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This paper discusses the relative performance of several climate models in providing reliable forcing for hydrological modeling in six representative catchments in the Mediterranean region. We consider 14 Regional Climate Models (RCMs), from the EU-FP6 ENSEMBLES project, run for the A1B emission scenario on a common 0.22- degree (about 24 km) rotated grid over Europe and the Mediterranean. In the validation period (1951 to 2010) we consider daily precipitation and surface temperatures from the E-OBS dataset, available from the ENSEMBLES project and the data providers in the ECA&D project. Our primary objective is to rank the 14 RCMs for each catchment and select the four best performing ones to use as common forcing for hydrological models in the six Mediterranean basins considered in the EU-FP7 CLIMB project. Using a common suite of 4 RCMs for all studied catchments reduces the (epistemic) uncertainty when evaluating trends and climate change impacts in the XXI century. We present and discuss the validation setting, as well as the obtained results and, to some detail, the difficulties we experienced when processing the data. In doing so we also provide useful information and hint for an audience of researchers not directly involved in climate modeling, but interested in the use of climate model outputs for hydrological modeling and, more in general, climate change impact studies in the Mediterranean. [ABSTRACT FROM AUTHOR]

A general consensus on the concept of rainfall intermittency has not yet been reached and intermittency is often referred to different aspects of rainfall variability, including the fragmentation of the wet-dry rainfall support, the strength of intensity fluctuations and of rainfall bursts, and sometimes also to the memory/correlation of the process. To explore these different aspects, a systematic analysis of rainfall intermittency properties in the time domain is presented using high-resolution (1-min) data recorded by a network of 201 tipping-bucket gages covering the entire island of Sardinia (Italy). Four techniques, including spectral and scale invariance analysis, and computation of clustering and intermittency exponents, are applied to quantify the contribution to the overall intermittency due to the alternation of dry and wet periods (i.e. the rainfall support fragmentation), and to the fluctuations of intensity amplitudes. The presence of three ranges of scaling regimes in the time interval from 1min to ˜45 days is first demonstrated. In accordance with past studies, these regimes can be associated with a range dominated by single storms, a regime typical of frontal systems, and a transition zone. The position of the breaking points separating these regimes change with the considered technique, suggesting that such tools explain different aspects of rainfall variability. Results indicate that the intermittency properties of rainfall support are fairly similar across the island, while metrics related to rainfall intensity fluctuations are characterized by significant spatial variability, implying that the local climate has a significant effect on the fluctuations of the rainfall amplitudes and minimal influence on the process of rainfall occurrence. Next, evidence is shown of spatial patterns of the scaling exponents computed, for each analysis tool, in the range of frontal systems. These patterns resemble the main pluviometric regimes observed in the island and, thus, can be associated with the corresponding synoptic circulation patterns. Last but not least, it is demonstrated how the methodology adopted to sample the rainfall signal from the records of the tipping instants can significantly affect the intermittency analysis, especially at smaller scales. The multifractal scale invariance analysis is the only tool that is insensitive to the sampling approach. Results of this work may be useful to improve the calibration of stochastic algorithms used to downscale coarse rainfall predictions of climate and weather forecasting models, as well as the parameterization of intensity-duration-frequency curves, adopted for land planning and design of civil infrastructures. [ABSTRACT FROM AUTHOR]

The accuracy of rainfall predictions provided by climate models is crucial for the assessment of climate change impacts on hydrological processes. In fact, the presence of bias in downscaled precipitation may produce large bias in the assessment of soil moisture dynamics, river flows and groundwater recharge. In this study, a comparison between statistical properties of rainfall observations and model control simulations from a Regional Climate Model (RCM) was performed through a robust and meaningful representation of the precipitation process. The output of the adopted RCM was analysed and re-scaled exploiting the structure of a stochastic model of the point rainfall process. In particular, the stochastic model is able to adequately reproduce the rainfall intermittency at the synoptic scale, which is one of the crucial aspects for the Mediterranean environments. Possible alteration in the local rainfall regime was investigated by means of the historical daily time-series from a dense rain-gauge network, which were also used for the analysis of the RCM bias in terms of dry and wet periods and storm intensity. The result is a stochastic scheme for bias-correction at the RCM-cell scale, which produces a realistic representation of the daily rainfall intermittency and precipitation depths, though a residual bias in the storm intensity of longer storm events persists. [ABSTRACT FROM AUTHOR]

A regional probabilistic model for the estimation of medium-high return period flood quantiles is presented. The model is based on the use of theoretically derived probability distributions of annual maximum flood peaks (DDF). The general model is called TCIF (Two-Component IF model) and encompasses two different threshold mechanisms associated with ordinary and extraordinary events, respectively. Based on at-site calibration of this model for 33 gauged sites in Southern Italy, a regional analysis is performed obtaining satisfactory results for the estimation of flood quantiles for return periods of technical interest, thus suggesting the use of the proposed methodology for the application to ungauged basins. The model is validated by using a jack-knife cross-validation technique taking all river basins into consideration. [ABSTRACT FROM AUTHOR]

In the present paper, the kinematics of a three-degree-of-freedom spherical wrist is investigated. The wrist consists of a fixed base connected to a moving platform by three identical legs, each with a RRUR chain (R and U denote a revolute pair and a universal pair, respectively). For each leg, the first R pair is to be considered actuated. Although in previous works the kinematics synthesis of this architecture was carried out, no detailed studies were presented on the kinematic issues of the wrist. This paper presents the mobility analysis, the direct and inverse position kinematics, the differential kinematics of the manipulator including inspection on the jacobian matrix and the analysis of the singularities. The geometrical condition matched in case of mechanical interference between legs is addressed, too. A numerical example of the manipulator kinematics was performed to obtain the workspace, the condition number and the mechanical inteference condition. [ABSTRACT FROM AUTHOR]

The accuracy of ensemble streamflow forecasts (ESFs) is impacted by the propagation of uncertainty associated with quantitative precipitation forecasts (QPFs) through the physical processes occurring in the basin. In this study, we consider consistent ESFs (i.e., observations and ensemble members are equally likely) and we study the effect of basin area (A) and antecedent rainfall (AR) on the ESF dispersion, a metric of flood forecast skill. Results from a set of numerical experiments indicate that: (i) for small basins (≲180 km²), ESF dispersion is mainly dominated by the runoff generation process and does not depend on the basin size A; (ii) for larger areas, ESF dispersion decreases with A according to a log-linear relation due to the decreasing variability of ensemble QPFs and, possibly, to the channel routing process. In addition, we found that, regardless the basin size, the ESF dispersion decreases as AR increases, and that the influence of AR is larger for basins with fast response times. Physical controls (land cover, soil texture and morphometric features) on the analyzed basin response confirm these interpretations. [ABSTRACT FROM AUTHOR]

In the context of climate changes, characterized by an increase of short but intense rainfall events and rise of the average temperature, the fast population growth and consequent urbanization require the implementation of innovative solutions to mitigate pluvial floods and, at the same time, reduce the water demand. Among the different nature-based solutions, multilayer blue-green roofs have been widely recognized for their high capacity of reducing runoff generation from rooftops, and their additional storage layer enables to collect water, which could be reused for different purposes. However, the quality of the collected water in a multilayer blue-green roof and the influence that the additional storage layer has on it have not been analysed yet. Following this knowledge gap, we investigated the potential benefits of a multilayer blue-green roof installed in Cagliari, with respect to a traditional roof. The outflow triggered by artificial irrigation and natural rainfall events was analysed, both from a quantitative and qualitative perspective. Results confirm the high contribution of multilayer blue-green roofs in mitigating runoff generation, which is however influenced by antecedent soil moisture and water level conditions. The outflow from the multilayer blue-green roof presents lower suspended solids and heavy metals concentrations than from a traditional roof. On the other hand, Carbon Oxigen Demand (COD) concentrations in the multilayer blue-green roof outflow exceed the limits defined by the Italian regulations (125 mg/l) for water discharge or reuse, partially due to the high residence time in the storage layer. Specific treatments could be planned to reuse the collected water for urban purposes., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

Green roofs have been extensively investigated in recent years, showing that their implementation in urban areas provides multiple benefits (e.g., pluvial flood mitigation, urban heat island reduction, energy saving, increase of biodiversity, CO 2 sequestration) and supports sustainable urban development. Although green roof benefits have been widely recognized, the perception that the community has of these nature-based solutions and the willingness to pay for their installation in urban areas is still not clear nor quantified. Societal perception and willingness to pay for green roofs are fundamental for urban planners and decision makers, since they represent the community participation in the sustainable development of urban areas. In this work, we aim to analyze how citizens perceive green roofs and how willing they are to pay for the installation and maintenance of these nature-based solutions. We used an online survey to investigate the perception and the knowledge of green roofs as a potential solution to common environmental issues (i.e., urban flood, increase of temperature, energy consumption, air pollution and lack of green spaces), and the interest and willingness to pay for green roof installation on both public and private roofs. Based on the answers of 389 respondents living in Sardinia (Italy), our analysis revealed that most citizens are aware of what green roofs are, and they are aware that, although these nature-based solutions can not completely solve environmental issues, they can greatly contribute to the mitigation of these phenomena. Results also show a higher interest in the installation of green roofs on public buildings than on private ones, due to the high installation costs. Moreover, for private roofs, the possibility to install photovoltaic panels instead of GRs is generally preferred. Most of the respondents are willing to spend less than 100 € per year for the maintenance of green roofs on public buildings and to invest less than 5000 € for the installation on their own house., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Multilayer Blue-Green Roofs are powerful nature-based solutions that can contribute to the creation of smart and resilient cities. These tools combine the retention capacity of traditional green roofs with the water storage of a rainwater harvesting tank. The additional storage layer enables to accumulate the rainwater percolating from the soil layer, that, if properly treated, can be reused for domestic purposes. Here, we explore the behavior of a Multilayer Blue-Green Roof prototype installed in Cagliari (Italy) in 2019, that have been equipped with a remotely controlled gate to regulate the storage capacity of the system. The gate installation allows to manage the Multilayer Blue-Green Roof in order to increase the flood mitigation capacity, minimizing the water stress for vegetation and limiting the roof load with adequate management practices. In this work, 10 rules for the management of the Multilayer Blue-Green Roof gate have been investigated and their performances in achieving different management goals (i.e., mitigating urban flood, increasing water storage and limiting roof load on the building) have been evaluated, with the aim to identify the most efficient approach to maximize the benefits of this nature based solution. An ecohydrological model have been calibrated based on field measurements carried out for 6 months. The model has been used to simulate the system performance in achieving the proposed goals, using as input nowdays and future rainfall and temperature time series. The analysis reveled the importance of the correct management of the gate, highthing how choosing and applying a specific management rule helps increasing the performance in reaching the desired goal., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The aim of this study was to evaluate the potential of ultra-high performance supercritical fluid chromatography (UHPSFC) for peptide analysis by comparing its analytical performance to several chromatographic approaches based on reversed-phase liquid chromatography (RPLC), hydrophilic interaction liquid chromatography (HILIC) and mixed-mode liquid chromatography. First, the retention behavior of synthetic peptides with 3 to 30 amino acids and different isoelectric points (acid, neutral, and basic) was evaluated. For all the tested conditions (13 peptides in 8 conditions), only 4 results were not exploitable (not retained or not eluted), confirming that all the tested chromatographic conditions can be successfully applied when analyzing a wide range of diverse peptides. Average tailing factor were quite comparable across all chromatographic modes, while the best peak capacity values were obtained under mixed-mode LC conditions. Selectivity for each chromatographic mode was also evaluated for six closely related peptides having minor modifications on their structures. The LC-based chromatographic modes confirmed their superior selectivity over UHPSFC. By contrast, when analyzing short peptides (di- or tripetides), UHPSFC was the only technique allowing to simultaneously separate highly polar and less polar peptides within the same run confirming its unique versatility. In addition, the sensitivity of each chromatographic approach was accessed by for two representative peptides by both UV and MS detection. With UV detection, limit of detection (LOD) values were comparable among the different chromatographic modes, ranging from 0.5 to 2 µg mL -1 . However, major differences were found when employing MS detection (LOD values ranged from 0.05 to 5 µg mL -1 ). The best results were obtained under HILIC conditions, followed by SFC, and finally mixed-mode LC and RPLC modes., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Author(s). Published by Elsevier B.V. All rights reserved.)

Cannabis has been at the center of scientific attention for some years now. Since its pharmacological potential has been highlighted, cannabis has become a hot topic in research laboratories, leading to the publication of many scientific studies. Focusing on analytical chemistry, an enormous number of analytical methods for cannabinoid (CNB) determination have been published, involving various techniques. However, no globally accepted reference method for CNB determination has yet been chosen. This review aims to identify very recent analytical methods developed to analyze phytocannabinoids in cannabis herbal samples. For certain techniques, stagnation in terms of employed operational conditions can be observed. In this context, a reference method of analysis should be proposed and accepted worldwide to standardize CNB determination. In contrast, for other techniques, we are witnessing a scientific ferment, which is resulting in the development of new interesting analytical options. In this regard, particular focus has been given to these niche techniques, which are now emerging in the analytical panorama of cannabis analysis, offering new important perspectives for the future of cannabis testing. Supercritical fluid chromatography and infrared spectroscopy showed tangible advantages when applied to CNB determination in herbal samples., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The aim of the present study was to explore the feasibility of applying near-infrared (NIR) spectroscopy for the quantitative analysis of Δ 9 -tetrahydrocannabinol (THC) in cannabis products using handheld devices. A preliminary study was conducted on different physical forms (entire, ground and sieved) of cannabis inflorescences in order to evaluate the impact of sample homogeneity on THC content predictions. Since entire cannabis inflorescences represent the most common types of samples found in both the pharmaceutical and illicit markets, they have been considered priority analytical targets. Two handheld NIR spectrophotometers (a low-cost device and a mid-cost device) were used to perform the analyses and their predictive performance was compared. Six partial least square (PLS) models based on reference data obtained by UHPLC-UV were built. The importance of the technical features of the spectrophotometer for quantitative applications was highlighted. The mid-cost system outperformed the low-cost system in terms of predictive performance, especially when analyzing entire cannabis inflorescences. In contrast, for the more homogeneous forms, the results were comparable. The mid-cost system was selected as the best-suited spectrophotometer for this application. The number of cannabis inflorescence samples was augmented with new real samples, and a chemometric model based on machine learning ensemble algorithms was developed to predict the concentration of THC in those samples. Good predictive performance was obtained with a root mean squared error of prediction of 1.75 % (w/w). The Bland-Altman method was then used to compare the NIR predictions to the quantitative results obtained by UHPLC-UV and to evaluate the degree of accordance between the two analytical techniques. Each result fell within the established limits of agreement, demonstrating the feasibility of this chemometric model for analytical purposes. Finally, resin samples were investigated by both NIR devices. Two PLS models were built by using a sample set of 45 samples. When the analytical performances were compared, the mid-cost spectrophotometer significantly outperformed the low-cost device for prediction accuracy and reproducibility., Competing Interests: Declaration of Competing Interest The authors report no declarations of interest., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Green roofs are strategic tools that can play a significant role in the creation of sustainable and resilient cities. They have been largely investigated thanks to their high retention capacity, which can be a valid support to mitigate the pluvial flood risk and to increase the building thermal insulation, ensuring energy saving. Moreover, green roofs contribute to restoring vegetation in the urban environment, increasing the biodiversity and adding aesthetic value to the city. The new generation of multilayer green roofs present an additional layer with respect to traditional ones, which allows rainwater to be stored, which, if properly treated, can be reused for different purposes. This paper offers a review of benefits and limitations of green roofs, with a focus on multilayer ones, within a Water-Energy-Food-Ecosystem nexus context. This approach enables the potential impact of green roofs on the different sectors to be highlighted, investigating also the interactions and interconnections among the fields. Moreover, the Water-Energy-Food-Ecosystem nexus approach highlights how the installation of traditional and multilayer green roofs in urban areas contributes to the Development Goals defined by the 2030 Sustainable Agenda., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Flooding risk in cities has been recently exacerbated by increased urbanization and climate change, often with catastrophic consequences in terms of casualties and economic losses. Rainwater harvesting systems and green roofs are recognized as being among the most effective blue-green mitigation measures. However, performances of these systems have currently been investigated only at laboratory or very-small local scales. In this work, we assess the potential benefit of the extensive installation of these solutions on all the rooftops of 9 cities, with different climatological and geographical characteristics. Both surface discharge reduction and delay between rainfall and runoff peak generation have been investigated. Green roofs ensure a larger average lag time between rainfall and runoff peaks than rainwater harvesting systems, without significant differences between intensive and extensive structures. On the other hand, the cost-efficiency analysis, considering the entire urban area, shows a higher retention capacity with a lower financial investment for rainwater harvesting rather than for green roofs in most cases. For extreme rainfall events, large-scale installation of rainwater harvesting systems coupled with intensive green roofs over the entire city have shown to be the most efficient solution, with a total discharge reduction that can vary from 5% to 15%, depending on the city characteristics and local climate., Competing Interests: The authors have declared that no competing interests exist.

The aim of this work was to develop a supercritical fluid chromatographic method to study the applicability of this emerging technique to cannabinoid analysis and showcase its advantages. During method development, the authors focused on nine phyto-cannabinoids to assess the selectivity needed to potentially perform the quantitation of each cannabinoid. After method development, robustness studies were carried out on this method to gain more information about its qualitative behavior (in terms of critical resolutions) when varying some crucial parameters (concentration of additive, column temperature, starting gradient conditions and column batch). Once the robustness was evaluated and the parameters most affecting the selected responses were individuated, the SFC method was applied for a simulated routine use to generate quantitative results concerning the concentrations of the main cannabinoids in real cannabis samples. The samples were also analyzed by means of an ultra-high-performance liquid chromatographic method currently used in the laboratory for the same objective. Finally, the results obtained with both analytical methods were compared to evaluate their accordance. The Bland-Altman method was applied as a statistical strategy to evaluate the degree of accordance between the results generated and display the data in a difference plot. The ultra-high performance supercritical fluid chromatography quantitative results were in accordance with the ultra-high performance liquid chromatography results, demonstrating the applicability of this technique for cannabinoid analysis., Competing Interests: The authors declare no conflict of interest., (© 2020 The Authors. Analytical Science Advances published by Wiley‐VCH GmbH.)

Cannabidiol (CBD) and Δ 9 -tetrahydrocannabinol (Δ 9 -THC) are considered as the most interesting cannabinoids in Cannabis sativa L. for the clinical practice. Since 2013, the Italian law allows pharmacists to prepare and dispense cannabis extracts to patients under medical prescription, and requires the evaluation of CBD and Δ 9 -THC content in cannabis extracts before sale. Cannabis olive oil extracts are prepared from dried female cannabis inflorescences, but a standard protocol is still missing. In this study, a fast RP-HPLC/UV method has been developed to quantify CBD and Δ 9 -THC in cannabis olive oil extracts. The analytical quality by design strategy has been applied to the method development, setting critical resolution and total analysis time as critical method attributes (CMAs), and selecting column temperature, buffer pH and flow rate as critical method parameters. Information from Doehlert Design in response surface methodology combined to Monte-Carlo simulations led to draw the risk of failure maps and to identify the method operable design region. The method was validated according to the International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use (ICH) guidelines and then implemented in routine analysis. A control strategy based on system control charts was planned to monitor the developed method performances. Evaluation data were recorded over a period of one year of routine use, and both the CMAs showed values within the specifications in every analysis performed. Hence, a new risk evaluation for the future performances of the method was achieved by using a Bayesian approach based on the routine use data, computing the future distribution of the two CMAs. Finally, a study focusing on the monitoring of CBD and Δ 9 -THC concentrations in cannabis olive oil extracts was carried out. The developed method was applied to 459 extracts. The statistical analysis of the obtained results highlighted a wide variability in terms of concentrations among different samples from the same starting typology of cannabis, underlining the compelling need of a standardised procedure to harmonise the preparation of the extracts., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Pharmaceutical regulatory bodies increasingly require the implementation of systematic approaches in pharmaceutical product development. Quality control methods play a key role in the control strategy of drugs manufacturing to assure their quality. A risk-based approach in the analytical method development is strongly recommended to ensure that the method performances fit the purpose of the method during its entire life-cycle. In the last decade, analytical quality by design (AQbD), as risk management oriented methodology, has been progressively integrated with method development for fulfilling this objective. This approach has successfully allowed the quality to be designed into the analytical processes by obtaining a deep understanding of the procedures. In this paper the AQbD workflow and its application in the development of methods to be used for pharmaceutical quality control have been treated and discussed. Recent publications regarding how AQbD has been applied in separation techniques were reviewed. The different development strategies have been also showcased, highlighting their advantages and disadvantages, in order to give a useful overview., (Copyright © 2018 Elsevier B.V. All rights reserved.)