流动注射/浊点萃取—光学仪器联用分析生物样品中痕量铬、砷、铅、镉的形态
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摘要
随着科学技术的发展,在进行地质、生物、环境等样品的分析时,经常要求测定ng/mL甚至pg/mL级的痕量元素,虽然流动注射分光光度法和原子光谱分析等技术具有很高的灵敏度,且在测定样品时所需样品量也不多,但要直接测定这些试样中的痕量组分往往会遇到困难,有时甚至是不可能的,这是因为:一方面,分析方法对极低含量的组分灵敏度不够,或者样品本身的物理化学状态有的不适合直接测定;另一方面是存在基体干扰,或者缺乏相应的校正标准和试剂。因此需要借助于分离富集技术来提高分析方法的灵敏度和选择性。
浊点萃取是近年来出现的一种新兴的液-液萃取技术,它不使用挥发性有机溶剂,不影响环境。它以中性表面活性剂胶束水溶液的溶解性和浊点现象为基础,通过改变实验参数引发相分离,将疏水性物质与亲水性物质分离。作为一种分离富集的手段,因其具有萃取效率高、富集因子大、操作简便、安全、经济、便于实现联用化等优点,受到人们的极大关注与重视,并在生物大分子的分离纯化、有机小分子的分离测定及金属离子的分离富集等方面得到广泛的应用。
本论文的目的是,以浊点萃取和氢化物发生器作为分离富集手段,以流动注射和可见分光光度计或原子光谱分析技术联用为检测手段,分析痕量铬、砷、铅、镉的形态,并将其应用于实际样品。
主要研究内容概括如下:
(1)采用浊点萃取作为分离富集手段,采用流动注射-分光光度计做为检测手段,系统地研究了痕量铬不同形态,通过单因素实验和正交试验确定了最佳的萃取条件和实验条件,在优化条件下,分析了生物样品中铬的不同形态,建立了一种铬的形态分析的新方法。
(2)采用流动注射-氢化物发生器作为分离富集手段,采用电加热原子吸收法作为检测手段,测定了痕量砷的不同形态,通过控制溶液pH值,即可达到分离(As(Ⅲ))和(As(Ⅴ)),并从理论上解释了原因。在优化的实验条件下,将建立的方法应用于不同水样中的测定,结果满意。
(3)采用浊点萃取作为分离富集手段,采用FAAS作为检测手段,对影响金属离子铅、镉的浊点萃取效率的各种因素进行研究,确定最佳的萃取条件和仪器条件,并将其应用于生物样品中不同形态铅、镉的分离和测定。
With the development of science and technology, the determination of trace elements often requires more sensitivity. FIA (flow injection spectrophotometry) and AAS (atomic absorption spectrophotometry) have a very High sensitivity and in the process of determination they require a few volume, but if determine the sample directly it will face a lot of difficulties or even impossible. Because on the one hand, the analysis of a very low content of elements lack of high sensitivity or the state of the samples do not suitable for direct determination, on the other hand, there exist matrix interference or lack of appropriate calibration standards and chemical reagent. Therefore, it is necessary to hire the separation and enrichment technology in order to improve the sensitivity and selectivity of the determination.
Cloud point extraction (CPE) is a new liquid-liquid extraction technology in recent years with the advantages of little uses volatile organic solvents and do not contaminate the environment. It is based on the solubility and cloud point phenomenon of the neutral surfactant micellar in aqueous solution, the hydrophobic and hydrophilic material will separate by changing the experiment parameters. CPE as a mean of separation and enrichment, it has a lot of merits, such as high extraction efficiency, great enrichment factors, easy to operate, convenient to operate, security, economic and convenient for coupling with other instrument. As a result, it takes people's great concern and recognition. Now, it has been widely used in the separation and purification of biological macromolecules, the separation and determination of small organic molecules and the separation and enrichment of metal ions and so on.
The purpose of this article is to use the cloud point extraction and hydride generator as a means of separation and enrichment, employ FIA coupled with visible spectrophotometer or AAS as the mean of detection to analysis the speciation of trace chromium, arsenic, lead, cadmium and applied to the actual samples.
The main contents of this paper can be summarized as follows:
(1) Use the cloud point extraction as a mean of separation and enrichment, hire the FIA-VIS spectrophotometer as a mean of detection, systematically studied the speciation of trace chromium. The optimal extraction conditions and experimental conditions were determined through single-factor experiment and orthogonal test. Under the best conditions, the different forms of chromium in biological samples were analyzed.
(2) Use the Flow Injection - Hydride Generator as a mean of separation and enrichment, employ the electrical heating atomic absorption spectrometry as a mean of detection, systematically studied the speciation of trace arsenic. As (III) and As (V) could be separated by controlling the pH value of the solution and explained in theory. Under the optimal conditions, the established method was used in different water samples with satisfactory results.
(3) Use the cloud point extraction as a mean of separation and enrichment; use FAAS as a mean of detection, systematically studied a variety of factors of the speciation of trace lead and cadmium, determined the optimal extraction conditions and equipment conditions. Furthermore, it was used in the speciation of trace lead and cadmium in biological samples.
浊点萃取是近年来出现的一种新兴的液-液萃取技术,它不使用挥发性有机溶剂,不影响环境。它以中性表面活性剂胶束水溶液的溶解性和浊点现象为基础,通过改变实验参数引发相分离,将疏水性物质与亲水性物质分离。作为一种分离富集的手段,因其具有萃取效率高、富集因子大、操作简便、安全、经济、便于实现联用化等优点,受到人们的极大关注与重视,并在生物大分子的分离纯化、有机小分子的分离测定及金属离子的分离富集等方面得到广泛的应用。
本论文的目的是,以浊点萃取和氢化物发生器作为分离富集手段,以流动注射和可见分光光度计或原子光谱分析技术联用为检测手段,分析痕量铬、砷、铅、镉的形态,并将其应用于实际样品。
主要研究内容概括如下:
(1)采用浊点萃取作为分离富集手段,采用流动注射-分光光度计做为检测手段,系统地研究了痕量铬不同形态,通过单因素实验和正交试验确定了最佳的萃取条件和实验条件,在优化条件下,分析了生物样品中铬的不同形态,建立了一种铬的形态分析的新方法。
(2)采用流动注射-氢化物发生器作为分离富集手段,采用电加热原子吸收法作为检测手段,测定了痕量砷的不同形态,通过控制溶液pH值,即可达到分离(As(Ⅲ))和(As(Ⅴ)),并从理论上解释了原因。在优化的实验条件下,将建立的方法应用于不同水样中的测定,结果满意。
(3)采用浊点萃取作为分离富集手段,采用FAAS作为检测手段,对影响金属离子铅、镉的浊点萃取效率的各种因素进行研究,确定最佳的萃取条件和仪器条件,并将其应用于生物样品中不同形态铅、镉的分离和测定。
With the development of science and technology, the determination of trace elements often requires more sensitivity. FIA (flow injection spectrophotometry) and AAS (atomic absorption spectrophotometry) have a very High sensitivity and in the process of determination they require a few volume, but if determine the sample directly it will face a lot of difficulties or even impossible. Because on the one hand, the analysis of a very low content of elements lack of high sensitivity or the state of the samples do not suitable for direct determination, on the other hand, there exist matrix interference or lack of appropriate calibration standards and chemical reagent. Therefore, it is necessary to hire the separation and enrichment technology in order to improve the sensitivity and selectivity of the determination.
Cloud point extraction (CPE) is a new liquid-liquid extraction technology in recent years with the advantages of little uses volatile organic solvents and do not contaminate the environment. It is based on the solubility and cloud point phenomenon of the neutral surfactant micellar in aqueous solution, the hydrophobic and hydrophilic material will separate by changing the experiment parameters. CPE as a mean of separation and enrichment, it has a lot of merits, such as high extraction efficiency, great enrichment factors, easy to operate, convenient to operate, security, economic and convenient for coupling with other instrument. As a result, it takes people's great concern and recognition. Now, it has been widely used in the separation and purification of biological macromolecules, the separation and determination of small organic molecules and the separation and enrichment of metal ions and so on.
The purpose of this article is to use the cloud point extraction and hydride generator as a means of separation and enrichment, employ FIA coupled with visible spectrophotometer or AAS as the mean of detection to analysis the speciation of trace chromium, arsenic, lead, cadmium and applied to the actual samples.
The main contents of this paper can be summarized as follows:
(1) Use the cloud point extraction as a mean of separation and enrichment, hire the FIA-VIS spectrophotometer as a mean of detection, systematically studied the speciation of trace chromium. The optimal extraction conditions and experimental conditions were determined through single-factor experiment and orthogonal test. Under the best conditions, the different forms of chromium in biological samples were analyzed.
(2) Use the Flow Injection - Hydride Generator as a mean of separation and enrichment, employ the electrical heating atomic absorption spectrometry as a mean of detection, systematically studied the speciation of trace arsenic. As (III) and As (V) could be separated by controlling the pH value of the solution and explained in theory. Under the optimal conditions, the established method was used in different water samples with satisfactory results.
(3) Use the cloud point extraction as a mean of separation and enrichment; use FAAS as a mean of detection, systematically studied a variety of factors of the speciation of trace lead and cadmium, determined the optimal extraction conditions and equipment conditions. Furthermore, it was used in the speciation of trace lead and cadmium in biological samples.
引文
[1]黄先飞,秦樊鑫,胡继伟.重金属污染与化学形态研究进展[J].微量元素与健康研究,2008,25(1):48-51
[2]杨忠芳,朱立,陈岳龙.现代环境地球化学,北京:地质出版社,1999:6-9
[3]欧小兵,李海云,陈永煌,等.铜、镉对水螅的急性和联合毒性作用[J].环境污染与防治,2006,28(8):584-588
[4]S.S.S.SARMA,Hilda Fabiola NU,NEZ-CRUZ,et al.Effects on the population dynamics of Brachionus rubens(Rotifera) caused by mercury and cadmium administered through medium and algal food Chlorella vulgaris[J].动物学报,2005,51(1):46-52
[5]王维岗,亚库甫江·吐尔逊.环境的重金属污染物来源和毒理作用[J].生态环保,2004(2):39
[6]Agata Kot,Jacek Namies(?)ik.The role of speciation in analytical chemistry[J].trends in analytical chemistry,2000,19:69-79
[7]刘冬莲.药用植物中重金属形态分析及其土壤重金属地球化学特征研究:[硕士学位论文].北京:中国地质大学,2006
[8]朱霞石,江祖成,胡斌.铬形态分析的分离富集/原子光谱分析研究进展[J].分析测试学报,2005,24(4):108-115
[9]Robinson NJ,Procter CM,Connolly EL,et al.A ferric-chelate reductase for iron uptake from soils[J].NATURE,1999,397(6721):694-697
[10]江桂斌,周群芳,何滨,等.江西猪油中毒事件中的有机锡形态[J].中国科学B辑,2000,30(4):378-384
[11]韦超.砷元素形态分析的方法研究及其在食品安全领域的应用:[硕士学位论文].北京:清华大学,2004
[12]穆从如,李森照,王立军,等.铬在水体、土壤和作物中的迁移转化规律[J].中国环境科学,1982,2(1):19-23.
[13]陈英旭,何增耀,吴建平.土壤中铬的形态及其转化[J].环境科学,1994,15(3):53-56
[14]刘英俊,曹励明.微量元素地球化学[M].北京:地质出版社,1984.65-76
[15]陈英旭,朱祖祥,何增耀.土壤中铬的有效性与污染生态效应[J].生态学报,1995,15(1):79-84.
[16]朱定祥,倪守斌.铬的生物地球化学及生物效应[J].广东微量元素科学, 2004,11(4):1-9
[17]黄坚,李建文,陈胜福,等.湘江(长沙段)水中铬的形态分布及其迁移[J].分析测试学报,2007,26(3):335-338
[18]刘二保,梁建功,韩素琴,等.铬的形态分析研究与进展[J].理化检验-化学分册,2003,39(6):368-372
[19]肖开提·阿布力孜,王吉德,胡西旦.用三正辛胺-苯萃取分离体系-原子吸收光谱对铬作形态分析[J].光谱学与光谱分析,2005,25(12):2082-2084
[20]朱霞石,江祖成,胡斌.铬形态分析的分离富集/原子光谱分析研究进展[J].分析测试学报,2005,24(4):108-115
[21]朱敏,林少美,姚琪,等.离子色谱-电感祸合等离子体质谱联用检测尿样中的三价铬和六价铬[J].浙江大学学报(理学版),2007,34(3):326-330
[22]李娜,玮炜.共振散射法测定环境水样中的不同形态的铬[J].南昌大学学报(理科版),2006,30:1371-1372
[23]乐上旺,李建平.电化学分析法在铬形态分析中应用进展[J].分析科学学报,2007,23(6):927-932
[24]李海敏,张勇.砷的形态分析方法研究进展[J].理化检验-化学分册,2006,42(4):315-320.
[25]王燕兰.1例长期服用牛黄解毒片致慢性砷中毒报告[J].中国职业医学,2007,34(3):258.
[26]李国明,刘社清,张雪静.雄黄对小鼠肾脏形念学的研究[J].河北医药,2002,24(1):60
[27]陈云嫩,柴立元.砷在地下水环境中的迁移转化[J].有色金属,2008,60(1):109-112
[28]胡省英,冉伟彦.土壤环境中砷元素的生态效应[J].物探与化探,2006,30(1):83-86
[29]傅平.砷的地球化学屏障作用初探[J].重庆环境科学,1999,21(6):48-49
[30]甄云鹏,范必威.砷形态分析方法进展[J].广东微量元素科学,2005,12(7):5-12.
[31]匡少平,徐倩.铅对泥鳅的致毒效应[J].环境科学技术,2003,26(6):11.
[32]刘文,叶长兵,韩相奎,等.水体中铅、酚对红虫的毒性研究[J].吉林建筑工程学院学报,2004,21(1):13-14.
[33]李丽光,何兴元,曹志强,等.土壤-作物系统中铅的研究进展[J].生态学杂志(Chinese Journal of Ecology),2004,23(1):78-82
[34]黄宝圣.镉的生物毒性及其防治策略[J].生物学通报,2005,40(11):26-28
[35]刘俐,高新华,宋存义,等.土壤中镉的赋存行为及迁移转化规律研究进展[J].能源环境保护,2006,20(2):6-9
[36]何红蓼,倪哲明,李冰,等.环境样品中痕量元素的化学形态分析Ⅱ.砷汞镉锡铅硒铬的形态分析[J].岩矿测试,2005,24(2):118-129
[37]吴宏,黄德乾,金焰,等.环境样品中铅、锑、汞、硒形态分析研究进展[J].环境监测管理与技术,2008,20(4):9-18
[38]张汉萍,赵秋香,张雪容,等.土壤中铅的含量及其化学形态分析[J].理化检验-化学分册,2006,42(9):705-710
[39]梁彦秋,刘婷婷,铁梅,等.镉污染土壤中镉的形态分析及植物修复技术研究[J].环境科学与技术,2007,30(2):57-61.
[40]党秀丽,张玉玲,虞娜,等.冻融作用对土壤中重金属镉赋存形态的影响[J].土壤通报,2008,39(4):826-831
[41]方肇伦.流动注射分析法.北京:北京科学出版社,1999
[42]Evangelos K.Paleologos,Athanasios G.Vlessidis,Miltiades I.Karayannis,et al.On-line sorption pre-concentration of metals based on mixed micelle cloud point extraction prior to their determination with micellar chemiluminescence Application to the determination of chromium at ng.L~(-1) levels.Analytica Chimica Acta,2003,477:223-231
[43]Vanessa G.K.Almeida,Mrnica F.Lima,Ricardo J.Cassella.Development of a reversed FIA system for the spectrophotometric determination of Sb(Ⅲ) and total Sb in antileishmanial drugs[J].Talanta,2007,71:1047-1053
[44]李紫薇,陆慧慧,陶冠红.流动注射分光光度法快速测定食品中微量甲醛[J].化检验-化学分册,2008,44(6):550-552.
[45]肖新峰,罗娅君,王照丽,等.反向流动注射分光光度法测定电镀废水和污泥中铬(Ⅵ)[J].冶金分析,2008,28(4):47-50
[46]朱金枝,杜建修,鹿艳秋.流动注射化学发光法测定盐酸氟桂利嗪[J].分析试验室,2008,27(9):66-68
[47]申丽华,黄婕,李晓霞,等.流动注射化学发光分析法测定利福平[J].分析试验室,2008,27(7):68-71
[48]柴晓莉,赵常志,陶晟辰,等.流动注射电化学发光法测定盐酸麻黄碱[J].分析试验室,2008,27(6):108-111
[49]Meng Shan Lin,Jun ShengWang,Chien Hung Lai.Electrochemiluminescent determination of nicotine based on tri(2,2'-bipyridyl) ruthenium(Ⅱ) complex through flow injection analysis[J].Electrochimica Acta,2008,53:7775-7780
[50]谢志鹏,肖友军,汪敬武.流动注射抑制电化学发光法测定维生素C[J].分析试验室,2007,26(11):64-66
[51]郑洪涛,汤志勇,李威,等.流动注射离子交换分离-火焰原子吸收光谱法连续测定铁的形态[J].2006,42(9):759-761
[52]吴冬梅,王爱霞.环境水样中镍的微型柱现场预富集流动注射火焰原子吸收测定[J].分析测试学报,2007,26(6):855-857
[53]杨晓华,刘英华,王玉春.流动注射-氢化物发生-原子吸收法测定土壤中微量砷[J].化工环保,2007,27(4):382-385
[54]张敬东,Reinhard Niessner.流动注射-荧光法同时测定水中的镍和锌[J].分析试验室,2002,21(4):1-4
[55]詹汉英,汤颖.微透析流动注射荧光法测定人体血液中的叶酸[J].西北大学学报(自然科学版),2006,36(5):768-772
[56]欧阳小清,谢增鸿,郭祖奉,等.静态抑制荧光法和流动注射抑制荧光法测定微量甲醛的研究[J].光谱学与光谱分析,2004,24(11):1395-1399
[57]刘丽娟,费学宁.流动注射分析技术及其在水质分析应用中的进展[J].天津城市建设学院学报,2005,11(2):111-114
[58]张兰英,饶竹,刘娜.等.环境样品前处理技术[M].北京:清华大学出版社,2008
[59]王少芬,魏建谟.超临界流体萃取金属离子在环境分析上的应用[J].分析化学(FENXI HUAXUE)研究报告,2004,32(8):1110-1115
[60]张艳君,肖军.金属离子的超临界流体萃取技术的进展[J].理化检验-化学分册,2001,37(12):576-578
[61]张国英,凌建亚,崔兆杰.衍生-超临界CO_2萃取土壤样品中的金属离子[J].化工学报,2005,56(5):883-884
[62]Maria C.Paraschivescu,Earl G.Alley,William T.French,Rafael Hernandez,Kevin Armbrust.Determination of methanol in biodiesel by headspace solid phase microextraction[J].Bioresource Technology,2008,(99):5901-5905
[63]Maria Rosa Ras,Rosa Maria Marc(?),Francesc Borrull.Solid-phase microextraction-Gas chromatography to determine volatile organic sulfur compounds in the air at sewage treatment plants[J].Talanta,2008,(77):774-778
[64]Lidia M.Ravelo-P(?)rez,Javier Hern(?)ndez-Borges,Teresa M.Borges-Miquel,et al.Solid-phase microextraction and sample stacking micellar electrokinetic chromatography for the analysis of pesticide residues in red wines[J].Food Chemistry,2008,(111):764-770
[65]王建华,储晓刚.凝胶渗透色谱-气相色谱-质谱测定花生中乙草胺的残留量[J].分析试验室,2007,26(12):23-24
[66]Young S.Doh,Serji N.Amirkhanian,Kwang W.Kim.Analysis of unbalanced binder oxidation level in recycled asphalt mixture using GPC[J].Construction and Building Materials,2008,(22):1253-1260
[67]于胜良,杨桂朋,付萌.凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中的36种农药残留[J].色谱,2007,25(4):581-585
[68]刘稷燕,江桂斌.固相微萃取技术及其在有机锡和有机汞分析中的应用[J].分析化学,1999,27(10):1226-1230
[69]栾天罡,张展霞.固相微萃取-衍生化技术及其在环境和生物分析中的应用[J].分析化学,2003,31(4):496-500
[70]张杰,曹全,张玉华,等.萃取色层-原子吸收法测定废水中痕量铅和镉[J].环境科学与管理,2007,32(8):124-126
[71]张成功,赵倩,陈波,等.液-液-液三相液相微萃取-高效液相色谱法检测尿样中的安非他明和氯胺酮[J].色谱,2007,25(5):641-645
[72]杜甫佑,肖小华,李攻科.离子液体在样品预处理中的应用[J].化学通报,2007,(9):647-654
[73]张莘民.吹扫-捕集/气相色谱法测定水中挥发性卤代烃[J].中国环境监测,18(2):38-41
[74]张玉玲,张兰英,阿布巴卡尔·达布雷.吹扫.捕集技术在GC法测定地下水中苯系物的条件研究[J].吉林大学学报(地球科学版),2003,33(2):255-256
[75]杨桂朋,尹士序,陆小兰,等.吹扫-捕集气相色谱法测定海水中挥发性卤代烃[J].中国海洋大学学报,2007,37(2):299-304
[76]张启修,肖连生.膜技术在稀有金属冶炼中的应用[J].稀有金属,2003,27(1):1-7
[77]陈绍华,邢丕峰,陈文梅.稀贵金属在氢气纯化中的应用[J].稀有金属,2003,27(1):9-17
[78]David L.Grzenia,Daniel J.Schell,S.Ranil Wickramasinghe.Membrane extraction for removal of acetic acid from biomass hydrolysates[J].Journal of Membrane Science,2008,(322):189-195
[79]吴礼康,邹晓春,刘祖强.空气中苯胺气(液)相色谱方法的改进研究[J].中国职业医学,2004,31(4):8-10
[80]李巧玲,陈则华.微波消解光度法测定奶粉中的磷[J].食品科学,2007, 28(6):303-305
[81]高岐,窦宪民,卢会杰.微波法测定面制食品中的铝含量[J].粮油食品,2007,79-80
[82]李静.浊点萃取技术在金属离子分离富集及形态分析中的应用:[硕士学位论文].武汉:华中师范大学,2004
[83]赵国玺.表面活性剂物理化学[M].北京:北京大学出版社,1991.35
[84]肖珊美,陈建荣,刘文涵.浊点萃取在痕量金属元素分析中的应用[J].理化检验-化学分册,2004,40(11):682-688
[85]梁沛,李静.浊点萃取技术在金属离子分离和富集以及形态分析中应用的进展[J].理化检验-化学分册,2006,42(7):582-587
[86]申进朝,邵学广.浊点萃取技术及其在有机化合物分离分析中的应用[J].化学进展,2006,18(4):482-487
[87]余益军,孙兆海,鲜放鸣,等.浊点萃取在环境有机分析中的影响因素及应用[J].理化检验-化学分册,2008,44:696-700
[88]马岳,阎哲,黄骏雄.浊点萃取在生物大分子分离及分析中的应用[J].化学进展,2001,13(1):25-32
[89]周锦兰,俞开潮.浊点萃取技术及其在食品工业中的应用[J].食品科学,2003,24(4):164-168
[90]黄晖,陈培珍.浊点萃取技术在痕量金属离子测定中的应用[J].三明高等专科学校学报,2004,21(4):66-72
[91]仇佩虹,杨小凤,叶筱琴.超声波提取电感耦合等离子体-原子发射光谱分析黄芪中7种元素的形态[J].光谱实验室,22(5):1035-1040
[92]任萍,汪明启.改进BCR法在分析水系沉积物样品铅形态中的应用[J].物探与化探,2004,28(3):222-225
[93]孙福生,谢敏,詹中英,等.超声波系列萃取土壤中重金属的形态分析研究[J].苏州科技学院学报(工程技术版),2003,16(4):1-6.
[94]杨祥,陈飞,窦希波,等.析相萃取富集火焰原子吸收法测定矿样中的金[J].理化检验-化学分册,2002,38(7):355-356.
[95]V.N.Bulut,C.Duran,M.Tufekci,et al.Speciation of Cr(Ⅲ) and Cr(Ⅵ) after column solid phase extraction on Amberlite XAD-2010[J].Journal of Hazardous Materials,2007,143:112-117
[96]李琳,冯易君,黄淦泉.氢氧化铝共沉淀浮选石墨炉原子吸收测水中铬(Ⅲ)与铬(Ⅵ)[J].光谱学与光谱分析,1998,18(3):354-358
[97]Sethsiri S.Samaratunga,Jun Nishimoto,Masaaki Tabata.Separation of Cr(Ⅵ) from Cr(Ⅲ) in CaCl_2 aqueous salt medium using hydrocarbon(as toluene,n-hexane,n-heptane or n-octane) mixed solvents of ter-butanol[J].Hydrometallurgy.2007,(89):207-216
[98]Ibrahim Narin,Ayse Kars,Mustafa Soylak.A novel solid phase extraction procedure on Amberlite XAD-1180 for speciation of Cr(Ⅲ),Cr(Ⅵ) and total chromium in environmental and pharmaceutical samples[J].Journal of Hazardous Materials,2008,150:453-458
[99]Jirasak Threeprom,Sumalee Purachaka,Lamfa Potipan.Simultaneous determination of Cr(Ⅲ)-EDTA and Cr(Ⅵ) by ion interaction chromatography using a C18 column[J].Journal of Chromatography A,2005,1073:291-295
[100]朱霞石,江祖成,胡斌,等.浊点萃取-电热原子吸收光谱法分析铬的形态[J].分析化学,2003,31(11):1312-1316
[101]夏玉宇.化学实验室手册[M].北京:化学工业出版社,2004:596.
[102]袁建,杨晓蓉,浮东宝,王建新.食品中铬(Ⅲ)与铬(Ⅵ)分析方法的探讨[J].中国粮油学报,1998,14(4):59-62
[103]盖秀兰.有毒微量元素砷的毒性研究[J].白城师范学院学报,2006,20(4):36-38
[104]中华人民共和国卫生部.生活饮用水卫生规范[M].北京:卫生部卫生法制与监督司,2001
[105]Marie Ponthieu,Pauline Pinel-Raffaitin,Isabelle Le Hecho,et al.Speciation analysis of arsenic in landfill leachate[J].Water Research,2007,41:3177-3185
[106]M.N.Matos Reyes,M.L.Cervera,R.C.Campos,et al.Determination of arsenite,arsenate,monomethylarsonic acid and dimethylarsinic acid in cereals by hydride generation atomic fluorescence spectrometry[J].Spectrochimica Acta Part B,2007,62:1078-1082.
[107]施凤宁.间隙进样氢化物还原体系-原子荧光法测定水样中的砷(Ⅲ)、砷(Ⅴ)及总砷[J].云南环境科学,2006,25:167-169.
[108]张力培,吴鹏,何靓,等.浊点萃取钨丝电热蒸发原子荧光光谱分析法测定水样中的As(Ⅲ)和As(Ⅴ)[J].四川大学学报(自然科学版),2007,44(3):645-648.
[109]M ingshengM al,X.Chris L el,胡斌.高效液相色谱/氢化物发生/原子荧光快速检测尿砷形态[J].分析科学学报(Journal of Analytical Science 2000,16(2):89-96
[110]Maria Jos(?) Ruiz-Chancho,Jos(?) Fermin L(?)pez-S(?)nchez,Ernst Schmeisser. Arsenic speciation in plants growing in arsenic-contaminated sites[J].Chemosphere,2008,71:1522-530
[111]郝春莉,曹煊,荆淼.鱿鱼丝中砷的形态分析[J].分析科学学报(Journal of Analytical Science),2007,23(6):621-626
[112]Amjad Shraim,Barry Chiswell,Henry Olszowy.Speciation of arsenic by hydride generation-atomic absorption spectrometry(HG-AAS) in hydrochloric acid reaction medium[J].Talanta,1999,50:1109-1127
[113]欧阳津,时彦,张新荣.液相色谱分离-氢化物原子吸收测定血清中不同形态的有机砷化合物[J].分析化学研究简报(Chinese Journal of Analytical Chemistry),1999,27(10):1151-1155
[114]陈寿椿,唐春元,于肇德.重要的无机化学反应[M].上海:上海科学技术出版社,1993
[115]邓勃,迟锡增,刘明钟,等.应用原子吸收与原子荧光光谱分析[M].北京:化学工业出版社,2007
[2]杨忠芳,朱立,陈岳龙.现代环境地球化学,北京:地质出版社,1999:6-9
[3]欧小兵,李海云,陈永煌,等.铜、镉对水螅的急性和联合毒性作用[J].环境污染与防治,2006,28(8):584-588
[4]S.S.S.SARMA,Hilda Fabiola NU,NEZ-CRUZ,et al.Effects on the population dynamics of Brachionus rubens(Rotifera) caused by mercury and cadmium administered through medium and algal food Chlorella vulgaris[J].动物学报,2005,51(1):46-52
[5]王维岗,亚库甫江·吐尔逊.环境的重金属污染物来源和毒理作用[J].生态环保,2004(2):39
[6]Agata Kot,Jacek Namies(?)ik.The role of speciation in analytical chemistry[J].trends in analytical chemistry,2000,19:69-79
[7]刘冬莲.药用植物中重金属形态分析及其土壤重金属地球化学特征研究:[硕士学位论文].北京:中国地质大学,2006
[8]朱霞石,江祖成,胡斌.铬形态分析的分离富集/原子光谱分析研究进展[J].分析测试学报,2005,24(4):108-115
[9]Robinson NJ,Procter CM,Connolly EL,et al.A ferric-chelate reductase for iron uptake from soils[J].NATURE,1999,397(6721):694-697
[10]江桂斌,周群芳,何滨,等.江西猪油中毒事件中的有机锡形态[J].中国科学B辑,2000,30(4):378-384
[11]韦超.砷元素形态分析的方法研究及其在食品安全领域的应用:[硕士学位论文].北京:清华大学,2004
[12]穆从如,李森照,王立军,等.铬在水体、土壤和作物中的迁移转化规律[J].中国环境科学,1982,2(1):19-23.
[13]陈英旭,何增耀,吴建平.土壤中铬的形态及其转化[J].环境科学,1994,15(3):53-56
[14]刘英俊,曹励明.微量元素地球化学[M].北京:地质出版社,1984.65-76
[15]陈英旭,朱祖祥,何增耀.土壤中铬的有效性与污染生态效应[J].生态学报,1995,15(1):79-84.
[16]朱定祥,倪守斌.铬的生物地球化学及生物效应[J].广东微量元素科学, 2004,11(4):1-9
[17]黄坚,李建文,陈胜福,等.湘江(长沙段)水中铬的形态分布及其迁移[J].分析测试学报,2007,26(3):335-338
[18]刘二保,梁建功,韩素琴,等.铬的形态分析研究与进展[J].理化检验-化学分册,2003,39(6):368-372
[19]肖开提·阿布力孜,王吉德,胡西旦.用三正辛胺-苯萃取分离体系-原子吸收光谱对铬作形态分析[J].光谱学与光谱分析,2005,25(12):2082-2084
[20]朱霞石,江祖成,胡斌.铬形态分析的分离富集/原子光谱分析研究进展[J].分析测试学报,2005,24(4):108-115
[21]朱敏,林少美,姚琪,等.离子色谱-电感祸合等离子体质谱联用检测尿样中的三价铬和六价铬[J].浙江大学学报(理学版),2007,34(3):326-330
[22]李娜,玮炜.共振散射法测定环境水样中的不同形态的铬[J].南昌大学学报(理科版),2006,30:1371-1372
[23]乐上旺,李建平.电化学分析法在铬形态分析中应用进展[J].分析科学学报,2007,23(6):927-932
[24]李海敏,张勇.砷的形态分析方法研究进展[J].理化检验-化学分册,2006,42(4):315-320.
[25]王燕兰.1例长期服用牛黄解毒片致慢性砷中毒报告[J].中国职业医学,2007,34(3):258.
[26]李国明,刘社清,张雪静.雄黄对小鼠肾脏形念学的研究[J].河北医药,2002,24(1):60
[27]陈云嫩,柴立元.砷在地下水环境中的迁移转化[J].有色金属,2008,60(1):109-112
[28]胡省英,冉伟彦.土壤环境中砷元素的生态效应[J].物探与化探,2006,30(1):83-86
[29]傅平.砷的地球化学屏障作用初探[J].重庆环境科学,1999,21(6):48-49
[30]甄云鹏,范必威.砷形态分析方法进展[J].广东微量元素科学,2005,12(7):5-12.
[31]匡少平,徐倩.铅对泥鳅的致毒效应[J].环境科学技术,2003,26(6):11.
[32]刘文,叶长兵,韩相奎,等.水体中铅、酚对红虫的毒性研究[J].吉林建筑工程学院学报,2004,21(1):13-14.
[33]李丽光,何兴元,曹志强,等.土壤-作物系统中铅的研究进展[J].生态学杂志(Chinese Journal of Ecology),2004,23(1):78-82
[34]黄宝圣.镉的生物毒性及其防治策略[J].生物学通报,2005,40(11):26-28
[35]刘俐,高新华,宋存义,等.土壤中镉的赋存行为及迁移转化规律研究进展[J].能源环境保护,2006,20(2):6-9
[36]何红蓼,倪哲明,李冰,等.环境样品中痕量元素的化学形态分析Ⅱ.砷汞镉锡铅硒铬的形态分析[J].岩矿测试,2005,24(2):118-129
[37]吴宏,黄德乾,金焰,等.环境样品中铅、锑、汞、硒形态分析研究进展[J].环境监测管理与技术,2008,20(4):9-18
[38]张汉萍,赵秋香,张雪容,等.土壤中铅的含量及其化学形态分析[J].理化检验-化学分册,2006,42(9):705-710
[39]梁彦秋,刘婷婷,铁梅,等.镉污染土壤中镉的形态分析及植物修复技术研究[J].环境科学与技术,2007,30(2):57-61.
[40]党秀丽,张玉玲,虞娜,等.冻融作用对土壤中重金属镉赋存形态的影响[J].土壤通报,2008,39(4):826-831
[41]方肇伦.流动注射分析法.北京:北京科学出版社,1999
[42]Evangelos K.Paleologos,Athanasios G.Vlessidis,Miltiades I.Karayannis,et al.On-line sorption pre-concentration of metals based on mixed micelle cloud point extraction prior to their determination with micellar chemiluminescence Application to the determination of chromium at ng.L~(-1) levels.Analytica Chimica Acta,2003,477:223-231
[43]Vanessa G.K.Almeida,Mrnica F.Lima,Ricardo J.Cassella.Development of a reversed FIA system for the spectrophotometric determination of Sb(Ⅲ) and total Sb in antileishmanial drugs[J].Talanta,2007,71:1047-1053
[44]李紫薇,陆慧慧,陶冠红.流动注射分光光度法快速测定食品中微量甲醛[J].化检验-化学分册,2008,44(6):550-552.
[45]肖新峰,罗娅君,王照丽,等.反向流动注射分光光度法测定电镀废水和污泥中铬(Ⅵ)[J].冶金分析,2008,28(4):47-50
[46]朱金枝,杜建修,鹿艳秋.流动注射化学发光法测定盐酸氟桂利嗪[J].分析试验室,2008,27(9):66-68
[47]申丽华,黄婕,李晓霞,等.流动注射化学发光分析法测定利福平[J].分析试验室,2008,27(7):68-71
[48]柴晓莉,赵常志,陶晟辰,等.流动注射电化学发光法测定盐酸麻黄碱[J].分析试验室,2008,27(6):108-111
[49]Meng Shan Lin,Jun ShengWang,Chien Hung Lai.Electrochemiluminescent determination of nicotine based on tri(2,2'-bipyridyl) ruthenium(Ⅱ) complex through flow injection analysis[J].Electrochimica Acta,2008,53:7775-7780
[50]谢志鹏,肖友军,汪敬武.流动注射抑制电化学发光法测定维生素C[J].分析试验室,2007,26(11):64-66
[51]郑洪涛,汤志勇,李威,等.流动注射离子交换分离-火焰原子吸收光谱法连续测定铁的形态[J].2006,42(9):759-761
[52]吴冬梅,王爱霞.环境水样中镍的微型柱现场预富集流动注射火焰原子吸收测定[J].分析测试学报,2007,26(6):855-857
[53]杨晓华,刘英华,王玉春.流动注射-氢化物发生-原子吸收法测定土壤中微量砷[J].化工环保,2007,27(4):382-385
[54]张敬东,Reinhard Niessner.流动注射-荧光法同时测定水中的镍和锌[J].分析试验室,2002,21(4):1-4
[55]詹汉英,汤颖.微透析流动注射荧光法测定人体血液中的叶酸[J].西北大学学报(自然科学版),2006,36(5):768-772
[56]欧阳小清,谢增鸿,郭祖奉,等.静态抑制荧光法和流动注射抑制荧光法测定微量甲醛的研究[J].光谱学与光谱分析,2004,24(11):1395-1399
[57]刘丽娟,费学宁.流动注射分析技术及其在水质分析应用中的进展[J].天津城市建设学院学报,2005,11(2):111-114
[58]张兰英,饶竹,刘娜.等.环境样品前处理技术[M].北京:清华大学出版社,2008
[59]王少芬,魏建谟.超临界流体萃取金属离子在环境分析上的应用[J].分析化学(FENXI HUAXUE)研究报告,2004,32(8):1110-1115
[60]张艳君,肖军.金属离子的超临界流体萃取技术的进展[J].理化检验-化学分册,2001,37(12):576-578
[61]张国英,凌建亚,崔兆杰.衍生-超临界CO_2萃取土壤样品中的金属离子[J].化工学报,2005,56(5):883-884
[62]Maria C.Paraschivescu,Earl G.Alley,William T.French,Rafael Hernandez,Kevin Armbrust.Determination of methanol in biodiesel by headspace solid phase microextraction[J].Bioresource Technology,2008,(99):5901-5905
[63]Maria Rosa Ras,Rosa Maria Marc(?),Francesc Borrull.Solid-phase microextraction-Gas chromatography to determine volatile organic sulfur compounds in the air at sewage treatment plants[J].Talanta,2008,(77):774-778
[64]Lidia M.Ravelo-P(?)rez,Javier Hern(?)ndez-Borges,Teresa M.Borges-Miquel,et al.Solid-phase microextraction and sample stacking micellar electrokinetic chromatography for the analysis of pesticide residues in red wines[J].Food Chemistry,2008,(111):764-770
[65]王建华,储晓刚.凝胶渗透色谱-气相色谱-质谱测定花生中乙草胺的残留量[J].分析试验室,2007,26(12):23-24
[66]Young S.Doh,Serji N.Amirkhanian,Kwang W.Kim.Analysis of unbalanced binder oxidation level in recycled asphalt mixture using GPC[J].Construction and Building Materials,2008,(22):1253-1260
[67]于胜良,杨桂朋,付萌.凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中的36种农药残留[J].色谱,2007,25(4):581-585
[68]刘稷燕,江桂斌.固相微萃取技术及其在有机锡和有机汞分析中的应用[J].分析化学,1999,27(10):1226-1230
[69]栾天罡,张展霞.固相微萃取-衍生化技术及其在环境和生物分析中的应用[J].分析化学,2003,31(4):496-500
[70]张杰,曹全,张玉华,等.萃取色层-原子吸收法测定废水中痕量铅和镉[J].环境科学与管理,2007,32(8):124-126
[71]张成功,赵倩,陈波,等.液-液-液三相液相微萃取-高效液相色谱法检测尿样中的安非他明和氯胺酮[J].色谱,2007,25(5):641-645
[72]杜甫佑,肖小华,李攻科.离子液体在样品预处理中的应用[J].化学通报,2007,(9):647-654
[73]张莘民.吹扫-捕集/气相色谱法测定水中挥发性卤代烃[J].中国环境监测,18(2):38-41
[74]张玉玲,张兰英,阿布巴卡尔·达布雷.吹扫.捕集技术在GC法测定地下水中苯系物的条件研究[J].吉林大学学报(地球科学版),2003,33(2):255-256
[75]杨桂朋,尹士序,陆小兰,等.吹扫-捕集气相色谱法测定海水中挥发性卤代烃[J].中国海洋大学学报,2007,37(2):299-304
[76]张启修,肖连生.膜技术在稀有金属冶炼中的应用[J].稀有金属,2003,27(1):1-7
[77]陈绍华,邢丕峰,陈文梅.稀贵金属在氢气纯化中的应用[J].稀有金属,2003,27(1):9-17
[78]David L.Grzenia,Daniel J.Schell,S.Ranil Wickramasinghe.Membrane extraction for removal of acetic acid from biomass hydrolysates[J].Journal of Membrane Science,2008,(322):189-195
[79]吴礼康,邹晓春,刘祖强.空气中苯胺气(液)相色谱方法的改进研究[J].中国职业医学,2004,31(4):8-10
[80]李巧玲,陈则华.微波消解光度法测定奶粉中的磷[J].食品科学,2007, 28(6):303-305
[81]高岐,窦宪民,卢会杰.微波法测定面制食品中的铝含量[J].粮油食品,2007,79-80
[82]李静.浊点萃取技术在金属离子分离富集及形态分析中的应用:[硕士学位论文].武汉:华中师范大学,2004
[83]赵国玺.表面活性剂物理化学[M].北京:北京大学出版社,1991.35
[84]肖珊美,陈建荣,刘文涵.浊点萃取在痕量金属元素分析中的应用[J].理化检验-化学分册,2004,40(11):682-688
[85]梁沛,李静.浊点萃取技术在金属离子分离和富集以及形态分析中应用的进展[J].理化检验-化学分册,2006,42(7):582-587
[86]申进朝,邵学广.浊点萃取技术及其在有机化合物分离分析中的应用[J].化学进展,2006,18(4):482-487
[87]余益军,孙兆海,鲜放鸣,等.浊点萃取在环境有机分析中的影响因素及应用[J].理化检验-化学分册,2008,44:696-700
[88]马岳,阎哲,黄骏雄.浊点萃取在生物大分子分离及分析中的应用[J].化学进展,2001,13(1):25-32
[89]周锦兰,俞开潮.浊点萃取技术及其在食品工业中的应用[J].食品科学,2003,24(4):164-168
[90]黄晖,陈培珍.浊点萃取技术在痕量金属离子测定中的应用[J].三明高等专科学校学报,2004,21(4):66-72
[91]仇佩虹,杨小凤,叶筱琴.超声波提取电感耦合等离子体-原子发射光谱分析黄芪中7种元素的形态[J].光谱实验室,22(5):1035-1040
[92]任萍,汪明启.改进BCR法在分析水系沉积物样品铅形态中的应用[J].物探与化探,2004,28(3):222-225
[93]孙福生,谢敏,詹中英,等.超声波系列萃取土壤中重金属的形态分析研究[J].苏州科技学院学报(工程技术版),2003,16(4):1-6.
[94]杨祥,陈飞,窦希波,等.析相萃取富集火焰原子吸收法测定矿样中的金[J].理化检验-化学分册,2002,38(7):355-356.
[95]V.N.Bulut,C.Duran,M.Tufekci,et al.Speciation of Cr(Ⅲ) and Cr(Ⅵ) after column solid phase extraction on Amberlite XAD-2010[J].Journal of Hazardous Materials,2007,143:112-117
[96]李琳,冯易君,黄淦泉.氢氧化铝共沉淀浮选石墨炉原子吸收测水中铬(Ⅲ)与铬(Ⅵ)[J].光谱学与光谱分析,1998,18(3):354-358
[97]Sethsiri S.Samaratunga,Jun Nishimoto,Masaaki Tabata.Separation of Cr(Ⅵ) from Cr(Ⅲ) in CaCl_2 aqueous salt medium using hydrocarbon(as toluene,n-hexane,n-heptane or n-octane) mixed solvents of ter-butanol[J].Hydrometallurgy.2007,(89):207-216
[98]Ibrahim Narin,Ayse Kars,Mustafa Soylak.A novel solid phase extraction procedure on Amberlite XAD-1180 for speciation of Cr(Ⅲ),Cr(Ⅵ) and total chromium in environmental and pharmaceutical samples[J].Journal of Hazardous Materials,2008,150:453-458
[99]Jirasak Threeprom,Sumalee Purachaka,Lamfa Potipan.Simultaneous determination of Cr(Ⅲ)-EDTA and Cr(Ⅵ) by ion interaction chromatography using a C18 column[J].Journal of Chromatography A,2005,1073:291-295
[100]朱霞石,江祖成,胡斌,等.浊点萃取-电热原子吸收光谱法分析铬的形态[J].分析化学,2003,31(11):1312-1316
[101]夏玉宇.化学实验室手册[M].北京:化学工业出版社,2004:596.
[102]袁建,杨晓蓉,浮东宝,王建新.食品中铬(Ⅲ)与铬(Ⅵ)分析方法的探讨[J].中国粮油学报,1998,14(4):59-62
[103]盖秀兰.有毒微量元素砷的毒性研究[J].白城师范学院学报,2006,20(4):36-38
[104]中华人民共和国卫生部.生活饮用水卫生规范[M].北京:卫生部卫生法制与监督司,2001
[105]Marie Ponthieu,Pauline Pinel-Raffaitin,Isabelle Le Hecho,et al.Speciation analysis of arsenic in landfill leachate[J].Water Research,2007,41:3177-3185
[106]M.N.Matos Reyes,M.L.Cervera,R.C.Campos,et al.Determination of arsenite,arsenate,monomethylarsonic acid and dimethylarsinic acid in cereals by hydride generation atomic fluorescence spectrometry[J].Spectrochimica Acta Part B,2007,62:1078-1082.
[107]施凤宁.间隙进样氢化物还原体系-原子荧光法测定水样中的砷(Ⅲ)、砷(Ⅴ)及总砷[J].云南环境科学,2006,25:167-169.
[108]张力培,吴鹏,何靓,等.浊点萃取钨丝电热蒸发原子荧光光谱分析法测定水样中的As(Ⅲ)和As(Ⅴ)[J].四川大学学报(自然科学版),2007,44(3):645-648.
[109]M ingshengM al,X.Chris L el,胡斌.高效液相色谱/氢化物发生/原子荧光快速检测尿砷形态[J].分析科学学报(Journal of Analytical Science 2000,16(2):89-96
[110]Maria Jos(?) Ruiz-Chancho,Jos(?) Fermin L(?)pez-S(?)nchez,Ernst Schmeisser. Arsenic speciation in plants growing in arsenic-contaminated sites[J].Chemosphere,2008,71:1522-530
[111]郝春莉,曹煊,荆淼.鱿鱼丝中砷的形态分析[J].分析科学学报(Journal of Analytical Science),2007,23(6):621-626
[112]Amjad Shraim,Barry Chiswell,Henry Olszowy.Speciation of arsenic by hydride generation-atomic absorption spectrometry(HG-AAS) in hydrochloric acid reaction medium[J].Talanta,1999,50:1109-1127
[113]欧阳津,时彦,张新荣.液相色谱分离-氢化物原子吸收测定血清中不同形态的有机砷化合物[J].分析化学研究简报(Chinese Journal of Analytical Chemistry),1999,27(10):1151-1155
[114]陈寿椿,唐春元,于肇德.重要的无机化学反应[M].上海:上海科学技术出版社,1993
[115]邓勃,迟锡增,刘明钟,等.应用原子吸收与原子荧光光谱分析[M].北京:化学工业出版社,2007