Replacing or repairing masonry mortar is usually necessary in the restoration of historical constructions, but the selection of a proper mortar is often problematic. An inappropriate choice can lead to failure of the restoration work, and perhaps even further damage. Thus, a thorough understanding of the original mortar technology and the fabrication of appropriate replacement materials are important research goals. Many kinds of materials have been used over the years in masonry mortars, and the technology has gradually evolved from the single-component mortar of ancient times to hybrid versions containing several ingredients. Beginning in 2450 BCE, lime was used as masonry mortar in Europe. In the Roman era, ground volcanic ash, brick powder, and ceramic chip were added to lime mortar, greatly improving performance. Because of its superior properties, the use of this hydraulic (that is, capable of setting underwater) mortar spread, and it was adopted throughout Europe and western Asia. Perhaps because of the absence of natural materials such as volcanic ash, hydraulic mortar technology was not developed in ancient China. However, a special inorganic-organic composite building material, sticky rice-lime mortar, was developed. This technology was extensively used in important buildings, such as tombs, in urban constructions, and even in water conservancy facilities. It may be the first widespread inorganic-organic composite mortar technology in China, or even in the world. In this Account, we discuss the origins, analysis, performance, and utility in historic preservation of sticky rice-lime mortar. Mortar samples from ancient constructions were analyzed by both chemical methods (including the iodine starch test and the acid attack experiment) and instrumental methods (including thermogravimetric differential scanning calorimetry, X-ray diffraction, Fourier transform infrared, and scanning electron microscopy). These analytical results show that the ancient masonry mortar is a special organic-inorganic composite material. The inorganic component is calcium carbonate, and the organic component is amylopectin, which is presumably derived from the sticky rice soup added to the mortar. A systematic study of sticky rice-lime mortar technology was conducted to help determine the proper courses of action in restoring ancient buildings. Lime mortars with varying sticky rice content were prepared and tested. The physical properties, mechanical strength, and compatibility of lime mortar were found to be significantly improved by the introduction of sticky rice, suggesting that sticky rice-lime mortar is a suitable material for repairing mortar in ancient masonry. Moreover, the amylopectin in the lime mortar was found to act as an inhibitor; the growth of the calcium carbonate crystals is controlled by its presence, and a compact structure results, which may explain the enhanced performance of this organic-inorganic composite compared to single-component lime mortar.
Research on the microbial communities that colonize stone monuments may provide a new understanding of stone biodeterioration and microbe-induced carbonate precipitation. This work investigated the seasonal variation of microbial communities in 2016 and 2017, as well as its effects on stone monuments. We determined the bacterial and fungal compositions of 12 samples from four well-separated geographic locations by using 16S rRNA and internal transcribed spacer gene amplicon sequencing. and Ascomycota were the predominant bacterial and fungal phyla, respectively, and differences in species abundance among our 12 samples and 2 years showed no consistent temporal or spatial trends. Alpha diversity, estimated by Shannon and Simpson indices, revealed that an increase or decrease in bacterial diversity corresponded to a decrease or increase in the fungal community from 2016 to 2017. Large-scale association analysis identified potential bacteria and fungi correlated with stone deterioration. Functional prediction revealed specific pathways and microbiota associated with stone deterioration. Moreover, a culture-dependent technique was used to identify microbial isolates involved in biodeterioration and carbonatogenesis; 64% of 85 bacterial isolates caused precipitation of carbonates in biomineralization assays. Imaging techniques including scanning electron microscopy with energy-dispersive spectroscopy, X-ray diffraction, and fluorescence imaging identified CaCO crystals as calcite and vaterite. Although CaCO precipitation induced by bacteria often has esthetically deleterious impacts on stone monuments, this process may potentially serve as a novel, environmentally friendly bacterial self-inoculation approach to the conservation of stone. Comprehensive analyses of the microbiomes associated with the deterioration of stone monuments may contribute to the understanding of mechanisms of deterioration, as well as to the identification of potentially beneficial or undesirable microbial communities and their genomic pathways. In our study, we demonstrated that was the predominant bacterial phylum and exhibited an increase from 2016 to 2017, while showed a decreasing trend. Apart from esthetic deterioration caused by cyanobacteria and fungi, white plaque, which is composed mainly of CaCO and is probably induced by and, was also considered to be another threat to stone monuments. We showed that there was no significant correlation between microbial population variation and geographic location. Specific functional genes and pathways were also enriched in particular bacterial species. The CaCO precipitation induced by an indigenous community of carbonatogenic bacteria also provides a self-inoculation approach for the conservation of stone.
The historical and cultural heritage of Qingxing palace and Lingyin and Kaihua temple, located in Hangzhou of China, include a large number of exquisite Buddhist statues and ancient stone sculptures which date back to the Northern Song (960–1219 A.D.) and Qing dynasties (1636–1912 A.D.) and are considered to be some of the best examples of ancient stone sculpting techniques. They were added to the World Heritage List in 2011 because of their unique craftsmanship and importance to the study of ancient Chinese Buddhist culture. However, biodeterioration of the surface of the ancient Buddhist statues and white marble pillars not only severely impairs their aesthetic value but also alters their material structure and thermo-hygric properties. In this study, high-throughput sequencing was utilized to identify the microbial communities colonizing the stone monuments. The diversity and distribution of the microbial communities in six samples collected from three different environmental conditions with signs of deterioration were analyzed by means of bioinformatics software and diversity indices. In addition, the impact of environmental factors, including temperature, light intensity, air humidity, and the concentration of NO2 and SO2, on the microbial communities’ diversity and distribution was evaluated. The results indicate that the presence of predominantly phototrophic microorganisms was correlated with light and humidity, while nitrifying bacteria and Thiobacillus were associated with NO2 and SO2 from air pollution.
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