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碳化温度对牛粪铜和锌形态及生态毒性的影响

碳化温度对牛粪铜和锌形态及生态毒性的影响

ISSN:1000-6923
2022年第42卷第9期
固体废物
黄辉1,2, 吕雨薇1, 梁敏3, 朱咏莉1, 梁文2, 蒋亚辉2, 张增强2, 李荣华2 HUANG Hui1,2, Lü Yu-wei1, LIANG Min3, ZHU Yong-li1, LIANG Wen2, JIANG Ya-hui2, ZHANG Zeng-qiang2, LI Rong-hua2
1. 南京林业大学生物与环境学院, 江苏 南京 210037;2. 西北农林科技大学资源环境学院, 陕西 杨凌 712100;3. 南京农业大学资源与环境科学学院, 江苏 南京 210095 1. College of Biology and the Environment, Nanjing Forestry University, Nanjing 210037, China;2. College of Natural Resources and Environment, Northwest A&F University, Yangling 712100, China;3. College of Resources and Environmental Sciences, Nanjing Agricultural University, Nanjing 210095, China

通过设置不同的热解温度(350,550和750℃)对牛粪废弃物进行碳化处理,并使用光谱技术手段对牛粪炭的微观特点及Cu、Zn赋存形态进行了分析表征,同时结合淋溶和毒性实验探究了热解温度对牛粪炭生态毒性的影响.结果表明,高温碳化明显改善牛粪孔隙结构,使其比表面积从牛粪原料的1.15m2/g提高至牛粪炭的5.51(350℃)~195.90m2/g(750℃).随着热解温度的提高,牛粪炭pH值从8.18(350℃)提高到了10.14(750℃);牛粪炭中Cu、Zn含量则从牛粪原料中的1.22和1.23mg/g分别升高至18.29~35.11和18.58~31.24mg/g.透射电镜-选区衍射以及X射线能谱分析表明,热解处理可使牛粪中Cu、Zn离子分别转化为副黑铜矿(Cu4O3)和红锌矿(ZnO)等金属氧化物,从而明显降低了牛粪炭中水溶态、DTPA提取态以及HNO3-H2SO4提取态的Cu、Zn离子浓度;此外,FTIR分析及混合有机酸浸提实验结果也表明,350℃牛粪炭中酚羟基、烷烃基、羧基、酰胺类等有机官能团通过吸附和络合作用固定未完全转化的Cu离子,而升高热解温度会使得这些官能团显著减少、促进Cu离子的完全转化以及无机物与Cu、Zn离子之间稳定金属氧化物化合键的形成.淋溶和生态毒性实验表明,高于550℃的热解温度能够显著降低牛粪炭中Cu、Zn的溶出率以及生态毒性,是高Cu、Zn含量牛粪废弃物无害化处理的一种推荐优选技术.

Pyrolysis to biochar is an efficient technique of disposing organic solid wastes. However, pyrolysis treatment of the cattle manure (CM) containing high concentrations of Cu and Zn is scarcely investigated, and the environmental behaviors of Cu and Zn in the cattle manure biochar (CMB) accompanying with their ecological risk keep unknown. In this study, the occurrence speciation of Cu and Zn in CMB, their leaching characteristics and the ecological risk of CMB from different pyrolysis temperatures (350, 550 and 750oC) were evaluated using spectrum technology (i.e., BET, TEM-SEAD, XPS, and FTIR), the leaching experiments, and the risk tests. Results show that carbonization of CM to CMB with an increasing temperature from 350 to 750oC improves the pore structure of CM and enlarges the specific surface area from 1.15m2/g in raw CM to 5.51~195.90m2/g in CMB. The pH value of the CMB increases from 8.18 (350℃) to pH 10.14 (750℃). Importantly, the Cu concentration increases from 1.22mg/g in raw CM to 18.29~35.11mg/g in CMB while the Zn concentration elevates from 1.23mg/g to 18.58~31.24mg/g. Meanwhile, most of the Cu and Zn are oxidized to paramelaconite (Cu4O3) and zincite (ZnO), which significantly reduces the concentrations of Cu and Zn in forms of extractable ones with deionized water, DTPA-TEA-CaCl2 and HNO3-H2SO4 as extracting agents, respectively. Furthermore, many functional groups (i.e., phenolic hydroxyl, alkane, carboxyl, amide, etc.) can immobilize labile Cu through adsorption and complexation, but a high pyrolysis temperature (>550oC) tends to arise a significant decrease in species and amounts of functional groups and promote the complete conversion of Cu ions and the formation of stable metal oxide bonds between inorganics and Cu or Zn ions. In summary, the pyrolysis temperature over 550oC could dramatically reduce the leaching rates of Cu and Zn and mitigate the ecotoxicity of CMB, which can be a potential approach to dispose the CM wastes with high concentrations of Cu and Zn.

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ISSN:1000-6923
2022年第42卷第9期
固体废物

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