Provenance Determination Research Articles

Provenance determination of sapphires and rubies using laser-induced breakdown spectroscopy and multivariate analysis

Determination of gem provenance is a topic of research in the gemological community for financial, security, and societal reasons. Laser-induced breakdown spectroscopy (LIBS) and multivariate analysis have the potential to revolutionize the field of gem provenance. This study acquired LIBS spectra from 569 rough sapphire and ruby specimens from 21 localities in 11 countries. The spectra were analyzed using the multivariate technique partial least-squares regression (PLSR) in separate algorithms for sapphires and rubies. Each algorithm consists of a series of PLS models. Each model compares the spectra from a locality of interest to the spectra from all other localities in the database. Success rates, as determined by the percent of correct provenance identifications, are 98.9% (sapphire) and 96.0% (ruby) for country of origin and 97.9% (sapphire) and 95.4% (ruby) for deposit of origin. Individual deposits are not recognized by the concentrations of a few elements; rather, the unique compositional signature of each deposit consists of the ratios of many elements, primarily Ca, Zr, Fe, Ba, Mt, Ti, Sr, Si, Cr, H, C, and Li, some of which may reside in inclusions. This work demonstrates that determination of country or deposit of origin may be related to a quantitative measure with a high level of success.

Placer Gold Composition and Provenance Studies in the Kuznetskiy Alatau and Western Sayan, South-East Siberia: Results of Field Trip, Summer 2014

This article presents the results of a study of gold samples obtained by students during a practical field trip in the summer of 2014. Placer gold samples retrieved from four rivers in southeast Siberia (Khakassia and Tyva territories) by panning and sluicing were described and analyzed compositionally by Scanning Electron Microscopy. There is evidence from grain flattening and morphology for significant variations in gold transport distance, both within and between sample locations. The composition and texture of gold is compared to similar studies in the Yukon, and it is inferred that most of the placer gold in the region originated from orogenic lode sources. This orogenic gold is of Devonian to Carboniferous age. There is also evidence for a contribution from igneous intrusion-related bedrock gold, which is supported by the presence of granite, granodiorite and sienite intrusions of Devonian age. There is scope for further study, since relatively few grains were analyzed here. In addition, if compositional data of the prospective primary gold deposits can be obtained, there would be potential for more precise determination of provenance.

Chemical Fingerprinting, A Precise and Efficient Method To Determine Sediment Sources

Abstract An accurate method of determining source locations for detrital sediment is presented using the chemical composition of Fe-oxide minerals like a fingerprint. This method is an improvement in the use of Fe-oxide minerals for provenance determinations because it requires less time and fewer source samples. A rigorous test of the method uses a database of more than 38,000 grains from known locations. The average error of matching grains back to 45 source locations designated for this database is less than 2%. The method allows for proportional matching of a grain to multiple sources if other grains in the source database meet the compositional match criteria, which helps reduce the error of incorrect matches. Most provenance studies do not involve source basins as large as the entire Arctic Ocean, where sediment can be ice-rafted several thousand kilometers. For most studies, only a few samples (∼ 100 grain analyses/sample) would be required to characterize a source if strategically placed, such as near a river mouth. Deposits more than 40 million years old can be traced to specific sources using this method because Fe-oxide grains are relatively stable in most deposits.

Textural and geochemical studies of detrital Fe–Ti oxides and test of their validity in provenance determination, a case study from Central Iran

This paper aims to test the reliability of texture and composition of detrital Fe–Ti oxides in provenance determination, via a case study on the most important siliciclastic unit of Central Iran (Upper Red Formation). Significant exposures of the formation in its basin margins and abundance of detrital Fe–Ti oxides in its component facies nominate it for this study. Samples from representative sections of the formation are studied by SEM, equipped with X-ray analyzer, for textural and compositional properties of the Fe–Ti oxides. In terms of texture, ∼75% of the studied grains are found heterogeneous with ilmenite exsolution/intergrowth in the titanomagnetite host (∼60%), magnetite–hematite exsolution/intergrowth (∼12%) and magnetite–pseudobrookite (∼2%) and magnetite–hematite–rutile (∼1%) intergrowths. Remaining grains (∼25%) are homogenous with titanomagnetite (∼19%), ilmenite (∼5%) and rutile and chromite (∼1%) composition. Four major types of texture (trellis, sandwich, composite and no distinct pattern) are discriminated in the heterogeneous grains, which characteristics and proportion provide significant information on their provenance. In terms of composition, majority of studied grains fall into magnetite–ulvöspinel and ilmenite–hematite solid solution series in the TiO2–FeO–Fe2O3 system. The FeO, MnO, MgO, ZnO, TiO2, Fe2O3, Al2O3 and Cr2O3 contents of the grains are used for their provenance determination.On the basis of results from textural and geochemical properties of the studied grains, intermediate (andesitic to dacitic) to basic volcanic rocks (dissected arc) are determined as parent rocks of the studied grains. These findings are combined with paleocurrent patterns of the hosting facies to locate the transportation pathways of the grains and their source area. Texture and composition of Fe–Ti minerals from nominated parent rocks are studied in similar methods. Comparison of texture and composition of the detrital Fe–Ti oxides with those in their nominated parent rocks clearly confirm the reliability of these parameters in provenance determination. Slight post-depositional alteration of the grains is understood from this comparison.

Determination of Provenance and Tectonic Settings of Niger Delta Clastic Facies Using Well-Y, Onshore Delta State, Nigeria

Provenance analysis serves to reconstruct the predepositional history of a sediment/sedimentary rock. This paper focuses on the reconstruction of the provenance and tectonic settings of the Niger delta clastic facies using geochemical approach. The main types of geochemical tests include major, trace, and rare earth element (REE) tests. Twenty-one samples of shales and sandstones units were purposely collected from a depth between 1160 and 11,480 m, grinded, pulverized, and sieved with a <75 μm. About 5 g was packed and sent to Acme analytical Laboratory Ltd., Vancouver, Canada. The analyses were carried out by both induced coupled plasma-mass spectrometry (ICP-MS) and induced coupled plasma-emission spectrometry (ICP-ES). Bulk-rock geochemistry of major oxides, trace elements, and rare earth elements was utilized for the provenance and tectonic setting determination. Based on the discrimination diagram for major oxides, the probable provenance of the south eastern Delta clastic sediments was mainly of the active continental margins. The bivariate plots of La versus Th, La/Y versus Sc/Cr, and Ti/Zr versus La/Sc and the trivariate plots of La-Th-Sc, Th-Sc-Zr/10, and Th-Co-Zr/10 are all plotted on the fields of active continental margin sediments which is consistent with the known actively opening of a failed arm of triple junction. The trace elements and REE analysis indicates that they are virtually Fe-rich, lithic/quartz arkosic sandstones. The normalizing factors used for the REE are Wakita chondrite. Their rare earth elements (REE) pattern displays high light REE/heavy REE (LREE/HREE) ratio, flat HREE, and a significant negative Eu anomaly which correlate well with the UCC and PAAS average composition. The source area may have contained felsic igneous rocks.

Determination of provenance and species of Japanese Jōmon lacquer by pyrolysis-gas chromatography/mass spectrometry and 87Sr/86Sr isotope ratio

One piece of Japanese Jōmon period lacquerware from the Yachi Relic in Niigata Prefecture and four pieces from the Shimoyakebe Relic in Tokyo of Japan were first analyzed by Py-GC/MS to determine the lacquer species, and secondly the strontium (87Sr/86Sr) isotope ratio was analyzed to examine the provenance of the lacquer. Compared with the pyrolysis products of standard lacquers, the results showed that all the original objects were coated by sap that was tapped from a Toxicodendron vernicifluum lacquer tree. The 87Sr/86Sr isotope ratios were 0.7056 at Yachi and an average 0.7052 at Shimoyakebe; both are lower than 0.71, the borderline (=0.71) between the Chinese mainland (>0.71) and Japanese islands (<0.71). Thus, all five Jōmon lacquerwares were coated with lacquer sap tapped from T. vernicifluum lacquer tree grown in the Japanese islands.

Turquoise Mine and Artefact Correlation for Some Bronze Age Archaeological Sites in Hubei Province, China

In China, there are places that are rich in gem-quality turquoise resources, including north-west Hubei Province and the nearby Baihe County in Shaanxi Province, and many ancient mining sites, although the mining history remains a mystery. Based on the compositional data from reference samples of known deposits, a comparison of the major and trace element contents of archaeological turquoise may help with determination of artefact provenance. This paper discusses new evidence of provenance-tracking of turquoise in this area, obtained from geochemical analyses using REE and other trace elements of 22 turquoises and their surrounding rock samples from six ancient mines and three archaeological sites. The results indicate that the three archaeological turquoises from the tomb of the Middle Spring and Autumn Period (580–560 bc) and the Warring States Period (476–221 bc) in Hubei Province were made of raw material from north-west Hubei Province and the nearby Baihe County in Shaanxi Province. [Correction added on 29 October 2014, after first online publication: In the preceding sentence, the correct dates for the Middle Spring and Autumn Period, and the Warring States Period have been added]

Multi-element analysis using inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectroscopy for provenancing of animals at the continental scale

Chemical signatures within the environment vary between regions as a result of climatological, geochemical and anthropogenic influences. These variations are incorporated into the region's geology, soils, water and vegetation; ultimately making their way through the food chain to higher level organisms. Because the variation in chemical signatures between areas is significant, a specific knowledge of differences in elemental distribution patterns between, and within populations, could prove beneficial for provenancing animals or animal related products when applied to indigenous and feral faunal populations. The domestic pig (Sus scrofa domestica) was used as an investigative model to determine the feasibility of using a chemical traceability method for the provenance determination of animal tissue. Samples of pig muscle, tongue, stomach, heart, liver and kidney were collected from known farming areas around Australia. Samples were digested in 1:3 H2O2:HNO3 and their elemental composition determined using solution based Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Pigs from different growing regions in Australia could be distinguished based on the chemical signature of each individual tissue type. Discrimination was possible at a region, state and population level. This investigation demonstrates the potential for multi-element analysis of low genetic variation native and feral species of forensic relevance.

INAA and the provenance of shell-tempered sherds in the ancestral Caddo region

Over the last two decades, archaeologists working in the ancestral Caddo area have amassed a sizeable instrumental neutron activation analysis (INAA) dataset (n = 1308 sherds). We examine a subset (n = 88 sherds) of that larger dataset—shell-tempered Caddo ceramics—to examine the issue of ceramic provenance determinations from INAA in the Caddo area. Current analyses of INAA data from Caddo area shell-tempered ceramics mistakenly suggest that very distinctive shell-tempered ceramics were manufactured throughout East Texas and not traded and/or exchanged from one sub-region to another. Through the protocol of removing calcium-related geochemicals from statistical calculations of elemental values, shell-tempered sherds have lost their distinctive chemical signature. The methodological approach employed herein illustrates the potential for significant gains in exploring the provenance of Caddo ceramics using INAA, through the use of geochemicals found to correlate with the inclusion of shell temper.

Petrographic Characterization and Provenance Determination of the Crystalline Marbles Used in the Roman City of Banasa (Morocco): New Data on the Import of Iberian Marble in Roman North Africa

This paper reports the results of an archaeometric study of the crystalline marbles used in the Roman city of Banasa (Morocco). On‐site surveys allowed a detailed inspection of the monuments of the ancient city and sampling of the different marble lithotypes used for architectural purposes and sculptures. The inventory was completed by the study of both the grey‐and‐white streaked or spotted marble items stored in the warehouse of the archaeological site and of those currently exhibited at the National Archaeological Museum of Rabat. Provenance determination of 28 samples was carried out by means of a multi‐method approach combining mineralogical–petrographic data and C–O stable isotope analyses as the first step, and cathodoluminescence microscopy as a complementary technique to verify possible unusual alternative origins of some marbles. The analytical results obtained were compared with both the most reliable international databases and the few available studies dealing with the use of marble in other Roman towns in Morocco (e.g., Volubilis, Thamusida and Sala‐Chellah). They point to a variety of classical marble sources such as Carrara, Mount Penteli, Paros, Marmara and probably Mount Filfila (Algeria), and prove a significant import of Iberian lithotypes.

Recent trends in IBA for cultural heritage studies

Ion beam analysis (IBA) techniques play an important role in the field of cultural heritage. IBA was one of the first physical methods applied to archaeology in the 70s. 40years later, more than 25 accelerator laboratories were or are involved in cultural heritage applications. The advantages of the IBA techniques match very well the requirements for the analysis of archaeological or museum objects: non destructiveness, major, minor and trace element analysis, information in depth, elemental mapping… Thanks to this collected information, IBA techniques can answer archaeological and conservation questions: provenance determination, ancient technologies (fabrication, transformation, recipes…) and conservation issues.In spite of the competition with portable devices and large facilities (such as synchrotron or neutron reactors), the IBA methods keep their interest due to the possibility of associating two or three of them according to the archaeological or art issue. In this article, some examples chosen for their original approach are presented: PIXE for X-radiography, provenance of prehistoric pigments and painting characterisation. They illustrate the useful versatility of IBA for cultural heritage studies. Perspectives for further improvements are also proposed.

Isotopes and Trace Elements as Natal Origin Markers of Helicoverpa armigera – An Experimental Model for Biosecurity Pests

Protecting a nation's primary production sector and natural estate is heavily dependent on the ability to determine the risk presented by incursions of exotic insect species. Identifying the geographic origin of such biosecurity breaches can be crucial in determining this risk and directing the appropriate operational responses and eradication campaigns, as well as ascertaining incursion pathways. Reading natural abundance biogeochemical markers using mass spectrometry is a powerful tool for tracing ecological pathways as well as provenance determination of commercial products and items of forensic interest. However, application of these methods to trace insects has been underutilised to date and our understanding in this field is still in a phase of basic development. In addition, biogeochemical markers have never been considered in the atypical situation of a biosecurity incursion, where sample sizes are often small, and of unknown geographic origin and plant host. These constraints effectively confound the interpretation of the one or two isotope geo-location markers systems that are currently used, which are therefore unlikely to achieve the level of provenance resolution required in biosecurity interceptions. Here, a novel approach is taken to evaluate the potential for provenance resolution of insect samples through multiple biogeochemical markers. The international pest, Helicoverpa armigera, has been used as a model species to assess the validity of using naturally occurring δ2H, 87Sr/86Sr, 207Pb/206Pb and 208Pb/206Pb isotope ratios and trace element concentration signatures from single moth specimens for regional assignment to natal origin. None of the biogeochemical markers selected were individually able to separate moths from the different experimental regions (150–3000 km apart). Conversely, using multivariate analysis, the region of origin was correctly identified for approximately 75% of individual H. armigera samples. The geographic resolution demonstrated with this approach has considerable potential for biosecurity as well as other disciplines including forensics, ecology and pest management.

Lithium distribution and isotopic fractionation during chemical weathering and soil formation in a loess profile

Lithium (Li) is a fluid-mobile element and δ7Li in secondary deposits represents an excellent proxy for silicate weathering and authigenic mineral formation. The soil samples from 1205 to 1295cm in the Weinan profile, one of the best developed loess-paleosol sequences covering the last glacial–interglacial climatic cycle, were collected and chemically separated into detritus and carbonate fractions for subsequent analyses of Li, δ7Li, major and trace elements. Other desert specimens (i.e., Qaidam Desert, Tengger Desert, Badain Juran Desert and Taklimakan Desert) near the Chinese Loess Plateau (CLP) and various standard clays were analyzed for assisting provenance determination. The Li and δ7Li distributions in the detritus are rather homogeneous, 1.4–2.0μg/g and +2.5‰ to +4.7‰, respectively, compared with the carbonate fraction. The detrital δ7Li varies systematically with magnetic susceptibility and grain size changes, reflecting significant Li isotopic variation associated with sources and mineralogy of detrital material. On the other hand, Li and δ7Li in carbonates show large changes, 781–963ng/g and −4.1‰ to +10.2‰, respectively. These carbonate δ7Li correlated well with the estimated index of chemical weathering, as a result of Li mobilization and soil formation during chemical weathering.

Black "marble" in the Polish architecture - characteristics and possibility of its provenance determination: the case of the Dębnik limestone

Black limestone, also known as black marble, was widely used in the Polish small-scale architecture and art of the 17th and 18th centuries. Besides the Devonian limestone from Debnik near Krakow, also popular were the Netherlandish (Wallonian), Devonian to Carboniferous limestones from the Meuse River and Schelde River valleys. This paper deals with the possibility of identifying the rocks imported to Poland. Macroscopic similarities between the Netherlandish rocks and some Debnik limestones have been highlighted for the oldest Carmelite quarry in Debnik, exploiting the best stones. The analyses include: optical microscopy, scanning electron microscopy with EDS, X-ray diffraction, X-ray fluorescence and isotope ratio mass spectrometry (13 C and 18 O stable isotopes). Carboniferous limestones from Netherlands can be identified within and distinguished from the Debnik limestone in the macroscopic observations. Differences, depending on the varieties, are associated primarily with the presence of white calcite fragments of fossils, calcite veins intersecting the rock in all directions or hardness of the limestones. Deeply black Devonian limestones from Wallonia and Debnik without macrofossils and calcite veins differ in microscopic observations considering their texture, type of microfossils and inventory of non-carbonate components. The characteristic graying and whitening of the black limestones has also been discussed as a possible feature of rock provenance.

The Neolithic Obsidians From Southeastern Ukraine First Characterization and Provenance Determination

Bu makale, Ukrayna'nın güneydoğusunda yer alan Lysa Gora Neolitik yerleşiminden altı, Semenovka 1 Neolitik yerleşiminden bir obsidiyen örneğin tanımlanmasından elde edilen sonuçları tartışır. Onlar Lysa Gora sakinleri tarafından kullanılmış farklı kaynaklardan obsidiyenleri gösterir, bunlar arasında Baksan (Rusya Federasyonu), Sjunik (Ermenistan) ve tanımsız başka bir kaynak vardır. Oysa Semenovka 1'de bulunan dilgicik parçasının menşei, Orta Anadolu'daki Göllüdağ kaynaklarından biri olduğu için özellikle ilgi çekicidir. Ukraynalı örneklerin ilk tanımlaması, doğuda Kafkaslar, batıda Karpatlar tarafından sınırlanmış geniş bir bölgede arkeolojik obsidiyenlerin dağılımı konusundaki bilgilerimizde bir boşluğu doldurur. Onlar Neolitik süresince Azak Denizi'nin kuzeybatısındaki step (bozkır) bölgede obsidiyenlerin tedarik edilme ve dolaşım modellerinin yorumlanmasına katkıda bulunur.

MICRO-PIXE STUDIES ON NATIVE TRANSYLVANIAN GOLD FOR ARCHAEOLOGICAL ARTIFACTS AUTHENTICATION

Determination of the geological provenance of gold is a powerful argument in the authentication of ancient gold artifacts. Small samples (hundreds of microns) of native gold from Transylvanian deposits were scanned by micro-PIXE to obtain information on the natural Au – Ag alloy composition and on the presence of trace elements such as Sn , Sb , and Cu . The experiments were performed at the AGLAE Louvre and LNL AN2000 accelerators. Mineral identification was confirmed by a micro-mineralogical study using the INFLPR-Magurele Scanning Electron Microscope associated with an Energy-dispersive X-ray spectroscopy (EDAX) facility.

Development of a Novel Method for Unraveling the Origin of Natron Flux Used in Roman Glass Production Based on B Isotopic Analysis via Multicollector Inductively Coupled Plasma Mass Spectrometry

The provenance of the flux raw material used in the manufacturing of Roman glass is an understudied topic in archaeology. Whether one or multiple sources of natron mineral salts were exploited during this period is still open for debate, largely because of the lack of a good provenance indicator. The flux is the major source of B in Roman glass. Therefore, B isotopic analysis of a sufficiently large collection and variety (origin and age) of such glass samples might give an indication of the number of flux sources used. For this purpose, a method based on acid digestion, chromatographic B isolation and B isotopic analysis using multicollector inductively coupled plasma mass spectrometry was developed. B isolation was accomplished using a combination of strong cation exchange and strong anion exchange chromatography. Although the B fraction was not completely matrix-free, the remaining Sb was shown not to affect the δ(11)B result. The method was validated using obsidian and archaeological glass samples that were stripped of their B content, after which an isotopic reference material with known B isotopic composition was added. Absence of artificial B isotope fractionation was demonstrated, and the total uncertainty was shown to be <2‰. A proof-of-concept application to natron glass samples showed a narrow range of δ(11)B, whereas first results for natron salt samples do show a larger difference in δ(11)B. These results suggest the use of only one natron source or of several sources with similar δ(11)B. This indicates that B isotopic analysis is a promising tool for the provenance determination of this flux raw material.

Obsidian provenance determination using the beam stability controlled BSC-XRF and the PIXE-alpha portable spectrometers of the LANDIS laboratory: the case of the Via Capuana settlement in Licodia Eubea (Sicily)

In the last decade about 800 obsidian artifacts coming from various archaeological sites of Sicily have been analyzed using the BSC-XRF (beam stability controlled-x-ray fluorescence) and PIXE-alpha (particle induced x-ray emission, using low-energy alpha particles) portable spectrometers developed at the Landis laboratory of the LNS?INFN and IBAM?CNR in Catania (Italy). The portable BSC-XRF system allows the non-destructive analysis of Rb, Sr, Y, Zr and Nb trace concentrations, which are considered to be characteristic of the obsidian samples and consequently are indicative of the provenance quarries. Quantitative data on the above trace-element concentrations were deduced using a method that makes use of a multi-parameter linear regression. The portable PIXE-alpha spectrometer allows the quantitative determination of the matrix major elements, from Na to Zn. In this paper the updated versions of the instrumental devices and methods are presented together with a review of all the obtained data from various Sicilian sites. Results on compositional data for trace elements and major elements allowed us to identify Lipari and Pantelleria islands as the only two sources of the analyzed samples. Recent data about the Via Capuana settlement in Licodia Eubea are also presented and discussed for the first time.

Safety issues in cultural heritage management and critical infrastructures management

Safety issues in cultural heritage management and critical infrastructures management

Improving provenance studies in migratory birds when using feather hydrogen stable isotopes

Hydrogen stable isotopes (δ2H) in feathers are used to determine the origin and migration strategy of birds. To identify the geographic location of the site of feather synthesis, calibration curves for the relation between feather δ2H and amount‐weighted growing‐season δ2H in precipitation are used to generate feather δ2H isoscapes. Factors like species, age and year might generate isotopic variation in calibration curves, but the extent to which accounting for variation may improve calibration curves and hence provenance determination of birds, is unknown. We compared three European calibration curves: 1) an existing multi‐species curve, uncorrected for age and year variation, and two species‐specific calibration curves, based on mallard Anas platyrhynchos feathers, of 2) varying age and year, and 3) juvenile natal origin, corrected for year variation. Calibration curves using ordinary least square linear regression (OLS) as opposed to standard major axis regression showed least bias in estimation. As expected, we found that a single species (mallard) OLS calibration curve corrected for age and year yielded the highest coefficient of determination, but was still surprisingly similar to the other two calibration curves. Nevertheless, when using feathers of known‐origin to assess provenance accuracy, the calibration curve that accounted for species, age and year variation yielded the best prediction in as many as 59% of the cases. Our study is the first to demonstrate implications of isotopic variation on assessing the origin of individual birds, but also highlights the relatively small gain in precision that is achieved by generating species, age and year specific calibration curves rather than resorting to more general alternatives.