Determining Water Transport Kinetics in Limestone by Dual-Wavelength Cavity Ring-Down Spectroscopy.

Water plays a major role in the deterioration of porous building materials such as those widely found in built heritage, influencing many physical, chemical, and biological decay processes. This article details a proof-of-principle study using near-infrared cavity ring-down spectroscopy (CRDS) to monitor the release of water and its artificially enriched isotopologues from small (ca. 25 × 25 × 5 mm) samples of limestone subject to drying by a fixed flow of nitrogen with varying levels of humidity and at room temperature and atmospheric pressure. Under low-humidity conditions, the drying kinetics are consistent with the well-established two-phase drying process exhibited by porous materials, namely, an initial constant drying rate period (phase I) followed by a falling drying rate period (phase II). The water diffusivity during phase II, DII, was measured (for Clipsham limestone) to be 3.0 × 10-9 ± 1 × 10-10 m2 s-1. The CRDS measurements allow spectroscopic determination of the total mass of water released by the sample, and the calculated values are in excellent agreement with gravimetric analysis. Importantly, the selectivity and sensitivity afforded by CRDS allows isotope analysis to be carried out, such that the flux of isotopically labeled water out of the sample can be determined under conditions of humidified flow where there may be a simultaneous ingress of water from the environment. Dual-wavelength CRDS distinguishes isotopic species, and it is demonstrated that the drying kinetics and physical properties of the samples are self-consistent when monitoring both HDO and H2O (for HDO, DII was 3.2 × 10-9 ± 4 × 10-10 m2 s-1). As the humidity levels in the flow increase, a departure from the distinct two-phase behavior is observed in the HDO drying curves. These new measurements of isotopically resolved mass fluxes will help refine models for drying mechanisms in porous media.

A review of the nature, role and control of lithobionts on stone cultural heritage: weighing-up and managing biodeterioration and bioprotection.

Lithobionts (rock-dwelling organisms) have been recognized as agents of aesthetic and physico-chemical deterioration of stonework. In consequence, their removal from cultural heritage stone surfaces (CHSS) is widely considered a necessary step in conservation interventions. On the other hand, lithobiontic communities, including microbial biofilms ('biological patinas'), can help integrate CHSS with their environmental setting and enhance biodiversity. Moreover, in some cases bioprotective effects have been reported and even interpreted as potential biotechnological solutions for conservation. This paper reviews the plethora of traditional and innovative methodologies to characterize lithobionts on CHSS in terms of biodiversity, interaction with the stone substrate and impacts on durability. In order to develop the best management and conservation strategies for CHSS, such diagnosis should be acquired on a case-by-case basis, as generalized approaches are unlikely to be suitable for all lithobionts, lithologies, environmental and cultural contexts or types of stonework. Strategies to control biodeteriogenic lithobionts on CHSS should similarly be based on experimental evaluation of their efficacy, including long-term monitoring of the effects on bioreceptivity, and of their environmental safety. This review examines what is known about the efficacy of control methods based on traditional-commercial biocides, as well as those based on innovative application of substances of plant and microbial origin, and physical techniques. A framework for providing a balanced scientific assessment of the role of lithobionts on CHSS and integrating this knowledge into management and conservation decision-making is presented.

Thermal blanketing by ivy (Hedera helix L.) can protect building stone from damaging frosts.

The impact of plants growing on buildings remains controversial, especially for vulnerable historic walls and ruins requiring on-going conservation. English ivy (Hedera helix L.) can cause considerable damage where it is able to grow into deteriorating masonry, yet in some circumstances it may be protective. Here we focus on the potential of ivy to buffer damaging thermal cycles and frost events that can contribute to the deterioration of masonry materials. On limestone masonry test walls in central Southern England (Wytham near Oxford, UK), ivy foliage had a significant influence on stone-surface freezing regimes. Over two successive winters (2012/13 and 2013/14) the frequency of freezing events under ivy was reduced on average by 26%, their duration by 34% and their severity by 32%. A subsequent laboratory simulation showed that stone mass loss, surface softening, and textural development were all significantly reduced under an 'ivy covered' thermal regime. Cautious extrapolation indicates that ivy can reduce frost-driven granular-scale decay of limestone by the order of 30 g m-2 yr-1, depending on the local freezing regime. Whilst the capacity of ivy to cause damage should not be underplayed, vertical greenery can aid heritage conservation efforts by mitigating specific environmental threats.

Durability of anti-graffiti coatings on stone: natural vs accelerated weathering.

Extending the use of novel anti-graffiti coatings to built heritage could be of particular interest providing the treatments are efficient enough in facilitating graffiti removal and long-lasting to maintain their protective properties without interfering with the durability of the substrates. However, studies of the durability of these coatings are scarce and have been mainly carried out under accelerated weathering conditions, the most common practice for assessing the durability of materials but one that does not reproduce accurately natural working conditions. The present study aimed to assess the durability of the anti-graffiti protection afforded by two anti-graffiti treatments (a water dispersion of polyurethane with a perfluoropolyether backbone and a water based crystalline micro wax) on Portland limestone and Woodkirk sandstone after 1 year of outdoor exposure in the South of England with periodic painting and cleaning episodes taking place. A parallel study under artificial weathering conditions in a QUV chamber for 2000 hours was also carried out. Changes to the coatings were assessed by measuring colour, gloss, water-repellency, roughness and microstructure, the latter through micro-Raman and optical microscope observations, periodically during the experiments. The results show that both anti-graffiti treatments deteriorated under both artificial and natural weathering conditions. For the polyurethane based anti-graffiti treatment, artificial ageing produced more deterioration than 1 year of outdoor exposure in the south of England due to loss of adhesion from the stones, whereas for micro wax coating there were no substantial differences between the two types of weathering.

Cool barnacles: Do common biogenic structures enhance or retard rates of deterioration of intertidal rocks and concrete?

Sedentary and mobile organisms grow profusely on hard substrates within the coastal zone and contribute to the deterioration of coastal engineering structures and the geomorphic evolution of rocky shores by both enhancing and retarding weathering and erosion. There is a lack of quantitative evidence for the direction and magnitude of these effects. This study assesses the influence of globally-abundant intertidal organisms, barnacles, by measuring the response of limestone, granite and marine-grade concrete colonised with varying percentage covers of Chthamalus spp. under simulated, temperate intertidal conditions. Temperature regimes at 5 and 10mm below the surface of each material demonstrated a consistent and statistically significant negative relationship between barnacle abundance and indicators of thermal breakdown. With a 95% cover of barnacles, subsurface peak temperatures were reduced by 1.59°C for limestone, 5.54°C for concrete and 5.97°C for granite in comparison to no barnacle cover. The amplitudes of short-term (15-30min) thermal fluctuations conducive to breakdown via 'fatigue' effects were also buffered by 0.70°C in limestone, 1.50°C in concrete and 1.63°C in granite. Furthermore, concentrations of potentially damaging salt ions were consistently lower under barnacles in limestone and concrete. These results indicate that barnacles do not enhance, but likely reduce rates of mechanical breakdown on rock and concrete by buffering near-surface thermal cycling and reducing salt ion ingress. In these ways, we highlight the potential role of barnacles as agents of bioprotection. These findings support growing international efforts to enhance the ecological value of hard coastal structures by facilitating their colonisation (where appropriate) through design interventions.

The spatial organization and microbial community structure of an epilithic biofilm.

Microbial biofilms are common on lithic surfaces, including stone buildings. However, the ecology of these communities is poorly understood. Few studies have focused on the spatial characteristics of lithobiontic biofilms, despite the fact that spatial structure has been demonstrated to influence ecosystem function (and hence biodegradation) and community diversity. Furthermore, relatively few studies have utilized molecular techniques to characterize these communities, even though molecular methods have revealed unexpected microbial diversity in other habitats. This study investigated (1) the spatial structure and (2) the taxonomic composition of an epilithic biofilm using molecular techniques, namely amplicon pyrosequencing and terminal restriction fragment length polymorphism. Dispersion indices and Mantel correlograms were used to test for the presence of spatial structure in the biofilm. Diversity metrics and rank-abundance distributions (RADs) were also generated. The study revealed spatial structure on a centimetre scale in eukaryotic microbes (fungi and algae), but not the bacteria. Fungal and bacterial communities were highly diverse; algal communities much less so. The RADs were characterized by a distinctive 'hollow' (concave up) profile and long tails of rare taxa. These findings have implications for understanding the ecology of epilithic biofilms and the spatial heterogeneity of stone biodeterioration.

Algal 'greening' and the conservation of stone heritage structures.

In humid, temperate climates, green algae can make a significant contribution to the deterioration of building stone, both through unsightly staining ('greening') and, possibly, physical and chemical transformations. However, very little is known about the factors that influence the deteriorative impact and spatial distribution of green algal biofilms, hindering attempts to model the influence of climate change on building conservation. To address this problem, we surveyed four sandstone heritage structures in Belfast, UK. Our research had two aims: 1) to investigate the relationships between greening and the deterioration of stone structures and 2) to assess the impacts of environmental factors on the distribution of green biofilms. We applied an array of analytical techniques to measure stone properties indicative of deterioration status (hardness, colour and permeability) and environmental conditions related to algal growth (surface and sub-surface moisture, temperature and surface texture). Our results indicated that stone hardness was highly variable but only weakly related to levels of greening. Stone that had been exposed for many years was, on average, darker and greener than new stone of the same type, but there was no correlation between greening and darkening. Stone permeability was higher on 'old', weathered stone but not consistently related to the incidence of greening. However, there was evidence to suggest that thick algal biofilms were capable of reducing the ingress of moisture. Greening was negatively correlated with point measurements of surface temperature, but not moisture or surface texture. Our findings suggested that greening had little impact on the physical integrity of stone; indeed the influence of algae on moisture regimes in stone may have a broadly bioprotective action. Furthermore, the relationship between moisture levels and greening is not straightforward and is likely to be heavily dependent upon temporal patterns in moisture regimes and other, unmeasured, factors such as nutrient supply.

Non-destructive sampling of rock-dwelling microbial communities using sterile adhesive tape.

Building stone provides a habitat for an array of microorganisms, many of which have been demonstrated to have a deleterious effect on the appearance and/or structural integrity of stone masonry. It is essential to understand the composition and structure of stone-dwelling (lithobiontic) microbial communities if successful stone conservation strategies are to be applied, particularly in the face of global environmental change. Ideally, the techniques used to sample such assemblages should be non-destructive due to the sensitive conservation status of many stone buildings. This paper quantitatively assesses the performance of sterile adhesive tape as a non-destructive sampling technique and compares the results of tape sampling with an alternative, destructive, sampling method. We used DNA fingerprinting (TRFLP) to characterise the algal, fungal and bacterial communities living on a stone slab. Our results demonstrate that tape sampling may be used to collect viable quantities of microbial DNA from environmental samples. This technique is ideally suited to the sampling of microbial biofilms, particularly when these communities are dominated by green algae. It provides a good approximation of total community diversity (i.e. the aggregate diversity of epilithic and endolithic communities). Tape sampling is straightforward, rapid and cost effective. When combined with molecular analytical techniques, this sampling method has the potential to make a major contribution to efforts to understand the structure of lithobiontic microbial communities and our ability to predict the response of such communities to future environmental change.

Polymer coatings to passivate calcite from acid attack: polyacrylic acid and polyacrylonitrile.

The extent of passivation of calcite toward dissolution by aqueous acids arising from polymeric coatings based on polyacrylic acid or polyacrylonitrile is evaluated using a channel flow cell technique with microdisc electrode detection. In situ passivation with polyacrylic acid leads to a reduction in the reactivity of calcite toward acid attack with a reduction in the rate constant by up to an order of magnitude compared with untreated calcite. Ex situ passivation with polyacrylic acid for 24 h results in good coverage of the calcite by the polymer but it is shown to erode from the surface when exposed to an aqueous acid solution. In contrast, polyacrylonitrile is demonstrated to form a regular coating after exposure for just 1 h and offers robust potent protection from aqueous acid attack.

Channel flow cell studies on the evaluation of surface pretreatments using phosphoric acid or polymaleic acid for calcite stone protection.

The dissolution kinetics of surface-pretreated and weathered calcite was investigated in dilute acid using a channel flow cell with microdisk detection. Two pretreatments were studied, polymaleic acid and phosphoric acid. Treatment with polymaleic acid was shown to significantly passivate calcite but to a lesser extent than the phosphoric acid and the former coating was found to be less effective for protection of calcite from acid attack. However, treatment of calcite with phosphoric acid resulted in the passivation of calcite from acid attack which strongly inhibited dissolution, an effect that was enhanced even further after exposure to the environment.

Channel Flow Cell Studies of the Inhibiting Action of Gypsum on the Dissolution Kinetics of Calcite: A Laboratory Approach with Implications for Field Monitoring.

The rate of dissolution of surface-treated calcite crystals in aqueous acidic solution has been studied using an adaptation of the channel flow cell method with microdisc electrode detection. Surface treatments of calcite with sulfuric acid lead to the nucleation of gypsum overgrowths, which reduce the rate of dissolution of calcite. Rate constants for untreated calcite and calcite pretreated with sulfuric acid conditions of 0.01 M for 1 h, 0.05 M for 5 h, and 0.1 M for 21 h are found to be 0.035, 0.018, 0.006, and 0.004 cm s(-1), respectively. Deterioration of calcite materials caused by acid deposition was investigated by field exposure of untreated and sulfate pretreated calcite rocks under urban conditions for 12 months. The rate constant for both pretreated and untreated calcite exposed to weathering is 0.003 cm s(-1). This suggests that calcite self-passivates the surface from further reaction when exposed to acid deposition. However, surface studies indicate that the surface undergoes erosion and dissolution before passivation. Pretreatment of the surface with sulfate protects the surface from acid deposition so it remains less reactive toward acid compared with untreated calcite. Copyright 2001 Academic Press.