Physical and mineralogical changes of Hungarian monumental stones exposed to different conditions: stone-testing in-situ and under laboratory conditions

The Székesfehérvár Ruin Garden is a unique assemblage of monuments belonging to the cultural heritage of Hungary due to its important role in the Middle Ages as the coronation and burial church of the Kings of the Hungarian Christian Kingdom. It has been nominated for “National Monument” and as a consequence, its protection in the present and future is required. Moreover, it was reconstructed and expanded several times throughout Hungarian history. By a quick overview of the current state of the monument, the presence of several lithotypes can be found among the remained building and decorative stones. Therefore, the research related to the materials is crucial not only for the conservation of that specific monument but also for other historic structures in Central Europe. The current research is divided in three main parts: i) description of lithologies and their provenance, ii) physical properties testing of historic material and iii) durability tests of analogous stones obtained from active quarries. The survey of the National Monument of Székesfehérvár, focuses on the historical importance and the architecture of the monument, the different construction periods, the identification of the different building stones and their distribution in the remaining parts of the monument and it also included provenance analyses. The second one was the in situ and laboratory testing of physical properties of historic material. As a final phase samples were taken from local quarries with similar physical and mineralogical characteristics to the ones used in the monument. The three studied lithologies are: fine oolitic limestone, a coarse oolitic limestone and a red compact limestone. These stones were used for rock mechanical and durability tests under laboratory conditions. The following techniques were used: a) in-situ: Schmidt Hammer Values, moisture content measurements, DRMS, mapping (construction ages, lithotypes, weathering forms) b) laboratory: petrographic analysis, XRD, determination of real density by means of helium pycnometer and bulk density by means of mercury pycnometer, pore size distribution by mercury intrusion porosimetry and by nitrogen adsorption, water absorption, determination of open porosity, DRMS, frost resistance, ultrasonic pulse velocity test, uniaxial compressive strength test and dynamic modulus of elasticity. The results show that initial uniaxial compressive strength is not necessarily a clear indicator of the stone durability. Bedding and other lithological heterogeneities can influence the strength and durability of individual specimens. In addition, long-term behaviour is influenced by exposure conditions, fabric and, especially, the pore size distribution of each sample. Therefore, a statistic evaluation of the results is highly recommended and they should be evaluated in combination with other investigations on internal structure and micro-scale heterogeneities of the material, such as petrographic observation, ultrasound pulse velocity and porosimetry. Laboratory tests used to estimate the durability of natural stone may give a good guidance to its short-term performance but they should not be taken as an ultimate indication of the long-term behaviour of the stone. The interdisciplinary study of the results confirms that stones in the monument show deterioration in terms of mineralogy, fabric and physical properties in comparison with quarried stones. Moreover stone-testing proves compatibility between quarried and historical stones. Good correlation is observed between the non-destructive-techniques and laboratory tests results which allow us to minimize sampling and assessing the condition of the materials. Concluding, this research can contribute to the diagnostic knowledge for further studies that are needed in order to evaluate the effect of recent and future protective measures.

Stone architecture in Carso plateau. Settlement patterns and construction techniques of historic buildings

The use of stone and its types of processing have been very important in the vernacular architecture of the cross-border Carso. In Carso this represents an important legacy of centuries and has a uniform typological characteristic to a great extent. The stone was the main constituent of the local architecture, setting and shaping the human environment, incorporating the history of places through their specific symbolic and constructive language. The primary aim of this research is the recognition of the constructive rules and the values embedded in the Carso rural architecture by use and processing of stone. Central to this investigation is the typological reading, aimed to analyze the constructive language expressed by this legacy, through the analysis of the relationship between type, technique and material.

Teos-based consolidants for stone conservation: evaluation of the effects and testing by x-ray imaging

Natural stones have been widely used in the construction field since antiquity. Building materials undergo decay processes due to mechanical,chemical, physical and biological causes that can act together. Therefore an interdisciplinary approach is required in order to understand the interaction between the stone and the surrounding environment. Utilization of buildings, inadequate restoration activities and in general anthropogenic weathering factors may contribute to this degradation process. For this reasons, in the last few decades new technologies and techniques have been developed and introduced in the restoration field. Consolidants are largely used in restoration and conservation of cultural heritage in order to improve the internal cohesion and to reduce the weathering rate of building materials. It is important to define the penetration depth of a consolidant for determining its efficacy. Impregnation mainly depends on the microstructure of the stone (i.e. porosity) and on the properties of the product itself. Throughout this study, tetraethoxysilane (TEOS) applied on globigerina limestone samples has been chosen as object of investigation. After hydrolysis and condensation, TEOS deposits silica gel inside the pores, improving the cohesion of the grains. X-ray computed tomography has been used to characterize the internal structure of the limestone samples,treated and untreated with a TEOS-based consolidant. The aim of this work is to investigate the penetration depth and the distribution of the TEOS inside the porosity, using both traditional approaches and advanced X-ray tomographic techniques, the latter allowing the internal visualization in three dimensions of the materials. Fluid transport properties and porosity have been studied both at macroscopic scale, by means of capillary uptake tests and radiography, and at microscopic scale,investigated with X-ray Tomographic Microscopy (XTM). This allows identifying changes in the porosity, by comparison of the images before and after the treatment, and locating the consolidant inside the stone. Tests were initially run at University of Bologna, where characterization of the stone was carried out. Then the research continued in Switzerland: X-ray tomography and radiography were performed at Empa, Swiss Federal Laboratories for Materials Science and Technology, while XTM measurements with synchrotron radiation were run at Paul Scherrer Institute in Villigen.

Transport of nanoparticles into polymersomes : a minimal model system of particles passage through biological membranes

This thesis focuses on the design and characterization of a novel, artificial minimal model membrane system with chosen physical parameters to mimic a nanoparticle uptake process driven exclusively by adhesion and softness of the bilayer. The realization is based on polymersomes composed of poly(dimethylsiloxane)-b-poly(2-methyloxazoline) (PMDS-b-PMOXA) and nanoscopic colloidal particles (polystyrene, silica), and the utilization of powerful characterization techniques. rnPDMS-b-PMOXA polymersomes with a radius, Rh ~100 nm, a size polydispersity, PD = 1.1 and a membrane thickness, h = 16 nm, were prepared using the film rehydratation method. Due to the suitable mechanical properties (Young’s modulus of ~17 MPa and a bending modulus of ~7⋅10-8 J) along with the long-term stability and the modifiability, these kind of polymersomes can be used as model membranes to study physical and physicochemical aspects of transmembrane transport of nanoparticles. A combination of photon (PCS) and fluorescence (FCS) correlation spectroscopies optimizes species selectivity, necessary for a unique internalization study encompassing two main efforts. rnFor the proof of concepts, the first effort focused on the interaction of nanoparticles (Rh NP SiO2 = 14 nm, Rh NP PS = 16 nm; cNP = 0.1 gL-1) and polymersomes (Rh P = 112 nm; cP = 0.045 gL-1) with fixed size and concentration. Identification of a modified form factor of the polymersome entities, selectively seen in the PCS experiment, enabled a precise monitor and quantitative description of the incorporation process. Combining PCS and FCS led to the estimation of the incorporated particles per polymersome (about 8 in the examined system) and the development of an appropriate methodology for the kinetics and dynamics of the internalization process. rnThe second effort aimed at the establishment of the necessary phenomenology to facilitate comparison with theories. The size and concentration of the nanoparticles were chosen as the most important system variables (Rh NP = 14 - 57 nm; cNP = 0.05 - 0.2 gL-1). It was revealed that the incorporation process could be controlled to a significant extent by changing the nanoparticles size and concentration. Average number of 7 up to 11 NPs with Rh NP = 14 nm and 3 up to 6 NPs with Rh NP = 25 nm can be internalized into the present polymersomes by changing initial nanoparticles concentration in the range 0.1- 0.2 gL-1. Rapid internalization of the particles by polymersomes is observed only above a critical threshold particles concentration, dependent on the nanoparticle size. rnWith regard possible pathways for the particle uptake, cryogenic transmission electron microscopy (cryo-TEM) has revealed two different incorporation mechanisms depending on the size of the involved nanoparticles: cooperative incorporation of nanoparticles groups or single nanoparticles incorporation. Conditions for nanoparticle uptake and controlled filling of polymersomes were presented. rnIn the framework of this thesis, the experimental observation of transmembrane transport of spherical PS and SiO2 NPs into polymersomes via an internalization process was reported and examined quantitatively for the first time. rnIn a summary the work performed in frames of this thesis might have significant impact on cell model systems’ development and thus improved understanding of transmembrane transport processes. The present experimental findings help create the missing phenomenology necessary for a detailed understanding of a phenomenon with great relevance in transmembrane transport. The fact that transmembrane transport of nanoparticles can be performed by artificial model system without any additional stimuli has a fundamental impact on the understanding, not only of the nanoparticle invagination process but also of the interaction of nanoparticles with biological as well as polymeric membranes. rn

Lunar tractive forces and renal stone incidence

Background. Several factors are implicated in renal stone formation and peak incidence of renal colic admissions to emergency departments (ED). Little is known about the influence of potential environmental triggers such as lunar gravitational forces. We conducted a retrospective study to test the hypothesis that the incidence of symptomatic renal colics increases at the time of the full and new moon because of increased lunar gravitational forces. Methods. We analysed 1500 patients who attended our ED between 2000 and 2010 because of nephrolithiasis-induced renal colic. The lunar phases were defined as full moon ± 1 day, new moon ± 1 day, and the days in-between as "normal" days. Results. During this 11-year period, 156 cases of acute nephrolithiasis were diagnosed at the time of a full moon and 146 at the time of a new moon (mean of 0.4 per day for both). 1198 cases were diagnosed on "normal" days (mean 0.4 per day). The incidence of nephrolithiasis in peak and other lunar gravitational phases, the circannual variation and the gender-specific analysis showed no statistically significant differences. Conclusion. In this adequate powered longitudinal study, changes in tractive force during the different lunar phases did not influence the incidence of renal colic admissions in emergency department.

Stable N isotope composition of nitrate reflects N transformations during the passage of water through a montane rain forest in Ecuador

Knowledge of the fate of deposited N in the possibly N-limited, highly biodiverse north Andean forests is important because of the possible effects of N inputs on plant performance and species composition. We analyzed concentrations and fluxes of NO3 −–N, NH4 +–N and dissolved organic N (DON) in rainfall, throughfall, litter leachate, mineral soil solutions (0.15–0.30 m depths) and stream water in a montane forest in Ecuador during four consecutive quarters and used the natural 15N abundance in NO3 − during the passage of rain water through the ecosystem and bulk δ15N values in soil to detect N transformations. Depletion of 15N in NO3 − and increased NO3 −–N fluxes during the passage through the canopy and the organic layer indicated nitrification in these compartments. During leaching from the organic layer to mineral soil and stream, NO3 − concentrations progressively decreased and were enriched in 15N but did not reach the δ15N values of solid phase organic matter (δ15N = 5.6–6.7‰). This suggested a combination of nitrification and denitrification in mineral soil. In the wettest quarter, the δ15N value of NO3 − in litter leachate was smaller (δ15N = −1.58‰) than in the other quarters (δ15N = −9.38 ± SE 0.46‰) probably because of reduced mineralization and associated fractionation against 15N. Nitrogen isotope fractionation of NO3 − between litter leachate and stream water was smaller in the wettest period than in the other periods probably because of a higher rate of denitrification and continuous dilution by isotopically lighter NO3 −–N from throughfall and nitrification in the organic layer during the wettest period. The stable N isotope composition of NO3 − gave valuable indications of N transformations during the passage of water through the forest ecosystem from rainfall to the stream.

Passage of Alabama's Hb 56: Fueled By Dominant Anti-Immigration Tropes

Abstract Background. In 2011, Alabama, neither a border state nor hold a significantly large Hispanic population, passed the most restrictive state immigration law, The Beason-Hammon Alabama Taxpayer and Citizen Protection Act, HB 56. This omnibus law was far-reaching in its restrictions, including, but not limited to, identification, public services, employment, housing, and law enforcement. Objectives. This research explores the dominant tropes present in the narrative surrounding the anti-immigration legislative activity in Alabama that created fertile ground for the passage of such a punitive immigration law. Methods. Newspaper articles from 2007 to 2011 in Alabama¿s Birmingham News and Press-Register, the two most circulated newspapers in the state, were attained from NewsLibrary.com, an online database of 5,311 newspapers and other news sources. Results. Seven dominant tropes were identified in the articles that pushed for anti-immigration policies. These tropes claimed (1) the US-Mexico border is not secure, (2) the federal government has failed to enact comprehensive immigration reform, (3) immigrants steal jobs, hurt the economy, and (4) burden public services, (5) immigrants are criminals and terrorists, (6) they refuse to assimilate and learn English, and (7) there has been a dramatic percent change in the Hispanic and illegal populations. These tropes cumulatively worked together to create anti-immigration sentiment that pushed for the passage of HB 56.

Pancreatic stone protein as a novel marker for neonatal sepsis

Early-onset sepsis (EOS) is one of the main causes for the admission of newborns to the neonatal intensive care unit. However, traditional infection markers are poor diagnostic markers of EOS. Pancreatic stone protein (PSP) is a promising sepsis marker in adults. The aim of this study was to investigate whether determining PSP improves the diagnosis of EOS in comparison with other infection markers.

Alternate or additional findings to stone disease on unenhanced computerized tomography for acute flank pain can impact management

PURPOSE: We evaluated the incidence and clinical relevance of alternate or additional findings on unenhanced CT in patients with acute flank pain and suspected urinary calculi. MATERIALS AND METHODS: A consecutive series of 1,500 patients underwent unenhanced CT due to acute flank pain. The absence or presence of urinary tract calculi and their localization were recorded. Alternate or additional CT findings were classified according to whether they required immediate or deferred treatment, or were of little or no clinical importance. RESULTS: Of the 1,500 patients 1,035 (69%) had urinary tract calculi, including 309 (30%) with nephrolithiasis, 377 (36%) with ureterolithiasis and 349 (34%) with the 2 conditions. Urolithiasis alone was found in 331 of these patients (32%) and additional pathological conditions were noted in 704 (68%). Of all patients 1,064 (71%) had other or additional CT findings. Of all patients 207 (14%) had nonstone related CT findings requiring immediate or deferred treatment, 464 (31%) had pathological conditions of little clinical importance and 393 (26%) had pathological conditions of no clinical relevance. CT was normal in 105 of all patients (7%). CONCLUSIONS: Unenhanced CT in patients with acute flank pain allows the accurate diagnosis of urinary stone disease and it can also provide further important information leading to emergency or deferred treatment in a substantial number of patients.

[Urine analyses for workup of kidney stone disease--interpretation and therapeutic consequences]

Nephrolithiasis is a disease with a high and even rising incidence. It has a high morbidity, generates high costs and has a high recurrence rate. Urinalysis is of importance especially in recurrent stone formers. It allows the identification and quantification of risk factors and the establishment of individual risk profiles. Based on these individual risk profiles, rational therapy for metaphylaxis of kidney stones lowers stone recurrence rates significantly. This review article aims to give a focussed overview of the most important risk factors for kidney stones and reasonable urine tests for evaluation of recurrent kidney stone formers.

Gain-of-function haplotype in the epithelial calcium channel TRPV6 is a risk factor for renal calcium stone formation

The rate-limiting step of dietary calcium absorption in the intestine requires the brush border calcium entry channel TRPV6. The TRPV6 gene was completely sequenced in 170 renal calcium stone patients. The frequency of an ancestral TRPV6 haplotype consisting of three non-synonymous polymorphisms (C157R, M378V, M681T) was significantly higher (P = 0.039) in calcium stone formers (8.4%; derived = 502, ancestral = 46) compared to non-stone-forming individuals (5.4%; derived = 645, ancestral = 37). Mineral metabolism was investigated on four different calcium regimens: (i) free-choice diet, (ii) low calcium diet, (iii) fasting and (iv) after a 1 g oral calcium load. When patients homozygous for the derived haplotype were compared with heterozygous patients, no differences were found with respect to the plasma concentrations of 1,25-vitamin D, PTH and calcium, and the urinary excretion of calcium. In one stone-forming patient, the ancestral haplotype was found to be homozygous. This patient had absorptive hypercalciuria. We therefore expressed the ancestral protein (157R+378V+681T) in Xenopus oocytes and found a significantly enhanced calcium permeability when tested by a (45)Ca(2+) uptake assay (7.11 +/- 1.93 versus 3.61 +/- 1.01 pmol/min/oocyte for ancestral versus derived haplotype, P < 0.01). These results suggest that the ancestral gain-of-function haplotype in TRPV6 plays a role in calcium stone formation in certain forms of absorptive hypercalciuria.