XRFX-ray Fluorescence

Spectrometry

Tom Murphy

XRFX-ray Fluorescence

Spectrometry

Tom Murphy

Qualitative ScreeningQualitative Screening

oror

Quantitative AnalysisQuantitative Analysis

Major Users of XRFMajor Users of XRF

GeoprospectingGeoprospecting

Alloy identification for safety and recyclingAlloy identification for safety and recycling

Remediation of lead in paint, metals in soilRemediation of lead in paint, metals in soil

Waste processing such as oil industryWaste processing such as oil industry

Forensics for legal analysisForensics for legal analysis

Consumer product analysis Consumer product analysis

Art and ArcheologyArt and Archeology

Industrial hygieneIndustrial hygiene

More powerful units More powerful units have radioactive have radioactive source, better source, better detection levels, detection levels, fewer interferences, fewer interferences, but are not usually but are not usually portable, and if portable, and if portable require portable require licensinglicensing

Hand-held XRF – Thermo Fisher Hand-held XRF – Thermo Fisher LoanLoan

-analysis in ~1 minute-analysis in ~1 minute -no extraction or other -no extraction or other

preparation of samplepreparation of sample -detects ppm concentrations of -detects ppm concentrations of

many metalsmany metals -non destructive-non destructive -no cross contamination or -no cross contamination or

fouling of sensorfouling of sensor

Sample Preparation/CalibrationSample Preparation/Calibration The sample matrix can be importantThe sample matrix can be important

The best cases really suitable for XRF analysis is The best cases really suitable for XRF analysis is the ‘atomic mixing level’ that is found in:the ‘atomic mixing level’ that is found in:

-All liquids (homogenous, one physical phase!)-All liquids (homogenous, one physical phase!) -Glass-Glass -Large crystals (used for “finger printing” gem -Large crystals (used for “finger printing” gem

origins)origins) -Most alloys-Most alloys

Mixing varies from impossible to Mixing varies from impossible to easyeasy-results vary from qualitative to -results vary from qualitative to quantitativequantitative

Oil in mineral Oil in mineral precipitant precipitant “impossible” to “impossible” to mixmix

Toxic skin Toxic skin cream can mix cream can mix but will but will separate, “Cao separate, “Cao Cap”Cap”

This fish needs This fish needs a better a better grinder but can grinder but can shoot shoot replicatesreplicates

InterferencesInterferences

A few elements interfere, arsenic and lead can A few elements interfere, arsenic and lead can effect each other, especially in low energy XRFseffect each other, especially in low energy XRFs-in samples with high lead, low arsenic results will -in samples with high lead, low arsenic results will be unreliable be unreliable

The Matrix can be an issue. If there is more than The Matrix can be an issue. If there is more than 10% water in a sample, it can either enhance or 10% water in a sample, it can either enhance or reduce the signal. Drying of the sample is reduce the signal. Drying of the sample is required.required.

Geoprospecting – Pathfinder analysisGeoprospecting – Pathfinder analysis-can’t see low concentrations of gold with XRF -can’t see low concentrations of gold with XRF but can find co-occurring elements like platinumbut can find co-occurring elements like platinum

JewelryJewelry-XRF quickly detects Pb, Hg, Cd -XRF quickly detects Pb, Hg, Cd etc.etc.-no sample preparation-no sample preparation

Found clasps with Found clasps with >40% Pb>40% Pb-ingestion has killed -ingestion has killed child in USAchild in USA-chronic toxicity -chronic toxicity more commonmore common

Lead Amulets/Curse Tablets -oral very dangerous, dermal less dangerous but not well documented, no sample preparation needed for XRF

Lead Amulets/Curse Tablets -oral very dangerous, dermal less dangerous but not well documented, no sample preparation needed for XRF

- Khmer Beads 45% - Khmer Beads 45% leadlead

ThaiThai CharmCharmRoman Roman Curse Curse TabletTablet

Other Consumer Other Consumer Products?Products?-cooking ware – old ceramics, poorly -cooking ware – old ceramics, poorly made metal waremade metal ware-Degree of extractability is important-Degree of extractability is important-Cooking acidic foods is more -Cooking acidic foods is more dangerousdangerous

-1/3-1/3rdrd of toys here are toxic by EU of toys here are toxic by EU regulationsregulations-a few times toys were removed from -a few times toys were removed from US StoresUS Stores

http://www.environment.gov.au/atmosphere/airquality/publications/ceramics.html-Lead glazes are most commonly used on earthenware, and on older bone china and porcelain.-If they are not properly prepared and fired, lead may leach (i.e. move from the glaze) into food stored in or on the ceramic ware.-Acidic foods will accelerate any leaching.-Ceramic ware with a corroded glaze is extremely dangerous.-Reheating coffee in an old mug in the microwave is a particularly risky thing to do.

Porcelain

Cooking Ware/ArcheologyCooking Ware/Archeology

Fall of Roman Empire – one theory of several

The presence of lead in the drinking water leached in from the water pipes, glazes on containers that came in contact with food and beverages, and food preparation techniques could have contributed to heavy metal poisoning.

It was also absorbed through the pores, since it was used in cosmetics.

Roman use of lead - as cosmetics, pipes, jewelry, - as cosmetics, pipes, jewelry, curse tablets, utensils and cooking pots, and, of curse tablets, utensils and cooking pots, and, of course course sapa and defrutum (wine boiled down in (wine boiled down in lead pots)lead pots)

Lead levels in bones from the Imperial Roman period had up to 30 mg/kg, which is three times higher than the level the WHO considers "very severe lead poisoning."

PaintPaint-lead in paint only found now in -lead in paint only found now in developing countriesdeveloping countries-essential and easy to mix can of paint-essential and easy to mix can of paint-to process dried paint on a surface -to process dried paint on a surface requires a more powerful XRF and requires a more powerful XRF and results are qualitativeresults are qualitative

Thai Paint with up to 5% Thai Paint with up to 5% leadlead

Problem?Problem?Small children put pieces Small children put pieces of old paint in their of old paint in their mouthsmouths..-price of renovation in -price of renovation in USAUSA

Previous Thermo CollaborationPrevious Thermo Collaboration -processed 675 skin -processed 675 skin

creamscreams -33% of samples -33% of samples

from beauty shops from beauty shops exceeded guidelines exceeded guidelines

-up to 3%Hg -up to 3%Hg

Murphy, T.P., S. Lim, S.P. Huong, K. Irvine, S. Bayen, B, Kelly and K. Wilson. 2012. Application of Handheld X-Ray Fluorescence Analyzers to Identify Mercury in Skin Whitening Creams in Cambodia. J Health Pollut. 3:21-31

The spiked recovery used The spiked recovery used DMSODMSO for good mixing. for good mixing.Quantitative for <2000 ppm HgQuantitative for <2000 ppm HgA reduced response for >2000 Hg but still useful.A reduced response for >2000 Hg but still useful.No certified reference materials available for this No certified reference materials available for this analysisanalysis. .

Skin Cream Validation -Skin Cream Validation -11

XRF Validation -2XRF Validation -2

Comparison of XRF and ICP-OES is fineComparison of XRF and ICP-OES is fineAgain, there were no certified reference materials for Again, there were no certified reference materials for skin creams.skin creams.There are several standard reference materials for There are several standard reference materials for fish etc. fish etc. When possible use certified reference materials.When possible use certified reference materials.

Product Name Apparent Source Total MercuryEucerin USA 23200Hua Tha Li China 19256Chang Chun China 18458Enjoy USA 13800Rojzy Jiali Vietnam 12528Yimei Yellow China 12014Guoyao China 11500Diamond Unknown 6147Hua Hin China 5454Qian Mei China 5110FC Cambodia 4979Malis Thailand 3552Lulanjena China 2990Oreal2 Unknown 2852Maly Thailand 1938Japanese Japan 1652SS-II Unknown 1410Britney Cambodia 1223Mlis Thailand 996

Mercury in Skin Creams in Phnom Mercury in Skin Creams in Phnom Penh ppmPenh ppm

Other cosmetics warrant analysis, Other cosmetics warrant analysis, managementmanagement-a blush containing 878 ppm of cadmium -a blush containing 878 ppm of cadmium -users all reacted to it and passed to their -users all reacted to it and passed to their friendsfriends

EnvironmentEnvironmentCanadaCanada

EnvironnementEnvironnementCanadaCanada

Waste disposal Waste disposal - PVC pipe has 7000 to 9000 ppm of lead- PVC pipe has 7000 to 9000 ppm of lead- Should not be burned without emission - Should not be burned without emission treatmenttreatment- Similar concerns about future oil and - Similar concerns about future oil and gas industry wastesgas industry wastes

Other Hydrocarbons, ThermalOther Hydrocarbons, ThermalThermal power plants to be fired by Khmer Thermal power plants to be fired by Khmer coalcoal-Sulphur, Arsenic, mercury content?-Sulphur, Arsenic, mercury content?-risk of acidification in soft water -risk of acidification in soft water environmentenvironment

-Mercury in natural gas?-Mercury in natural gas?

Khmer CoalKhmer Coal

Units ppm, Khmer coal formed in freshwater, low Units ppm, Khmer coal formed in freshwater, low SulphurSulphur

Source Mean Sulphur

Arsenic Mercury

Preah Vihear, Cam.

8419 30 ND

Springfield USA1

32000 9.8 0.12

Appalachian1

USA280002 351 0.211

Wyoming USA3 6300 2.6 0.13

Concerns with CoalConcerns with CoalThe Cardamom mountains are granitic and thus they The Cardamom mountains are granitic and thus they have little buffering capacity.have little buffering capacity.Burning coal produces sulphuric acid.Burning coal produces sulphuric acid.Without emission treatment acid rain from burning Without emission treatment acid rain from burning coal in such an environment could kill most plants and coal in such an environment could kill most plants and water lifewater lifeAt least the sulphur content is not highAt least the sulphur content is not high

Fish Anemia Study Fish Anemia Study

-Some fish have more iron content than beef -Some fish have more iron content than beef

and could be used to treat anemia. and could be used to treat anemia.

-so far <30 species processed for [Fe]-so far <30 species processed for [Fe]