An archaeologically validated protocol for computing obsidian hydration rates from laboratory data

This paper reports the computation of hydration rate for Topaz Mountain obsidian from laboratory data, and a comparison with archaeological data from a well-dated site, Camels Back Cave, in western Utah. Topaz Mountain obsidian is found to be slow-hydrating, with a rate of 0.071 ± 0.021 μ/yr^½ at an effective hydration temperature of 16.01 °C. This rate agrees with a rate developed from archaeological data from Camels Back Cave within ∼6%. Activation energy of Topaz Mountain obsidian is 10370 ± 544 K, and its diffusion constant is (1.87 ± 9.13) × 10¹³ μ²/yr, both of which are independent of temperature. Its intra-source variability in hydration rate is very low (CV < 0.01), implying a low variability in intrinsic water. We present a model of chemical erosion which shows why earlier laboratory-determined rates were incorrect, and discuss the implications of our findings on the determination of experimentally derived rates in obsidian hydration dating.     

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.     

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.     

Possible obsidian sources for artifacts from Timor: narrowing the options using chemical data

Measurements made at the Australian National University using laser ablation ICPMS show that none of the 88 analyzed obsidian artifacts from East Timor match either the known Papua New Guinea or the five Island SE Asian source samples in our ANU collections. There is a coastal journey of more than 3000 km between the occurrence of obsidians from the Bismarck Archipelago volcanic province of Papua New Guinea and the Sunda-Banda Arc volcanic chain, yet obsidian artifacts from the two important PNG sources of Talasea and Lou Island are found at coastal Bukit Tengkorak in eastern Sabah at a similar distance along with material that has no known source. Timor lies south of the eastern section of the active volcanic Banda Arc island chain but it is within range of possible rhyolite sources from there. Although there is a continuous chain of around 60 active volcanoes stretching from west Sumatra to the Moluccas most are basaltic to andesitic with few areas likely to produce high silica dacite–rhyolite deposits. This does not exclude the possibility that the volcanic landscapes may contain obsidian, but without detailed survey and chemical analysis of sources from the Sunda-Banda Arc the attribution of the Timor obsidian artifacts remains to be demonstrated. Timor may seem to be an unlikely source for the presence of obsidians as it lacks reports of the silica-rich rhyolite volcanic centers necessary to produce this material. Despite the absence of detailed survey and analysis of Indonesian obsidian sources, especially from the volcanically active Banda Arc, this paper presents evidence that one of two obsidian sources is clearly from Timor while the other, with less certainty, is also from an unknown local source.     

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.     

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.     

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.     

Characterization of New Zealand obsidian using PXRF

New Zealand has some of the most active areas of rhyolitic volcanism in the world and this has produced numerous obsidian sources in the northern half of the North Island. In total archaeologists have recognized 27 named locations from which obsidian can be obtained scattered across 4 geological source regions. Shortly after colonization in the late 13th century AD Polynesian settlers began transporting this material some thousands of kilometers throughout the country and across the sea in small quantities to distant neighbors in the Kermadecs and Chatham islands. Although considerable research has been conducted on obsidian sourcing in New Zealand the complexity of geochemical source discrimination and the lack of a practical method of non-destructive geochemical analysis has hindered progress. We present the results of our use of PXRF to provide geochemical data on New Zealand obsidian sources and to compare the use of discriminant analysis and classification tree analysis to discriminate among sources and attribute archaeological samples to sources. Our research suggests that classification tree analysis is superior to discriminant analysis in sourcing studies. A large case study using an important settlement phase site (S11/20) from the Auckland region demonstrates the utility of the methods and the results support a model of high degrees of mobility and interaction during the early settlement of New Zealand.     

Ancient social landscapes of northwestern Argentina: preliminary results of an integrated approach to obsidian and ceramic provenance

This article presents the results of ongoing instrumental neutron activation analyses (INAA) conducted on archaeological artifacts from the Formative period of northwestern Argentina (NWA). These studies are part of a wider archaeological project that seeks to understand the structure of the social landscape of the period by examining domestic and burial evidence from a wide range of villages across the area known as the southern Calchaquí valleys. Elemental data is discussed in the light of its potential contribution to reassess past social interaction strategies in the region.     

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.     

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.     

The prehistoric sources of Palliser Bay obsidian

A sample of 210 pieces of archaeologically derived obsidian from settlement sites in Palliser Bay, New Zealand, was subjected to X-ray fluorescent analysis, in order to define the petrographic sources exploited by these prehistoric groups. It was found that the material had been derived from sources at Mayor Island, Huruiki, Rotorua, Cooks Bay, Purangi, Ongaroto and Taupo, and with the exception of the last 3, all were being quarried as early as the 12th century AD. Problems were encountered in assessing the significance of trends in source exploitation which had been proven on other grounds, and these suggested that future analyses must involve far larger archaeological samples.     

The magnetic sourcing of obsidian samples from Mediterranean and near Eastern sources

The magnetic properties of obsidians are examined for their potential in sourcing obsidian artifacts. The three simplest to determine magnetic parameters—initial intensity of magnetization, saturation magnetization and low field susceptibility—are found to be effective discriminants of many Mediterranean, Central European and near Eastern sources. Although the between-source precision is not as good as geochemical analyses of minor and rare-earth elements, the technique demonstrated the existence of new sources that were subsequently confirmed by minor element analyses. Unfortunately some key sources do not appear to be readily distinguishable on these three simple magnetic parameters alone, although more sophisticated magnetic analyses may prove diagnostic. Despite this, it would appear that effective discrimination can be made in many cases, occasionally with more precision than minor element analyses. This technique therefore offers, as a minimum, a preliminary sourcing tool for use in many areas of the world, thus reducing the number of expensive geochemical analyses. Furthermore, its very low cost, non-destructive nature and speed open the possibility of quantitative evaluation of trade routes based on obsidian distributions, particularly as versions of the equipment are now suitable for use in the field.     

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).     

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.     

Provisioning of the Inka army in wartime: obsidian procurement in Pambamarca,Ecuador

Ninety-nine obsidian artifacts from fortified and non-fortified sites in the Pambamarca region of northern Ecuador were analyzed with XRF to examine patterns of procurement of obsidian by soldiers in the Inka army and by the local Cayambes who were resisting Inka conquest. The results show that the Inkas acquired material from several different sources, a pattern consistent with provisioning by subject peoples in partial fulfillment of labor obligations. The Cayambes also acquired material from multiple sources, although they may not have directly procured material from all of the sources because the external boundary of Inka territory bisected the region of obsidian sources. That frontier may have prevented the Inkas from accessing one source, Callejones, from which the Cayambes acquired some of their obsidian. In addition, the Inkas were acquiring some obsidian from the Yanaurco-Quiscatola source, which had been previously abandoned around AD 1000.     

From flow to quarry: magnetic properties of obsidian and changing the scale of archaeological sourcing

Previous studies have endeavored to use petrophysical traits of obsidian, particularly its magnetic properties, as an alternative to conventional geochemical sourcing, one of the greatest successes in archaeological science. Magnetic approaches, however, have not seen widespread application due to their mixed successes. In a time when geochemical analyses can be conducted non-destructively, in the field, and in a minute or two, magnetic measurements of obsidian must offer novel archaeological insights to be worthwhile, not merely act as a less successful version of geochemistry. To this end, we report the findings of our large-scale study of obsidian magnetism, which includes 734 geological obsidian specimens and 97 artifacts measured for six simple magnetic parameters. Based on our results, we propose, rather than using magnetic properties to source artifacts to a particular obsidian flow (inter-flow sourcing), these properties are best used to differentiate quarrying sites within an individual flow (intra-flow sourcing). Our results also demonstrate that certain magnetic properties are highly affected by ancient knappers' material selection criteria. Furthermore, depending on the spatial scales of variation, which likely vary from flow to flow, we envision several potential applications of this approach, including integration into minimum analytical nodule analysis (MANA). Magnetic data appear to shift the scale of obsidian sourcing from flows to quarries and, in turn, enable new insights into raw-material procurement strategies, group mobility, lithic technology, and the organization of space and production.     

The source of obsidian artefacts found at East Chia Sabz,Western Iran

Excavations at the site of East Chia Sabz in western Iran uncovered deposits dating from the 9th through 7th millennium BC showing evidence of obsidian use. A total of twenty obsidian artefacts was found at the site and they were analyzed by X-ray fluorescence and neutron activation analysis. The results show all of the obsidian found at East Chia Sabz came from the Nemrut Da? source in southeastern Turkey located a distance of almost 750 km from East Chia Sabz. The results and their archaeological implications are discussed.     

Provenance of prehistoric obsidian artefacts from Kul Tepe,northwestern Iran using X-ray fluorescence (XRF) analysis

Analysis by X-ray fluorescence of 53 obsidian artifacts the main source of obsidian for the workshops in Kul Tepe was Syunik but obsidian sources as far as west as the Lake Van region (Nemrut Da? and Meydan Da?) and as far north as Gutansar were also utilized. These new results indicate a broad network of trade and exchange.