Biochars derived from wasted marine macro-algae (Saccharina japonica and Sargassum fusiforme) and their potential for heavy metal removal in aqueous solution.

For the purpose of reusing wasted marine macro-algae generated during cultivation, harvesting, processing and selling processes, biochars derived from Saccharina japonica (known as kelp) and Sargassum fusiforme (known as hijikia) were characterized and their removal capacities for Cu, Cd, and Zn in aqueous solution were assessed. Feedstocks, S. japonica, S. fusiforme, and also pinewood sawdust as a control, were pyrolyzed at 250, 400, 500, 600 and 700 °C. In evaluating heavy metal removal capacities, SJB (S. japonica biochar) showed the best performance, with removal efficiencies of more than 98% for the three heavy metals when pyrolyzed at over 400 °C. SFB (S. fusiforme biochar) also showed good potential as an adsorbent, with removal efficiencies for the three heavy metals of more than 86% when pyrolyzed at over 500 °C. On the contrary, the maximum removal efficiencies of PSB (pinewood sawdust biochar) were 81%, 46%, and 47% for Cu, Cd, and Zn, respectively, even at 700 °C, the highest pyrolysis temperature. This demonstrates that marine macro-algae were advantageous in terms of production energy for removing heavy metals even at relatively low pyrolysis temperatures, compared with PSB. The excellent heavy metal adsorption capacities of marine macro-algae biochars were considered due to their higher pH and more oxygen-containing functional groups, although the specific surface areas of SJB and SFB were significantly lower than that of PSB. This research confirmed that the use of marine macro-algae as a heavy metal adsorbent was suitable not only in the removal of heavy metals, but also in terms of resource recycling and energy efficiency.

Heavy metal removal from aqueous solutions using engineered magnetic biochars derived from waste marine macro-algal biomass.

Despite the excellent sorption ability of biochar for heavy metals, it is difficult to separate and reuse after adsorption when applied to wastewater treatment process. To overcome these drawbacks, we developed an engineered magnetic biochar by pyrolyzing waste marine macro-algae as a feedstock, and we doped iron oxide particles (e.g., magnetite, maghemite) to impart magnetism. The physicochemical characteristics and adsorption properties of the biochar were evaluated. When compared to conventional pinewood sawdust biochar, the waste marine algae-based magnetic biochar exhibited a greater potential to remove heavy metals despite having a lower surface area (0.97m2/g for kelp magnetic biochar and 63.33m2/g for hijikia magnetic biochar). Although magnetic biochar could be effectively separated from the solution, however, the magnetization of the biochar partially reduced its heavy metal adsorption efficiency due to the biochar's surface pores becoming plugged with iron oxide particles. Therefore, it is vital to determine the optimum amount of iron doping that maximizes the biochar's separation without sacrificing its heavy metal adsorption efficiency. The optimum concentration of the iron loading solution for the magnetic biochar was determined to be 0.025-0.05mol/L. The magnetic biochar's heavy metal adsorption capability is considerably higher than that of other types of biochar reported previously. Further, it demonstrated a high selectivity for copper, showing two-fold greater removal (69.37mg/g for kelp magnetic biochar and 63.52mg/g for hijikia magnetic biochar) than zinc and cadmium. This high heavy metal removal performance can likely be attributed to the abundant presence of various oxygen-containing functional groups (COOH and OH) on the magnetic biochar, which serve as potential adsorption sites for heavy metals. The unique features of its high heavy metal removal performance and easy separation suggest that the magnetic algae biochar can potentially be applied in diverse areas that require biosorbents for pollutant removal.

A novel approach to developing a reusable marine macro-algae adsorbent with chitosan and ferric oxide for simultaneous efficient heavy metal removal and easy magnetic separation.

Chitosan modified magnetic kelp biochar (Chi-KBm) was successfully synthesized for efficient removal of heavy metals (Cu2+) from wastewater. Interestingly, the characterization results indicated that Chi-KBm showed 6 times higher surface area (6.17 m2/g) than the pristine magnetic kelp biochar KBm (0.97 m2/g). In addition, new functional groups, such as NH and CN group, have been created on the surface of biochar as a result of chitosan modification process, which in turns led to improve the Cu2+ adsorption capacity. The effect of pH and chitosan loading on heavy metal adsorption, and competition reaction of different metal ions adsorption were also investigated. Chi-KBm exhibited a separation efficiency of more than 99.8%, which allows to recovery and reusability of the adsorbent material and heavy metals simultaneously. Overall, this study highlighted the Chi-KBm is a promise adsorbent for heavy metal removal without sacrificing of the separation ability using magnetism.