Search results for: value added intellectual coefficient

Authors: Atish Bagchi, Siva Chandrasekaran

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Background: According to World Bank national accounts data, the estimated global manufacturing value-added output in 2020 was 13.74 trillion USD. These manufacturing processes are monitored, modelled, and controlled by advanced, real-time, computer-based systems, e.g., Industrial IoT, PLC, SCADA, etc. These systems measure and manipulate a set of physical variables, e.g., temperature, pressure, etc. Despite the use of IoT, SCADA etc., in manufacturing, studies suggest that unplanned downtime leads to economic losses of approximately 864 billion USD each year. Therefore, real-time, accurate detection, classification and prediction of machine behaviour are needed to minimise financial losses. Although vast literature exists on time-series data processing using machine learning, the challenges faced by the industries that lead to unplanned downtimes are: The current algorithms do not efficiently handle the high-volume streaming data from industrial IoTsensors and were tested on static and simulated datasets. While the existing algorithms can detect significant 'point' outliers, most do not handle contextual outliers (e.g., values within normal range but happening at an unexpected time of day) or subtle changes in machine behaviour. Machines are revamped periodically as part of planned maintenance programmes, which change the assumptions on which original AI models were created and trained. Aim: This research study aims to deliver a Graph Neural Network(GNN)based hybrid forecasting model that interfaces with the real-time machine control systemand can detect, predict machine behaviour and behavioural changes (anomalies) in real-time. This research will help manufacturing industries and utilities, e.g., water, electricity etc., reduce unplanned downtimes and consequential financial losses. Method: The data stored within a process control system, e.g., Industrial-IoT, Data Historian, is generally sampled during data acquisition from the sensor (source) and whenpersistingin the Data Historian to optimise storage and query performance. The sampling may inadvertently discard values that might contain subtle aspects of behavioural changes in machines. This research proposed a hybrid forecasting and classification model which combines the expressive and extrapolation capability of GNN enhanced with the estimates of entropy and spectral changes in the sampled data and additional temporal contexts to reconstruct the likely temporal trajectory of machine behavioural changes. The proposed real-time model belongs to the Deep Learning category of machine learning and interfaces with the sensors directly or through 'Process Data Historian', SCADA etc., to perform forecasting and classification tasks. Results: The model was interfaced with a Data Historianholding time-series data from 4flow sensors within a water treatment plantfor45 days. The recorded sampling interval for a sensor varied from 10 sec to 30 min. Approximately 65% of the available data was used for training the model, 20% for validation, and the rest for testing. The model identified the anomalies within the water treatment plant and predicted the plant's performance. These results were compared with the data reported by the plant SCADA-Historian system and the official data reported by the plant authorities. The model's accuracy was much higher (20%) than that reported by the SCADA-Historian system and matched the validated results declared by the plant auditors. Conclusions: The research demonstrates that a hybrid GNN based approach enhanced with entropy calculation and spectral information can effectively detect and predict a machine's behavioural changes. The model can interface with a plant's 'process control system' in real-time to perform forecasting and classification tasks to aid the asset management engineers to operate their machines more efficiently and reduce unplanned downtimes. A series of trialsare planned for this model in the future in other manufacturing industries.

Keywords: GNN, Entropy, anomaly detection, industrial time-series, AI, IoT, Industry 4.0, Machine Learning

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Authors: Philipp Sommer, Amgad Agoub

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The construction sector significantly impacts global CO₂ emissions, particularly through the energy usage of residential buildings. To address this, various governments, including Germany's, are focusing on reducing emissions via sustainable refurbishment initiatives. This study examines the application of machine learning (ML) to estimate energy demands dynamically in residential buildings and enhance the potential for large-scale sustainable refurbishment. A major challenge in Germany is the lack of extensive publicly labeled datasets for energy performance, as energy performance certificates, which provide critical data on building-specific energy requirements and consumption, are not available for all buildings or require on-site inspections. Conversely, England and other countries in the European Union (EU) have rich public datasets, providing a viable alternative for analysis. This research adapts insights from these English datasets to the German context by developing a comprehensive data schema and calibration dataset capable of predicting building energy demand effectively. The study proposes a minimal feature set, determined through feature importance analysis, to optimize the ML model. Findings indicate that ML significantly improves the scalability and accuracy of energy demand forecasts, supporting more effective emissions reduction strategies in the construction industry. Integrating energy performance certificates into municipal heat planning in Germany highlights the transformative impact of data-driven approaches on environmental sustainability. The goal is to identify and utilize key features from open data sources that significantly influence energy demand, creating an efficient forecasting model. Using Extreme Gradient Boosting (XGB) and data from energy performance certificates, effective features such as building type, year of construction, living space, insulation level, and building materials were incorporated. These were supplemented by data derived from descriptions of roofs, walls, windows, and floors, integrated into three datasets. The emphasis was on features accessible via remote sensing, which, along with other correlated characteristics, greatly improved the model's accuracy. The model was further validated using SHapley Additive exPlanations (SHAP) values and aggregated feature importance, which quantified the effects of individual features on the predictions. The refined model using remote sensing data showed a coefficient of determination (R²) of 0.64 and a mean absolute error (MAE) of 4.12, indicating predictions based on efficiency class 1-100 (G-A) may deviate by 4.12 points. This R² increased to 0.84 with the inclusion of more samples, with wall type emerging as the most predictive feature. After optimizing and incorporating related features like estimated primary energy consumption, the R² score for the training and test set reached 0.94, demonstrating good generalization. The study concludes that ML models significantly improve prediction accuracy over traditional methods, illustrating the potential of ML in enhancing energy efficiency analysis and planning. This supports better decision-making for energy optimization and highlights the benefits of developing and refining data schemas using open data to bolster sustainability in the building sector. The study underscores the importance of supporting open data initiatives to collect similar features and support the creation of comparable models in Germany, enhancing the outlook for environmental sustainability.

Keywords: machine learning, remote sensing, residential building, energy performance certificates, data-driven, heat planning

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Authors: Joyjit Dey, Souvik Sen

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Middle Permian Barakar formation is the major economic coal bearing unit of vast east-west trending Damodar Valley basin of Gondwana coalfield. Primary sedimentary structures were studied from the core holes, which represent majorly four facies groups: sandstone dominated facies, sandstone-shale heterolith facies, shale facies and coal facies. Total eight major coal seams have been identified with the bottom most seam being the thickest. Laterally, continuous coal seams were deposited in the calm and quiet environment of extensive floodplain swamps. Channel sinuosity and lateral channel migration/avulsion results in lateral facies heterogeneity and coal splitting. Geophysical well logs (Gamma-Resistivity-Density logs) have been used to establish the vertical and lateral correlation of various litho units field-wide, which reveals the predominance of repetitive fining upwards cycles. Well log data being a permanent record, offers a strong foundation for generating log based property evaluation and helps in characterization of depositional units in terms of lateral and vertical heterogeneity. Low gamma, high resistivity, low density is the typical coal seam signatures in geophysical logs. Here, we have used a density cutoff of 1.6 g/cc as a primary discriminator of coal and the same has been employed to compute various coal assay parameters, which are ash, fixed carbon, moisture, volatile content, cleat porosity, vitrinite reflectance (VRo%), which were calibrated with the laboratory based measurements. The study shows ash content and VRo% increase from west to east (towards basin margin), while fixed carbon, moisture and volatile content increase towards west, depicting increased coal quality westwards. Seam wise cleat porosity decreases from east to west, this would be an effect of overburden, as overburden pressure increases westward with the deepening of basin causing more sediment packet deposited on the western side of the study area. Coal is a porous, viscoelastic material in which velocity and strain both change nonlinearly with stress, especially for stress applied perpendicular to the bedding plane. Usually, the coal seam has a high velocity contrast relative to its neighboring layers. Despite extensive discussion of the maceral and chemical properties of coal, its elastic characteristics have received comparatively little attention. The measurement of the elastic constants of coal presents many difficulties: sample-to-sample inhomogeneity and fragility and velocity dependence on stress, orientation, humidity, and chemical content. In this study, a conclusive empirical equation VS= 0.80VP-0.86 has been used to model shear velocity from compression velocity. Also the same has been used to compute various geomechanical moduli. Geomech analyses yield a Poisson ratio of 0.348 against coals. Average bulk modulus value is 3.97 GPA, while average shear modulus and Young’s modulus values are coming out as 1.34 and 3.59 GPA respectively. These middle Permian Barakar coals show an average 23.84 MPA uniaxial compressive strength (UCS) with 4.97 MPA cohesive strength and 0.46 as friction coefficient. The output values of log based proximate parameters and geomechanical moduli suggest a medium volatile Bituminous grade for the studied coal seams, which is found in the laboratory based core study as well.

Keywords: core analysis, coal characterization, geophysical log, geo-mechanical moduli

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Authors: Istvan Csarnovics, Attila Bonyar, Miklos Veres, Laszlo Himics, Attila Csik, Judit Kaman, Julia Burunkova, Geza Szanto, Laszlo Balazs, Sandor Kokenyesi

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In this work, the performance of gold nanoparticles were investigated for stimulation of photosensitive materials for photonic applications. It was widely used for surface plasmon resonance experiments, not in the last place because of the manifestation of optical resonances in the visible spectral region. The localized surface plasmon resonance is rather easily observed in nanometer-sized metallic structures and widely used for measurements, sensing, in semiconductor devices and even in optical data storage. Firstly, gold nanoparticles on silica glass substrate satisfy the conditions for surface plasmon resonance in the green-red spectral range, where the chalcogenide glasses have the highest sensitivity. The gold nanostructures influence and enhance the optical, structural and volume changes and promote the exciton generation in gold nanoparticles/chalcogenide layer structure. The experimental results support the importance of localized electric fields in the photo-induced transformation of chalcogenide glasses as well as suggest new approaches to improve the performance of these optical recording media. Results may be utilized for direct, micrometre- or submicron size geometrical and optical pattern formation and used also for further development of the explanations of these effects in chalcogenide glasses. Besides of that, gold nanoparticles could be added to the organic light-sensitive material. The acrylate-based materials are frequently used for optical, holographic recording of optoelectronic elements due to photo-stimulated structural transformations. The holographic recording process and photo-polymerization effect could be enhanced by the localized plasmon field of the created gold nanostructures. Finally, gold nanoparticles widely used for electrochemical and optical sensor applications. Although these NPs can be synthesized in several ways, perhaps one of the simplest methods is the thermal annealing of pre-deposited thin films on glass or silicon surfaces. With this method, the parameters of the annealing process (time, temperature) and the pre-deposited thin film thickness influence and define the resulting size and distribution of the NPs on the surface. Localized surface plasmon resonance (LSPR) is a very sensitive optical phenomenon and can be utilized for a large variety of sensing purposes (chemical sensors, gas sensors, biosensors, etc.). Surface-enhanced Raman spectroscopy (SERS) is an analytical method which can significantly increase the yield of Raman scattering of target molecules adsorbed on the surface of metallic nanoparticles. The sensitivity of LSPR and SERS based devices is strongly depending on the used material and also on the size and geometry of the metallic nanoparticles. By controlling these parameters the plasmon absorption band can be tuned and the sensitivity can be optimized. The technological parameters of the generated gold nanoparticles were investigated and influence on the SERS and on the LSPR sensitivity was established. The LSPR sensitivity were simulated for gold nanocubes and nanospheres with MNPBEM Matlab toolbox. It was found that the enhancement factor (which characterize the increase in the peak shift for multi-particle arrangements compared to single-particle models) depends on the size of the nanoparticles and on the distance between the particles. This work was supported by GINOP- 2.3.2-15-2016-00041 project, which is co-financed by the European Union and European Social Fund. Istvan Csarnovics is grateful for the support through the New National Excellence Program of the Ministry of Human Capacities, supported by the ÚNKP-17-4 Attila Bonyár and Miklós Veres are grateful for the support of the János Bolyai Research Scholarship of the Hungarian Academy of Sciences.

Keywords: light sensitive nanocomposites, metallic nanoparticles, photonic application, plasmonic nanostructures

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Authors: F. Varga, Z. Liber, J. Jakše, A. Turudić, Z. Šatović, I. Radosavljević, N. Jeran, M. Grdiša

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Dalmatian pyrethrum (Tanacetum cinerariifolium (Trevir.) Sch. Bip.; Asteraceae), a source of the commercially dominant plant insecticide pyrethrin, is a species endemic to the eastern Adriatic. Genetic diversity of T. cinerariifolium was previously studied using amplified fragment length polymorphism (AFLP) markers. However, microsatellite markers (single sequence repeats - SSRs) are more informative because they are codominant, highly polymorphic, locus-specific, and more reproducible, and thus are most often used to assess the genetic diversity of plant species. Dalmatian pyrethrum is an outcrossing diploid (2n = 18) whose large genome size and high repeatability have prevented the success of the traditional approach to SSR markers development. The advent of next-generation sequencing combined with the specifically developed method recently enabled the development of, to the author's best knowledge, the first set of SSRs for genomic characterization of Dalmatian pyrethrum, which is essential from the perspective of plant genetic resources conservation. To evaluate the effectiveness of the developed SSR markers in genetic differentiation of Dalmatian pyrethrum populations, a preliminary genetic diversity study was conducted on 30 individuals from three geographically distinct natural populations in Croatia (northern Adriatic island of Mali Lošinj, southern Adriatic island of Čiovo, and Mount Biokovo) based on 12 SSR loci. Analysis of molecular variance (AMOVA) by randomization test with 10,000 permutations was performed in Arlequin 3.5. The average number of alleles per locus, observed and expected heterozygosity, probability of deviations from Hardy-Weinberg equilibrium, and inbreeding coefficient was calculated using GENEPOP 4.4. Genetic distance based on the proportion of common alleles (DPSA) was calculated using MICROSAT. Cluster analysis using the neighbor-joining method with 1,000 bootstraps was performed with PHYLIP to generate a dendrogram. The results of the AMOVA analysis showed that the total SSR diversity was 23% within and 77% between the three populations. A slight deviation from Hardy-Weinberg equilibrium was observed in the Mali Lošinj population. Allele richness ranged from 2.92 to 3.92, with the highest number of private alleles observed in the Mali Lošinj population (17). The average observed DPSA between 30 individuals was 0.557. The highest DPSA (0.875) was observed between several pairs of Dalmatian pyrethrum individuals from the Mali Lošinj and Mt. Biokovo populations, and the lowest between two individuals from the Čiovo population. Neighbor-joining trees, based on DPSA, grouped individuals into clusters according to their population affiliation. The separation of Mt. Biokovo clade was supported (bootstrap value 58%), which is consistent with the previous study on AFLP markers, where isolated populations from Mt. Biokovo differed from the rest of the populations. The developed SSR markers are an effective tool for assessing the genetic diversity and structure of natural Dalmatian pyrethrum populations. These preliminary results are encouraging for a future comprehensive study with a larger sample size across the species' range. Combined with the biochemical data, these highly informative markers could help identify potential genotypes of interest for future development of breeding lines and cultivars that are both resistant to environmental stress and high in pyrethrins. Acknowledgment: This work has been supported by the Croatian Science Foundation under the project ‘Genetic background of Dalmatian pyrethrum (Tanacetum cinerariifolium /Trevir./ Sch. Bip.) insecticidal potential’- (PyrDiv) (IP-06-2016-9034) and by project KK.01.1.1.01.0005, Biodiversity and Molecular Plant Breeding, at the Centre of Excellence for Biodiversity and Molecular Plant Breeding (CoE CroP-BioDiv), Zagreb, Croatia.

Keywords: Asteraceae, genetic diversity, genomic SSRs, NGS, pyrethrum, Tanacetum cinerariifolium

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Authors: Yimer Mohammed Assen, Abiyot Legesse Kura, Engida Esyas Dube, Asebe Regassa Debelo, Girma Kelboro Mensuro, Lete Bekele Gure

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Climate change has posed severe threats to many cultural landscapes of UNESCO world heritage sites recently. The UNESCO State of Conservation (SOC) reports categorized flooding, temperature increment, and drought as threats to cultural landscapes. This study aimed to examine variations and trends of rainfall and temperature extreme events and their threats to the UNESCO-designated Konso Cultural Landscape in southern Ethiopia. The study used dense merged satellite-gauge station rainfall data (1981-2020) with spatial resolution of 4km by 4km and observed maximum and minimum temperature data (1987-2020). Qualitative data were also gathered from cultural leaders, local administrators, and religious leaders using structured interview checklists. The spatial patterns, coefficient of variation, standardized anomalies, trends, and magnitude of change of rainfall and temperature extreme events both at annual and seasonal levels were computed using the Mann-Kendall trend test and Sen’s slope estimator under the CDT package. The standard precipitation index (SPI) was also used to calculate drought severity, frequency, and trend maps. The data gathered from key informant interviews and focus group discussions were coded and analyzed thematically to complement statistical findings. Thematic areas that explain the impacts of extreme events on the cultural landscape were chosen for coding. The thematic analysis was conducted using Nvivo software. The findings revealed that rainfall was highly variable and unpredictable, resulting in extreme drought and flood. There were significant (P<0.05) increasing trends of heavy rainfall (R10mm and R20mm) and the total amount of rain on wet days (PRCPTOT), which might have resulted in flooding. The study also confirmed that absolute temperature extreme indices (TXx, TXn, and TNx) and the percentile-based temperature extreme indices (TX90p, TN90p, TX10p, and TN10P) showed significant (P<0.05) increasing trends which are signals for warming of the study area. The results revealed that the frequency as well as the severity of drought at 3-months (katana/hageya seasons) was more pronounced than the 12-months (annual) time scale. The highest number of droughts in 100 years is projected at a 3-months timescale across the study area. The findings also showed that frequent drought has led to loss of grasses which are used for making traditional individual houses and multipurpose communal houses (pafta), food insecurity, migration, loss of biodiversity, and commodification of stones from terrace. On the other hand, the increasing trends of rainfall extreme indices resulted in destruction of terraces, soil erosion, loss of life and damage of properties. The study shows that a persistent decline in farmland productivity, due to erratic and extreme rainfall and frequent drought occurrences, forced the local people to participate in non-farm activities and retreat from daily preservation and management of their landscape. Overall, the increasing rainfall and temperature extremes coupled with prevalence of drought are thought to have an impact on the sustainability of cultural landscape through disrupting the ecosystem services and livelihood of the community. Therefore, more localized adaptation and mitigation strategies to the changing climate are needed to maintain the sustainability of Konso cultural landscapes as a global cultural treasure and to strengthen the resilience of smallholder farmers.

Keywords: adaptation, cultural landscape, drought, extremes indices

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Authors: Joanna Szymanska, Paulina Wawulska-Marek, Jaroslaw Mizera

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Nowadays, the rapid growth of global energy consumption and uncontrolled depletion of natural resources become a serious problem. Shale rocks are the largest and potential global basins containing hydrocarbons, trapped in closed pores of the shale matrix. Regardless of the shales origin, mining conditions are extremely unfavourable due to high reservoir pressure, great depths, increased clay minerals content and limited permeability (nanoDarcy) of the rocks. Taking into consideration such geomechanical barriers, effective extraction of natural gas from shales with plastic zones demands effective operations. Actually, hydraulic fracturing is the most developed technique based on the injection of pressurized fluid into a wellbore, to initiate fractures propagation. However, a rapid drop of pressure after fluid suction to the ground induces a fracture closure and conductivity reduction. In order to minimize this risk, proppants should be applied. They are solid granules transported with hydraulic fluids to locate inside the rock. Proppants act as a prop for the closing fracture, thus gas migration to a borehole is effective. Quartz sands are commonly applied proppants only at shallow deposits (USA). Whereas, ceramic proppants are designed to meet rigorous downhole conditions to intensify output. Ceramic granules predominate with higher mechanical strength, stability in strong acidic environment, spherical shape and homogeneity as well. Quality of ceramic proppants is conditioned by raw materials selection. Aim of this study was to obtain the proppants from aluminosilicates (the kaolinite subgroup) and mix of minerals with a high alumina content. These loamy minerals contain a tubular and platy morphology that improves mechanical properties and reduces their specific weight. Moreover, they are distinguished by well-developed surface area, high porosity, fine particle size, superb dispersion and nontoxic properties - very crucial for particles consolidation into spherical and crush-resistant granules in mechanical granulation process. The aluminosilicates were mixed with water and natural organic binder to improve liquid-bridges and pores formation between particles. Afterward, the green proppants were subjected to sintering at high temperatures. Evaluation of the minerals utility was based on their particle size distribution (laser diffraction study) and thermal stability (thermogravimetry). Scanning Electron Microscopy was useful for morphology and shape identification combined with specific surface area measurement (BET). Chemical composition was verified by Energy Dispersive Spectroscopy and X-ray Fluorescence. Moreover, bulk density and specific weight were measured. Such comprehensive characterization of loamy materials confirmed their favourable impact on the proppants granulation. The sintered granules were analyzed by SEM to verify the surface topography and phase transitions after sintering. Pores distribution was identified by X-Ray Tomography. This method enabled also the simulation of proppants settlement in a fracture, while measurement of bulk density was essential to predict their amount to fill a well. Roundness coefficient was also evaluated, whereas impact on mining environment was identified by turbidity and solubility in acid - to indicate risk of the material decay in a well. The obtained outcomes confirmed a positive influence of the loamy minerals on ceramic proppants properties with respect to the strict norms. This research is perspective for higher quality proppants production with costs reduction.

Keywords: aluminosilicates, ceramic proppants, mechanical granulation, shale gas

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Authors: Maria João Ferreira, Natalia Sierra-Garcia, Javier Cremades, Carla António, Ana M. Rodrigues, Helena Silva, Ângela Cunha

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Salicornia ramosissima, a halophyte that grows naturally in coastal areas of the northern hemisphere, is often considered the most promising halophyte candidate for extensive crop cultivation and saline agriculture practices. The expanding interest in this plant surpasses its use as gourmet food and includes their potential application as a source of bioactive compounds for the pharmaceutical industry. Despite growing well in saline soils, sustainable and ecologically friendly techniques to enhance crop production and the nutritional value of this plant are still needed. The root microbiome of S. ramosissima proved to be a source of taxonomically diverse plant growth-promoting bacteria (PGPB). Halotolerant strains of Bacillus, Salinicola, Pseudomonas, and Brevibacterium, among other genera, exhibit a broad spectrum of plant-growth promotion traits [e.g., 3-indole acetic acid (IAA), 1-aminocyclopropane-1-carboxylic acid (ACC) deaminase, siderophores, phosphate solubilization, Nitrogen fixation] and express a wide range of extracellular enzyme activities. In this work, three plant growth-promoting bacteria strains (Brevibacterium casei EB3, Pseudomonas oryzihabitans RL18, and Bacillus aryabhattai SP20) isolated from the rhizosphere and the endosphere of S. ramosissima roots from different saltmarshes along the Portuguese coast were inoculated in S. ramosissima seeds. Plants germinated from inoculated seeds were grown for three months in pots filled with a mixture of perlite and estuarine sediment (1:1) in greenhouse conditions and later transferred to a growth chamber, where they were maintained two months with controlled photoperiod, temperature, and humidity. Pots were placed on trays containing the irrigation solution (Hoagland’s solution 20% added with 10‰ marine salt). Before reaching the flowering stage, plants were collected, and the fresh and dry weight of aerial parts was determined. Non-inoculated seeds were used as a negative control. Selected dried stems from the most promising treatments were later analyzed by GC-TOF-MS for primary metabolite composition. The efficiency of inoculation and persistence of the inoculum was assessed by Next Generation Sequencing. Inoculations with single strain EB3 and co-inoculations with EB3+RL18 and EB3+RL18+SP20 (All treatment) resulted in significantly higher biomass production (fresh and dry weight) compared to non-inoculated plants. Considering fresh weight alone, inoculation with isolates SP20 and RL18 also caused a significant positive effect. Combined inoculation with the consortia SP20+EB3 or SP20+RL18 did not significantly improve biomass production. The analysis of the profile of primary metabolites will provide clues on the mechanisms by which the growth-enhancement effect of the inoculants operates in the plants. These results sustain promising prospects for the use of rhizospheric and endophytic PGPB as biofertilizers, reducing environmental impacts and operational costs of agrochemicals and contributing to the sustainability and cost-effectiveness of saline agriculture. Acknowledgments: This work was supported by project Rhizomis PTDC/BIA-MIC/29736/2017 financed by Fundação para a Ciência e Tecnologia (FCT) through the Regional Operational Program of the Center (02/SAICT/2017) with FEDER funds (European Regional Development Fund, FNR, and OE) and by FCT through CESAM (UIDP/50017/2020 + UIDB/50017/2020), LAQV-REQUIMTE (UIDB/50006/2020). We also acknowledge FCT/FSE for the financial support to Maria João Ferreira through a PhD grant (PD/BD/150363/2019). We are grateful to Horta dos Peixinhos for their help and support during sampling and seed collection. We also thank Glória Pinto for her collaboration providing us the use of the growth chambers during the final months of the experiment and Enrique Mateos-Naranjo and Jennifer Mesa-Marín of the Departamento de Biología Vegetal y Ecología, the University of Sevilla for their advice regarding the growth of salicornia plants in greenhouse conditions.

Keywords: halophytes, PGPB, rhizosphere engineering, biofertilizers, primary metabolite profiling, plant inoculation, Salicornia ramosissima

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Authors: Mina Naeini, Thomas A. Adams II

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Solid Oxide Fuel Cells (SOFCs) feature high electrical efficiency and generate substantial amounts of waste heat that make them suitable for integrated community energy systems (ICEs). By harvesting and distributing the waste heat through hot water pipelines, SOFCs can meet thermal demand of the communities. Therefore, they can replace traditional gas boilers and reduce greenhouse gas (GHG) emissions. Despite these advantages of SOFCs over competing power generation units, this technology has not been successfully commercialized in large-scale to replace traditional generators in ICEs. One reason is that SOFC performance deteriorates over long-term operation, which makes it difficult to find the proper sizing of the cells for a particular ICE system. In order to find the optimal sizing and operating conditions of SOFCs in a community, a proper knowledge of degradation mechanisms and effects of operating conditions on SOFCs long-time performance is required. The simplified SOFC models that exist in the current literature usually do not provide realistic results since they usually underestimate rate of performance drop by making too many assumptions or generalizations. In addition, some of these models have been obtained from experimental data by curve-fitting methods. Although these models are valid for the range of operating conditions in which experiments were conducted, they cannot be generalized to other conditions and so have limited use for most ICEs. In the present study, a general, detailed degradation-based model is proposed that predicts the performance of conventional SOFCs over a long period of time at different operating conditions. Conventional SOFCs are composed of Yttria Stabilized Zirconia (YSZ) as electrolyte, Ni-cermet anodes, and LaSr₁₋ₓMnₓO₃ (LSM) cathodes. The following degradation processes are considered in this model: oxidation and coarsening of nickel particles in the Ni-cermet anodes, changes in the pore radius in anode, electrolyte, and anode electrical conductivity degradation, and sulfur poisoning of the anode compartment. This model helps decision makers discover the optimal sizing and operation of the cells for a stable, efficient performance with the fewest assumptions. It is suitable for a wide variety of applications. Sulfur contamination of the anode compartment is an important cause of performance drop in cells supplied with hydrocarbon-based fuel sources. H₂S, which is often added to hydrocarbon fuels as an odorant, can diminish catalytic behavior of Ni-based anodes by lowering their electrochemical activity and hydrocarbon conversion properties. Therefore, the existing models in the literature for H₂-supplied SOFCs cannot be applied to hydrocarbon-fueled SOFCs as they only account for the electrochemical activity reduction. A regression model is developed in the current work for sulfur contamination of the SOFCs fed with hydrocarbon fuel sources. The model is developed as a function of current density and H₂S concentration in the fuel. To the best of authors' knowledge, it is the first model that accounts for impact of current density on sulfur poisoning of cells supplied with hydrocarbon-based fuels. Proposed model has wide validity over a range of parameters and is consistent across multiple studies by different independent groups. Simulations using the degradation-based model illustrated that SOFCs voltage drops significantly in the first 1500 hours of operation. After that, cells exhibit a slower degradation rate. The present analysis allowed us to discover the reason for various degradation rate values reported in literature for conventional SOFCs. In fact, the reason why literature reports very different degradation rates, is that literature is inconsistent in definition of how degradation rate is calculated. In the literature, the degradation rate has been calculated as the slope of voltage versus time plot with the unit of voltage drop percentage per 1000 hours operation. Due to the nonlinear profile of voltage over time, degradation rate magnitude depends on the magnitude of time steps selected to calculate the curve's slope. To avoid this issue, instantaneous rate of performance drop is used in the present work. According to a sensitivity analysis, the current density has the highest impact on degradation rate compared to other operating factors, while temperature and hydrogen partial pressure affect SOFCs performance less. The findings demonstrated that a cell running at lower current density performs better in long-term in terms of total average energy delivered per year, even though initially it generates less power than if it had a higher current density. This is because of the dominant and devastating impact of large current densities on the long-term performance of SOFCs, as explained by the model.

Keywords: degradation rate, long-term performance, optimal operation, solid oxide fuel cells, SOFCs

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