New investigations into the Uluburun resin cargo

Resin found within Canaanite amphorae from the Late Bronze Age shipwreck discovered off the coast of southwest Turkey at Uluburun has previously been identified as Pistacia sp. Although evidence from Egypt suggests that this resin was in high demand and typically transported in such amphorae, it has also been proposed that the amphorae contained wine, with the resin used to seal the interior surfaces and to flavour and/or preserve the wine. To attempt to resolve this question, we have analysed five samples of pistacia resin found in amphorae from the shipwreck using a range of analytical techniques which have used in the past for the analysis of wine residues: spot tests, FT-IR, and HPLC-MS-MS. As well as the archaeological samples, we have analysed modern samples of pistacia resin, leaves and fruit to determine the effectiveness of each technique and to exclude the possibility of false positive results. In addition to the analyses for wine we also detail analysis (GC-MS) of the terpenoids for the purpose of further molecular characterisation of the resin. Bulk stable isotope analysis was used in comparison with similar resins to attempt to identify the geographical origin of the resin.     

老化丝织品的氨基酸分析研究

为了解氨基酸分析能否成为有效的研究丝织品老化原因及检测丝织品老化程度的方法,选用经光老化、热老化和水解老化的现代白色丝织品和出土于湖北、内蒙古、青海的古代丝织品为样品,将称好的样品用6mol／L的HCl在110℃恒温烘箱中水解22小时,然后用美国Waters公司产的氨基酸自动分析仪进行分离及检测,根据色谱图中各个氨基酸的峰面积得出各个氨基酸的百分含量。实验结果表明,光老化和热老化时,丝织品强度的损失与酪氨酸含量的降低呈线性关系;水解老化时,丝织品强度的损失与天门冬氨酸含量的降低呈线性关系。结果说明,氨基酸分析从分子水平上给出各种老化的特征及老化程度,无论是对于机理研究还是对于老化程度的判定,都很有实用意义。     

Experimental chemical degradation compared to natural diagenetic alteration of collagen: implications for collagen quality indicators for stable isotope analysis

Stable isotopic ratios from archaeological bone collagen are valid palaeodietary indicators, but depend on sufficiently well preserved molecules and several collagen quality criteria have to be fulfilled (mostly collagen wt%, C%; N%, C/N molar ratio). For a reassessment of these quality criteria, and a better understanding of the chemical degradation of bone collagen, experimentally degraded modern bones and 54 archaeological human bones were investigated. In the course of the experimental degradation, alterations of isotopic ratios were paralleled by altered collagen quality criteria. The contrary was found in the case of the archaeological specimens. This implies that the commonly used collagen quality criteria may be insufficient and do not guarantee that stable isotopic values of the gelatine extracts will still represent the original biological signal.     

Aspartic acid racemization variability in ancient human remains: implications in the prediction of ancient DNA recovery

The extent of racemization of aspartic acid (Asp) – expressed as d/l ratio – has been used as a marker of biomolecular degradation in ancient remains. However, Asp racemization rate is highly variable, and depends on biochemical and geochemical factors. In this paper we aim to determine to which extent the fraction analyzed and the kind of sample used may influence the d/l Asp ratios. Other factors, such as burial site and sample preservation conditions, are also considered.     

A new method to remove copper corrosion stains from stone surfaces

This paper reports on a methodological study carried out in order to propose a cleaning procedure to remove stains produced by bronze corrosion products on surface of limestone (namely travertine); the procedure is effective and more environmentally friendly than the methods commonly used today. Several copper complexing or chelating agents were considered, including three amino acids and compared with some ion exchange resins. After a first laboratory phase on pure copper products and on artificially stained quarry samples, the optimized procedure was tested on the pedestal of a bronze statue in the Sapienza campus, in Rome. Colorimetry and ICP/OES were used to evaluate the efficiency of the cleaning procedure.     

Mold-deteriorated archaeological Egyptian papyri: Biodeteriogens,monitoring the deterioration,and treatment approach

Fungi play a critical role in the deterioration of ancient papyri due to their organic and hygroscopic nature. Fourteen fungal species belonging to five genera—Aspergillus, Cladosporium, Penicillium, Talaromyces, and Ulocladium—were isolated and identified from 20 Egyptian papyrus artifacts located at the Grand Egyptian Museum—Conservation Center (GEM-CC). The biodeterioration mechanism was evaluated by two analyses: cellulase enzyme activity and acid production assay. The isolated fungus P. lanosum showed potent biodeterioration power as it exhibited the highest enzymatic activity and could produce acid as well. Four different analyses were performed to assess the entity of the biodeterioration phenomenon: scanning electron microscopy, Fourier transform infrared spectroscopy, colorimetry, and pH measurements. The analyses demonstrated considerable changes in surface morphology, chemical structure (mainly represented by oxidation and hydrolysis of infected papyrus samples), darkness of the papyrus samples (ΔE 3.84–7.33), and pH (which dropped to 5.2 in the case of A. niger-infected sample. This article builds a preliminary perception for monitoring the biodeterioration of archaeological papyri and a trial for in vitro treatment to prevent further degradation, which may lead to loss of our valuable artifacts over a prolonged period.     

The geochronological potential of isoleucine epimerisation in cassowary and megapode eggshells from archaeological sites

Our research demonstrates that the extent of isoleucine epimerisation (A/I) in fragments of avian eggshells provides geochronological information in archaeological contexts. In the archaeological sequence of Hay Cave, northern Queensland, Australia, there is an excellent correspondence between the A/I values of Australian brush-turkey (Alectura lathami) eggshells (n = 99) and independent geochronological control (n = 16 radiocarbon ages including 4 on eggshell calcite). The A/I values identify three phases of deposition during the Holocene at Hay Cave. In contrast to the Alectura eggshell A/I values, a poor correspondence was observed between the A/I values of cassowary (Casuarius) eggshells from Toé (n = 35) and Kria caves (n = 23) (Ayamaru Plateau, Papua) and the depths from which the specimens were recovered in these stratified sequences. Given coherent archaeofauna trends and radiocarbon chronologies (n = 8 and 2 eggshell calcite radiocarbon ages at Toé and Kria, respectively) with respect to depth, the variable A/I values are not explicable in terms of mixing. Rather, the variability is most likely due to exposure of the eggshells to the high temperatures of campfires. Despite the variability, eggshells with relatively low A/I values amongst specimens recovered from similar depths (and therefore presumably least influenced by high temperatures) exhibit a gradual increase in A/I with respect to depth, as expected in a stratified deposit. From this observation it is suggested that the identification of heated eggshells will increase confidence in geochronological information provided by A/I. These studies illustrate the complications that arise from campfire-induced acceleration of amino acid racemisation and emphasise that although this phenomenon is common, it is not universally encountered in archaeological contexts.     

陕西历史博物馆藏汉代“华仓”瓦当表面析出物的分析研究

陶质文物表面析出物中含有机酸盐的现象在国内鲜有报道。本研究采用离子色谱仪(IC)、扫描电子显微镜-能谱仪(SEM-EDS)、X射线衍射仪(XRD)、傅里叶变化显微红外光谱仪(FTIR)、超景深显微镜(DM)对一件馆藏汉代“华仓”瓦当表面析出物进行了表征和检测。结果表明,瓦当表面析出物主要由少量的二水硫酸钙和大量有机酸钙盐[Ca₃(CH₃COO)₃Cl(NO₃)₂·6H₂O]组成,两种盐的形成与瓦当的制作过程、埋藏环境和灰尘有关,有机酸盐的形成还与馆藏环境中的乙酸有关。这种析出物不仅影响瓦当表面的真实文物信息,还会进一步腐蚀瓦当本体,建议从展柜中取出瓦当进行脱盐处理,存放在无酸的环境中。本检测分析为这件瓦当的保护修复方案的制定提供理论依据,也为类似文物样品的分析提供借鉴。     

古代青铜器修复钎焊用钎剂与钎料的改性研究

锡铅钎料和氯化锌钎剂的烙铁钎焊是传统的工艺方法。由于氯化锌钎剂中含有大量的氯离子,对青铜物的长期保存带来不利的影响。本工作通过对钎剂筛选和复配及钎料的选择,研制了针对青铜物修复钎焊用新型无氯钎剂和含银钎料匹配,并在8种古青铜模拟试样上进行一系列性能测试,结果表明新型无氯钎剂和含银钎料匹配有良好的工艺性、抗腐蚀性、可获得高强度的钎缝。新型无氯钎剂和含银钎料匹配在青铜物修复中应用结果表明,新型无氯钎剂和含银钎料有较好的钎焊工艺,钎焊接头饱满光亮,对于不同时期及不同合金的青铜物具有很好的钎焊性,钎焊后青铜物存放半年,钎焊接头依然保持光亮,焊缝周围没有出现锈蚀物和氧化现象。用新型无氯钎剂替代传统氯化锌钎剂,并且和含银钎料匹配进行古青铜的钎焊是可行的,改良后的钎剂进行青铜物修复过程符合物保护原则,避免了钎剂在钎焊过程中产生的气体对操作人员身体健康的影响。     

馆藏金属器物上浅蓝色铜锈蚀物的辨别与成因分析

不同于新出土青铜器上的锈蚀物,博物馆藏金属器物上经常可见浅蓝色铜的锈蚀物。为辨别和探析其成因,通过采用扫描电子显微镜-能谱仪(SEM-EDX)、X射线衍射仪(XRD)和激光拉曼光谱仪(Raman)进行元素成分和物相综合分析,发现其为铜的有机盐。这些有机盐包括简单(或碱式)的甲酸铜和乙酸铜,也包括复杂的含有钠离子和碳酸根的乙酸铜NaCu(CO₃)(CH₃CO₂)、含有钠离子和氧离子的水合甲酸铜Cu₄Na₄O(HCOO)₈(OH)₂·4H₂O。这种浅蓝色铜的有机盐形成根源主要有两种:储存或展览环境的不当;用于除锈的化学试剂的残留。要杜绝这类锈蚀物的形成需要确保储存和展览器物的环境低湿度且无有机酸释放材料的存在。对经过化学处理的器物应确保将化学试剂清理干净且无任何残留以绝后患。对复合材料器物的处理更应谨慎,因为对不同材质的处理和保存环境要求不一样,要个例对待。