Application of ICP-MS trace element analysis in study of ancient Chinese ceramics

Thirty-nine trace elements of the Song-Yuan period (960-1368 AD) porcelain bodies from Cizhou, Jizhou and Longquanwu kilns were analyzed with ICP-MS, a technique rarely used in Chinese archaeometry, to investigate its potential application in such studies. Trace element compositions clearly reflect the distinctive raw materials and their mineralogy at the three kilns and allow their products to be distinguished. Significant chemical variations are also observed between Yuan and Song-Jing dynasties samples from Cizhou as well as fine and coarse porcelain bodies from Longquanwu. In Cizhou, porcelains of better quality which imitate the famous Ding kiln have trace element features distinctive from ordinary Cizhou products, that indicates geochemically distinctive raw materials were used and which possibly also underwent extra refining prior to use. The distinct trace element features of different kilns and the various types of porcelains from an individual kiln can be interpreted from a geochemical perspective. ICP-MS can provide a large amount of valuable information about ancient Chinese ceramics as it is capable of analyzing >40 elements with a typical of precision < 2%.

ICP-MS Trace Element Analysis of Song Dynasty Porcelains from Ding, Jiexiu and Guantai kilns, North China

Bodies of Ding kiln white porcelains and their imitations from Guantai and Jiexiu kilns of the Chinese Song dynasty (960-1279 AD) were analysed for 40 trace elements by inductively coupled plasma mass spectrometry (ICP-MS). Numerous trace element compositions and ratios allow these visually similar products to be distinguished, and a Ding-style shard of uncertain origin is identified as a likely genuine Ding product. In Jiexiu kiln, Ding-style products have trace element features distinctive from blackwares of an inferior quality intended for the lower end market. Based on geochemical behaviour of these trace elements, we propose that geochemically distinctive raw materials were used for Ding-style products of a higher quality, which possibly also underwent purification by levigation prior to use. Capable of analysing over 40 elements with a typical long term precision of < 2%, this high precision ICP-MS method proves to be very powerful for grouping and characterising archaeological ceramics. Combined with geochemical interpretation, it can provide insights into the raw materials and techniques used by ancient potters. (C) 2004 Elsevier Ltd. All rights reserved.

(Table 2) Trace element composition of seleceted clast and matrix materials from ODP Site 125-786

Shipboard examination of volcanic and sedimentary strata at Site 786 suggested that at least four types of breccias are present: flow-top breccias, associated with cooling and breakup on the upper surface of lava flows; autobreccias, formed by in-situ alteration at the base of flows; fault-gouge breccias; and true sedimentary breccias derived from weathering and erosion of underlying flows. It is virtually impossible to assess the origin of breccia matrix by textural and mineralogical analyses alone. However, it is fundamental for our understanding of breccia provenance to determine the source component of the matrix material. Whether the matrix is uniquely clastderived can be determined by geochemical fingerprinting. Trace elements that are immobile during weathering and alteration do not change their relative abundances. A contribution to the matrix from any source with an immobile trace element signature different from that of the clasts would appear as a perturbation of the trace element signature of the matrix. Trace element analysis of bulk samples from clasts and matrix material in individual breccia units was undertaken in a fashion similar to that used by Brimhall and Dietrich (1987, doi:10.1016/0016-7037(87)90070-6) in analyzing soil provenance: (1) to help distinguish between sedimentary and volcanic breccias, (2) to determine the degree of mixing and depth of erosion in sedimentary breccias, and (3) to analyze the local provenance of the individual breccia components (matrix and clasts). The following elements were analyzed by X-ray fluorescence (XRF): Rb, Sr, Ba, U, Zr, Cu, Zn, Ti, Cr, and V. Of these elements, Zr and Ti probably exhibit truly immobile behavior (Humphris and Thompson, 1978, doi:10.1016/0016-7037(78)90222-3 ). The remaining elements are useful as a reference for the extent of compositional change during the formation of matrix material (Brimhall and Dietrich, 1987, doi:10.1016/0016-7037(87)90070-6).

Foraminiferal trace element ratios from South Atlantic sediments

The rate of uranium accumulation in oceanic sediments from seawater is controlled by bottom water oxygen concentrations and organic carbon fluxes-two parameters that are linked to deep ocean storage of CO2. To investigate glacial-interglacial changes in what is known as authigenic U, we have developed a rapid method for its determination as a simple addition to a procedure for foraminiferal trace element analysis. Foraminiferal calcite acts as a low U substrate (U/Ca < 15 nmol/mol) upon which authigenic U accumulates in reducing sediments. We measured a downcore record of foraminiferal U/Ca from ODP Site 1090 in the South Atlantic and found that U/Ca ratios increase by 70-320 nmol/mol during glacial intervals. There is a significant correlation between U/Ca records of benthic and planktonic foraminiferal species and between U/Ca and bulk sediment authigenic U. These results indicate that elevated U/Ca ratios are attributable to the accumulation of authigenic U coatings in sediments. Foraminiferal Mn/Ca ratios were lower during the glacial intervals, suggesting that the observed U accumulation on the shells is not directly linked to U incorporation into secondary manganese phases. Thus, foraminiferal U/Ca ratios may provide useful information on past changes in sediment redox conditions.

High temporal resolution insights into early life histories: integrating histomorphometric, trace element and isotopic analyses of dental hard tissues in archaeological populations from Italy

Teeth, with their high mineralisation, incremental growth, and lack of remodelling, serve as biological archives that document an individual's development. This project aims to utilise the potential of teeth in bioarchaeological studies to achieve three primary objectives: 1) to investigate the application of histological and histochemical methods in reconstructing developmental bio-chronologies and early life histories; 2) to refine the temporal precision of isotopic analysis of dentine collagen by developing a novel protocol that integrates micro-sampling techniques with high-resolution histomorphometrics; and 3) to synthesise data from enamel and dentine for a comprehensive understanding of early life development and dietary transitions. This study adopts an integrated multidisciplinary bioarchaeological approach, conducting histomorphometric analysis on enamel and dentine across deciduous and permanent dentitions. It applies high-temporal resolution trace element analysis to enamel using LA-ICPMS and δ13C and δ15N isotope analyses through sequential micro-sampling to dentine of permanent teeth. Samples were selected from diverse archaeological contexts across the Italian peninsula, covering the Upper Palaeolithic, Copper Age, and Early Medieval periods, providing insight into diachronic variations in infant development and life history. Findings highlight the efficacy of histological and histochemical techniques in accurately determining growth rates, physiological stress, dietary shifts (particularly timing of weaning), and age at death in infant remains. The consistency and comparison between enamel and dentine underscores the enhanced insight obtained from integrating information from both tissues. Importantly, the newly proposed protocol significantly improves the temporal accuracy of dentine collagen analysis, facilitating precise chronological placement of the results over broad developmental associations. This study reaffirms the significance of teeth as valuable bioarchaeological instruments. By introducing and testing multidisciplinary methods, it provides deeper insights into early life history and cultural practices across diverse chronological contexts, highlighting the importance of advanced methodologies in extracting detailed, accurate, and nuanced information from past populations.

Morphological ripening of fluid inclusions and coupled zone-refining in quartz crystals revealed by cathodoluminescence imaging: Implications for CL-petrography, fluid inclusion analysis and trace-element geothermometry

Cathodoluminescence (CL) studies have previously shown that some secondary fluid inclusions in luminescent quartz are surrounded by dark, non-luminescent patches, resulting from fracture-sealing by late, trace-element-poor quartz. This finding has led to the tacit generalization that all dark CL patches indicate influx of low temperature, late-stage fluids. In this study we have examined natural and synthetic hydrothermal quartz crystals using CL imaging supplemented by in-situ elemental analysis. The results lead us to propose that all natural, liquid-water-bearing inclusions in quartz, whether trapped on former crystal growth surfaces (i.e., of primary origin) or in healed fractures (i.e., of pseudosecondary or secondary origin), are surrounded by three-dimensional, non-luminescent patches. Cross-cutting relations show that the patches form after entrapment of the fluid inclusions and therefore they are not diagnostic of the timing of fluid entrapment. Instead, the dark patches reveal the mechanism by which fluid inclusions spontaneously approach morphological equilibrium and purify their host quartz over geological time. Fluid inclusions that contain solvent water perpetually dissolve and reprecipitate their walls, gradually adopting low-energy euhedral and equant shapes. Defects in the host quartz constitute solubility gradients that drive physical migration of the inclusions over distances of tens of μm (commonly) up to several mm (rarely). Inclusions thus sequester from their walls any trace elements (e.g., Li, Al, Na, Ti) present in excess of equilibrium concentrations, thereby chemically purifying their host crystals in a process analogous to industrial zone refining. Non-luminescent patches of quartz are left in their wake. Fluid inclusions that contain no liquid water as solvent (e.g., inclusions of low-density H2O vapor or other non-aqueous volatiles) do not undergo this process and therefore do not migrate, do not modify their shapes with time, and are not associated with dark-CL zone-refined patches. This new understanding has implications for the interpretation of solids within fluid inclusions (e.g., Ti- and Al-minerals) and for the elemental analysis of hydrothermal and metamorphic quartz and its fluid inclusions by microbeam methods such as LA-ICPMS and SIMS. As Ti is a common trace element in quartz, its sequestration by fluid inclusions and its depletion in zone-refined patches impacts on applications of the Ti-in-quartz geothermometer.

U-Pb, trace element, and Hf isotope analysis for Macquarie Island detrital zircon

Oceanic zircon trace element and Hf-isotope geochemistry offers a means to assess the magmatic evolution of a dying spreading ridge and provides an independent evaluation of the reliability of oceanic zircon as an indicator of mantle melting conditions. The Macquarie Island ophiolite in the Southern Ocean provides a unique testing ground for this approach due to its formation within a mid-ocean ridge that gradually changed into a transform plate boundary. Detrital zircon recovered from the island records this change through a progressive enrichment in incompatible trace elements. Oligocene age (33-27 Ma) paleo-detrital zircon in ophiolitic sandstones and breccias interbedded with pillow basalt have trace element compositions akin to a MORB crustal source, whereas Late Miocene age (8.5 Ma) modern-detrital zircon collected from gabbroic colluvium on the island have highly enriched compositions unlike typical oceanic zircon. This compositional disparity between age populations is not complimented by analytically equivalent eHf data that primarily ranges from 14 to 13 for sandstone and modern-detrital populations. A wider compositional range for the sandstone population reflects a multiple pluton source provenance and is augmented by a single cobble clast with eHf equivalent to the maximum observed composition in the sandstone (~17). Similar sandstone and colluvium Hf-isotope signatures indicate inheritance from a similar mantle reservoir that was enriched from the depleted MORB mantle average. The continuity in Hf-isotope signature relative to trace element enrichment in Macquarie Island zircon populations, suggests the latter formed by reduced partial melting linked to spreading-segment shortening and transform lengthening along the dying spreading ridge.

(Table 1) Trace element and age analysis from the Porites coral from IODP Exp 310

Climate responses and changes in marine environments during the last deglaciation have been controversial and few paleoceanographic data are available from the tropical South Pacific, though this region is crucial in the investigations of ocean-atmosphere interactions. Integrated Ocean Drilling Program Expedition 310 was conducted to establish the time course of the postglacial sea-level rise at Tahiti in the South Pacific. A principal objective of this expedition was to examine the variation of marine environments during the last deglaciation. As fossil Porites coral is ideal for assessing past marine environments, we selected only Porites specimens from the many coral specimens retrieved, examined them by XRD, and dated them by the 14C method. In all, we obtained 17 pristine Porites specimens composed of only aragonite with ages from 15 to 9 ka. Then, we measured Mg/Ca, Ba/Ca, and U/Ca ratios and Cd contents as proxies for upwelling and sea surface temperature. Higher Ba/Ca ratios and Cd content together with lower reconstructed SSTs using U/Ca ratios in the coral specimens between 12.6 and 9.8 cal ka compared to around 15 cal ka suggest that upwelling and/or entrainment of subsurface water into mixed layer was enhanced around Tahiti during this period. This finding is consistent with previous reports and supports the idea that the South Pacific was characterized by La Niña-like conditions at least from 12.6 to 9.8 cal ka.

Characterisation of Chinese Tang sancai from Gongxian and Yaozhou kilns using ICP-MS trace element and TIMS Sr–Nd isotopic analysis

Tang sancai is one of the most important types of Chinese ceramics. To determine the provenance of Tang sancai is important to study ancient trade and other issues. In this paper we compare ICP-MS trace elements and TIMS Sr-Nd isotopes of visibly similar Tang sancai from two major production centres Gongxian and Yaozhou. The variation in contents/ratios of many of > 40 trace elements is small for samples from Gongxian, yet is considerably bigger for that from Yaozhou. However, the variation in Sr-87/Sr-86 and Nd-143/Nd-144 isotopic ratios is very small for samples from both places. Gongxian and Yaozhou samples have distinctive Sr-Nd isotopic and trace element features despite their similarity in major elements, and these analysis data can be interpreted with geochemistry, indicating that Sr and Nd isotopes have great potential in ceramic provenance studies. The distinct characterisation of these samples provides valuable criteria for identifying provenance of Tang sancai of uncertain origin. Two modern fakes are also analysed, and they can as well be distinguished from antique Tang sancai using above criteria. (c) 2005 Published by Elsevier Ltd.