Determination of Inorganic and Total Mercury in Biological Tissuesby Electrothermal Vaporization Inductively Coupled Plasma MassSpectrometry
Identifieur interne : 000F90 ( Istex/Corpus ); précédent : 000F89; suivant : 000F91Determination of Inorganic and Total Mercury in Biological Tissuesby Electrothermal Vaporization Inductively Coupled Plasma MassSpectrometry
Auteurs : Scott N. Willie ; D. Conrad Grégoire ; Ralph E. SturgeonSource :
- Analyst [ 0003-2654 ] ; 1997.
Abstract
A rapid method for the determination of total and inorganic mercury inbiological tissues is presented using electrothermal vaporizationinductively coupled plasma mass spectrometry (ETV ICP–MS). Sampleswere solubilized using tetramethylammonium hydroxide. For thedetermination of total mercury sample aliquots (10 µl) are dried andvaporized into the plasma. For the determination of inorganic mercury,iodoacetic acid, sodium thiosulfate and acetic acid are added to thesample, cleaving the methylmercury from the tissue. Volatile methylmercuryiodide is formed and removed from the ETV as the sample dries, leavingonly inorganic mercury to be quantified. A limit of detection of 0.05µg g-1 in solid samples was obtained. NationalResearch Council of Canada reference materials DORM-2 (dogfish muscle),DOLT-2 (dogfish liver) and TORT-2 (lobster hepatopancreas) were used toassess the accuracy of the method.
Url:
DOI: 10.1039/a701169e
Links to Exploration step
ISTEX:C55EA6472DB0549A789E8C8D7B5F588CBF6E089DLe document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title>Determination of Inorganic and Total Mercury in Biological Tissuesby Electrothermal Vaporization Inductively Coupled Plasma MassSpectrometry</title><author wicri:is="90%"><name sortKey="N Willie, Scott" sort="N Willie, Scott" uniqKey="N Willie S" first="Scott" last="N. Willie">Scott N. Willie</name></author><author wicri:is="90%"><name sortKey="Conrad Gregoire, D" sort="Conrad Gregoire, D" uniqKey="Conrad Gregoire D" first="D." last="Conrad Grégoire">D. Conrad Grégoire</name></author><author wicri:is="90%"><name sortKey="E Sturgeon, Ralph" sort="E Sturgeon, Ralph" uniqKey="E Sturgeon R" first="Ralph" last="E. Sturgeon">Ralph E. Sturgeon</name></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:C55EA6472DB0549A789E8C8D7B5F588CBF6E089D</idno><date when="1997" year="1997">1997</date><idno type="doi">10.1039/a701169e</idno><idno type="url">https://api-v5.istex.fr/document/C55EA6472DB0549A789E8C8D7B5F588CBF6E089D/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">000F90</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Corpus" wicri:corpus="ISTEX">000F90</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">Determination of Inorganic and Total Mercury in Biological Tissuesby Electrothermal Vaporization Inductively Coupled Plasma MassSpectrometry</title><author wicri:is="90%"><name sortKey="N Willie, Scott" sort="N Willie, Scott" uniqKey="N Willie S" first="Scott" last="N. Willie">Scott N. Willie</name></author><author wicri:is="90%"><name sortKey="Conrad Gregoire, D" sort="Conrad Gregoire, D" uniqKey="Conrad Gregoire D" first="D." last="Conrad Grégoire">D. Conrad Grégoire</name></author><author wicri:is="90%"><name sortKey="E Sturgeon, Ralph" sort="E Sturgeon, Ralph" uniqKey="E Sturgeon R" first="Ralph" last="E. Sturgeon">Ralph E. Sturgeon</name></author></analytic><monogr></monogr><series><title level="j">Analyst</title><title level="j" type="abbrev">Analyst</title><idno type="ISSN">0003-2654</idno><idno type="eISSN">1364-5528</idno><imprint><publisher>The Royal Society of Chemistry.</publisher><date type="published" when="1997">1997</date><biblScope unit="volume">122</biblScope><biblScope unit="issue">8</biblScope><biblScope unit="page" from="751">751</biblScope><biblScope unit="page" to="754">754</biblScope></imprint><idno type="ISSN">0003-2654</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0003-2654</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract">A rapid method for the determination of total and inorganic mercury inbiological tissues is presented using electrothermal vaporizationinductively coupled plasma mass spectrometry (ETV ICP–MS). Sampleswere solubilized using tetramethylammonium hydroxide. For thedetermination of total mercury sample aliquots (10 µl) are dried andvaporized into the plasma. For the determination of inorganic mercury,iodoacetic acid, sodium thiosulfate and acetic acid are added to thesample, cleaving the methylmercury from the tissue. Volatile methylmercuryiodide is formed and removed from the ETV as the sample dries, leavingonly inorganic mercury to be quantified. A limit of detection of 0.05µg g-1 in solid samples was obtained. NationalResearch Council of Canada reference materials DORM-2 (dogfish muscle),DOLT-2 (dogfish liver) and TORT-2 (lobster hepatopancreas) were used toassess the accuracy of the method.</div></front></TEI><istex><corpusName>rsc-journals</corpusName><author><json:item><name>Scott N. Willie</name></json:item><json:item><name>D. Conrad Grégoire</name></json:item><json:item><name>Ralph E. Sturgeon</name></json:item></author><language><json:string>eng</json:string></language><originalGenre><json:string>ART</json:string></originalGenre><abstract>A rapid method for the determination of total and inorganic mercury inbiological tissues is presented using electrothermal vaporizationinductively coupled plasma mass spectrometry (ETV ICP–MS). Sampleswere solubilized using tetramethylammonium hydroxide. For thedetermination of total mercury sample aliquots (10 µl) are dried andvaporized into the plasma. For the determination of inorganic mercury,iodoacetic acid, sodium thiosulfate and acetic acid are added to thesample, cleaving the methylmercury from the tissue. Volatile methylmercuryiodide is formed and removed from the ETV as the sample dries, leavingonly inorganic mercury to be quantified. A limit of detection of 0.05µg g-1 in solid samples was obtained. NationalResearch Council of Canada reference materials DORM-2 (dogfish muscle),DOLT-2 (dogfish liver) and TORT-2 (lobster hepatopancreas) were used toassess the accuracy of the method.</abstract><qualityIndicators><score>6.052</score><pdfWordCount>2612</pdfWordCount><pdfCharCount>15829</pdfCharCount><pdfVersion>1.2</pdfVersion><pdfPageCount>4</pdfPageCount><pdfPageSize>590 x 842 pts</pdfPageSize><refBibsNative>true</refBibsNative><abstractWordCount>120</abstractWordCount><abstractCharCount>903</abstractCharCount><keywordCount>0</keywordCount></qualityIndicators><title>Determination of Inorganic and Total Mercury in Biological Tissuesby Electrothermal Vaporization Inductively Coupled Plasma MassSpectrometry</title><genre><json:string>article</json:string></genre><host><title>Analyst</title><language><json:string>unknown</json:string></language><publicationDate>1997</publicationDate><issn><json:string>0003-2654</json:string></issn><eissn><json:string>1364-5528</json:string></eissn><volume>122</volume><issue>8</issue><pages><first>751</first><last>754</last></pages><genre><json:string>journal</json:string></genre></host><categories><wos><json:string>science</json:string><json:string>chemistry, analytical</json:string></wos><scienceMetrix><json:string>natural sciences</json:string><json:string>chemistry</json:string><json:string>analytical chemistry</json:string></scienceMetrix><inist><json:string>sciences appliquees, technologies et medecines</json:string><json:string>sciences biologiques et medicales</json:string><json:string>sciences biologiques fondamentales et appliquees. psychologie</json:string><json:string>biochimie analytique, structurale et metabolique</json:string></inist></categories><publicationDate>1997</publicationDate><copyrightDate>1997</copyrightDate><doi><json:string>10.1039/a701169e</json:string></doi><id>C55EA6472DB0549A789E8C8D7B5F588CBF6E089D</id><fulltext><json:item><extension>pdf</extension><original>true</original><mimetype>application/pdf</mimetype><uri>https://api-v5.istex.fr/document/C55EA6472DB0549A789E8C8D7B5F588CBF6E089D/fulltext/pdf</uri></json:item><json:item><extension>zip</extension><original>false</original><mimetype>application/zip</mimetype><uri>https://api-v5.istex.fr/document/C55EA6472DB0549A789E8C8D7B5F588CBF6E089D/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api-v5.istex.fr/document/C55EA6472DB0549A789E8C8D7B5F588CBF6E089D/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a">Determination of Inorganic and Total Mercury in Biological Tissuesby Electrothermal Vaporization Inductively Coupled Plasma MassSpectrometry</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>The Royal Society of Chemistry.</publisher><availability><p>This journal is © The Royal Society of Chemistry</p></availability><date>1997</date></publicationStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a">Determination of Inorganic and Total Mercury in Biological Tissuesby Electrothermal Vaporization Inductively Coupled Plasma MassSpectrometry</title><author xml:id="author-0000"><persName><forename type="first">Scott</forename><surname>N. Willie</surname></persName></author><author xml:id="author-0001"><persName><forename type="first">D.</forename><surname>Conrad Grégoire</surname></persName></author><author xml:id="author-0002"><persName><forename type="first">Ralph</forename><surname>E. Sturgeon</surname></persName></author><idno type="istex">C55EA6472DB0549A789E8C8D7B5F588CBF6E089D</idno><idno type="DOI">10.1039/a701169e</idno><idno type="ms-id">a701169e</idno></analytic><monogr><title level="j">Analyst</title><title level="j" type="abbrev">Analyst</title><idno type="pISSN">0003-2654</idno><idno type="eISSN">1364-5528</idno><idno type="coden">ANALAO</idno><idno type="RSC-sercode">AN</idno><imprint><publisher>The Royal Society of Chemistry.</publisher><date type="published" when="1997"></date><biblScope unit="volume">122</biblScope><biblScope unit="issue">8</biblScope><biblScope unit="page" from="751">751</biblScope><biblScope unit="page" to="754">754</biblScope></imprint></monogr></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>1997</date></creation><langUsage><language ident="en">en</language></langUsage><abstract><p>A rapid method for the determination of total and inorganic mercury inbiological tissues is presented using electrothermal vaporizationinductively coupled plasma mass spectrometry (ETV ICP–MS). Sampleswere solubilized using tetramethylammonium hydroxide. For thedetermination of total mercury sample aliquots (10 µl) are dried andvaporized into the plasma. For the determination of inorganic mercury,iodoacetic acid, sodium thiosulfate and acetic acid are added to thesample, cleaving the methylmercury from the tissue. Volatile methylmercuryiodide is formed and removed from the ETV as the sample dries, leavingonly inorganic mercury to be quantified. A limit of detection of 0.05µg g-1 in solid samples was obtained. NationalResearch Council of Canada reference materials DORM-2 (dogfish muscle),DOLT-2 (dogfish liver) and TORT-2 (lobster hepatopancreas) were used toassess the accuracy of the method.</p></abstract></profileDesc><revisionDesc><change when="1997">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><extension>txt</extension><original>false</original><mimetype>text/plain</mimetype><uri>https://api-v5.istex.fr/document/C55EA6472DB0549A789E8C8D7B5F588CBF6E089D/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="corpus rsc-journals not found" wicri:toSee="no header"><istex:xmlDeclaration>version="1.0" encoding="UTF-8"</istex:xmlDeclaration><istex:document><article type="ART" xsi:schemaLocation="http://www.rsc.org/schema/rscart38 http://www.rsc.org/schema/rscart38/rscart38.xsd" dtd="RSCART3.8"><metainfo><articletype code="ART" pubmedForm="research-article" headingForm="Papers" group="Paper" fullForm="Paper"></articletype></metainfo><art-admin><ms-id>a701169e</ms-id><doi>10.1039/a701169e</doi></art-admin><published type="print"><journalref><link>AN</link></journalref><volumeref><link>122</link></volumeref><issueref><link>8</link></issueref><pubfront><fpage>751</fpage><lpage>754</lpage><no-of-pages></no-of-pages><date><year>1997</year><month></month><day></day></date></pubfront></published><published type="subsyear"><journalref><title type="abbreviated">Analyst</title><title type="full">Analyst</title><title type="journal">Analyst</title><title type="display">Analyst</title><title type="pubmed">Analyst</title><sercode>AN</sercode><publisher><orgname><nameelt>The Royal Society of Chemistry</nameelt></orgname></publisher><issn type="print">0003-2654</issn><issn type="online">1364-5528</issn><coden>ANALAO</coden><cpyrt>This journal is © The Royal Society of Chemistry</cpyrt></journalref><volumeref><link>122</link></volumeref><issueref><link>8</link></issueref><pubfront><fpage>751</fpage><lpage>754</lpage><no-of-pages></no-of-pages><date><year>1997</year><month></month><day></day></date></pubfront></published><art-front><titlegrp><title>Determination of Inorganic and Total Mercury in Biological Tissues by Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry</title></titlegrp><authgrp><author><person><persname><fname>Scott</fname><surname>N. Willie</surname></persname></person></author><author><person><persname><fname>D.</fname><surname>Conrad Grégoire</surname></persname></person></author><author><person><persname><fname>Ralph</fname><surname>E. Sturgeon</surname></persname></person></author></authgrp><abstract> A rapid method for the determination of total and inorganic mercury in biological tissues is presented using electrothermal vaporization inductively coupled plasma mass spectrometry (ETV ICP–MS). Samples were solubilized using tetramethylammonium hydroxide. For the determination of total mercury sample aliquots (10 µl) are dried and vaporized into the plasma. For the determination of inorganic mercury, iodoacetic acid, sodium thiosulfate and acetic acid are added to the sample, cleaving the methylmercury from the tissue. Volatile methylmercury iodide is formed and removed from the ETV as the sample dries, leaving only inorganic mercury to be quantified. A limit of detection of 0.05 µg g<sup>-1</sup> in solid samples was obtained. National Research Council of Canada reference materials DORM-2 (dogfish muscle), DOLT-2 (dogfish liver) and TORT-2 (lobster hepatopancreas) were used to assess the accuracy of the method. </abstract></art-front><art-body><section type="PDFExtract"><title></title><p> Determination of Inorganic and Total Mercury in Biological Tissues by Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry Scott N. Willie*a, D. Conrad Gr´egoireb and Ralph E. Sturgeona a Institute for National Measurement Standards, National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R9 b Geological Survey of Canada, 601 Booth Street, Ottawa, Ontario, Canada K1A 0E8 A rapid method for the determination of total and inorganic mercury in biological tissues is presented using electrothermal vaporization inductively coupled plasma mass spectrometry (ETV ICP–MS). </p><p>Samples were solubilized using tetramethylammonium hydroxide. For the determination of total mercury sample aliquots (10 ml) are dried and vaporized into the plasma. For the determination of inorganic mercury, iodoacetic acid, sodium thiosulfate and acetic acid are added to the sample, cleaving the methylmercury from the tissue. Volatile methylmercury iodide is formed and removed from the ETV as the sample dries, leaving only inorganic mercury to be quantified. </p><p>A limit of detection of 0.05 mg g21 in solid samples was obtained. National Research Council of Canada reference materials DORM-2 (dogfish muscle), DOLT-2 (dogfish liver) and TORT-2 (lobster hepatopancreas) were used to assess the accuracy of the method. Keywords: Mercury; inorganic mercury; biological tissues; electrothermal vaporization inductively coupled plasma mass spectrometry; tetramethylammonium hydroxide solubilization Mercury is a ubiquitous element in the environment resulting from both anthropogenic and natural geological activities. </p><p>In the marine environment the distribution and speciation of Hg is of considerable interest as biomethylation1 and subsequently bioconcentration in the food chain2 can occur. As a result, mercury is predominantly present in marine biological samples as methylmercury. It is well known that organomercury compounds are more toxic than metallic or aquo Hg forms; consequently, considerable effort and progress have been made in the development of techniques capable of separating and identifying the various mercury species.3 Common methods for the determination of total mercury require sample digestion followed by chemical reduction and subsequent gas phase transfer of the element to a detector. </p><p>Approaches for speciation analysis involve milder sample preparation procedures to preserve the integrity of any organic mercury.4 Frequently, these are variations of the classical West¨o¨o5 procedure involving solvent extraction, cleanup of the extract, isolation of the organomercurial as the corresponding halide derivative and detection by gas chromatography with electron capture detection (GC–ECD)6 or atomic emission detection (GC–AED).7 Methods using liquid chromatography (LC) also require sample extraction and cleanup steps.8,9 Alternatively, procedures utilizing derivatisation of organomercury via ethylating10 or butylating11 agents followed by isolation and detection have been reported. </p><p></p><p>Generally, these procedures require less sample cleanup than GC or LC methods but separation via a chromatographic column or cryogenic trapping is necessary. Another method that does not require extensive sample extraction and cleanup utilizes headspace sampling. A cleaving agent is used to liberate the methylmercury from the biological tissue, whereupon it is subsequently converted to volatile methylmercury iodide, sampled, desorbed onto a column and detected using GC–MIP (microwave induced plasma).12,13 The determination of Hg by thermal vaporization from solid samples is an attractive approach that requires minimal sample preparation.14 This technique has been applied to environmental samples15 and rocks and sediments16 using quartz tube AAS detection. </p><p>As well as total Hg, direct methods for the speciation of mercury in soils and sediments17 and biologicals18 have been reported. </p><p>ETV ICP-MS is well-suited for application to thermal vaporization methodology as the temperature of the graphite tube can be accurately controlled, small samples can be easily injected and the sampling frequency is relatively high. In addition, the tolerance of ICP-MS to the solvent and matrix components in the sample is superior to the less powerful microwave He plasma system.19 The determination of total and inorganic mercury in biological tissues is reported here. </p><p>Extraction or acid digestion of the samples is replaced by room temperature treatment of the tissue with tetramethylammonium hydroxide (TMAH). TMAH, an alkali tissue solublizer, has been utilized for the speciation analysis of tin and mercury and also for total element analysis using flame,20 graphite furance21,22 and ICP-AES.23 Additionally, a method to determine the inorganic Hg content of the tissues has been developed by capitalizing on the volatility of methylmercury halide derivatives. </p><p>Iodoacetic acid (IOAc) is added to the alkaline digest and the methylmercury iodide (MeHgI) is distilled from the sample as the graphite tube is gently heated. The inorganic mercury remaining in the graphite tube after heating to 120 °C is then quantified. Experimental Instrument A Perkin-Elmer SCIEX ELAN 5000 ICP mass spectrometer equipped with a HGA-600MS electrothermal vaporizer (ETV) and Model AS-60 autosampler was used. </p><p>The experimental conditions for the mass spectrometer are given in Table 1. The Table 1 Instrumental operating conditions and data acquisition parameters ICP mass spectrometer— Rf power 1050 W Outer argon flow rate 15.0 l min21 Intermediate argon flow rate 850 ml min21 Carrier argon flow rate 900 ml min21 Sampler-skimmer Nickel Data acquistion— Dwell time 30 ms Scan mode Peak hopping Signal measurement mode Integrated response Analyst, August 1997, Vol. 122 (751–754) 751 HGA-600 MS has been described previously24 and was interfaced to the plasma via a 0.8 m length of 6 mm id poly(tetrafluoroethylene) tubing. </p><p>The 202Hg isotope was monitored. The ETV program is outlined in Table 2. An initial high temperature step cleans the furnace. Following furnace cooling in step 2, the sample is injected. The sample is dried in step 3 and the moisture and vapours are vented through the dosing hole. In step 4 a graphite probe is pneumatically activated to seal the dosing hole and the carrier gas is directed from one end of the ETV workhead to the argon plasma at a flow rate of 900 ml min21 prior to heating the graphite tube to 800 °C. </p><p>The graphite tube is not cleaned at high temperature immediately after the analytical signal has been obtained, rather cleaning occurs when the next analysis cycle is initiated. This prevents the residue remaining after the 800 °C pyrolysis from entering the plasma and transfer line. </p><p>Reagents TMAH (30% in methanol, Aldrich, Milwaukee, WI, USA) was used to solubilize the samples. A 37 mg ml21 iodoacetic acid solution (IOAc, Aldrich) was prepared in water. A 25 mg ml21 sodium thiosulfate (Na2S2O3) solution was prepared by dissolution of the salt in high purity water. Reagent grade acetic acid (HOAc; Environmental Grade, Anachemia, Montreal, QC, Canada) was used. High purity water was produced by passage through a commercial reverse osmosis unit followed by a mixed bed ion-exchange system (Barnstead Nanopure, Barnstead, Dubuque, IA, USA). </p><p>Mercury solutions were prepared by dissolution of HgCl2 (gold star, Alfa Chemicals, Ward Hill, MA, USA) in dilute nitric acid. A methylmercury standard was prepared by dissolving MeHgCl (Alpha Division, Danvers, MA, USA) in an appropriate amount of propan-2-ol. Working solutions were prepared daily by serial dilution with high purity water. National Research Council of Canada (NRCC) reference materials DORM-2 (dogfish muscle), DOLT-2 (dogfish liver) and TORT-2 (lobster hepatopancreas) were used to assess the accuracy of the method. </p><p>Sample preparation A 0.250 g sample was weighed into a beaker and 4 ml of TMAH was added. Following the reaction of the tissue with the TMAH for approximately 5 min, the solution was transferred to a 25 ml calibrated flask and diluted to volume with high purity water. Samples of DORM-2 were diluted ten fold prior to analysis. Total mercury A portion (10 ml) of the above sample was injected into the HGA furnace and the program listed in Table 2 was initiated. </p><p>Quantification was accomplished by the method of standard additions using either standards of methyl or inorganic mercury. Inorganic mercury A 250 ml aliquot of the sample was pipetted into a sample cup along with 125 ml of the IOAc solution and 125 ml of Na2S2O3 solution. The mixture was acidified by addition of 20 ml of HOAc. The mixture (10 ml) was injected into the graphite tube. </p><p>Quantification was accomplished by the method of standard additions using standards of inorganic mercury. Results and Discussion TMAH is an efficient reagent for solubilizing tissue samples. Although the resulting sample ‘digest’ is not clear and colourless, an unmodified autosampler can be used to pipette the samples into the graphite tube as ultrasonic mixing of the solution is not required. Thus, the ease of sample preparation using this approach is a distinct advantage over conventional slurry methods and solid sampling techniques where a weighed dry mass is inserted into the graphite tube. </p><p>Also, imprecision due to inhomogeneity inherent to the sample can be minimized as larger masses can be subsampled. Other reports have suggested that high-pressure homogenization22 or heating23 of the alkaline digest is required to solubilize the tissue; this was not found necessary for this study. On standing, the digest becomes less cloudy in appearance but no difference in final results was found for samples prepared 5 min or 2 months prior to determination. Total mercury (inorganic and organic) could be determined in a solution of solubilized biological tissue using the ETV program outlined in Table 2. </p><p>No modifiers were required and a single peak was observed using a temperature of 800 °C to vaporize the mercury. This temperature was chosen as the minimum required to give a single peak but not so high that less volatile matrix components would be transferred to the plasma. </p><p>Lower vaporization temperatures resulted in multiple peaks. Matrix modifiers are important in ETV ICP-MS not only for altering the chemical composition of the sample, but to act as physical carriers to help transfer the analyte from the graphite tube to the plasma.24 In the present study, sufficient matrix components are present in the sample to serve as a physical carrier for the inorganic Hg. </p><p>The instrument software would not permit the gas flow to be redirected through the dosing hole in the final steps of the furnace program. Thus, to prevent residue from the 800 °C vaporization from entering the transfer line, a high temperature cleaning of the graphite tube was not performed at the end of the furnace program. Rather, prior to sample introduction, each furnace cycle commenced with a high-temperature heating step with gas flow directed through the dosing hole. This ensured removel of residue from the previous sample from the system. </p><p>Minimisation of sample material entering the transfer line reduced problems encountered from the build up of condensed matrix components which over a period of 40 to 50 cycles reduced the sensitivity. The determination of inorganic mercury was achieved by adding IOAc, Na2S2O3 and HOAc to the sample. IOAc cleaves the methylmercury from the biological tissue and the MeHgI that is formed is volatilized as the sample dries and is removed from the system through the dosing hole. </p><p>Na2S2O3 was added to prevent degradation of MeHgI and a small amount of HOAc (20 ml) was added to prevent formation of MeHgOH.12 The gas flow was then redirected to the plasma, the tube heated to 800 °C and the inorganic Hg remaining in the sample was volatilized and quantified. Fig. 1 shows the peak obtained for a sample of DOLT-2 with and without a spike of inorganic Hg. The concentrations of IOAc and Na2S2O3 were not reoptimized in this study but chosen from ref. 12. A subsequent paper by Lansens and Baeyens25 improved the headspace chromatography procedure by replacing Na2S2O3 with H2SO4 to enhance cleaving of methylmercury from the Table 2 Electrothermal vaporizer program Time/s Gas to Temperature/ Gas Flow/ Step °C Ramp Hold ml min21 Vent ICP 1 2500 1 5 300 X 2 20 1 20 300 X 3 120 1 25 300 X 4 120 1 10 0 X 5 800 1 7 0 X 6 20 1 10 0 X 752 Analyst, August 1997, Vol. 122 biological tissue. </p><p>This was not utilized here as the conditions used in this study indicated complete conversion of the methylmercury to the iodide form and the use of H2SO4 is detrimental to the lifetime of the graphite tube. The vaporization of methylmercury as well as inorganic mercury from a biological tissue is shown in Fig. 2. To obtain this figure the ETV gas flow was directed to the plasma during the sample drying step and step 3 of the ETV program (Table 2) was modified to a 40 s ramp and 20 s hold to ensure a very slow drying of the sample. </p><p>Signals due to methylmercury and inorganic mercury occur at 15 and 55 s, respectively. Attempts to separately quantify the organic mercury peak were unsuccessful because, under the conditions used to obtain this data, carryover of inorganic mercury augments the methylmercury peak. It appears that too rapid drying of the sample physically carries a fraction of the inorganic mercury along with water vapour to the plasma. </p><p>This was confirmed by adding a spike of inorganic 201Hg to the sample and monitoring the 201/202Hg ratio. A slow dry period was required to eliminate this problem. Unfortunately, by increasing the drying time, the peak for methylmercury becomes too broad to be accurately quantified and is not well separated from the inorganic mercury peak. The early peak response from organic mercury is 20 fold less sensitive (peak hight) than that from an inorganic spike that occurs later in the vaporization program. </p><p>This is a result of the combination of little or no useful physical carrier at low temperatures and the water vapour which enters and perturbs the plasma. Effect of Sample Mass on Analyte Response Fig. 3 shows the effect on the response for various amounts of diluted DORM-2 added to the ETV. Response is normalized to 1 ng of total mercury. At optimum ( Ã… 60 mg), the signal obtained is 21 fold greater than the response in deionized, distilled water. </p><p>At lower masses, analyte transport becomes less efficient and at higher masses it is suspected that space charge effects reduce sensitivity or perhaps condensation of matrix components on colder parts of the system scavenges the analyte. Although response varies substantially with sample mass, the certified value for total Hg in DORM-2 was obtained at masses of 25 mg, 60 mg and 250 mg using the method of additions. Figures of Merit A limit of detection of 0.05 mg g21 in the solid tissue is obtained based on 3 s of a blank TMAH solution. </p><p>The Hg content of the blank varied with the stock solutions of TMAH. Dilutions using a bottle of TMAH stored for several years in the laboratory gave a blank of 23 ng, whereas that from a new bottle of TMAH was 12 ng. The precision of replicate measurement was determined to be ±7.8% using a solution of DORM-2 at a concentration 50 fold above the detection limit. Analytical Results The accuracy of the method was evaluated by analysing a suite of marine biological certified reference materials.6 DORM-2, dogfish flesh material, DOLT-2, dogfish liver tissue and TORT- 2, lobster hepatopancreas, are all certified for total and methylmercury content. </p><p>The determined values for total mercury agree with the certified values (see Table 3). The determined values for inorganic mercury agree with the Fig. 1 ETV ICP-MS signals for (a) DOLT-2 and (b) DOLT-2 spiked with 9.6 pg inorganic Hg. </p><p>Fig. 2 ETV ICP-MS signals for DOLT-2 using a slow drying step. Fig. 3 Effect of total mass of DORM-2 on normalized response for 1 ng of inorganic Hg. Table 3 Analytical results Certified/mg g21 Determined/mg g21 Reference Methyl Total Total Inorganic material mercury mercury mercury mercury DORM-2 4.47 ± 0.32 4.64 ± 0.26 4.3 ± 0.5 0.33 ± 0.02 DOLT-2 0.693 ± 0.053 2.14 ± 0.28 2.20 ± 0.11 1.4 ± 0.2 TORT-2 0.152 ± 0.013 0.27 ± 0.06 0.25 ± 0.04 0.10 ± 0.02 Analyst, August 1997, Vol. 122 753 difference between the certified total and methyl mercury content. These results demonstrate the ETV device can serve as a thermochemical reactor wherein samples may be subjected to a controlled thermal and chemical atmosphere, permiting speciation based on vapour pressures. References 1 Organometallic Compounds in the Environment, ed. Craig, P. J., Wiley, New York, 1986, p. 65. 2 Surma-Aho, K., Paasivirta, J., Rekolainen, S., and Verta, M., Chemosphere, 1986, 15, 353. 3 Baeyens, W., Trends Anal. </p><p>Chem., 1992, 11, 245. 4 Kiceniuk, J. W., and Ray S., Analysis of Contaminants in Edible Aquatic Resources, VCH, Weinheim, Germany, 1994, ch. 8. 5 West¨o¨o, G., Acta. Chem. Scand., 1968, 22B, 2277. 6 Berman, S. S., Siu, K. W. M., Maxwell, P. S., Beauchemin, D., and Clancy, V. P., Fresenius’ Z. Anal. Chem., 1989, 333, 641. 7 Donais, M. K., Uden, P. C., Schantz, M. M., and Wise, S. A., Anal. Chem., 1996, 68, 3859. 8 Huang, C.-W., and Jiang, S.-J., J. </p><p>Anal. At. Spectrom., 1993, 8, 681. 9 Bloxam, M. J., Gachanja, A., Hill, S. J., and Worsfold, P. J., J. Anal. At. Spectrom., 1996, 11, 145. 10 Rapsomanikis, S., Donard, O. F. X., and Weber, J. H., Anal. Chem., 1986, 58, 35. 11 Bulska, E., Baxter, D. C., and Frech, W., Anal. Chim. Acta, 1991, 249, 545. 12 Decadt, G., Baeyens, W., Bradley, D., and Goeyens, L., Anal. Chem., 1985, 57, 2788. 13 Lansens, P., Mueleman, C., Casais, C., and Baeyens, W., Appl. Organomet. Chem., 1993, 7, 45. 14 Campos, R. C., Curtius, A. J., and Berndt, H., J. Anal. At. Spectrom., 1990, 5, 669. 15 Dumarey, R., and Dams, R., Mikrochim. Acta, 1984, 3, 191. 16 Nicholson, R. A., Analyst, 1977, 102, 399. 17 Bombach, G., Bombach, K., and Klemm, W., Fresenius’ J. Anal. Chem., 1994, 350, 18. 18 Hanamura, S., Smith, B. W., and Winefordner, J. D., Anal. Chem., 1983, 55, 2026. 19 Bauer, C. F., and Natusch, D. F. S., Anal. Chem., 1981, 53, 2020. 20 Jackson, A. J., Michael, L. W., and Schumacher, H. </p><p>J., Anal. Chem., 1972, 44, 1064. 21 Gross, S. B., and Parkinson, E. A., At. Absorpt. Newsl., 1974, 13, 387. 22 Tan, Y., Blais, J.-S., and Marshall, W. D., Analyst, 1996, 121, 1419. 23 Uchida, T., Isoyama, H., Yamada, K., Oguchi, K., Nakagawa, G., Sugie, H., and Iida, C., Anal. Chim. Acta, 1992, 256, 277. 24 Sturgeon, R. E., Willie, S. N., Zheng, J., Kudo, A., and Gr´egoire, D. C., J. Anal. At. Spectrom., 1993, 8, 1053. 25 Lansens, P., and Baeyens, W., Anal. Chim. Acta, 1990, 228, 93. </p><p>Paper 7/01169E Received February 19, 1997 Accepted April 15, 1997 754 Analyst, August 1997, Vol. 122 Determination of Inorganic and Total Mercury in Biological Tissues by Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry Scott N. Willie*a, D. Conrad Gr´egoireb and Ralph E. Sturgeona a Institute for National Measurement Standards, National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R9 b Geological Survey of Canada, 601 Booth Street, Ottawa, Ontario, Canada K1A 0E8 A rapid method for the determination of total and inorganic mercury in biological tissues is presented using electrothermal vaporization inductively coupled plasma mass spectrometry (ETV ICP–MS). Samples were solubilized using tetramethylammonium hydroxide. </p><p>For the determination of total mercury sample aliquots (10 ml) are dried and vaporized into the plasma. For the determination of inorganic mercury, iodoacetic acid, sodium thiosulfate and acetic acid are added to the sample, cleaving the methylmercury from the tissue. </p><p>Volatile methylmercury iodide is formed and removed from the ETV as the sample dries, leaving only inorganic mercury to be quantified. A limit of detection of 0.05 mg g21 in solid samples was obtained. National Research Council of Canada reference materials DORM-2 (dogfish muscle), DOLT-2 (dogfish liver) and TORT-2 (lobster hepatopancreas) were used to assess the accuracy of the method. </p><p>Keywords: Mercury; inorganic mercury; biological tissues; electrothermal vaporization inductively coupled plasma mass spectrometry; tetramethylammonium hydroxide solubilization Mercury is a ubiquitous element in the environment resulting from both anthropogenic and natural geological activities. In the marine environment the distribution and speciation of Hg is of considerable interest as biomethylation1 and subsequently bioconcentration in the food chain2 can occur. As a result, mercury is predominantly present in marine biological samples as methylmercury. </p><p>It is well known that organomercury compounds are more toxic than metallic or aquo Hg forms; consequently, considerable effort and progress have been made in the development of techniques capable of separating and identifying the various mercury species.3 Common methods for the determination of total mercury require sample digestion followed by chemical reduction and subsequent gas phase transfer of the element to a detector. Approaches for speciation analysis involve milder sample preparation procedures to preserve the integrity of any organic mercury.4 Frequently, these are variations of the classical West¨o¨o5 procedure involving solvent extraction, cleanup of the extract, isolation of the organomercurial as the corresponding halide derivative and detection by gas chromatography with electron capture detection (GC–ECD)6 or atomic emission detection (GC–AED).7 Methods using liquid chromatography (LC) also require sample extraction and cleanup steps.8,9 Alternatively, procedures utilizing derivatisation of organomercury via ethylating10 or butylating11 agents followed by isolation and detection have been reported. Generally, these procedures require less sample cleanup than GC or LC methods but separation via a chromatographic column or cryogenic trapping is necessary. Another method that does not require extensive sample extraction and cleanup utilizes headspace sampling. </p><p></p><p></p><p>A cleaving agent is used to liberate the methylmercury from the biological tissue, whereupon it is subsequently converted to volatile methylmercury iodide, sampled, desorbed onto a column and detected using GC–MIP (microwave induced plasma).12,13 The determination of Hg by thermal vaporization from solid samples is an attractive approach that requires minimal sample preparation.14 This technique has been applied to environmental samples15 and rocks and sediments16 using quartz tube AAS detection. </p><p>As well as total Hg, direct methods for the speciation of mercury in soils and sediments17 and biologicals18 have been reported. ETV ICP-MS is well-suited for application to thermal vaporization methodology as the temperature of the graphite tube can be accurately controlled, small samples can be easily injected and the sampling frequency is relatively high. In addition, the tolerance of ICP-MS to the solvent and matrix components in the sample is superior to the less powerful microwave He plasma system.19 The determination of total and inorganic mercury in biological tissues is reported here. </p><p>Extraction or acid digestion of the samples is replaced by room temperature treatment of the tissue with tetramethylammonium hydroxide (TMAH). TMAH, an alkali tissue solublizer, has been utilized for the speciation analysis of tin and mercury and also for total element analysis using flame,20 graphite furance21,22 and ICP-AES.23 Additionally, a method to determine the inorganic Hg content of the tissues has been developed by capitalizing on the volatility of methylmercury halide derivatives. </p><p>Iodoacetic acid (IOAc) is added to the alkaline digest and the methylmercury iodide (MeHgI) is distilled from the sample as the graphite tube is gently heated. The inorganic mercury remaining in the graphite tube after heating to 120 °C is then quantified. Experimental Instrument A Perkin-Elmer SCIEX ELAN 5000 ICP mass spectrometer equipped with a HGA-600MS electrothermal vaporizer (ETV) and Model AS-60 autosampler was used. </p><p>The experimental conditions for the mass spectrometer are given in Table 1. The Table 1 Instrumental operating conditions and data acquisition parameters ICP mass spectrometer— Rf power 1050 W Outer argon flow rate 15.0 l min21 Intermediate argon flow rate 850 ml min21 Carrier argon flow rate 900 ml min21 Sampler-skimmer Nickel Data acquistion— Dwell time 30 ms Scan mode Peak hopping Signal measurement mode Integrated response Analyst, August 1997, Vol. 122 (751–754) 751 HGA-600 MS has been described previously24 and was interfaced to the plasma via a 0.8 m length of 6 mm id poly(tetrafluoroethylene) tubing. The 202Hg isotope was monitored. The ETV program is outlined in Table 2. An initial high temperature step cleans the furnace. Following furnace cooling in step 2, the sample is injected. The sample is dried in step 3 and the moisture and vapours are vented through the dosing hole. In step 4 a graphite probe is pneumatically activated to seal the dosing hole and the carrier gas is directed from one end of the ETV workhead to the argon plasma at a flow rate of 900 ml min21 prior to heating the graphite tube to 800 °C. </p><p>The graphite tube is not cleaned at high temperature immediately after the analytical signal has been obtained, rather cleaning occurs when the next analysis cycle is initiated. </p><p>This prevents the residue remaining after the 800 °C pyrolysis from entering the plasma and transfer line. Reagents TMAH (30% in methanol, Aldrich, Milwaukee, WI, USA) was used to solubilize the samples. A 37 mg ml21 iodoacetic acid solution (IOAc, Aldrich) was prepared in water. A 25 mg ml21 sodium thiosulfate (Na2S2O3) solution was prepared by dissolution of the salt in high purity water. Reagent grade acetic acid (HOAc; Environmental Grade, Anachemia, Montreal, QC, Canada) was used. </p><p>High purity water was produced by passage through a commercial reverse osmosis unit followed by a mixed bed ion-exchange system (Barnstead Nanopure, Barnstead, Dubuque, IA, USA). Mercury solutions were prepared by dissolution of HgCl2 (gold star, Alfa Chemicals, Ward Hill, MA, USA) in dilute nitric acid. A methylmercury standard was prepared by dissolving MeHgCl (Alpha Division, Danvers, MA, USA) in an appropriate amount of propan-2-ol. Working solutions were prepared daily by serial dilution with high purity water. </p><p>National Research Council of Canada (NRCC) reference materials DORM-2 (dogfish muscle), DOLT-2 (dogfish liver) and TORT-2 (lobster hepatopancreas) were used to assess the accuracy of the method. Sample preparation A 0.250 g sample was weighed into a beaker and 4 ml of TMAH was added. Following the reaction of the tissue with the TMAH for approximately 5 min, the solution was transferred to a 25 ml calibrated flask and diluted to volume with high purity water. </p><p>Samples of DORM-2 were diluted ten fold prior to analysis. Total mercury A portion (10 ml) of the above sample was injected into the HGA furnace and the program listed in Table 2 was initiated. Quantification was accomplished by the method of standard additions using either standards of methyl or inorganic mercury. Inorganic mercury A 250 ml aliquot of the sample was pipetted into a sample cup along with 125 ml of the IOAc solution and 125 ml of Na2S2O3 solution. </p><p>The mixture was acidified by addition of 20 ml of HOAc. The mixture (10 ml) was injected into the graphite tube. Quantification was accomplished by the method of standard additions using standards of inorganic mercury. Results and Discussion TMAH is an efficient reagent for solubilizing tissue samples. Although the resulting sample ‘digest’ is not clear and colourless, an unmodified autosampler can be used to pipette the samples into the graphite tube as ultrasonic mixing of the solution is not required. </p><p>Thus, the ease of sample preparation using this approach is a distinct advantage over conventional slurry methods and solid sampling techniques where a weighed dry mass is inserted into the graphite tube. Also, imprecision due to inhomogeneity inherent to the sample can be minimized as larger masses can be subsampled. Other reports have suggested that high-pressure homogenization22 or heating23 of the alkaline digest is required to solubilize the tissue; this was not found necessary for this study. </p><p>On standing, the digest becomes less cloudy in appearance but no difference in final results was found for samples prepared 5 min or 2 months prior to determination. Total mercury (inorganic and organic) could be determined in a solution of solubilized biological tissue using the ETV program outlined in Table 2. No modifiers were required and a single peak was observed using a temperature of 800 °C to vaporize the mercury. </p><p>This temperature was chosen as the minimum required to give a single peak but not so high that less volatile matrix components would be transferred to the plasma. Lower vaporization temperatures resulted in multiple peaks. Matrix modifiers are important in ETV ICP-MS not only for altering the chemical composition of the sample, but to act as physical carriers to help transfer the analyte from the graphite tube to the plasma.24 In the present study, sufficient matrix components are present in the sample to serve as a physical carrier for the inorganic Hg. </p><p>The instrument software would not permit the gas flow to be redirected through the dosing hole in the final steps of the furnace program. Thus, to prevent residue from the 800 °C vaporization from entering the transfer line, a high temperature cleaning of the graphite tube was not performed at the end of the furnace program. Rather, prior to sample introduction, each furnace cycle commenced with a high-temperature heating step with gas flow directed through the dosing hole. </p><p>This ensured removel of residue from the previous sample from the system. Minimisation of sample material entering the transfer line reduced problems encountered from the build up of condensed matrix components which over a period of 40 to 50 cycles reduced the sensitivity. The determination of inorganic mercury was achieved by adding IOAc, Na2S2O3 and HOAc to the sample. </p><p>IOAc cleaves the methylmercury from the biological tissue and the MeHgI that is formed is volatilized as the sample dries and is removed from the system through the dosing hole. Na2S2O3 was added to prevent degradation of MeHgI and a small amount of HOAc (20 ml) was added to prevent formation of MeHgOH.12 The gas flow was then redirected to the plasma, the tube heated to 800 °C and the inorganic Hg remaining in the sample was volatilized and quantified. Fig. 1 shows the peak obtained for a sample of DOLT-2 with and without a spike of inorganic Hg. The concentrations of IOAc and Na2S2O3 were not reoptimized in this study but chosen from ref. 12. A subsequent paper by Lansens and Baeyens25 improved the headspace chromatography procedure by replacing Na2S2O3 with H2SO4 to enhance cleaving of methylmercury from the Table 2 Electrothermal vaporizer program Time/s Gas to Temperature/ Gas Flow/ Step °C Ramp Hold ml min21 Vent ICP 1 2500 1 5 300 X 2 20 1 20 300 X 3 120 1 25 300 X 4 120 1 10 0 X 5 800 1 7 0 X 6 20 1 10 0 X 752 Analyst, August 1997, Vol. 122 biological tissue. This was not utilized here as the conditions used in this study indicated complete conversion of the methylmercury to the iodide form and the use of H2SO4 is detrimental to the lifetime of the graphite tube. The vaporization of methylmercury as well as inorganic mercury from a biological tissue is shown in Fig. 2. To obtain this figure the ETV gas flow was directed to the plasma during the sample drying step and step 3 of the ETV program (Table 2) was modified to a 40 s ramp and 20 s hold to ensure a very slow drying of the sample. </p><p>Signals due to methylmercury and inorganic mercury occur at 15 and 55 s, respectively. Attempts to separately quantify the organic mercury peak were unsuccessful because, under the conditions used to obtain this data, carryover of inorganic mercury augments the methylmercury peak. It appears that too rapid drying of the sample physically carries a fraction of the inorganic mercury along with water vapour to the plasma. </p><p>This was confirmed by adding a spike of inorganic 201Hg to the sample and monitoring the 201/202Hg ratio. A slow dry period was required to eliminate this problem. Unfortunately, by increasing the drying time, the peak for methylmercury becomes too broad to be accurately quantified and is not well separated from the inorganic mercury peak. The early peak response from organic mercury is 20 fold less sensitive (peak hight) than that from an inorganic spike that occurs later in the vaporization program. </p><p>This is a result of the combination of little or no useful physical carrier at low temperatures and the water vapour which enters and perturbs the plasma. Effect of Sample Mass on Analyte Response Fig. 3 shows the effect on the response for various amounts of diluted DORM-2 added to the ETV. Response is normalized to 1 ng of total mercury. At optimum ( Ã… 60 mg), the signal obtained is 21 fold greater than the response in deionized, distilled water. </p><p>At lower masses, analyte transport becomes less efficient and at higher masses it is suspected that space charge effects reduce sensitivity or perhaps condensation of matrix components on colder parts of the system scavenges the analyte. Although response varies substantially with sample mass, the certified value for total Hg in DORM-2 was obtained at masses of 25 mg, 60 mg and 250 mg using the method of additions. </p><p>Figures of Merit A limit of detection of 0.05 mg g21 in the solid tissue is obtained based on 3 s of a blank TMAH solution. The Hg content of the blank varied with the stock solutions of TMAH. Dilutions using a bottle of TMAH stored for several years in the laboratory gave a blank of 23 ng, whereas that from a new bottle of TMAH was 12 ng. The precision of replicate measurement was determined to be ±7.8% using a solution of DORM-2 at a concentration 50 fold above the detection limit. </p><p>Analytical Results The accuracy of the method was evaluated by analysing a suite of marine biological certified reference materials.6 DORM-2, dogfish flesh material, DOLT-2, dogfish liver tissue and TORT- 2, lobster hepatopancreas, are all certified for total and methylmercury content. The determined values for total mercury agree with the certified values (see Table 3). The determined values for inorganic mercury agree with the Fig. 1 ETV ICP-MS signals for (a) DOLT-2 and (b) DOLT-2 spiked with 9.6 pg inorganic Hg. Fig. 2 ETV ICP-MS signals for DOLT-2 using a slow drying step. Fig. 3 Effect of total mass of DORM-2 on normalized response for 1 ng of inorganic Hg. Table 3 Analytical results Certified/mg g21 Determined/mg g21 Reference Methyl Total Total Inorganic material mercury mercury mercury mercury DORM-2 4.47 ± 0.32 4.64 ± 0.26 4.3 ± 0.5 0.33 ± 0.02 DOLT-2 0.693 ± 0.053 2.14 ± 0.28 2.20 ± 0.11 1.4 ± 0.2 TORT-2 0.152 ± 0.013 0.27 ± 0.06 0.25 ± 0.04 0.10 ± 0.02 Analyst, August 1997, Vol. 122 753 difference between the certified total and methyl mercury content. These results demonstrate the ETV device can serve as a thermochemical reactor wherein samples may be subjected to a controlled thermal and chemical atmosphere, permiting speciation based on vapour pressures. </p><p>References 1 Organometallic Compounds in the Environment, ed. Craig, P. J., Wiley, New York, 1986, p. 65. 2 Surma-Aho, K., Paasivirta, J., Rekolainen, S., and Verta, M., Chemosphere, 1986, 15, 353. 3 Baeyens, W., Trends Anal. Chem., 1992, 11, 245. 4 Kiceniuk, J. W., and Ray S., Analysis of Contaminants in Edible Aquatic Resources, VCH, Weinheim, Germany, 1994, ch. 8. 5 West¨o¨o, G., Acta. Chem. Scand., 1968, 22B, 2277. 6 Berman, S. S., Siu, K. W. M., Maxwell, P. S., Beauchemin, D., and Clancy, V. P., Fresenius’ Z. Anal. Chem., 1989, 333, 641. 7 Donais, M. K., Uden, P. C., Schantz, M. M., and Wise, S. A., Anal. Chem., 1996, 68, 3859. 8 Huang, C.-W., and Jiang, S.-J., J. Anal. At. Spectrom., 1993, 8, 681. 9 Bloxam, M. J., Gachanja, A., Hill, S. J., and Worsfold, P. J., J. Anal. At. Spectrom., 1996, 11, 145. 10 Rapsomanikis, S., Donard, O. F. X., and Weber, J. H., Anal. Chem., 1986, 58, 35. 11 Bulska, E., Baxter, D. C., and Frech, W., Anal. Chim. Acta, 1991, 249, 545. 12 Decadt, G., Baeyens, W., Bradley, D., and Goeyens, L., Anal. Chem., 1985, 57, 2788. 13 Lansens, P., Mueleman, C., Casais, C., and Baeyens, W., Appl. Organomet. Chem., 1993, 7, 45. 14 Campos, R. C., Curtius, A. J., and Berndt, H., J. Anal. At. Spectrom., 1990, 5, 669. 15 Dumarey, R., and Dams, R., Mikrochim. Acta, 1984, 3, 191. 16 Nicholson, R. A., Analyst, 1977, 102, 399. 17 Bombach, G., Bombach, K., and Klemm, W., Fresenius’ J. Anal. Chem., 1994, 350, 18. 18 Hanamura, S., Smith, B. W., and Winefordner, J. D., Anal. Chem., 1983, 55, 2026. 19 Bauer, C. F., and Natusch, D. F. S., Anal. Chem., 1981, 53, 2020. 20 Jackson, A. J., Michael, L. W., and Schumacher, H. J., Anal. Chem., 1972, 44, 1064. 21 Gross, S. B., and Parkinson, E. A., At. Absorpt. Newsl., 1974, 13, 387. 22 Tan, Y., Blais, J.-S., and Marshall, W. D., Analyst, 1996, 121, 1419. 23 Uchida, T., Isoyama, H., Yamada, K., Oguchi, K., Nakagawa, G., Sugie, H., and Iida, C., Anal. Chim. Acta, 1992, 256, 277. 24 Sturgeon, R. E., Willie, S. N., Zheng, J., Kudo, A., and Gr´egoire, D. C., J. Anal. At. Spectrom., 1993, 8, 1053. 25 Lansens, P., and Baeyens, W., Anal. Chim. Acta, 1990, 228, 93. Paper 7/01169E Received February 19, 1997 Accepted April 15, 1997 754 Analyst, August 1997, Vol. 122 </p></section></art-body><art-back><biblist><citgroup id="cit1"><citation type="book"><title>Organometallic Compounds in the Environment</title>, ed. <editor>Craig, P. J.</editor>, <citpub>Wiley</citpub>, <pubplace>New York</pubplace>, <year>1986</year>, <biblscope>p. 65</biblscope></citation></citgroup><citgroup id="cit2"><journalcit><citauth><fname>K.</fname><surname>Surma-Aho</surname></citauth><citauth><fname>J.</fname><surname>Paasivirta</surname></citauth><citauth><fname>S.</fname><surname>Rekolainen</surname></citauth><citauth><fname>M.</fname><surname>Verta</surname></citauth><title>Chemosphere</title><year>1986</year><volumeno>15</volumeno><pages><fpage>353</fpage></pages></journalcit></citgroup><citgroup id="cit3"><journalcit><citauth><fname>W.</fname><surname>Baeyens</surname></citauth><title>Trends Anal. Chem.</title><year>1992</year><volumeno>11</volumeno><pages><fpage>245</fpage></pages></journalcit></citgroup><citgroup id="cit4"><citation type="book"><citauth><fname>J. W.</fname><surname>Kiceniuk</surname></citauth> and <citauth><fname>S.</fname><surname>Ray</surname></citauth>, <title>Analysis of Contaminants in Edible Aquatic Resources</title>, <citpub>VCH</citpub>, <pubplace>Weinheim, Germany</pubplace>, <year>1994</year>, ch. 8</citation></citgroup><citgroup id="cit5"><journalcit><citauth><fname>G.</fname><surname>Westöö</surname></citauth><title>Acta. Chem. Scand.</title><year>1968</year><volumeno>22B</volumeno><pages><fpage>2277</fpage></pages></journalcit></citgroup><citgroup id="cit6"><journalcit><citauth><fname>S. S.</fname><surname>Berman</surname></citauth><citauth><fname>K. W. M.</fname><surname>Siu</surname></citauth><citauth><fname>P. S.</fname><surname>Maxwell</surname></citauth><citauth><fname>D.</fname><surname>Beauchemin</surname></citauth><citauth><fname>V. P.</fname><surname>Clancy</surname></citauth><title>Fresenius' Z. Anal. Chem.</title><year>1989</year><volumeno>333</volumeno><pages><fpage>641</fpage></pages></journalcit></citgroup><citgroup id="cit7"><journalcit><citauth><fname>M. K.</fname><surname>Donais</surname></citauth><citauth><fname>P. C.</fname><surname>Uden</surname></citauth><citauth><fname>M. M.</fname><surname>Schantz</surname></citauth><citauth><fname>S. A.</fname><surname>Wise</surname></citauth><title>Anal. Chem.</title><year>1996</year><volumeno>68</volumeno><pages><fpage>3859</fpage></pages></journalcit></citgroup><citgroup id="cit8"><journalcit><citauth><fname>C.-W.</fname><surname>Huang</surname></citauth><citauth><fname>S.-J.</fname><surname>Jiang</surname></citauth><title>J. Anal. At. Spectrom.</title><year>1993</year><volumeno>8</volumeno><pages><fpage>681</fpage></pages></journalcit></citgroup><citgroup id="cit9"><journalcit><citauth><fname>M. J.</fname><surname>Bloxam</surname></citauth><citauth><fname>A.</fname><surname>Gachanja</surname></citauth><citauth><fname>S. J.</fname><surname>Hill</surname></citauth><citauth><fname>P. J.</fname><surname>Worsfold</surname></citauth><title>J. Anal. At. Spectrom.</title><year>1996</year><volumeno>11</volumeno><pages><fpage>145</fpage></pages></journalcit></citgroup><citgroup id="cit10"><journalcit><citauth><fname>S.</fname><surname>Rapsomanikis</surname></citauth><citauth><fname>O. F. X.</fname><surname>Donard</surname></citauth><citauth><fname>J. H.</fname><surname>Weber</surname></citauth><title>Anal. Chem.</title><year>1986</year><volumeno>58</volumeno><pages><fpage>35</fpage></pages></journalcit></citgroup><citgroup id="cit11"><journalcit><citauth><fname>E.</fname><surname>Bulska</surname></citauth><citauth><fname>D. C.</fname><surname>Baxter</surname></citauth><citauth><fname>W.</fname><surname>Frech</surname></citauth><title>Anal. Chim. Acta</title><year>1991</year><volumeno>249</volumeno><pages><fpage>545</fpage></pages></journalcit></citgroup><citgroup id="cit12"><journalcit><citauth><fname>G.</fname><surname>Decadt</surname></citauth><citauth><fname>W.</fname><surname>Baeyens</surname></citauth><citauth><fname>D.</fname><surname>Bradley</surname></citauth><citauth><fname>L.</fname><surname>Goeyens</surname></citauth><title>Anal. Chem.</title><year>1985</year><volumeno>57</volumeno><pages><fpage>2788</fpage></pages></journalcit></citgroup><citgroup id="cit13"><journalcit><citauth><fname>P.</fname><surname>Lansens</surname></citauth><citauth><fname>C.</fname><surname>Mueleman</surname></citauth><citauth><fname>C.</fname><surname>Casais</surname></citauth><citauth><fname>W.</fname><surname>Baeyens</surname></citauth><title>Appl. Organomet. Chem.</title><year>1993</year><volumeno>7</volumeno><pages><fpage>45</fpage></pages></journalcit></citgroup><citgroup id="cit14"><journalcit><citauth><fname>R. C.</fname><surname>Campos</surname></citauth><citauth><fname>A. J.</fname><surname>Curtius</surname></citauth><citauth><fname>H.</fname><surname>Berndt</surname></citauth><title>J. Anal. At. Spectrom.</title><year>1990</year><volumeno>5</volumeno><pages><fpage>669</fpage></pages></journalcit></citgroup><citgroup id="cit15"><journalcit><citauth><fname>R.</fname><surname>Dumarey</surname></citauth><citauth><fname>R.</fname><surname>Dams</surname></citauth><title>Mikrochim. Acta</title><year>1984</year><volumeno>3</volumeno><pages><fpage>191</fpage></pages></journalcit></citgroup><citgroup id="cit16"><journalcit><citauth><fname>R. A.</fname><surname>Nicholson</surname></citauth><title>Analyst</title><year>1977</year><volumeno>102</volumeno><pages><fpage>399</fpage></pages></journalcit></citgroup><citgroup id="cit17"><journalcit><citauth><fname>G.</fname><surname>Bombach</surname></citauth><citauth><fname>K.</fname><surname>Bombach</surname></citauth><citauth><fname>W.</fname><surname>Klemm</surname></citauth><title>Fresenius' J. Anal. Chem.</title><year>1994</year><volumeno>350</volumeno><pages><fpage>18</fpage></pages></journalcit></citgroup><citgroup id="cit18"><journalcit><citauth><fname>S.</fname><surname>Hanamura</surname></citauth><citauth><fname>B. W.</fname><surname>Smith</surname></citauth><citauth><fname>J. D.</fname><surname>Winefordner</surname></citauth><title>Anal. Chem.</title><year>1983</year><volumeno>55</volumeno><pages><fpage>2026</fpage></pages></journalcit></citgroup><citgroup id="cit19"><journalcit><citauth><fname>C. F.</fname><surname>Bauer</surname></citauth><citauth><fname>D. F. S.</fname><surname>Natusch</surname></citauth><title>Anal. Chem.</title><year>1981</year><volumeno>53</volumeno><pages><fpage>2020</fpage></pages></journalcit></citgroup><citgroup id="cit20"><journalcit><citauth><fname>A. J.</fname><surname>Jackson</surname></citauth><citauth><fname>L. W.</fname><surname>Michael</surname></citauth><citauth><fname>H. J.</fname><surname>Schumacher</surname></citauth><title>Anal. Chem.</title><year>1972</year><volumeno>44</volumeno><pages><fpage>1064</fpage></pages></journalcit></citgroup><citgroup id="cit21"><journalcit><citauth><fname>S. B.</fname><surname>Gross</surname></citauth><citauth><fname>E. A.</fname><surname>Parkinson</surname></citauth><title>At. Absorpt. Newsl.</title><year>1974</year><volumeno>13</volumeno><pages><fpage>387</fpage></pages></journalcit></citgroup><citgroup id="cit22"><journalcit><citauth><fname>Y.</fname><surname>Tan</surname></citauth><citauth><fname>J.-S.</fname><surname>Blais</surname></citauth><citauth><fname>W. D.</fname><surname>Marshall</surname></citauth><title>Analyst</title><year>1996</year><volumeno>121</volumeno><pages><fpage>1419</fpage></pages></journalcit></citgroup><citgroup id="cit23"><journalcit><citauth><fname>T.</fname><surname>Uchida</surname></citauth><citauth><fname>H.</fname><surname>Isoyama</surname></citauth><citauth><fname>K.</fname><surname>Yamada</surname></citauth><citauth><fname>K.</fname><surname>Oguchi</surname></citauth><citauth><fname>G.</fname><surname>Nakagawa</surname></citauth><citauth><fname>H.</fname><surname>Sugie</surname></citauth><citauth><fname>C.</fname><surname>Iida</surname></citauth><title>Anal. Chim. Acta</title><year>1992</year><volumeno>256</volumeno><pages><fpage>277</fpage></pages></journalcit></citgroup><citgroup id="cit24"><journalcit><citauth><fname>R. E.</fname><surname>Sturgeon</surname></citauth><citauth><fname>S. N.</fname><surname>Willie</surname></citauth><citauth><fname>J.</fname><surname>Zheng</surname></citauth><citauth><fname>A.</fname><surname>Kudo</surname></citauth><citauth><fname>D. C.</fname><surname>Grégoire</surname></citauth><title>J. Anal. At. Spectrom.</title><year>1993</year><volumeno>8</volumeno><pages><fpage>1053</fpage></pages></journalcit></citgroup><citgroup id="cit25"><journalcit><citauth><fname>P.</fname><surname>Lansens</surname></citauth><citauth><fname>W.</fname><surname>Baeyens</surname></citauth><title>Anal. Chim. Acta</title><year>1990</year><volumeno>228</volumeno><pages><fpage>93</fpage></pages></journalcit></citgroup></biblist><compoundgrp></compoundgrp><annotationgrp></annotationgrp><datagrp></datagrp><resourcegrp></resourcegrp></art-back></article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo><title>Determination of Inorganic and Total Mercury in Biological Tissuesby Electrothermal Vaporization Inductively Coupled Plasma MassSpectrometry</title></titleInfo><titleInfo type="alternative" contentType="CDATA"><title>Determination of Inorganic and Total Mercury in Biological Tissuesby Electrothermal Vaporization Inductively Coupled Plasma MassSpectrometry</title></titleInfo><name type="personal"><namePart type="given">Scott</namePart><namePart type="family">N. Willie</namePart></name><name type="personal"><namePart type="given">D.</namePart><namePart type="family">Conrad Grégoire</namePart></name><name type="personal"><namePart type="given">Ralph</namePart><namePart type="family">E. Sturgeon</namePart></name><typeOfResource>text</typeOfResource><genre type="article" displayLabel="ART"></genre><originInfo><publisher>The Royal Society of Chemistry.</publisher><dateIssued encoding="w3cdtf">1997</dateIssued><copyrightDate encoding="w3cdtf">1997</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType></physicalDescription><abstract>A rapid method for the determination of total and inorganic mercury inbiological tissues is presented using electrothermal vaporizationinductively coupled plasma mass spectrometry (ETV ICP–MS). Sampleswere solubilized using tetramethylammonium hydroxide. For thedetermination of total mercury sample aliquots (10 µl) are dried andvaporized into the plasma. For the determination of inorganic mercury,iodoacetic acid, sodium thiosulfate and acetic acid are added to thesample, cleaving the methylmercury from the tissue. Volatile methylmercuryiodide is formed and removed from the ETV as the sample dries, leavingonly inorganic mercury to be quantified. A limit of detection of 0.05µg g-1 in solid samples was obtained. NationalResearch Council of Canada reference materials DORM-2 (dogfish muscle),DOLT-2 (dogfish liver) and TORT-2 (lobster hepatopancreas) were used toassess the accuracy of the method.</abstract><relatedItem type="host"><titleInfo><title>Analyst</title></titleInfo><titleInfo type="abbreviated"><title>Analyst</title></titleInfo><genre type="journal">journal</genre><originInfo><publisher>The Royal Society of Chemistry.</publisher><dateIssued encoding="w3cdtf">1997</dateIssued></originInfo><identifier type="ISSN">0003-2654</identifier><identifier type="eISSN">1364-5528</identifier><identifier type="coden">ANALAO</identifier><identifier type="RSC sercode">AN</identifier><part><date>1997</date><detail type="volume"><caption>vol.</caption><number>122</number></detail><detail type="issue"><caption>no.</caption><number>8</number></detail><extent unit="pages"><start>751</start><end>754</end></extent></part></relatedItem><identifier type="istex">C55EA6472DB0549A789E8C8D7B5F588CBF6E089D</identifier><identifier type="DOI">10.1039/a701169e</identifier><identifier type="ms-id">a701169e</identifier><accessCondition type="use and reproduction" contentType="copyright">This journal is © The Royal Society of Chemistry</accessCondition><recordInfo><recordContentSource>RSC Journals</recordContentSource><recordOrigin>The Royal Society of Chemistry</recordOrigin></recordInfo></mods></metadata><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Wicri/Canada/explor/ParkinsonCanadaV1/Data/Istex/Corpus
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 000F90 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Istex/Corpus/biblio.hfd -nk 000F90 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Wicri/Canada
|area= ParkinsonCanadaV1
|flux= Istex
|étape= Corpus
|type= RBID
|clé= ISTEX:C55EA6472DB0549A789E8C8D7B5F588CBF6E089D
|texte= Determination of Inorganic and Total Mercury in Biological Tissuesby Electrothermal Vaporization Inductively Coupled Plasma MassSpectrometry
}}
| This area was generated with Dilib version V0.6.29. |  |