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Crystallisation of alkaline earth metal carbonates from water is important for biomineralisation and environmental geochemistry. Here large-scale computer simulations are a useful approach to complement experimental studies by providing atomistic insights and even by quantitatively determining the thermodynamics of individual steps. However, this is dependent on the existence of force field models that are sufficiently accurate while being computationally efficient enough to sample complex systems. Here we introduce a revised force field for aqueous alkaline earth metal carbonates that reproduces both the solubilities of the crystalline anhydrous minerals, as well as the hydration free energies of the ions. The model is also designed to run efficiently on GPUs thereby reducing the cost of such simulations. The performance of the revised force field is compared against previous results for important properties relevant to crystallisation, including ion-pairing and mineral-water interfacial structure and dynamics.

Carbon dots are emerging in the nanotechnology field as the newest class of fluorescent probes, owing to their high water-solubility, good chemical and photo-stability and tunable photoluminescence. The ability of metal cations to quench carbon dots fluorescence is already well known. Anyway, a dedicated study directed to the rational design of the optimal carbon dot probe is still missing. Herein we present a novel synthetic method for the production of carbon nanodots from an economic and environmental polluting starting material: olive solid wastes. The obtained carbon dots are efficiently quenched in presence of Fe3+, allowing the cation detection. Starting from a comprehensive study on their quenching mechanism, we have been able to develop effective strategies to modulate the sensing properties of these carbon dots. The sensitivity and linear range of the probe have been tuned by modulating the surface functionalization of the nanoparticles. The selectivity toward Fe3+ has been improved by growing around the dots a porous microsphere of ion imprinted polymer. The results highlighted in this work demonstrate that the carbon dots sensing properties can be modulated to meet the requirement of the users, allowing the design of tailored probes for a wide range of applications.

Nano-bionics have the potential of revolutionizing modern medicine. Among nano-bionic devices, body sensors allow to monitor in real-time the health of patients, to achieve personalized medicine, and even to restore or enhance human functions. The advent of two-dimensional (2D) materials is facilitating the manufacturing of miniaturized and ultrathin bioelectronics, that can be easily integrated in the human body. Their unique electronic properties allow to efficiently transduce physical and chemical stimuli into electric current. Their flexibility and nanometric thickness facilitate the adaption and adhesion to human body. The low opacity permits to obtain transparent devices. The good cellular adhesion and reduced cytotoxicity are advantageous for the integration of the devices in vivo. Herein we review the latest and more significant examples of 2D material-based sensors for health monitoring, describing their architectures, sensing mechanisms, advantages and, as well, the challenges and drawbacks that hampers their translation into commercial clinical devices.

Enzymes are ideal receptors for biosensors since they offer excellent selectivity and high catalytic activity. However, once removed from their native environment, enzymes present a short lifespan determining a huge drawback for their application in bio-analytical systems. The use of appropriate immobilization matrices is an effective strategy to preserve enzymatic activity. In this work, an enzymatic amperometric biosensor is designed by entrapping lactate oxidase into a protein-based immobilization matrix, formed by the self-assembly of engineered repeat proteins. Electrochemically exfoliated graphene, functionalized with cobalt phthalocyanine, is employed as electroactive material and transducer of the sensor. Due to the extraordinary enzymatic stabilization provided by the engineered protein film, the device sensitivity is preserved for more than 6 months at room temperature. Furthermore, the presented biosensor can detect lactate with outstanding performance in terms of sensitivity, repeatability, and reproducibility.

Objective Pierre Robin Sequence (PRS) is a heterogeneous pathological condition characterized by the coexistence of micrognathia, glossoptosis, and cleft palate, resulting in upper airway tract obstruction. Among the treatment modalities, the orthodontic approach is one part of the comprehensive care of those patients and will be present in the treatment modalities during all the growth period of the child. Methods All patients with PRS observed in the period 2013-2017 were treated with a definite functional approach. The results were retrospectively analyzed with regard to functional outcome, total treatment time, and number of plates provided for a single patient. Results In all the patients, the indicated treatment protocol has been applied as early impression and plate supply, stimulation of bottle feeding with the use of the plate, eventual substitution of the plate if no more adequate to the transverse and sagittal growth of the palate, and continuing the use until the surgical closure of the cleft. All the patients showed a positive outcome to the proposed treatment approach, evaluated with regard to the incidence of feeding improvement and weight gain, to the limit for the surgical phase, in the absence of adverse effects. Conclusion The use of a functional obturator plate, removing functional alterations to mandibular growth, reduces and, in some cases, eliminates the need for surgical intervention. As also stated in the literature, if despite the presence of the plate nutritional problems persist, immediate different surgical approaches, mainly mandibular osteodistraction, become necessary.

Since graphene was exfoliated in 2004, two-dimensional (2D) materials have received great attention due to their physical and chemical properties associated with their nanosized thickness and the correlated quantum size effect. 2D planes allow the confinement of charge carriers, heat, and photons, leading to the remarkable electronic and optical properties of these materials. The Faraday Discussion "Chemistry of 2-dimensional materials: beyond graphene" has been an incredible showcase for a variety of highly interesting contributions in the field. This conference comprised a large number of aspects of the topic: from their synthesis and the study of their optical and physical properties to their numerous applications. These concluding remarks aim to capture the recent developments in 2D materials chemistry and physics that were presented and debated during this Faraday Discussion, and more generally in the research field in recent years. Particular attention will be paid to aspects like the synthesis of the materials, their toxicity and biodegradation, and some of their major applications in catalysis, as well as Li-ion batteries, water filtration and sensing. In addition we aim to highlight future challenges that still need to be addressed.

The detection of cancer biomarkers at an early stage of tumor development is vital for effective diagnosis and treatment of cancer. Current diagnostic tools can often detect cancer only when the biomarker levels are already too high, so that the tumors have spread and treatments are less effective. It is urgent therefore to develop highly sensitive assays for the detection of such biomarkers at the lowest possible concentration. In this context, we developed a sandwich immunoassay based on surface-enhanced Raman scattering (SERS) for the ultrasensitive detection of α-fetoprotein (AFP), which is typically present in human serum as a biomarker indicative of early stages of hepatocellular carcinoma. In the immunoassay design, molybdenum disulfide (MoS2) modified with a monoclonal antibody was used as a capture probe for AFP. A secondary antibody linked to an SERS-encoded nanoparticle was employed as the Raman signal reporter, that is, the transducer for AFP detection. The sandwich immunocomplex “capture probe/target/SERS tag” was deposited on a silicon wafer and decorated with silver-coated gold nanocubes to increase the density of “hot spots” on the surface of the immunosensor. The developed SERS immunosensor exhibits a wide linear detection range (1 pg mL–1 to 10 ng mL–1) with a limit of detection as low as 0.03 pg mL–1 toward AFP with good reproducibility (RSD < 6%) and stability. These parameters demonstrate that the proposed immunosensor has the potential to be used as an analytical platform for the detection of early-stage cancer biomarkers in clinical applications.

Background: The present work starts from a literature review of the evolution of Integrated Management Systems (IMSs), considering different points of view and standards: quality, environmental, occupational health and safety, sustainability and social issues. Even if the benefits are possible, there is not a common approach and a clear link between the integration of management systems and business performance, in particular considering safety performance. Methods: The present study analyzes the application of Risk Assessment in order to realize the integration of management systems. The main objective is to provide a tool for an integrated evaluation of all company performances, starting from the definition of some Key Performance Indicators—KPIs—proposed for a particular case study, even if their choice is not the core of the paper. The assessment team members on the basis of their knowledge, experience and useful literature, could choose the right KPIs for the specific application, able to take a picture of the current state and to suggest a possible recommended action of improving. The proposed Risk Assessment approach is an integration of modern management techniques: Integrated Management System and Improving Cycle DMAIC. Results: The new method, called the Global Performance Index for Integrated Management System—GPI-IMS, has been applied to a real case study in the logistic field in order to evaluate its goodness and possible generalization. Conclusions: The proposed method allows to define the requirements that any company must have to perform the best. The role of the assessment team is very important to evaluate the global performance of the company and to suggest the corrective actions to be adopted.

In the last twenty years, anthropologists, archivists, and historians have dedicated increased attention to the study of archives as objects of research themselves. In so doing, scholars have predominantly examined the emergence and transformations of archives during the early modern age, focusing mostly on political and diplomatic depositories. They have tended to neglect financial archives, which is unfortunate, as—alongside judicial archives—they were probably the largest documentary repositories of the pre-modern world and those that first faced the problem of managing huge masses of documentation. This article discusses the formation and development of the Kingdom of Sicily’s financial archives in the later Middle Ages, arguing that this repository evolved into a collecting archive by the early fifteenth-century, when it preserved not only the records and accounts produced by the central financial administration, but also those from a number of territorial officers and magistracies. This archival turn, I suggest, originated from the fact that the Crown of Aragon’s rulers constantly needed increased incomes to fund bureaucracies and warfare and exercise patronage, and thus needed financial information organized, at hand, and under their control. After briefly discussing the emergence of the financial archive in the thirteenth-century, this essay traces the Crown’s attempts to create a stable repository for storing financial records and accounts and its continuous struggles to prevent documentation from being scattered and dispersed. Finally, it examines the successful strategy that King Alfonso V of Aragon (1416–58), called the Magnanimous, pursued to organize financial documentation and concentrate records and accounts produced by financial administration into a stable building. The essay pays particular attention to the material aspects of preserving records, e.g., the restoration of buildings, construction of chests, and preparation of secure locks that were integral to the emergence of collecting archives for financial documents in the later Middle Ages., This work was supported by the Beatriu de Pinós programme (2018 BP 00274), funded by the Direcció General de Recerca de la Generalitat de Catalunya and by the European Union through the COFUND programme (contract no. 801370) for Marie-Skłodowska-Curie actions in the “Horizon 2020” programme, and and by the research project ‘Movement and mobility in the medieval Mediterranean. People, terms, and concepts (PGC2018-094502-B-I00), funded by the Spanish Ministry of the Science, Innovation and Universities (MICINN). Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature.

In this paper the first example of using C-dots (CDs) as sensing nanomaterial for monitoring low concentrations of NO2 in ambient air is reported. In the logic to support a green circular economy, CDs were prepared from a natural low cost precursor consisting in olive solid waste (OSW) by a simple pyrolysis process combined with chemical oxidation. Characterization data showed the formation of spherical CDs with dimensions in the narrow size range from 0.5 to 5 nm and charged with functional groups (COO- (carboxylate), C-O-C (epoxide) and C-OH (hydroxyl) imprinting excellent water colloidal dispersion. The nanomaterial was used to fabricate and test a conductometric gas sensor (CDs-sensor) that was found to exhibit excellent performances in terms of high and selective response to sub-ppm concentration of NO2 at low temperature (150 °C), low limit of detection (LOD) of 50 ppb, good reproducibility and stability over use and aging. To the best of our knowledge, this is the first example reported in the literature of CDs high performances gas sensing material. Results here presented pave the way for a new class of a carbon nanomaterial for gas sensing to be applied in the field of environmental monitoring.

The detection of cancer biomarkers at an early stage of tumor development is vital for effective diagnosis and treatment of cancer. Current diagnostic tools can often detect cancer only when the biomarker levels are already too high, so that the tumors have spread and treatments are less effective. It is urgent therefore to develop highly sensitive assays for the detection of such biomarkers at the lowest possible concentration. In this context, we developed a sandwich immunoassay based on surface-enhanced Raman scattering (SERS) for the ultrasensitive detection of alpha-fetoprotein (AFP), which is typically present in human serum as a biomarker indicative of early stages of hepatocellular carcinoma. In the immunoassay design, molybdenum disulfide (MoS2) modified with a monoclonal antibody was used as a capture probe for AFP. A secondary antibody linked to an SERS-encoded nanoparticle was employed as the Raman signal reporter, that is, the transducer for AFP detection. The sandwich immunocomplex "capture probe/target/SERS tag" was deposited on a silicon wafer and decorated with silver-coated gold nanocubes to increase the density of "hot spots" on the surface of the immunosensor. The developed SERS immunosensor exhibits a wide linear detection range (1 pg mL(-1) to 10 ng mL(-1)) with a limit of detection as low as 0.03 pg mL(-1) toward AFP with good reproducibility (RSD < 6%) and stability. These parameters demonstrate that the proposed immunosensor has the potential to be used as an analytical platform for the detection of early-stage cancer biomarkers in clinical applications E.E. is grateful for a fellowship from the Scientific and Technological Research Council of Turkey (TUBITAK). A.C. and A.S. thank MINECO for their research grant (Juan de la Cierva.Incorporacion/no. IJCI-2016-31113, Juan de la Cierva. Formacion/no. FJC2018-036777-I, respectively). We thank Dr. Judith Langer for support in the interpretation of SERS results. This work was supported by the European Union's Horizon 2020 research and innovation program under Grant Agreements 785219 and 881603 Graphene Flagship. L.M.L.-M. acknowledges funding from the European Research Council (ERC-AdG-2017#787510). M.P., as the recipient of the AXA Bionanotechnology Chair, is grateful to the AXA Research Fund for financial support. This work was performed under the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency.grant no. MDM-20170720

Objective Our aim is to test the Nahoum Index as a support in the cephalometric study of vertical dimension and therapeutic orientation in adult patients suffering from Class II malocclusion, deep bite, or short face syndrome. Methods Twenty-three patients with molar Class II and an overbite >4 mm were stratified into two groups: orthodontic (G2) and surgical orthodontic (G1). The ANB angle and Nahoum Index were calculated for cephalometric tracing pre- and post-treatment. The difference between the ANB and Nahoum Index values were analyzed using the Statistical Package for the Social Sciences software. Results In G1, the Nahoum Index decreased from 0.954 to 0.797, and the ANB angle decreased from 5.2° to 3.2°. In G2, the Nahoum Index decreased from 0.825 to 0.817, and the ANB angle decreased from 4.4° to 4°. Conclusion In G1, the difference between before and after treatment was significant for the Nahoum Index only. The difference between before and after values was not significant in the G2 group. It is possible to indicate the Nahoum Index of 0.934 as the limit value in case of which a patient may be treated with orthodontics only. This limit is the opposite of the limit proposed by Nahoum for vertical excess cases and respect the same interval. Therefore, we can consider the range 0.81-0.934 to indicate borderline patients, and >0.934 to indicate surgical patients. If the ratio is close to the normal value as 0.81, the treatment will be orthodontic; if it is further increased, the treatment will be surgical.

In recent years, the most common need for companies consists in an increasingly efficient business process management and its continuous improvement. Companies are achieving this goal by implementing innovative approaches targeted on the individual project requirements. In this scenario, the present research aims to investigate, through a real pilot project, the benefits of implementing the agile project management (APM) framework based on a multi tools approach in order to re-engineering a business process (BPR). A real case study concerning a manufacturing plant is analyzed, in order to assess and highlight the effectiveness of the proposed model.

Ferrol, N.; Lanfranco, L. (Eds.) 2020 Arbuscular Mycorrhizal Fungi. Methods and Protocols. Vol 2146. pp. 257. ISBN 978 1 0716-0602-5, Gene expression analysis is a broadly used and powerful technique in many fields of biological research. The expression pattern of specific marker genes provides an insight into complex regulatory networks and leads to the identification of relevant genes associated to specific biological processes, such as arbuscular mycorrhizal symbiosis. Among the existing gene expression analysis toolbox, reverse transcriptase coupled to quantitative polymerase chain reaction (qRT-PCR) is considered the gold standard for accurate, sensitive, fast, and relatively inexpensive measurement. However, for a correct identification of differentially expressed genes, appropriate controls are required in order to minimize nonspecific variations associated with intrinsic technical variability. In this chapter, we recommend a number of tips to use qRT-PCR analysis in mycorrhizal roots and fungal mycelium.

This study focuses on the accounting and auditing system of the Kingdom of Sicily during the reign of Alfonso V of Aragon (1416–58), known as the Magnanimous. In particular, it discusses the operation of and the relationships between the two offices entrusted with the management of the kingdom’s accounts: the century-old magna curia rationum and the new office of the conservator maior regii patrimonii (established in 1414), modelled on the Castilian contaduría mayor de hacienda. This essay adopts the approach associated with the ‘archival turn’, to show that studying the accounting and bookkeeping practices, as well as their developments and innovations, is crucial to understand the operation of the Sicilian auditing system and its function in the broader political system of the Crown of Aragon. As a result of the perpetual state of conflict generated by the political agenda of Alfonso the Magnanimous in Italy and of his increasing war-funding demands, the Aragonese strategically exploited the new accounting and bookkeeping practice of the conservator to increase royal influence over the local financial apparatus. Relying on the exceptional amount of original accounting and financial records preserved at the State Archives of Palermo, this study is the first detailed examination of the auditing system and accounting practice of late-medieval Sicily. At the same time, the analysis shows that the operation and the transformations of the accounting system of a polity such as Sicily is fully intelligible only if examined in connection with the broader government of the political union of which that polity was a constituent member., The conceptual development, preparation and following improvement of this article were possible thanks to the fellowships granted by Villa I Tatti | The Harvard University Research Center for Italian Renaissance Studies and The Warburg Institute, School of Advanced Study, University of London.

In late medieval Sicily, the 'conservator' and the 'magistri rationales' conducted two separate but intertwined reviews of the accounts annually produced by the various monetary officers operating in the fragmented financial administration of the island. Whereas the control exercised by the 'magna curia rationum' followed the traditional procedure based on the audit of the accounts at the end of the administrative year, the conservator introduced an innovative revision practice that continued into the modern era. Through thorough inspection of the financial records, the 'conservatoria'’s staff were able to verify if the actual revenues and expenditures of the various officers in charge of collecting and delivering moneys and goods on behalf of the Crown were consistent with the budget that had been produced at the beginning of the year. The monitoring activity of the 'conservator' was possible thanks to the development since 1414 of an ingenious information management technology that combined bookkeeping and record-keeping methods. The material result of this intellectual development was the creation of a system through which the 'conservatoria'’s staff could organise an unprecedented amount of information, including any privilege, letter, decree, or any other documentation concerning the royal patrimony of the kingdom of Sicily into a book system of series and subseries dedicated to various specific financial matters. Among the various book series of the 'conservator', the so-called books of the accounts stand out as its most significant tools of administrative and financial knowledge. In essence, these books allowed the 'conservatoria'’s staff to produce annual accounts parallel to those officially prepared by the treasurer and the other principal financial officers of the realm. This system of information management gave the authorities – the Aragonese monarchs and the Sicilian viceroys on their behalf – the unique opportunity to collect detailed knowledge of the financial condition of the kingdom, even before the 'magistri rationales' conducted their formal auditing after the conclusion of the administrative year. In a composite polity such as the late medieval Crown of Aragon, whose territories were scattered across the Western Mediterranean, the many series of books of the 'conservator' thus resulted in a formidable governmental tool through which the monarchs could exercise their authority from afar on one of their dominions: the kingdom of Sicily. This vast financial and bureaucratic knowledge proved crucial for allocating the revenues and expenditures of the island according to the monarchs’ needs, in essence for supporting the expensive campaign for the conquest of Naples and the later Aragonese wars in Italy and in the Mediterranean basin.

Assessment of the risks and environmental impacts of carbon geosequestration requires knowledge about the wetting behavior of mineral surfaces in the presence of CO2 and the pore fluids. In this context, the interfacial tension (IFT) between CO2 and the aqueous fluid and the contact angle, theta, with the pore mineral surfaces are the two key parameters that control the capillary pressure in the pores of the candidate host rock. Knowledge of these two parameters and their dependence on the local conditions of pressure, temperature and salinity is essential for the correct prediction of structural and residual trapping. We have performed classical molecular dynamics simulations to predict the CO2–water IFT and the CO2–water–calcite contact angle. The IFT results are consistent with previous simulations, where simple point charge water models have been shown to underestimate the water surface tension, thus affecting the simulated IFT values. When combined with the EPM2 CO2 model, the SPC/Fw water model indeed underestimates the IFT in the low pressure region at all temperatures studied. On the other hand, at high pressure and low temperature, the IFT is overestimated by ~5 mN/m. Literature data regarding the water contact angle on calcite are contradictory. Using our new set of force field parameters, we performed NVT simulations at 323 K and 20 MPa to calculate the contact angle of a water droplet on the calcite {10.4} surface in a CO2 atmosphere. We performed simulations for both spherical and cylindrical droplet configurations for different initial radii, to study the size dependence of the water contact angle on calcite in the presence of CO2. Our results suggest that the contact angle of a cylindrical water droplet on calcite {10.4}, in the presence of CO2, is independent of droplet size, for droplets with a radius of 50 Å or more. On the contrary, spherical droplets make a contact angle that is strongly influenced by their size. At the largest size explored in this study, both spherical and cylindrical droplets converge to the same contact angle, 38 degrees, indicating that calcite is strongly wetted by water.

This paper analyses both the attributes of carsharing transport modes (station-based and free-floating) and their relationship with other transport modes. Users' and stakeholders’ perspectives are synthesized from in-depth interviews in Spain. The elicitation of the comparative advantages of the two carsharing modes with respect to public transport and private vehicles helps identifying factors such as availability of parking, road pricing and convenience that drive the complementary and substitution property of carsharing with other transport modes. Interviews show the limited complementarity of carsharing with public transport, as well as the limited substitutability with private vehicles. Potential policy instruments to make carsharing coexist with public transport are discussed. The authors acknowledge support from the European Union Horizon 2020 research and innovations programme under grant agreement N?727524, Project: ?Enabling the Energy Union through understanding the drivers of individual and collective energy choices, in Europe?. This research is also supported by the Spanish State Research Agency through Mar?a de Maeztu Excellence Unit accreditation 2018?2022 (Ref. MDM-2017-0714); and by the Basque Government through the BERC 2018?2021 program. Alberto Ansuategi gratefully acknowledges financial support from the Spanish Ministry of Science and Innovation (grant RTI2018-093352-B-100) and the UPV/EHU (grant GIC18/29). Ibon Galarraga also wishes to acknowledge the financial support from the Government of Spain and the European Regional Development Fund through grant RTI2018-093692-B-I00.

In the biomedical applications of nanoparticles (NPs), the proper choice of surface chemistry is a crucial aspect in their design. The nature of the coating can heavily impact the interaction of NPs with biomolecules, affect the state of aggregation, and ultimately determine their biological fate. As such, protein corona formation and the aggregation behaviour of gold NPs (Au NPs) are studied here. Au NPs are prepared with four distinct surface functionalisations, namely mercaptosuccinic acid (MSA), N-4-thiobutyroil glucosamine, HS-PEG(5000) and HS-alkyl-PEG(600). Corona formation, aggregation, and the intracellular behaviour of the Au NPs are then investigated by means of Fluorescence Correlation Spectroscopy (FCS) in cell culture media and in live cells. To evaluate the state of aggregation and the formation of a protein corona, the Au NPs are incubated in cell media and the diffusion coefficient is determined via FCS. The in vitro behaviour is compared with the level of aggregation of the NPs in cells. Diffusion times of the NPs are estimated at different positions in the cell after a one hour incubation period. It is found that the majority of MSA and glucose-Au NPs are present inside the cell as slowly diffusing species with diffusion times (tau(D)) greater than 6000 mu s (hydrodynamic diameter > 250 nm). PEGylated Au NPs adsorb a small amount of protein and manifest low agglomeration both in media and in living cells. In particular, the HS-alkyl-PEG(600) coating shows an excellent correlation between lower protein adsorption, 4-fold lower compared to the MSA coated NPs, and limited intracellular aggregation. In the case of single HS-alkylPEG(600) coated NPs, it is found that typical intracellular tD values range from 500 to 1500 mu s, indicating that these particles display reduced aggregation in the intracellular environment.

The development of new molecules able to efficiently act as long-circulating computed tomography (CT) contrast agents is one of the most crucial topics in the biomedical field. In the last years, the chance to manipulate materials at the nano-size level gave new boost to this research, with the specific aim to design innovative nanoprobes. Gold nanoparticles (AuNPs) have showed unique X-rays attenuation properties which, combined with their easy surface functionalization, makes them ideal candidates for the next generation of contrast agents. In this paper, we present a rational and facile approach to synthesize engineered and water-stable AuNPs, achieving concentrated colloidal solution with high Hounsfield Units (HU). An accurate control of reagents ratio allowed us to design AuNPs with different shapes, from symmetrical to anisotropic morphology, in a convenient ‘one-pot’ fashion. Their activity as efficient and reliable CT contrast agents has been evaluated and compared. Moreover, glucosamine-functionalized gold nanoparticles have been developed ([Au] = 31.20 mg/mL; HU = 2453), in order to obtain a CT contrast agent able to combine spatial resolution with metabolic information. Copyright © 2016 John Wiley & Sons, Ltd.

From the late medieval period the Crown of Aragon was at the forefront of archival innovation. Culminating in the establishment of the Royal Archive of Barcelona in 1318, this development was not, as is traditionally stated, a mere imitation of external models but the result of an innovative historical process that had its roots in local history and reflected the structure of the Aragonese monarchy. As a result of the later enlargement and decentralization of the Crown, and especially after the advent of the House of Trastámara in 1414, the Aragonese developed an extensive system for record-keeping across the Mediterranean. By focusing on what I describe as a complex archival network, this article analyses a series of administrative developments, which are generally studied in isolation, as interrelated responses to similar needs across disparate and far-flung territories. The results differed within the Iberian dominions (Aragon, Majorca and Valencia) and in the Italian kingdoms of Sicily and Naples, with Sardinia somewhere in between. For all these differences, however, the establishment of a number of financial archives shows that this network had an especially crucial role in defending the royal patrimony in all the territories under the rule of the Crown of Aragon. The authorities also tried to use archives as tools for exercising pressure upon local political elites, as demonstrated, for instance, by the systematic inquiry into feudal possessions and pecuniary rights instigated by King Ferdinand II in early sixteenth-century Sicily. The outcome, however, was totally unexpected.

Assessment of the risks and environmental impacts of carbon geosequestration requires knowledge about the wetting behavior of mineral surfaces in the presence of CO2 and the pore fluids. In this context, the interfacial tension (IFT) between CO2 and the aqueous fluid and the contact angle, θ, with the pore mineral surfaces are the two key parameters that control the capillary pressure in the pores of the candidate host rock. Knowledge of these two parameters and their dependence on the local conditions of pressure, temperature, and salinity is essential for the correct prediction of structural and residual trapping. We have performed classical molecular dynamics simulations to predict the CO2-water IFT and the CO2-water-calcite contact angle. The IFT results are consistent with previous simulations, where simple point charge water models have been shown to underestimate the water surface tension, thus affecting the simulated IFT values. When combined with the EPM2 CO2 model, the SPC/Fw water model indeed underestimates the IFT in the low-pressure region at all temperatures studied. On the other hand, at high pressure and low temperature, the IFT is overestimated by ∼5 mN/m. Literature data regarding the CO2/water/calcite contact angle on calcite are contradictory. Using our new set of force field parameters, we performed NVT simulations at 323 K and 20 MPa to calculate the contact angle of a water droplet on the calcite {10.4} surface in a CO2 atmosphere. We performed simulations for both spherical and cylindrical droplet configurations for different initial radii to study the size dependence of the water contact angle on calcite in the presence of CO2. Our results suggest that the contact angle of a cylindrical droplet, is independent of droplet size, for droplets with a radius of 50 Å or more. On the contrary, spherical droplets make a contact angle that is strongly influenced by their size. At the largest size explored in this study, both spherical and cylindrical droplets converge to the same contact angle, 38°, indicating that calcite is strongly wetted by water.

In this study we investigated fluid displacement water with supercritical (sc) CO2 in chalk under conditions close to those used for geologic CO2 sequestration (GCS), to answer two main questions: How much volume is available for scCO2 injection? And what is the main mechanism of displacement over a range of temperatures? Characterization of immiscible scCO2 displacement, at the pore scale in the complex microstructure in chalk reservoirs, offers a pathway to better understand the macroscopic processes at the continuum scale. Fluid behavior was simulated by solving the Navier-Stokes equations, using finite-volume methods within a pore network. The pore network was extracted from a high resolution 3D image of chalk, obtained using X-ray nanotomography. Viscous fingering dominates scCO2 infiltration and pores remain only partially saturated. The unstable front, developed with high capillary number, causes filling of pores aligned with the flow direction, reaching a maximum of 70% scCO2 saturation. The saturation rate increases with temperature but the final saturation state is the same for all investigated temperatures. The higher the saturation rate, the higher the dynamic capillary pressure coefficient. A higher dynamic capillary pressure coefficient indicates that scCO2 needs more time to reach capillary equilibrium in the porous medium.