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.

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.

Stone-built heritage as a proxy archive for long-term historical air quality: A study of weathering crusts on three generations of stone sculptures on Broad Street, Oxford.

Black crusts on historic buildings are mainly known for their aesthetic and deteriorative impacts, yet they also can advance air pollution research. Past air pollutants accumulate in distinct layers of weathering crusts. Recent studies have used these crusts to reconstruct pollution to improve our understanding of its effects on stone-built heritage. However, the majority of the studies provide only coarse resolution reconstruction of pollution, able to distinguish between 'inner = old' and 'outer = modern' crust layers. In contrast, very few studies have linked distinct periods of exposure to pollution variations in the composition of these crusts. Here we address this research gap by developing a finer-scale resolution pollution record. Our study explored the unique configuration of limestone sculptures in central Oxford, which have been exposed over the last 350 years to three different periods of atmospheric pollution; the early Industrial Revolution, the Victorian period and the 20th century. When the first two generations of sculptures were moved to less polluted areas, their 'pollution clocks' were stopped. Here we discuss the potential of investigating the 'pollution clock' recorded in the geochemical makeup of each sculpture generation's weathering crust layers. We found the analysed crusts record clear changes related to the evolution of modes of transport and industrial and technological development in Oxford. Higher levels of Arsenic (As), Selenium (Se) are linked to pollution from coal burning during Victorian times and Lead (Pb) indicated leaded petrol use in modern times. Our work shows that stone-built heritage with a known history of air pollution exposure allows improving the pollution reconstruction resolution of these weathering crusts. The results provide the basis for calibrating long-term geochemical archives. This approach may be used to reconstruct past air quality and has the potential to inform stone weathering research and conservation, in addition to improving the reconstruction of historical pollution.

Wind-driven rain and future risk to built heritage in the United Kingdom: Novel metrics for characterising rain spells.

Wind-driven rain (WDR) is rain given a horizontal velocity component by wind and falling obliquely. It is a prominent environmental risk to built heritage, as it contributes to the damage of porous building materials and building element failure. While predicted climate trends are well-established, how they will specifically manifest in future WDR is uncertain. This paper combines UKCP09 Weather Generator predictions with a probabilistic process to create hourly time series of climate parameters under a high-emissions scenario for 2070-2099 at eight UK sites. Exposure to WDR at these sites for baseline and future periods is calculated from semi-empirical models based on long-term hourly meteorological data using ISO 15927-3:2009. Towards the end of the twenty-first century, it is predicted that rain spells will have higher volumes, i.e. a higher quantity of water will impact façades, across all 8 sites. Although the average number of spells is predicted to remain constant, they will be shorter with longer of periods of time between them and more intense with wind-driven rain occurring for a greater proportion of hours within them. It is likely that in this scenario building element failure - such as moisture ingress through cracks and gutter over-spill - will occur more frequently. There will be higher rates of moisture cycling and enhanced deep-seated wetting. These predicted changes require new metrics for wind-driven rain to be developed, so that future impacts can be managed effectively and efficiently.