Stabilization of the Tlaltecuhtli monolith pigments

A painted monolith, as important as the Aztec Calendar or the Coyolxauhqui, has been discovered in the ritual Aztec center of Mexico City. It represents Tlaltecuhtli, the bisexual manifestation of the Earth from whom all life comes. Still, pigments, which have lost their conglomerating resins, have to be retained. In this study, the consolidation of ochre pigment on original fragments from the Aztec sculpture is presented. Several compounds were tested as consolidants, on the one hand natural polysaccharides, Funori and Slobber of Nopal exudate, on the other derivatives of cellulose, Methocel^® and Klucel^®, and also commercial consolidants as KSE 300^® and Paraloid B72^®. To simulate the ageing of consolidated samples, they were treated in an Accelerated Weathering Tester. Then, both sets of samples, fresh and aged, were characterized structural, morphological and texturally by using X-ray diffraction, electronic microscopy and nitrogen adsorption, respectively. A leaching test was performed on consolidated samples to evaluate the consolidant efficiency.     

DETERIORATION ASSESSMENT OF WATERLOGGED ARCHAEOLOGICAL LIGNOCELLULOSIC MATERIAL VIA 13C CP/MAS NMR*

This study investigates the residual chemical composition of waterlogged archaeological lignocellulosic material found in Greece. Hazelnut pericarps and oak wood found in a 16th‐century wreck, along with endocarps of olives dated at 300 bc , were examined. ¹³C CP/MAS NMR was applied to compare fresh and waterlogged archaeological materials. Results show qualitative alterations in their composition. The virtual absence of peaks at ~21 ppm and ~173 ppm, corresponding to hemicelluloses in all archaeological materials, indicates that these constituents can be an important indicator in assessing the type and degree of deterioration.     

Shape recovery of collapsed archaeological wood ware with active alkali-urea treatment

Most wooden remains from archaeological sites in waterlogged burial environments are found to be intact without shrinkage despite centuries of storage. However, waterlogged wooden remains are subject to shrinkage damage and some even lose up to 80% of their original volume when exposed to air. The shrinkage of archaeological waterlogged wood with the loss of a large part of the initial volume of the wooden remains has been considered irreversible. Here we show that “active alkali-urea”, serving as a re-swelling chemical agent, can almost fully restore the collapsed archaeological wood to its original shape. The restoration experiment showed that the main reason for the restoration of collapsed wood is that the collapsed cell cavity almost completely recovered its original shape during active alkali-urea treatment. We suggest that the shape of collapsed archaeological wood remains can be fully recovered, and that the collapsed archaeological wood can thereby recover its valuable cultural properties.     

古代饱水木材脱水定型机理探讨

从木材干缩的一般理论出发,探讨了古代饱水木材脱水变形的主要影响因素。阐述了古代饱水木材与新鲜木材的区别,提出饱水木材发生形变的主要影响因素同现代木材一样,是由于氢键缔合的结合水挥发,从而引起干缩和开裂。要保持脱水后的定型一方面要加固细胞壁外壁,更重要的从细胞壁内壁进行加固。     

Stable carbon and oxygen isotopic compositions of wood ash: an experimental study with archaeological implications

Wood ash, composed mainly of the mineral calcite, is an important component in many archaeological sites. Identification of wood ash in the archaeological record is often difficult due to mixing of ash with other calcitic components of geogenic origin and/or due to diagenetic changes. A recent empirical study using the stable isotope compositions of carbon (δ¹³C) and oxygen (δ¹⁸O) in wood ash enabled the identification of mixtures of wood ash with geogenic calcite and to follow diagenetic changes due to partial dissolution and re-precipitation of ash in two prehistoric cave sites in Israel. Little however is known about the processes responsible for the isotopic compositions of wood ash in relation to formation at various temperatures and the influence on isotopic composition of ash from a variety of plant species. Here we present an experimental study of wood ash formed by burning three C3 tree species and one C4 desert bush at different temperatures. The results indicate that there are significant differences in the isotopic compositions of carbon and oxygen between wood ash that forms by combustion at a relatively low temperature (500 °C) and at a higher temperature (900 °C). In addition, we show that the isotopic composition of carbon and oxygen in high temperature wood ash approaches equilibrium over a period of several months and that the carbon isotopic composition of low temperature wood ash may reflect the photosynthetic pathway of the burnt woody species. Lastly, we show that the isotopic compositions obtained from wood ash prepared at different temperatures do not reflect a temperature dependent fractionation process, but a mixing line between calcite that formed by low temperature combustion and calcite formed by high temperature combustion which later underwent re-carbonation with atmospheric CO₂. In addition, we suggest that exchange processes may possibly occur during combustion between decomposing calcium-oxalate and atmospheric O₂, CO₂ and CO. The archaeological implications of this study are discussed in relation to identification of wood ash in the archaeological record, identification of fuel sources and burning temperatures, and diagenetic changes expected in karstic cave environments. The method presented here can be applied at any archaeological site.     

Preservation,storage and display of waterlogged wood and wrecks in an aquarium: “Project Aquarius”

A test aquarium containing water and waterlogged historical wooden material was observed during a three-year period at Vänernmuseum, Sweden, to test the feasibility of preserving and exhibiting archaeological wood or shipwrecks in a way accessible to the public. Experiments were also set up in a laboratory environment, to provide information on single factors that could influence the long-term preservation state of wood, and other processes that may occur in the water.     

POROSITY DETERMINATION WITH HELIUM PYCNOMETRY AS A METHOD TO CHARACTERIZE WATERLOGGED WOODS AND THE EFFICACY OF THE CONSERVATION TREATMENTS

The helium pycnometer allows us to measure the cell‐wall density of dry woods and the basic density of wood samples soaked with water and/or a consolidant solution if a non‐volatile solvent is used. These parameters were correlated to the porosity, which for degraded waterlogged wood is related to the maximum water content. Moreover, this has revealed the possibility of investigating, by means of accurate cell‐wall density determination, the efficacy of several consolidants in the treatment of waterlogged woods.     

Near infrared spectroscopy as a tool for archaeological wood characterization

Archaeological wood, as most of natural materials, is slowly decomposing on the archaeological site due to various biological factors. Rapid and accurate estimation of the degradation level is extremely important for optimal restoration and conservation. The goal of this research was to verify the effectiveness of Fourier transform near infrared (FT-NIR) spectroscopy for archaeometry. The important advantage of the NIR spectroscopy is its accuracy, simplicity and ability to perform very high number of tests without needs of any destruction to the workpiece. Five oak pieces of the archaeological wood collected from waterlogged sites in Poland have been used. Cellulose and lignin contents, as well as crystallinity and the degree of polymerization were measured with standard reference methods and compared to the contemporary wood. The near infrared spectra represent all the physical/chemical changes of the wood due to waterlogging. This technique was successfully validated in rapid estimation of the cellulose and lignin contents. The method explored in this research might be a novel tool assisting experts in evaluation of the degradation state of archaeological and historical wooden materials.     

饱水文物传统脱水方法与超临界流体干燥技术的应用

饱水文物的脱水加固是文物保护中的一个重要组成部分,为了克服干燥应力引起的文物结构的收缩和塌陷,传统脱水方法中常采用加填充剂浸渍等方法,从而使文物处理周期延长。超临界流体干燥技术利用气体在临界温度以上无论加多大压力都不能液化的特性,控制饱水文物内部的液体在临界点之上,使气/液界面消失,在无液相表面张力情况下进行的干燥过程。本工作在回顾传统饱水文物脱水加固的常用方法和存在问题的基础上,利用液体表面张力与温度的关系,从理论上解释超临界流体干燥技术用于干燥饱水文物具有能消除干燥应力的特点,介绍了国外学者利用该技术实际处理饱水文物时采用的实验装置、操作条件和干燥效果。与传统脱水方法对照,超临界流体干燥技术还具有能缩短文物处理周期、干燥过程中能同时杀菌等优点。     

Investigations on pre-treatment prior to freeze-drying of archaeological pine wood with abnormal shrinkage anisotropy

The current research is aimed at determining the nature of changes in the dimensions and hygroscopicity of archaeological Scots pine (Pinus sylvestris L.) wood after treatment with polyethylene glycols and vacuum freeze-drying. The research was undertaken on mature sapwood with narrow annual rings and a small percentage of latewood. The experimental material used in a comparative assessment is characterised by a considerable degree of wood degradation, but low tangential and radial shrinkage and relatively high longitudinal shrinkage. The waterlogged samples were treated with aqueous solutions of PEG 300 with final concentrations: 8, 12, 16 and 20% (v/v), to which PEG 4000 with final concentration: 15, 20 and 25% (w/v) was added. After freeze-drying and seasoning of samples in the air at RH 30, 40, 50 and 65%, the water content of the samples and the degree of shrinkage of wood in three anatomical directions were determined. The dimensional stability of the samples was also determined on the basis of ASE values at RH 50%.     

饱水古木材难溶盐分析

为研究饱水古木材中难溶盐的成分和分布,基于电感耦合等离子体光谱、X射线衍射以及显微共聚焦激光拉曼等分析手段对出土出水饱水古木材表面和纵向横向不同取样深度的元素含量和分布、表面凝结物以及纵向横向切面颗粒物的物相进行了分析。分析结果表明饱水古木材含有大量的Fe、S和Ca元素,包含这三种元素的凝结物主要由难溶盐和不溶物组成。难溶盐主要分为两大类,一类为钙盐(包括硫酸盐、碳酸盐和磷酸盐等),一类为硫铁化合物(包括硫铁矿、黄铁矿、磁黄铁矿等);不溶物包括各类铁氧化物(如针铁矿、纤铁矿、赤铁矿和水合氧化铁)以及硫单质等。难溶盐分析结果有助于有针对性地对饱水古木材难溶盐尤其是对古木材危害比较大难溶盐进行预防控制和有效脱除。     

Study of interactions between polyethylene glycol and archaeological wood components by C high-resolution solid-state CP-MAS NMR

While use of polyethylene glycols, PEG, polymers for archaeological wood conservation has been well established, there is almost no study of such composite materials with carbon thirteen high-resolution solid-sate NMR. We demonstrate that NMR is an useful analytical tool to characterize rapidly samples of conserved wooden objects. By choosing an appropriate value of the contact time (from 3 to 5 ms) for which the PEG component gives only a small residual NMR signal in the CP-MAS experiment, it is possible to edit selectively the spectra of the wood components. It allows one to visualize the degradation extent of the archaeological wood even when the conservation processes have been already applied. Moreover, by studying the kinetics of CP-MAS experiments, the time constants, T_1ρH and T_CH values for PEG moiety were computed. From these data, it is shown that either in the crude commercial product or in incorporated in archaeological woods, two components are present and they are the signatures of crystalline (or ordered) and amorphous (or disordered) molecular domains. Moreover, it was shown in the archaeological woods that almost 30% of PEG was in close molecular interactions with lignins. This study is the first evidence that the PEG in conserved wood can interact at a molecular level with wood components. It also demonstrates that the PEG diffuses inside the residual cell walls of archaeological wood. This data are important for scientists in charge of process development for the conservation of wooden artifacts.     

How an integrated diagnostic approach can help in a correct evaluation of the state of preservation of waterlogged archaeological wooden artefacts

Artefacts made of wood coming from archaeological excavations provide insights into human cultural behaviour of the past. They show how man utilised natural resources and how the development of woodworking techniques and artistic endeavour were developed. Within archaeological contexts, waterlogged anaerobic conditions generally preserve the appearance of artefacts, although wood is subject to severe decay processes. The said conditions can transform the original material into a new one, thus demonstrating specific differences from those of the “fresh” wood of the same species. In order to assess these new properties correctly, an integrated diagnostic approach is needed, one which includes a multidisciplinary (micromorphological, physical and chemical) evaluation of the state of preservation.     

The Use and Deployment of Modern Wood Samples as a Proxy Indicator for Biogeochemical Processes on Archaeological Sites Preserved in situ in a Variety of Environments of Differing Saturation Level

Abstract

In situ preservation of archaeological sites is becoming an ever increasing trend as a means of preserving our cultural heritage. In connection with this the environmental conditions, such as water level, dissolved oxygen, temperature, pH and water chemistry, of a site are often monitored. It is generally agreed that a waterlogged and anoxic environment is essential for optimal preservation conditions but the set-up and maintenance of an environmental monitoring programme can be costly.

This paper discusses the design and use of a system whereby modern samples of wood can, with a minimal disturbance of the soil, easily be deployed and retrieved from archaeological sites. The system was deployed in an unsaturated environment, an environment with fluctuating water levels and a fully saturated peat bog. The samples were assessed after two years using microscopic, physical and molecular biological methods, and the types of wood-degrading organisms seen were compared with the results of environmental measurements. Modern wood samples were used, as the microbial ecology of wood-degrading organisms in these different types of environments is relatively well documented. Preliminary conclusions show that the deterioration processes of modern wood samples in these environments act as a good proxy indicator of the environmental conditions and biogeochemical processes ongoing at a site.     

Investigating the processes necessary for satisfactory freeze-drying of waterlogged archaeological wood

Preliminary studies into methods for improving and safeguarding the preservation of waterlogged archaeological wooden artefacts are presented. Mannitol, sorbitol and trehalose have been tested as replacements for polyethylene glycol (PEG) as a treatment prior to freeze-drying of wooden archaeological objects. The highest anti-shrink efficiency achieved in this short experiment was (70 ± 15) % using a 20% weight per volume solution of sorbitol after soaking for one week. The collapse or eutectic temperature of each solution used was determined using a freeze-drying microscope. Importantly, it was noted that the collapse temperature of the solutions was reduced by several degrees after use for treatment of the wood samples for one month. A freeze-drying microscope with a cold light source has been used to observe the real-time freeze-drying behaviour of various treatments inside a thin section of wood, confirming that this novel technique is indeed possible and useful. Lastly, the effects of magnesium phytate as an iron chelator have been studied. It was found that the treatment lowers the collapse temperature of a PEG 600/2000 solution by roughly 3 °C meaning that objects must be freeze-dried at a correspondingly lower temperature. Iron K-edge X-ray absorption near-edge spectroscopy analysis showed that the treatment extracted approximately half of the iron(III) ions present in the timbers.     

Laboratory Experiments as Support for Development of In Situ Conservation Methods

Abstract

Within the EU-Project BACPOLES (EVK4-CT-2001-00043) bacterial wood degradation could be simulated in laboratory experiments to investigate the living conditions of the up to now unknown bacteria consortia, named erosion bacteria (EB), which cause considerable decay on waterlogged archaeological wood. In these Microcosm (MC) experiments the role of oxygen and chemical composition of the sediment were investigated. Therefore, the microcosms were subjected to different gassing treatments and the free dissolved oxygen was measured in different depths of the microcosms by special oxygen sensors (optodes). In further experiments the chemical composition of the sediment was verified to investigate the influence of different nutrient concentrations to the degradation process by EB.

From the findings it can be concluded that bacterial wood decay can proceed without free oxygen present but that it is more intense if oxygen is available. A water flow like streams in the sea, simulated by vertical water circulation, seems to stimulate the degradation activity and the degradation of wood by EB seems to be a result of low nutrient levels in the surrounding area.     

Reasoned use of chemical parameters for the diagnostic evaluation of the state of preservation of waterlogged archaeological wood

Waterlogged archaeological wood undergoes decay processes that depend on both the burial conditions and the constituting species, and which cause the depletion of the structural components of wood cells. To quantitatively assess the state of preservation of the decayed material, specific parameters are usually measured by means of both chemical and physical analyses. In this paper an innovative approach in the use of the data obtained from these kinds of measurements is developed. A series of 132 archaeological wood samples of different wood species, burial times and states of preservation, and coming from different sites in Italy, was analysed. Their residual chemical composition, maximum water content and basic density were measured, and a reasoned use of these parameters was carried out through their elaboration, with the aim of both evaluating eventual incongruence or anomalies in the raw physical and chemical data (which has never been accomplished so far) and directly comparing in a reliable way the analytical results obtained from archaeological samples with very different states of preservation. This approach allowed defining the effective values of chemical parameters related to wood decay according to a same reference basis of calculation among the various data. By this way, it was possible to state that lignin can be also attacked by the agents causing biotic decay, and that in hardwoods its decay is more related to the burial conditions than to the wood species. Instead, the mechanism of polysaccharide depletion is diversified: conifers showed a uniform behaviour whereas hardwoods were more species-dependent. Moreover, in addition to the chemical composition, also anatomical factors influence the carbohydrate rate of decay in waterlogged wood.     

PEG稳定河姆渡遗址出土香樟的干燥特性研究

研究饱水古木材的干燥特性可以对古木材的定型保护提供重要的参考,因此本研究以河姆渡遗址出土的香樟木材为试样,在加热的条件下,用不同质量百分比浓度的聚乙二醇(PEG 2000)为定形加固剂,研究了降解饱水香樟在自然条件下的干燥特性。结果表明降解饱水香樟的自然干燥过程可以分为干燥初期试样质量的快速下降和干燥后期试样质量平稳变化两个阶段。干燥初期试样质量下降比与干燥时间符合m/m0=-kt+c的干燥方程且线性良好。随着PEG处理浓度的升高,两个阶段之间逐渐出现一个过渡过程,PEG处理浓度越高,过渡过程越明显。达到干燥终点时,香樟试样的尺寸稳定性随着PEG浓度的升高而显著增强,当浓度达到70%时,纵向、径向和弦向的收缩率下降明显,但弦向的收缩率仍相对较大。随着PEG处理浓度的增加,自然干燥后的香樟试样表观色泽逐渐加深。因此,PEG 2000浓度以不超过40%为宜。     

Provenancing East Mediterranean cedar wood with the <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr strontium isotope ratio

⁸⁷Sr/⁸⁶Sr isotope ratios of cedar wood from forests in the East Mediterranean have been compiled in order to investigate the feasibility of provenancing archaeological cedar wood finds. Cedrus sp. forests furnished a great amount of wood in antiquity, for purposes ranging from ship to temple construction, and for fashioning cult statues and sarcophagi. The ⁸⁷Sr/⁸⁶Sr signatures of archaeological cedar samples may be compared with the preliminary dataset presented here to help determine the geographic origin of wooden artifacts. Sample sites include two forest areas in the Troodos Massif of Cyprus, five in the Lebanon, and two in Turkey’s Taurus Mountains. Sr ratios for wood varieties (i.e., early heartwood, late heartwood, sapwood, and twig wood) demonstrate relative uniformity between the xylem types frequently recovered from archaeological contexts. As such, this pilot study also assesses important issues of archaeological sampling and the geographical factors that influence Sr uptake in cedar trees of this region. While the regional signatures are distinct in most cases, small sample sizes and range overlap indicate the need for additional methods to make a case for a certain source forest. Alone, this method continues to be best used to disprove assumed wood provenances.