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
Abstract：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.
葛勉慎,周海宾,沈玉君,等.添加剂对牛粪堆肥不同阶段真菌群落演替的影响 [J]. 中国环境科学, 2019,39(12):5173-5181. Ge M S, Zhou H B, Shen Y J, et al. Effect of additives on the succession of fungal community in different phases of cattle manure composting [J]. China Environmental Science, 2019,39(12):5173- 5181.
[2]
吴浩玮,孙小淇,梁博文,等.我国畜禽粪便污染现状及处理与资源化利用分析 [J]. 农业环境科学学报, 2020,39(6):1168-1176. Wu H W, Sun X Q, Liang B W, et al. Analysis of livestock and poultry manure pollution in China and its treatment and resource utilization [J]. Journal of Agro-Environment Science, 2020,39(6):1168-1176.
[3]
岳 霞,陈德珍,安 青,等.生物炭对污泥热解液与牛粪共厌氧发酵的影响 [J]. 中国环境科学, 2022,42(3):1267-1277. Yue X, Chen D Z, An Q, et al. Biochars enhancing anaerobic co-digestion of sewage sludge pyrolysis liquid and cow dung: influences of inorganics in biochar raw [J]. China Environmental Science, 2022,42(3):1267-1277.
[4]
Ahadi N, Sharifi Z, Hossaini S M T, et al. Remediation of heavy metals and enhancement of fertilizing potential of a sewage sludge by the synergistic interaction of woodlice and earthworms [J]. Journal of Hazardous Materials, 2020,385:121573.
[5]
Li Y X, Xiong X, Lin C Y, et al. Cadmium in animal production and its potential hazard on Beijing and Fuxin farmlands [J]. Journal of Hazardous Materials, 2010,177(1):475-480.
[6]
潘 寻,韩 哲,贲伟伟.山东省规模化猪场猪粪及配合饲料中重金属含量研究 [J]. 农业环境科学学报, 2013,32(1):160-165. Pan X, Han Z, Ben W W. Heavy metal contents in pig manure and pig feeds from intensive pig farms in Shandong Province, China [J]. Journal of Agro-Environment Science, 2013,32(1):160-165.
[7]
朱建春,李荣华,张增强,等.陕西规模化猪场猪粪与饲料重金属含量研究 [J]. 农业机械学报, 2013,44(11):98-104. Zhu J C, Li R H, Zhang Z Q, et al. Heavy metal contents in pig manure and feeds under intensive farming and potential hazard on farmlands in Shananxi Province, China [J]. Transactions of the Chinese Society for Agricultural Machinery, 2013,44(11):98-104.
[8]
Chen H, Yuan X, Li T, et al. Characteristics of heavy metal transfer and their influencing factors in different soil–crop systems of the industrialization region, China [J]. Ecotoxicology and Environmental Safety, 2016,126:193-201.
[9]
Liu Z, Tran K Q. A review on disposal and utilization of phytoremediation plants containing heavy metals [J]. Ecotoxicology and Environmental Safety, 2021,226:112821.
[10]
Gholizadeh M, Hu X, Liu Q. Progress of using biochar as a catalyst in thermal conversion of biomass [J]. Reviews in Chemical Engineering, 2021,37(2):229-258.
[11]
Guo H N, Wu S B, Tian Y J, et al. Application of machine learning methods for the prediction of organic solid waste treatment and recycling processes: A review [J]. Bioresource Technology, 2021,319: 124114.
[12]
Mahima J, Sundaresh R K, Gopinath K P, et al. Effect of algae (Scenedesmus obliquus) biomass pre-treatment on bio-oil production in hydrothermal liquefaction (HTL): Biochar and aqueous phase utilization studies [J]. Science of the Total Environment, 2021,778: 146262.
[13]
Nanda S, Berruti F. A technical review of bioenergy and resource recovery from municipal solid waste [J]. Journal of Hazardous Materials, 2021,403:123970.
[14]
Devi P, Saroha A K. Risk analysis of pyrolyzed biochar made from paper mill effluent treatment plant sludge for bioavailability and eco-toxicity of heavy metals [J]. Bioresource Technology, 2014,162: 308-315.
[15]
龙秋宁,王润松,徐涵湄,等.沼液与生物炭联合施用对杨树人工林土壤甲螨密度的影响 [J]. 南京林业大学学报(自然科学版), 2021, 44(3):211-215. Long Q N, Wang R S, Xu H M, et al. Effects of biogas slurry and biochar on oribatida density in poplar plantation [J]. Journal of Nanjing Forestry University (Natural Science Edition), 2021,44(3): 211-215.
[16]
姚晶晶,冯象千,肖 贺,等.不同固废及其处理产物对黄骅港盐碱土的改良效果 [J]. 南京林业大学学报(自然科学版), 2021,45(3):45- 52. Yao J J, Feng X Q, Xiao H, et al. Improvement effects of different solid waste and their disposal by products on saline-alkali soil in Huanghua Port [J]. Journal of Nanjing Forestry University (Natural Science Edition), 2021,45(3):45-52.
[17]
马锋锋,赵保卫,钟金魁,等.牛粪生物炭对磷的吸附特性及其影响因素研究 [J]. 中国环境科学, 2015,35(4):1156-1163. Ma F F, Zhao B W, Zhong J K, et al. Characteristics phosphate adsorption onto biochars derived from dairy manure and its influencing factor [J]. China Environmental Science, 2015,35(4): 1156-1163.
[18]
Mendez A, Terradillos M, Gasco G. Physicochemical and agronomic properties of biochar from sewage sludge pyrolysed at different temperatures [J]. Journal of Analytical and Applied Pyrolysis, 2013, 102:124-130.
[19]
Yuan H, Tao L, Huang H, et al. Influence of pyrolysis temperature on physical and chemical properties of biochar made from sewage sludge [J]. Journal of Analytical and Applied Pyrolysis, 2015,112:284-289.
[20]
Jeong C Y, Dodla S K, Wang J J. Fundamental and molecular composition characteristics of biochars produced from sugarcane and rice crop residues and by-products [J]. Chemosphere, 2016,142:4-13.
[21]
Jin J, Li Y, Zhang J, et al. Influence of pyrolysis temperature on properties and environmental safety of heavy metals in biochars derived from municipal sewage sludge [J]. Journal of Hazardous Materials, 2016,320:417-426.
Chen T, Zhang Y, Wang H, et al. Influence of pyrolysis temperature on characteristics and heavy metal adsorptive performance of biochar derived from municipal sewage sludge [J]. Bioresource Technology, 2014,164:47-54.
[25]
Ma F, Dai J S, Fu Z, et al. Biochar for asphalt modification: A case of high-temperature properties improvement [J]. Science of the Total Environment, 2022,804:150194.
[26]
Zhang P Z, Zhang X X, Li Y F, et al. Influence of pyrolysis temperature on chemical speciation, leaching ability, and environmental risk of heavy metals in biochar derived from cow manure [J]. Bioresource Technology, 2020,302:122850.
[27]
Zhang H Z, Chen C R, Gray E M, et al. Effect of feedstock and pyrolysis temperature on properties of biochar governing end use efficacy [J]. Biomass & Bioenergy, 2017,105:136-146.
[28]
Park J, Hung I, Gan Z H, et al. Activated carbon from biochar: Influence of its physicochemical properties on the sorption characteristics of phenanthrene [J]. Bioresource Technology, 2013,149: 383-389.
[29]
Zhang P, Huang P, Xu X J, et al. Spectroscopic and molecular characterization of biochar-derived dissolved organic matter and the associations with soil microbial responses [J]. Science of the Total Environment, 2020,708:134619.
[30]
Cheng Y, Luo L, Lv J, et al. Copper speciation evolution in swine manure induced by pyrolysis [J]. Environmental Science & Technology, 2020,54(14):9008-9014.
[31]
Mobaraki M, Afshang B, Rahimpour M R, et al. Effect of cracking feedstock on carburization mechanism of cracking furnace tubes [J]. Engineering Failure Analysis, 2020,107:104216.
[32]
Huang H, Liang W, Li R, et al. Converting spent battery anode waste into a porous biocomposite with high Pb (II) ion capture capacity from solution [J]. Journal of Cleaner Production, 2018,184:622-631.
[33]
Din S U, Awan J M, Imran M, et al. Novel nanocomposite of biochar-zerovalent copper for lead adsorption [J]. Microscopy Research and Technique, 2021,84(11):2598-2606.
[34]
Liu W J, Tian K, Jiang H, et al. Harvest of Cu NP anchored magnetic carbon materials from Fe/Cu preloaded biomass: their pyrolysis, characterization, and catalytic activity on aqueous reduction of 4-nitrophenol [J]. Green Chemistry, 2014,16(9):4198-4205.
[35]
Liu W J, Tian K, Jiang H, et al. Selectively improving the bio-oil quality by catalytic fast pyrolysis of heavy-metal-polluted biomass: Take copper (Cu) as an example [J]. Environmental Science & Technology, 2012,46(14):7849-7856.
[36]
Wang Q, Wang B, Ma Y, et al. Stabilization of heavy metals in biochar derived from plants in antimony mining area and its environmental implications [J]. Environmental Pollution, 2022,300:118902.
[37]
Zhang X, Zhao B, Liu H, et al. Effects of pyrolysis temperature on biochar’s characteristics and speciation and environmental risks of heavy metals in sewage sludge biochars [J]. Environmental Technology & Innovation, 2022,26:102288.
[38]
Yang G X, Jiang H. Amino modification of biochar for enhanced adsorption of copper ions from synthetic wastewater [J]. Water Research, 2014,48:396-405.
