EMBARGOED FOR RELEASE: Monday, April 8, 2013, 11:30 a.m. Eastern Time

Note to journalists: Please report that this research was presented at a meeting of the American Chemical Society.

Newswise — NEW ORLEANS, April 8, 2013 — A scientist who helped verify authenticity of the fabled Gospel of Judas today revealed how an ancient Egyptian marriage certificate played a pivotal role in confirming the veracity of inks used in the controversial text. The disclosure, which sheds new light on the intensive scientific efforts to validate the gospel, was made here today at the 245th National Meeting & Exposition of the American Chemical Society (ACS), the world’s largest scientific society.

"If we hadn't found a Louvre study of Egyptian wedding and land contracts, which were from the same time period and had ink similar to that used to record the Gospel of Judas, we would have had a much more difficult time discerning whether the gospel was authentic,” said Joseph G. Barabe. A senior research microscopist at McCrone Associates, he led an analytical team of five scientists who worked on the project at McCrone, a consulting laboratory in microscopy and microanalysis in Westmont, Ill. “That study was the key piece of evidence that convinced us that the gospel ink was probably okay." 

Barabe’s team was part of a multidisciplinary effort organized in 2006 by the National Geographic Society to authenticate the Gospel of Judas, which was discovered in the late 1970s after having been hidden for nearly 1,700 years. The text, written in Egyptian Coptic, is compelling because — unlike other Biblical accounts that portray Judas Iscariot as a reviled traitor — it suggests that Jesus requested that his friend, Judas, betray him to authorities.

Barabe’s presentation was part of an ACS symposium on archeological chemistry. Other presentations included:

•Announcement of the unprecedented discovery of the most sacred Biblical dye at Masada, an ancient mountain fortress in Israel.

•Examination of the glues George Washington’s mother used to repair her ceramics and what it tells us about her life and the mending of china in the 18th century.

•Exploration of the use and trade of pulque — an alcoholic beverage made from the fermented sap of the maguey plant —in prehistoric Mexico and Central America.

After analyzing a sample, Barabe and his colleagues concluded that the gospel was likely penned with an early form of iron gall ink that also included black carbon soot bound with a gum binder. While this finding suggested that the text may have been written in the third or fourth century A.D., the researchers were perplexed by one thing: The iron gall ink used in the gospel was different than anything they’d ever seen before. Typically, iron gall inks — at least those from the Middle Ages — were made from a concoction of iron sulfate and tannin acids, such as those extracted from oak gall nuts. But the iron gall ink used to produce the Gospel of Judas didn’t contain any sulfur. And that, Barabe said, was troubling.

“We didn’t understand it. It just didn’t fit in with anything that we had ever encountered,” he said. “It was one of the most anxiety-producing projects I’ve ever had. I would lie awake at night trying to figure it out. I was frantically searching for answers.”

Ultimately, Barabe found a reference to a small French study conducted by scientists at the Louvre who analyzed Egyptian marriage and land records written in Coptic and Greek and dating from the first to third centuries A.D. Much to Barabe’s relief, those researchers had determined that a wedding certificate and other documents were written in ink made with copper, but little or no sulfur.

“Finding that study, and realizing its implications, tilted my opinion a little in the direction of it being appropriate for the era,” Barabe said. “My memory of that experience remains quite vivid. I had a sudden feeling of peace that things were okay, and that I could submit my data without qualms.” 

Barabe now suspects that the ink used in the Gospel of Judas was probably transitional, a “missing link” between the ancient world’s carbon-based inks and the iron gall inks (made with iron sulfate) that became popular in medieval times.

The scientists acknowledged funding from the National Geographic Society to complete this analysis.

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Note to journalists: Please report that this research was presented at a meeting of the American Chemical Society.

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Abstracts

Characterization of the ink on the Gospel of Judas: A collaborative approach 

In 2006, the National Geographic Society (NGS) contracted with McCrone Associates to characterize the ink in a purportedly 3rd century document, the Gospel of Judas, in order to determine whether the ink was consistent with materials and manufacturing methods of 3rd century Egypt. McCrone's approach was to assemble a group of scientists with expertise in different aspects of microanalysis: The project required taking the initial ink samples in Geneva, Switzerland, specimen preparation for each of the instruments, and analysis by polarized light microscopy, scanning electron microscopy with high-resolution imaging and energy dispersive X-ray spectrometry (EDS), X-ray diffraction, transmission microscopy with EDS, and infrared and Raman spectroscopy. The ink turned out to be an unexpected mix of a traditional carbon black ink in a gum binder with an iron gall component which lacked the expected sulfur. Altogether, our findings are not inconsistent with 3rd century Egyptian ink.

Unprecedented archaeo-chemical discovery of the 2,000-year old “Biblical-Blue” Tekhelet at Masada 

There has been much confusion as to the malacological provenance, color, and chemical constitution of Tekhelet – the most sacred of the three Biblical dyes. For the first time, a two-millennia archaeological dyeing from the famous Judean palatial fortress of King Herod at Masada has been unambiguously identified as Biblical Tekhelet based on archaeo-chemical and physical evidence. Multicomponent HPLC analyses on purple archaeological dyeings and pigments produced from the most important Muricidae mollusk, Hexaplex (= Murex) trunculus, have shown that they consist mostly of three indigoidal colorants: red-purple 6,6'-dibromoindigo (“DBI”), violet 6-monobromoindigo (“MBI”), and dark-blue indigo (“IND”) [Koren ZC, Microchim. acta 2008, 162, 381-392]. Two chromatic sub-species of H. trunculus were used in antiquity, one that produced reddish-purple dyeings and hence richer in DBI, while the other produced bluish-purple dyeings richer in IND. This talk will discuss this unprecedented find, which may alter many people's perception of the color of “Biblical-Blue”.

Identifying glue residues on 18th-century ceramics from Ferry Farm, George Washington's boyhood home 

Archaeological investigations at Ferry Farm, home to the Washington family from 1738-1772, have yielded numerous ceramic artifacts associated with Mary Washington, George Washington's mother. Several of these bear residues of historic mending. The nature of the glues, and the relationship between these various artifacts, remains poorly understood. We are using direct analysis in real time mass spectrometry to investigate the composition of replica glues made from historic recipes. The adhesives fall into three classes: hide glues, resin glues, and casein-based “cheese” glues. While there is some overlap in recipes, marker compounds like abietic acid derivatives from pine resins and hydroxyproline from hide can help to rule determine which, if any, class was used on the excavated ceramics. Understanding the composition of the glues provides insight into Mary Washington's relationship to her ceramics and their uses, as well as information about the practice of china mending in the 18thcentury.

Chemical evidence for the archaeological use of pulque, a pre-Columbian fermented beverage made from agave 

Despite ethnographic, visual artistic, and early historical evidence for the consumption of pulque in Mesoamerica, no direct chemical evidence for the fermented agave beverage pulque has been reported within these archeological contexts. An organic residue study was conducted on ancient ceramic samples from the site of Tula, Hidalgo, Mexico. These samples associated with the Toltec site (c. 900 CE) were compared to lipid extracts from modern samples of pulque in order to establish the possibility of determining a chemical biomarker for its pre-historic consumption. Gas chromatography-mass spectrometry (GC-MS) analysis was used to identify surviving lipid contents embedded within thirteen different sherds, as well as to analyze the components of five different modern pulque samples. A terpenoid compound was found in each of the modern pulque samples, as well as many of the ancient ceramic sherds analyzed. The correlation of this compound, combined with characteristic fatty acids, provide strong evidence for the storage of this fermented beverage within the archaeological ceramics tested. The identification of these compounds as biomarkers for pulque consumption offers a valuable tool for identifying the use and trade of this important resource throughout prehistoric Mesoamerica.

Source of red pigments in Lower Pecos pictographs 

Laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) was used to characterize the chemical composition of red pictograph pigments from the Lower Pecos Archaeological Region with the goal of identifying the source of the iron-based pigments. Thirteen paint specimen collected from two southwest Texas rock art sites were compared with three potential source materials (ochre, yellow siltstone and rhyolite), and two pigment cakes (crayons) that were excavated near the sampling sites. The chemical signature of the pictograph paints was strikingly similar to that of the yellow siltstone. If this material was the primary source for red pigments then we could conclude that the hunter-gatherers in the region 3000-4000 years ago had the technology to isolate the iron-oxide from the quartz matrix and convert the yellow goethite into red hematite.

pXRF analysis of arsenic when lead is present: A cautionary tale 

Although the InnovXAlpha Series portable X-ray fluorescence device we used to qualitatively analyze ceramics pigments and Lowry Pueblo Kiva white paint repeatedly reported As (in hundreds of measurements), there was no significant amounts of As present in those samples. Obviously, care must be taken when using that device to determine As when there are significant amounts of Pb present in the samples.

Characterizing organic colorants in mock-ups of a 15th century Iranian Timurid Qur'an by direct analysis in real time time-of-flight mass spectrometry 

The Detroit Institute of Arts has in its Islamic collection a unique 15th century Timurid Qur'an. The Qur'an contains brilliantly-colored painted and polished paper with the calligraphy text inked onto the pages. The Qur'an is currently undergoing a multidisciplinary study to identify the inks, pigments, binders, dyes, gold alloys, and fibers used to construct the manuscript. X-ray fluorescence has shown that the colored pages contain primarily lead, suggesting that most of the colors are due to organic colorants. Raman microscopy indicated the presence of indigo in the blue pages, but fluorescence from organics, thought to be binder, was significant. We report here results from direct analysis in real time mass spectrometry (DART-MS) identifying organic dyes in mock-ups with a matrix that mimics that of the DIA Qur'an. These results will provide optimized methods for future work with authentic microsamples.

Use of isotopes to determine geographic origins of humans: Cautionary tales 

After decades of measuring various isotope ratios to determine geographic origins of humans, we have progressed beyond necessarily simplistic concepts to uncover dietary, ontogenetic, and methodological effects that create both problems and opportunities for a richer understanding of past human behavior. Illustrative case studies will be presented.

Lipid analysis on Mapungubwe ceramics: Determining past function and foodstuffs

Lipid analysis has been used in archaeology to analyse the residues left in ceramics, ranging from ancient Rome amphorae to the ceramics used during ancient Greek times. The use of lipids in other areas of the world has shown the potential of this method to explore the actual use of ceramics. A single study using lipid analysis through GC/MS on Iron Age ceramics in southern Africa showed that lipids were present in a sample of ceramics, due to lipids seeping into the ceramics as a result of cooking activities. The present study will elaborate on this previous research through the examination of ceramics from the archaeological settlement of Mapungubwe. Previous ceramic studies have focused mainly on the stylistic characteristics instead of their function. This study will aim to determine the past use of ceramics and whether this is linked to form/decoration.

Energy dispersive X-ray fluorescence analysis of sets of coins of the Kushan Empire, revolutionary France, and the state of Mysore: Three case studies throughout history 

Three series of copper coins have been analyzed by energy dispersive X-ray fluorescence spectrometry for elements including copper, zinc, tin, lead, silver, gold, and several other, possibly trace, elements. The coin sets are from the ancient Kushan Empire, from France during the revolutionary government of the late 1790's, and from the Indian state of Mysore. The elemental, compositional make up of each set, as well as the implications of the findings, will be presented and discussed.

Preliminary results on biomimetic methods based on soluble ammonium phosphate precursors for the consolidation of archaelogical wall paintings 

This research develops hydroxyapatite (HAP)-based, inorganic mineral systems with improved properties for the consolidation of powdery wall paintings of archaeological significance. The scientific approach exploits biomimetic (biologically inspired design) principles to induce the formation of protective HAP crystals by triggering reactions between the calcium carbonate-rich layers in wall paintings and ammonium phosphate precursors. The high solubility and absence of toxicity of ammonium phosphates (precursors) and the stability of the calcium hydroxyapatite (reaction product) at varying pH, renders this treatment extremely promising for consolidation and protection of weathered wall paintings. Tests were carried out on experimental wall painting panels (representing the most common typologies across space and time) applying cellulose compresses of 1M and 2M solutions of diammonium hydrogen phosphate for 3 to 6 hours contact time. The consolidating effect, influence of the solution and conditions (composition, pH, contact time, application method) on hydroxyapatite formation (rate, extent) was evaluated through a series of structurally and compositionally sensitive analytics including: VPSEM-EDS, 3D-microstructure reconstructions, optical and mechanical analyses. Preliminary results indicated the formation of a porous hydroxyapatite network at the subsurface of the wall painting test panels, reduction of water absorption and dissolution at low pH and insignificant color change. These data show the potential of this treatment for the consolidation of powdery multi-layered wall paintings and their protection from weathering and deterioration induced by passage-of-time and environmental action linked effects.

Organic residues in archaeology: The highs and lows of recent research 

The analysis of organic residues from archaeological materials has become increasingly important to our understanding of ancient diet, trade and technology. Residues from many diverse contexts have been retrieved and analysed from the remains of food, medicine and cosmetics to hafting material on stone arrow heads, pitch and tar from shipwrecks, even ancient manure from soils. There have been many advances in our understanding of this kind of research over the past two decades. Some have led to the ability to give very specific and detailed interpretations of the materials preserved in the archaeological record. However there are still areas where we know very little, like the mechanisms at work during the formation and preservation of residues, and areas where each advance produces more questions rather than answers, as in the identification of degraded fats. This talk will discuss some of the most significant achievements in the field to date and the ongoing challenges for research in this area.

Identifying ancient population movement in Honduras using strontium and oxygen isotopes: New values and interpretations 

Strontium isotope ratios in human tooth enamel show widespread population movement among the Classic period Maya, including in-migration to both large centers and rural communities. Our ability to identify potential homelands for migrants is based on (1) understanding the relationship between geologic variability and 87Sr/86Sr values, and (2) obtaining values for all likely homelands in each study. This is particularly important for studies of sites like Copan, which is the major urban center located at the periphery of the Maya region. Thirty-four modern plant and animal samples from western Honduras show that the area's geologic regions have distinct average strontium isotope values. These data elucidate additional potential homelands for non-local individuals buried at Copan and other Maya sites, which we demonstrate by re-interpreting conclusions in previously published studies. Equally important is the potential for exploring migration patterns among diverse indigenous populations in Honduras, like the Maya, Jicaque, and Lenca.

Investigating human social dynamics and interaction in Ecuadorian prehistory through obsidian artifact provenience 

The exchange of non-local goods has long been considered an important component of life throughout much of Ecuadorian prehistory. While a large portion of our understanding of exchange in this region comes from ethnohistoric records, archaeologists primarily have contributed to the study of exchange by sourcing obsidian. We present the results of recent geochemical sourcing research with portable X-Ray Fluorescence (pXRF) instrumentation that analyzed more than 2500 obsidian artifacts from more than 60 archaeological sites, quadrupling the number of sourced obsidian artifacts from Ecuador. In addition to providing new insights on the relevant geochemical signatures for the region, this robust dataset allows for the opportunity to go beyond documenting the presence of various raw material sources at particular sites and begin to consider the potential processes that could have produced the wide distribution of non-local goods in Ecuadorian prehistory.

Seasonal reproduction patterns by isotopic signatures ( δ18O) on early Eneolithic sheep of Cheia (beginning of the 5th mil. cal BC, Romania) 

Cheia is an Early Eneolithic site (beginning of the Vth mill. BC; Hamangia culture) settled in the central hills of the Dobrodgea province in south-eastern Romania. The site delivered an exceptional collection of faunal remains. Although the economy relied heavily on cattle husbandry, an important secondary role was given to domestic caprines. The recovered assemblage includes an important number of sheep tooth rows. We performed stable isotope analyses in tooth enamel from the second and third molars of different individuals. Variations in the sequential analyses of carbonate δ18O values in both molars are used to investigate seasonal reproduction patterns. The results obtained are compared with recently available data from modern referential breed sheep populations in Europe with known birth dates. High seasonal resolution is finally obtained and the distribution of sheep births throughout the year is represented, adding significance information to the study of sheep management.

Research funded by the ERC Starting Grant SIANHE and the CNCS – UEFISCDI (ProjectPN-II-ID-PCE-2011- 3-1015)

HyLoggerTM near-infrared spectral analysis: A non-destructive mineral analysis for Aboriginal Australian objects 

The CSIRO Australia HyLoggerTM technology has been adapted from mineral exploration and mining applications to the high-resolution non-destructive infrared and visible light spectroscopic mineral analysis of Aboriginal Australian objects. Aboriginal Australian people primarily applied mineral pigments to wood, fiber, bark, resin or other organic substrates, making non-destructive in-situ scientific analyses of cultural objects challenging. This proof of concept study demonstrated the utility of the near-IR technology for the visual and mineralogical analysis of Aboriginal Australian objects, as case studies for the development of methods to identify and differentiate types of mineral pigments regardless of substrate or binder. While many identified pigments such as hematite and goethite were expected for the red, orange and yellow pigments, HyloggerTM in combination with The Spectral GeologistTM software identified additional mixtures of previously unknown mineral components.

Geochemical analysis of occupational surfaces at Augusta, an 18th century English/Miskitu settlement on Roatan Island, Honduras 

Geochemical analyses of archaeological soils have been used in a variety of contexts to prospect for activity loci, with the greater goal of identifying the nature and extent of past human behaviors. However, much of this work has focused on prehistoric settlements, leaving gaps in our understanding about the fate and transport of chemical residues in historical settings. This paper reports the results of our ICP and colorimetric analyses of a range of earthen substances—soil, sediment, clay, plaster, and daub—from Augusta, Honduras. Now a major heritage site, Augusta was founded as an English stronghold on Roatan Island from 1742-1748 and hosted a mix of English militia and indigenous Miskitu. While historical documents provide details on the intentions of English settlers, we know very little about how English and Miskitu interacted on a daily basis. Here we discuss our research that integrates the geochemical and archaeological records to better understand the community.

Stone tools: Stable isotope analysis of organic residues 

We utilized plasma oxidation and stable isotope mass spectrometry to study organic residues on stone tools. Corn, a C4 plant, was processed using modern tools. Two different washing techniques were performed to remove surface contamination from handling prior to placing stone tools in an oxygen glow discharge. Organic residues trapped in stone tool micro-fracture cracks were oxidized to carbon dioxide for stable isotope mass spectrometry. This preliminary study demonstrates proof of concept for stable isotope analysis and radiocarbon dating of organic residues on stone tools using plasma oxidation.

Lead and strontium isotopes in archaeology 

Lead and strontium isotopes are among the most powerful and widely applied tracers in archaeometry. Both together and separately, they are used to determine the provenance of many archaeological materials, including metals, glasses, glazes, minerals, ceramics, bone, teeth, and wood. Advances in the past decade have made these isotopic measurements more precise, rapid, and affordable than ever, creating opportunities to both re-examine older studies of provenance and initiate new ones. This talk describes recent applications of lead and strontium isotopes to materials preserved in the archaeological record of the American Southwest and Mexico (e.g. turquoise, metals, glazes). These new isotopic data revise our knowledge of artifact provenance across these regions and challenge long-held ideas about the nature of long-distance exchange networks in Prehispanic North America. The novel insights gained through these studies highlight the continuing power and potential of lead and strontium isotopes as tracers of archaeological materials.

Interregional interaction and Dilmun power in the Bronze Age: A provenance study of ceramics from Bronze Age sites in Kuwait, Bahrain, and the Indus Valley using non-destructive pXRF analysis 

Known as the most interactive period of trade and interregional interaction, socio-political regions in the Bronze Age were highly involved in the Near Eastern economy. Dilmun was in charge to control the commodities and transshipment between Gulf political entities such as Mesopotamia as well as Eastern Arabia and far-distance ones such as the Indus Valley. This paper seeks to launch the first scientific provenance study on a regional scale for 2nd millennium Dilmun pottery in the Persian-Arabian Gulf, particularly Kuwait and Bahrain. Going beyond typological technique, our aim is to reconstruct a chemical database of Bronze Age ceramics and fingerprint the production centers in the Persian-Arabian Gulf using trace elements Rb, Sr, Y, Zr, and Nb obtained with a non-destructive portable X-ray fluorescence spectrometer. Multiple spots on artifact surfaces were tested to inspect the quantitative precision of the technique and the homogeneity of ceramics analyzed non-destructively.

Analysis of samples excavated from a royal tomb in El Zotz: Application of materials science characterization techniques in archaeology 

This project focuses on the characterization of materials from burial offerings and painted decoration in a royal Maya tomb at El Zotz, Guatemala and their association to mortuary rituals. Archaeological findings included vessels, jade masks, organic materials (wood, cord, and textiles), specular hematite cubes, shells with powdered cinnabar, green (malachite) painted stucco assumed to have decorated the wooden bier where the king was resting, and cashes of lip-to-lip orange bowls containing human phalanges. This paper describes preliminary findings from non-invasive and non-destructive analysis techniques including XRF, VPSEM-EDS, XRD, and Raman spectroscopy, emphasizing the potential of these combined technologies in the identification of organic and inorganic markers to infer burial customs. The nature and location of the findings, the evidence of pigment coloration on the bones employing hematite and cinnabar, and the indication of exposure of the bones to high temperatures suggest highly complex mortuary practices of Maya elite.

Archaeological chemistry: A career in ruins 

This paper will give a brief review of the history of the applications of chemistry to archaeology, highlight a few modern examples, and discuss the challenges presented by the need to integrate research from two very different cultural traditions, straddling the science/humanities 'divide'.

Biogeochemical contributions to our understanding of hominin diet 

Biogeochemical approaches have provided insights into the diets of early hominins and more recent humans. Revelations in the past few years, in particular, have fundamentally changed our understanding of the diets of several hominin taxa, and in so doing, are shaping the dialogue about the selective pressures faced by our ancestors. Moreover, data have recently been generated for nearly the entire suite of African hominins, which allows us to address questions about regional and temporal differences, as well as about the relationship between diet and morphology in new ways. Here, I discuss these data, how they are shaping our thinking about human evolution, and try to draw some general conclusions about the contributions of biogeochemistry to our understanding of the past.

Portable X-ray fluorescence in archaeology: Issues related to limitations of instrumentation and suggested methods to achieve desired results 

This is an exciting time for archaeology. The ongoing miniaturization of analytical instrumentation has advanced to a state where traditional lab based analysis can now be performed in the field (i.e. XRF, Raman, FITR etc…). This in situ analysis can be enormously advantageous for archaeologists providing identification of artifacts on the spot and even helping guide excavation to be more beneficial. But what seems advantageous can also be detrimental if not fully understood. pXRF offers a utopian view of this on site elemental analysis, but what is often offered and promoted by manufacturers rarely will produce viable results when investigating the material types we encounter. The underlying physics of XRF limit what we should consider acceptable data, yet we can extract exceptionally useful information when this instrument is used responsibly. Several examples will be given to emphasize this position and methods of analysis will be recommended to aid in proper interpretation of raw data.

Geochemical exploration of pottery and kiln fragments by ICP-OES at Aquabona (northeast Italy): Identifying late Republican and early Imperial Roman amphora production 

Major and trace-element concentrations determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) show that three pottery groups can be distinguished involving the characterization of new amphora production sites at the Adriatic coast. This paper focuses on three different research questions: (1) characterize the amphora production at Acquabona, (2) identify possible chronological differences in raw material use, (3) define the relation of the ceramics with the excavated kilns and samples clay and soil material. The selection of raw materials is chronologically diversified and corresponds with the local production of amphora (175-25 BC). Groups are distinguished using SiO2, CaO, Sr and Zr data combined with statistical factor and cluster analysis. Using geochemical analysis in determining pottery production proved to be successful in determining local signatures of ceramics and clays. In this study alkaline earth minerals (e.g. Ba and Sr) and high field strength elements (e.g. Zr) are considered useful for provenance studies taking into account the variety of clays and non-plastic materials used in manufacturing ceramics.