譚靖 郭冬發(fā) 張彥輝

(核工業(yè)北京地質(zhì)研究院分析測(cè)試研究所,北京 100029)

激光燒蝕光譜-電感耦合等離子體質(zhì)譜聯(lián)用技術(shù)應(yīng)用進(jìn)展

譚靖 郭冬發(fā)＊張彥輝

(核工業(yè)北京地質(zhì)研究院分析測(cè)試研究所,北京 100029)

激光燒蝕光譜(LAS)分析技術(shù)是一種全光譜分析技術(shù),具有分析速度快、制樣簡(jiǎn)單、成本低、設(shè)備緊湊、可遠(yuǎn)程、實(shí)時(shí)在線監(jiān)測(cè)的特點(diǎn),但對(duì)痕量元素分析能力不足。電感耦合等離子體質(zhì)譜(ICP-MS)分析技術(shù)則具有靈敏度高和多元素及同位素分析能力,但對(duì)基體元素分析存在困難。將LAS和ICPMS分析技術(shù)相結(jié)合構(gòu)成LAS-ICP-MS聯(lián)用分析技術(shù),可相互彌補(bǔ)LAS和ICP-MS技術(shù)的缺陷。介紹了近10年來(lái)LAS-ICP-MS聯(lián)用技術(shù)的應(yīng)用進(jìn)展及發(fā)展趨勢(shì),并詳細(xì)闡述了近年來(lái)LA-ICP-MS分別在地質(zhì)、礦冶、材料、環(huán)境監(jiān)測(cè)以及其它分析領(lǐng)域的應(yīng)用。

激光燒蝕光譜;激光燒蝕電感耦合等離子體質(zhì)譜;應(yīng)用進(jìn)展

1 前言

激光燒蝕光譜(LAS、LIBS)技術(shù)是近20年來(lái)光譜領(lǐng)域發(fā)展起來(lái)的一種嶄新的分析手段。該技術(shù)利用聚焦強(qiáng)激光束激發(fā)樣品靶面,產(chǎn)生高溫等離子體,通過(guò)測(cè)定等離子體冷卻過(guò)程中發(fā)射光譜的波長(zhǎng)和強(qiáng)度來(lái)進(jìn)行元素定性、定量分析。該技術(shù)不需要對(duì)樣品進(jìn)行繁瑣的化學(xué)處理,對(duì)樣品破壞小,具有快速、實(shí)時(shí)、可遠(yuǎn)程監(jiān)測(cè)等特點(diǎn),廣泛應(yīng)用于環(huán)境[1-5]、地質(zhì)[6]、冶金[7]、燃料能源[8-9],核工業(yè)[10-13]、材料[14-17]、生物醫(yī)藥[18-19]等領(lǐng)域;但激光燒蝕光譜技術(shù)對(duì)于痕量元素的分析能力不足。電感耦合等離子體質(zhì)譜(ICP-MS)分析技術(shù)是一種公認(rèn)的、強(qiáng)有力的高靈敏度、多元素及同位素分析技術(shù)。但對(duì)固體樣品而言,ICP-MS技術(shù)通常是先將其消解,后轉(zhuǎn)入溶液,容易造成樣品污染和易揮發(fā)組分的丟失;同時(shí),水溶液的存在增加了干擾和氧化物的產(chǎn)生。

將LAS與ICP-MS分析技術(shù)相結(jié)合構(gòu)成LASICP-MS,可充分發(fā)揮兩種技術(shù)的優(yōu)勢(shì),形成實(shí)用的互補(bǔ)測(cè)試技術(shù)。LAS可用來(lái)定性、定量分析樣品中的主量元素和可能存在的干擾;LA可直接、快速將固體樣品直接引入ICP,避免濕法消解樣品的種種困難和缺點(diǎn),消除水和酸所致的多原子離子干擾,從而提高進(jìn)樣效率,增強(qiáng) ICP-MS的實(shí)際檢測(cè)能力[20];ICP-MS可用于準(zhǔn)確測(cè)定元素含量或同位素比值。LAS-ICP-MS聯(lián)用技術(shù)展現(xiàn)出良好的應(yīng)用前景。

國(guó)內(nèi)外對(duì)于LAS與ICP-MS的聯(lián)用技術(shù)報(bào)道很少,僅有幾篇文章對(duì)LIBS與LA-ICP-MS聯(lián)用技術(shù)及各自的分析能力進(jìn)行了比較闡述。Meissner等[21]對(duì)含有 KBr和兩種氧化物的固體基質(zhì)中痕量金屬元素的LIBS與LA-ICP-MS同時(shí)分析結(jié)果進(jìn)行了比較。實(shí)驗(yàn)表明,LIBS定量分析的最大難點(diǎn)是由基體效應(yīng)和自吸收引起,樣品制備對(duì)于分析結(jié)果影響不大,常規(guī)分析相對(duì)標(biāo)準(zhǔn)偏差＜10%,檢測(cè)限可達(dá)μg量級(jí)[22];LA-ICP-MS通常情況下檢測(cè)限更低,定量結(jié)果更準(zhǔn)確,可準(zhǔn)確測(cè)定μg級(jí)以下的金屬元素,但分析結(jié)果受樣品制備影響大。在某些情況下,LIBS可以成為L(zhǎng)A-ICP-MS很好的補(bǔ)充技術(shù)。Latkoczy等[23]采用LIBS與LA-ICP-MS技術(shù)同時(shí)分析鎂基合金工業(yè)樣品中的主量及痕量元素的分布情況,對(duì)死時(shí)間、脈寬、不同氣氛(空氣,氦氣,氬氣)、激光波長(zhǎng)、束斑直徑及激發(fā)次數(shù)等基本參數(shù)對(duì)激光誘導(dǎo)等離子體的影響進(jìn)行了優(yōu)化實(shí)驗(yàn)。實(shí)驗(yàn)表明,該聯(lián)用技術(shù)可用于工業(yè)樣品微米區(qū)域內(nèi)的主量及痕量元素分布圖象快速分析,也可用于元素同位素比值分析;在不久的將來(lái),LAS-ICP-MS將成為研究LIBS過(guò)程基本參數(shù)機(jī)理的理想診斷工具:可通過(guò)實(shí)驗(yàn)ICP-MS中激光燒蝕產(chǎn)生粒子的響應(yīng)與相應(yīng)的激光燒蝕過(guò)程中發(fā)射光譜信號(hào)來(lái)研究激光燒蝕過(guò)程中的分餾效應(yīng);也可用于不同激光誘導(dǎo)等離子體隨時(shí)間、空間發(fā)展變化及燒蝕產(chǎn)生粒子間的相互作用研究。

LAS與 ICP-MS聯(lián)用技術(shù)實(shí)際上是LAS與LA-ICP-MS技術(shù)的復(fù)合,隨著新儀器的開(kāi)發(fā)、基礎(chǔ)理論的深化及各種技術(shù)的改進(jìn),極大推動(dòng)了LAS與LA-ICP-MS技術(shù)的應(yīng)用發(fā)展。對(duì)于LAS技術(shù)的應(yīng)用進(jìn)展,馬藝聞等[24]作了詳細(xì)的報(bào)道。近年來(lái),有關(guān)LA-ICP-MS技術(shù)的應(yīng)用報(bào)道,主要集中在地質(zhì)、礦冶、材料分析、環(huán)境污染監(jiān)測(cè)、生物、醫(yī)藥等領(lǐng)域,對(duì)此作了分類綜述,更早的評(píng)述資料可參考文獻(xiàn)[20,25-28]。

2 LA-ICP-MS的應(yīng)用領(lǐng)域

2.1 地質(zhì)、礦冶分析

LA技術(shù)高空間分辨(μm)進(jìn)樣與ICP-MS高靈敏度的痕量元素分析技術(shù)結(jié)合,使LA-ICP-MS具有快速、實(shí)時(shí)、多元素同時(shí)測(cè)量的特點(diǎn),廣泛應(yīng)用于地質(zhì)、礦冶分析領(lǐng)域。如在地球科學(xué)領(lǐng)域,LA-ICPMS已被廣泛用于地質(zhì)樣品整體分析,礦物微區(qū)分析,單顆粒鋯石U/Pb,Pb/Pb地質(zhì)定年研究及單個(gè)流體包裹體成分等研究。巖石礦物尤其是沒(méi)有基體匹配標(biāo)準(zhǔn)物質(zhì)的巖石礦物中痕量、超痕量元素分析研究報(bào)道[29]很多。LA-ICP-MS用于地球年代學(xué)分析(鋯石中U/Th/Pb系列)[30-38],分析結(jié)果與二次離子探針質(zhì)譜(SHRIMP)、熱電離質(zhì)譜(TIMS)具有較好的一致性;雖然LA-ICP-MS分析精度沒(méi)有前兩者高,但LA-ICP-MS在分析大通量樣品中優(yōu)勢(shì)顯著。Zhaoshan Chang等[39]采用 Thermo Finnigan Element2雙聚焦 ICP-MS與 New Wave Research UP-213組成的LA-ICP-MS系統(tǒng),測(cè)量5個(gè)已知年齡(約1800～50 Ma)的鋯石標(biāo)本年齡,來(lái)檢驗(yàn)該技術(shù)的重現(xiàn)性、精密度與準(zhǔn)確度。燒蝕坑直徑為30～40μm,校正激光誘導(dǎo)隨時(shí)間的分餾、靜態(tài)分餾的影響,評(píng)估單次測(cè)量結(jié)果,精密度和準(zhǔn)確度優(yōu)于4%(2σ),標(biāo)準(zhǔn)的測(cè)量不確定度是總不確定度的最大來(lái)源,與TIMS測(cè)定的年齡相比較,準(zhǔn)確度偏差大約為1%。LA-ICP-MS應(yīng)用于流體包裹體成分分析,對(duì)研究流體及巖石物理化學(xué)機(jī)制、礦物形成過(guò)程研究具有重要意義。MURRA Y M.ALLAN[40]等采用193 nm的A rF準(zhǔn)分子激光器和四極桿ICP-MS (裝配有八極桿碰撞池以去除A r基干擾)對(duì)人工模擬的多元素包裹體進(jìn)行分析,Na是內(nèi)標(biāo)。K,Rb,和Cs的RSD≤15%;Li,Mg,Ca,Sr,Ba,Mn,Fe,Cu, Zn和 Cl的 RSD≤30%;大部分元素的 RSD≤15%;檢測(cè)限隨包裹體容量變化,但對(duì)于大多數(shù)元素來(lái)說(shuō)為1～100μg/g;這些分析結(jié)果與以前的研究數(shù)據(jù)吻合;并證明,在分析區(qū)域外,包裹體的大小和深度對(duì)分析結(jié)果的精密度和準(zhǔn)確度影響不大。TORSTENGRAUPNER[41]等采用商用 Merchantek 266 nm Nd:YAG LA-ICP-MS系統(tǒng)對(duì)德國(guó)Zinnwald的Sn礦床中石英流體包裹體進(jìn)行微區(qū)分析,15種元素(Li,Na,K,Mg,Fe,A s,Rb,Sr,Sn, Ba,Mo,U,W,Mn,Pb)測(cè)量值與其它文獻(xiàn)相同分析點(diǎn)的參考值一致。首次分析數(shù)據(jù)評(píng)估表明,含Sn流體中,高溫包裹體(Th:400～370℃)含有高含量的Fe、Na,Sn。高溫流體包裹體到低溫二次包裹體鹽分的降低很可能反映了巖漿流體被外部流體稀釋的趨勢(shì)。

ALANE.KOENIG[42]對(duì)LA-ICP-MS技術(shù)在美國(guó)地質(zhì)調(diào)查礦床研究中的應(yīng)用作了介紹:研究對(duì)象包括地化參考物、地質(zhì)相關(guān)參考物和大量沉積參考物,取得滿意結(jié)果。稀土元素(REE)的化學(xué)屬性使它很適合地質(zhì)中對(duì)巖石歷史的研究,Helene Bratz[43]采用LA-ICP-MS分析了三種REE參考物質(zhì),分析結(jié)果相對(duì)標(biāo)準(zhǔn)偏差2%～14%(主量元素3%～8%),并與X-射線熒光光譜(XRF)和文獻(xiàn)參考值相比較,主量元素及一些痕量元素具有很好的一致性;與其它常規(guī)稀土分析方法相比,LA-ICPMS技術(shù)避免了樣品溶解、分離的耗時(shí),節(jié)約了分析成本。張彥輝等[44]利用LA-ICP-MS法快速測(cè)定地質(zhì)樣品中鈮鉭鋯鉿等難溶元素,取得滿意結(jié)果。近來(lái),沉積物中痕量元素指紋識(shí)別,包括磁鐵礦[45]、黃鐵礦[46]、瀝青[47]和石英[48]等,快速甄別礦物相關(guān)物質(zhì),巖石礦物痕量元素成像,以及標(biāo)準(zhǔn)物質(zhì)研究得到了廣泛關(guān)注。

2.2 材料分析

由于LA-ICP-MS技術(shù)測(cè)試對(duì)象幾乎涵蓋所有元素,因而廣泛應(yīng)用于固體、液體和氣體等各種材料的成分分析,尤其是低含量、難溶材料或其他原料、陶瓷以及高端光學(xué)器件的末端產(chǎn)品分析方面[49-51]。與其他材料分析方法(AAS,ICP-OES,ICP-MS)相比,LA-ICP-MS不需要繁瑣的樣品處理,減少了過(guò)程污染與有害試劑使用,提高了分析效率。而且LA-ICP-MS技術(shù)憑借其快速、多元素同時(shí)測(cè)量,分析結(jié)果在可接受水平等特點(diǎn),在研究不同類型樣品微區(qū)元素分布方面得到了越來(lái)越多的應(yīng)用,可以與XRF或二次離子質(zhì)譜(SIMS)等專用儀器相媲美。潘煒娟[52]建立了LA-ICP-MS法測(cè)定塑料中鉛、鎘、鉻、汞等有毒有害元素的方法,以聚丙烯標(biāo)準(zhǔn)物質(zhì)及其空白片作校準(zhǔn)曲線,直接分析了各種實(shí)際塑料樣品。該法樣品處理簡(jiǎn)單、操作方便快速、結(jié)果可靠,滿足日常檢測(cè)要求。考察了單點(diǎn)和線掃描兩種激光剝蝕方式的行為。以方法的靈敏度和穩(wěn)定性為原則,逐級(jí)優(yōu)化了激光剝蝕過(guò)程中激光功率、脈沖頻率、剝蝕孔徑、掃描速率、散焦距離以及ICP-MS中的RF功率、采樣深度和載氣流量等工作參數(shù)。方法測(cè)定結(jié)果與等離子體發(fā)射光譜(ICP-A ES)法測(cè)定值基本吻合,Pb、Cd、Cr、Hg的檢出限分別為0.002、0.001、0.08、1.5 mg/kg。

2.3 環(huán)境監(jiān)測(cè)

隨著工業(yè)、城市污染的加劇和農(nóng)用化學(xué)物質(zhì)的過(guò)度使用,環(huán)境污染特別是重金屬污染問(wèn)題得到了廣泛關(guān)注。LA-ICP-MS技術(shù)以其制樣簡(jiǎn)單、破壞性小、多元素同時(shí)快速分析的特點(diǎn),廣泛應(yīng)用于土壤、水及空氣等環(huán)境污染方面的監(jiān)測(cè)。美國(guó)地質(zhì)調(diào)查中[53],采用LA-ICP-MS對(duì)于礦井排水區(qū)的樹(shù)木年輪進(jìn)行分析。假設(shè)可被樹(shù)木木質(zhì)部吸附的元素在特定年限內(nèi)被吸附固定,通過(guò)測(cè)定不同年輪內(nèi)元素的含量,可以判斷元素被固定的時(shí)間以及判斷廢棄礦區(qū)對(duì)周圍環(huán)境元素水平的影響。Luis A rroyo等[54]采用LA-ICP-MS快速測(cè)定土壤和沉積物中的元素,并與常見(jiàn)酸消解方法試驗(yàn)結(jié)果進(jìn)行比較。分析結(jié)果表明,LA-ICP-MS與ICP-OES,ICP-MS的分析結(jié)果在95%置信區(qū)間內(nèi)保持一致;對(duì)采自南弗羅里達(dá)大學(xué)的48個(gè)沉積物樣品進(jìn)行LA-ICP-MS篩選分析,以此來(lái)評(píng)估LA-ICP-MS技術(shù)在環(huán)境診斷分析中的應(yīng)用。使用A l結(jié)合非參數(shù)相關(guān)測(cè)試以及主成份分析手段,比較LA-ICP-MS與常規(guī)部分溶解ICP-MS方法的結(jié)果,標(biāo)準(zhǔn)物質(zhì)全流程RSD為8%～15%,樣品＜10%。H.Sela等[55]采用雙聚焦-ICP-MS測(cè)定了單根頭發(fā)中基本元素Zn、Fe、Cu及有毒元素Cr,Pb和U,并將結(jié)果與四極桿 ICPMS消解溶樣相比較,數(shù)據(jù)吻合;比較了LA-ICPMS(附加超聲霧化)外標(biāo)法、內(nèi)標(biāo)加入法和同位素稀釋法對(duì)某人生活環(huán)境改變前后頭發(fā)中鈾元素的分析結(jié)果,單根頭發(fā)中的鈾含量隨著飲用水中鈾含量2000～30 ng/L的降低而降低,由212 ng/g降至18 ng/g。LA-ICP-MS在環(huán)境監(jiān)測(cè)分析中表現(xiàn)出良好的應(yīng)用潛力。

2.4 生物醫(yī)學(xué)分析

在生命科學(xué)中,金屬(必需的、有益的、有害的)、非金屬以及生物組織中的非金屬的分布與生命體健康密切相關(guān)。過(guò)去幾年中,LA-ICP-MS作為一種強(qiáng)有力的元素分析技術(shù),迅速應(yīng)用于生物醫(yī)學(xué)分析領(lǐng)域。其中,LA-ICP-MS成像技術(shù)應(yīng)用廣泛,J.Sabine Becker等[56]對(duì)LA-ICP-MS生物成像技術(shù)的發(fā)展、應(yīng)用做了詳細(xì)報(bào)道。LA-ICP-MS可以快速提供腦部組織薄切片微區(qū)范圍內(nèi)的某種元素的分布信息(Feldmann,Kindness,&Ek,2002;Ghazi et al., 2002;Kindness,Sekaran,&Feldmann,2003;Becker et al.,2005b,2007b,2008d;Hutchinson et al., 2005;Zoriy et al.,2008a;Austin et al.,2009),檢測(cè)限低于μg/g,為進(jìn)一步了解許多腦部疾病的發(fā)生、發(fā)展提供了分析手段。LA-ICP-MS對(duì)生物切片中必需和有毒元素成像分析,可以對(duì)元素的分布、遷移過(guò)程、生物藥效率以及可能的污染進(jìn)行研究。在生態(tài)病理學(xué)研究中,最小取樣分析技術(shù)是保證實(shí)驗(yàn)動(dòng)物暴露污染可持續(xù)評(píng)測(cè)的首要條件,LA-ICP-MS技術(shù)在該領(lǐng)域顯示出優(yōu)越性。Jackson等[57]采用LA-ICP-MS分析水蛇尾部切片,這些水蛇被喂食含有低、中、高含量的A s、Se和 Sr元素的魚(yú)達(dá)2 a。該分析結(jié)果與將剩余的水蛇尾部薄片酸消解、均一化處理后用ICP-MS分析的結(jié)果相比,具有一致性。J.Kaiser[58]等對(duì)向日葵葉子平方厘米區(qū)域中的Pb、Mg、Cu的富集做了LIBS、LA-ICP-MS成像技術(shù)研究,空間分辨率為200μm,分析結(jié)果與原子吸收光譜(AAS)、薄層色譜(TLC)相比具有一致性,適用于大量樣品中多元素的快速分析。

2.5 其它

LA-ICP-MS也被用于工業(yè)控制、寶石鑒定[59]、法庭鑒定[60-61]等領(lǐng)域。Stefan Becker[62]等對(duì)于LA-ICP-MS技術(shù)應(yīng)用于法醫(yī)領(lǐng)域玻璃碎片分析進(jìn)行了介紹,總結(jié)該技術(shù)在法醫(yī)領(lǐng)域中應(yīng)用的優(yōu)勢(shì)并對(duì)某種新的玻璃標(biāo)準(zhǔn)物質(zhì)進(jìn)行分析,幾乎所有元素的RSD＜10%,證明了LA-ICP-MS技術(shù)在法庭玻璃碎片或其它領(lǐng)域中優(yōu)越的快速分析能力。

3 結(jié)語(yǔ)

激光燒蝕技術(shù)作為一種適用于多種類型樣品的引入方法,與干擾少、靈敏度高的ICP-MS聯(lián)用[63],開(kāi)拓了質(zhì)譜分析技術(shù)的新領(lǐng)域。固體進(jìn)樣減少了繁瑣的樣品制備過(guò)程,不僅省時(shí)且減少了污染的可能,并避免了溶液制備中的稀釋效應(yīng),對(duì)降低檢出限有利,而引入等離子體的干氣溶膠使得質(zhì)譜干擾較濕法更少。將LAS與ICP-MS分析技術(shù)相結(jié)合構(gòu)成LAS-ICP-MS,可充分發(fā)揮兩種技術(shù)的優(yōu)勢(shì),形成實(shí)用的互補(bǔ)測(cè)試技術(shù)。隨著儀器結(jié)構(gòu)性能的改善、對(duì)燒蝕過(guò)程及分餾效應(yīng)機(jī)理的深入了解和各種校正方法的研究應(yīng)用,LAS-ICP-MS作為一種高靈敏度、高精度的元素分析技術(shù),以及能夠提供多維的、高分辨信息的原位微區(qū)分析技術(shù),將在痕量元素定量分析及空間分布分析中占據(jù)重要的地位。

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Review on Application of Laser Ablation Spectroscopy(LAS) Coupled with Inductively Coupled Plasma Mass Spectrometry(ICP-MS)

TANJing,GUO Dongfa,ZHANG Yanhui
(Analytical Laboratory,Beijing Research Institute of Uranium Geology,Beijing100029,China)

Laser ablation spectroscopy(LAS)is an elemental analysismethod that requires in p rincip le only op tical access to sample surface and can therefore be used as a real in-situ method.The advantages of LAS include fast speed of analysis,ease o r absence of samp le p reparation,relatively low cost,and possibility to build portable instruments for real field analysis.However,itsmajor restriction is poorer detection capabilities for trace elements compared to inductively coup led p lasma mass spectrometry(ICP-MS).ICP-MS is a pow erful tool for m ulti-element and iso topic analysis with high sensitivity and low detection lim it.But it is difficult to analyze elements of thematrix using ICP-MS.Com bination of LASwith ICP-MS can overcome the weaknesses of each technique.This paper gives a review on the app lication and developmental trend of LAS-ICP-MSespecially in the fields such as geology,mining and metallurgy,material analysis,environment monitoring and biomedicine in last ten years.

LAS(LIBS);LA-ICP-MS;app lication

郭冬發(fā),男,研究員級(jí)高級(jí)工程師,博士生導(dǎo)師,從事核地質(zhì)分析測(cè)試技術(shù)研究。E-mail:guodongfa@263.net

O657.63;TH843

A

2095-1035(2011)03-0016-07

10.3969/j.issn.2095-1035.2011.03.0003

2011-07-05

2011-07-27

中國(guó)核工業(yè)地質(zhì)局資助項(xiàng)目(HD200801)

譚靖,女,博士研究生,從事激光光譜與質(zhì)譜技術(shù)研究。E-mail:jing.t@live.com