High Temperature Co-pyrolysis Thermal Air Activation Enhances Biochar Adsorption of Herbicides from Surface Water

Recent interest has arisen in the use of biochar as a low-cost adsorbent for control of organic micropollutants in water. However, compared with activated carbon (AC), biochar adsorption capacity is typically one to two orders of magnitude lower. This study reports batch mode adsorption of anionic (2,4-D, C-0 100 mu g/L) and neutral (simazine [SZN], C-0 1.5 mu g/L) herbicides from surface water containing dissolved organic matter at 4 mg/L total organic carbon concentration. Enhanced adsorption was observed by biochars generated from updraft gasifiers under conditions of simultaneous co-pyrolysis thermal air activation (CPTA). 2,4-D adsorption by >= 850 degrees C CPTA biochars was more than 10 times greater on a mass basis compared with biochars generated from a conventional anoxic pyrolysis (CAP) reactor and was equivalent to AC reference adsorbents on a surface area normalized basis. Biochars generated at >= 850 degrees C under CPTA conditions had similar micropore surface area to CAP biochars (similar to 330 m(2)/g) but about 2.5 times the mesopore surface area (similar to 110 m(2)/g CPTA, similar to 40 m(2)/g CAP), suggestive of increased pore accessibility generated by thermochemical widening of pores and/or removal of pyrolysis tars by CPTA. 2,4-D adsorption from surface water was shown to correlate strongly with biochar H:C molar ratio within but not between biochars grouped by CAP and CPTA generation conditions. Comparing adsorption of 2,4-D and SZN by biochars generated from CAP and CPTA conditions suggested that herbicide interaction with biochar surface functional groups through formation of charge-assisted H-bonds did not play a significant role in herbicide uptake from surface water.