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Application of Combustion/Trap/CVAFS Technique for Determination of Mercury in Various Environmental Samples

DOECAP Workshop September 17-20, 2012 Idaho Falls. Application of Combustion/Trap/CVAFS Technique for Determination of Mercury in Various Environmental Samples. Elizabeth A. Bennett and Lian Liang Cebam Analytical, Inc. The Technique. 1996: at 4 th ICMGP, Hamburg, Germany

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Application of Combustion/Trap/CVAFS Technique for Determination of Mercury in Various Environmental Samples

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  1. DOECAP Workshop September 17-20, 2012 Idaho Falls Application of Combustion/Trap/CVAFS Technique for Determination of Mercury in Various Environmental Samples Elizabeth A. Bennett and Lian Liang Cebam Analytical, Inc

  2. The Technique • 1996: at 4th ICMGP, Hamburg, Germany • Cebam was the firstto present the technique, specifically for determination of mercury in crude oil and related products using a Cebam built combustion/trap/CVAFS system • 1998:Commercial instruments become available • Using Commercial instruments, the following methods are published • EPA method 7473: 1998 • UOP Method 938-00: 2000 • ASTM D7622: 2010 • ASTM D7623: 2010

  3. Today,the Technique has become powerful for • Determination and speciation of mercury in variety of samples including liquids, solids and gases • Encompassing the whole environment! • Environmental • Industrial • Pharmaceutical • Agricultural Adopted from Elinger et al. 1988. Mercury Biogeochemical Cycling

  4. Advantages of the Technique Direct analysis without sample preparation • Eliminate positive and/or negative deviations from sample preparation • Simple handling and less time consuming • Reliable results for samples that would difficult to generate using wet digestion methods • All sample phases, including liquids, solids, and gases can be analyzed

  5. Principle of the Technique Analysis of Solid Samples B. Solids Sample Boat Analysis of Liquid Samples

  6. Limitations of the Technique • Critical requirement for sample homogeneity • Lack of standards, physically/chemically, similar to natural samples

  7. Ideal Samples Naturally homogeneous samples :  • Hydrocarbons, crude oils, refinery products, • Biological fluids, blood, urine, • Fish fillet • Micro-size biota • Drugs • Cosmetics • Various industrial materials

  8. Not Recommended Samples • Low level mercury water samples • 20 to 200 uL of 10 ng/L water contains only 0.2 to 2 pg Hg • Heterogeneous soil and sediment

  9. Determination of Hg inDOE MAPEP MaS26 Standard Calibration Curve

  10. Ensuring Reliable Results for Soil/Sediment • Soil/sediment samples must be well homogenized • Using standards physically/chemically similar to samples

  11. Mercury in Cosmetics Important source of human exposure to mercury • Risk not only for women • Everyone, due to volatility • Especially dangerous for children Cosmetic mercury may enter the human body through: • Skin adsorption • Air inhalation

  12. FDA Regulations • According to the Code of Federal Regulations, Title 21, Part 700 • Eye area cosmetics not exceeding 65 ppm • All other cosmetics must be below 1 ppm • only if it’s presence is UNAVOIDABLE under good conditions and manufacturing practices • State regulations: Minnesota first state to ban mercury in Cosmetic products in January of 2010

  13. Regulations, World Health Organization 2011

  14. Mercury in Medications Status: • No substitutes for species needs • No current legal limit exists for mercury in pharmaceuticals • EPA, safe exposure limit for methyl mercury • 0.1 µg/kg bodyweight/day

  15. Special Needs of Mercury in Drug/Biological Products (FDA)

  16. Samples Analyzed • 62 various cosmetics and medications • Produced from countries • China • France • Hong Kong • Korea • USA • How did foreign samples enter in the United States? • Brought to the US individually by travelers • Imported through US Customs

  17. Samples

  18. Samples

  19. Samples

  20. Samples

  21. Determination of Mercury inCosmeticsandMedications Nature of the samples: • Homogeneous • Oil containing • Difficult to analyze using wet digestion methods The best choice: • Combustion/trap/CVAFS

  22. Analytical Results, ppm

  23. Results and Discussion What we found from analyzed samples: • All samples produced in countries other than China were safe • All samples produced in China that went through U.S. Custom were safe • Most samples produced in China and brought to the U.S. by individuals were safe, however some products were extremely high in mercury

  24. Results of Two Cream Samples with High Level Hg *: 21 CFR Part 700

  25. Skin Lightening Creams • Similar high mercury creams from East Asia • Official warning about these products from the FDA • Most of them contain mercury higher than the cream we analyzed.

  26. Risk Assessment onElemental Hg Evaporation from Cream • We found, 1 g cream on the face can evaporate 200 µgof elemental mercury (Hg0)into the air overnight. To determine evaporation rates, 5 mg cream is placed on tissue in bubbler and left for different periods of time. Evaporated mercury is trapped and analyzed as a function of time.

  27. How Much is200 µg Hg? • EPA drinking water limit for inorganic mercury (Hg2+) is: Maximum Contaminant Level (MCL) = 0.002 mg/L (2 µg/L) 200 µg Hg corresponds to drinking 100 L water at 2µg/L level! Generally drinking waters contain Hg < 0.01 µg/L! 1 Liter 100 Liters

  28. Mercury Pathways Inorganic Mercury, Hg2+ Elemental Mercury, Hg0 When inhalation and/or absorption occurs following facial application, Hg0enters the lungs and crosses into bloodstream When ingested, 95% of Hg2+is excreted out of the body In the blood, it can cross the blood-brain barrier and cause nervous system damage Mercury restrictions are only for inorganic mercury!

  29. Mercury as aGlobal Pollutant • How can we disregardHg0from creams as an environmental pollutant? • Mercury is volatile and thus a global pollutant, pollution from one area affects everyone, regardless of source

  30. Important to Understand Dangers of Mercury • How to Protect Yourself • What to do if you believe you have been exposed • Tracking Skin Products Containing Mercury • Find information at http://www.fda.gov/ForConsumers/ConsumerUpdates/ucm294849.htm

  31. ResultsofTwo Medication Samples withHigh Level Hg Both medications work by affecting the nervous system directly and are very effective.

  32. SignsandSymptomsofMercury Poisoning Memory problems Depression Numbness and tingling in hands, feet or around mouth • Irritability • Shyness • Tremors • Changes in vision or hearing Source: Agency for Toxic Substances and Disease Registry

  33. Who Should be Responsible? • Cosmetics as a source of mercury impact the whole environment. • Which government agency should be responsible for cosmetics? • EPA? • DOE? • FDA?

  34. Continued Research • Cebamsponsored this research, and intends to continue • Youare encouraged to contribute by sending samples to Cebam for analysis • Free analytical servicesare done tohelp keep You healthy and happy This is our goal!

  35. References Liang L., Horvat M., Danilchik P., 1996, A novel analytical method for determination of picogram levels of mercury in petroleum based products, The Science of the Total Environment, 187, 57-64 Liang, L., Horvat, M., Fajon, V., Prosenc, N., Li, H., Pang, P., 2003, Comparison of Improved Combustion/Trap Technique to Wet Extraction Methods for Determination of Mercury in Crude Oil and Related Products by Atomic Fluorescence, Energy & Fuels, 17, 5, 1175-1179 Liang, L., Horvat, M., Li, H.,. Pang, P., 2003, Determination of Mercury in minerals by Combustion/Trap/Atomic Fluorescence Spectrometry, JAAS, 18, 1383-1385 Liang, L., Lazoff, S., Swain, E., Gilkeson, J., Horvat, M., 2000, Determination of Mercury in crude oil by in-situ thermal decomposition using a simple lab built system, Fresenius J Anal Chem, 367: 8-11 “Mercury in Drug and Biologic Products” FDA.gov Food and Drug Administration, 13 Jun. 2006 Web 10 Aug. 2012 http://www.fda.gov/RegulatoryInformation/Legislation/FederalFoodDrugandCosmeticActFDCAct/SignificantAmendmentstotheFDCAct/FDAMA/ucm100218.htm “Mercury in Skin Lightening Creams.” WHO.int/en/ World Health Organization, 2011. Web 10 Aug 2012. http://www.who.int/ipcs/assessment/public_health/mercury_flyer.pdf "Mercury Poisoning Linked to Skin Products." FDA.gov. U.S. Food and Drug Administration, 6 Mar. 2012. Web. 21 Aug. 2012. <http://www.fda.gov/ForConsumers/ConsumerUpdates/ucm294849.htm>. “Methyl Mercury (MeHg).” EPA.gov Environmental Protection Agency 31 Jan. 1987 Web 21 Aug. 2012 http://www.epa.gov/iris/subst/0073.htm "Public Health Statement for Mercury." Center for Disease Control. Agency for Toxic Substances & Disease Registry, 3 Mar. 2011. Web. 21 Aug. 2012. <• http://www.atsdr.cdc.gov/PHS/PHS.asp?id=112&tid=24>. Requirements for specific cosmetic products, 21 CFR, pt.700 (2004). "Skin-Lightening Products Found to Contain Mercury." Minnesota Department of Health. Minnesota Department of Health, 9 Mar. 2012. Web. 21 Aug. 2012. <http://www.health.state.mn.us/topics/skin/>.

  36. Thank You! Any Questions?

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