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.     

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.     

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.     

云南剑川海门口遗址饱水古木降解的微观构造分析

文中采用扫描电镜(SEM)和透射电镜(TEM)对海门口遗址饱水古木进行降解机理分析。结果表明:古木细胞次生壁收缩严重并与胞间层分离;胞间层保存较完好,呈连续网状。说明古木纤维素和半纤维素降解相对严重,木质素降解相对较轻。古木主要是受细菌降解,通过SEM和TEM均可见明显的细菌腐朽特征。细菌首先侵入细胞腔,再通过S3层侵入细胞壁内部。细胞壁内由于降解而产生的空隙在几十到几百纳米之间。饱水古木也受到了一定程度的真菌降解,但这类真菌主要降解古木内淀粉等物质,对细胞壁物质降解能力差,主要是使古木变色。     

A preliminary study on using enzymes in cleaning archaeological wood

The main goal of this study was to study and evaluate the effect of hydrolyzing enzymes on the anatomical structure and chemical composition of archaeological wood samples. Pine and beech wood samples, which were taken from anonymous mashrabia, have been cleaned with three types of enzymes then a scanning electron microscopy (SEM) and infrared spectroscopy (FTIR) study were undertaken, to see if any significant structural or chemical differences could be detected between “untreated” and “treated” wood. No dramatic changes in functional groups on the wood surface, as monitored by infrared spectroscopy, occurred in the samples before and after enzymatic cleaning. SEM data, however, show that protease and lipase enzymes may give good results in cleaning wood surface, but the enzyme residues remaining on the cell walls of archaeological wood are another point to consider.     

New data on relevant ancient Egyptian wooden artifacts: Identification of wooden species and study of the state of conservation with multidisciplinary analyses

Wood species identification and characterization of its weathering processes are crucial steps in the scientific approach of conservation of wooden cultural heritage. Many precious wooden objects of ancient Egypt are largely present in museums, nevertheless relatively little information is available concerning the nature of timber used and on their status of conservation. To address this gap, the wooden species of three relevant archaeological wood objects (statue, box, and coffin) arising from different Egyptian archaeological sites dated from the Old Kingdom (2,686–2,181 BC) to New Kingdom (1,550–1,069 BC) were deeply studied. Five hardwood and softwood species were identified belonging to Tamarix mannifera, T. gennessarensis, Ficus sycomorus, Vachellia nilotica, and Cedrus sp. Such data confirmed the recurrence of Vachellia and Tamarix among the most common timbers found in ancient Egypt. Scanning electron microscope, Fourier transform spectroscopy, and synchrotron x-ray radiation diffraction were conducted to evaluate the archaeological wood deterioration. The formation of microcracks, biological degradation patterns (fungal colonization), or chemical characterization (accumulation of salts on and in-between wooden cells) were detected. SEM micrographs showed the presence of fungal hyphae and conidial spores on the wooden cells. Significant changes in the chemical wood composition and decrease in the crystallinity index were detected.     

Degradation of Archaeological Wood Under Freezing and Thawing Conditions—Effects of Permafrost and Climate Change

The degradation of archaeological wood at freezing and thawing temperatures is studied at the site of Qajaa in West Greenland through a combination of environmental monitoring, measurement of oxygen consumption and microscopy of wood samples. Permanently frozen wood is still very well preserved after 2–4000 years, while wood samples that thaw every summer show attack by soft rot and an average density loss of 0.1 g cm^–3 (corresponding to 25% of the dry mass) over the past 27 years. Future increases in temperature may increase the decay rate significantly (Q₁₀ = 4.2 at 0–10°C) but the effects on site depend on local hydrology.     

古旧木材保存状况多参数检测研究进展

作为人类文化遗产的重要组成部分,古旧木材保存状态的评价及保护至关重要。为了推进对古木材保存评价的深入研究,通过对多参数检测(微形态学、物理学、化学)在微观尺度下评价古旧木材保存状况及腐蚀机理的研究成果进行了综述,在介绍了从木材细胞形态、物理孔隙结构、化学组分含量、分子结构、分子量分布等方面对古旧木材进行评价的基础上,较为全面地阐述了检测各参数的不同表征方法,包括扫描电镜法、氮气吸附法、高效液相色谱法、气相色谱/质谱联用法等,具体分析了不同表征方法间的优缺点,说明了多参数检测古旧木材保存状况的可行性及重要性,并希望以此为切入点探讨古旧木材的宏观力学性能。研究结果在木质文化遗产和历史木构建筑的保护方面具有极大价值。     

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%.     

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.     

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。     

Biodeterioration dynamics of marine wreck-sites determine the need for their in situ protection

The condition of a wooden shipwreck varies considerably according to the nature of the site environment. Each marine site exhibits a unique biodeteriogenic potential influenced by prevailing hydrographic factors. The potential rate of degradation of organic archaeological material can be determined by monitoring the diversity and activity of marine organisms and is important in determining if in situ protection is required. To illustrate the deteriogenic potential of marine archaeological sites a cold water site (Langstone Harbour, UK) was compared with a warm water site (Zakynthos, Greece). The warm water site supported a greater diversity and activity of wood-boring crustaceans and molluscs than the cold water site. However, although the mycodiversity at the two sites was different the deteriogenic potential was similar. These results indicated that warm water sites are more hazardous and in situ protection is required during and after excavation.     

Methodological problems in the analysis of fossil non-artifactual wood assemblages from archaeological sites

The analysis of fossil wood fragments is often undertaken in relation to the archaeological excavation of a site. However, such analysis does not yet appear to have the strong methodological foundation that the investigation of many other classes of palaeoenvironmental evidence (e.g. seeds and pollen) have. Consequently, it is difficult to evaluate the value of fossil wood analysis at an archaeological site. Using data regarding non-artifactual wood assemblages at one site in southern Scotland, the relative merits of possible analysis are described and discussed. The results from such analyses tend to fall into two broad groups: (I) those of relatively high reliability, and (2) those of relatively low reliability. The results in the former group are often based on moderately secure methodology and tend to provide relatively non-interpretative information (e.g. species lists). On the other hand, those in the latter group are more often based on insecure interpretive methodology and provide relatively more stimulating information, such as evidence for prehistoric woodland management. There are many reasons for this situation, and these are discussed. In conclusion, it is argued that to increase the reliability of results in the second group (in particular), a full understanding of the taphonomy of non-artifactual fossil wood assemblages is needed, and that once this is available attention can then be paid, as elsewhere in environmental archaeology, to the problems of providing statistically valid samples for analysis.     

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.     

出土饱水云南松的超微构造特征

对云南剑川县出土的木质文物进行了研究,从超微结构层面更深入地解析了饱水古木的降解情况。出土的云南松(Pinus yunnansis)古木在饱水环境中淹埋了4 000多年。降解主要发生在晚材管胞,而且降解在晚材部分并不均匀:一些未降解的完好管胞分布在降解严重的管胞中。透射电镜观察显示:降解从S1/S2和S2/S3的界面开始;对于一些降解较严重的管胞,到腐朽后期细胞次生壁全部发生降解,只留下复合胞间层;细菌侵蚀是云南松饱水古木降解的主要原因。固体核磁共振结果表明:纤维素和半纤维素降解严重,木质素也出现了一定程度的降解。本研究可为其后续的加固保护提供科学的参考依据。     

考古木材降解评价的物理指标

为寻找一种能较为科学、方便地反映木材降解程度的指标,共收集不同地方出土的13种木材,8个树种,对这些树种的考古木材与新鲜木材的含水率、干缩性、基本密度、气干密度、综纤维素等指标进行对比分析。实验表明,基本密度和最大含水率(饱水含水率)基本上能够反映古木的降解程度,可以作为反映古木降解程度的物理评价指标。     

Preservation of fungi in archaeological charcoal

During the analysis of wood charcoal remains from archaeological sites, it is common to find different microorganisms and different forms of degradation present in the plant tissue. However, one may encounter difficulties when attempting to identify these microorganisms and determine when their attack occurred. This paper focuses on preservation aspects related to the microorganisms in wood and demonstrates the structural changes that take place in different types of decayed wood after it was converted into charcoal. The study seeks to determine whether the microbial attack found in archaeological woods took place before the burning of the wood or after. Burning experiments were conducted using wood that had been decayed by various types of fungi including white-rot, brown-rot, and soft-rot. The laboratory burnt wood samples showed decay patterns that were comparable to those observed in archaeological charcoal samples, indicating that signs of fungal infestation and features of decay can be preserved after burning with micromorphological details of mycelium and cell wall attack evident. This indication may provide important information related to the gathering of deadwood as fuelwood. In addition, examples of decayed wood preserved in archaeological charcoal assemblages are described. Their relationship to the archaeological context and environmental conditions may suggest different interpretative models concerning wood management strategies applied by past societies.     

Three-dimensional (3D) visualisation: the application of terrestrial laser scanning in the investigation of historical Scottish farming townships

Recent developments in digital technologies are heralding significant changes in the way we acquire, visualise and analyse archaeological data. Terrestrial laser scanners can be used to create photo-realistic virtual copies of landscapes, and archaeological features, and offer the potential to improve our understanding of three-dimensional (3D) spatial relationships at study sites. Here we present a methodology for the integration of a high-resolution 3D site model with soil chemical data obtained from an abandoned settlement site located in the Central Highlands of Scotland. At this site, the multi-element concentration in soil, co-visualised within a topographic setting, has an important role to play in elucidating settlement layout and activity. The methods described here are also of significance in archiving sites of archaeological/historical importance where development activities and/or environmental processes may destroy remains, or where access to field sites is restricted.     

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.     

海洋出水木质文物保护中的硫铁化合物问题

海洋出水的木质文物中通常会沉积硫铁化合物。打捞出水后,硫铁化合物遇到空气和水分后会发生氧化,生成硫酸以及各种硫酸盐,并引起有机质的降解。近年来,硫铁化合物对海洋出水木质文物的危害已引起广泛关注。为此,本工作阐述了硫铁化合物相关问题的研究现状,就硫铁化合物的产生原因、危害以及目前控制方法的研究进展进行了总结,同时评述了针对硫铁化合物的处理方法。