羟基磷灰石类纳米材料磷释放特征及影响因素  

Characteristics and influencing factors of phosphorus release from hydroxyapatite nanomaterials

作　　者：张文轩 李青青[3] 杨柳塘 李云桂[1,2] ZHANG Wenxuan;LI Qingqing;YANG Liutang;LI Yungui(School of Environment and Resources,Southwest University of Science and Technology,Mianyang 621010,China;NHC Key Laboratory of Nuclear Technology and Medical Transformation,Mianyang 621010,China;Advanced Institute of Natural Sciences,Beijing Normal University,Zhuhai 519087,China)

机构地区：[1]西南科技大学环境与资源学院,绵阳621010 [2]国家卫生健康委员会核技术医学转化重点实验室,绵阳621010 [3]北京师范大学自然科学高等研究院,珠海519087

出　　处：《环境工程学报》2024年第9期2567-2576,共10页Chinese Journal of Environmental Engineering

基　　金：四川省国际科技创新合作项目(2021YFH0046);国家卫生健康委员会核技术医学转化重点实验室开放课题资助项目(2021HYX030)。

摘　　要：羟基磷灰石类纳米材料(nHAP)因具有良好的重金属污染阻控性能和植物营养作用而被广泛关注,磷素释放动力学是决定其截污效率和供肥性能的关键过程,但其释放动力学特征及其影响因素尚不清楚。采用湿化学共沉淀方法调控老化时间(2、12 h)合成获得2种具有短棒状结构的nHAPs(nHAP_(2h)和nHAP_(12h)),系统探究纳米材料老化时间、温度/溶液pH值/共存腐殖酸和土壤溶液环境对nHAP磷释放动力学的影响。结果表明:材料老化时间越长,nHAP晶体越大,nHAP_(12h)晶体长度比nHAP2 h高17%。在实验条件下,晶体尺寸更大的nHAP_(12h)磷酸根释放量比nHAP2 h低61%~232%,温度升高、pH增大和土壤溶液会扩大材料老化时间引起的磷释放差距,而共存腐殖酸会缩小这种差距。除土壤溶液体系外,nHAPs磷酸根释放一般分为早期快速释放阶段和后期慢速积累阶段直至达到平衡,其磷酸根表观释放速率常数K从0.09~4.36 min^(−1)变化至0.01~0.78 min^(−1)。温度从5℃升至25℃时会促进nHAPs磷酸根释放(2%~19%),10、50 mg C·L^(−1)的共存腐殖酸的羧基和酚基与nHAPs作用同样会促进nHAPs磷酸根释放(10%~195%),pH从5提高到8.5时会抑制nHAPs磷酸根释放(3%~15%),nHAPs在土壤溶液体系中磷有效性显著下降(18%~76%)。本研究为nHAP作为土壤助剂和新型农用纳米助剂应用提供新的理论参考。The excellent ability of hydroxyapatite nanoparticles(nHAP)to resist heavy metal contamination and its impacts on plant nutrition have drawn much attention.The characteristics of phosphorus release kinetics and the factors that influence it remain obscure,despite the fact that this process is crucial in determining phosphorus interception efficiency and fertilizer supply performance.Here,two types of nHAPs(nHAP_(2h)and nHAP_(12h))with short rod-like structures were synthesized using wet chemical co-precipitation method to regulate the aging time(2 and 12 h).The effects of temperature,pH of the solution,coexisting humic acid,and soil solution environment on the phosphorus release kinetics from nHAPs were systematically investigated.The results revealed that the nHAP crystal grew larger with longer age times and that the nHAP_(12h)crystal length was 17%longer than the nHAP_(2h)crystal length.Under experimental conditions,phosphate release from nHAP_(12h)of larger crystal size was 61%~232%lower than that from nHAP2 h.The phosphorus release gap caused by the ageing time of the material was widened by elevated temperature,increased pH,or soil solutions,however,the gap was narrowed by coexisting humic acid.With the exception of the soil solution system,nHAPs phosphate release typically occurring in two phases:an early rapid release phase and a later slow buildup phase until equilibrium was attained,with the apparent phosphate release rate constant K varying from 0.09~4.36 min^(−1)to 0.01~0.78 min^(−1).Raising the temperature from 5℃to 25℃increased nHAPs phosphate release(2%~19%),while 10 and 50 mg C·L^(−1)of co-existing humic acids with carboxyl and phenolic groups interacting with nHAPs similarly promoted nHAPs phosphate release(10%~195%)and raising the pH from 5 to 8.5 decreased nHAPs phosphate release(3%~15%).In the soil solution system,the phosphorus effectiveness of nHAPs was drastically decreased(18%~76%).This work paves a new theoretical reference for the application of nHAP as soil aids and novel agr

关 键 词：纳米羟基磷灰石 磷释放 老化时间 有机酸 土壤 

分 类 号：X703[环境科学与工程—环境工程]