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Widespread tree growth decline and absence of acorn production are observed in formerly coppiced Quercus pyrenaica stands. Attempts to convert oak coppices into high forests by thinning have failed to date, possibly due to the massive root system developed by trees after centuries of coppicing. We tested root trenching and stem girdling as silvicultural treatments to mitigate this hypothetical root-to-shoot imbalance and enhance the physiological performance of multi-stemmed clonal trees. We expected that severing the roots within a clone by trenching would reduce root respiratory carbon losses. Alternatively, stem girdling would increase carbon availability above the girdled zone, whilst the communal root system is maintained by non-girdled stems. After clonal structure delineation in a one-hectare experimental plot, root trenching and stem girdling were applied to stems belonging to different clones. Twig hydraulic traits, leaf water potential, non-structural carbohydrates (NSC) concentration in twigs, stems and roots, stem xylem [CO2] as an indicator of root respiration, stem growth, and acorn production were discretely monitored up to 12 years after treatment application for comparison with control stems. Stem girdling led to short-term enhancements in NSC pools above the girdled zone. However, hydraulic dysfunction symptoms and canopy dieback were observed four years after girdling, eventually causing mortality. Root trenching initially increased root respiration and reduced stem growth without an apparent decline in the hydraulic function and NSC pools above-ground. Ten years after trenching, stem [NSC] increased while stem growth limitations diminished. Although not statistically significant, slight enhancements in acorn production were observed 6 and 12 years after trenching. We discourage stem girdling as a silvicultural practice to mitigate a root-to-shoot imbalance in abandoned oak coppices, as long-term detrimental effects outweighed potential benefits.

Global warming modulates the spatial and temporal occurrence of insect outbreaks, leading to as-yet-unknown effects on forests ecosystems. Warmer trends may favour the upward and northward expansion of pests, albeit increased exposure to heat events and droughts may also hamper insect growth and development. Thus far, further research is needed about the balance of climate warming on pine processionary moth (PPM) (Thaumetopoea pityocampa) development stages, especially at broader scales, despite being the main conifer-defoliating insect in the Mediterranean area. This research analyses the relationships of PPM with the climatic conditions during its most vulnerable development phases in Spain to provide base-information for forest managers. We hypothesize that warmer winter temperatures will increase PPM growth at their larval feeding stage, whereas summer-heat events will reduce PPM rates from egg and early larval stages, leading to counterbalanced effects of climate warming. Furthermore, we expect dry springs will allow an earlier development of PPM and higher incidence of outbreaks. To analyse climate effects on PPM populations in Andalusia, Castilla-La Mancha, and Navarre (37 to 42°N), we compiled information from the Regional Forest Services comprising up to 26 years of monitoring data from 2465 forest stands dominated by Pinus nigra and Pinus sylvestris. We fitted Cumulative Link Mixed Models (CLMM) to test the climate effects on four PPM defoliation severity levels. Our results support higher PPM larvae survival and incidence due to warmer winter conditions, but also the reduction of PPM population size under summer heat conditions. Particularly, the increasing incidence associated to warmer winters during the larval defoliating stage is counterbalanced by the decreasing population at earlier life stages during summer heat events. Spring drought also plays an important role on PPM incidence rates, but its effect is idiosyncratic to each region, suggesting an

We lack understanding of how variable is radial growth of coexisting tree and shrub species, and how growth is constrained by drought depending on site aridity. Here, we compared the radial growth of two widespread and coexisting species, a winter deciduous shrub (Amelanchier ovalis Medik.) and an evergreen conifer tree (Pinus sylvestris L.). We sampled four sites in Northeastern Spain subjected to different aridity levels and used dendrochronological methods to quantify growth patterns and responses to climate variables. The growth of the two species varied between regions, being lower in the driest sites. The first-order autocorrelation (growth persistence) was higher in more mesic sites but without clear differences between species. Tree and shrub growth negatively responded to elevated summer temperatures and positively to spring-summer precipitation and wet conditions. However, negative growth responses of the shrub to drought were only observed in the two driest sites in contrast to widespread responses of the tree. Abrupt growth reductions were common in the drier sites, but resilience indices show that the two species rapidly recovered pre-drought growth levels. The lower growth synchrony of the shrub as compared to the tree can be due to the multistemmed architecture, fast growth and low stature of the shrub. Besides, the high dependency of the shrub growth on summer rainfall can explain why drought limitations were only apparent in the two driest sites. In any case, results point out to the dendrochronological potential of shrubs, which is particularly relevant giving its ability to inhabit woodlands and treeless regions under harsh climatic conditions. Nevertheless, further research is required to elucidate the capacity of shrub species to tolerate drought, as well as to understand how shrubs thrive in water- and cold-limited environments.

Badlands are often the source of a significant fraction of the sediment reaching the river network due to the exposure of the bare soil to the impact of rain drops and to the bed shear stress generated by the surface runoff. Hence, a correct understanding of the soil erosion and sediment transport processes inside badlands can help to a better characterisation of the suspended sediment production at the catchment scale. In this work we study the suitability of a two-dimensional (2D) physically-based event-scale erosion model as a tool to represent soil erosion and sediment transport in badlands at a seasonal scale. The model solves the 2D shallow water equations, including infiltration and rainfall, in order to compute the generation and routing of surface runoff within the badland. Coupled to the hydrodynamic equations, the model solves a 2D suspended sediment transport equation with source terms that account for rainfall- and runoff-driven erosion and sediment deposition. Based on this model, an overall procedure was developed and tested considering, as case study, a badland located in El Soto catchment (central Pyrenees, Iberian Peninsula). For the analysed badland, several high-resolution topography surveys were available, which allowed for the estimation of the soil loss and the spatial distribution of erosion patterns for periods of 3–4 months over two years. These data sets were used to calibrate and validate the proposed modelling approach, and to analyse its capabilities and limitations for the assessment of soil erosion at the seasonal scale.

Benzene, mostly produced from fossil fuel sources, is an essential chemical to many modern industries. Alternatively to non-renewable methods currently used, the present work explores using fast pyrolysis biomass-derived bio-oils to furnish this valuable platform molecule. Notably, we report for the first time the impact of different operational parameters on the highly selective continuous catalytic hydrodeoxygenation of guaiacol, a bio-oil model compound, into benzene using a Mo2C/CNF-based catalyst. The parametric study includes a first evaluation of the effect of the hydrogen pressure (25, 50 and 75 bar), temperature (300, 325 and 350 °C) and weight hourly space velocity (4 and 10 gorg gcat−1 h−1) on the guaiacol conversion and product distribution, and a subsequent long-term evaluation (30 h on stream) of the catalyst under appropriate processing conditions The experimental results revelated that our Mo2C/CNF was able to achieve a conversion of 90–98% with a relative amount of benzene in the liquid product up to 81% for at least 30 h without any sign of deactivation at 75 bar of H2 and 350 °C, which is a landmark achievement in the conversion of bio-oil derived molecules into platform chemicals.

The apple cultivar, known for its adaptability and diverse varieties, has been extensively utilized for cider production, particularly in climatically suitable regions. Cider, an age-old alcoholic beverage derived from fermenting apple juice, is gaining popularity, especially among younger generations. Despite this trend, comprehensive knowledge regarding the toxicological profile of ciders remains limited, leaving room for potential chemical contaminants from raw ingredients or production methods. To address this gap, we conducted an unprecedented study analyzing sixty-eight cider samples from the Spanish market, encompassing both traditional ciders and newly developed apple-based flavored drinks referred to as “ciders.” Our investigation focused on pesticide residues, elemental profiles, and mycotoxin residues. In a groundbreaking approach, our study integrated the analysis of 225 pesticide residues, 50 Persistent Organic Pollutants (POPs), 11 mycotoxins (AFB1, AFB2, AFG1, AFG2, DON, FB1, FB2, H-2, HT-2, OTA, PAT, and ZEN), and a total of 50 elements. Pesticide residues were identified using GCMSMS and LCMSMS, elemental composition determined via ICPMS, and mycotoxins analyzed using LCMSMS. The significance of our research lies in addressing the dearth of toxicological analyses of ciders, despite their burgeoning global consumption and production. For pesticide residues and elemental composition, our results underwent statistical processing, revealing distinct differences between the elemental profiles of traditional ciders and “ciders.” Additionally, disparities were observed between cider and other low-alcohol fermented beverages like wines and beers. Concentrations of most pesticide residues and elements in the cider samples were deemed non-toxic, falling below allowable limits established by international organizations for other beverages such as water or wine. However, certain elements, notably Br and Pb in traditional ciders, raised potential concerns. Our f

Ultrasound imaging for Non Destructive Testing is frequently performed in an immersion setup, where water is used as coupling medium between the probe and the component under test. For the computation of the time delays needed for beam-forming, the shape of the component surface and probe location and orientation (PLO) must be known. In this work we develop methods for the automatic detection of the surface and the estimation of PLO for 2D array probes. In particular, the methods developed apply to three types of elementary surfaces which are usually found in industrial and structural components: planes, cylinders and spheres. The methods use the measured surface echoes Time of Flight (TOF) to fit parametric models based on ray propagation and reflection on the surface, giving the coordinates and Euler angles that define the PLO relative to the component under test. Validation experiments with four test specimens representing the three types of surfaces are presented. The accuracy and precision of estimated PLO coordinates and angles are analyzed, and a Total Focusing Method (TFM) imaging example is shown achieving a correct detection of artificial defects in the component for a different PLOs.

Submarine Groundwater Discharge (SGD) delivers nutrients to the coastal sea triggering phytoplankton blooms, eutrophication, and can also serve as a pathway for contaminants. Wastewater treatment plants (WWTP) including injection wells in coastal areas influence coastal aquifers and might impact the composition and magnitude of SGD fluxes. In tourist areas, wastewater treatment may be less efficient and larger in volume during high seasons, potentially impacting nutrient fluxes from SGD and exacerbating environmental impacts. This study analyzes the nutrient transfer from treated wastewater injection in karstic aquifers to the coastal sea via SGD, considering the impacts of tourism seasonality. This study is conducted in Cala Deià, a small cove in the Balearic Islands, a Mediterranean tourist destination. The findings suggest that the seasonality of tourism, leading to variations in the volume of wastewater treated in the WWTP, influences the dynamics of the coastal aquifer. This leads to increased SGD water and nutrient fluxes to the sea in summer, i.e. the peak tourist season. The measured DIN, DIP, and DSi inventories in the cove are much larger in August than in April (3, 10, and 1.5 times higher, respectively) due to higher input of nutrients in summer due to SGD impacted by the WWTP. These elevated nutrient flows can support algal blooms in the cove, compromising water quality for local swimmers and tourists. Indeed, in August, shoreline stations exhibited eutrophic Chl-a concentrations, with peaks reaching approximately 4 mg Chl-a L−1. These elevated levels suggest the presence of an algal bloom during the survey. The anthropogenic origin of SGD-driven nutrients is traced in seawater and seagrass meadows, as evidenced by high ∂15N signatures indicative of polluted areas. Thus, the high pressure exerted on coastal areas by tourism activities increased the magnitude of SGD nutrient fluxes, thereby threatening coastal ecosystems and the services they provide.

Cells vary in volume throughout their life cycle and in many other circumstances, while their genome remains identical. Hence, the RNA production factory must adapt to changing needs, while maintaining the same production lines. This paradox is resolved by different mechanisms in distinct cells and circumstances. RNA polymerases have evolved to cope with the particular circumstances of each case and the different characteristics of the several RNA molecule types, especially their stabilities. Here we review current knowledge on these issues. We focus on the yeast Saccharomyces cerevisiae, where many of the studies have been performed, although we compare and discuss the results obtained in other eukaryotes and propose several ideas and questions to be tested and solved in the future.

Extra virgin olive oil (EVOO) from Olea europaea (cultivated olive tree) and the oil obtained from the wild olive variety or acebuche (ACE oil from Olea oleaster) contain an extraordinary number of bioactive molecules. These include oleic acid, sterols, tocopherols, triterpene compounds, and polyphenols. Both oils are known for their healthy properties and are considered to be a nutraceutical tool against cardiovascular diseases, including arterial hypertension, preeclampsia, and ocular diseases such as glaucoma or diabetic retinopathy. The benefits of EVOO and ACE oil stem from their anti-inflammatory, antioxidant, and anti-cancer properties. They also have potential as prebiotic compounds. In this update, we synthesise and illustrate the various characteristics and beneficial effects of olive oils from different varieties of olive trees, with special emphasis on Olea oleaster, also known as Olea europaea, L. var. sylvestris.

In an effort to reduce pesticide use, agronomists and computer scientists have joined forces to develop site-specific weed detection and classification systems. These systems aim to recognize and locate weed species within a crop field, using precision equipment to apply required herbicides timely and only where needed, with the objective of reducing the sprayable surface required to eliminate the given weed and protect the crop, with both economic and environmental benefits. Yet, with climate change on the rise, common weeds are expected to undergo some changes to adapt to their environment, possibly with new or invasive weeds spreading to areas where they did not exist before. These changes (often morphological) as well as new invasions need to be taken into account by future classifiers and detection algorithms to ensure system robustness and adaptation to new habitats/climate dynamics. This paper proposes a set of experiments evaluating the use of transfer learning and zero-shot learning for weed classification using our novel TomatoWeeds dataset. Residual networks of variable depth, pretrained on the Imagenet and/or DeepWeeds datasets were evaluated. A ResNet50 pretrained on both datasets and fine-tuned on the TomatoWeeds dataset performed best, returning a holdout set accuracy of 77.8%, showing the advantageous use of transfer learning in this domain. Zero-shot learning, using both embeddings of images and morphological and habitat text-based descriptions, is implemented to test the ability of machine learning pipelines of recognizing unseen classes at test time (which may arise e.g. due to changing climate dynamics), a learning task in which the field (and our experiments) are still far from satisfactory results. Further research could benefit from larger weed-specific datasets for transfer learning as well as deeper network architectures to improve model performance. The projection-based ZSL could also benefit from larger datasets and new zero-shot learning

A marginal snowpack is a recent concept that refers to snow cover that is relatively shallow and transient but still has important environmental and socioeconomic functions. This class of snow cover influences environments over large areas of the world and is very common in the Mediterranean climates, but also in the transition zone between persistent seasonal and ephemeral snowpacks all over the world. However, a globally-accepted definition to identify these environments has not been reached yet. Most of the modelling and monitoring tools for snow have been developed in cold and alpine areas with persistent snowpacks. The study and modelling of shallower snowpacks in milder environments are complicated by their high temporal variability, frequently patchy nature and typical coexistence with shrubs and forest. However, in recent years new remote sensing tools and more complex modelling approaches and specific parametrizations are facilitating their study. This paper provides a definition for marginal snowpacks, identifying them as those with: (i) seasonal peak depths that only occasionally surpass 1.5 m in favorable deposition zones such as wind drifts, ii) having typical seasonal durations ranging from 60 to 120 days, and (iii) that are predominantly in an isothermal state (on >75% of days) with high densification rates and several cycles of accumulation-ablation during each snow season. We review the main existing research challenges to improve scientific capabilities for their study and we discuss their hydrological and environmental relevance at different spatial scales.

Defoliating insects’ outbreaks play a critical role in trees’ carbon cycle. The pine processionary moth (PPM; Thaumetopoea pityocampa) is the major defoliating insect of Mediterranean coniferous forests. The frequency and intensity of PPM outbreaks is projected to increase as winter temperatures become milder due to climate warming. An accurate evaluation of this projection requires a wide spatial baseline of the historical PPM incidence. PPM outbreaks affect tree secondary growth leading to narrow rings, providing a tree level signal. However, PPM defoliation rings can be confounded with drought rings, the most frequent cause of narrow rings in Mediterranean environments. Thus, an accurate identification of PPM rings demands the consideration of additional tree ring traits. Here, we introduce a multiproxy approach to identify and distinguish PPM and drought events. We sampled four Pinus nigra (3) and P. sylvestris (1) stands in Spain. We identified and verified years of PPM defoliation using remote sensing analysis and field observations of Regional Forest Service. We identified drought events through the combination of climatic data with radial growth reductions. We considered climate growth residuals, among-trees growth variability, latewood percentage (%LW), intrinsic water-use efficiency (iWUE) and minimum blue intensity (BI) to discern between droughts and PPM outbreaks. In comparison with drought rings, PPM rings showed 1) more negative residuals in climate growth models, 2) higher secondary growth variance, 3) higher percentage of latewood and 4) lower iWUE. Minimum BI did not differ between drought and PPM rings, but was lower than in the rest of the rings. The combination of these traits provides a signature to identify PPM rings, opening the opportunity to reconstruct PPM incidence on a broad spatio-temporal scale.

Snow patterns in ice-free areas of Greenland play important roles in ecosystems. Within a changing climate, a comprehensive understanding of the snow responses to climate change is of interest to anticipate forthcoming dynamics in these areas. In this study, we analyze the future snowpack evolution of a polar maritime Arctic location, Qeqertarsuaq (Disko Island, Central-Western Greenland). A physically-based snow model (FSM2) is validated and forced with CMIP6 projections for SSP2–4.5 and SSP5–8.5 greenhouse gasses emission scenarios, using two models: CanESM5 and MIROC6. The future snowpack evolution is assessed through four key seasonal (October to May) snow climate indicators: snow depth, snow days, snowfall fraction and ablation rate. Comparison against the observed air temperature for the reference climate period demonstrates superior accuracies for MIROC6 SSP2.4–5, with anomalies at 19 %, compared to CanESM5 SSP5.8–5 (25 %) and CanESM5 SSP2.4–5 (78 %). In terms of precipitation, CanESM5 SSP2.4–5 and SSP2.4–5 exhibit smaller anomalies against the observed data (5 %) in contrast to MIROC6 SSP2.4–5 (15 %) and MIROC6 SSP2.8–5 (17 %). Results demonstrate distinct snowpack responses to climate change depending on the model and emission scenario. For CanESM5, seasonal snow depth anomalies with respect to the reference period range from – 38 % (SSP2–4.5, 2040–2050 period) to – 74 % (SSP5–8.5, 2090–2100 period). MIROC6 projects lower snowpack reductions, with a decrease ranging from – 38 % (SSP2–4.5, 2040–2050 period) to – 57 % (SSP5–8.5, 2090–2100 period). Similar reductions are anticipated for snowfall and snow days. Changes in the snowpack evolution are primarily driven by positive trends in downwelling longwave radiation and air temperature. The projected increase in precipitation by the mid to late 21st century will lead to more frequent rain-on-snow events, intensifying snowpack melting. These findings help enhance the comprehension of future snow dynamics in the

Autophagy is a catabolic process in which a double-membrane organelle, the autophagosome (AP), engulfs cellular components that will be degraded in the lysosomes. ATG8 protein family members participate at various stages of AP formation. The present study compares the capacity to induce lipid-vesicle tethering and fusion of two ATG8 family members, LC3B and LC3C, with model membranes. LC3B is the most thoroughly studied ATG8 protein. It is generally considered as an autophagosomal marker and a canonical representative of the LC3 subfamily. LC3C is less studied, but recent data have reported its implication in various processes, crucial to cellular homeostasis. The results in this paper show that LC3C induces higher levels of tethering and of intervesicular lipid mixing than LC3B. As the N-terminus of LC3C is different from that of the other family members, various mutants of the N-terminal region of both LC3B and LC3C were designed, and their activities compared. It was concluded that the N-terminal region of LC3C was responsible for the enhanced vesicle tethering, membrane perturbation and vesicle-vesicle fusion activities of LC3C as compared to LC3B. The results suggest a specialized function of LC3C in the AP expansion process.

Iberian pigs are renowned for their high-quality products and distinctive characteristics, including high fat accumulation, low protein deposition rate, and a long productive cycle. The study aimed to assess in vivo body composition of purebred Iberian pigs using bioimpedance analysis (BIA) and ultrasonography. Accurate estimation of body composition in live animals is crucial for adopting decisions at the farm level. The experiment involved three groups of pure male Iberian pigs differing in body weight (BW; 60, 80 and 100 kg) with the same nutritional management. Body measurements, BIA and back fat and loin thickness (measured by ultrasonography) were obtained before slaughter. After slaughter pig carcasses were chemically analysed. A strong correlation between BIA measurements, specifically resistance (R) values, and body chemical parameters (total protein, lipids, ash, and water contents; p < 0.001 for all) was found. Reactance values (X), however, did not exhibit significant correlations. Regression analyses were conducted to predict carcass composition based on BIA measurements, BW, ultrasonography and linear corporal measurements. The prediction models achieved high R values for lipids, protein, total ash, water, and lean tissue (0.957, 0.968, 0.936, 0.961 and 0.976, respectively, p < 0.001 for all), indicating strong predictive power. These findings demonstrate the potential of non-invasive techniques such as BIA for estimating body chemical composition and quality of pig carcasses. However, it is important to acknowledge that the prediction models developed may not be applicable to other pig populations, as they were based on a specific sample of pigs.

The increasing expansion of the invasive Asian alga Rugulopteryx okamurae along the Andalusian coasts is a major challenge to marine biodiversity, and urgent coordinated measures are required for its removal or elimination. Among the different actions, the biotechnological valorisation could be a strategy for the management of alien biomass within the frame of the Blue Economy. This work evaluates the potential of R. okamurae biomass, either raw or processed by biotechnological treatments based on enzymatic hydrolysis and fermentation processes, to be used as a dietary ingredient in juvenile seabass (Dicentrarchus labrax). These treatments, intended primarily to improve the nutrient availability, might also decrease the content of undesirable and potentially harmful algal metabolites, such as the diterpenoid dilkamural. To this end, a 90-day feeding trial was carried out using four experimental diets containing 5% (w/w) crude or processed R. okamurae biomass. The results obtained revealed that the inclusion in the diet of raw R. okamurae caused adverse effects on fish growth, yielding lower values than those of the control group (p < 0.05), although this detrimental effect was negligible when the algae was processed prior to its inclusion in the experimental feeds. In terms of muscle composition, diets supplemented with the algal biomass induced an increase in protein content, especially in fish fed with pre-treated biomass. Qualitative differences (p < 0.05) were also found in muscle fatty acid profile, with a significant increase in ARA and DHA contents in fish fed on algae-supplemented diets. A significant reduction (p < 0.05)in muscle and liver lipid oxidation was evidenced in fish fed the algae-enriched diets, especially with treated biomass. Finally, 5% R. okamurae raw biomass caused negative effects on gut functionality, although these effects were not observed when the algal biomass was previously processed. In conclusion, the results revealed the potential

The fusion peptide (FP) and the Trp-rich membrane proximal external region (MPER) display membrane activity during HIV-1 fusion. These domains are highly conserved in the envelope glycoprotein (Env) and, consequently, antibodies targeting these regions block entry of divergent HIV strains and isolates into target cells. With the aim of recovering concurrent responses against the membrane-active Env domains, we have produced hybrid peptides that connect FP and MPER sequences via flexible aminohexanoic acid tethers, and tested their potential as immunogens. We demonstrate that liposome-based formulations containing FP-MPER hybrid peptides could elicit in rabbits, antibodies with the binding sequence specificity of neutralizing antibodies that engage with the N-terminal MPER sub-region. Determination of the thermodynamic parameters of binding using the Fab 2F5 as an N-terminal MPER antibody model, revealed that the hydrophobic interaction surface for epitope engagement appears to be optimal in the FP-MPER hybrid. In general, our data support: i) the use of liposomes as carriers for membrane active peptides; ii) the capacity of these liposome-based vaccines to focus humoral responses to N-terminal MPER epitopes; and iii) the need to include lipid membranes in immunogens to elicit such specific responses.

Cu is a vital micronutrient, but free Cu ions (Cu2+) in seawater, even at subnanomolar concentrations, can impede phytoplankton growth. Natural Cu complexation with organic ligands regulates Cu acquisition and, in most instances, reduces Cu2+ concentrations below toxic thresholds. Along the Antarctic coast, the sources and sinks of Cu and its associated ligands remain poorly defined. Despite the high productivity in the area, there are no studies on the role of trophic transfer in Cu cycling. This study explores penguin guano release of Cu and Cu ligands and its potential in neutralizing copper toxicity along the Antarctic coast. We collected guano in a Chinstrap penguin nesting location in the West coast of Deception Island and extracted its components into aqueous solution imitating natural processes. Copper concentration in guano was 0.4 mg (dry weight g)−1 constituting a potential toxic threat and showed biomagnification with respect to krill. Surface seawater samples collected from various locations varying in penguin activity, were analyzed to assess the potential influence of guano on the area. Visual examination and elevated levels of Al suggested that a substantial portion of guano was lithogenic. Consequently, only a modest 16 % of the total Cu present in guano could be extracted using mechanical methods. Notably, the concentrations of the extracted organic ligands were approximately 23 times higher than the concentrations of the extracted Cu. This significant presence of ligands effectively nullifies any potential toxicity that could have arisen from free Cu2+ ions. Guano ligands' conditional stability constants were lower than those in surface seawater suggesting phytoplankton exudation was the main ligand source in the area. Overall, guano acts as a key node for Cu cycling in coastal Antarctic waters but its deleterious potential is neutralized by ligands from krill digestion and the high background concentration of phytoplankton exudates.

Drought is the most critical environmental stress limiting crop productivity and yield. Rice is one of the top leading food crops worldwide and modern rice varieties are notably drought-sensitive due to their high-water requirements. Generating drought-resilient varieties and fine-tuning their yield performance are time-consuming tasks that could be achieved by exploiting the genetic diversity expressed by the wild ancestors of current-day crop species. We conducted a large-scale field experiment, imposing pre-flowering and post-flowering water shortages on 20 Oryza genotypes. Using detailed agro-physiological, isotopomics, and metabolite characterization of different Asian and African rice accessions, we shed light on the evolutionary biases that have evolved into the spectrum of strategies used to adapt to drought and have added to the rice knowledge base. We find that relevant decreases in photosynthetic rates (linked with stomatal opening) that differed between genotypes. We also identified genotypic differences in core C and N metabolism, and central metabolic pathways, highlighting the possible mechanisms of drought tolerance. Additionally, data suggest strong genetic associations of several amino acids that are significantly enriched during drought. We provide strong evidence of the distinctiveness of agro-physiological and metabolic pathway behaviors to drought across the use of diverse germplasm resources. Also, the resulting data provide insight into the wide variety of germplasm responses triggered by drought.

In France, oyster aquaculture has been historically developed in intertidal zones, with shellfish farming areas covering much of the Atlantic coast. Monitoring these off-bottom cultures where oysters are grown in plastic mesh-bags set on trestle tables is mandatory for the maritime administration to check compliance with a Structural Plan Document (SPD), while also being important for stock assessment in relation to carrying capacity issues. However, traditional monitoring methods are time-consuming, labor-intensive, and inefficient in covering large intertidal areas. In this study, we used a new GIS-based analytical method to assess the potential of high-resolution Unmanned Aerial Vehicle (UAV) multispectral data to retrieve spatial information on oyster-farming structures using Bourgneuf Bay (France) as a case-study. A non-parametric machine learning algorithm was applied to four UAV flight orthomosaics collected at different altitudes (12, 30, 50, and 120 m) to identify oyster mesh-bags. These supervised classifications achieved overall accuracies above 95% for all tested altitudes. In addition, an accurate distinction of oyster-bag mesh sizes (4, 9 and 14 mm) was obtained for 12–50 m flights, but there was a lower accuracy at 120 m. Across all flights, the 4 mm mesh size was the least well detected (72.14% Producer Accuracy). This information can be used to identify bags with specific mesh-sizes used for spat or adult grow out. Finally, we accurately measured oyster table heights using a high-resolution Digital Surface Model (DSM) derived from Structure from Motion (SfM) photogrammetry. The 50 m flight was suggested as the best compromise to obtain precise measurements of the oyster table heights while covering larger areas than lower altitude flights. This demonstrates that UAV technology can provide a set of spatial variables relevant for shellfish farmers and coastal managers in an efficient, rapid, and non-destructive way to monitor the extent and characteri

Metallurgical industries are a continuous source of air pollution due to the amount of settleable particulate matter (SePM) they release. This SePM is a complex mixture formed by metallic nanoparticles and metals, which reach terrestrial and aquatic ecosystems and can be a significant source of contamination. The aim of this study was to evaluate the adverse effects of SePM at different levels of biological organization in order to estimate its ecological impacts on aquatic ecosystems. For this purpose, the crustacean Daphnia magna was exposed to different concentrations of SePM (0.01, 0.1, 1, 5, 10 g/L) using a multi-level response approach. The endpoints studied were: avoidance throughout 24 h in a non-forced exposure system, reproduction (total number of neonates per female after 21 days of exposure), acetylcholinesterase activity (AChE) after 48 h, and finally, the feeding rates during a short-term exposure (48 h) and a long-term exposure (21 day + 48 h). There was a negative effect of SePM on all responses measured at high concentrations. The avoidance was concentration-dependent and represented 88 % and 100 % at the two highest concentrations. The AChE activity was significantly inhibited at 5 and 10 g/L. The total number of neonates increased from 1 g/L of SePM and the first brood occurred earlier as of 5 g/L compared to control. The post-exposure feeding rates were lower during long-term exposure at the highest concentration. Chemical analyses were performed to characterize the metals present in this SePM, but this study did not report any direct relationship with toxicity, due to the chemical heterogeneity of the particles. The emission of compounds caused by anthropogenic activity may have significant ecological consequences, so it is important to consider these possible effects on aquatic biota generated by the mixture of metals present in SePM originated from metallurgical activities. Environmental and sectorial regulations are needed to prevent contamin

[Introduction] Paslahepevirus balayani (HEV) is an endemic zoonotic disease ranked as a major cause of acute hepatitis in Europe. Most infections occurring in Europe are due to the endemic several subtypes of genotype 3, through the consumption of raw or undercooked pork, observing a genotype geographical distribution pattern among countries Because of global changes in the pig and pork trading markets, subtype distribution might vary. We aimed to evaluate the temporal distribution of HEV genotypes in patients from southern Spain with acute hepatitis to determine whether these changes were related to the pig import trade during the study period between 2018 and 2022., [Methods] Prospective longitudinal study including patients with acute hepatitis from southern Spain between 2018 and 2022. HEV RNA and antibodies was tested in all patients. In patients with detectable HEV RNA, genotype was obtained. To determine the number of imported pigs and their origins, we checked the official data from the Spanish statistics on international trade of Spanish Minister of Industry during by country of origin during the same study period., [Results] A total of 659 patients with acute hepatitis were included in the study. Among them, 162 (24.5%) had at least one marker (IgM or RNA) of acute HEV infection. Among the 71 patients with detectable viral RNA, genotypes could be obtained for 58 (81.6%). The most prevalent HEV genotype was 3f (n = 48; 78.6%), showing a decreasing prevalence of over time, from 100% in 2018 to 70.6% in 2022. Since 2021, the emergence of other genotypes has been determined. A significant increase in the number of animals imported was observed since the beginning of the study. Denmark experienced a significant rise, from 0.03% in 2018 of total imports to 10.4% in 2022., [Conclusions] HEV molecular diversity is changing in Spain, could be linked to changes in fattening pig import origin.

Robotic manipulation of cloth is a complex task because of the infinite-dimensional shape-state space of textiles, which makes their state estimation very difficult. In this paper we introduce the dGLI Cloth Coordinates, a finite low-dimensional representation of cloth states that allows us to efficiently distinguish a large variety of different folded states, opening the door to efficient learning methods for cloth manipulation planning and control. Our representation is based on a directional derivative of the Gauss Linking Integral and allows us to represent spatial as well as planar folded configurations in a consistent and unified way. The proposed dGLI Cloth Coordinates are shown to be more accurate in the representation of cloth states and significantly more sensitive to changes in grasping affordances than other classic shape distance methods. Finally, we apply our representation to real images of a cloth, showing that with it we can identify the different states using a distance-based classifier.

Atmospheric deposition of desert dust and other aerosols influence on the open ocean ecosystem and climate. These aerosols provide iron, phosphorus and bio-essential trace elements, which affect the composition and growth of phytoplankton, generating new organic matter that is distributed across the food web. Although this process has an impact on upper trophic levels and fisheries, direct evidence is lacking. Skipjack tropical tuna (Katsuwonus pelamis) is the most important commercial tuna in the Atlantic, main stocks occur in the tropical and subtropical North-East Atlantic. We found that the migrations and fisheries of skipjack are connected to Saharan dust variability. From boreal winter to summer, skipjack performs an Atlantic-Saharan migration, from equatorial (0-5°N) to subtropical waters of the North-East Atlantic (regularly reaching open waters off Mauritania ∼20°N and the Canary Islands ∼28°N), tracking the seasonal shift of dust deposition in the North-East Atlantic. The observed long-term associations of skipjack catch with the seasonal cycles, anomalies and meridional variability of dust over the North-East Atlantic, shows that along the year skipjack catches mainly occur in waters affected by massive dust deposition linked (i) to dust wet deposition in tropical waters and (ii) to dust dry deposition in the Saharan desert-dust outflow. Atmospheric deposition of dust in the open ocean and in upwelling waters contributes to support zooplankton-rich areas, which are optimal for feeding small fish, molluscs and cephalopods, and suitable for feeding large predators, as skipjacks, where they are caught in abundance. The most important fishing area of Atlantic skipjack tuna is located off North West Africa in the waters affected by massive dust deposition that underly the dusty airstream from the North Africa desert. The role of dust as fertilizing and supporter of phytoplankton and zooplankton rich areas also has implications for other species of fishing inte

The topological structure of interaction networks determines community dynamics and stability. Closeness centrality is a species-level attribute that measures the relative position and proximity of species in the interaction network. We assessed the link between closeness centrality of crops in plant-pollinator interaction networks and crop seed production. We worked with five crop species used for seed production distributed in 14 farms. At each farm we recorded pollinators’ interactions with the crop and with the co-flowering plants at crop edges and built quantitative plant-pollinator interaction networks. For each network, we calculated weighted closeness centrality of crops and related it to crop seed set by using generalized linear mixed models. Our results show that crop centrality is positively associated with crop seed production, and suggest that the use of ecological interaction network metrics in agricultural systems could be useful to design agronomic management plans and enhance crop yields.

Novel insights were provided by contrasting the composition of wild and farmed fish gut microbiomes because the latter had essentially different environmental conditions from those in the wild. This was reflected in the gut microbiome of the wild Sparus aurata and Xyrichtys novacula studied here, which showed highly diverse microbial community structures, dominated by Proteobacteria, mostly related to an aerobic or microaerophilic metabolism, but with some common shared major species, such as Ralstonia sp. On the other hand, farmed non-fasted S. aurata individuals had a microbial structure that mirrored the microbial composition of their food source, which was most likely anaerobic, since several members of the genus Lactobacillus, probably revived from the feed and enriched in the gut, dominated the communities. The most striking observation was that after a short fasting period (86 h), farmed gilthead seabream almost lost their whole gut microbiome, and the resident community associated with the mucosa had a very much reduced diversity that was highly dominated by a single potentially aerobic species Micrococcus sp., closely related to M. flavus. The results pointed to the fact that, at least for the juvenile S. aurata studied, most of the microbes in the gut were transient and highly dependent on the feed source, and that only after fasting for at least 2 days could the resident microbiome in the intestinal mucosa be determined. Since an important role of this transient microbiome in relation to fish metabolism could not be discarded, the methodological approach needs to be well designed in order not to bias the results. The results have important implications for fish gut studies that could explain the diversity and occasional contradictory results published in relation to the stability of marine fish gut microbiomes, and might provide important information for feed formulation in the aquaculture industry.

[EN] Flint was the most widely used lithic raw material in Europe in Prehistory and, more specifically, was a fundamental resource in the economic and social networks of hunter-gatherer groups in the Cantabrian Spain during the Upper Palaeolithic. The undeniable preference for it compared with other resources was due to a series of factors, such as its easy availability because of its abundance and wide distribution of outcrops, and its excellent qualities for knapping. This summary of the available information about flint and other raw materials used by hunter-gatherers is framed in the context of Upper Palaeolithic occupations in Cantabrian Spain. First, it presents the studies focusing on the provenance of the different types of flint that are found in those occupations; their quantitative representation at each of the sites; their preference, if that is the case, over other raw materials; and the model of their diffusion across the territory. Then other resources are considered, such as quartzite, ochre and different metamorphic, sedimentary and igneous rocks, as well as some materials of biological origin, such as amber, jet/lignite and fossils of animal origin. However, the information available about the use of the latter raw materials in Cantabrian Spain during the Upper Palaeolithic is quite limited and studies of their characterisation are very recent., [FR] Le silex est la principale matière première lithique utilisée dans la Préhistoire du continent européen et c’est une ressource fondamentale dans les circuits économiques et sociaux des groupes de chasseurs-cueilleurs pendant le Paléolithique supérieur de la région cantabrique (nord de l’Espagne). Sa préférence incontestable par rapport aux autres ressources repose sur une série de qualités telles qu’une disponibilité facile du fait de sa grande abondance, de la grande dispersion des affleurements, ainsi que les excellentes qualités pour sa taille. Dans cet article, nous présentons une synthèse des informations disponibles à partir des études sur le silex et d’autres matières premières utilisées par les groupes de chasseurs-cueilleurs. Cette révision a été abordée dans le cadre des occupations archéologiques de la région cantabrique datées du Paléolithique supérieur. D’une part, il s’agit des études relatives à la provenance des différents types de silex trouvés, leur représentation quantitative dans chacun des gisements révisées, préférence, si c’est le cas, par rapport aux autres matières premières documentées, ainsi que leur modèle de diffusion sur le territoire. D’autre part, d’autres ressources sont traitées, comme le quartzite, l’ocre et différentes roches métamorphiques, sédimentaires et ignées, ainsi que quelques matériaux d’origine biologique, comme l’ambre, le jais/lignite et les fossiles d’origine animale. Les informations disponibles concernant l’utilisation de ces matières premières dans le contexte du Paléolithique supérieur cantabrique sont assez rares et leurs études de caractérisation sont récentes.

Amber is fossilized resin that preserves biological remains in exceptional detail, study of which has revolutionized understanding of past terrestrial organisms and habitats from the Early Cretaceous to the present day. Cretaceous amber outcrops are more abundant in the Northern Hemisphere and during an interval of about 54 million years, from the Barremian to the Campanian. The extensive resin production that generated this remarkable amber record may be attributed to the biology of coniferous resin producers, the growth of resiniferous forests in proximity to transitional sedimentary environments, and the dynamics of climate during the Cretaceous. Here we discuss the set of interrelated abiotic and biotic factors potentially involved in resin production during that time. We name this period of mass resin production by conifers during the late Mesozoic, fundamental as an archive of terrestrial life, the `Cretaceous Resinous Interval (CREI).

Feed passage time throughout the digestive tract of three daily consecutive meals containing three different inert markers respectively and the gut luminal ionic conditions generated during a daily cycle have been examined in juveniles of greater amberjack (Seriola dumerili) growing at 18, 22 and 26 °C of water temperature. As expected, transit time tended to decrease with increasing temperature in the tested range. However, each meal progressed in a different manner affecting the ionic daily pattern within the tract lumen and the residence time within the different gut segments, two parameters of primary importance for the digestion efficiency. At 22 and 26 °C the gastric acidification effort was focused on the first meal whilst at 18 °C it was on the second and third meal. Intestinal alkalinisation was maintained during more hours at 22 °C than at 18 °C and 26 °C coinciding with the moments of highest chyme content in the intestine. At 26 °C, the three meals transited fast enough to progress clearly as separate batches. On the contrary, at 18 and 22 °C the consecutive meals became mixed in the stomach and intestine. Transit time was progressively shorter from the first to third meals at 18 and 22 °C, while at 26 °C it was shorter for the second meal and similar for the first and third meals when 95% total gut evacuation was considered. Total transit time ranged from 12 to 24 h approximately and the posterior intestine was completely emptied before the first morning meal in all cases. Interestingly, the residence time of ingested food in the middle intestine was longer at 22 °C than at the other two temperatures.

Harmful algal blooms (HABs) in coastal areas similarly impact both ecosystems and human health. The translocation of phytoplankton species via maritime transport can potentially promote the growth of HABs in coastal systems. Accordingly, ballast water must be disinfected. The main goal of this study is to assess the effectiveness of different emerging biocides, including H2O2, peracetic acid (PAA), peroxymonosulfate (PMS), and peroxydisulfate (PDS). The effectiveness of these biocides is compared with that of conventional chlorination methods. Their effects on two ichthyotoxic microalgae with worldwide distribution, i.e., Prymnesium parvum and Heterosigma akashiwo, are examined. To ensure the prolonged effectiveness of the different reagents, their concentration-response curves for 14 days are constructed and examined. The results suggest a strong but shorter effect by PMS (EC50 = 0.40-1.99 mg·L-1) and PAA (EC50 = 0.32-2.70 mg·L-1), a maintained effect by H2O2 (EC50 = 6.67-7.08 mg·L-1), and a negligible effect by PDS. H. akashiwo indicates higher resistance than P. parvum, except when H2O2 is used. Based on the growth inhibition performance and consumption of the reagents as well as a review of important aspects regarding their application, using H2O2, PAA, or PMS can be a feasible alternative to chlorine-based reagents for inhibiting the growth of harmful phytoplankton.

Eutrophication is still a serious problem in many coastal areas, including the tropics, where river discharges of nutrients is usually high. The ecological stability and ecosystem services of the Mesoamerican Barrier Reef System (MBRS), the world's second-largest coral reef system, suffer a generalized impact by riverine discharge of sediment and organic and inorganic nutrients, which may lead to coastal eutrophication and a coral-macroalgal phase shift. However, few data exist on the MRBS coastal zone status, particularly in Honduras. Here, two in situ sampling campaigns were carried out (May 2017 and January 2018) in the Alvarado Lagoon and Puerto Cortés Bay (Honduras). Measurements included water column nutrients, chlorophyll-a (Chla), particulate organic and inorganic matter and net community metabolism, completed with satellite images analysis. The lagoon and bay environments are ecologically different systems and present different sensitivities to seasonal changes in precipitation as shown by the multivariate analysis. Nonetheless, net community production and respiration rates were neither different spatially, nor seasonally. In addition, both environments were highly eutrophic as shown by the TRIX index. Thus, the Puerto Cortés system represents an important source of dissolved nutrients and particulate matter to the coastal zone. Even though offshore, water quality, based on estimated outwelling rates from the Puerto Cortés system to the coastal waters of the southern MRBS region, improved considerably, concentrations of Chla and nutrients remained higher than those typically measured in non-polluted coral reefs in the Caribbean region and the suggested threshold values. In situ monitoring and assessment of these aspects are crucial to evaluate the ecological functioning of and threats on the MBRS, and elaborate and implement adequate policies for integrated management given its regional and global importance.

In keeping with the premises of Blue Circular Economy in the European Union, the present study explored the possibility of using the invasive brown alga Rugulopteryx okamurae in aquafeeds for European sea bass (Dicentrarchus labrax). Assuming the raw algae biomass could negatively impact animal performance, four experimental formulations were prepared, by including macroalgae material at 5%, using crude (CR), enzymatically hydrolysed and fermented (EF), enzymatically hydrolysed (E), or fermented (F) R. okamurae biomass, which we tested against a control feed (CT). To evaluate the effects of the experimental diets, besides animal growth performance and biometric parameters, we devised a toolbox focused on the intestine and intestinal function: i) ex-vivo epithelial resistance and permeability in Ussing chambers; ii) microbiota composition through NGS; iii) expression profiles of selected markers for epithelial integrity, transport, metabolism, and immune response, by qPCR. Our results show differentiated allometric growth among diets, coupled with intestinal epithelium alterations in permeability, integrity, and amino acid transport. Additionally, evidence of microbiota dysbiosis and contrasting immune responses between experimental diets, i.e. pro-inflammatory vs. anti-inflammatory, are also described. In conclusion, we believe that R. okamurae could be a suitable resource for aquafeeds for the European sea bass, although its use requires a pre-treatment before inclusion. Otherwise, while the fish still have a positive growth performance, the gastrointestinal tract pays a toll on the integrity, transport, and inflammatory processes.

This study was conducted to address the changes in the surface distribution of trace metals (cobalt, copper, iron, cadmium, nickel, zinc, lead and molybdenum) as they are advected from the Gulf of Cadiz to the Alboran Sea, through the Strait of Gibraltar (south Iberian Peninsula), regions of great ecosystemic importance. Trace metals concentrations were measured in samples collected during two oceanographic cruises, together with the main factors affecting their spatial distribution and temporal variability (i.e., wind and surface currents). Several rivers, the main source of trace metals in this region, flow into the Gulf of Cadiz which is connected with the Alboran Sea through the Strait of Gibraltar by the general circulation pattern. The surface circulation pattern leads to an offshore-eastward gradient that is highly influenced by wind variability. An increase in vertical turbulence induced by the winds or the tidal cycle causes the dilution of trace metals' concentration by mixing rich-metal superficial waters with poor-metal subsurface waters. Additionally, along the eastward displacement of surface waters, several water retention zones have been described (Trafalgar, Camarinal, the Coastal Cyclonic Gyre) that imply an increase in trace metals concentration close to the coast. In addition, our results suggest that the coastal edges of the Strait of Gibraltar also act as a source of certain metals to the Alboran Sea, probably due to the industries in the proximity areas.

Nearshore bathymetry is one of the main parameters used in coastal studies. However, regular and continuous bathymetries are scarce due to the difficulty of continuous data collection using traditional surveys. Remote sensing offers an attractive alternative to conventional collection methods for acquiring freely available, reliable, and frequent high-resolution data from space missions, such as the European Union's Copernicus programme Sentinel-2A/B satellites, which are increasingly demonstrating their potential to derive bathymetric information. Consequently, satellite-derived bathymetry (SDB) is being used more regularly because of its low cost and high efficiency. In this study, we apply a log-transformed band ratio SDB model in the Western Mediterranean Sea (Mallorca Island, Spain). This model has been widely used in the Caribbean and along the U.S. coast, among other sites, with outstanding results in heterogeneous environments. The SDB model consists of an automatic multi-scene approach applied over several images corrected by a robust atmospheric correction model (ACOLITE), a switching model, and a procedure to remove pixels from optically deep waters. We retrieve depths up to 14 m with a mean bias of 0.02 m and a median absolute error of 0.71 m compared with multibeam echo-sounder (MBES) data. The outcomes of this study confirm the effectiveness of the multi-scene approach to automatically correct the imagery to derive accurate depths and characterize erosional and accretion patterns annually. Furthermore, it highlights the benefit of the switching model to take advantage of the spectral sensitivity of different multi-band ratio approaches. This study will provide the scientific community with substantial knowledge and improved SDB techniques to consolidate the understanding of nearshore processes in such a relevant ecosystem as the Mediterranean Sea.

[EN] Covalent organic Frameworks (COFs) are a class of crystalline macromolecular materials build-up by monomers with specific symmetries or functionalities. There are important limitations in the synthesis of highly ordered COFs, such as the shape and packing of the building blocks. Thus, the presence of fluorine atoms that lie perpendicular to the bisecting plane of BODIPY derivatives together with the presence of four bulky methyl groups could hinder the crystallization process in COF synthesis. For that reason, BODIPY-based COFs are rarely incorporated to COF networks. In this work, following the mixed linker strategy, a pre-synthetic method to dope COF structures with BODIPY units was developed. The materials have been processed into fluorescent Covalent Organic Nanosheets (CONs) with defined particle-size distributions around 100 nm, suitable for cellular biomedical applications. The viability of the CONs was evaluated using Sk-Mel-103 cells, demonstrating the internalization showing 100% cell viability. We envisage that this work could accelerate the discovery of new COF-based materials for biomedical sciences.

Spectral instruments can be useful for the rapid assessment of chemical compounds in different targets, and their use have been already reported for the modeling of grape composition comparing two spectral ranges. Still, with the increased easiness of acquiring data with several sensors, it would be valuable to explore spectral fusion techniques for the modeling with deep learning, seeking to obtain improved performance. Therefore, the objective of this work was to develop multi-sensor spectral fusion approaches for the deep learning modeling of grape composition. From 128 grape samples, two spectra per sample were acquired from two different ranges using two sensors (visible and shortwave near infrared, 570–1000 nm; and wider NIR 1100–2100 nm). From each sample, 15 grape nitrogen compounds were analyzed by wet chemistry. Three different data fusion approaches are defined using neural networks and deep learning, testing several ways of structuring and merging the input spectra. Statistical analyses supported that (i) the proposed deep learning fusion architectures performed better than single spectral range models, and (ii) neural networks have better modeling capabilities than partial least squares in spectral fusion. The results demonstrate the potential of deep learning for spectral data fusion in grape nitrogen composition regression, and potentially other traits in food and agriculture spectroscopy.

In plasmon-based devices, the choice of metal for the nanostructures often leads to an undesirable tradeoff between either the superb performance of Ag or the stability of Au. There is a great interest in combining Au and Ag in a way that preserves both their favourable properties, while also exploiting synergistic effects to boost surface-enhanced Raman scattering (SERS) performance beyond the capabilities of a single metal. To address this issue, a large-area nanofabrication procedure based on galvanic replacement was used to create hybrid Au–Ag nanoislands with a diverse morphology and highly tunable (through visible to NIR) plasmon resonance. Their stability was comprehensively studied and shown to be complex to achieve. However, in the right conditions, Au–Ag nanoislands with silver-like plasmonic properties were fabricated, and shown to be stable over a period of at least 5 months. Moreover, their SERS efficiency considerably outperformed even that of Ag nanoislands. Computational investigation helped explain the advantageous properties and provided insights for future sensor design. Detection of the model molecules was achieved in the nanomolar range and in mild conditions (low laser power), indicating great potential for biomedicine sensing. Beyond that, nanoislands with simultaneous stability and good plasmonic properties can find application in a wide variety of photonic devices.

At the initial stage of the oxygen evolution reaction (OER) most electrocatalysts undergo structural and chemical surface reconstruction. While this reconstruction strongly influences their performance, it is frequently overlooked. Herein, we analyze the role of the oxidized anions, which is particularly neglected in most previous works. We introduce a range of different anionic groups (Cl-, CH3COO-, NO3-, SO42-) on the surface of an amorphous ZnCoxNiyOz catalyst by a facile proton etching and ion exchange method from a ZIF-8 self-sacrificial template. The structural and chemical properties of the obtained set of materials are thoroughly analysed and correlated with their electrocatalytic performance to study the effect of surface anionic groups, phase transition, metal leaching and defect generation on OER activity. Exploiting the control possibilities provided by the synthesis method here described and employing the uncovered property-performance correlations, the electrocatalyst is optimized. As a result, we produce ZnCo1.25Ni0.73Ox-SO4 catalysts with outstanding OER performances, including a low overpotential of 252 mV at 10 mA cm−2 with a small Tafel slope of 41.6 mV dec−1. Furthermore, this catalyst exhibits remarkable stability with negligible overpotential variation for 100 h. The excellent catalytic properties are rationalized using density functional theory calculations, showing that the surface-adsorbed anions, particularly SO42−, can stabilize the OOH* intermediate, thus enhancing the OER activity. This work offers new insight into the roles of metal leaching and surface-adsorbed anions in the OER progress and facilitates the rational design of highly-efficient electrocatalysts for OER.

[EN] Ultra-thin alkali halide films are an important substrate for studying single quantum objects at the atomic scale, as they serve as decoupling scaffolds. However, their stability upon exposure to electrons and photons, the most common probes used to study nanomaterials, is not fully understood. Here we present a study of the evolution of the structure of ultra-thin LiCl films, grown on graphene, upon low-energy electron irradiation by means of microspot-low-energy electron diffraction and microscopy. We find that the intensity of the LiCl diffraction spots irradiated at various electron energies follows a bi-exponential decay function, which can be rationalized by two different desorption regimes. In addition, we detect a change in the work function caused by the electron irradiation, confirming desorption of the LiCl film from the graphene layer. We understand the underlying mechanisms for the electron-induced desorption of the salt film in terms of the evolution of the elementary quasiparticles involved in the process: holes, excitons and F and H center pairs. Moreover, a direct comparison of the electron-induced and the soft X-ray photon-induced processes reveal that, in addition to LiCl desorption, the intercalation of lithium into graphene reported for X-ray induced desorption does not take place in electron-stimulated desorption.

Soils provide key ecosystem services and are crucial to combat climate change. Agriculture provides important ecosystem services but also causes negative environmental effects depending on agricultural management. In this regard, crop diversification is a promising sustainable land management strategy to combat soil erosion and degradation, mitigate climate change and ensure food security. Here, we assess the combined short-term effects of crop diversification and no tillage on several key soil physico-chemical parameters related to soil functioning as well as on crop yields in a rainfed almond (Prunus dulcis Mill.) orchard under semiarid Mediterranean conditions. Almond trees were inter-cropped with Capparis spinosa L. (caper) or Thymus hyemalis Lange (winter thyme) and compared with the almond monocrop system. The experimental design consisted of three plots in a randomized-block design, with three replicates for each crop management treatment (almond monocrop, almond inter-cropped with caper, and almond inter-cropped with winter thyme). Along with crop yields, the combined effects of crop diversification and no tillage on a range of soil quality and health indicators including soil physical (bulk density, aggregate stability, water retention and availability) and chemical (total and particulate organic carbon and nitrogen, ammonium and nitrate content, available macro- and micro-nutrients) properties were monitored in the topsoil and subsoil (at 0–10 and 10–30 cm depth, respectively) one and three years from establishment

Monitoring the complex seafloor morphology that drives the functioning of shallow coastal ecosystems is vital for assessing marine activities. Satellite-derived bathymetry (SDB) can provide a crucial dataset for creating the bathymetry maps needed to understand hazards and impacts produced by climate change in vulnerable coastal zones. SDB is effective in clear water, but still has limitations in application to areas with some turbidity. Here, using the twin satellites Sentinel-2A/B, we integrate water quality information from the satellite with a multi-temporal compositing method to demonstrate a potential for comprehensively operational bathymetric mapping over a range of environments. The automated compositing method diminishes the turbidity impact in addition to inferring the maximum detectable depth and removing optically deep-water areas. Examining a wide range of conditions along the Caribbean and eastern coast of the U.S. shows detailed bathymetry as deep as 30 m at 10 m spatial resolution with median errors <1 m when compared to high-resolution lidar surveys. These results demonstrate that the model adopted can provide useful bathymetry in areas that do not have consistently clear water and can be extended across multiple geographic regions and optical conditions at local, regional, and national scales.

Despite their potential to reduce energy consumption in buildings and increase user's comfort, the general application of smart windows is currently hampered by economic and technological factors. To overcome these limitations, herein we report a new strategy for the fabrication of thermoresponsive smart windows based on polymer films loaded with paraffin nanoparticles. Proper selection of these components allows refractive index matching when the paraffin nanoparticles are in their solid state - i.e., high visible and near-infrared light transparency -, which is lost after melting, thereby resulting in pronounced light scattering - i.e., opacity. As a result, these films show ample modulation of sunlight transmittance upon heating, while additionally exhibiting other advantageous features: facile preparation from low-cost materials; high photostability, flexibility and scalability; and fine tunability of their thermal response. Moreover, by deposition onto transparent electrodes or incorporation of nanostructured photothermal agents, the solar transmittance modulation of our paraffin-polymer composites can also be triggered with low voltages - i.e., to warrant user's control - or sunlight absorption - i.e., to improve self-adaptation to ambient conditions. Actually, films with combined thermal and photothermal activity allow high sunlight transmission in cold weather while efficiently reducing solar heat gain indoors in sunny hot days.

The deployment of direct formate fuel cells (DFFCs) relies on the development of active and stable catalysts for the formate oxidation reaction (FOR). Palladium, providing effective full oxidation of formate to CO2, has been widely used as FOR catalyst, but it suffers from low stability, moderate activity, and high cost. Herein, we detail a colloidal synthesis route for the incorporation of P on Pd2Sn nanoparticles. These nanoparticles are dispersed on carbon black and the obtained composite is used as electrocatalytic material for the FOR. The Pd2Sn0.8P-based electrodes present outstanding catalytic activities with record mass current densities up to 10.0 A mgPd-1, well above those of Pd1.6Sn/C reference electrode. These high current densities are further enhanced by increasing the temperature from 25 °C to 40 °C. The Pd2Sn0.8P electrode also allows for slowing down the rapid current decay that generally happens during operation and can be rapidly re-activated through potential cycling. The excellent catalytic performance obtained is rationalized using density functional theory (DFT) calculations.

In this work, we developed a hybrid nanosystem able to simultaneously combine its potential as a photodynamic (PDT) and plasmonic photothermal (PPTT) therapeutic agent to kill malignant cells. To do that, AuNRs were functionalized by means of the layer-by-layer (LbL) assembly technique using alternating layers of anionic poly(styrene sulfonate) (PSS) and cationic poly-L-lysine (PLL) as polyelectrolytes (PEs), and an outer final layer of hyaluronic acid (HA) to provide the hybrid particles with both sufficient colloidal stability and targeting ability to tumoral cells overexpressing CD44 receptors. To provide the nanoplatform with PDT capabilities, the near-infrared (NIR) sensitive photosensitizer (PS) indocyanine green (ICG) was previously grafted to the PLL PE and assembled on the particle surface coating; in this manner, PSS/PLL-ICG/HA-coated AuNRs hybrid particles were obtained. Then, the conditions for optimized reactive oxygen species (ROS) production under NIR light excitation were elucidated, reaching ca. 80% after 5 min irradiation at 2.0 W/cm2 compared to positive control (H2O2). Since ICG can also absorb near infrared (NIR) light and transforms it by internal conversion into heat under suitable irradiation conditions, which adds to the photothermal plasmonic effect provided by the metallic NP, the heating profiles provided by the present hybrid nanoparticles (NPs) were measured, being observed temperature increments ranging from 9 to 22 °C. The potential contribution of its different components to both PDT and PPTT were deeply analyzed in vitro for intended cancer therapeutics at several power intensities but also at different temperatures with the aim of elucidating the role played by both phototherapies on cell cytotoxicity, the optimal illumination conditions for effective bimodal phototherapy as well as the elucidation of the main cell death mechanism involved. Under optimized conditions and after the administration of 2.5 ·1010 NPs/mL, cell cytotoxici

Free and glycosylated sterols localize in the plant cell plasma membrane, where in combination with other lipids regulate its structure and function. The role of glycosylated sterols in regulating membrane-associated biological processes is more relevant in plants like tomato (Solanum lycopersicum), in which glycosylated sterols are the predominant sterols. A proper ratio of free sterols versus glycosylated sterols has proven to be essential for proper plant performance in several species, but almost nothing is known in tomato. To assess the role of glycosylated sterols in tomato plant and fruit development, we generated transgenic lines of tomato cultivar Micro-Tom expressing two different amiRNAs devised to silence STEROL GLYCOSYLTRANSFERASE 1, the most actively expressed of the four genes encoding sterol glycosyltransferases in this plant. STEROL GLYCOSYLTRANSFERASE 1 gene silencing caused moderate plant dwarfism and reduced fruit size. Analysis of the profile of glycosylated sterols throughout fruit development demonstrated that the maintenance of proper levels of these compounds during the early stages of fruit development is essential for normal fruit growth, since reduced levels of glycosylated sterols trigger a transcriptional downregulatory response that affects genes involved in processes that are critical for proper fruit development, such as seed filling, cell wall extension and auxin signaling.

The development of cost-effective, high-activity and stable bifunctional catalysts for the oxygen reduction and evolution reactions (ORR/OER) is essential for zinc–air batteries (ZABs) to reach the market. Such catalysts must contain multiple adsorption/reaction sites to cope with the high demands of reversible oxygen electrodes. Herein, we propose a high entropy alloy (HEA) based on relatively abundant elements as a bifunctional ORR/OER catalyst. More specifically, we detail the synthesis of a CrMnFeCoNi HEA through a low-temperature solution-based approach. Such HEA displays superior OER performance with an overpotential of 265 mV at a current density of 10 mA/cm2, and a 37.9 mV/dec Tafel slope, well above the properties of a standard commercial catalyst based on RuO2. This high performance is partially explained by the presence of twinned defects, the incidence of large lattice distortions, and the electronic synergy between the different components, being Cr key to decreasing the energy barrier of the OER rate-determining step. CrMnFeCoNi also displays superior ORR performance with a half-potential of 0.78 V and an onset potential of 0.88 V, comparable with commercial Pt/C. The potential gap (Egap) between the OER overpotential and the ORR half-potential of CrMnFeCoNi is just 0.734 V. Taking advantage of these outstanding properties, ZABs are assembled using the CrMnFeCoNi HEA as air cathode and a zinc foil as the anode. The assembled cells provide an open-circuit voltage of 1.489 V, i.e. 90% of its theoretical limit (1.66 V), a peak power density of 116.5 mW/cm2, and a specific capacity of 836 mAh/g that stays stable for more than 10 days of continuous cycling, i.e. 720 cycles @ 8 mA/cm2 and 16.6 days of continuous cycling, i.e. 1200 cycles @ 5 mA/cm2.

The implementation of alley cropping in orchards has been suggested as a sustainable strategy to increase farmer revenues by crop diversification, enhance soil organic matter (SOM) and fertility, water retention, overall biodiversity, and contribute to climate change mitigation. Thus, the objective of this study was to assess if alley cropping with annual crops can contribute to i) mitigate soil greenhouse gas (GHG) emissions, ii) enhance C sequestration in a semiarid Mediterranean irrigated citrus orchard, and iii) increase land productivity. For this, two different treatments were established: i) conventional mandarin monoculture (MC) with no alley cropping; and ii) mandarin diversified with alley cropping of barley/vetch and fava bean (DIV). Measurements of soil CO2 and N2O emissions were periodically performed (every 7–20 days) during two years. Soil CO2 emission rates followed the soil moisture trend, and showed no significant differences between treatments. As an average, soil CO2 emission rates were 147 mg m-2 h-1 in MC and 196 mg m-2 h-1 in DIV. Soil N2O emission rates were not correlated to soil moisture nor temperature, and showed average values of 0.026 mg m-2 h-1 in MC and − 0.002 mg m-2 h-1 in DIV. Alley cropping did not contribute to significantly increase soil organic C and total nitrogen in two years’ time. With regard to production, mandarin yield showed no significant differences between treatments, but alley crops contributed to complementary commodities to the main cash crop, increasing overall land productivity. Thus, alley cropping in irrigated Mediterranean orchards has no significant effect on soil C sequestration and GHG emissions at short-term, with increased land productivity owing to new commodities grown in the alleys. These results confirm that under semiarid Mediterranean climate, long periods are needed to efficiently assess soil C sequestration potential of sustainable practices in orchards.

Hydroxyalkanoyloxyalkanoates (HAA) are lipidic surfactants with a number of potential applications, but more remarkably, they are the biosynthetic precursors of rhamnolipids (RL), which are preferred biosurfactants thanks to their excellent physicochemical properties, biological activities, and environmental biodegradability. Because the natural highest producer of RLs is the pathogenic bacterium Pseudomonas aeruginosa, important efforts have been dedicated to transfer production to heterologous non-pathogenic microorganisms. Unicellular photosynthetic microalgae are emerging as important hosts for sustainable industrial biotechnology due to their ability to transform CO2 efficiently into biomass and bioproducts of interest. Here, we have explored the potential of the eukaryotic green microalgae Chlamydomonas reinhardtii as a chassis to produce RLs. Chloroplast genome engineering allowed the stable functional expression of the gene encoding RhlA acyltransferase from P. aeruginosa, an enzyme catalyzing the condensation of two 3-hydroxyacyl acid intermediaries in the fatty acid synthase cycle, to produce HAA. Four congeners of varying chain lengths were identified and quantified by UHPLC-QTOF mass spectrometry and gas chromatography, including C10-C10 and C10-C8, and the less abundant C10-C12 and C10-C6 congeners. HAA was present in the intracellular fraction, but also showed increased accumulation in the extracellular medium. Moreover, HAA production was also observed under photoautotrophic conditions based on atmospheric CO2. These results establish that RhlA is active in the chloroplast and is able to produce a new pool of HAA in a eukaryotic host. Subsequent engineering of microalgal strains should contribute to the development of an alternative clean, safe and cost-effective platform for the sustainable production of RLs.

Sputtering of silicon in a Helium magnetron discharge has been reported as a bottom-up procedure to obtain amorphous Si films containing high amounts of gas-filled nanopores. Here we compare the microstructure and composition of Si–He nanocomposite films deposited by magnetron sputtering (MS) with 4He in DC or RF and 3He in RF operation modes. Electron microscopy (SEM and TEM), X-ray diffraction (XRD) and ion beam analysis (IBA) have been used to analyze the films and to investigate the in-situ and ex-situ thermal evolution. Depending on deposition conditions different in depth compositions, nanopore size and shape distributions, porosity and He content could be obtained. The presence of impurities (i.e. oxygen) has shown to promote He diffusivity reducing He accumulation. The start temperature of He-release varied in the range 473–723 K without films crystallization. Films grown in RF mode reached contents of 32 and 29 at% of 4He and 3He and were respectively stable up to 573 and 723 K both in vacuum and under inert gas flow. In-situ p-EBS (proton Elastic Back Scattering) allowed monitoring the He release accompanied by blistering/delamination effects visualized by SEM. These results show the potentiality of annealing to hold nano-porous structures after liberation of trapped gas.