基于红壤制备的沸石基材料用于重金属污染红壤修复研究

近年来，由于矿业、冶金、化工、电子制造等行业的迅速发展，大量
排放的工业废水、废物等对土壤安全造成了极大的威胁，土壤污染已经成
为危害人类健康和生态环境的关键性问题。通过对我国2014 年发布的《全
国土壤污染状况调查公报》中污染分布和污染类型的研究，本论文将问题
聚焦于我国南方地区广泛分布的、本身具有酸性且贫瘠的红壤重金属污染，
旨在寻求绿色、高效、低成本的土壤修复剂，对我国南方地区的红壤进行
重金属污染的修复和综合改良。
沸石，是目前最常见的重金属修复材料之一，具有良好的化学稳定性
和离子交换性能,被广泛应用于土壤原位修复。然而，仅靠单一的沸石材料，
不能同时满足重金属修复和营养改良的目的。生物炭因其多孔结构、较大
的比表面积和丰富的官能团，被认为是一种经济有效的土壤改良剂。因此，
本研究针对上述两种材料用于红壤重金属污染修复与改良展开研究，取得
的成果如下：
（1） 就地取材，采用我国南方地区广泛分布、廉价易得的红壤作为主要
硅源和铝源，合成多种不同结构的低硅铝比、高电荷密度的沸石分子筛。
以ANA 沸石分子筛为例，通过密度泛函理论（DFT）模拟计算的手段，探
究沸石与常见重金属离子之间，发生离子交换过程的能量变化，从理论上
评估ANA 沸石用于交换土壤中典型重金属离子的可行性。
（2） 基于前期对沸石材料与重金属进行离子交换性能的评估，进一步将
沸石与生物炭进行复合，构筑了ANA 型沸石/生物炭复合材料，用于重金
属污染红壤的改良和修复。该复合材料被添加至人工配置的铅和镉复合污
染红壤中，通过盆栽实验探究其对于铅和镉复合污染红壤的原位修复与改
良性能。此外，采用扫描电子显微镜（SEM）、X 射线光电子能谱仪（XPS）
以及双球差校正透射电子显微镜（ AC-TEM）等微观手段，解析沸石/生物
炭复合材料的协同作用机制。
本研究为我国南方红壤资源化利用及其原位修复与改良提供了新的思
路，贯彻了“以土治土”的绿色环保理念。

[1] HOU D, O’CONNOR D, IGALAVITHANA A D, et al. Metal contamination andbioremediation of agricultural soils for food safety and sustainability[J]. Nat . Rev.Earth and Environ., 2020, 1(7): 366-381.
[2] WANG J, HU Q, WANG X, et al. Protecting China’s soil by law[J]. Science, 2016,354(6312): 562.
[3] 全国土壤污染状况调查公报[J].环境教育,2014,06:8-10.
[4] HU B, SHAO S, NI H, et al. Current status, spatial features, health risks, andpotential driving factors of soil heavy metal pollution in China at province level[J].Environ. Pollut., 2020, 266: 114961.
[5] WU Q, HU W, WANG H, et al. Spatial distribution, ecological risk and sources ofheavy metals in soils from a typical economic development area, SoutheasternChina[J]. Sci. Total Environ., 2021, 780: 146557.
[6] ZOU Y, WANG X X, KHAN A, et al. Environmental remediation and application ofnanoscale zero-valent iron and its composites for the removal of heavy metal ions: Areview[J]. Environ. Sci. Technol., 2016, 50(14): 268-276.
[7] 徐阳.关注云南血铅村[J].绿色中国,2015:71-73.
[8] 王焰,钟宏,曹勇华,等.我国铂族元素、钴和铬主要矿床类型的分布特征及成矿机制[J].科学通报,2020,65(33):3825-3838.
[9] LI X, ZHANG J, MA J, et al. Status of chromium accumulation in agricultural soilsacross China (1989–2016)[J]. Chemosphere, 2020, 256: 127036.
[10] SHI T, ZHANG Y, GONG Y, et al. Status of cadmium accumulation in agriculturalsoils across China (1975–2016): From temporal and spatial variations to riskassessment[J]. Chemosphere, 2019, 230: 136-143.
[11] FU Y, LI F, GUO S, et al. Cadmium concentration and its typical input and outputfluxes in agricultural soil downstream of a heavy metal sewage irrigation area[J]. J .Hazard. Mater., 2021, 412: 125203.
[12] MEN C, LIU R, XU L, et al. Source-specific ecological risk analysis and criticalsource identification of heavy metals in road dust in Beijing, China[J]. J. Hazard.Mater., 2020, 388: 121763.
[13] FALAHI-ARDAKANI A. Contamination of environment with heavy metals emittedfrom automotives[J]. Ecotoxicol. Environ. Saf., 1984, 8: 152-161.
[14] HU B, SHAO S, NI H, et al. Assessment of potentially toxic element pollution insoils and related health risks in 271 cities across China[J]. Environ. Pollut., 2021,270: 116196.
[15] HE Z, ZHANG M, WILSON M J. Distribution and classification of red soils inChina[J]. Red Soils China, 2004: 29-33.
[16] ZHU Z, ZHU Z, ZHOU H, et al. Environmental problems of red soil along the coastof South China[J]. Soil Use Manag., 2006, 18: 39-44.
[17] LI Z, MA Z, VAN DER KUIJP T J, et al. A review of soil heavy metal pollutionfrom mines in China: Pollution and health risk assessment[J]. Sci. Total Environ.,2014, 468-469: 843-853.
[18] ZHUANG P, ZOU B, LI N Y, et al. Heavy metal contamination in soils and foodcrops around Dabaoshan mine in Guangdong, China: Implication for human health[J].Environ. Geochem. Health, 2009, 31(6): 707-715.
[19] YU Z, ZHOU L, HUANG Y, et al. Effects of a manganese oxide -modified biocharcomposite on adsorption of arsenic in red soil[J]. J . Environ. Manage., 2015, 163:155-162.
[20] DUAN Q, LEE J, LIU Y, et al. Distribution of heavy metal pollution in surface soilsamples in China: A graphical review[J]. Bull. Environ. Contam. Toxicol., 2016, 97:303-309.
[21] FENG X, QIU G. Mercury pollution in Guizhou, southwestern China-An overview[J].Sci. Total Environ., 2008, 400: 227-237.
[22] DUBEY S, SHRI M, GUPTA A, et al. Toxicity and detoxification of heavy metalsduring plant growth and metabolism[J]. Environ. Chem. Lett., 2018, 16: 1169-1192.
[23] ZHAO F J, MA Y, ZHU Y G, et al. Soil contamination in China: current status andmitigation strategies[J]. Environ. Sci. Technol., 2015, 49: 750-759.
[24] 国外工业公害[J].工业安全与环保,1972,02:40-49.
[25] MA L, SUN J, YANG Z, et al. Heavy metal contamination of agricultural soilsaffected by mining activities around the Ganxi River in Chenzhou, Southern Chin a[J].Environ. Monit. Assess., 2015, 187: 1-9.
[26] ZHUANG P, LI Z A, ZOU B, et al. Heavy metal contamination in soil and soybeannear the dabaoshan mine, south China[J]. Pedosphere, 2013, 23(3): 298-304.
[27] JIANG C, JUN Z, GAO L. Sources and ecological risk assessment of heavymetal(loid)s in agricultural soils of Huzhou, China[J]. Soil Sediment Contam., 2015,24(4): 437-453.
[28] GONG X, HUANG D, LIU Y, et al. Stabilized nanoscale zerovalent iron mediatedcadmium accumulation and oxidative damage of boehmeria nivea (L.) gaudichcultivated in cadmium contaminated sediments[J]. Environ. Sci. Technol., 2017,51(19): 11308-11316.
[29] CHEN X, LI X, XU D, et al. Application of nanoscale zero-valent iron in hexavalentchromium-contaminated soil: A review[J]. Nanotechnol. Rev., 2020, 9(1): 736-750.
[30] GE Q, FENG X, WANG R, et al. Mixed redox-couple-involved chalcopyrite phaseCuFeS2 quantum dots for highly efficient Cr(VI) removal[J]. Environ. Sci. Technol.,2020, 54: 8022-8031.
[31] YANG D, CHU Z, ZHENG R, et al. Remediation of Cu-polluted soil with analcimesynthesized from engineering abandoned soils through green chemistryapproaches[J]. J. Hazard. Mater., 2020, 406: 124673.
[32] QIU W, ZHENG Y. Removal of lead, copper, nickel, cobalt, and zinc from water bya cancrinite-type zeolite synthesized from fly ash[J]. Chem. Eng. J., 2009, 145(3):483-488.
[33] AYANGBENRO A S, BABALOLA O O. A new strategy for heavy metal pollutedenvironments: A review of microbial biosorbents[J]. Int . J. Environ. Res. PublicHealth, 2017, 14(1): 94.
[34] CHAISENA A, RANGSRIWATANANON K. Synthesis of sodium zeolites fromnatural and modified diatomite[J]. Mater . Lett., 2005, 59: 1474-1479.
[35] DUSSELIER M, DAVIS M E. Small -pore zeolites: Synthesis and catalysis[J]. Chem.Rev., 2018, 118(11): 5265-5329.
[36] FLANIGEN E M,Broach R W, Wilson S T. Introduction. In: Kulprathipanja S (ed)Zeolites in industrial separation and catalysis, 1st edn[M]. Weinheim: Wiley-VCH,2010: 1–26.
[37] LOEWENSTEIN W. The distribution of aluminum in the tetrahedra of silicates andaluminates.[J]. Am. Mineral., 1954, 39(1-2): 92-96.
[38] COLLINS F, ROZHKOVSKAYA A, OUTRAM J G, et al. A critical review of wasteresources, synthesis, and applications for Zeolite LTA[J]. Microporous MesoporousMater., 2020, 291: 109667.
[39] 徐如人,庞文琴,霍启升,等.分子筛与多孔材料化学[M].北京:科学出版社,2015.
[40] SMITH J V. Topochemistry of Zeolites and Related Materials. 1. Topology andGeometry[J]. Chem. Rev., 1988, 88(1): 149-182.
[41] N M W. Monograph on “molecular sieves”[M]. London: Society of chemicalindustry, 1968.
[42] KNIGHT C T G. Are zeolite secondary building units really red herrings?[J].Zeolites, 1990, 10(2): 140-144.
[43] KASNERYK V, SHAMZHY M, ZHOU J, et al. Vapour -phase-transportrearrangement technique for the synthesis of new zeolites[J]. Nat. Commun., 2019,10(1): 1-8.
[44] MA Y, HAN S, WU Q, et al. One-pot fabrication of metal-zeolite catalysts from acombination of solvent-free and sodium-free routes[J]. Catal. Today, 2021, 371: 64-68.
[45] LIU Y, HAN S, GUAN D, et al. Rapid green synthesis of ZSM-5 zeolite fromleached illite clay[J]. Microporous Mesoporous Mater ., 2019, 280: 324-330.
[46] MAIA A Á B, NEVES R F, ANGÉLICA Rô S, et al. Synthesis, optimisation andcharacterisation of the zeolite NaA using kaolin waste from the Amazon Region.Production of zeolites KA, MgA and CaA[J]. Appl . Clay Sci., 2015, 108: 55-60.
[47] MENG Q, CHEN H, LIN J, et al. Zeolite A synthesized from alkaline assisted pre -activated halloysite for efficient heavy metal removal in polluted river water a ndindustrial wastewater[J]. J. Environ. Sci. (China), 2017, 56: 254-262.
[48] XIE W M, ZHOU F P, BI X L, et al. Accelerated crystallization of magnetic 4Azeolitesynthesized from red mud for application in removal of mixed heavy metalions[J]. J. Hazard. Mater., 2018, 358: 441-449.
[49] BELVISO C, CAVALCANTE F, FIORE S. Synthesis of zeolite from Italian coal flyash: Differences in crystallization temperature using seawater instead of distilledwater[J]. Waste Manag., 2010, 30(5): 839-847.
[50] GARCIA G, CARDENAS E, CABRERA S, et al. Synthesis of zeolite Y fromdiatomite as silica source[J]. Microporous Mesoporous Mater ., 2016, 219: 29-37.
[51] KIM D J, CHUNG H S. Synthesis and characterization of ZSM-5 zeolite fromserpentine[J]. Appl. Clay Sci., 2003, 24(1-2): 69-77.
[52] CHAVES LIMA R, BIESEKI L, VINACHES MELGUIZO P, et al. Environmentallyfriendly zeolites: Synthesis and source materials[M]. Cham: Springer InternationalPublishing, 2019.
[53] JOHNSON E B G, ARSHAD S E. Hydrothermally synthesized zeoli tes based onkaolinite: A review[J]. Appl. Clay Sci., 2014, 97-98: 215-221.
[54] YU J. Chapter 3: Synthesis of zeolites. [J]. Stud. Surf. Sci. Catal., 2007, 168: 39 -103.
[55] SZOSTAK R. Molecular Sieves: Principles of synthesis and identification[M]. NewYork: Van Nostrand Reunbold, 1989.
[56] CABALLERO I, COLINA F G, COSTA J. Synthesis of X-type zeolite fromdealuminated kaolin by reaction with sulfuric acid at high temperature[J]. Ind . Eng.Chem. Res., 2007, 46(4): 1029-1038.
[57] MALDONADO M, OLEKSIAK M D, CHINTA S, et al. Controlling crystalpolymorphism in organic-free synthesis of Na-zeolites[J]. J. Am. Chem. Soc., 2013,135(7): 2641-2652.
[58] AYELE L, PÉREZ-PARIENTE J, CHEBUDE Y, et al. Synthesis of zeolite A fromEthiopian kaolin[J]. Microporous Mesoporous Mater., 2015, 215: 29-36.
[59] 孙晓勃,杜艳泽,秦波,等.“蒸汽相转化”法制备纳米多级Beta沸石催化材料[J].无机材料学报,2018,33(1):27-34.
[60] CONATO M T, OLEKSIAK M D, PETER MCGRAIL B, et al. Frameworkstabilization of Si-rich LTA zeolite prepared in organic-free media[J]. Chem.Commun., 2015, 51(2): 269-272.
[61] ZHANG H, ZHANG H, WANG P, et al. Organic template-free synthesis of zeolitemordenite nanocrystals through exotic seed-assisted conversion[J]. RSC Adv., 2016,6(53): 47623-47631.
[62] PARK S H, YANG J K, KIM J H, et al. Eco-friendly synthesis of zeolite A fromsynthesis cakes prepared by removing the liquid phase of aged synthesis mixtures[J].Green Chem., 2015, 17(6): 3571-3578.
[63] LECHERT H. The pH-value and its importance for the crystallization of zeolites[J].Microporous Mesoporous Mater., 1998, 22(4-6): 519-523.
[64] CAPUTO D, DE GENNARO B, LIGUORI B, et al. A Preliminary investigation onkinetics of zeolite A crystallization using optical diagnostics[J]. Mater . Chem. Phys.,2000, 66(2): 120-125.
[65] OSACKÝ M, PÁLKOVÁ H, HUDEC P, et al. Effect of alkaline synthesis conditionson mineralogy, chemistry and surface properties of phillipsite, P and X zeoliticmaterials prepared from fine powdered perlite by-product[J]. MicroporousMesoporous Mater., 2020, 294: 20-23.
[66] CUNDY C S, COX P A. The hydrothermal synthesis of zeolites: Precursors,intermediates and reaction mechanism[J]. Microporous Mesoporous Mater ., 2005,82(1-2): 1-78.
[67] GRAND J, AWALA H, MINTOVA S. Mechanism of zeolites crystal growth: Newfindings and open questions[J]. CrystEngComm, 2016, 18(5): 650-664.
[68] SOLANS-MONFORT X, BERTRAN J, BRANCHADELL V, et al. Keto-enolisomerization of acetaldehyde in HZSM5. A theoretical study using the ONIOM2method[J]. J. Phys. Chem. B, 2002, 106(39): 10220-10226.
[69] GAO J, FREINDORF M. Hybrid ab initio QM/MM simulation of N-methylacetamidein aqueous solution[J]. J. Phys. Chem. A, 1997, 101: 3182-3188.
[70] CHU C H, LEUNG C W. Inhomogeneous electron gas[J]. Phys. Rev., 1964, 136:B864-871.
[71] KOHN W, L.J.SHAM. Self-consistent equations including exchange and correlationeffects[J]. Phys. Rev., 1965, 140: A1133-1138.
[72] ZHENG R, FENG X, ZOU W, et al. Converting loess into zeolite for heavy metalpolluted soil remediation based on “soil for soil -remediation” strategy[J]. J. Hazard.Mater., 2021, 412: 125199.
[73] SELLAOUI L, HESSOU E P, BADAWI M, et al. Trapping of Ag+, Cu2+, and Co2+ byfaujasite zeolite Y: New interpretations of the adsorption mechanism via DFT andstatistical modeling investigation[J]. Chem. Eng. J., 2021, 420: 127712.
[74] MISAELIDES P. Application of natural zeolites in environmental remediation: Ashort review[J]. Microporous Mesoporous Mater ., 2011, 144(1-3): 15-18.
[75] DANG V M, VAN H T, VINH N D, et al. Enhancement of exchangeable Cd an d Pbimmobilization in contaminated soil using Mg/Al LDH-zeolite as an effectiveadsorbent[J]. RSC Adv., 2021, 11(28): 17007-17019.
[76] CASTALDI P, SANTONA L, MELIS P. Heavy metal immobilization by chemicalamendments in a polluted soil and influence on white lupin growth[J]. Chemosphere,2005, 60(3): 365-371.
[77] TRIPATHI M, SAHU J N, GANESAN P. Effect of process parameters on productionof biochar from biomass waste through pyrolysis: A review[J]. Renew. Sustain.Energy Rev., 2016, 55: 467-481.
[78] MULLEN C A, BOATENG A A, GOLDBERG N M, et al. Bio-oil and bio-charproduction from corn cobs and stover by fast pyrolysis[J]. Biomass Bioenergy, 2010,34(1): 67-74.
[79] MOHAN D, PITTMAN C U, PHILIP S. Pyrolysis of wood/biomass for bio-oil: Acritical review dinesh[J]. Energ. Fuel. 2006, 20: 848-889.
[80] CAO X, MA L, GAO B, et al. Dairy-manure derived biochar effectively sorbs leadand atrazine[J]. Environ. Sci. Technol., 2009, 43(9): 3285-3291.
[81] BASHIR S, ZHU J, FU Q, et al. Cadmium mobility, uptake and anti-oxidativeresponse of water spinach (Ipomoea aquatic) under rice straw biochar, zeolite androck phosphate as amendments[J]. Chemosphere, 2018, 194: 579-587.
[82] JIANG J, XU R kou, JIANG T yu, et al. Immobilization of Cu(II), Pb(II) and Cd(II)by the addition of rice straw derived biochar to a simulated polluted Ultisol[J]. J .Hazard. Mater., 2012, 229-230: 145-150.
[83] AHMAD Z, GAO B, MOSA A, et al. Removal of Cu(II), Cd(II) and Pb(II) ions fromaqueous solutions by biochars derived from potassium-rich biomass[J]. J. Clean.Prod., 2018, 180: 437-449.
[84] KOŁODYŃSKA D, KRUKOWSKA J, THOMAS P. Comparison of sorption anddesorption studies of heavy metal ions from biochar and commercial active carbon[J].Chem. Eng. J., 2017, 307: 353-363.
[85] YUAN J H, XU R K, ZHANG H. The forms of alkalis in the biochar produced fromcrop residues at different temperatures[J]. Bioresour . Technol., 2011, 102(3): 3488-3497.
[86] AHMAD M, RAJAPAKSHA A U, LIM J E, et al. Biochar as a sorbent forcontaminant management in soil and water: A review[J]. Chemosphere, 2014, 99:19-33.
[87] AKHIL D, LAKSHMI D, KARTIK A, et al. Production, characterization, activationand environmental applications of engineered biochar: A review[J]. Environ. Chem.Lett., 2021, 19(3): 2261-2297.
[88] YUAN T, HE W, YIN G, et al. Comparison of bio-chars formation derived from fastand slow pyrolysis of walnut shell[J]. Fuel, 2020, 261: 116450.
[89] ANTUNES E, JACOB M V., BRODIE G, et al. Silver removal from aqueous solutionby biochar produced from biosolids via microwave pyrolysis[J]. J. Environ. Manage.,2017, 203: 264-272.
[90] XU H J, WANG X H, LI H, et al. Biochar impacts soil microbial communitycomposition and nitrogen cycling in an acidic soil planted with rape[J]. Environ . Sci.Technol., 2014, 48: 9391-9399.
[91] CAO X, MA L, LIANG Y, et al. Simultaneous immobilization of lead and atrazine incontaminated soils using dairy-manure biochar.[J]. Environ. Sci. Technol., 2011, 45:4884-4889.
[92] GUNARATHNE V, ASHIQ A, RAMANAYAKA S, et al. Biochar from municipalsolid waste for resource recovery and pollution remediation[J]. Environ . Chem. Lett.,2019, 17: 1225-1235.
[93] LEI S, SHI Y, QIU Y, et al. Performance and mechanisms of emerging animal -derived biochars for immobilization of heavy metals[J]. Sci. Total Environ., 2019,646: 1281-1289.
[94] ALLISON S D, MARTINY J B H. Resistance, resilience, and redundancy inmicrobial communities[J]. Proc. Natl. Acad. Sci., 2009, 2: 149-166.
[95] FISCHER B M C, MANZONI S, MORILLAS L, et al. Improving agricultu ral wateruse efficiency with biochar–A synthesis of biochar effects on water storage andfluxes across scales[J]. Sci. Total Environ., 2019, 657: 853-862.
[96] MEIER S, CURAQUEO G, KHAN N, et al. Chicken-manure-derived biocharreduced bioavailability of copper in a contaminated soil[J]. J. Soils Sediments, 2017,17(3): 741-750.
[97] YAO Q, LIU J, YU Z, et al. Three years of biochar amendment alters soilphysiochemical properties and fungal community composition in a black soil ofnortheast China[J]. Soil Biol. Biochem., 2017, 110: 56-67.
[98] SHAABAN M, VAN ZWIETEN L, BASHIR S, et al. A concise review of biocharapplication to agricultural soils to improve soil conditions and fight pollution[J]. J .Environ. Manage., 2018, 228: 429-440.
[99] TAN Z, YUAN S, HONG M, et al. Mechanism of negative surface charge formationon biochar and its effect on the fixation of soil Cd[J]. J . Hazard. Mater., 2020, 384:121370.
[100] 杨于兴,漆睿.X射线衍射分析[M].上海:上海交通大学出版社,1989.
[101] Leng Y. Materials Characterization: Introduction to Microscopic andSpectroscopic Methods[M]. 2009.
[102] EMMETT P H, DEWITT T W. The low temperature adsorption of nitrogen,oxygen, argon, hydrogen, n-butane and carbon dioxide on porous glass and onpartially dehydrated chabazite[J]. J. Am. Chem. Soc., 1943, 65(7): 1253-1262.
[103] GOLDSTEIN J I, YAKOWITZ H. Practical scanning electron microscopy[M].New York：Plenum Press, 1977.
[104] SMITH B C. Fundamentals of fourier transform infrared spectroscopy[M]. BocaRaton: CRC Press, 1996.
[105] JENKINS R. X-ray fluorescence spectrometry, 2nd edition[M]. New York: JohnWiley&Sons, 1999.
[106] BAGUS P S, ILTON E S, NELIN C J. The interpretation of XPS spectra:Insights into materials properties[J]. Surf . Sci. Rep., 2013, 68(2): 273-304.
[107] SPENCE J C H. Experimental high-resolution electron microscopy, 2ndedition[M]. Oxford: Oxford University Express, 1988.
[108] UHLEMANN S, HAIDER M. Residual wave aberrations in the first sphericalaberration corrected transmission electron microscope[J]. Ultramicroscopy, 1998, 72:109-119.
[109] RODRIGUES M, SOUZA A, SANTOS I. Brazilian kaolin wastes: Synthesis ofzeolite P at low-temperature[J]. Am. Chem. Sci. J., 2016, 12(4): 1-11.
[110] LI Q. Red Soils of China[M]. Beijing: Science Press, 1983.
[111] SATHUPUNYA M, GULARI E, WONGKASEMJIT S. ANA and GIS zeolitesynthesis directly from alumatrane and silatrane by sol -gel process and microwavetechnique[J]. J. Eur. Ceram. Soc., 2002, 22(13): 2305-2314.
[112] LTAIEF O O, SIFFERT S, FOURMENTIN S, et al. Synthesis of Faujasite typezeolite from low grade Tunisian clay for the removal of heavy metals from aqueouswaste by batch process: Kinetic and equilibrium study[J]. Comptes Rendus Chim.,2015, 18(10): 1123-1133.
[113] PECHAR F. An X-ray diffraction refinement of the crystal structure of naturalorthorhombic analcime (NaAlSi2O6·H2O)[J]. Zeolites, 1988, 8: 247-249.
[114] ALKAN M, HOPA Ç, YILMAZ Z, et al. The effect of alkali concentration andsolid/liquid ratio on the hydrothermal synthesis of zeolite NaA from naturalkaolinite[J]. Microporous Mesoporous Mater., 2005, 86: 176-184.
[115] HANSEN S, FÄLTH L. X-ray study of the nepheline hydrate I structure[J].Zeolites, 1982, 2: 162-166.
[116] ZHANG M K, XU J M. Restoration of surface soil fertility of an eroded red soilin southern China[J]. Soil Tillage Res., 2005, 80: 13-21.
[117] http://www.fao.org/3/cb4894en/online/cb4894en.html
[118] QIN X, LIU Y, HUANG Q, et al. In-Situ remediation of cadmium and atrazinecontaminated acid red soil of south China using sepiolite and biochar[J]. Bull.Environ. Contam. Toxicol., 2019, 102(1): 128-133.
[119] HONMA T, OHBA H, KANEKO-KADOKURA A, et al. Optimal soil Eh, pH,and water management for simultaneously minimizing arsenic and cadmiumconcentrations in rice grains[J]. Environ. Sci. Technol., 2016, 50: 4178-4185.
[120] LEE D S, LIM S S, PARK H J, et al. Fly ash and zeolite decrease metal uptakebut do not improve rice growth in paddy soils contaminated with Cu and Zn[J].Environ. Int., 2019, 129: 551-564.
[121] XIAO J, ZHOU S, CHU L, et al. Electrokinetic remediation of uranium(VI) -contaminated red soil using composite electrolyte of citric acid and ferric chloride[J].Environ. Sci. Pollut. Res., 2020, 27: 4478-4488.
[122] ZHOU D mei, DENG C fen, CANG L. Electrokinetic remediation of a Cucontaminated red soil by conditioning catholyte pH with different enhancingchemical reagents[J]. Chemosphere, 2004, 56: 265-273.
[123] HONG M, YU L, WANG Y, et al. Heavy metal adsorption with zeolites: Therole of hierarchical pore architecture[J]. Chem. Eng. J., 2019, 359: 363-372.
[124] ZOU W, FENG X, WEI W, et al. Converting spent LiFePO4 battery into zeoliticphosphate for highly efficient heavy metal adsorption[J]. Inorg. Chem., 2021, 60:9496-9503.
[125] LI Z, LU W, MENG J, et al. Zeolite-supported nanoscale zero-valent iron: Newfindings on simultaneous adsorption of Cd(II), Pb(II), and As(III) in aqueoussolution and soil[J]. J. Hazard. Mater., 2017, 344: 1-11.
[126] KHAN S, CHAO C, WAQAS M, et al. Sewage sludge biochar influence uponrice (Oryza sativa L) yield, metal bioaccumulation and greenhouse gas emissionsfrom acidic paddy soil[J]. Environ. Sci. Technol., 2013, 47(15): 8624-8632.
[127] WANG L, O’CONNOR D, RINKLEBE J, et al. Biochar aging: Mechanisms,physicochemical changes, assessment, and implications for field applications[J].Environ. Sci. Technol., 2020, 54: 14797-14814.
[128] SHNEOUR E A. Oxidation of graphitic carbon in certain soils[J]. Science, 1966,151: 991-992.
[129] GUO J, CHEN B. Insights on the molecular mechanism for the recalcitrance ofbiochars: Interactive effects of carbon and silicon components [J]. Environ. Sci.Technol., 2014, 48: 9103-9112.
[130] CAO X, HARRIS W. Properties of dairy-manure-derived biochar pertinent to itspotential use in remediation[J]. Bioresour. Technol., 2010, 101: 5222-5228.
[131] MIA S, DIJKSTRA F A, SINGH B. Aging induced changes in biochar’sfunctionality and adsorption behavior for phosphate and ammonium[J]. Environ. Sci.Technol., 2017, 51: 8359-8367.
[132] WANG Y, ZHANG W, SHANG J, et al. Chemical aging changed aggregationkinetics and transport of biochar colloids[J]. Environ. Sci. Technol., 2019, 53: 8136-8146.
[133] CHENG S. Effects of heavy metals on plants and resistance mechanisms[J].Environ. Sci. Pollut. Res., 2003, 10(4): 256-264.
[134] BASHIR S, SHAABAN M, MEHMOOD S, et al. Efficiency of C3 and C4 plantderived-biochar for Cd mobility, nutrient cycling and microbial biomass incontaminated soil[J]. Bull. Environ. Contam. Toxicol., 2018, 100(6): 834-838.
[135] WANG A S, ANGLE J S, CHANEY R L, et al. Soil pH effects on uptake of Cdand Zn by thlaspi caerulescens[J]. Plant Soil, 2006, 281(1-2): 325-337.
[136] ROUPHAEL Y, REA E, CARDARELLI M, et al. Can adverse effects of acidityand aluminum toxicity be alleviated by appropriate rootstock selection incucumber?[J]. Fron. Plant Sci., 2016, 7: 1-12.
[137] ZHOU Z, DAI C, ZHOU X, et al. The removal of antimony by novel NZVI -zeolite: The role of iron transformation[J]. Water . Air. Soil Pollut., 2015, 226: 76.
[138] KIM J H, KIM S H, KIM H K, et al. Synthesis and characterization ofhydroxyapatite crystals: A review study on the analytical methods[J]. J. Biomed.Mater. Res., 2002, 62: 600-612.