X-ray Fluorescence Spectrometry
Major Users of XRF
Alloy identification for safety and recycling
Remediation of lead in paint, metals in soil
Waste processing such as oil industry
Forensics for legal analysis
Consumer product analysis
Art and Archeology
More powerful units
source, better detection
interferences, but are
not usually portable,
and if portable require
Hand-held XRF – Thermo Fisher
-analysis in ~1 minute
-no extraction or other preparation of
-detects ppm concentrations of many
-no cross contamination or fouling of
The sample matrix can be important
The best cases really suitable for XRF analysis is the
‘atomic mixing level’ that is found in:
-All liquids (homogenous, one physical phase!)
-Large crystals (used for “finger printing” gem origins)
Mixing varies from impossible to easy
-results vary from qualitative to
Oil in mineral Toxic skin cream This fish needs a
precipitant can mix but will better grinder but
“impossible” to mix separate, “Cao can shoot
A few elements interfere, arsenic and lead can effect
each other, especially in low energy XRFs
-in samples with high lead, low arsenic results will be
The Matrix can be an issue. If there is more than 10%
water in a sample, it can either enhance or reduce the
signal. Drying of the sample is required.
Geoprospecting – Pathfinder analysis
-can’t see low concentrations of gold with XRF but can
find co-occurring elements like platinum
-XRF quickly detects Pb, Hg, Cd etc.
-no sample preparation
Found clasps with
-ingestion has killed
child in USA
-chronic toxicity more
Lead Amulets/Curse Tablets -
oral very dangerous, dermal less dangerous but not well
documented, no sample preparation needed for XRF
Thai Charm - Khmer Beads 45% lead Curse
Other Consumer Products?
-cooking ware – old ceramics, poorly made
-Degree of extractability is important
-Cooking acidic foods is more dangerous
-1/3rd of toys here are toxic by EU regulations
-a few times toys were removed from US
-Lead glazes are most commonly used on earthenware, and on older bone china
-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.
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
It was also absorbed through the pores, since
it was used in cosmetics.
Roman use of lead - as cosmetics, pipes, jewelry, curse
tablets, utensils and cooking pots, and, of course sapa
and defrutum (wine boiled down in 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."
-lead in paint only found now in developing
-essential and easy to mix can of paint
-to process dried paint on a surface requires
a more powerful XRF and results are
Thai Paint with up to 5% lead
Small children put pieces of
old paint in their mouths.
-price of renovation in USA
Previous Thermo Collaboration
-processed 675 skin
-33% of samples from
beauty shops exceeded
-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
Skin Cream Validation -1
The spiked recovery used DMSO for good mixing.
Quantitative for <2000 ppm Hg
A reduced response for >2000 Hg but still useful.
No certified reference materials available for this analysis.
XRF Validation -2
Comparison of XRF and ICP-OES is fine
Again, there were no certified reference materials for skin
There are several standard reference materials for fish etc.
When possible use certified reference materials.
Mercury in Skin Creams in Phnom Penh ppm
Product Name Apparent Source Total Mercury
Eucerin USA 23200
Hua Tha Li China 19256
Chang Chun China 18458
Enjoy USA 13800
Rojzy Jiali Vietnam 12528
Yimei Yellow China 12014
Guoyao China 11500
Diamond Unknown 6147
Hua Hin China 5454
Qian Mei China 5110
FC Cambodia 4979
Malis Thailand 3552
Lulanjena China 2990
Oreal2 Unknown 2852
Maly Thailand 1938
Japanese Japan 1652
SS-II Unknown 1410
Britney Cambodia 1223
Mlis Thailand 996
Other cosmetics warrant analysis, management
-a blush containing 878 ppm of cadmium
-users all reacted to it and passed to their friends
- PVC pipe has 7000 to 9000 ppm of lead
- Should not be burned without emission
- Similar concerns about future oil and gas
Other Hydrocarbons, Thermal
Thermal power plants to be fired by Khmer coal
-Sulphur, Arsenic, mercury content?
-risk of acidification in soft water environment
-Mercury in natural gas?
Source Mean Sulphur Arsenic Mercury
Preah Vihear, 8419 30 ND
Springfield USA1 32000 9.8 0.12
Appalachian1 USA 280002 351 0.211
Wyoming USA3 6300 2.6 0.13
Units ppm, Khmer coal formed in freshwater, low Sulphur
Concerns with Coal
The Cardamom mountains are granitic and thus they have little
Burning coal produces sulphuric acid.
Without emission treatment acid rain from burning coal in such
an environment could kill most plants and water life
At least the sulphur content is not high
Fish Anemia Study
-Some fish have more iron content than beef and
could be used to treat anemia.
-so far <30 species processed for [Fe]