White hard clam (Meretrix lyrata) shells as novel filter media to augment the phosphorus removal from wastewater.

It is well recognized that filter media play a crucial role in constructed wetlands (CWs) for decontamination of phosphorus (P)-rich wastewater. This study investigates the suitability of raw white hard clam shells (WHC) and white hard clam shells thermally modified at 800 °C (WHC-M800) as potential media to enhance P treatment performance in CWs. The results indicated that both WHC and WHC-M800 displayed appropriate physicochemical properties, such as high porosity, excellent hydraulic conductivity, and rich Ca content. WHC-M800 exhibited a superior P adsorption capacity (38.7 mg/g) to WHC (12.8 mg/g). However, the practical utilization of WHC-M800 as filter media in CWs may be compromised, due to certain limitations, for example: extremely high pH values in the post-adsorption solutions; high weight losses during calcination and adsorption processes; low mechanical strength; and intensive energy consumption. In contrast, the WHC demonstrated significant advantages of reasonably high P adsorption capacity, locally abundant availability, low cost, and marginal side effects. The fractionation of inorganic P of WHC and WHC-M800 revealed that Ca-bounded P was the most dominant binding form, followed by loosely bound P, Fe-P, occluded P, and Al-P. The present study demonstrates that recycling of WHC shells as a potential substrate in CWs provides a feasible method for upgrading P removal in CWs. Additionally, it helps to reduce waste WHC shells in a simple, cheap, and eco-friendly way, thus can double environmental benefits.

White hard clam (Meretrix lyrata) shells media to improve phosphorus removal in lab-scale horizontal sub-surface flow constructed wetlands: Performance, removal pathways, and lifespan.

This work examined the phosphorus (P) removal from the synthetic pretreated swine wastewater using lab-scale horizontal sub-surface flow constructed wetlands (HSSF-CWs). White hard clam (Meretrix lyrata) shells (WHC) and Paspalum atratum were utilized as substrate and plant, respectively. The focus was placed on treatment performance, removal mechanisms and lifespan of the HSSF-CWs. Results indicated that WHC-based HSSF-CW with P. atratum exhibited a high P removal (89.9%). The mean P efluent concentration and P removal rate were 1.34 ± 0.95 mg/L and 0.32 ± 0.03 g/m2/d, respectively. The mass balance study showed that media sorption was the dominant P removal pathway (77.5%), followed by microbial assimilation (14.5%), plant uptake (5.4%), and other processes (2.6%). It was estimated the WHC-based bed could work effectively for approximately 2.84 years. This WHC-based HSSF-CWs technology will therefore pave the way for recycling Ca-rich waste materials as media in HSSF-CWs to enhance P-rich wastewater purification.

Adsorption of phosphate from aqueous solutions and sewage using zirconium loaded okara (ZLO): Fixed-bed column study.

This study explores the potential of removing phosphorus from aqueous solutions and sewage by Zr(IV)-loaded okara (ZLO) in the fixed-bed column. Soybean residue (okara) was impregnated with 0.25M Zr(IV) solution to prepare active binding sites for phosphate. The effect of several factors, including flow rate, bed height, initial phosphorus concentration, pH and adsorbent particle size on the performance of ZLO was examined. The maximum dynamic adsorption capacity of ZLO for phosphorus was estimated to be 16.43mg/g. Breakthrough curve modeling indicated that Adams-Bohart model and Thomas model fitted the experimental data better than Yoon-Nelson model. After treatment with ZLO packed bed column, the effluent could meet the discharge standard for phosphorus in Australia. Successful desorption and regeneration were achieved with 0.2 NaOH and 0.1 HCl, respectively. The results prove that ZLO can be used as a promising phosphorus adsorbent in the dynamic adsorption system.

Modification of agricultural waste/by-products for enhanced phosphate removal and recovery: potential and obstacles.

There is a growing trend to employ agricultural waste/by-products (AWBs) as the substrates for the development of phosphate biosorbents. Nevertheless, due to the lack of anion binding sites, natural AWBs are usually inefficient in phosphate decontamination. Consequently, modification plays a vital role in improving phosphate sorption's property of raw AWBs. This review paper evaluates all existing methods of modification. The literatures indicate that modification can significantly improve phosphate removal ability of AWBs by retaining phosphate ion onto modified AWBs principally via ion exchange (electrostatic interaction) and ligand exchange mechanisms. So far, little work has been done on the beneficial use of modified AWBs for the phosphorus recovery from aqueous solutions. The poor recyclability of modified AWBs could be responsible for their limited application. Hence, further study is essential to search for novel, cost-effective, and green methods of modification.

Phosphorus elimination from aqueous solution using 'zirconium loaded okara' as a biosorbent.

This work deals with the capture of phosphorus from aqueous solutions by biosorption onto zirconium loaded okara (ZLO). The batch-mode experiments were conducted to examine the effect of pH, biosorbent dose, initial phosphorus concentration, contact time, and temperature on the process. It was found that, the adsorption was most favored in the pH range of 2-6. The optimal doses for the adsorption, at initial phosphorus concentrations of 5, 10, 25, 50mg/L were 2, 3, 7, 10g/L, respectively. The maximum adsorption capacity of ZLO was approximately 44.13mg PO4/g at 298K. The phosphate removal was rapid, reaching 95% in 30min. Freundlich model best fitted the equilibrium data, while Pseudo-second order model satisfactorily described the kinetic results. Thermodynamic analysis revealed feasible, spontaneous, and endothermic nature of the process. The research would be beneficial for developing a promising, eco-friendly phosphorus biosorbent from a plentiful AWB - okara.

A comparative study on different metal loaded soybean milk by-product 'okara' for biosorption of phosphorus from aqueous solution.

Cationization of agricultural by-products using metal salts is widely used to activate their phosphorous capture ability. This study developed three kinds of new metal loaded soybean milk by-product 'okara' for phosphorus biosorption. A comparative study among these biosorbents was carried out with respect to their performances in terms of affinity, stability and reusability. Zirconium loaded okara (ZLO) was found to have the highest affinity towards PO(4)(3-) anions (47.88 mg/g), followed by iron/zirconium loaded okara--IZLO (40.96 mg/g) and iron loaded okara--ILO (16.39 mg/g). ZLO was successfully desorbed with 0.2M NaOH and activated with 0.1 HCl prior to the next cycle. After five consecutive cycles, the efficiency of both adsorption and desorption of ZLO remained about 85% whilst no Zr(IV) leakage was observed. Conversely, IZLO and ILO suffered from vital short comings such as high metal release and/or sharp reduction in PO4(3-) sequestering capability after multi operation cycles.

Feasibility of iron loaded 'okara' for biosorption of phosphorous in aqueous solutions.

This study investigated the feasibility of using soybean milk by-products (okara) as a sustainable biosorbent for phosphate removal in water and wastewater. The results show that raw okara could hardly decontaminate phosphate from aqueous solutions. Hence, in this work, okara was modified by being cationized using FeCl3 0.25 M (namely iron loaded okara, ILO) to enhance the phosphorus adsorption capacity. The phosphate sorption onto ILO was well achieved under the conditions of pH 3, initial phosphorous concentration of 25 mg/L, biosorbent dose of 20 mg/L and contact time of 7 h. Based on Langmuir model, the maximum adsorption capacity of phosphate by ILO was 4.785 mg/g. The effects of interfering anions were in the order of CO3(2-)>SO4(2-)>NO3(-). It was also observed that Fe(III) was detached during operation. This problem can hinder the sustainable usability of ILO. Thus, further research would be necessary for improving the modification method.

Applicability of agricultural waste and by-products for adsorptive removal of heavy metals from wastewater.

This critical review discusses the potential use of agricultural waste based biosorbents (AWBs) for sequestering heavy metals in terms of their adsorption capacities, binding mechanisms, operating factors and pretreatment methods. The literature survey indicates that AWBs have shown equal or even greater adsorption capacities compared to conventional adsorbents. Thanks to modern molecular biotechnologies, the roles of functional groups in biosorption process are better understood. Of process factors, pH appears to be the most influential. In most cases, chemical pretreatments bring about an obvious improvement in metal uptake capacity. However, there are still several gaps, which require further investigation, such as (i) searching for novel, multi-function AWBs, (ii) developing cost-effective modification methods and (iii) assessing AWBs under multi-metal and real wastewater systems. Once these challenges are settled, the replacement of traditional adsorbents by AWBs in decontaminating heavy metals from wastewater can be expected in the future.