Effective hydration temperature of obsidian: a diffusion theory analysis of time-dependent hydration rates

An estimate of effective hydration temperature (EHT) is needed for chronological use of obsidian hydration data. This paper describes a method for calculating EHT by the practicing archaeologist, replacing three techniques that are in general use today: estimates based on mean temperature, numerical integration of models of diurnal and annual temperature variations, and use of temperature cells. The hydration (or diffusion) coefficient of obsidian is a function of temperature and thus is time varying, while the classic quadratic law of hydration is not valid for time-varying diffusion coefficients. This paper presents a mathematical solution to the case of a time-varying hydration coefficient, based on diffusion theory, with a concise definition of EHT. It is shown that the results are not affected by concentration dependence in the diffusion coefficient. A computer program to compute the rigorous solution is described, and data are presented to explore the resulting range of variation. That use of the Lee equation to compute EHT is not appropriate for obsidian hydration studies is evident from the data presented. The effects of paleoclimatic variation are estimated, and an algebraic best fit equation and worksheet are provided as practical aids to the archaeologist.     

Induced hydration of obsidian: a simulation study of accuracy requirements

Determination of the hydration rate constant of obsidian is basic to the use of obsidian for establishing chronologies. The constant can, in principle, be determined in either of two ways: by correlations with archaeological sequences, or by laboratory experiments using induced hydration. Induced hydration holds promise of great accuracy, but results reported to date have been disappointing. This paper is based on the hypothesis that the outcomes are the result of error build-up in the induced hydration protocol, and describes an analysis based on a Monte Carlo simulation of the measurement and analysis process. Data are presented which show that the poor results are due to errors inherent in optical measurement of hydration rim thickness. It is concluded that successful use of induced hydration requires an order of magnitude improvement in accuracy of hydration rim measurement over the accuracies currently claimed for optical microscopy. The results do not affect the validity of hydration dating based on archaeological correlations.     

Obsidian hydration dating: accuracy and resolution limitations imposed by intrinsic water variability

Obsidian hydration dating typically yields a range of ages for a single chronometric measurement, even after controlling for source chemistry and effective hydration temperature. Previously published data suggest that this range is due to hydration rate variations caused by variability in the concentration of intrinsic water, and specifically hydroxyl ions, in the obsidian. Such variability exists within any given obsidian source, and even within any particular specimen. This paper analyzes the effect on age estimates of intrinsic water variability and concludes that if a controlled sample of obsidian yields a range of ages, there is no way to tell whether the range is due to long site use or to variations in hydroxyl concentration. At present there is no robust and cost-effective protocol for measuring hydroxyl concentration. Suggested guidelines for obsidian hydration dating are developed using a case study. These findings do not invalidate obsidian hydration as a chronometric technique, but they do suggest limits to the temporal resolution achievable.     

Obsidian hydration at high elevation: Archaic quarrying at the Chivay source,southern Peru

We examine obsidian hydration as a means to date archaeological sites at high elevation in the central Andes, and in particular quarry sites that are difficult to date by radiocarbon means. The Chivay obsidian source lies in a volcanic depression above the Colca Valley in Arequipa, Peru (71.5355° S, 15.6423° E) at 4950 masl. We compare obsidian hydration readings from one quarry and two workshop locations. Ninety-one flakes from the quarry pit, and 61 and 33 flakes from the workshops were analyzed for hydration bands. Of these, 68 from the quarry, and 54 and 33, respectively from the workshops produced at least one culturally meaningful hydration band. As expected, obsidian appears to hydrate slowly at this high elevation. Yet, variation in hydration readings is low within stratigraphic contexts, suggesting relatively narrow windows of knapping activities in each excavation level. A small number of radiocarbon dates allow us to develop a preliminary hydration rate for Chivay obsidian in this high elevation location. Hydration data indicate that intensive quarrying began by 3800 cal. BC and stopped ca. 2300 cal. BC. By contrast, the two workshops appear to have been deposited 2900 and 1200 cal. BC, and 2700 and 2400 cal. BC. The data are consistent with an uptick in obsidian use by at least the Terminal Archaic period.     

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.     

Field data validation of an algorithm for computing obsidian effective hydration temperature

This paper describes an analysis to validate the effective hydration temperature (EHT) algorithm for obsidian [Rogers, A.K., 2007. Effective hydration temperature of obsidian: a diffusion-theory analysis of time-dependent hydration rates. J. Arch. Sci. 34, 656-665], using hourly temperature data from the Amargosa Desert Research Site near Beatty, NV. These data were used as input to a numerical model of the temperature-dependent diffusion process, and EHT was calculated yearly and for the aggregate. The same temperature data were processed to extract input parameters for the climatic model reported and used as input for EHT computation. EHT as computed from recorded hourly data was found to be within 1 °C of that computed from the climatic model. It is also shown that computed EHT differences between sites are not sensitive to whether air or surface temperature data are used, as long as they are used consistently; however, surface temperature data must be used if depth corrections are to be made.     

A comprehensive numerical chronology for the pre-Columbian cultures of the Palpa valleys,south coast of Peru

Before the arrival of the Spaniards in Peru in 1532, many different societies flourished in the coastal desert of southern Peru. Of these, one of the best known is the Nasca culture (living in the area between about 260 cal BC and 640 cal BC.), which created the famous geoglyphs on the desert floor. In this paper we present a numerical chronology for the cultural development in the valleys of Palpa, in the northern part of the Nazca region, which spans the time from the Archaic Period (starting there around 3760 cal BC) to the Late Intermediate Period (terminating with the arrival of the Spaniards in 1532 AD). The chronology is based on more than 150 ¹⁴C samples collected by our project from well-documented archaeological excavations of 17 different sites in and around Palpa. Thanks to the advanced AMS-¹⁴C dating technique, demanding only few milligrams of organic material, we could focus on samples of plants, like beans, corn, or reed, representing single years of growth or use, and also on delicate materials like straw from clay bricks (adobe) and textiles. All single ¹⁴C dates were combined to cultural phases using a Bayesian statistical model, implementing the a priori information of the archaeological contexts, and adopting the relative ceramic chronologies available for this area.     

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.     

Comparison of XRF and PXRF for analysis of archaeological obsidian from southern Perú

Chemical sourcing is becoming an increasingly important component of archaeological investigation. Instruments used for elemental analysis generally must be operated in a controlled laboratory environment. Further, many methods require destruction of a small portion of the objects under investigation. These facts inhibit the application of chemical sourcing studies in a number of research contexts. Use of portable non-destructive instruments would resolve these issues. Sixty-eight obsidian artifacts from the site of Jiskairumoko, in southern Perú, were examined by X-ray fluorescence spectrometry (XRF) and portable X-ray fluorescence spectrometry (PXRF). Results were compared for consistency in terms of source determination and individual element concentrations. Both instruments determined that the same sixty-six artifacts derived from the Chivay obsidian source and both identified the same two artifacts that could not be assigned to source. Individual element comparisons showed significant differences, but these can be resolved through instrument cross calibration, and differences had no bearing on source identification. PXRF was found suitable for determining obsidian sources in southern Perú and for identifying specimens that require more sensitive analytical methods such as, instrumental neutron activation analysis (INAA). Regular use of Chivay at Jiskairumoko suggests consistent trade relationships developed during the Archaic.     

Strofilas (Andros Island,Greece): new evidence for the cycladic final neolithic period through novel dating methods using luminescence and obsidian hydration

The recently excavated coastal prehistoric settlement of Strofilas on Andros Island (Cyclades, Greece) in the Aegean sheds new light on the transitional phase from the Final Neolithic to Early Cycladic period regarding masonry, fortification, and richly engraved rock art. The fortification possesses early evidence of preserved defensive architecture, as evidenced from the plethora of scattered finds from within and around the settlement. Important features are carvings on rock walls which mainly depict ships, animals, and fish. Initial archaeometric dating via the application of luminescence dating of two samples from the fortified wall bearing engraved ships, and by obsidian hydration of two blades employing the new SIMS-SS method (secondary ion mass spectrometry via surface saturation), has been undertaken to determine the site's chronology. The former yields an average date of 3520 (±540) BC and the latter an average date of 3400 (±200) years BC, both of which, within overlapping errors, suggest the main settlement occurred during the Final Neolithic.     

Accuracy of obsidian hydration dating based on obsidian–radiocarbon association and optical microscopy

Most archaeologists using obsidian hydration dating (OHD) in the United States develop hydration rates from association of obsidian hydration rims with dates based on radiocarbon, subsequently using the rate for chronometric analysis. The overall accuracy of the process has never been quantified. This paper reports an accuracy analysis in which sources of uncertainty are defined and modeled and their effects quantified. A Monte Carlo simulation is used to quantify errors from rate development, while uncertainties in age resulting from chronometric analysis are calculated analytically. For typical ranges of error values, hydration rate errors of ∼5% or less are achievable in the absence of systematic errors, with errors of chronometric age estimates ∼20–30% or less.     

A provenance study of archaeological obsidian from the Andahuaylas region of southern Peru

To date, most obsidian sourcing studies in the Andes have concentrated on the highlands and Titicaca Basin of far southern Peru and northern Bolivia. Toward achieving a more complete understanding of the region, this paper offers new data on the long-term prehistoric obsidian procurement and consumption patterns in the Andahuaylas region of the south-central Peruvian highlands. Obsidian sourcing data from Andahuaylas are particularly interesting since the area is centrally located among several important regional obsidian sources. A total of 94 obsidian samples from a range of sites of different temporal periods were chemically analyzed using portable X-ray fluorescence (PXRF), as well as laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The results demonstrate a number of interesting trends, the first of which is the long-term importance of the Potreropampa obsidian source to populations of the Andahuaylas region from at least the early Formative period (∼2500 BCE). Secondly, the results indicate that procurement strategies by local populations in Andahuaylas were primarily reliant on nearby (<150 km) obsidian sources. Finally, the paucity of more distant, yet widely exchanged, high quality obsidian (i.e., Chivay, Alca) confirm that as a region, Andahuaylas was more heavily connected economically (and likely culturally) with local areas to the south (Apurímac) and to the west (Ayacucho).     

New discoveries in the Piramide Naranjada in Cahuachi (Peru) using satellite,Ground Probing Radar and magnetic investigations

The detection of buried earthen structures by using remote sensing techniques is still an open issue and a strategic challenge as crucial as it is complex. It is crucial because earthen archaeological remains are widely present thoughtout the world (in South America, Asia, Africa) and it is complex due to the subtle physical contrast between earthen remains and the surrounding subsoil.     

Dietary shifting in the Nasca Region as inferred from the carbon- and nitrogen-isotope compositions of archaeological hair and bone

The topography of the Andean Region results in short travelling distances among ecologically distinct production zones. As such, it is possible to infer relative changes in residence based on the spatial variability in the isotopic composition of food resources. Here, we determine long-term diet through carbon- and nitrogen-isotope analysis of bone collagen for twenty-nine individuals from Cahuachi, an important ceremonial centre in the Nasca Region. We also reconstruct the temporal sequence of change in dietary isotopic compositions along hair samples for seventeen individuals buried at Cahuachi and the neighbouring site of Huaca del Loro.     

Prehistoric settlement chronology on Rapa Nui,Chile: obsidian hydration dating using infrared photoacoustic spectroscopy

The prehistoric Polynesian inhabitants of Rapa Nui (Easter Island) utilized obsidian for nearly 700 years in many activities connected with daily life. The near ubiquitous occurrence of the natural glass in both domestic residences and religious structures makes the application of obsidian hydration dating highly suitable for the investigation of cultural change. We have applied previously developed calibrations that estimate hydration rates for obsidian based upon the structural water content of the glass as determined by infrared spectroscopy. The archaeological ages estimated by this method were compared with accelerator mass spectrometry (AMS) dates using short-lived woody species endemic to the island. The convergence between the two dating methods is strong and we suggest that obsidian hydration dating may be used on Rapa Nui to reliably date contexts where suitable material for AMS dating may not be available.     

Wari’s imperial influence on local Nasca diet: The stable isotope evidence

The highland Wari Empire established a presence within the Nasca region of south coastal Peru during the Middle Horizon period. To clarify the nature of this interaction, we analyzed stable carbon and nitrogen isotope ratios of human bone collagen from individuals living in the Southern Nasca Region (SNR) before (1–750 AD) and during (750–1000 AD) imperial influence. The stable isotope data do not indicate that the Wari Empire transformed maize agricultural labor in the Las Trancas Valley of the SNR. In fact, during both time periods, Nasca people had access to a wide range of food items.     

Assessing the applicability of portable X-ray fluorescence spectrometry for obsidian provenance research in the Maya lowlands

Recent innovations in portable energy-dispersive X-ray fluorescence (PXRF) spectrometry have increased its utility for the geochemical characterization of obsidian artifacts for archaeological provenance research. However, concerns over the utility of PXRF instrumental analyses have been raised, focused on the validity and reliability of the geochemical data produced. Here we adopt the framework of Richard Hughes (On Reliability, Validity, and Scale in Obsidian Sourcing Research, 1998), whereby reliability addresses instrument stability and issues of measurement while validity pertains to an instrument’s ability to discern geochemical source provenance. This is done in order to test the utility of PXRF instruments for archaeological provenance research. k-Means cluster analysis was used to test the accuracy of PXRF through statistical comparison of data acquired via laboratory and portable energy-dispersive XRF instruments. Multivariate analysis was employed to demonstrate obsidian source representation at two Classic Maya archaeological sites in southern Belize – Uxbenká and Ek Xux – and to test the validity of data obtained from a PXRF instrument in answering archaeological research questions pertaining to regional interactions between lowland Maya polities. Results suggest that portable XRF instruments produce internally consistent results. However, data acquired from a PXRF instrument are not statistically equivalent to other XRF instruments. This is to say that while PXRF is not a reliable technique, it is valid for questions pertaining to geochemical source representation.     

The archaeology of radiocarbon accelerator dating

Accelerator mass spectrometry (AMS) allows radiocarbon dating to be carried out by direct counting of¹⁴C atoms, rather than the conventional counting of radioactive disintegrations. The result is that samples up to 1000 times smaller can be handled. The approach was tested in principle by 1977 and for archaeological operation by 1983. More than 2000 samples per year are now being dated worldwide. The machines can now operate to about ± 80 years or better. Dates older than 40,000 years have not yet been achieved, but the ability to use small samples has already had considerable impact on dating the period 10,000–30,000 years ago. Bone is an ideal material for the new technique, since amino acids can normally be isolated and purified from gram-size samples. Studies of the origins of domestication are aided by the dating of individual grains and seeds. Because small samples can be mobile in the soil, careful sample selection strategies and procedures are required. The full impact of the technique can be assessed only through the rapid and comprehensive publication of archaeological results.