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Red Earth, Green Glass, and Compositional Data: A New Procedure for Solid-State Elemental Characterization, Source Discrimination, and Provenience Analysis of Ochres

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A Correction to this article was published on 09 March 2020

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Abstract

Ochres are a diverse category of naturally occurring iron-enriched earths and rocks, as well as iron oxide minerals, that derive their color from iron-containing chromophores and are suitable for use as pigments. Over the last two decades, provenience studies of archaeological ochres have grown from a rarity largely of interest only to specialists to an accepted and expected part of the archaeological science panoply. The most effective approach to distinguishing among sources of ochre and assigning archaeological pigments to their origin is multi-elemental characterization or “elemental fingerprinting.” In this study, we coupled a sample preparation method not previously used in ochre archaeometry with elemental fingerprinting by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) and Electron Probe MicroAnalysis (EPMA). We present a procedure for lithium borate (LiBo) fusion of samples for solid-state analysis, optimized for use with ochres, and designed for the budget and laboratory equipment constraints faced by many professional and student archaeologists. This method development research is part of the broader project “OLKARIA: Ochre Landscapes of Kenya – Anthropological Research and Iron-oxide Archaeometry,” which seeks in part to characterize the elemental composition of all known geologic ochre sources in the Kenya Rift Valley. Using a subset of project OLKARIA samples prepared by LiBo fusion and measured with LA-ICP-MS and EPMA, we successfully distinguished among six geologic ochre sources and a sample of commercially available iron oxide pigment. Our ability to uphold the Provenience Postulate for this data set compared favorably with source discrimination analyses done using data from Neutron Activation Analysis (NAA) of whole ochre for the same samples. LiBo fusion presents potential solutions to some criticisms of solid-state analysis of ochre using beam techniques, including issues arising from mineralogical heterogeneity, variable surface topography, the presence of free and chemically bound water, and the lack of matrix-matched standard reference materials. We also address the challenges of applying compositional data analysis best practices to ochre with an emphasis on the issues of rounded zero replacement and multivariate normality and highlight the work that remains to be done in this area.

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Change history

  • 09 March 2020

    The Online First version of this article unfortunately contained an error in the dimensions of LiBo fused bead shards described in the section “Lithium Borate Fusion Methods”.

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Acknowledgments

All EPMA measurements were taken by Dr. Philip Piccoli of the University of Maryland at College Park Department of Geology. All NAA measurements were made by staff of the Missouri University Research Reactor Archaeometry Laboratory. Mr. Benoit Bouchard of Katanax/SPEX SamplePrep assisted in the initial development of the LiBo fusion procedure for ochre.

We thank the Kenya National Commission for Science, Technology, and Innovation (NACOSTI), Republic of Kenya Ministry of Higher Education Science and Technology, and National Council for Science and Technology for research clearance (Permit No. NACOSTI/P/15/6102/6746). This work would not have been possible without the efforts of our Maasai, Dorobo, and Samburu field guides, informants, and hosts (ashe oleng!), and John Munyiri of the National Museums of Kenya Archaeology Department. We also thank Ms. Mercy Gakii (National Museums of Kenya Cultural Heritage Department) and Mr. Matthew Magnani (Harvard University Department of Anthropology) for help in documenting ochre deposits and ethnography of traditional source exploitation and cultural practices.

Funding

This project was supported by grants for ochre ethnography and source sampling in Kenya and geochemical characterization in the USA: National Science Foundation (NSF) SBE Interdisciplinary Postdoctoral Fellowship SMA-1513984 (Zipkin, Ambrose, Lundstrom), NSF Senior Archaeology Research Grant BCS-15-61176 (Zipkin, Ambrose), and Wenner-Gren Foundation Post-Ph.D. Research Grant 02628 (Zipkin). LA-ICP-MS was made possible by NSF Instrumentation and Facilities Grant EAR-1441465 (Lundstrom, Ambrose, Johnson, Guenthner).

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Authors and Affiliations

  1. Department of Anthropology, University of Illinois at Urbana-Champaign, 109 Davenport Hall, 607 S. Mathews Ave, Urbana, IL, 61801, USA

    Andrew M. Zipkin & Stanley H. Ambrose

  2. School of Human Evolution and Social Change, Arizona State University, P.O. Box 872402, Tempe, AZ, 85287-2402, USA

    Andrew M. Zipkin

  3. Department of Geology, University of Illinois at Urbana-Champaign, 3086 Natural History Building, 1301 West Green Street, Urbana, IL, 61801, USA

    Craig C. Lundstrom, Gideon Bartov & Alexander H. Taylor

  4. Department of Chemistry, University of Illinois at Urbana-Champaign, 505 S. Mathews Avenue, Urbana, IL, 61801, USA

    Alyssa Dwyer

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  1. Andrew M. Zipkin
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  2. Stanley H. Ambrose
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Correspondence to Andrew M. Zipkin.

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The original version of this article was revised: It contained an error in the dimensions of LiBo fused bead shards described in the section "Lithium Borate Fusion Methods".

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Zipkin, A.M., Ambrose, S.H., Lundstrom, C.C. et al. Red Earth, Green Glass, and Compositional Data: A New Procedure for Solid-State Elemental Characterization, Source Discrimination, and Provenience Analysis of Ochres. J Archaeol Method Theory 27, 930–970 (2020). https://doi.org/10.1007/s10816-020-09448-9

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