针对海洋生物附着对出水古陶瓷釉层的腐蚀变化,以山东省荣成市所属黄海水域出水古陶瓷样品为研究对象,综合采用微区X射线荧光光谱(μ-X-ray fluorescence spectrometer,m-XRF)、扫描电子显微镜(scanning electron microscope,SEM)-能量色散光谱(energy dispersive spectroscope,EDS)、X射线衍射(X-ray diffraction,XRD)、X射线光电子能谱(X-ray photoelectron spectroscope,XPS)、热裂解-气相色谱-质谱(pyrolysis-gas chromatography-mass spectrometry,PY-GC/MS)及微生物测序等技术,系统分析了苔藓虫、盘管虫和牡蛎等生物沉积附着对陶瓷釉层的腐蚀特性.结果表明:苔藓虫附着在古陶瓷器表面呈点式密集分布,粘结区域附着明显的有机蛋白胶结质,呈现黑色,且主要成分为Fe/Mn氧化物的腐蚀质;牡蛎附着在古陶瓷器粗糙表面,且分布有大量孢子状含C物质;盘管虫粘结面呈条带状且内部为鳞片状,其附着区域伴随有大量硅藻,并在古陶瓷器表面形成了由羟基氧化铁(FeO (OH))组成的黑色腐蚀产物;古陶瓷器表面附着代尔夫特菌属(Delftia)和假单胞菌属(Pseudomonas)等微生物;腐蚀区域含有生物蛋白胶结质的丙氨酸、甘氨酸,以及经过微生物降解后产生的硬脂酸甲酯等.这些结果进一步确定了海洋微生物及其代谢和降解对古陶瓷器表面生物沉积的腐蚀影响,为海洋生物沉积物对出水古陶瓷器的界面腐蚀提供了重要的科学依据.
This study aimed to investigate the corrosion of glaze layers on ancient ceramics recovered from waters under the influence of marine biofouling. Taking the ancient ceramic samples recovered from the Yellow Sea waters of Rongcheng City, Shandong Province as the research objects, the study analyzed the characteristics of corrosion on the ceramic glaze layers due to the biological sedimentation and adhesion of bryozoans, hydroides, oysters, etc. It was employed m-X-ray fluorescence spectrometer (m-XRF), scanning electron microscope (SEM)-energy dispersive spectroscope (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscope (XPS), pyrolysis-gas chromatography-mass spectrometry (PY-GC/MS), and microbial sequencing. The results showed that bryozoans densely colonized the ceramic surfaces in a punctate pattern. At attachment sites, organic proteinaceous cements were present, appearing black in color, with the corrosive material primarily composed of Fe/Mn oxides. Oysters adhered preferentially to roughened ceramic areas and were associated with abundant spore-like carbonaceous particles. Hydroides exhibited a striated external morphology and internal scale-like structures at the interface, with the attachment zones being rich in diatoms, which contributed to the formation of black corrosion products composed primarily of FeO(OH). Microbial communities such as Delftia and Pseudomonas were detected on the ceramic surfaces. Furthermore, the corrosion areas contained alanine and glycine derived from proteinaceous cements, as well as methyl stearate produced through microbial degradation. These findings further confirmed the corrosive effects of marine microorganisms, as well as their metabolism and degradation, on biological sedimentation on ceramic surfaces. The results provided important scientific evidences for understanding marine-biofouling-induced interfacial corrosion of recovered ceramics from waters.
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