应用生态学报 ›› 2022, Vol. 33 ›› Issue (12): 3448-3456.doi: 10.13287/j.1001-9332.202212.032
• 综合评述 • 上一篇
刘战明1, 曾悦1,2,3*, 李云琴1, 穆景利4, 吴名秀1, 曹文珍1
收稿日期:
2021-12-12
接受日期:
2022-05-27
出版日期:
2022-12-15
发布日期:
2023-07-05
通讯作者:
* E-mail: yzeng@fzu.edu.cn
作者简介:
刘战明, 男, 1995年生, 硕士研究生。主要从事污染物环境过程研究。E-mail: 1907365893@qq.com
基金资助:
LIU Zhan-ming1, ZENG Yue1,2,3*, LI Yun-qing1, MU Jing-li4, WU Ming-xiu1, CAO Wen-zhen1
Received:
2021-12-12
Accepted:
2022-05-27
Online:
2022-12-15
Published:
2023-07-05
摘要: 环境中铂族金属(PGMs)的赋存形态多样,形态分析对识别其生态风险具有十分重要的意义。本文综述了环境中3种主要铂族金属(铂、钯、铑)的形态分析方法,包括化学顺序提取、仪器联用技术及计算机模拟等,概述了这些方法的类型、特点及应用,同时阐述了它们存在的不足,并对未来发展方向进行了展望。化学顺序提取法普遍用于固相样品形态分析,当前研究中提出的提取条件和步骤多样,但不能很好地标准化;仪器联用技术在溶液元素形态分析上具有显著优势,毛细管电泳联用系统能够分离具有相同电泳能力的相似物质,但在分离能力和检出限方面不如液相色谱联用系统;计算机模拟则进一步拓展了形态分析的途径,能够实现复杂的形态计算。建议今后将多个方法进行结合,通过相互补充与完善,不断提高分析技术准确性。
刘战明, 曾悦, 李云琴, 穆景利, 吴名秀, 曹文珍. 环境介质中铂族金属形态分析方法的研究进展[J]. 应用生态学报, 2022, 33(12): 3448-3456.
LIU Zhan-ming, ZENG Yue, LI Yun-qing, MU Jing-li, WU Ming-xiu, CAO Wen-zhen. Review on the speciation analysis methods of platinum group metals in environmental media[J]. Chinese Journal of Applied Ecology, 2022, 33(12): 3448-3456.
[1] Sobrova P, Zehnalek J, Adam V, et al. The effects on soil/water/plant/animal systems by platinum group elements. Central European Journal of Chemistry, 2012, 10: 1369-1382 [2] Buchspies B, Thormann L, Mbohwa C, et al. PGE production in southern Africa, Part II: Environmental aspects. Minerals, 2017, 7: 225 [3] Zereini F, Wiseman CLS. Platinum Metals in the Environment. Berlin: Springer, 2015: 243-255 [4] Dubiella-Jackowska A, Kudak B, Polkowska Z, et al. Environmental fate of traffic-derived platinum group metals. Critical Reviews in Analytical Chemistry, 2009, 39: 251-271 [5] Ek KH, Morrison GM, Rauch S. Environmental routes for platinum group elements to biological materials: A review. Science of the Total Environment, 2004, 334: 21-38 [6] Lesniewska BA, Godlewska-Zylkiewicz B, Bocca B, et al. Platinum, palladium and rhodium content in road dust, tunnel dust and common grass in Bialystok area (Poland): A pilot study. Science of the Total Environment, 2004, 321: 93-104 [7] Savignan L, Faucher S, Chery P, et al. Platinum group elements contamination in soils: Review of the current state. Chemosphere, 2021, 271: 129517 [8] Rinkovec J. Platinum, palladium, and rhodium in airborne particulate matter. Archives of Industrial Hygiene and Toxicology, 2019, 70: 224-231 [9] Khan RK, Strand MA. Road dust and its effect on human health: A literature review. Epidemiology and Health, 2018, 40: e2018013 [10] Templeton DM, Ariese F, Cornelis R, et al. Guidelines for terms related to chemical speciation and fractionation of elements. Definitions, structural aspects, and methodological approaches (IUPAC Recommendations 2000). Pure and Applied Chemistry, 2000, 72: 1453-1470 [11] Templeton DM. Speciation in metal toxicity and metal-based therapeutics. Toxics, 2015, 3: 170-186 [12] Zereini F, Skerstupp B, Alt F, et al. Geochemical behaviour of platinum-group elements (PGE) in particulate emissions by automobile exhaust catalysts: Experimental results and environmental investigations. Science of the Total Environment, 1997, 206: 137-146 [13] 侯松, 曾悦, 税伟, 等. 水环境中铂族元素的环境化学行为. 环境化学, 2020, 39(8): 2055-2064 [14] Zereini F, Wiseman CLS, Poprizki J, et al. Assessing the potential of inorganic anions (C1(-), NO3-, SO42- and PO43-) to increase the bioaccessibility of emitted palladium in the environment: Experimental studies with soils and a Pd model substance. Environmental Pollution, 2017, 220: 1050-1058 [15] Kubrakova IV, Tyutyunnik OA, Koshcheeva IY, et al. Migration behavior of platinum group elements in natural and technogeneous systems. Geochemistry International, 2017, 55: 108-124 [16] 刘凯, 高学鲁, 李力. 海水中痕量铂族元素的赋存形态及螯合树脂富集研究进展. 应用生态学报, 2017, 28(10): 3424-3432 [17] Egorova KS, Sinjushin AA, Posvyatenko AV, et al. Evaluation of phytotoxicity and cytotoxicity of industrial catalyst components (Fe, Cu, Ni, Rh and Pd): A case of lethal toxicity of a rhodium salt in terrestrial plants. Chemosphere, 2019, 223: 738-747 [18] Dubiella-Jackowska A, Polkowska Z, Namiennik J. Platinum group elements in the environment: Emissions and exposure. Reviews of Environmental Contamination and Toxicology, 2009, 199: 111-135 [19] Ravindra K, Bencs L, Van Grieken R. Platinum group elements in the environment and their health risk. Science of the Total Environment, 2004, 318: 1-43 [20] 李培苗, 高学鲁. 环境中人为来源的铂族元素及其迁移转化研究进展. 应用生态学报, 2012, 23(12): 3514-3525 [21] Schmid M, Zimmermann S, Krug HF, et al. Influence of platinum, palladium and rhodium as compared with cadmium, nickel and chromium on cell viability and oxidative stress in human bronchial epithelial cells. Environment International, 2007, 33: 385-390 [22] 刘少轻, 施燕支, 朱若华. 铂族金属及其形态分析进展. 光谱实验室, 2007, 24(2): 43-49 [23] Wojcieszek J, Szpunar J, Lobinski R. Speciation of technologically critical elements in the environment using chromatography with element and molecule specific detection. Trends in Analytical Chemistry, 2018, 104: 42-53 [24] Balcerzak M. Methods for the determination of platinum group elements in environmental and biological materials: A review. Critical Reviews in Analytical Chemistry, 2011, 41: 214-235 [25] Fliegel D, Berner Z, Eckhardt D, et al. New data on the mobility of Pt emitted from catalytic converters. Analytical and Bioanalytical Chemistry, 2004, 379: 131-136 [26] Tessier AP, Campbell PGC, Bisson MX. Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry, 1979, 51: 844-851 [27] Rauret G, López-Sánchez JF, Sahuquillo A, et al. Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials. Journal of Environmental Monitoring, 1999, 1: 57-61 [28] Sutherland RA. BCR (R)-701: A review of 10-years of sequential extraction analyses. Analytica Chimica Acta, 2010, 680: 10-20 [29] Bahaloo-Horeh N, Mousavi SM. Comprehensive characterization and environmental risk assessment of end-of-life automotive catalytic converters to arrange a sustainable roadmap for future recycling practices. Journal of Hazardous Materials, 2020, 400: 123186 [30] Leopold K, Denzel A, Gruber A, et al. Mobility of traffic-related Pd and Pt species in soils evaluated by sequential extraction. Environmental Pollution, 2018, 242: 1119-1127 [31] 王琳, 来新泽, 唐志中, 等. 改进BCR法测定公路两旁表层土壤中铂钯铑的化学形态. 岩矿测试, 2012, 31(6): 954-960 [32] 王娟, 朱若华, 施燕支. 北京市区公路旁尘土中铂族元素的化学形态. 环境化学, 2007, 26(4): 528-530 [33] 吕娅丽, 毛雪瑛, 李晓林, 等. 分子活化分析法研究地质样品中铂族元素的化学种态. 核化学与放射化学, 2002, 24(1): 11-15 [34] 闫红岭, 连文莉, 来新泽, 等. 白云岩和石英岩型铂族矿床中铂钯金的相态分析. 贵金属, 2016, 37(1): 56-62 [35] Li CS, Chai CF, Mao XY, et al. Chemical speciation study of platinum group elements in geological samples by stepwise dissolution and inductively coupled plasma mass spectrometry. Analytica Chimica Acta, 1998, 374: 93-98 [36] Heltai G, Gyori Z, Fekete I, et al. Longterm study of transformation of potentially toxic element pollution in soil/water/sediment system by means of fractionation with sequential extraction procedures. Microchemical Journal, 2018, 136: 85-93 [37] 庞文品, 秦樊鑫, 吕亚超, 等. 贵州兴仁煤矿区农田土壤重金属化学形态及风险评估. 应用生态学报, 2016, 27(5): 1468-1478 [38] 黄志勇, 吴熙鸿, 胡广林, 等. 高效液相色谱/电感耦合等离子体质谱联用技术用于元素形态分析的研究进展. 分析化学, 2002, 30(11): 1387-1393 [39] Thornton MJ, Fritz JS. Separation of inorganic anions in acidic solution by capillary electrophoresis. Journal of Chromatography A, 1997, 770: 301-310 [40] Hamacek J, Havel J. Determination of platinum(Ⅱ,Ⅳ) and palladium (Ⅱ) as thiocyanate complexes by capillary zone electrophoresis: Analysis of carboplatin and similar drugs. Journal of Chromatography A, 1999, 834: 321-327 [41] Aleksenko SS, Gumenyuk AP, Mushtakova SP, et al. Speciation studies by capillary electrophoresis: Distribution of rhodium (Ⅲ) complexed forms in acidic media. Fresenius Journal of Analytical Chemistry, 2001, 370: 865-871 [42] Standler A, Koellensperger G, Buchberger W, et al. Determination of chloroplatinates by CE coupled to inductively coupled plasma sector field MS. Electrophoresis, 2007, 28: 3492-3499 [43] Menzel CM, Berner Z, Stuben D. Coupling size-exclusion chromatography and ICP-MS to investigate the speciation of platinum-group elements in environmental samples. Journal of Geostandards and Geoanalysis, 2001, 25: 239-251 [44] Lesniewska BA, Messerschmidt J, Jakubowski N, et al. Bioaccumulation of platinum group elements and characterization of their species in Lolium multiflorum by size-exclusion chromatography coupled with ICP-MS. Science of the Total Environment, 2004, 322: 95-108 [45] Cobelo-Garcia A. Kinetic effects on the interactions of Rh(III) with humic acids as determined using size-exclusion chromatography (SEC). Environmental Science and Pollution Research, 2013, 20: 2330-2339 [46] Liu QP, Liu JC, Tong Y, et al. Separation and determination of Pt(Ⅱ), Rh(Ⅲ), Pd(Ⅱ), Os(Ⅳ), Ni(Ⅱ) and Co(Ⅱ) complexes by reversed-phase liquid-chromatography. Analytica Chimica Acta, 1992, 269: 223-228 [47] Nachtigall D, Artelt S, Wunsch G. Speciation of platinum-chloro complexes and their hydrolysis products by ion chromatography: Determination of platinum oxidation states. Journal of Chromatography A, 1997, 775: 197-210 [48] Nischwitz V, Michalke B, Kettrup A. Speciation of Pt(Ⅱ) and Pt (Ⅳ) in spiked extracts from road dust using on-line liquid chromatography-inductively coupled plasma mass spectrometry. Journal of Chromatography A, 2003, 1016: 223-234 [49] Weber G, Alt F, Messerschmidt J. Characterization of low-molecular-weight metal species in plant extracts by using HPLC with pulsed amperometric detection and cyclic voltammetry. Fresenius Journal of Analytical Chemistry, 1998, 362: 209-214 [50] Gerber WJ, Koch KR, Rohwer HE, et al. Separation and quantification of [RhCln(H2O)(6-n)](3-n) (n=0-6) complexes, including stereoisomers, by means of ion-pair HPLC-ICP-MS. Talanta, 2010, 82: 348-358 [51] Volchek VV, Berdyugin SN, Shuvaeva OV, et al. Rh(Ⅲ) hydroxocomplexes speciation using HPLC-ESI-MS. Analytical Methods, 2020, 12: 2631-2637 [52] van Wyk PH, van Dyk JB, Gerber WJ, et al. Speciation of [(PtCl6-nBrn)-Cl-IV]2-(n=0-6) and some of their mono-aquated [(PtCl5-nBrn)-Cl-IV(H2O)]-(n=0-5) anions in solution at low concentrations by means of ion-pairing reversed-phase ultra-high-performance liquid chromatography coupled to electrospray ionization quadrupole time-of-flight mass spectrometry. Rapid Communications in Mass Spectrometry, 2014, 28: 505-519 [53] Alt F, Messerschmidt J, Weber G. Investigation of low molecular weight platinum species in grass. Analytica Chimica Acta, 1998, 359: 65-70 [54] Vidmar J, Martincic A, Milacic R, et al. Speciation of cisplatin in environmental water samples by hydrophilic interaction liquid chromatography coupled to inductively coupled plasma mass spectrometry. Talanta, 2015, 138: 1-7 [55] Lenz K, Koellensperger G, Hann S, et al. Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents. Chemosphere, 2007, 69: 1765-1774 [56] Tu Q, Wang TB, Welch CJ, et al. Identification and characterization of isomeric intermediates in a catalyst formation reaction by means of speciation analysis using HPLC-ICPMS and HPLC-ESI-MS. Analytical Chemistry, 2006, 78: 1282-1289 [57] Kinska K, Bierla K, Godin S, et al. A chemical speciation insight into the palladium (Ⅱ) uptake and metabolism by Sinapis alba. Exposure to Pd induces the synthesis of a Pd-histidine complex. Metallomics, 2019, 11: 1498-1505 [58] Lustig S, Michalke B, Beck W, et al. Platinum speciation with hyphenated techniques: High performance liquid chromatography and capillary electrophoresis on-line coupled to an inductively coupled plasma-mass spectrometer - application to aqueous extracts from a platinum treated soil. Fresenius Journal of Analytical Chemistry, 1998, 360: 18-25 [59] Vogt C, Werner G. Speciation of heavy-metals by capillary electrophoresis. Journal of Chromatography A, 1994, 686: 325-332 [60] Michalke B. Capillary electrophoresis: A useful tool in speciation investigations. Fresenius Journal of Analytical Chemistry, 1996, 354: 557-565 [61] Gouyon J, D’Orlye F, Zimmerman J, et al. Speciation and quantitation of precious metals in model acidic leach liquors, theoretical and practical aspects of recycling. Analytical and Bioanalytical Chemistry, 2020, 412: 4595-4608 [62] Samuels AC, Boele CA, Bennett KT, et al. Integrated Computational and experimental protocol for understanding Rh (Ⅲ) speciation in hydrochloric and nitric acid solutions. Inorganic Chemistry, 2014, 53: 12315-12322 [63] Lustig S, De Kimpe J, Cornelis R, et al. Platinum speciation in clinical and environmental samples: Scrutiny of data obtained by using electrophoresis techniques (flatbed and capillary). Electrophoresis, 1999, 20: 1627-1633 [64] Timerbaev AR, Kung A, Keppler BK. Capillary electrophoresis of platinum-group elements analytical, speciation and biochemical studies. Journal of Chromatography A, 2002, 945: 25-44 [65] Domotor O, Enyedy EA. Binding mechanisms of half-sandwich Rh(Ⅲ) and Ru(Ⅱ) arene complexes on human serum albumin: A comparative study. Journal of Biological Inorganic Chemistry, 2019, 24: 703-719 [66] Johnson BW, Burgess MW, Murray V, et al. The interactions of novel mononuclear platinum-based complexes with DNA. BMC Cancer, 2018, 18: 1284 [67] Klueppel D, Jakubowski N, Messerschmidt J, et al. Speciation of platinum metabolites in plants by size-exclusion chromatography and inductively coupled plasma mass spectrometry. Journal of Analytical Atomic Spectrometry, 1998, 13: 255-262 [68] Weber G, Messerschmidt J, von Bohlen A, et al. Improved separation of palladium species in biological matrices by using a combination of gel permeation chromatography and isotachophoresis. Electrophoresis, 2004, 25: 1758-1764 [69] Nischwitz V, Michalke B, Kettrup A. Investigations on extraction procedures for Pt species from spiked road dust samples using HPLC-ICP-MS detection. Analytica Chimica Acta, 2004, 521: 87-98 [70] Di Marco VB, Bombi GG. Electrospray mass spectrometry (ESI-MS) in the study of metal-ligand solution equilibria. Mass Spectrometry Reviews, 2006, 25: 347-379 [71] Jo JY, Tu Q, Xiang R, et al. Metal speciation in pharmaceutical process development: Case studies and process/analytical challenges for a palladium-catalyzed cross-coupling reaction. Organometallics, 2019, 38: 185-193 [72] 王新宇, 施泽明, 倪师军. 环境地球化学模型的应用与发展. 物探化探计算技术, 2013, 35(6): 722-726 [73] 蒋美玲, 陈涛, 康明亮, 等. 地球化学模拟在高放废物地质处置中的应用与发展. 中国科学:化学, 2014, 44(10): 1508-1520 [74] 刘杰安, 冯孝贵. 几个常用地球化学模拟软件的比较. 核化学与放射化学, 2011, 33(1): 32-41 [75] Colombo C, Oates CJ, Monhemius AJ, et al. Complexation of platinum, palladium and rhodium with inorganic ligands in the environment. Geochemistry-Exploration Environment Analysis, 2008, 8: 91-101 [76] le Roux CJ, Kriek RJ. A detailed spectrophotometric investigation of the stability constants of [PdCln(OH)4-n]2- and [PdBrn(OH)4-n]2- (n=0-4). Hydrometallurgy, 2019, 186: 21-29 [77] le Roux CJ, Kriek RJ. A detailed spectrophotometric investigation of the complexation of palladium(Ⅱ) with chloride and bromide. Hydrometallurgy, 2017, 169: 447-455 [78] Sucha V, Mihaljevic M, Ettler V, et al. The pH-dependent release of platinum group elements (PGEs) from gasoline and diesel fuel catalysts: Implication for weathering in soils. Journal of Environmental Management, 2016, 171: 52-59 [79] Aruguete DM, Wallace A, Blakney T, et al. Palladium release from catalytic converter materials induced by road de-icer components chloride and ferrocyanide. Chemosphere, 2020, 245: 125578 [80] Sebek O, Mihaljevic M, Strnad L, et al. Dissolution kinetics of Pd and Pt from automobile catalysts by naturally occurring complexing agents. Journal of Hazardous Materials, 2011, 198: 331-339 [81] Mosai AK, Johnson RH, Tutu H. Modelling of palladium(Ⅱ) adsorption onto amine-functionalised zeolite using a generalised surface complexation approach. Journal of Environmental Management, 2021, 277: 111416 [82] Tagirov BR, Filimonova ON, Trigub AL, et al. Platinum transport in chloride-bearing fluids and melts: Insights from in situ X-ray absorption spectroscopy and thermodynamic modeling. Geochimica et Cosmochimica Acta, 2019, 254: 86-101 [83] Bazarkina EF, Pokrovski GS, Hazemann JL. Structure, stability and geochemical role of palladium chloride complexes in hydrothermal fluids. Geochimica et Cosmochimica Acta, 2014, 146: 107-131 [84] Barnes SJ, Liu WH. Pt and Pd mobility in hydrothermal fluids: Evidence from komatiites and from thermodynamic modelling. Ore Geology Reviews, 2012, 44: 49-58 [85] Cobelo-Garcia A, Turner A, Millward GE, et al. Beha-viour of palladium(Ⅱ), platinum(Ⅳ), and rhodium(Ⅲ) in artificial and natural waters: Influence of reactor surface and geochemistry on metal recovery. Analytica Chimica Acta, 2007, 585: 202-210 [86] Turner A, Xu J. Influence of ionic surfactants on the flocculation and sorption of palladium and mercury in the aquatic environment. Water Research, 2008, 42: 318-326 [87] Kubrakova IV, Fortygin AV, Lobov SG, et al. Migration of platinum, palladium, and gold in the water systems of platinum deposits. Geochemistry International, 2011, 49: 1072-1084 [88] Folens K, van Hulle S, Vanhaecke F, et al. Chemical fractionation and speciation modelling for optimization of ion-exchange processes to recover palladium from industrial wastewater. Water Science and Technology, 2016, 73: 1738-1745 [89] Jmii S, Dewez D. Toxic responses of palladium accumulation in duckweed (Lemna minor): Determination of biomarkers. Environmental Toxicology and Chemistry, 2021, 40: 1630-1638 [90] Balamurugan R, Liu JH, Liu BT. A review of recent developments in fluorescent sensors for the selective detection of palladium ions. Coordination Chemistry Reviews, 2018, 376: 196-224 [91] Chen CY, Zhou LF, Liu FL, et al. V-shaped bis-coumarin based fluorescent probe for detecting palladium in natural waters. Journal of Hazardous Materials, 2020, 386: 121943 [92] Luo WF, Liu WS. A two-photon ratiometric ESIPT probe for the discrimination of different palladium species and its application in bioimaging. Journal of Materials Chemistry B, 2016, 4: 3911-3915 [93] Bezerra MA, Cerqueira UMFD, Ferreira SLC, et al. Recent developments in the application of cloud point extraction as procedure for speciation of trace elements. Applied Spectroscopy Reviews, 2021, 57: 338-352 [94] Mortada WI, Hassanien MM, El-Asmy AA. Speciation of platinum in blood plasma and urine by micelle-mediated extraction and graphite furnace atomic absorption spectrometry. Journal of Trace Elements in Medicine and Biology, 2013, 27: 267-272 [95] Serbin R, Bazel Y, Ruzickova S. Speciation of platinum by GFAAS using various possibilities of analytical signal enhancement. Talanta, 2017, 175: 46-52 |
[1] | 王毅焕, 靳一丹, 姜铭楷, 马书琴, 陈有超, 蔡延江. 短期氮沉降改变毛竹林凋落物和土壤有机质化学组成 [J]. 应用生态学报, 2023, 34(10): 2593-2600. |
[2] | 郭梁, 任伟征, 胡亮亮, 张剑, 罗均, 谌洪光, 姚红光, 陈欣. 传统稻鱼系统中“田鲤鱼”的形态特征 [J]. 应用生态学报, 2017, 28(2): 665-672. |
[3] | 铁梅1,2;梁彦秋2;臧树良1;潘伟1;孙铁彪1;李华为3. 工业污染土壤中镉的化学形态及植物修复研究 [J]. 应用生态学报, 2006, 17(02): 348-350 . |
[4] | 刘迎湖;谢利;骆世明;陈实;曾任森. 入侵杂草化感作用的细胞自动机模拟研究 [J]. 应用生态学报, 2006, 17(02): 229-232 . |
[5] | 郭线茹, 原国辉, 蒋金炜, 罗梅浩, 马继盛. 不同季节黑杨萎蔫叶片挥发物的化学成分分析 [J]. 应用生态学报, 2005, 16(10): 1822-1825. |
[6] | 李硕, 孙波, 曾志远, 赵其国. 遥感和GIS辅助下流域养分迁移过程的计算机模拟 [J]. 应用生态学报, 2004, (2): 278-282. |
[7] | 李硕, 孙波, 曾志远, 赵其国. 遥感和GIS辅助下流域养分迁移过程的计算机模拟 [J]. 应用生态学报, 2004, (2): 278-282. |
[8] | 李硕[1] 孙波[1] 曾志远[2] 赵其国[1]. 遥感和GIS辅助下流域养分迁移过程的计算机模拟 [J]. 应用生态学报, 2004, 15(02): 278-282 . |
[9] | 蔡燕飞, 廖宗文, 王德汉, 李育锐. 化学-生物发酵联用技术对稻草腐熟的效果及红外光谱研究 [J]. 应用生态学报, 2003, (8): 1269-1272. |
[10] | 蔡燕飞, 廖宗文, 王德汉, 李育锐. 化学-生物发酵联用技术对稻草腐熟的效果及红外光谱研究 [J]. 应用生态学报, 2003, (8): 1269-1272. |
[11] | 杨居荣, 查燕. 食品中重金属的存在形态及其与毒性的关系 [J]. 应用生态学报, 1999, 10(6): 766-770. |
[12] | 王本楠, 裴铁璠. 树干径流过程的计算机模拟 [J]. 应用生态学报, 1991, 2(1): 14-22. |
阅读次数 | ||||||
全文 |
|
|||||
摘要 |
|
|||||