Limitations of Handheld XRF Instruments as Quantitative Tools for Analyzing Heavy Metal Pesticides on Organic Art ObjectsIARC Symposium Native Collections and Pesticides: Testing, Analysis and Mediationzge Genay stn28 May 2009
**IntroductionHandheld X-Ray Florescence instruments are used to test for heavy metal pesticides in ethnographic objects in museums. These objects are made up of organic materials varying in thickness, density, surface features, and shapes. These variables will affect the readings along with the errors inherent in the handheld analyzers.
**SummaryBrief info and history about pesticides and their detection (slides 3-11)X-Ray Fluorescence techniqueXRF instrumentsLimitations of the XRF instruments - experimental demonstrations (slides 22-41)Documentation done at the Southwest Museum
**What are pesticides?Museums provide food (organic objects) and a suitable habitat (quite, dark, and comfortable place) for pests.Pesticides, fungicides, herbicides, and other substances are chemicals that have been used to prevent, destroy, or repel pests in order to preserve museum collectionsPesticides applied in the past are now known to be toxic to humans
**What are pesticides?Poisons or toxins are used to kill pests by entering the organisms through their:Respiratory systems (inhalation)Digestive systems (mouth)Dermal contact (skin)come in many names (trade names, chemical names, synonyms)
**What are these toxic pesticides applied in the past?Types of pesticides used in the museums:Inorganic pesticides - contain heavy metals that are highly toxic to any living creature. Arsenic, lead, and mercury containing ones are common. Due to their physical and chemical nature they are persistentOther type of pesticides - are usually volatile organic chemical compositions, yet poisonous by-products may not readily be decomposedSometimes the mixture of the two
*The history of pesticide usePesticides use by field collectors and museum personnel on natural history collections and ethnological artifacts was common from the late 19th century to the mid-20th century.Arsenical soaps and mercuric chloride were used in taxidermy collections, which was adapted later to natural history and ethnographic collections
*The history of pesticide useAlong with inorganic pesticides some toxic organic pesticides such as dichloro-dihpenyl-trichloroethane (DDT), dichlorvos (DDVP), and mothballs (paradichlorobenzene or naphthalene) have been used. Applications involved fumigation, dusting, spraying, and sometimes shoveling chemical concoctions onto artifacts
*The history of pesticide use1980 arsenic containing pesticides are restricted, but the utilization was ceased in the late 80s.Mercuric chloride restricted in the 1970s and ceased in the late 80s.
*The pesticide issueNAGPRA objects1995 Hopi Friends at Harvard Peabody Museum contaminated with AsHandling the sacred objects extensively during initial cleaning, repair, and preparation for storage, almost daily during their long-term careStorage places used by most family members newborns to elders, were underground ceremonial chambers that were overcrowded and had no ventilation along with houses where dry food was kept and daily activities took place.
*The pesticide issueNAGPRA (January 1996 addition 10.10(e) t) that gives the museums the responsibility to report on pesticides treatment histories. SeminarsIt was required that a proper documentation to inform tribes during repatriation process is prepared by the museums because there was no recognition of the educational needs of tribes who would need to interpret the technical information (Lomaomvaya).
*The pesticide issueIt was decided toxicologists and museum health professionals should be involved in to decide the levels of toxic inorganics (Pb, As, and Hg) found in these objects.Nature of the pesticidePlace of the pesticide within the artifactAmount of the pesticide in/on the artifact
*Detection and analysis of inorganic pesticidesNo sampling requiredVisual inspection (qualitative)Spot tests (qualitative)Portable XRF analysis (semi-quantitative)Sampling requiredICP-AES (quantitative)AAS (quantitative)
*X-Ray Florescence TechniqueOffers elemental analysis of materialsElements with an atomic number of 15 (phosphorus) and higher can be identified with air path XRF instrumentsFor lighter elements a vacuum can be used.
*X-Ray Florescence TechniquenucleuselectronsBohr model showing the structure of a Titanium atomAtom: basic unit of matter consisting of:NucleusProtons (+ charged particles) and neutrons (neutral)Electron cloud (- charged particles)
*X-Ray Florescence TechniquenucleuselectronsXRF source(tube or radioisotope)Bohr model showing the structure of a Titanium atomX-rays emitted by the electrons moving between the shells
*How portable XRF instruments workDetectorX-ray beams generated by the tube or isotope sourceX-ray beams emitted by the excitation of an electron in the materialSource Target material Analyzer
*How portable XRF instruments workResults are reported as:Tabulated numerical results showing the amount of metals foundSpectra showing each elements peak count of the characteristic energy levels
*Handheld XRF analyzers have advantages and disadvantagesSome advantages are.
*Detection and analysis with handheld XRF instrumentsCost-efficientFast
*Detection and analysis with handheld XRF instrumentsIn-situ analysis
*Detection and analysis with handheld XRF instrumentsEasy to use
*Limiting factors in quantitative analysis of organic objectsSome disadvantages of the portable XRF instruments are due to:ObjectInstrumentOr both
*Limiting factors in quantitative analysis of organic objectsSome disadvantages are:Relative humidity and/or temperature affect both the analyzer and the substrateDensity and geometry of the substrate, instruments calibrated for the soil and scrap metal industry.Interferences caused by elements other than the metal of interest (by absorption, scattering, or enhancing the fluorescence)Detection limits of the element of interestElements in question are not homogenously distributed in or on the artifact
*Limiting factors in quantitative analysis of organic objectsLets investigate these limiting factorsDensity and geometry (thickness and surface geometry) of the substrateInterferences caused by elements other than the metal of interest (by absorption, scattering, or enhancing the fluorescence)Relative humidity and/or temperature
*Experimental designThicknessEpoxy samplesPaper samplesWool samplesA known amount of copper oxide embedded in Devcon epoxy and cut in different thicknesses
*Experimental designThicknessEpoxy samplesPaper samplesWool samplesBlotter paper sprayed with a known quantity of CuSO4 solution
*Experimental designThicknessEpoxy samplesPaper samplesWool samplesWool fabric samples sprayed with the same amount of CuSO4 solution
*Experimental designGeometry
*Experimental designGeometry
*Experimental designDistance
*
*Experimental designInterferences by other elements
*Experimental designRelative HumiditySamples are conditioned at 50-55% RH and then 68-70% RHPaper samplesWool samples
*Results-Thickness
*Results-ThicknessVarying thicknesses of epoxy embedded with CuOVarying thicknesses of paper embedded with CuSO4
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