated, including Xijiang River (XR), Beijiang River (BR), Lingdingyang Estuary (LE), and Guangzhou River (GR) in South China. Six target PAEs were identified in surface water and sediment at almost all sites in the Pearl River, with di(2-ethyl-ethyl) phthalate (DEHP) and dibutyl phthalate (DBP) as dominant PAEs. Total 6 PAEs (ΣPAEs) in surface water and sediment ranged from 1,797.5 to 4,968.5 ng L-1 and 95.24 to 3,677.26 ng g-1 dw, respectively. In addition, the contamination levels of PAEs in the Pearl River are in the following order: XR > BR > GR > LE for surface water and BR > XR > GR for sediment. Local agricultural activities, industrial production, water confluence, and seawater intrusion are the probable sources of PAEs in the Pearl River. Based on correlation analysis, the possible collocation patterns of different PAEs were revealed. The risk assessment indicates that residual PAEs in the Pearl River pose a serious threat to the ecological environment. According to risk characterization of fish living in the Pearl River, the decreasing order of health risks was: GR > LE > XR > BR.

Restoring phosphorus from water to soil: Using calcined eggshells for P adsorption and subsequent application of the adsorbent as a P fertilizer.

This study investigated the solution for two environmental issues: excess of P in water and its deficiency in soil, which is restored by transferring the adsorbed P from water into the soil using eggshell as an adsorbent. The eggshells were calcined at different temperatures to improve their adsorption capacity, and evaluated for their physical/chemical properties and P adsorption capacity. The eggshells calcined at 800 °C (CES-800) had the highest P adsorption; CaCO3 decomposed into 23.6% of CaO and 40.8% of Ca(OH)2, eluting more Ca that reacted with soluble P in water. X-ray diffraction analysis confirmed that CES-800 removed P as hydroxylapatite by reacting with Ca. Pseudo-first-order and Langmuir models suitably described the kinetic and equilibrium of P adsorption by CES-800, respectively. The maximum adsorption capacity of CES-800 was 108.2 mg g-1. As the solution pH increased from 3 to 11, the adsorption amount decreased from 99.8 mg g-1 to 62.3 mg g-1. The feasibility of CES-800 as a filter medium was assessed using real lake water under dynamic flow conditions; > 90% of P removal was achieved at 158 h, and the P adsorbed was 11.5 mg g-1. When CES-800 and P adsorbed CES-800 (P-CES-800) were applied to the soil at the studied rates, the earthworms were unaffected by toxicity, suggesting the use of both adsorbents in soil without adverse effects. The shoot fresh weight, tiller number, and total dry weight significantly increased in P-CES-800 applied rice plants compared to the control plants, indicating that P-CES-800 can be a good alternative to conventional P-fertilizer in rice cultivation.

Conversion of cattle manure into functional material to remove selenate from wastewater.

Herein, pyrolysis of cattle manure was conducted to synthesize an effective material for removing heavy metals (e.g., selenium) from water environments. To remove selenate from aqueous solution, iron-impregnated cattle manure biochar (Fe/CM-biochar) was synthesized. The Fe-impregnation was performed by pre-treating cattle manure before its pyrolysis. The pretreatment increased the biochar yield. Influence of various factors such as contacting time, initial selenate concentration, reaction temperature, pH, and presence of coexisting anions were explored by performing batch adsorption experiments. The selenate adsorption reached equilibrium within 15 min. The Langmuir model was better fitted to equilibrium adsorption data than the Freundlich model. The maximum adsorption capacity of Fe/CM-biochar was calculated to be 52.56 mg-Se/g, which is superior to other adsorbents reported in the literature. As the reaction temperature increased in the range (15-35) °C, selenate adsorption on Fe/CM-biochar showed an endothermic and nonspontaneous reaction. The enthalpy change during selenate adsorption was 18.44 kJ/mol, which ranges in physical adsorption. The increase of solution pH (3-11) reduced the selenate adsorption (46.4-37.7 mg-Se/g). The extent of co-existing anion impact on selenate adsorption followed an order of HPO42- > HCO3- > SO42- > NO3-. These results indicate that Fe/CM-biochar is an effective functional material for the removal of selenate from wastewater.

Bisphenol A degradation using waste antivirus copper film with enhanced sono-Fenton-like catalytic oxidation.

This study investigated the applicability of waste antivirus copper film (CF) as a Fenton-like catalyst. The reaction activity of H2O2 and CF in combination was significantly enhanced by ultrasound (US) irradiation, and the synergy factor calculated from bisphenol A (BPA) degradation using CF-H2O2-US was 9.64 compare to that of dual factors. Photoluminescence analyses were conducted to compare the generation of hydroxyl radicals during both processes. In this sono-Fenton-like process, BPA degradation was affected by solution pH, temperature, ultrasound power, CF size, H2O2 dose, and initial BPA concentration. The BPA degradation curves showed an induction period (first stage) and a rapid degradation period (second stage). Process efficiency was totally and partially enhanced in the presence of chloride and carbonate ions, respectively. Chemical scavenger tests showed that both free and surface-bound hydroxyl radicals participate in BPA degradation under the sono-Fenton-like process using CF. The functional groups and copper crystals on the CF surface remained unchanged after five consecutive reuses, and the BPA degradation efficiency of CF was maintained over 80% during the reuse processes as a sono-Fenton-like catalyst.

Fluoride removal by thermally treated egg shells with high adsorption capacity, low cost, and easy acquisition.

In this study, the use of eggshells was suggested as an adsorbent for fluoride removal, and their mechanism of fluoride removal was investigated. The eggshells underwent thermal treatment to improve their adsorption capacity; 800 °C was found to be the optimal temperature for treatment. Eggshells thermally treated at 800 °C (ES-800) were mainly composed of Ca (82.4%) and C (15.9%), and the peaks of ES-800 obtained from X-ray diffraction (XRD) corresponded to calcite, portlandite, and lime. Fluorine adsorption by ES-800 reached 70% of the equilibrium adsorption amount within 15 min and gradually increased until 24 h. The maximum adsorption capacity of ES-800 at pH 7 and 25 °C was 258.28 mg/g, which is 18 times larger than that of activated alumina; this is classified as the best available technology by the United States Environmental Protection Agency. Both enthalpy and entropy increased in the process of fluoride adsorption onto ES-800. Fluoride adsorption of ES-800 decreased from 59.16 to 11.85 mg/g with an increase in pH from 3 to 11. Fluoride adsorption decreased in the presence of anions, whose impact follows the order: HPO43- > HCO3- >> SO42- > Cl-. XRD, and X-ray photoelectron spectroscopy analysis revealed that fluoride removal was achieved by the formation of calcium fluorite (CaF2). Thus, it can be concluded that eggshells can function as highly efficient adsorbents for fluoride removal, replacing bone char and activated alumina; further, their adsorption capacity can be improved by thermal treatment.

As(III) adsorption onto Fe-impregnated food waste biochar: experimental investigation, modeling, and optimization using response surface methodology.

Biochar derived from food waste was modified with Fe to enhance its adsorption capacity for As(III), which is the most toxic form of As. The synthesis of Fe-impregnated food waste biochar (Fe-FWB) was optimized using response surface methodology (RSM), and the pyrolysis time (1.0, 2.5, and 4.0 h), temperature (300, 450, and 600 °C), and Fe concentration (0.1, 0.3, and 0.5 M) were set as independent variables. The pyrolysis temperature and Fe concentration significantly influenced the As(III) removal, but the effect of pyrolysis time was insignificant. The optimum conditions for the synthesis of Fe-FWB were 1 h and 300 °C with a 0.42-M Fe concentration. Both physical and chemical properties of the optimized Fe-FWB were studied. They were also used for kinetic, equilibrium, thermodynamic, pH, and competing anion studies. Kinetic adsorption experiments demonstrated that the pseudo-second-order model had a superior fit for As(III) adsorption than the pseudo-first-order model. The maximum adsorption capacity derived from the Langmuir model was 119.5 mg/g, which surpassed that of other adsorbents published in the literature. Maximum As(III) adsorption occurred at an elevated pH in the range from 3 to 11 owing to the presence of As(III) as H2AsO3- above a pH of 9.2. A slight reduction in As(III) adsorption was observed in the existence of bicarbonate, hydrogen phosphate, nitrate, and sulfate even at a high concentration of 10 mM. This study demonstrates that aqueous solutions can be treated using Fe-FWB, which is an affordable and readily available resource for As(III) removal.

Thermally treated Mytilus coruscus shells for fluoride removal and their adsorption mechanism.

We evaluated Mytilus coruscus shells (MCS) as an adsorbent for fluoride removal. Its removal efficiency was enhanced by thermal treatment and MCS at 800 °C (MCS-800) increased significantly its fluoride adsorption capacity from 0 to 12.28 mg/g. While raw MCS is mainly composed of calcium carbonate (CaCO3), MCS-800 consisted of 56.9% of CaCO3 and 43.1% of calcium hydroxide (Ca(OH)2). The superior adsorption capacity of MCS-800 compared to untreated MCS can be also explained by its larger specific surface area and less negative charge after the thermal treatment. X-ray photoelectron spectroscopy and X-ray diffraction analysis revealed that the fluoride adsorption of MCS-800 occurred via the formation of calcium fluorite (CaF2). Fluoride adsorption of MCS-800 approached equilibrium within 6 h and this kinetic adsorption was well-described by a pseudo-second-order model. The Langmuir model was suitable for describing the fluoride adsorption of MCS-800 under different initial concentrations. The maximum fluoride adsorption amount of MCS-800 was 82.93 mg/g, which was superior to those of other adsorbents derived from industrial byproducts. The enthalpy change of fluoride adsorption was 78.75 kJ/mol and the negative sign of free energy indicated that this phenomenon was spontaneous. The increase of pH from 3.0 to 11.0 slightly decreased the fluoride adsorption capacity of MCS-800. The adsorption was inhibited in the presence of anions and their impact increased with following trend: chloride < sulfate < carbonate < phosphate. The fluoride adsorption capacities of MCS-800 after washing with deionized water and 0.1 M NaOH were reduced by 31.5% and 57.4%, respectively.