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New certified reference material supporting mercury speciation analysis of blood


Environmental and occupational exposure to toxic metals is often assessed through whole blood or urine analysis. While mercury measurements in urine are commonly used to evaluate exposure to inorganic mercury, whole blood is used to evaluate exposure to the
highly toxic organomercury compounds (i.e. methylmercury and
ethylmercury). Although methylmercury mainly resulting from the exposure through seafood is the predominant form, inorganic mercury is also present in blood. Ethylmercury has been of interest due to exposure from thimerosal (sodium ethylmercurithiosalicylate) which had been added (0.003–0.01%) to several vaccines for preservative and antimicrobial purposes and is being studied in the proposed link between autism and Hg exposure (see the EVISA News related to Thimerosal below).

Due to advances in measurement technology, clinical laboratories that perform whole blood analyses are moving away from single-element methods towards methods capable of measuring panels of toxic elements and species. The driving force behind such development is the fact that toxic effects of elements such as mercury are dependent on its chemical form and total element concentration measurements do not necessarily provide sufficient information for toxicity and bioavailability assessments.

The new material:
The National Institute of Standards and Technology (NIST) is supporting the development of analytical methodology and improvement of  quality assurance of clinical measurements of toxic metals in blood by providing values for inorganic arsenic (As), cadmium (Cd), total mercury (THg), inorganic mercury (iHg), methylmercury (MeHg) and ethylmercury (EtHg) in two levels of the existing Standard Reference Material (SRM) 955c Toxic Elements in Caprine Blood.  SRM 955c will serve as a replacement for SRM 966 Toxic Elements in Bovine Blood.

NIST issued SRM 966 Toxic Elements in Bovine Blood in 2000. SRM 966 was originally produced at the Centers for Disease Control and Prevention (CDC), and comprises a two level material containing Cd, Pb, THg, iHg, and MeHg. As a consequence of the demand for this reference material, the stock of SRM 966 is rapidly running out. The CDC no longer has the capability to produce a renewal batch of this SRM. An alternative replacement material is SRM 955c Toxic Elements in Caprine Blood, which was issued as Led in Caprine Blood by NIST in 2007 with support from the CDC. SRM 955c is heavily relied upon for quality assurance of clinical blood Pb measurements, and is certified for Pb at four concentration levels: a base level and three progressively elevated levels.  When SRM 955c was produced at the Wadsworth Center, New York State Department of Health (NYDOH), it was also spiked with As, Cd, iHg, MeHg, and EtHg.

New ICP-MS-based technologies are being utilized to measure As and Hg species in SRM 955c, Level 1 and Level 3. The certification of methylmercury, ethylmercury, and inorganic mercury was carried out by triple spike speciated isotope dilution inductively coupled plasma mass spectrometry (TS-SID-GC/ICP-MS) and represents the first whole blood material certified for three mercury species. The certified values (±expanded uncertainty) of methylmercury, ethylmercury, inorganic mercury and total mercury in SRM 955c are 4.5 ± 1.0 µg L-1, 5.1 ± 0.5 µg L-1, 9.0 ± 1.3 µg L-1, and 17.8 ± 1.6 µg L-1 respectively.

The cited study

W. Clay. Davis, Stephen E. Long, Measurements of methylmercury, ethylmercury, and inorganic mercury species in a whole blood standard reference material: SRM 955c—Toxic Elements in Caprine Blood, J. Anal. At. Spectrom, 26/2 (2011) 431-435. DOI: 10.1039/c0ja00175a

Related studies (mercury speciation in blood)

Jairo L. Rodrigues, Samuel S. de Souza, Vanessa C. de Oliveira Souza, Fernando Barbosa Jr., Methylmercury and inorganic mercury determination in blood by using liquid chromatography with inductively coupled plasma mass spectrometry and a fast sample preparation procedure, Talanta, 80 (2010) 1158–1163. doi: 10.1016/j.talanta.2009.09.001

J. Hippler, H.W. Hoppe, F. Mosel, A.W. Rettenmeier, A.V. Hirner, Comparative determination of methyl mercury in whole blood samples using GC–ICP-MS and GC–MS techniques, J. Chromatogr. B, 877 (2009) 2465–2470.  doi:10.1016/j.jchromb.2009.06.004

Stefan Trümpler, Sascha Nowak, Björn Meermann, Gerhard A. Wiesmüller, Wolfgang Buscher, Michael Sperling, Uwe Karst, Detoxification of mercury species—an in vitro study with antidotes in human whole blood, Anal. Bioanal. Chem., 395 (2009) 1929–1935. DOI: 10.1007/s00216-009-3105-1

George A. Zachariadis, Dimitra C. Kapsimali, Effect of sample matrix on sensitivity of mercury and methylmercury quantitation in human urine, saliva, and serum using GC-MS, J. Sep. Sci., 31 (2008) 3884 – 3893. DOI 10.1002/jssc.200800345

S. Halbach, S. Vogt, W. Köhler, N. Felgenhauer, G. Welzl, L. Kremers, T. Zilker, D. Melchart, Blood and urine mercury levels in adult amalgam patients of a randomized controlled trial: Interaction of Hg species in erythrocytes, Environ. Res., 107/1 (2008) 69-78. doi: 10.1016/j.envres.2007.07.005

Yan Li, Xiu-Ping Yan, Chen Chen, Yun-Long Xia, Yan Jiang, Human Serum Albumin-Mercurial Species Interactions, J. Proteome Res., 6/6 (2007) 2277-2286. doi: 10.1021/pr0700403

Darija Gibicar, Martina Logar, Nuša Horvat, Andreja Marn-Pernat,  Rafael Ponikvar, Milena Horvat, Simultaneous determination of trace levels of ethylmercury and methylmercury in biological samples and vaccines using sodium tetra(n-propyl)borate as derivatizing agent, Anal. Bioanal. Chem., 388 (2007) 329–340. DOI: 10.1007/s00216-007-1208-0

Douglas C. Baxter, Ilia Rodushkin, Emma Engström, Dennis Klockare, Hans Waara, Methylmercury Measurement in Whole Blood by Isotope-Dilution GC-ICPMS with 2 Sample Preparation Methods, Clinical Chem., 53/1 (2007) 111–116. doi: 10.1373/clinchem.2007.072520

Marika Berglund, Birger Lind, Karolin Ask Björnberg, Brita Palm, Östen Einarsson, Marie Vahter, Inter-individual variations of human mercury exposure biomarkers: a cross-sectional assessment, Environ. Health, 4 (2005) 20.  doi:10.1186/1476-069X-4-20

Ingvar A. Bergdahl, Andrejs Schütz, Margareta Ahlqwist, Calle Bengtsson, Leif Lapidus,Lauren Lissner, Bodil Hultén, Methylmercury and Inorganic Mercury in Serum—Correlation to Fish Consumption and Dental Amalgam in a Cohort of Women Born in 1922, Environ. Res. , A 77 (1998) 20-24. doi:10.1006/enrs.1997.3820

Lian Liang, Nicolas S. Bloom, Milena Horvat, Simultaneous determination of mercury speciation in biological materials by GC/CVAFs after ethylation and room-temperature precollection, Clin.  Chem., 40/4 (1994) 602-7.

P. Brunmark, G. Skarpin, A. Schütz, Determination of methylmercury in human blood using capillary gas chromatography and selected-ion monitoring, J. Chromatogr., 573 (1992) 35-41. doi: 0.1016/0378-4347(92)80471-2

Related Information

NIST Project description: Development of SRM 955c Toxic Elements in Caprine Blood
NIST: Development of Reference Methods and Reference Materials for Clinical Diagnostic Markers
NEMC 2009 Conference Presentation: Patrick Parsons, Christopher Palmer
Mary Verostek and Ciaran Geraghty - Preparation of a new Caprine Blood
Reference Material for Mercury Speciation Studies: NIST SRM 955c

Related EVISA Resources

Brief summary: GC-ICP-MS: A very sensitive hyphenated system for speciation analysis
Brief summary: Speciation Analysis - Striving for Quality
Brief summary: Certified Reference Materials for Speciation Analysis
Link database: Toxicity of Organic mercury compounds
Brief summary: Speciation and Toxicity
Material Database: SRM 955c - Toxic Metals in Caprine Blood / Level 3
Material Database: Materials certified for methylmercury
Link page: All about CRMs

Related News (about CRMs for speciation analysis)

February 3, 2009: New Reference Material for Hexavalent Chromium in Contaminated Soil
November 15, 2005: NIST/EPA/NJ DEP embark on the preparation of a soil reference materials for chromium speciation
August 2, 2005: New CRM for Selenomethionine in yeast developed by NRC Canada is now on the market
May 6, 2004: Reference materials producers launch new European initiative

Related EVISA News (about mercury species)

September 25, 2010: The European Chemical Agency (ECHA) calls for comments on reports proposing restrictions on mercury and phenylmercury
September 17, 2010: Occurrence of monoethylmercury in the Florida Everglades verified
September 16, 2010: Rice is the Major Pathway for Methylmercury Exposure in Inland China
August 16, 2010: Methylmercury: What have we learned from Minamata Bay?
June 28, 2010: New Study Examines Why Mercury is More Dangerous in Oceans
October 30, 2009: New quick test for methylmercury
September 24, 2009: Huge field experiment for assessing human ethylmercury risk starting in October
September 8, 2009: Inorganic Mercury Level in US Women increases
August 21, 2009: USGS Study Reveals Mercury Contamination in Fish Nationwide
July 15, 2009: New Study Finds: Thimerosal Induces Autism-like Neurotoxicity
June 16, 2009: 'Surprisingly High Levels' of Methylmercury Contamination found in Groundwater
May 3, 2009: Ocean mercury on the rise
February 11, 2009: Mercury in Fish is a Global Health Concern
December 12, 2008: New study investigates the interaction of thimerosal with proteins
October 30, 2008: Precautionary approach to methylmercury needed
July 10, 2008: Methyl mercury metabolism in man influenced by genetic factors
May 14, 2008: Autism risk linked to distance from power plants and other mercury-releasing sources
January 12, 2008: New California study concludes that thimerosal seems not to be the major cause for autism
October 9, 2007: New CDC study on the effect of thimerosal exposure on neuropsychological characteristics of children is fueling the debate about the origin of autism
May 3, 2007:  More nutritious food helps reduce methylmercury in the aquatic food chain
March 11, 2007: Methylmercury contamination of fish warrants worldwide public warning
February 18, 2007: New research results suggest that mercury hotspots in the northeastern US are home made
October 8, 2006: Linking atmospheric mercury to methylmercury in fish
September 23, 2006: Report Finds Mercury Contamination Permeates Wildlife Systems
August 16, 2006: Mercury pollution threatens health worldwide, scientists say
June 16, 2006: Sulfur fuels the methylation of mercury
June 8, 2006: Methylmercury in fish: Can you cook it out ?
May 3, 2006: Texas Study Relates Autism to Environmental Mercury
March 24, 2006: Mercury Containing Preservative Alters Immune Function
February 17, 2006: Study shows link between clear lakes and methylmercury contamination in fish
February 9, 2006: Study show high levels of mercury in women related to fish consumption
September 13, 2005: Regulating Mercury Emissions from Power Plants: Will It Protect Our Health?
August 28, 2005: Is methyl mercury limiting the delight of seafood ? - To answer this question is a challenge for elemental speciation analysis
April 27, 2005: New results about toxicity of thimerosal
April 3, 2005: Dissension on the best way to fight mercury pollution
March 20, 2005: New results on the distribution of mercury in the USA is fueling the discussion on the necessity of the reduction of its emission
February 11, 2005: New findings about Thimerosal Neurotoxicity
November 23, 2004: Is the methylmercury paradox real ?
April 27, 2004: New kind of mercury found in fish
April 27, 2004: FDA/EPA recommends pregnant women to restrict their fish consumption because of methylmercury content

last time modified: November 23, 2010


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