Gold fingerprinting

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Gold fingerprinting is a method of identifying an item made of gold based on the impurities or trace elements it contains. [1]

Contents

Importance

This technique has been used to lay claim to stolen or relocated gold, including gold that has undergone salting can be identified by its multiple sources. Gold fingerprinting also assists in understanding the origins of gold artifacts. [2]

This method is used to characterize gold or a gold-containing item by its trace elements, a.k.a. fingerprinting the sample by mineralizing event and to the particular mine or bullion source. Elements that measure above the detection limits include : Ag, Cu, Ti, Fe, Pt, Pd, Mn, Cr, Ni, Sn, Hg, Pb, As and Te can be used for gold fingerprinting and geochemical characterization. [3] In order for this technique to be used to identify the origins of the gold in question a database made from fingerprinting samples of gold from mines and bullion sources is required. [1]

Method

Electron microprobe (EMP), [4] Synchrotron micro-XRF (SR-M-XRF), [4] Time-of-flight secondary ion mass spectrometry (TOF-SIMS), [4] Laser induced breakdown spectroscopy (LIBS), [5] Atomic emission spectrometry, [2] x-ray fluorescence spectrometry with higher energy synchrotron radiation (SR-XFS) [6] and Laser ablation-Inductively coupled plasma mass spectrometry (LA-ICP-MS) [5] are all methods of gold fingerprinting.

The most common method is LA-ICP-MS primarily because it is quasi-nondestructive, allowing for the preservation of the samples and convenient as samples require little to no preparation. [5] Laser ablation allows for high spatial resolution sampling [2] while the inductively coupled plasma mass spectrometry provides high sensitivity [2] to identify extremely small amounts of trace elements within the gold. This method can also be conducted outside of a lab with the assistance of a portable device that uses a diode pumped solid state laser and fiber-optics, [5] making fingerprinting more convenient as it eliminates the need for transfer of gold to a specific lab.

Advantages of LA-ICP-MS include reduced sample preparation, no sample size requirements, reduced spectral interference and increased sample throughput. [7] Over the past 32 years, LA-ICP-MS has been used for archaeological, biological and forensic purposes. For example a group of gold foil fragments dating back to the 5th Century B.C.E. were analysized by LA-ICP-MS uncovering information on their manufacturing process, function and relationship to one another. [8]

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Complications

LA-ICP-MS function optimally with gold particles greater than 60 μm in diameter to avoid any contamination during measurements. Although LA-ICP-MS has a lower detection limit, its overall precision was lower than other analysis techniques for trace element concentrations such as field emission-electron probe microanalysis (FE-EPMA) and synchrotron micro X-ray fluorescence spectroscopy (SR-l-XRF). [3]

Due to the small size of gold (<5μm-250μm) small fragments of minerals need to be separated from the gold before analysis can occur. [4]

Gold fingerprinting has limitations including elemental fractionation (the non-sample related analyte) and calibration requires matrix-matched standards. [7]

A few other problems exist that limit actual sourcing or provencancing of gold in relation to manufactured art objects. These problems include: a lack of an extensive database of elemental profiles in gold ores, the natural differences that coexist in ore geology and the difficulties of accurately analyzing trace elements. Also, trading, looting and re-melting of so called “precious” metal objects add to the problem of sourcing. [8]

See also

Related Research Articles

Inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) is a type of mass spectrometry that uses an inductively coupled plasma to ionize the sample. It atomizes the sample and creates atomic and small polyatomic ions, which are then detected. It is known and used for its ability to detect metals and several non-metals in liquid samples at very low concentrations. It can detect different isotopes of the same element, which makes it a versatile tool in isotopic labeling.

Atomic spectroscopy is the study of the electromagnetic radiation absorbed and emitted by atoms. Since unique elements have characteristic (signature) spectra, atomic spectroscopy, specifically the electromagnetic spectrum or mass spectrum, is applied for determination of elemental compositions. It can be divided by atomization source or by the type of spectroscopy used. In the latter case, the main division is between optical and mass spectrometry. Mass spectrometry generally gives significantly better analytical performance, but is also significantly more complex. This complexity translates into higher purchase costs, higher operational costs, more operator training, and a greater number of components that can potentially fail. Because optical spectroscopy is often less expensive and has performance adequate for many tasks, it is far more common Atomic absorption spectrometers are one of the most commonly sold and used analytical devices.

Inductively coupled plasma

An inductively coupled plasma (ICP) or transformer coupled plasma (TCP) is a type of plasma source in which the energy is supplied by electric currents which are produced by electromagnetic induction, that is, by time-varying magnetic fields.

Elemental analysis Process of analytical chemistry

Elemental analysis is a process where a sample of some material is analyzed for its elemental and sometimes isotopic composition. Elemental analysis can be qualitative, and it can be quantitative. Elemental analysis falls within the ambit of analytical chemistry, the set of instruments involved in deciphering the chemical nature of our world.

Laser ablation

Laser ablation or photoablation is the process of removing material from a solid surface by irradiating it with a laser beam. At low laser flux, the material is heated by the absorbed laser energy and evaporates or sublimates. At high laser flux, the material is typically converted to a plasma. Usually, laser ablation refers to removing material with a pulsed laser, but it is possible to ablate material with a continuous wave laser beam if the laser intensity is high enough. While relatively long laser pulses can heat and thermally alter or damage the processed material, ultrashort laser pulses cause only minimal material damage during processing due to the ultrashort light-matter interaction and are therefore also suitable for micromaterial processing. Excimer lasers of deep ultra-violet light are mainly used in photoablation; the wavelength of laser used in photoablation is approximately 200 nm.

Vapour phase decomposition (VPD) is a method used in the semiconductor industry to improve the sensitivity of total-reflection x-ray fluorescence spectroscopy by changing the contaminant from a thin layer to a granular residue. When using granular residue the limits of detection are improved because of a more intense fluorescence signal in angles smaller than the isokinetic angle.

Inductively coupled plasma atomic emission spectroscopy

Inductively coupled plasma atomic emission spectroscopy (ICP-AES), also referred to as inductively coupled plasma optical emission spectrometry (ICP-OES), is an analytical technique used for the detection of chemical elements. It is a type of emission spectroscopy that uses the inductively coupled plasma to produce excited atoms and ions that emit electromagnetic radiation at wavelengths characteristic of a particular element. The plasma is a high temperature source of ionised source gas. The plasma is sustained and maintained by inductive coupling from cooled electrical coils at megahertz frequencies. The source temperature is in the range from 6000 to 10,000 K. The intensity of the emissions from various wavelengths of light are proportional to the concentrations of the elements within the sample.

Spark ionization Ionization method to produce gas phase ions from a solid sample

Spark ionization is a method used to produce gas phase ions from a solid sample. The prepared solid sample is vaporized and partially ionized by an intermittent discharge or spark. This technique is primarily used in the field of mass spectrometry. When incorporated with a mass spectrometer the complete instrument is referred to as a spark ionization mass spectrometer or as a spark source mass spectrometer (SSMS).

Velmer A. Fassel was an American chemist who developed the inductively coupled plasma (ICP) and demonstrated its use as ion source for mass spectrometry.

Atomic emission spectroscopy Analytical method using radiation to identify chemical elements in a sample

Atomic emission spectroscopy (AES) is a method of chemical analysis that uses the intensity of light emitted from a flame, plasma, arc, or spark at a particular wavelength to determine the quantity of an element in a sample. The wavelength of the atomic spectral line in the emission spectrum gives the identity of the element while the intensity of the emitted light is proportional to the number of atoms of the element. The sample may be excited by various methods.

Spectroscopy is a trade magazine published since 1985. Spectroscopy has an editorial goal to promote and support the use of spectroscopic instrumentation in applied research, environmental testing, quality control, and the life sciences.

Single particle analysis

Single particle analysis is a group of related computerized image processing techniques used to analyze images from transmission electron microscopy (TEM). These methods were developed to improve and extend the information obtainable from TEM images of particulate samples, typically proteins or other large biological entities such as viruses. Individual images of stained or unstained particles are very noisy, and so hard to interpret. Combining several digitized images of similar particles together gives an image with stronger and more easily interpretable features. An extension of this technique uses single particle methods to build up a three-dimensional reconstruction of the particle. Using cryo-electron microscopy it has become possible to generate reconstructions with sub-nanometer resolution and near-atomic resolution first in the case of highly symmetric viruses, and now in smaller, asymmetric proteins as well. Single particle analysis can also be performed by Induced Coupled Plasma Mass Spectroscopy (ICP-MS).

CyTOF

Cytometry by time of flight, or CyTOF, is an application of mass cytometry used to quantify labeled targets on the surface and interior of single cells. CyTOF allows the quantification of multiple cellular components simultaneously using an ICP-MS detector.

Otolith microchemical analysis is a technique used in fisheries management and fisheries biology to delineate stocks and characterize movements, and natal origin of fish. The concentrations of elements and isotopes in otoliths are compared to those in the water in which the fish inhabits in order to identify where it has been. In non-ostariophysian fishes, the largest of the three otoliths, or ear bones, the sagitta is analyzed by one of several methods to determine the concentrations of various trace elements and stable isotopes. In ostariophysian fishes, the lapilli is the largest otolith and may be more commonly analysed.

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Resonance ionization

Resonance ionization is a process in optical physics used to excite a specific atom beyond its ionization potential to form an ion using a beam of photons irradiated from a pulsed laser light. In resonance ionization, the absorption or emission properties of the emitted photons are not considered, rather only the resulting excited ions are mass-selected, detected and measured. Depending on the laser light source used, one electron can be removed from each atom so that resonance ionization produces an efficient selectivity in two ways: elemental selectivity in ionization and isotopic selectivity in measurement.

Candice Mae Bridge is an American chemist and Associate Professor of Chemistry and Forensic Science at the University of Central Florida. Her research considers the development of mass spectroscopy for forensic analysis, including the characterization of lubricant from rape victims and residue from gunshots as well as the identification of drugs in urine samples.

References

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  3. 1 2 Gauert, Christoph; Schannor, Mathias; Hecht, Lutz; Radtke, Martin; Reinholz, Uwe (2016-06-01). "A Comparison ofIn SituAnalytical Methods for Trace Element Measurement in Gold Samples from Various South African Gold Deposits". Geostandards and Geoanalytical Research (in French). 40 (2): 267–289. doi:10.1111/j.1751-908x.2015.00362.x. ISSN   1751-908X.
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  7. 1 2 Mokgalaka, N. S.; Gardea-Torresdey, J. L. (August 21, 2006). "Laser Ablation Inductively Coupled Plasma Mass Spectrometry: Principles and Applications". Applied Spectroscopy Reviews. 41 (2): 131–150. doi:10.1080/05704920500510703.
  8. 1 2 Brostoff, Lynn B.; González, Jhanis J.; Jett, Paul; Russo, Richard E. (February 2009). "Trace element fingerprinting of ancient Chinese gold with femtosecond laser ablation-inductively coupled mass spectrometry". Journal of Archaeological Science. 36 (2): 461–466. doi:10.1016/j.jas.2008.09.037.