Historic Lime Research Articles

Characterization of Historic Lime Mortars from the Arch of San Martin to Identify the Construction Phases of the City Wall of Burgos (Spain)

Historical lime mortars provide valuable information on the construction phases of buildings and allow reconstruction of the chronology of the historical structures. The City Wall of Burgos and the Mudejar Arch of San Martin were declared an Asset of Cultural Interest and have been protected since 1949. Several restorations at the end of the 20th century altered the original appearance of the wall and the current gate, making it difficult to establish stratigraphic relationships between the two structures. Given the scarcity of information on the construction phases of the wall and the uncertainty of the historical dates, a mineralogical and chemical characterization of the mortars was carried out, and the suitability of the binder for radiocarbon dating was assessed. The petrographic, mineralogical and chemical analyses of the lime mortars from the Arc of San Matin show distinctive characteristics, suggesting different construction periods and production processes, where the selection of raw materials and production methods was conducted according to the construction requirements. Moreover, the presence of contaminant phases and microparticles of charcoal in the binder fraction led to discard all the samples for mortar radiocarbon dating.

An agronomic study of legacy effects from annual legume pastures in acid soils

AbstractThe use of acid soil‐tolerant annual legume pasture species and liming to raise soil pH can have legacy effects that improve subsequent wheat crop growth in acid soils. We established a two‐year experiment in a semi‐arid environment with and without historical lime application to investigate how acid soils (±lime) influence the legacy effects of annual legume pastures. We measured legume and cereal growth and yield, soil‐borne disease incidence, rhizosheath organic acid type and amount, legume biological nitrogen fixation (BNF) and soil moisture in Year 1, and soil microbial biomass carbon (MBC) and wheat yield and quality in Year 2. Minor differences in soil moisture and soil‐borne diseases occurred between cereals and legumes, and the poor BNF contribution of all pasture legumes improved in lime treatments. Pasture legumes produced more organic acids than cereals, which increased in limed treatments. Soil MBC in Year 2 was greater following legumes than cereals. Year 2 wheat grain yield increased following pasture legumes, more so in limed treatments. The contribution of organic acid exudation by annual legume pastures to microbial community legacy effects warrants further scrutiny in semi‐arid environments, particularly when acid soils limit typical rotational benefits.

Estimation of the linseed oil content in historic lime mortar

Estimation of the linseed oil content in historic lime mortar

Types of lime binders in mortars used for the construction of the Ming Great Wall of China and their importance for the development of a conservation strategy

The most obvious characteristics of the Ming Great Wall are external masonry walls made of natural stones, bricks and lime mortars. According to the chemical and mineralogical compositions of the original bedding and pointing mortars, dolomitic lime binder was used dominantly in the construction of the Ming Great Wall in provinces such as those around Beijing and Hebei. Calcium-rich lime and air lime with low natural hydraulically reactive phases, which are hydrated and react slowly with the carbon dioxide in air to form calcium carbonate, were used in some western provinces. Chemical and microscopic investigations show that both dolomitic and calcium-rich lime mortars are almost aggregate-free. Historic dolomitic lime mortars are characterised by high strengths, low porosities and dense micro-scale textures. The most recent conservation principle is to preserve the Ming Great Wall as a ruin. Therefore, the conservation strategy should be redefined in terms of mortars. Since some of the damage to the Great Wall is related to reactions between dolomitic lime mortars and air pollutants, calcium-rich lime binders should be used for conservation and even for restoration of those parts of the Great Wall that were originally built with dolomitic lime. Binders based on natural hydraulic lime and calcium-rich lime gauged with natural pozzolana might be more compatible than other binders” for the structural consolidation of the ruins of the Great Wall.

Deforestation by historical lime industry in an arid aeolian sedimentary system: An applied and methodological research

Traditional land uses have been altering aeolian sedimentary systems for centuries through the removal of plant material for grazing, fuel or farming purposes. However, few studies have been able to quantify the deforestation process associated with these land uses due to the complexity that this entails and the limitations of the historical sources. In this context, the aim of this work is to develop a methodology that allows to reconstruct, evaluate, measure and locate the effects of deforestation processes. The methodology, based on the interpretation of historical documents, oral interviews and publications in the literature; was applied to a case study in Jandía (Fuerteventura, Canary Islands, Spain). On the basis of morphological measurements of the types of plant used to fire lime kilns, the current available biovolume was determined and an estimation made of the surface area affected by plant removal. The data obtained were integrated and analysed through a geographic information system (GIS) in order to quantify the impact of the lime kiln industry on the vegetation in the study area. The main results show that to fire a large-sized lime kiln oven it would be necessary to clear a low-density vegetation area of 21,826.08 m2 (or a a high-density vegetation area of 3075.72 m2) using three main species (Launaea arborescens, Lycium intricatum and Convolvulus caput-madusae). It was also found that distances of up to 38 km had to be travelled to obtain the vegetation required to fire the kilns. It is concluded that a number of impacts resulted from the demands of the limestone industry, particularly on plant communities, the abundance of certain species and flora richness, as well as modifications to geomorphological processes and the eventual collapse of the activity in the 1960s through overexploitation of the plant material. The present research allows us to learn from past experiences in which industries lacked proper planning and thus their activity led to their own collapse and rapid environmental degradation.

Biologically induced calcium oxalate mineralization on 15th century lime mortar, Murud Sea fort, India

The historic lime mortar of Murud Seafort, Western India has endured the strong oceanic current in contrast to the basaltic stone blocks used in construction that have extensively weathered. The reason for the survival of the historic lime mortar was predominantely researched. The mortar samples were therefore characterized for their composition and microstructure, using granulometric analysis, thin section analysis, X-ray Fluorescence (XRF), X-ray powder diffraction (XRD), Fourier transform infrared (FTIR), Nuclear Magnetic Resonance (NMR), and Scanning Electron Microscopy with Energy Dispersive X-Ray Analysis (SEM-EDX). The analytical data confirmed the presence of water-insoluble calcium oxalate being formed at the surface crust, superficially on the mortar due to bacterial biomineralization. This biomineralization was responsible for its survival in saline conditions. The mercury intrusion porosimetry (MIP) revealed reduced porosity of the outer mortar surface by 9–14% besides a considerable reduction in mean pore diameter and void ratio to that of the same mortar’s inner core. The bacterial cell count and microbial identification of bacterial isolates method based on 16 S rRNA sequencing identified Bacillus spp. to be mainly responsible for biomineralization. The bacterial action has contributed to the hardening of the superficial material on the outer mortar that saved the historic mortar from the striking sea waves. The granulometric analysis shows the mixing of fine to coarse sized sand grains of basaltic origin sourced from the nearby river channel. With the aid of NMR analysis, it was concluded that calcium phosphate was not as evident as the calcium oxalate on the mortar surface in any of the samples analyzed.

A multi-analytical approach for pore structure assessment in historic lime mortars

Porosity of a mortar significantly influences its mechanical characteristics as well as durability. To ensure compatibility while designing a repair mortar for historic masonry, it is important to have both a qualitative and quantitative description of the pore structure. In this paper, we present the porosity investigations of two types of historic lime mortars by scanning electron microscopy (SEM), X-ray tomography (XRT), water sorptivity and mercury intrusion porosimetry (MIP). The overflow method is used to quantify the porosity from the frames/slices obtained from the SEM/XRT respectively. Different techniques measure different aspects of the pore structure and a comparison of results from different analytical methods allowed overcoming their specific limitations and achieving a better knowledge of the pore system of historic mortars.

Surface mediated Ca-phosphate biomineralization and characterization of the historic lime mortar, Janjira Sea Fort, India

Abstract The role of microbes in strengthening the ancient lime mortar has not been thoroughly explored so far. The main objective of this research is to study the formation of Ca-phosphate surface crust on the mortar surface of the 16th-century Janjira Sea Fort by the process of biomineralization. The lime mortars of Janjira sea fort were characterized for its composition, microstructure, bacterial cell count and microbial identification of bacterial isolates based on 16S rRNA sequencing. The XRD, FTIR, NMR and SEM studies confirmed the formation of surface crust comprising of Ca-phosphate on the mortar surface in saline conditions. The SEM-EDX elemental mapping of the mortar surface for bulk composition evidenced the formation of apatite. The mercury intrusion porosimetry (MIP) revealed reduced porosity of the top lime surface layer by a factor of 7–15% to its inner core. The 16S rRNA sequencing identified Actinobacter sp. and Bacillus sp. as the main phosphate solubilizing bacteria. The bacterial action caused the material hardening of the mortar top surface that survived the strong oceanic current. The surface crust formed due to bacterial biomineralization has saved the historic lime binder of the Janjira Sea Fort.

Lime binders for the repair of historic buildings: Considerations for CO2 abatement

Abstract Lime binders are utilised worldwide and are associated with a considerable scale of production and corresponding CO2 emissions. The relevance of this review is therefore international in scope, with production transcending geographical boundaries and construction practices. An holistic view of lime binders, considering their provenance, production and utilisation offers the potential for significant CO2 savings urgently required globally. Importantly, the technical aspects of lime materials production is critical, but the alteration of behaviour of both specifier and those undertaking the construction processes is also essential in achieving meaningful CO2 emission reduction. This review paper investigates the life cycle stages of lime binders in line with the features highlighted in the Scottish Building Alliance (SBA) ‘building life cycle stages model’. It attempts to determine what can be learnt from our understanding of the manufacture and use of binders from historic, current and future perspectives in the context of reconciling the production of historically authentic materials in a decarbonising environment. The production and use of such authentic historic lime binders initially appears highly carbon intensive through its utilisation of relatively inefficient kiln technologies and loss of economies of scale associated with larger operations. However, this review shows numerous benefits in the production of such binders; including their CO2 sequestration capability, lower potential processing energy, and a reduction in excessive ‘carbon miles’ associated with transportation. Importantly, we show how historic production and on-site manufacture approaches with lime-based materials also offers exciting potential for carbon savings. Importantly, hot mixed lime mortars offer the promise of higher durability materials compared to their modern cold manufactured counterparts, thereby reducing the frequency of repeat maintenance interventions, again yielding CO2 savings. We suggest hot mixing, whether in an innovative contemporary materials realm or within traditional contexts should be explored. In addition, hot mixed materials can concomitantly satisfy conservation requirements for repairs through better reflecting the aspired to building conservation requirement of like for like materials replacement reflected with historically produced binders. We suggest future paths for the industry that would simultaneously reconcile demands for authentic materials and production methods for the conservation sector with the necessity of achieving cleaner production in a decarbonizing world.

Tilia cultivars in historic lime avenues and parks in the UK, Estonia and other European countries

Trees have been planted in cities, towns and notable places for many centuries. Here we investigate which genotypes (cultivars) of Tilia have been used in Europe. Accessions of trees from across the UK, Estonia, Denmark, Belgium and the Netherlands were analysed and compared to nursery material, using nuclear microsatellites. The majority of accessions (141 out of 166) appeared to be the hybrid Tilia x europaea, and remarkably there were two cultivars, named Pallida and Zwarte Linde that were commonly planted across north-western Europe and Estonia. The cultivar Hatfield was only found in the UK. In addition, some trees had genotypes only found at one or two locations. Some of the named commercial cultivars also were the Pallida or Zwarte Linde genotype. For the species T. cordata and T. platyphyllos there were relatively more unique genotypes among the planted specimens. The three most planted cultivars, Pallida, Zwarte Linde and Hatfield, were not genetically closely related. Pallida and Zwarte Linde showed some genetic similarity to Belgian and Dutch material, but Hatfield did not seem similar to mainland Europe genotypes. The genetic analysis confirmed the limited source of the widely planted Tilia trees across many European countries, from the 1600s up till now. When supplementation or replanting is necessary genotyping should be used to confirm the historically correct type and maintain uniformity.

Wheat grain-yield response to lime application: relationships with soil pH and aluminium in Western Australia

Soil acidity, or more specifically aluminium (Al) toxicity, is a major soil limitation to growing wheat (Triticum aestivum L.) in the south of Western Australia (SWA). Application of calcium carbonate (lime) is used to correct Al toxicity by increasing soil pH and decreasing soluble soil Al3+. Soil testing using a 0.01 m calcium chloride (CaCl2) solution can measure both soil pH (pHCaCl2) and soil Al (AlCaCl2) for recommending rates of lime application. This study aimed to determine which combination of soil pHCaCl2 or soil AlCaCl2 and sampling depth best explains the wheat grain-yield increase (response) when lime is applied. A database of 31 historical lime experiments was compiled with wheat as the indicator crop. Wheat response to lime application was presented as relative yield percentage (grain yield for the no-lime treatment divided by the highest grain yield achieved for lime treatments × 100). Soil sampling depths were 0–10, 10–20 and 20–30 cm and various combinations of these depths. For evidence that lime application had altered soil pHCaCl2, we selected the change in the lowest pHCaCl2 value of the three soil layers to a depth of 30 cm as a result of the highest lime application (ΔpHmin). When ΔpHmin <0.3, the lack of grain-yield response to lime suggested that insufficient lime had leached into the 10–30 cm soil layer to remove the soil Al limitation for these observations. Also, under high fallow-season rainfall (228 and 320 mm) and low growing-season rainfall (GSR) (<140 mm), relative yield was lower for the measured level of soil AlCaCl2 than in the other observations. Hence, after excluding observations with ΔpHmin <0.3 or GSR <140 mm (n = 19), soil AlCaCl2 provided a better definition of the relationship between soil test and wheat response (r2 range 0.48–0.74) than did soil pHCaCl2 (highest r2 0.38). The critical value (defined at relative yield = 90%) ranged from 2.5 mg Al kg–1 (for soil Al calculated according to root distribution by depth within the 0–30 cm layer) to 4.5 mg Al kg–1 (calculated from the highest AlCaCl2 value from the three soil layers to 30 cm depth). We conclude that 0.01 m CaCl2 extractable Al in the 0–30 cm layer will give the more accurate definition of the relationship between soil test and wheat response in SWA.

Chemical and mineralogical investigations of lime plasters of medieval structures of Hampi, India

ABSTRACTThe historical lime plasters of World Heritage Site of Hampi were analyzed using X-ray fluorescence (XRF), petrological microscope, granulometric analysis, X-ray Diffraction (XRD), Fourier transform Infrared spectroscopy (FTIR), and Scanning Electron Microscopy (SEM). The studies indicated presence of aragonite and vaterite, i.e., the polymorphs of calcite in the lime platers of Hampi. The crystallization of calcite has significantly been influenced by self-healing of lime due to wet and dry cycle in the presence of magnesium that promoted formation of calcite polymorphs. The increasing solubility of metastable calcite led to loss of plaster by water dissolution. Granulometric analysis revealed inclusion of sub-angular to sub-rounded medium-sized aggregate grains of granitic origin and the sediments were medium transported before its deposition in fluvial river basin. The cementation index and mineralogical composition point use of air lime/sub-hydraulic lime admixed with non-hydraulic components sourced differently for Hampi plaster. Petrological analysis confirmed the plaster rich in essential minerals like quartz, orthoclase, plagioclase, and other clay components. The presence of chlorite and cristobalite revealed from SEM studies may be resultant minerals from the river sand of Tungabhadra. The scientific studies yielded information about the mineralogical, micro-structural, and chemical composition of the Hampi plasters useful to tailor compatible lime plaster for future conservation works.

Fast quantitative elemental mapping of highly inhomogeneous materials by micro-Laser-Induced Breakdown Spectroscopy

In this work, a fast method for obtaining a quantitative elemental mapping of highly inhomogeneous samples by μ-LIBS maps is proposed. The method, transportable and cheap, allows the analysis of large maps through the use of a Self-Organizing Map clustering method coupled to Calibration-Free LIBS for quantification of cluster prototypes. The method proposed has been verified on heterogeneous materials such historical lime mortars but it can be easily applied to a larger class of inhomogeneous materials for very different applications (modern building materials, biological samples, industrial materials, etc.).

Mineralogical, Chemical, and Thermal Characterizations of Historic Lime Plasters of Thirteenth–Sixteenth-century Daulatabad Fort, India

ABSTRACTIron ore as pozzolanic filler is an uncommon constituent of historic plaster rarely reported in any research. This paper presents one such study from western India where hematite instead of crushed bricks was identified as admixture in thirteenth–sixteenth-century CE Mughal masonry lime works of Daulatabad Fort. The outer/inner coat plasters from different locations of the fort were examined for morphological, mineralogical, chemical, and basic physical properties. The analytical investigative study was performed by optical microscopy, sieve analysis, X-ray fluorescence, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, SEM-EDX, and thermal analyzer. Although the plaster is dominantly made of micritic calcite and aggregate, incorporation of gypsum in the outer and inner coats has been detected and probably acted as a second binder. Cannabis sativa was mixed in the plaster, pointing to the knowledge of hempcrete technology by the makers of Daulatabad Fort. This investigation has now provided essential information with enough precision about this historic plaster for formulation of compatible repair materials essential for the site restoration.

Correlation Between Computed Stress Response and Observed Damage of a Heritage Masonry Building

There is a large number of historical brick masonry buildings vulnerable worldwide against seismic forces and required to be safeguarded. Therefore, a need arises for developing a cost-efficient and easily executable retrofitting strategy. To serve this purpose, a massive historical lime mortar brick masonry building: Forest Research Institute Dehradun has been analyzed in an uncracked form. A multifaceted assessment in the form of historical investigation about the building, geometrical reconnaissance survey, foundation soil characterization has been done. Material identification by means of laboratory testing, surveys and the literature indications has been carried out prior to numerical structural assessment. The structural assessment was carried out by using finite element method with masonry non-linearity defined by proper constitutive assumptions. The non-linear static pushover analysis has been carried out and the results were compared with existing in situ cracked conditions prevailing in the building. Comparisons of the expected seismic demand of uncracked structure with in situ existing damages were close which validated the damage to be seismically induced and confirm the vulnerability of such buildings to pervasive damages and a possibility of collapse against seismic loading.

Draft Whole-Genome Sequence of the Alkaliphilic Alishewanella aestuarii Strain HH-ZS, Isolated from Historical Lime Kiln Waste-Contaminated Soil.

Here, we present the whole-genome sequence of an environmental Gram-negative Alishewanella aestuarii strain (HH-ZS), isolated from the hyperalkaline contaminated soil of a historical lime kiln in Buxton, United Kingdom.

Singing with the Bees: Abeille, an exhibition

Singing with the Bees: Abeille, an exhibition

Determination of the pozzolanic activity of mortar’s components by thermal analysis

Historic lime mortars are complex multicomponent system whose mineralogical and chemical composition changes over time. With age, hydraulic phases are converted by carbonation process to calcium carbonate and reactive silicon and aluminium oxides. The consolidation of lime mortars is usually based on the dotation of the Ca(OH)2 into its matter so pozzolanic reaction may possibly take place. The study was aimed to explore pozzolanic potential of sand grains and degraded binder with respect to renewal of hydraulic phases which could contribute to mortar’s mechanical strength and therefore prolong its durability. For this purpose, pastes of mortar components with lime hydrate were prepared and stored in wet conditions (RH = 99 ± 1 %, T = 30 ± 1 °C) for 180 days. Pozzolanic reaction products were studied at different ages using thermal analysis and X-ray diffraction. With respect to sand grains pozzolanic activity, both methods confirmed the presence of newly formed monocarboaluminate as an only hydraulic phase; moreover, CSH and hydrocalumite have been found in degraded binder pastes. CSH, stratlingite and monocarboaluminate were detected as products of pozzolanic reaction of silicate and metakaolin with calcium hydroxide.

Lime mortar and sacrificial protection of heritage stonework

Microstructural characteristics of historic Scottish sandstone and lime mortar are reviewed against the physical principles underlying the function of a desalination poultice. The functional role of lime mortar as a permanent poultice enhancing the durability of heritage masonry is presented. The materials’ porosities and pore size distributions are characterised using mercury intrusion porosimetry and validated through scanning electron microscopy. Key findings include the respective predominant pore ranges exhibited by lime mortar (c. 500–2000 nm) and sandstone (c. 10 000–25 000 nm), which together interact to invoke stonework’s unique response to moisture. A technical understanding of this sacrificial protection to stonework afforded by lime mortar is imperative to avoid the use of inappropriate materials. Such incompatible materials upset the mechanisms underlying the functional role of the mortar, leading to damage of heritage stonework. The optimal example set down by historic limes appears to be best replicated by the specification of lime mortars with a high degree of carbonation set, to which much of the predominant 500–2000 nm pore range formation is attributable.

Chemical Analysis of Historic Lime Mortars: Role of Sample Preparation

The characterization of historic lime mortars is crucial for many cultural heritage conservation issues. In this work, the characterization of a historical lime mortar is described. Samples for chemical analysis were obtained after different milling times and using the RILEM acid digestion method on several replicates. Qualitative and quantitative determination of phases in the mortar and in the residues after acid attack and the potential presence of CaCO3 polymorphs, were accomplished with X-ray powder diffraction. Results suggest that representativeness of the sample and the homogenisation, although not always achievable in conservation practice, are strongly affecting results.