Dan-Hua Zhao1, Hong-Wen Gao. 1. State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai, 200092, China.
Abstract
BACKGROUND, AIM, AND SCOPE: Over the years, organic pollution in the environment has aroused people's concern worldwide, especially persistent organic pollutants (POPs). Particularly in developing countries, plenty of concentrated organic wastewaters treated noneffectively are discharged into aquatic environments from chemical, textile, paper-making, and other industries to seriously threaten the surface and drinking water. The conventional wastewater treatment techniques are often helpless due to high cost with multilevel processing. Adsorption as an efficient method is often applied to the treatment of wastewater. The aim of this work is to develop an eco-friendly and cost-effective wastewater-sorbing material with weak acidic pink red B (APRB) and calcium carbonate (CaCO(3)) by reusing highly concentrated dye wastewater. MATERIALS AND METHODS: On the basis of the chemical coprecipitation of APRB with growing CaCO(3) particles, an inclusion material was prepared. The composition of material was determined by atomic absorption spectrometry, thermogravimetric analysis, and transmission electron microscopy (TEM)-energy dispersive X-ray, and its morphology characterized by X-ray diffraction, scanning electron microscopy, TEM, and particle-size analysis. Two cationic dyes, ethyl violet (EV) and methylene blue (MB), and four POPs, phenanthrene (Phe), fluorene (Flu), biphenyl (Bip), and biphenol A (Bpa), were used to investigate the adsorption selectivity, capacity, and mechanism of the new material, where spectrophotometry, fluorophotometry, and high-performance liquid chromatography were used for determination. An APRB-producing wastewater was reused for preparing the cost-effective wastewater-sorbing material instead of the APRB reagent and then treating cationic dye wastewaters. The remove rates of colority and chemical oxygen demand (COD) were evaluated. RESULTS AND DISCUSSION: The CO(3) (2-)-APRB-Ca(2+) addition sequence is most favorable for the occlusion of APRB into the growing CaCO(3) particles, and the occlusion of APRB corresponded to the Langmuir isothermal adsorption with the binding constant (K) of 5.24 x 10(4) M(-1) and the Gibbs free energy change (Delta G) of -26.9 kJ/mol. The molar ratio of Ca(2+) to CO(3) (2-) and APRB was calculated to be 1:0.94:0.0102, i.e., approximately 92 CaCO(3) molecules occluded only one APRB. Approximately 78% of the inclusion aggregates are between 3 and 20 mm and the particles are global-like with 50-100 nm. The element mapping on Ca, S, and C indicated APRB distributed a lot of CaCO(3), i.e., the APRB layer may be pressed between both sides of CaCO(3) layers. The molar ratio of Ca to S was calculated to 44, i.e., 88 CaCO(3) molecules carried one APRB, according to the above data. During the growing of CaCO(3) particles, APRB may be attracted into the temporary electric double layer in micelle form by the strong charge interaction between sulfonic groups of APRB and Ca(2+) and the hydrophobic stack of long alkyl chains. Four dyes were adsorbed: reactive brilliant red X-3B and weak acid green GS as anionic dyes and EV and MB as cationic dyes. The removals of EV and MB are extremely obvious and the saturation adsorption of EV and MB just neutralized all the negative charges in the inclusion particles. The selectivity demonstrated the ion-pair attraction, i.e., the cationic adsorption capacity depends on the negative charge number of the inclusion material. By fitting the Langmuir isotherm model, the monolayer adsorptions of EV and MB were confirmed. Their K values were calculated to be 2.4 x 10(6) and 7.3 x 10(5) M(-1), and Delta G was calculated to be 36.4 and -33.4 kJ/mol. The adsorption of four POPs on the material obeyed the lipid-water partition law, and their partition coefficients (K (pw)) were calculated to be 9,342 L/kg for Phe, 7,301 L/kg for Flu, 1,226 L/kg for Bip, and 870 L/kg for Bpa. The K (pw) is the direct ratio to their lipid-water partition coefficients (K (ow)) with 0.314 of slope. Besides this, a cost-effective CaCO(3)/APRB inclusion material was prepared with an APRB-producing wastewater instead of APRB reagent, and it was used in the treatment of two practical cationic dye wastewaters (samples A and B). The colority and COD in sample B are 18 and 13 times high as those of sample A. The decolorization of sample A is over 96%, and the removal of COD is between 70% and 80% when more than 0.3% adsorbent was added. However, those of sample B are over 98% and 88% in the presence of over 1% adsorbent. The adsorbent added in sample B, which was only two to three times as high as that in sample A, brought a similar removal rate of colority and COD. The inclusion material is more efficient for treatment of a highly concentrated dye wastewater because it may adsorb the most cationic dye up to saturation. CONCLUSIONS: A cost-effective onion-like inclusion material was synthesized with the composition ratio 90 +/- 2 of CaCO(3) to APRB, and it carried a lot of negative charges and lipophilic groups. It has a high adsorption capacity and rapid saturation for cationic dye and POPs. The adsorption of cationic dyes corresponded to the Langmuir isothermal model and that of POPs to the lipid-water partition law. The adsorbent is suitable for treatment of concentrated cationic dye and POPs wastewater in neutral media. The addition quantity of the calcium carbonate-APRB adsorbent was suggested below: only 3-5 kg per ton of wastewater (<1,000 colority or <2 mg/L POPs) and 20-30 kg per ton of highly concentrated wastewater (>20,000 colority or >50 mg/L POPs). RECOMMENDATIONS AND PERSPECTIVES: The skeleton reactants are low-cost, easily available, and harmless to the ecological environment; additionally, the APRB reactant can reuse APRB-producing wastewater. The dye-contaminated sludge can potentially be reused as the color additive in building material and rubber and plastics industries. However, the APRB and dye contaminant would be released from the sludge when exposed to an acidic media (pH <4) for long time. This work has developed a simple, eco-friendly and practical method for the production of a cost-effective wastewater-sorbing material.
BACKGROUND, AIM, AND SCOPE: Over the years, organic pollution in the environment has aroused people's concern worldwide, especially persistent organic pollutants (POPs). Particularly in developing countries, plenty of concentrated organic wastewaters treated noneffectively are discharged into aquatic environments from chemical, textile, paper-making, and other industries to seriously threaten the surface and drinking water. The conventional wastewater treatment techniques are often helpless due to high cost with multilevel processing. Adsorption as an efficient method is often applied to the treatment of wastewater. The aim of this work is to develop an eco-friendly and cost-effective wastewater-sorbing material with weak acidic pink red B (APRB) and calcium carbonate (CaCO(3)) by reusing highly concentrated dye wastewater. MATERIALS AND METHODS: On the basis of the chemical coprecipitation of APRB with growing CaCO(3) particles, an inclusion material was prepared. The composition of material was determined by atomic absorption spectrometry, thermogravimetric analysis, and transmission electron microscopy (TEM)-energy dispersive X-ray, and its morphology characterized by X-ray diffraction, scanning electron microscopy, TEM, and particle-size analysis. Two cationic dyes, ethyl violet (EV) and methylene blue (MB), and four POPs, phenanthrene (Phe), fluorene (Flu), biphenyl (Bip), and biphenol A (Bpa), were used to investigate the adsorption selectivity, capacity, and mechanism of the new material, where spectrophotometry, fluorophotometry, and high-performance liquid chromatography were used for determination. An APRB-producing wastewater was reused for preparing the cost-effective wastewater-sorbing material instead of the APRB reagent and then treating cationic dye wastewaters. The remove rates of colority and chemical oxygen demand (COD) were evaluated. RESULTS AND DISCUSSION: The CO(3) (2-)-APRB-Ca(2+) addition sequence is most favorable for the occlusion of APRB into the growing CaCO(3) particles, and the occlusion of APRB corresponded to the Langmuir isothermal adsorption with the binding constant (K) of 5.24 x 10(4) M(-1) and the Gibbs free energy change (Delta G) of -26.9 kJ/mol. The molar ratio of Ca(2+) to CO(3) (2-) and APRB was calculated to be 1:0.94:0.0102, i.e., approximately 92 CaCO(3) molecules occluded only one APRB. Approximately 78% of the inclusion aggregates are between 3 and 20 mm and the particles are global-like with 50-100 nm. The element mapping on Ca, S, and C indicated APRB distributed a lot of CaCO(3), i.e., the APRB layer may be pressed between both sides of CaCO(3) layers. The molar ratio of Ca to S was calculated to 44, i.e., 88 CaCO(3) molecules carried one APRB, according to the above data. During the growing of CaCO(3) particles, APRB may be attracted into the temporary electric double layer in micelle form by the strong charge interaction between sulfonic groups of APRB and Ca(2+) and the hydrophobic stack of long alkyl chains. Four dyes were adsorbed: reactive brilliant red X-3B and weak acid green GS as anionic dyes and EV and MB as cationic dyes. The removals of EV and MB are extremely obvious and the saturation adsorption of EV and MB just neutralized all the negative charges in the inclusion particles. The selectivity demonstrated the ion-pair attraction, i.e., the cationic adsorption capacity depends on the negative charge number of the inclusion material. By fitting the Langmuir isotherm model, the monolayer adsorptions of EV and MB were confirmed. Their K values were calculated to be 2.4 x 10(6) and 7.3 x 10(5) M(-1), and Delta G was calculated to be 36.4 and -33.4 kJ/mol. The adsorption of four POPs on the material obeyed the lipid-water partition law, and their partition coefficients (K (pw)) were calculated to be 9,342 L/kg for Phe, 7,301 L/kg for Flu, 1,226 L/kg for Bip, and 870 L/kg for Bpa. The K (pw) is the direct ratio to their lipid-water partition coefficients (K (ow)) with 0.314 of slope. Besides this, a cost-effective CaCO(3)/APRB inclusion material was prepared with an APRB-producing wastewater instead of APRB reagent, and it was used in the treatment of two practical cationic dye wastewaters (samples A and B). The colority and COD in sample B are 18 and 13 times high as those of sample A. The decolorization of sample A is over 96%, and the removal of COD is between 70% and 80% when more than 0.3% adsorbent was added. However, those of sample B are over 98% and 88% in the presence of over 1% adsorbent. The adsorbent added in sample B, which was only two to three times as high as that in sample A, brought a similar removal rate of colority and COD. The inclusion material is more efficient for treatment of a highly concentrated dye wastewater because it may adsorb the most cationic dye up to saturation. CONCLUSIONS: A cost-effective onion-like inclusion material was synthesized with the composition ratio 90 +/- 2 of CaCO(3) to APRB, and it carried a lot of negative charges and lipophilic groups. It has a high adsorption capacity and rapid saturation for cationic dye and POPs. The adsorption of cationic dyes corresponded to the Langmuir isothermal model and that of POPs to the lipid-water partition law. The adsorbent is suitable for treatment of concentrated cationic dye and POPs wastewater in neutral media. The addition quantity of the calcium carbonate-APRB adsorbent was suggested below: only 3-5 kg per ton of wastewater (<1,000 colority or <2 mg/L POPs) and 20-30 kg per ton of highly concentrated wastewater (>20,000 colority or >50 mg/L POPs). RECOMMENDATIONS AND PERSPECTIVES: The skeleton reactants are low-cost, easily available, and harmless to the ecological environment; additionally, the APRB reactant can reuse APRB-producing wastewater. The dye-contaminated sludge can potentially be reused as the color additive in building material and rubber and plastics industries. However, the APRB and dye contaminant would be released from the sludge when exposed to an acidic media (pH <4) for long time. This work has developed a simple, eco-friendly and practical method for the production of a cost-effective wastewater-sorbing material.
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