Obsidian hydration dating by infrared spectroscopy: method and calibration

Low temperature (90–190 °C) hydrothermal experiments have been conducted on seven obsidians where composition of the glass varies significantly in the concentration of structural water within the unhydrated bulk material. Infrared transmission spectroscopy was used to track the diffusion of molecular water into the glass surface as a function of time and temperature. Long-term (60–360 days) hydration sequences at 90 °C show a t^0.6 time dependence for the mass uptake of molecular water that forms the hydration layer. The structural water concentration of the unhydrated bulk obsidian is highly correlated with the pre-exponential and activation energy and may be used to estimate the Arrhenius constants. In addition, secondary ion mass spectrometry (SIMS) hydrogen profiling of Napa Glass Mountain obsidian hydrated at 90 °C reveals that the early stages of diffusion exhibit a dynamic behavior that includes a fluctuating hydrogen concentration and a changing diffusion coefficient that slows with time.     

Radiocarbon dating and the “old shell” problem: direct dating of artifacts and cultural chronologies in coastal and other aquatic regions

Archaeologists have long recognized the problem of the “old wood” effect in radiocarbon dating charcoal and wood samples, the age of which may be hundreds of years older than their use by humans. Such problems have resulted in significant changes in how most researchers select wood and charcoal samples for ¹⁴C dating, with many now using relatively short-lived carbonized materials for dating. Despite the significant strides made in our understanding of the potential biases of the “old wood” effect, little emphasis has been placed on the possible impacts of dating “old shell” in archaeological deposits. The use of marine shell for ¹⁴C dating is widespread in coastal areas around the world, including a growing emphasis on the dating of individual shell artifacts via Accelerator Mass Spectrometry (AMS). In dating shell artifacts, we have obtained several dates older than associated ¹⁴C dates for short-lived subsistence remains from the same deposits, including great disparities (>10,000 years) and more subtle differences (≥100 years). These discrepancies appear to be due to the use of old shells by humans to make beads and other artifacts, including shells collected from fossil deposits, older archaeological sites, and beaches. The problems caused by the use of old shells to make beads and other artifacts are surmountable through careful sample selection, analysis of multiple ¹⁴C dates on a variety of materials, and proper calibration procedures.     

SIMS‐SS,A NEW OBSIDIAN HYDRATION DATING METHOD: ANALYSIS AND THEORETICAL PRINCIPLES*

The water diffusion mechanism in obsidian has been revisited with the advent of a new dating approach employing secondary ion mass spectrometry (SIMS). The water diffusion SIMS(+) profile and the concept of a surface saturation (SS) layer in obsidians both provide a sound basis for the new diffusion age equation (SIMS‐SS) and are supported by dated world examples ( Liritzis et al. 2004 ). Here, we present the basic physical–chemical analysis of the mass transport phenomenon on which the new dating method is based. The crucial age parameter of the SIMS‐SS dating approach for archaeological obsidians—that is, the surface saturation (SS) layer—is supported by both theoretical and experimental data.     

Infra-red Photoacoustic and Secondary Ion Mass Spectrometry Measurements of Obsidian Hydration Rims

A procedure has been developed for measuring obsidian hydration rim thicknesses on archaeological artefacts using infra-red photoacoustic spectroscopy (IR-PAS). Calibration of the IR-PAS values with depth was completed using secondary ion mass spectrometry (SIMS) and optical microscopy to relate the quantity of diffused water to the measured thickness of the hydration layer. By monitoring the absorbance intensity at 1630 cm⁻¹wavenumbers, hydration rims between approximately 1 μm and 12 μm may be accurately measured and used for chronometric age estimates. SIMS depth profiling has the ability to measure layers less than 1 μm thick, extending the age calibration to samples of less than 100 years in age.     

Melian obsidian in NW Turkey: Evidence for early Neolithic trade

Abstract

Archaeological investigations carried out at the Early Neolithic coastal site of Co?kuntepe in northwestern Turkey yielded an assemblage of 110 obsidian artifacts displaying the macroscopic characteristics of the well-known obsidian deposits on the Cycladic island of Melos. Analysis of three samples from this homogeneous obsidian assemblage using both X-Ray Fluorescence and Laser Ablation High Resolution Inductively Coupled Plasma Mass Spectrometry confirmed that these artifacts were derived from Melos. The presence of these Melian obsidian artifacts at Co?kuntepe, along with a few pieces with central Anatolian macroscopic characteristics, is intriguing because intensive production of tools made of local flint was also identified at the site through the analysis of surface scatters. This finding raises the question of the status of obsidian and associated procurement systems. The presence of obsidian can be also used to argue that certain coastal villages acted as nodes of exchange for Aegean seafarers at times in the late 7th millennium B.C.     

Increasing data (INAA) on Ecuadorian obsidian artifacts: preliminary provenance and a clue for pre-Columbian eastward trade

In this work we carried out INAA major (Na, K, Ca and Fe %) and trace (ppm) elements (plus Mn by FAAS analysis) of 15 obsidian samples (waste flakes) coming from an unknown archaeological site (¹⁴C-AMS age of 1425 AD) located on the south-eastern flank of the back-arc Sumaco volcano (to the east of the Cordillera Real) and from two already known pre-Columbian archaeological localities: La Florida (Quito) and Milan (Cayambe). Literature compositional data of the Ecuadorian obsidian outcrops provide some constraints on the provenance of the analyzed waste flakes, even though different methods of analyses make comparisons a difficult task. Concerning the obsidian artifacts of La Florida and Milan, they come from the well known Sierra de Guamanì obsidian sources (Cordillera Real). By contrast, the obsidian fragments of the Sumaco settlement show some compositional characters compatible with obsidian erratic pebbles recently discovered in some river banks of the Amazonian foothills draining the easternmost flanks of the Antisana volcano in the Cordillera Real as well. In this way, the obsidian artifacts found at the Sumaco site reinforce the opinion that Ecuadorian source inventory is not yet exhaustive. Although the Antisana volcano seems to be the best candidate to find out additional primary outcrops of obsidian sources, it cannot be also excluded that sub-Andean and Amazonian people directly took advantage from obsidian secondary sources (e.g. river banks), rather than procurements from primary outcrops in the Cordillera Real. The new archaeological findings at the Sumaco volcano are really of paramount importance in tracing the ancient routes of a possible obsidian eastward trade toward the Amazonian region.     

Late Pleistocene/Early Holocene seafaring in the Aegean: new obsidian hydration dates with the SIMS-SS method

Archaeological evidence regarding the presence of obsidian in levels that antedate the food production stage could have been the result of usage or intrusion of small obsidian artifacts from overlying Neolithic layers. The new obsidian hydration dates presented below employing the novel SIMS-SS method, offers new results of absolute dating concordant with the excavation data. Our contribution sheds new light on the Late Pleistocene/Early Holocene exploitation of obsidian sources on the island of Melos in the Cyclades reporting dates c. 13th millennium - end of 10th millennium B.P.     

The antiquity of Olivella shell beads at CA-ORA-64: AMS radiocarbon dated between 9420 and 7780 cal BP

Investigations in the 1960s and 1970s showed the Irvine site (CA-ORA-64) to be among the oldest shell middens known from the Pacific Coast of North America. The site chronology, based on conventional analysis of mixed shell samples collected from heavily bioturbated soils, extended back to ca. 8440 RYBP. Recent work at the site provided an opportunity to refine the CA-ORA-64 chronology via AMS ¹⁴C dating of single shell fragments, including 14 Olivella beads. Long considered to be one of the earliest ornament types made by Pacific Coast peoples, such spire-removed Olivella beads were used through much of the Holocene and generally are not good chronological indicators. AMS analysis of the CA-ORA-64 specimens, however, produced a consistent series of Early Holocene dates that includes some of the oldest securely dated shell beads in North America. Along with obsidian from interior sources, Olivella beads played an important role in early exchange networks between coastal and interior peoples. Methodologically, our research demonstrates the utility of AMS ¹⁴C dating in determining the age of key artifact types found in multicomponent sites with assemblages affected by stratigraphic mixing.     

Isothermal Time‐Series Determination of the Rate of Diffusion of Water in Pachuca Obsidian*

Friedman and Smith's (1960) article introducing an exciting, potentially precise and inexpensive method of dating obsidian artefacts has thus far failed to reach its potential. Numerous efforts to refine, improve and even redevelop the method since that time have similarly failed to achieve the original promise. Only within the last eight years have significant improvements been made, due to both improved analytical techniques and a better understanding of the hydration process. However, most of our mechanistic understanding of the interaction of water with rhyolitic glass is based on experiments performed on melts and glasses at temperatures above their glass transitions, conditions inappropriate for investigation of near‐surface environmental conditions. Unfortunately, studies detailing the temporal evolution of the diffusion profile at low temperatures are rare, and few useful data are available on the low‐temperature diffusive hydration of silicate glasses. This paper presents data on the experimental hydration of obsidian from the Pachuca source (a.k.a. Sierra de las Navajas, Basin of Mexico) at 75°C for times ranging from 3 to 562 days, and compares these results with data for samples obtained from a stratigraphic excavation of the Chalco site in the Basin of Mexico. Samples have been analysed using secondary ion mass spectrometry (SIMS) to provide concentration/depth data. While 75°C is still significantly above the temperatures at which archaeological obsidians hydrate, it is well below the glass transition temperature (approx. 400°C) and thus processes are likely to be similar to those that occur in nature, but fast enough to be observed over a laboratory timescale. The results demonstrate that a simple square‐root‐of‐time model of the evolution of the diffusion profile is not adequate to describe the diffusion process, as measured diffusion profiles exhibit the effects of concentration‐ and time‐dependent, non‐Fickian diffusion. With progressive hydration, characteristic diffusion coefficients first decrease, then increase with time. Surface concentration increases with time, but an intermediate plateau is observed in its time evolution that is consistent with results obtained from the suite of Chalco samples. Both of these effects have been observed during diffusion in glassy polymer systems and are associated with the build‐up and relaxation of self‐stress caused by the influx of diffusing material.     

Forensic Ar/Ar dating: a provenance study of Middle Stone Age obsidian artifacts from Ethiopia

Obsidian sourcing based on geochemistry is widely applied to reconstruct commerce patterns and dissemination of early hominid groups. Due to problems concerning potential intra-source variability or homogeneity of a geological source over large areas, parameters additional to this classical approach are desirable. Here we present the first ⁴⁰Ar/³⁹Ar investigation of Middle Stone Age (MSA) obsidian artifacts (i.e. debitage pieces) for this purpose, as well as of potential geological obsidian sources from Ethiopia. With the present pilot study we demonstrate that ⁴⁰Ar/³⁹Ar geochronology represents a reliable and powerful tool for archaeological provenance studies complementary to the geochemical approach and more recently applied techniques like fission track counting or Mössbauer spectroscopy. Two independent sets of debitage and potential source rock samples were dated by the ⁴⁰Ar/³⁹Ar method. Debitage pieces from the Kulkuletti excavation site and obsidian samples from the nearby obsidian outcrop Worja (central Ethiopia) exhibit basically identical age ranges as well as similar Ca/K and Cl/K ratios, supporting the debitage/source rock relationship previously inferred on geochemical grounds. A second small set of geochemically characterized debitage samples from the Porc Epic cave and potential source rocks from an obsidian outcrop at Kone (Eastern Ethiopia) however have different ⁴⁰Ar/³⁹Ar ages and Ca/K and Cl/K ratios. These results contradict the previous conclusion about a debitage/source rock relationship of the Porc Epic and Kone samples made on the basis of geochemistry [A. Negash, M.S. Shackley, Archaeometry 48 (2006) 1]. Additional sampling at the Kone outcrop as well as of other obsidian occurrences in the greater area is needed to unambiguously pinpoint the origin of these obsidian tools.     

“The Good,the Bad,and the Ugly”: evaluating the radiocarbon chronology of the middle and late Upper Paleolithic in the Enisei River valley,south-central Siberia

The ¹⁴C record for the Upper Paleolithic in Siberia has remained largely unevaluated and includes good, bad, and ugly dates. Too often researchers accept either all published dates or only those dates that tend to support proposed chronological hypotheses, regardless of sample quality and association. This article systematically evaluates all published ¹⁴C dates (including several newly obtained AMS dates) from middle and late Upper Paleolithic sites in the Enisei River valley of south-central Siberia to establish a reliable chronology for the region and address the tempo of modern human dispersals in Siberia during late Pleistocene times. The revised chronology indicates humans were present before and after the Last Glacial Maximum, but absent during this climatic event. Results also suggest that human population in the region may have increased during the Oldest Dryas.     

Obsidian hydration dating on the South Coast of Peru

We compare over 230 obsidian hydration readings from 30 individual site components from the Southern Nasca Region (SNR) with independent age estimates based on radiocarbon dates and temporally diagnostic artifacts. Although there are problems with small sample sizes, and readings must be adjusted for elevation, a very strong relationship accounting for nearly 90% of the total variation in the data set is found. This suggests that obsidian hydration dating (OHD) works in the SNR and is a viable means of independently estimating age. Residual values from our regression suggest that hydration age estimates are usually within 15% of the radiocarbon estimates. Finally, we present an equation other scholars can use to estimate age for Quispisisa obsidian in the SNR.     

Geochemical composition of source obsidians from Kenya

Here we provide a reference resource to archaeologists interested in the sources of obsidian in Kenya, through electron microprobe analyses of 194 obsidian samples from 90 localities. Averaged analyses of each sample and eleven published analyses are categorized into 84 compositional groups of which only about 21 are known to have been used to produce artifacts, possibly because studies of artifactual material in the region are lacking. We also provide trace element analyses determined by XRF and LA-ICP-MS for these same obsidians. In northern Kenya 27 distinct compositions of obsidian have been found, including some of Miocene age, but the source of the most abundant obsidian found in archaeological sites in this part of Kenya remains obscure. The Baringo region contains at least 13 varieties of low-silica obsidian. The Naivasha–Nakuru region contains an abundance of obsidian with 38 compositional types recognized, and is the only region in Kenya apart from the Suregei (northern Kenya) that contains rhyolitic obsidian. Nine compositionally distinct types of obsidian are known from southern Kenya. Although Kenyan obsidians span the compositional range from phonolite to rhyolite, low-silica, nepheline-normative obsidians occur only south of 1°N latitude. One obsidian type, the Lukenya Hill Group, appears to have been derived from a regionally extensive ash flow tuff with a distribution of over 8000 km². From previous studies it is known that obsidians of lowest (Mundui) and highest iron content were used for tool manufacture, as were some obsidians (e.g., Kisanana) with the highest alkali content, and obsidians with both high (Njorowa) and low (Kisanana) silica content.     

Possible isotopic fractionation of argon in source obsidians and archeological artifacts from Kulkuletti, Ethiopia

Despite uniform geochemistry ⁴⁰Ar/³⁹Ar ages of 0.6, 1.25, and 1.3 Ma on obsidians from a source flow (Worja) and from archeological artifacts at the sites of Kulkuletti (near Gademotta, Ethiopia) have been interpreted to suggest that they derive from different source flows of different ages. A further suggestion is that the magmatic source of the obsidian flows was chemically homogeneous between 1.3 Ma and 0.6 Ma. Chemical analysis of these obsidians indeed suggests that they derive from a single flow. Reexamination of the argon isotopic data reveals that argon isotopes may have been fractionated within the flow, so that the assumption of an atmospheric ⁴⁰Ar/³⁶Ar ratio of 295.5 is inappropriate to use for computing ages. Three groups of data are apparent, and internally all yield ages near 1.3 Ma if the intercept value for ⁴⁰Ar/³⁶Ar from an isotope correlation plot is used for computation instead of using the atmospheric ratio. The Soret thermal diffusion effect provides a possible mechanism of fractionation of argon within the obsidian flow that is of approximately the right magnitude to explain the observations by in-diffusion of already fractionated atmospheric argon.     

Radiocarbon Chronometry of Site QJ-280, Quebrada Jaguay,a Terminal Pleistocene to Early Holocene Fishing Site in Southern Peru

Excavations in 1970, 1996, and 1999 at Site QJ-280, Quebrada Jaguay, in southern Peru, yielded enough dateable terrestrial plant material to establish an extensive radiocarbon chronology for the site. QJ-280 is one of oldest well-dated fishing sites in the Americas: it was occupied from the terminal Pleistocene to the mid-Holocene (about 13,000–8,300 calibrated years BP) based on 42 terrestrial radiocarbon dates, encompassing the Jaguay and Machas Phases of the local archaeological sequence. In addition to the terrestrial dates, radiocarbon measurements on valves of two marine surf clam (Mesodesma donacium) individuals from a single, well-dated mid-Holocene Manos Phase archaeological context have provided insight into marine upwelling conditions during the occupation of Quebrada Jaguay. The marine reservoir age varied between 130 and 730 ¹⁴C years during the brief lives of the two clams (up to 5 years each), and varied by up to 530 ¹⁴C years within an individual valve, suggesting strong and variable deep marine upwelling; conditions broadly similar to those that exist in coastal Peru today. These rapid variations in marine radiocarbon age suggest that marine radiocarbon dates from environments with variable upwelling could be skewed by up to hundreds of years.     

RADIOCARBON TRENDS AND THE EAST TEXAS CADDO TRADITION (CA. A.D. 800–1680)

Abstract

Through the employment of radiocarbon (¹⁴C) dates as data, we use the date combination process to refine site-specific summed probability distributions for 555 dates from Caddo sites (n = 19) in East Texas with 10 or more ¹⁴C dates. Summed probability distributions are then contrasted across river basins and natural regions with the remainder of the East Texas Caddo Radiocarbon Database (n = 338 dates from 132 other Caddo sites), highlighting the temporal and spatial character of Caddo archaeological sites throughout East Texas.     

Macusani obsidian from southern Peru: A characterization of its elemental composition with a demonstration of its ancient use

Transparent obsidian artifacts have been reported for the northern Lake Titicaca Basin. Based on instrumental neutron activation analysis (INAA) of these artifacts a distinct chemical group was identified. Yet, the location of the source of transparent obsidian in the southern Andes remained unreported in the archaeological literature. This paper reports on the chemical composition and geographic location of a source of transparent obsidian from the Macusani region of Peru. Through the use of INAA and portable X-ray fluorescence (PXRF) we demonstrate that Macusani obsidian or macusanite comprises (at least) two chemical groups. One of these groups was used for making artifacts during the Archaic Period. Artifacts made of this obsidian were found more than 120 km from the source and yet, one-third of the obsidian artifacts encountered at Macusani were from the non-local source of Chivay which is 215 km to the southwest.     

Topographical evolution and C age dating of the construction of the Eurimji reservoir (Jecheon,Korea)

The Eurimji site in Jecheon City, Chungcheong Province holds major importance for Korean cultural heritage because it is assumed to be the oldest man-made reservoir for rice field irrigation in Korea. A multiproxy study provides the first scientific dating of the levee construction. The authors retrieved two sediment cores from the levee (core ER-1, 18.00 m long) and the reservoir bottom (core ER-3-1, 6.98 m long). Several plant fragment layers were observed between layers of dark gray clay–silt sediment in unit 2 of both cores. The spacing and thickness of these plant layers was relatively uniform (from 50 to 90 cm, and 5 to 6 cm, respectively). These features are interpreted to represent part of a man-made sedimentary sequence created using the consolidation-settlement drain method (tamped-earth or rammed-earth method) commonly used for dam or fortress construction in ancient times, as the features are not characteristic of natural river sedimentary processes. In this alternating sequence, bulk carbon from the sediment yielded AMS ¹⁴C dates of 2000–1400 ¹⁴C yr BP, and the plant materials yielded dates of 1300–1200 ¹⁴C yr BP. If workers at that time used two different materials such as available plant materials and clays for levee construction, the plant material is preferred for ¹⁴C age dating. This is because the origin of the carbon in the sediments is ambiguous, but the source of the plant materials has been confidently determined to be equivalent to the time of the levee construction. Therefore, the levee was constructed between 1200 and 1100 ¹⁴C yr BP (AD 800–900), which is later than previously thought (i.e., AD 300 or AD 550). The results of our study also indicate that wetlands existed in the area before the construction of the Eurimji levee.     

Early Maya Ritual Practices and Craft Production: Late Middle Preclassic Ritual Deposits Containing Obsidian Artifacts at Ceibal,Guatemala

This article examines Preclassic Maya ritual practices and craft production by means of a study of ritual deposits containing obsidian artifacts dated mostly to the late Middle Preclassic period (700–350 b.c.) at Ceibal, Guatemala. New ritual practices developed at Ceibal during this period, possibly through political interactions and negotiation involving emerging elites and other diverse community members. Common objects in ritual deposits in the public plaza shifted from greenstone celt caches to other artifacts, including those made of obsidian. The inhabitants of Ceibal engaged in various kinds of craft production, including the manufacture of obsidian prismatic blades. They also conducted public rituals in the Central Plaza, depositing exhausted polyhedral obsidian cores and other artifacts with symbolic significance in caches and as offerings in incipient elite burials and interments of sacrificed individuals. These cores clearly demonstrate the use of a sophisticated blade technology. Like greenstone objects, exhausted polyhedral obsidian cores deposited in cruciform arrangements along the east–west axis of the central E-Group plaza were used as symbols and markers of the center and four cardinal directions within the Maya cosmos. Public rituals were important for creating collective identities and for processes of political negotiation within the community. Emerging elites likely came to play an increasingly important role in public rituals as principal performers and organizers, setting the stage for later public events centered on rulers.     

Comments on Graf, Journal of Archaeological Science 36, 2009 “ “The Good, the Bad, and the Ugly”: evaluating the radiocarbon chronology of the middle and late Upper Paleolithic in the Enisei River valley, south-central Siberia”

Here I present a critical evaluation of the analysis conducted by Graf [Graf, K.E., 2009. “The Good, the Bad, and the Ugly”: Evaluating the radiocarbon chronology of the middle and late Upper Paleolithic in the Enisei River valley, south-central Siberia. Journal of Archaeological Science 36, 694–707] of the Paleolithic radiocarbon (¹⁴C) dataset for the Upper Paleolithic sites in the Yenisei River basin of Central Siberia. Graf applied a rating system to the corpus of existing ¹⁴C data for the region, and announced some new ¹⁴C dates. The results obtained, however, are highly biased due to several factors, including prejudice concerning the higher accuracy of the AMS technique in ¹⁴C dating and that ¹⁴C dates from the same cultural component should overlap with plus–minus two sigmas; ambiguities with the subdivision of the Lateglacial period; artificially high sample selection criteria; incomplete factual material; and unjustifiable and misleading statements on the ¹⁴C dating of fossil bones and the issue of Last Glacial Maximum human presence in Siberia. As a result, the conclusions made by Graf [Graf, K.E., 2009. “The Good, the Bad, and the Ugly”: Evaluating the radiocarbon chronology of the middle and late Upper Paleolithic in the Enisei River valley, south-central Siberia. Journal of Archaeological Science 36, 694–707] are unconvincing. New analysis is necessary in order to improve the quality of treatment of the original data for the Upper Paleolithic ¹⁴C chronology in the Yenisei River basin.