Modeled versus Experimental Salt Mixture Behavior under Variable Humidity.

This study investigates the kinetics of salt mixture crystallization under relative humidity (RH) conditions, varying between 15 and 95% (at 20 °C), to inform applications in built heritage preservation, geology, and environmental sciences. We focused on commonly found, sulfate-rich and calcium-rich salt mixtures containing five to six ions, Cl-, NO3-, Na+, and K+, including or excluding less common Mg2+, and including either an excess of SO42- or Ca2+, with respect to gypsum. Using time-lapse micrographs and dynamic vapor sorption, we explore how crystallization and dissolution behavior depend on RH and mixture composition under constant temperature. A range of RH change rates were studied to simulate realistic weather events. Microstructural analyses through environmental scanning electron microscopy (ESEM) confirmed the crystal habit corresponding with RH transitions. Phases predicted from thermodynamic modeling (ECOS/RUNSALT) were confirmed using micro-Raman spectroscopy, X-ray diffraction (XRD), and elemental mapping via energy-dispersive X-ray spectroscopy (EDX). We identify a strong correlation between phase transition kinetics and RH change rates, with crystallization deviating by -15% and dissolution by +7% from modeled values under rapid (several seconds) and slow (several days) RH changes. These insights are important for preservation strategies in built heritage, salt deposition, and dissolution mechanisms in diverse geological and realistic environmental contexts, laboratory experiments, future modeling efforts, and the understanding of stone decay in general.

Microplastic pollution on historic facades: Hidden 'sink' or urban threat?

Despite the increasing concerns surrounding the health and environmental risks of microplastics (MPs), the research focus has primarily been on their prevalence in air and the oceans, consequently neglecting their presence on urban facades, which are integral to our everyday environments. Therefore, there is a crucial knowledge gap in comprehending urban MP pollution. Our pioneering interdisciplinary study not only quantifies but also identifies MPs on historic facades, revealing their pervasive presence in a medium-sized urban area in the UK. In this case study, we estimated a mean density of 975,000 fibres/m^2 (0.10 fibres/mm^2) for fibre lengths between 30 and 1000 µm with a ratio of 1:5 for natural to artificial fibres. Our research identifies three groups of fibre length frequencies across varied exposure scenarios on the investigated urban facade. Sheltered areas (4m height) show a high prevalence of 60-120 µm and 180-240 µm fibres. In contrast, less sheltered areas at 3m exhibit lower fibre frequencies but similar lengths. Notably, the lowest area (2-1.5m) features longer fibres (300-1000 µm), while adjacent area S, near a faulty gutter, shows no fibres, highlighting the impact of exposure, altitude, and environmental variables on fibre distribution on urban facades. Our findings pave one of many necessary paths forward to determine the long-term fate of these fibres and provoke a pertinent question: do historic facades serve as an urban 'sink' that mitigates potentially adverse health impacts or amplifies the effects of mobile microplastics? Addressing MP pollution in urban areas is crucial for public health and sustainable cities. More research is required to understand the multi-scale factors behind MP pollution in large cities and to find mitigation strategies, paving the way for effective interventions and policies against this growing threat.

Salt mixtures in stone weathering.

Salt related weathering of stones has been attributed to pressures exerted by repeated cycles of crystallization within pores. Relative Humidity (RH) is a key driver for dissolution and crystallization processes. Despite the prevalence of salt mixtures in natural environments, most experimental work has focused on single salts. Thus, the identification of salt mixture composition and their behavior is necessary to understand weathering. Thermodynamic calculations are used to analyze several thousand realistic salt mixtures found in weathered stone. We identify two common mixture types and their behavior. From at least 85 salt species theoretically present, 14 common salts are identified that occur most frequently and their critical RH points are discussed. These findings have wide-reaching implications for understanding salt weathering processes and informing the design of experimental stone weathering research.

The Historic Built Environment As a Long-Term Geochemical Archive: Telling the Time on the Urban "Pollution Clock".

This study introduces a novel methodology for utilizing historic built environments as reliable long-term geochemical archives, addressing a gap in the reconstruction of past anthropogenic pollution levels in urban settings. For the first time, we employ high-resolution laser ablation mass spectrometry for lead isotope (206Pb/207Pb and 208Pb/206Pb) analysis on 350-year-old black crust stratigraphies found on historic built structures, providing insights into past air pollution signatures. Our findings reveal a gradual shift in the crust stratigraphy toward lower 206Pb/207Pb and higher 208Pb/206Pb isotope ratios from the older to the younger layers, indicating changes in lead sources over time. Mass balance analysis of the isotope data shows black crust layers formed since 1669 primarily contain over 90% Pb from coal burning, while other lead sources from a set of modern pollution including but not limited to leaded gasoline (introduced after 1920) become dominant (up to 60%) from 1875 onward. In contrast to global archives such as ice cores that provide integrated signals of long-distance pollution, our study contributes to a deeper understanding of localized pollution levels, specifically in urban settings. Our approach complements multiple sources of evidence, enhancing our understanding of air pollution dynamics and trends, and the impact of human activities on urban environments.

Charge balance calculations for mixed salt systems applied to a large dataset from the built environment.

Understanding salt mixtures in the built environment is crucial to evaluate damage phenomena. This contribution presents charge balance calculations applied to a dataset of 11412 samples taken from 338 sites, building materials showing signs of salt deterioration. Each sample includes ion concentrations of Na+, K+, Mg2+, Ca2+, Cl-, NO3-, and SO42- adjusted to reach charge balance for data evaluation. The calculation procedure follows two distinct pathways: i) an equal adjustment of all ions, ii) adjustments to the cations in sequence related to the solubility of the theoretical solids. The procedure applied to the dataset illustrates the quantification of salt mixture compositions and highlights the extent of adjustments applied in relation to the sample mass to aid interpretation. The data analysis allows the identification of theoretical carbonates that could influence the mixture behavior. Applying the charge balance calculations to the dataset validated common ions found in the built environment and the identification of three typical mixture compositions. Additionally, the data can be used as direct input for thermodynamic modeling.

Understanding the Microstructure of Mortars for Cultural Heritage Using X-ray CT and MIP.

In this study, the microstructure of mock-up mortar specimens for a historic environment, composed of different mixtures, was studied using mercury intrusion porosity (MIP) and microcomputed tomography (µCT), highlighting the advantages and drawbacks of both techniques. Porosity, sphericity, and pores size distribution were studied, evaluating changes according to mortar composition (aerial and hydraulic binders, quartz sand, and crushed limestone aggregate). The µCT results were rendered using 3D visualization software, which provides complementary information for the interpretation of the data obtained using 3D data-analysis software. Moreover, µCT contributes to the interpretation of MIP results of mortars. On the other hand, MIP showed significant ink-bottle effects in lime and cement mortars samples that should be taken into account when interpreting the results. Moreover, the MIP results highlighted how gypsum mortar samples display a porosity distribution that is best studied using this technique. This multi-analytical approach provides important insights into the interpretation of the porosimetric data obtained. This is crucial in the characterization of mortars and provides key information for the study of building materials and cultural heritage conservation.

Differential colonization of microbial communities inhabiting Lede stone in the urban and rural environment.

Air pollution is one of the main actors of stone deterioration. It influences not only the material itself but also prokaryotes colonizing rocks. Prokaryotes can affect rock substrates and biological colonization will most likely become relatively more important during the course of the 21st century. Therefore, it is necessary to understand the effects of air pollution on biological colonization and on the impact of this colonization on rock weathering. For this reason, we studied the prokaryotic community of Lede stone from two deteriorated monuments in Belgium: one in the urban and one in the rural environment. This research conducts 16S rRNA gene Next Generation Sequencing combined with an isolation campaign. It revealed diverse and complex prokaryotic communities with more specialized bacteria present in the urban environment, while archaea were barely detected. Some genera could cause biodeterioration but the isolates did not produce a significant amount of acid. Soluble salts analysis revealed an important effect of salts on the prokaryotic community. Colour measurements at least indicate that a main effect of prokaryotes might be on the aesthetics: In the countryside prokaryotic communities seemed to discolour Lede stone, while pollution most likely blackened building stones in the urban environment.

Impact of the urban heat island on freeze-thaw risk of natural stone in the built environment, a case study in Ghent, Belgium.

Freeze-thaw cycles are important in the weathering behaviour of natural building stones in humid, cold to temperate climates. It is expected that the elevated air temperatures in urban environments, the so-called urban heat island (UHI), will have an impact on freeze-thaw weathering. In this study, the impact of the urban heat island on the potential freeze-thaw risk is assessed by parameterization of climatic data of 1 year (07/2016-06/2017) from the MOCCA (Monitoring the City's Climate and Atmosphere) project, which studies the urban heat island in Ghent, Belgium. The dose-response of Savonnières, a French limestone often used as building stone, is investigated in laboratory and by HAM simulations. Analysis of the MOCCA data demonstrates that the urban heat island phenomenon decreases the number and intensity of freeze-thaw cycles in an urban environment with 42% and 41% respectively for the studied year in Ghent. This decrease suggests a mitigation of frost risk in urban environments. Laboratory tests and computational simulations confirm that this leads indeed to a decreased freeze-thaw risk in urban landscapes compared to the surrounding rural environment.

Neutron Radiography Study of Laboratory Ageing and Treatment Applications with Stone Consolidants.

A nano-silica consolidant and nano-titania modified tetraethyl-orthosilicate were applied on two building stones, a carbonate and a silicate, by brush, poultice or capillary absorption. Neutron radiography was used to monitor capillary water absorption, and to analyse changes in physical properties caused by heat treatment of specimens for the purposes of artificially ageing and different treatment applications with stone consolidants. Moreover, ultrasonic pulse velocity and gravimetrically determined water absorption were analysed to cross-validate neutron radiography. The results reveal that reactive systems like tetraethyl-orthosilicates need an unknown period for polymerisation, which makes nano-silica consolidants more favourable for construction follow-up work. While polymerisation is incomplete, hydrophobic behaviour, water trapping and pore clogging are evident. Within the tetraethyl-orthosilicate treatment, poultice and brushing are strongly influenced by the applicant, which results in wide ranging amounts of water absorbed and anomalous water distributions and kinetics. The carbonate lithotype displays polymerisation initiated in the core of the specimen, while the lateral surfaces are still mostly hydrophobic. Reaction time differences can be attributed to the different amounts of consolidants applied, which is a result of the chosen application settings. Artificial ageing of stone specimens is a prerequisite when mechanical strength gain is studied, as demonstrated by sound speed propagation.

In Situ Triaxial Testing To Determine Fracture Permeability and Aperture Distribution for CO2 Sequestration in Svalbard, Norway.

On Svalbard, Arctic Norway, an unconventional siliciclastic reservoir, relying on (micro)fractures for enhanced fluid flow in a low-permeable system, is investigated as a potential CO2 sequestration site. The fractures' properties at depth are, however, poorly understood. High resolution X-ray computed tomography (micro-CT) imaging allows one to visualize such geomaterials at reservoir conditions. We investigated reservoir samples from the De Geerdalen Formation on Svalbard to understand the influence of fracture closure on the reservoir fluid flow behavior. Small rock plugs were brought to reservoir conditions, while permeability was measured through them during micro-CT imaging. Local fracture apertures were quantified down to a few micrometers wide. The permeability measurements were complemented with fracture permeability simulations based on the obtained micro-CT images. The relationship between fracture permeability and the imposed confining pressure was determined and linked to the fracture apertures. The investigated fractures closed due to the increased confining pressure, with apertures reducing to approximately 40% of their original size as the confining pressure increased from 1 to 10 MPa. This coincides with a permeability drop of more than 90%. Despite their closure, fluid flow is still controlled by the fractures at pressure conditions similar to those at the proposed storage depth of 800-1000 m.

Methane Bubble Growth and Migration in Aquatic Sediments Observed by X-ray µCT.

Methane bubble formation and transport is an important component of biogeochemical carbon cycling in aquatic sediments. To improve understanding of how sediment mechanical properties influence bubble growth and transport in freshwater sediments, a 20-day laboratory incubation experiment using homogenized natural clay and sand was performed. Methane bubble development at high resolution was characterized by µCT. Initially, capillary invasion by microbubbles (<0.1 mm) dominated bubble formation, with continued gas production (4 days for clay; 8 days for sand), large bubbles formed by deforming the surrounding sediment, leading to enhanced of macropore connectivity in both sediments. Growth of large bubbles (>1 mm) was possible in low shear yield strength sediments (<100 Pa), where excess gas pressure was sufficient to displace the sediment. Lower within the sand, higher shear yield strength (>360 Pa) resulted in a predominance of microbubbles where the required capillary entry pressure was low. Enhanced bubble migration, triggered by a controlled reduction in hydrostatic head, was observed throughout the clay column, while in sand mobile bubbles were restricted to the upper 6 cm. The observed macropore network was the dominant path for bubble movement and release in both sediments.

Laminar gypsum crust on lede stone: Microspatial characterization and laboratory acid weathering.

Gypsum crusts are typical decay forms on limestone in polluted urban environments. Their origin and relation to the stone facies have been thoroughly investigated in the past three decades. Here, we present the combined use of novel techniques for a microspatial structural, chemical and mechanical characterization of a laminar black gypsum crust on a sandy limestone. These techniques include i.a. X-ray computed microtomography, X-ray Fluorescence micromapping, permeability mapping and the scratch test. They reveal the typical architecture of a laminar gypsum crust, with an outer opaque layer, a subsurface gypsum crystallization layer and a deeper cracked zone passing irregularly into the sound stone. Gypsum crystallization is mostly restricted to an irregular outer zone with an average thickness of 500µm, while cracks are found deeper within the rock. These cracks decrease the rock strength to more than 27.5mm below the surface. Because of their surface parallel orientation and thickness of >10-100µm, they create the potential for surface scaling. This is shown by a laboratory acid test where the crack network extensively developed due to further exposure to an SO2 environment. The use of novel techniques opens potential for the study of different decay forms and can be used for stone diagnosis with regards to conservation studies.

A pore-scale study of fracture dynamics in rock using X-ray micro-CT under ambient freeze-thaw cycling.

Freeze-thaw cycling stresses many environments which include porous media such as soil, rock and concrete. Climate change can expose new regions and subject others to a changing freeze-thaw frequency. Therefore, understanding and predicting the effect of freeze-thaw cycles is important in environmental science, the built environment and cultural heritage preservation. In this paper, we explore the possibilities of state-of-the-art micro-CT in studying the pore scale dynamics related to freezing and thawing. The experiments show the development of a fracture network in a porous limestone when cooling to -9.7 °C, at which an exothermal temperature peak is a proxy for ice crystallization. The dynamics of the fracture network are visualized with a time frame of 80 s. Theoretical assumptions predict that crystallization in these experiments occurs in pores of 6-20.1 nm under transient conditions. Here, the crystallization-induced stress exceeds rock strength when the local crystal fraction in the pores is 4.3%. The location of fractures is strongly related to preferential water uptake paths and rock texture, which are visually identified. Laboratory, continuous X-ray micro-CT scanning opens new perspectives for the pore-scale study of ice crystallization in porous media as well as for environmental processes related to freeze-thaw fracturing.

Monitoring of stainless-steel slag carbonation using X-ray computed microtomography.

Steel production is one of the largest contributors to industrial CO2 emissions. This industry also generates large amounts of solid byproducts, such as slag and sludge. In this study, fine grained stainless-steel slag (SSS) is valorized to produce compacts with high compressive strength without the use of a hydraulic binder. This carbonation process is investigated on a pore-scale level to identify how the mineral phases in the SSS react with CO2, where carbonates are formed, and what the impact of these changes is on the pore network of the carbonated SSS compact. In addition to conventional research techniques, high-resolution X-ray computed tomography (HRXCT) is applied to visualize and quantify the changes in situ during the carbonation process. The results show that carbonates mainly precipitate at grain contacts and in capillary pores and this precipitation has little effect on the connectivity of the pore space. This paper also demonstrates the use of a custom-designed polymer reaction cell that allows in situ HRXCT analysis of the carbonation process. This shows the distribution and influence of water and CO2 in the pore network on the carbonate precipitation and, thus, the influence on the compressive strength development of the waste material.

High-resolution X-ray CT for 3D petrography of ferruginous sandstone for an investigation of building stone decay.

Diestian ferruginous sandstone has been used as the dominant building stone for monuments in the Hageland, a natural landscape in east-central Belgium. Like all rocks, this stone type is sensitive to weathering. Case hardening was observed in combination with blackening of the exterior parts of the dressed stones. To determine the 3D petrography and to identify the structural differences between the exterior and interior parts, X-ray computed tomography was used in combination with more traditional research techniques like optical microscopy and scanning electron microscopy. The 3D characterization of the ferruginous sandstone was performed with a high-resolution X-ray CT scanner (www.ugct.ugent.be) in combination with the flexible 3D analysis software Morpho+, which provides the necessary petrophysical parameters of the scanned samples in 3D. Besides providing the required 3D parameters like porosity, pore-size distribution, grain size, grain orientation, and surface analysis, the results of the 3D analysis can also be visualized, which enables to understand and interpret the analysis results in a straightforward way. The complementarities between high-quality X-ray CT images and flexible 3D software and its relation with the more traditional microscopical research techniques are opening up new gateways in the study of weathering processes of natural building stones.