绿色合成纳米氧化铁对污染土壤中镉的钝化研究
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摘要
虽然绿色合成纳米材料已成功地用于去除废水中的重金属,但利用绿色合成纳米材料钝化土壤中重金属的报道很少.本文利用植物叶提取液制备纳米氧化铁(GION),并将其用于钝化土壤中重金属镉的研究,观察中、短培养周期下对镉钝化的稳定性.实验室条件下设置50%田间最大持水量培养,对照、1%、3%、9%GION 4个处理.分别于第60、120 d采样分析土壤中镉、pH、铁、酶等相关指标的变化.结果表明,GION对土壤中镉有较好的钝化效果,60 d与120 d之间有效态镉的含量无显著差异,说明GION对土壤中镉的钝化作用随时间增长相对稳定.120 d的数据显示,相比对照组,1%、3%、9%GION处理下有效态Cd(0.1 mol·L~(-1) CaCl_2)分别降低了19.1%、16.7%、66.7%,交换态Cd(Tessier法)分别降低了12.5%、18.8%、56.3%.GION能够显著提高土壤的pH和铁的含量.pH提高能够显著降低Cd的有效性.(NH_4)C_2O_4-Fe则分别增加了0.7、1.1、1.9倍,DCB-Fe分别增加了0.4、2.9、6.0倍.另外,随培养时间的延长,(NH_4)C_2O_4-Fe和DCB-Fe增加而HCl-Fe~(2+)含量降低.说明GION影响土壤中铁物种的活性,增强其生物化学过程而转化为更加稳定的形态,该过程将改变镉在土壤中的赋存形态.通过扫描电镜-能谱(SEM-EDS)发现,GION处理残渣态中Fe的含量远高于对照组,说明镉可能随铁进入残渣态.土壤中脲酶和转化酶活性升高而过氧化氢酶则没有显著的变化.该结果说明GION降低了土壤中镉的生物有效性,土壤得以恢复,从而提升了土壤酶活性.综上所述,GION具有环境友好的特点,且对镉具有稳定的钝化作用,可作为一种良好的中低污染重金属污染土壤的修复剂.
Green synthesized nanomaterials have been successfully used to remove heavy metals in wastewater, immobilizing heavy metals in soils is still unclear.In this study, iron oxide nanoparticles(GION) were prepared from euphorbia cochinchinensis extract and following used to immobilize cadmium(Cd) in soil, where soil was tested under after 60 and 120 d incubation with a 50% water hold capacity with control.Results show ①the Cd in soil were immobilized effectively by GION, and there was no significantly difference between 60 and 120 d, indicating that the immobilization of Cd by GION was stability in 60 d and 120 d incubation.At 120 d, the available Cd(0.1 mol·L~(-1) CaCl_2) in the 1%, 3% and 9% GION treatments decreased by 19.1%, 16.7%, 66.7%, and he exchangeable Cd(Tessier) decreased by 12.5%, 18.8%, 56.3% respectively.②the pH and Fe species in soil increased with increasing GION dosage, resulting in decreasing the available of Cd effectively.With increasing in pH.The(NH_4)C_2O_4-Fe and DCB-Fe increased by 0.4, 2.9, 6.0 times and 0.7, 1.1 and 1.9 times, respectively.In addition, in the GION treatments,(NH_4)C_2O_4-Fe and DCB-Fe increased, while HCl-Fe~(2+) decreased with incubation time, indicating that GION affected the activity of iron species in soil, and enhancing its biochemical process and transform it into a more stable fractions, leading to further change the fraction of Cd in soil by SEM-EDS. Furthermore, the abundance of Fe in the 9% GION treatment was much higher than that of the control.③the activity of urease and invertase activity increased, while catalase did not change significantly, revealing that GION immobilized Cd by reducing the bioavailability of cadmium in soil, resulting in the increasing enzyme activity.Since GION is environmentally friendly and in the stable immobilizing Cd.GION could be potentially used to Cd in contaminated soil.
Green synthesized nanomaterials have been successfully used to remove heavy metals in wastewater, immobilizing heavy metals in soils is still unclear.In this study, iron oxide nanoparticles(GION) were prepared from euphorbia cochinchinensis extract and following used to immobilize cadmium(Cd) in soil, where soil was tested under after 60 and 120 d incubation with a 50% water hold capacity with control.Results show ①the Cd in soil were immobilized effectively by GION, and there was no significantly difference between 60 and 120 d, indicating that the immobilization of Cd by GION was stability in 60 d and 120 d incubation.At 120 d, the available Cd(0.1 mol·L~(-1) CaCl_2) in the 1%, 3% and 9% GION treatments decreased by 19.1%, 16.7%, 66.7%, and he exchangeable Cd(Tessier) decreased by 12.5%, 18.8%, 56.3% respectively.②the pH and Fe species in soil increased with increasing GION dosage, resulting in decreasing the available of Cd effectively.With increasing in pH.The(NH_4)C_2O_4-Fe and DCB-Fe increased by 0.4, 2.9, 6.0 times and 0.7, 1.1 and 1.9 times, respectively.In addition, in the GION treatments,(NH_4)C_2O_4-Fe and DCB-Fe increased, while HCl-Fe~(2+) decreased with incubation time, indicating that GION affected the activity of iron species in soil, and enhancing its biochemical process and transform it into a more stable fractions, leading to further change the fraction of Cd in soil by SEM-EDS. Furthermore, the abundance of Fe in the 9% GION treatment was much higher than that of the control.③the activity of urease and invertase activity increased, while catalase did not change significantly, revealing that GION immobilized Cd by reducing the bioavailability of cadmium in soil, resulting in the increasing enzyme activity.Since GION is environmentally friendly and in the stable immobilizing Cd.GION could be potentially used to Cd in contaminated soil.
引文
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Li M,Cheng X,Guo H.2013.Heavy metal removal by biomineralization of urease producing bacteria isolated from soil[J].International Biodeterioration&Biodegradation,76:81-85
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Liu C,Yu H Y,Liu C,et al.2015.Arsenic availability in rice from a mining area:is amorphous iron oxide-bound arsenic a source or sink[J].Environmental Pollution,199:95-101
Luo F,Chen Z,Megharaj M,et al.2016.Simultaneous removal of trichloroethylene and hexavalent chromium by green synthesized agarose-Fe nanoparticles hydrogel[J].Chemical Engineering Journal,294:290-297
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Poulain A J,Newman D K.2009.Rhodobacter capsulatus catalyzes lightdependent Fe(II)oxidation under anaerobic conditions as a potential detoxification mechanism[J].Applied and Environmental Microbiology,75:6639-6646
Qasim B,Motelica-Heino M,Bourgerie S,et al.2015.Effect of nitrate and ammonium fertilization on Zn,Pb,and Cd phytostabilization by Populus euramericana Dorskamp in contaminated technosol[J].Environmental Science&Pollution Research,22(23):18759-18771
Shipley H J,Engates K E,Guettner A M.2011.Study of iron oxide nanoparticles in soil for remediation of arsenic[J].Journal of Nanoparticle Research,13(6):2387-2397
Sima B,Ronald J,Smernik,et al.2018.The application of a spectrophotometric method to determine pH in acidic(pH<5)soils[J].Talanta,186:421-426
Sulu G,Dorina S,Filip J R,et al.2016.Cable bacteria control ironphosphorus dynamics in sediments of a coastal hypoxic basin[J].Environmental Science&Technology,50(3):1227-1233
Tang X,Shen C,Shi D,et al.2010.Heavy metal and persistent organic compound contamination in soil from Wenling:an emerging e-waste recycling city in Taizhou area,China[J].Journal of Hazardous Materials,173:653-660
Tessier A,Campbell P G C,Bisson M.1979.Sequential extraction procedure for the speciation of particulate trace metals[J].Analytical Chemistry,51(7):844-851
Weng X,Jin X,Lin J,et al.2016.Removal of mixed contaminants Cr(VI)and Cu(II)by green synthesized iron based nanoparticles[J].Ecological Engineering,97:32-39
Xue W,Huang D,Zeng G,et al.2018.Nanoscale zero-valent iron coated with rhamnolipid as an effective stabilizer for immobilization of Cd and Pb in river sediments[J].Journal of Hazardous Materials,341:381-389
向倩,许超,张杨,等.2014.控释尿素对污染土壤镉有效性的影响[J].中国环境科学,34(12):3150-3156
Zeng F,Ali S,Zhang H,et al.2011.The influence of p H and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants[J].Environmental pollution,159(1):84-91
Zhang W M,Li Q X,Wen F C,et al.2016.Remediation effects of maizestraw-derived biochar on rice grown in cadmium-contaminated soil in North China[J].Fresenius Environmental Bulletin,25:602-611
周莉娜,蔡函臻,李荣华.2017.膨润土调质对污泥堆肥的脱毒及重金属钝化和雌酮消除作用[J].环境科学,38(7):3061-3069
周琴,姜军,徐仁扣.2018.Cu(II)、Pb(II)和Cd(II)在红壤胶体和非胶体颗粒上吸附的比较[J].土壤学报,55(1):131-138
Bhattacharya A,Naik S N,Khare S K.2018.Harnessing the biomineralization ability of urease producing Serratia marcescens and Enterobacter cloacae EMB19 for remediation of heavy metal cadmium(II)[J].Journal of Environmental Management,215:143-152
Carla E R,Rufus L C,Carmen E M.2018.Soil geochemical factors regulate Cd accumulation by metal hyperaccumulating Noccaea caerulescens(J.Presl&C.Presl)F.K.Mey infield-contaminated soils[J].Science of the Total Environment,(616-617):279-287
陈卫平,杨阳,谢天,等.2018.中国农田土壤重金属污染防治挑战与对策[J].土壤学报,55(2):1-12
迟荪琳,徐卫红,熊仕娟,等.2017.不同镉水平下纳米沸石对土壤p H、CEC及Cd形态的影响[J].环境科学,38(4):1654-1666
崔红标,范玉超,周静,等.2016.改良剂对土壤铜镉有效性和微生物群落结构的影响[J].中国环境科学,36(1):197-205
Gueye M T,Di P L,G A,et al.2016.The influence of heavy metals and organic matter on hexavalent chromium reduction by nano zero valent iron in soil[J].Chemical Engineering Transactions,47:289-294
Hartley W,Edwards R,Lepp N W.2004.Arsenic and heavy metal mobility in iron oxide-amended contaminated soils as evaluated by short-and long-term leaching tests[J].Environmental Pollution,131:495-504
Hua M,Zhang S,Pan B,Zhang W,et al.2012.Heavy metal removal from water/wastewater by nanosized metal oxides:A review[J].Journal of Hazardous Materials,211-212:317-331
Huang D,Xue W,Zeng G,et al.2016.Immobilization of Cd in river sediments by sodium alginate modified nanoscale zero-valent iron:Impact on enzyme activities and microbial community diversity[J].Water Research,106:15-25
Huang G Y,Su X J,Rizwan M S,et al.2016.Chemical immobilization of Pb,Cu,and Cd by phosphate materials and calcium carbonate in contaminated soils[J].Environmental Science&Pollution Research International,23(16):1-12
Lefevre E,Bossa N,Wiesner M R,et al.2016.A review of the environmental implications of in situ remediation by nanoscale zero valent iron(n ZVI):behavior,transport and impacts on microbial communities[J].Science of the Total Environment,565:889-901
Li M,Cheng X,Guo H.2013.Heavy metal removal by biomineralization of urease producing bacteria isolated from soil[J].International Biodeterioration&Biodegradation,76:81-85
Lin J,Su B,Sun M,et al.2018.Biosynthesized iron oxide nanoparticles used for optimized removal of cadmium with response surface methodology[J].Science of the Total Environment,627:314-321
Liu C,Yu H Y,Liu C,et al.2015.Arsenic availability in rice from a mining area:is amorphous iron oxide-bound arsenic a source or sink[J].Environmental Pollution,199:95-101
Luo F,Chen Z,Megharaj M,et al.2016.Simultaneous removal of trichloroethylene and hexavalent chromium by green synthesized agarose-Fe nanoparticles hydrogel[J].Chemical Engineering Journal,294:290-297
鲁如坤.2000.土壤农业化学分析方法[M].北京:中国农业科技出版社
Poulain A J,Newman D K.2009.Rhodobacter capsulatus catalyzes lightdependent Fe(II)oxidation under anaerobic conditions as a potential detoxification mechanism[J].Applied and Environmental Microbiology,75:6639-6646
Qasim B,Motelica-Heino M,Bourgerie S,et al.2015.Effect of nitrate and ammonium fertilization on Zn,Pb,and Cd phytostabilization by Populus euramericana Dorskamp in contaminated technosol[J].Environmental Science&Pollution Research,22(23):18759-18771
Shipley H J,Engates K E,Guettner A M.2011.Study of iron oxide nanoparticles in soil for remediation of arsenic[J].Journal of Nanoparticle Research,13(6):2387-2397
Sima B,Ronald J,Smernik,et al.2018.The application of a spectrophotometric method to determine pH in acidic(pH<5)soils[J].Talanta,186:421-426
Sulu G,Dorina S,Filip J R,et al.2016.Cable bacteria control ironphosphorus dynamics in sediments of a coastal hypoxic basin[J].Environmental Science&Technology,50(3):1227-1233
Tang X,Shen C,Shi D,et al.2010.Heavy metal and persistent organic compound contamination in soil from Wenling:an emerging e-waste recycling city in Taizhou area,China[J].Journal of Hazardous Materials,173:653-660
Tessier A,Campbell P G C,Bisson M.1979.Sequential extraction procedure for the speciation of particulate trace metals[J].Analytical Chemistry,51(7):844-851
Weng X,Jin X,Lin J,et al.2016.Removal of mixed contaminants Cr(VI)and Cu(II)by green synthesized iron based nanoparticles[J].Ecological Engineering,97:32-39
Xue W,Huang D,Zeng G,et al.2018.Nanoscale zero-valent iron coated with rhamnolipid as an effective stabilizer for immobilization of Cd and Pb in river sediments[J].Journal of Hazardous Materials,341:381-389
向倩,许超,张杨,等.2014.控释尿素对污染土壤镉有效性的影响[J].中国环境科学,34(12):3150-3156
Zeng F,Ali S,Zhang H,et al.2011.The influence of p H and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants[J].Environmental pollution,159(1):84-91
Zhang W M,Li Q X,Wen F C,et al.2016.Remediation effects of maizestraw-derived biochar on rice grown in cadmium-contaminated soil in North China[J].Fresenius Environmental Bulletin,25:602-611
周莉娜,蔡函臻,李荣华.2017.膨润土调质对污泥堆肥的脱毒及重金属钝化和雌酮消除作用[J].环境科学,38(7):3061-3069
周琴,姜军,徐仁扣.2018.Cu(II)、Pb(II)和Cd(II)在红壤胶体和非胶体颗粒上吸附的比较[J].土壤学报,55(1):131-138