Preservation of York Minster historic limestone by hydrophobic surface coatings

Magnesian limestone is a key construction component of many historic buildings that is under constant attack from environmental pollutants notably by oxides of sulfur via acid rain, particulate matter sulfate and gaseous SO 2 emissions. Hydrophobic surface coatings offer a potential route to protect existing stonework in cultural heritage sites, however, many available coatings act by blocking the stone microstructure, preventing it from 'breathing' and promoting mould growth and salt efflorescence. Here we report on a conformal surface modification method using self-assembled monolayers of naturally sourced free fatty acids combined with sub-monolayer fluorinated alkyl silanes to generate hydrophobic (HP) and super hydrophobic (SHP) coatings on calcite. We demonstrate the efficacy of these HP and SHP surface coatings for increasing limestone resistance to sulfation, and thus retarding gypsum formation under SO/H O and model acid rain environments. SHP treatment of 19th century stone from York Minster suppresses sulfuric acid permeation.

The role of environmental factors in industrial site selection activities:a case of limestone quarry expansion in Barbados, West Indies

Site selection is a key activity for quarry expansion to support cement production, and is governed by factors such as resource availability, logistics, costs, and socio-environmental factors. Adequate consideration of all factors facilitates both industrial productivity and sustainable economic growth. This study illustrates the site selection process that was undertaken for the expansion of limestone quarry operations to support cement production in Barbados. First, alternate sites with adequate resources to support a 25-year development horizon were identified. Second, socio-environmental conditions were described and potential impacts identified. Third, a comparative matrix was constructed to evaluate relative site characteristics with respect to physical, ecological, socio-cultural and economic factors. The study shows that environmental factors were essential to the final site recommendation.

Positive relationship between genetic- and species diversity on limestone outcrops in the Carpathian Mountains

We asked if the genetic diversity of Saponaria bellidifolia (a habitat specialist plant) and the species diversity of its habitat are driven by parallel landscape level processes in an island-like system of limestone outcrops in the Carpathian Mountains. We tested the relationship of these two diversity levels at local and regional geographic scales. Local genetic and species diversity showed parallel patterns influenced by the number of plant communities. Likewise, at regional level there was strong evidence for parallel equilibrial dynamics of genotypes and species. However, a superimposed matrix effect enhanced the regional species diversity only. Genetic diversity of habitat specialist organisms and species diversity of these limestone outcrop islands on mainland are modulated by parallel landscape-level processes at different geographic scales, and mechanisms may be identified at very high spatial resolutions.

Larger foraminiferal biostratigraphy, systematics and paleoenvironments of the Avon Park Formation and Ocala Limestone, Highlands County, Florida

This study investigates the use of larger foraminifera in determining the biostratigraphy of the Avon Park Formation and the Ocala Limestone in central Florida. Sedimentary rocks of the Avon Park Formation are the oldest exposed deposits in the state of Florida, and together with the Ocala Limestone comprise a part of the confining unit of the Floridan Aquifer, a major source of Florida's water supply. ^ Material from the ROMP 29A core collected by the U.S. Geological Survey was evaluated and compared to previous studies of the biostratigraphy of the formations. The larger foraminifera of the Avon Park Formation were examined in thin section, and those of the Ocala Limestone were free specimens. The larger foraminifera from both units were described and identified, and the biostratigraphy determined. The morphological features of the larger foraminifera of the Ocala Limestone were measured and analyzed at various depths within the ROMP 29A core.^ The Avon Park Formation contains predominantly the shallow-water, conical foraminifera Fallotella cookei, Fallotella floridana, Pseudochrysalidina floridana, Coleiconus christianaensis, Coleiconus sp. A, Coskinolina sp. A, Coskinolina sp. B, Fallotella sp. A, Fallotella sp. B, Fabularia vaughani and larger miliolids. ^ The Ocala Limestone contains a different, deeper water assemblage that included the larger foraminifera Heterostegina ocalana, Lepidocyclina ocalana varieties, Lepidocyclina chaperi, Lepidocyclina pustulosa, Nummulites willcoxi, Nummulites striatoreticulatus, Nummulites floridensis and Pseudophragmina spp. A, B, and C. The age of the Avon Park Formation was corroborated by the occurrence of the biomarker echinoid Neolaganum dalli as Eocene, and the Ocala Limestone also contained Eocene larger foraminifera with Eocene to possibly Oligocene calcareous nannofossils. The distribution of the larger foraminifera of the Avon Park Formation was correlated with the subtidal and peritidal zones of the continental shelf. Analyses of variance showed that the changes in measurements of the morphology in Heterostegina ocalana, Lepidocyclina spp. and Nummulites spp. were correlated with change in the depositional environments.^

Adsorption and desorption of phosphate on limestone in experiments simulating seawater intrusion

This study investigates the potential release of from carbonate aquifers exposed to seawater intrusion. Adsorption and desorption of in the presence of deionized water (DIW) and seawater were conducted on a large block of Pleistocene age limestone to simulate the effects of seawater intrusion into a coastal carbonate aquifer at the laboratory scale. The limestone showed strong adsorption of in DIW, while adsorption was significantly less in the presence of seawater. Dissolution of CaCO3 was found to prevent adsorption at salinities less than 30 psu. Adsorption of was limited at higher salinities (30–33 psu), due to competition with ions for adsorption sites. At a salinity3 precipitated. Concentrations of between 2 and 5 μmol/L were released by desorption when the limestone was exposed to seawater. The results of this study suggest that as seawater intrudes into an originally freshwater coastal aquifer, adsorbed may be released into the groundwater. Consequently, adsorbed is expected to be released from coastal carbonate aquifers world-wide as sea level continues to rise exposing more of the freshwater aquifer to seawater.

Geochemical and stable isotope composition of Middle Campanian marl-limestone rhythmites of the Lehrte West Syncline near Hannover (Lower Saxony, northern Germany)

A cyclic marl-limestone succession of Middle-Late Campanian age has been investigated with respect to a Milankovitch-controlled origin of geochemical data. In general, the major element geochemistry of the marl-limestone rhythmites can be explained by a simple two-component mixing model with the end-members calcium carbonate and 'average shale'-like material. Carbonate content varies from 55 to 90%. Non-carbonate components are clay minerals (illite, smectite) and biogenic silica from sponge spicules, as well as authigenically formed zeolites (strontian heulandite) and quartz. The redox potential suggests oxidizing conditions throughout the section. Trace element and stable isotopic data as well as SEM investigations show that the carbonate mud is mostly composed of low-magnesium calcitic tests of planktic coccolithophorids and calcareous dinoflagellate cysts (calcispheres). Diagenetic overprint results in a decrease of 2% d18O and an increase in Mn of up to 250 ppm. However, the sediment seems to preserve most of its high Sr content compared to the primary low-magnesium calcite of co-occurring belemnite rostra. The periodicity of geochemical cycles is dominated by 413 ka and weak signals between 51 and 22.5 ka, attributable to orbital forcing. Accumulation rates within these cycles vary between 40 and 50 m/Ma. The resulting cyclic sedimentary sequence is the product of (a) changes in primary production of low-magnesium calcitic biogenic material in surface waters within the long eccentricity and the precession, demonstrated by the CaCO3 content and the Mg/Al, Mn/Al and Sr/Al ratios, and (b) fluctuations in climate and continental weathering, which changed the quality of supplied clay minerals (the illite/smectite ratio), demonstrated by the K/Al ratio. High carbonate productivity correlates with smectite-favouring weathering (semi-arid conditions, conspicuously dry and moist seasonal changes in warmer climates). Ti as the proxy indicator for the detrital terrigenous influx, as well as Rb, Si, Zr and Na, shows only low frequency signals, indicating nearly constant rates of supply throughout the more or less pure pelagic carbonate deposition of the long-lasting third-order Middle-Upper Campanian sedimentary cycle.

Chemical composition of ferromanganese nodules from the Western Sicily Jurassic limestone beds

The stratigraphic study focuses on the description of lithofacies and geological sections of secondary, tertiary and quaternary formations in different parts of western Sicily. The tectonic analysis derived from field studies is used to trace the history and effects of the Alpine orogeny on the geology of Western Sicily. During his field study the author conducted several chemical element analysis on fossil manganese nodules extracted from Jurassic limestone beds.

Tropical limestone forest resilience and late Pleistocene foraging during MIS-2 in the Tràng An massif, Vietnam

In this paper we present a multi-proxy study of tropical limestone forest and its utilization by human groups during the major climatic and environmental upheavals of MIS-2 (29-11.7 kBP). Our data are drawn from new field research within the Tràng An World Heritage property on the edge of the Red River Delta, northern Vietnam. Key findings from this study include 1) that limestone forest formations were resilient to the large-scale landscape transformation of the Sunda continent at the end of the last glaciation; 2) that prehistoric human groups were probably present in this habitat through-out MIS-2; and 3) that the forested, insular, karst of Tràng An provided foragers with a stable resource-base in a wider changing landscape. These results have implications for our understanding of the prehistoric utilization of karst environments, and resonance for their conservation in the face of climate and environmental change today.

Development of an Economic Dust Palliative for Limestone Surfaced Secondary Roads, HR-297, Progress Report, 1988

Research activities during this period concentrated on continuation of field and laboratory testing for the Dallas County test road. Stationary ditch collection of dust was eliminated because of inconsistent data, and because of vandalism to collectors. Braking tests were developed and initiated to evaluate the influence of treatments on braking and safety characteristics of the test sections. Dust testing was initiated for out of the wheelpath conditions as well as in the wheelpath. Contrary to the results obtained during the summer and fall of 1987, the 1.5 percent bentonite treatment appears to be outperforming the other bentonite treated sections after over a year of service. Overall dust reduction appears to average between 25 to 35 percent. Dallas County applied 300 tons per mile of class A roadstone maintenance surfacing to the test road in August 1988. Test data indicates that the bentonite is capable of interacting and functioning to reduce dust generation of the new surfacing material. Again, the 1.5 percent bentonite treatment appeared the most effective. The fine particulate bonding and aggregation mechanism of the bentonite appears recoverable from the environmental effects of winter, and from alternating wet and dry road surface conditions. The magnesium chloride treatment appears capable of long-term (over one year) dust reduction and exhibited an overall average reduction in the range of 15 to 30 percent. The magnesium chloride treatment also appears capable of interacting with newly applied crushed stone to reduce dust generation. Two additional one mile test roads were to have been constructed early this year. Due to an extremely dry spring and summer, construction scheduling was not possible until August. This would have allowed only minimal data collection. Considering this and the fact that this was an atypically dry summer, it was our opinion that it would be in the best interest of the research project to extend the project (at no additional cost) for a period of one year. The two additional test roads will be constructed in early spring 1989 in Adair and Marion counties.

Durability performance of self-compacting concrete (SCC) with binary and ternary mixes of fly ash and limestone filler

The basic objective of this work is to evaluate the durability of self-compacting concrete (SCC) produced in binary and ternary mixes using fly ash (FA) and limestone filler (LF) as partial replacement of cement. The main characteristics that set SCC apart from conventional concrete (fundamentally its fresh state behaviour) essentially depend on the greater or lesser content of various constituents, namely: greater mortar volume (more ultrafine material in the form of cement and mineral additions); proper control of the maximum size of the coarse aggregate; use of admixtures such as superplasticizers. Significant amounts of mineral additions are thus incorporated to partially replace cement, in order to improve the workability of the concrete. These mineral additions necessarily affect the concrete's microstructure and its durability. Therefore, notwithstanding the many well-documented and acknowledged advantages of SCC, a better understanding its behaviour is still required, in particular when its composition includes significant amounts of mineral additions. An ambitious working plan was devised: first, the SCC's microstructure was studied and characterized and afterwards the main transport and degradation mechanisms of the SCC produced were studied and characterized by means of SEM image analysis, chloride migration, electrical resistivity, and carbonation tests. It was then possible to draw conclusions about the SCC's durability. The properties studied are strongly affected by the type and content of the additions. Also, the use of ternary mixes proved to be extremely favourable, confirming the expected beneficial effect of the synergy between LF and FA.

A first insight on the biodegradation of limestone - the case of the World Heritage Convent of Christ

The present study is a multidisciplinary approach applied to architectural stone materials of the Convent of Christ in Tomar (Portugal) in order to understand and mitigate the active decay processes. The structure and appearance of the stonework from the Convent of Christ are strongly affected by stains, biofilms and structural degradation. To investigate these phenomena, a multianalytical approach comprising X-ray microdiffraction, scanning electron microscopy, microRaman and microinfrared spectroscopy was applied to the examination of altered outdoor stone areas being detected calcium oxalates, carotenoids and microbial proliferation. The presence of these alteration products seems to be correlated with the microbial activity of bacteria, microalgae, cyanobacteria and filamentous fungi. This work showed that the application of complementary methodologies is an efficient strategy to characterise the stone decay, and constitute a starting point for successful conservation intervention plans that are urgent to ensure the preservation and safeguard of this emblematic monument.

Managing hostile environments : journalists and media workers : learning to survive the world's difficult, remote and hostile environments

The aim of this research is to examine the changing nature of risks that face journalists and media workers in the world's difficult, remote and hostile environments, and consider the 'adequacy' of managing hostile environment safety courses that some media organizations require prior to foreign assignments. The study utilizes several creative works and contributions to this area of analysis, which includes a documentary film production, course contributions, an emergency reference handbook, security and incident management reviews and a template for evacuation and contingency planning. The research acknowledges that employers have a 'duty of care' to personnel working in these environments, identifies the necessity for pre-deployment training and support, and provides a solution for organizations that wish to initiate a comprehensive framework to advise, monitor, protect and respond to incidents. Finally, it explores the possible development of a unique and holistic service to facilitate proactive and responsive support, in the form of a new profession of 'Editorial Logistics Officer' or 'Editorial Safety Officer' within media organizations. This area of research is vitally important to the profession, and the intended contribution is to introduce a simple and cost-efficient framework for media organizations that desire to implement pre-deployment training and field-support – as these programs save lives. The complete proactive and responsive services may be several years from implementation. However, this study demonstrates that the facilitation of Managing Hostile Environment (MHE) courses should be the minimum professional standard. These courses have saved lives in the past and they provide journalists with the tools to "cover the story, and not become the story."

Pre-eruptive uplift in the Emeishan? [Correspondence]

In their correspondence, He and colleagues question our conclusion of little or no uplift preceding Emeishan volcanism that we reported in our letter1. Debate concerns the nature of the contact between the Maokou limestone and Emeishan volcanics, the depositional environment and volumetric significance of mafic hydromagmatic deposits (MHDs), and evidence for symmetrical domal thinning. MHDs in the Daqiao section are separated from the Maokou limestone by 100 m of subaerial basaltic lavas, but elsewhere MHDs — previously interpreted as basal conglomerates2, 3 — directly overlie the Maokou2, 3. MHDs thus feature strongly in basal sections of the Emeishan lava succession, as also recently shown4 elsewhere in the Emeishan. An irregular surface at the top of the Maokou limestone has been interpreted as an erosional unconformity2, 3, but clastic deposits presented as evidence of this erosion2, 3 are MHDs produced by explosive magma–water interaction1. A clear demonstration that this irregular top surface is an erosional truncation of limestone reef facies (slope/rim, flat, lagoonal) is currently lacking, but is critical because reefs and carbonate platforms show considerable natural relief of tens of metres. The persistent hot, wet climate since the Oligocene has produced well-developed weathering profiles on exposed Palaeozoic marine sedimentary sequences5, but weathering and karst relief of the uppermost Maokou limestone underlying the flood basalts have not been properly documented, nor shown to be of middle Permian age and immediately preceding emplacement of the large igneous province.