Climate-driven shifts in decapod larvae assemblages in a temperate estuary.

The study examines the complex impact of climatic patterns, driven by the North Atlantic Oscillation (NAO), on regional climate, hydrology, and sea surface temperatures. Focused on the period from 2003 to 2012, the research specifically investigates the influence of thermal variability on decapod larval communities. Monthly zooplanktonic sampling conducted at the Mondego Estuary, Portugal, entrance over a decade revealed the prevalence of Carcinus maenas, Diogenes pugilator, and Pachigrapsus marmoratus larvae. These assemblages displayed notable interannual and seasonal fluctuations, often corresponding with changes in sea surface temperatures. Significant system shifts around 2007, instigated by the large-scale NAO, led to subsequent modifications in sea surface temperature and decapod larvae communities' dynamics. Post-2007, there was an upward trajectory in both species' abundance and richness. Phenologically during the former period, the community exhibited two abundance peaks, with the earlier peak occurring sooner, attributed to heightened temperatures instead of the unique peak exhibited before 2007. The research further elucidated the occurrences of Marine Heatwaves (MHW) in the region, delving into their temporal progression influenced by the NAO. Although water temperature emerged as a crucial factor influencing decapod larvae communities annually and seasonally, the study did not observe discernible impacts of MHW events on these communities. These communities represent essential trophic links and are crucial for the survival success of adult decapods. Given the rapid pace of climate change and increasing temperatures, it is imperative to assess whether these environmental shifts, particularly in thermal conditions, affect these meroplanktonic communities.

Opportunities of MXenes in Heterogeneous Catalysis: V2C as Aerobic Oxidation Catalyst.

MXenes are two-dimensional nanomaterials having alternating sheets of one atom-thick early transition metal layer and one atom-thick carbide or nitride layer. The external surface contains termination groups, whose nature depends on the etching agent used in the preparation procedure from the MAX phase. The present concept proposes that, due to their composition, the metal-surface termination groups make MXenes particularly suited as heterogeneous catalysts for some reactions. This proposal comes from the consideration that early transition metal atoms bonded to hydroxyl and oxo groups are a general type of active sites in heterogeneous catalysis and that similar catalytic centers can also be present in the MXene structure. After having presented the concept, we have selected V2C Mxene as an example to illustrate its catalytic activity and to show how the catalytic performance varies when the surface groups are modified. As a test reaction, we selected the aerobic oxidation of indane to the corresponding indanol/indanone mixture using molecular oxygen as terminal oxidizing reagent. Two previously reported procedures to modify the surface groups, namely surface dehydroxylation by thermal treatment under diluted hydrogen flow and surface oxidation with ammonium persulfate to convert some surface groups into oxo groups were used, observing in both cases a decrease in the catalytic activity of V2C. Based on this, VIII/IV-OH are proposed as catalytic centers in this aerobic oxidation. Overall, the present concept shows the merits of MXenes in heterogeneous catalysis, based on their chemical composition and the surface functionality.

Nanometric Cu-ZnO Particles Supported on N-Doped Graphitic Carbon as Catalysts for the Selective CO2 Hydrogenation to Methanol.

The quest for efficient catalysts based on abundant elements that can promote the selective CO2 hydrogenation to green methanol still continues. Most of the reported catalysts are based on Cu/ZnO supported in inorganic oxides, with not much progress with respect to the benchmark Cu/ZnO/Al2O3 catalyst. The use of carbon supports for Cu/ZnO particles is much less explored in spite of the favorable strong metal support interaction that these doped carbons can establish. This manuscript reports the preparation of a series of Cu-ZnO@(N)C samples consisting of Cu/ZnO particles embedded within a N-doped graphitic carbon with a wide range of Cu/Zn atomic ratio. The preparation procedure relies on the transformation of chitosan, a biomass waste, into N-doped graphitic carbon by pyrolysis, which establishes a strong interaction with Cu nanoparticles (NPs) formed simultaneously by Cu2+ salt reduction during the graphitization. Zn2+ ions are subsequently added to the Cu-graphene material by impregnation. All the Cu/ZnO@(N)C samples promote methanol formation in the CO2 hydrogenation at temperatures from 200 to 300 °C, with the temperature increasing CO2 conversion and decreasing methanol selectivity. The best performing Cu-ZnO@(N)C sample achieves at 300 °C a CO2 conversion of 23% and a methanol selectivity of 21% that is among the highest reported, particularly for a carbon-based support. DFT calculations indicate the role of pyridinic N doping atoms stabilizing the Cu/ZnO NPs and supporting the formate pathway as the most likely reaction mechanism.

Selective Gas-Phase Hydrogenation of CO2 to Methanol Catalysed by Metal-Organic Frameworks.

Large scale production of green CH3 OH obtained from CO2 and green H2 is a highly wanted process due to the role of CH3 OH as H2 /energy carrier and for producing chemicals. Starting with a short summary of the advantages of metal-organic frameworks (MOFs) as catalysts in liquid-phase reactions, the present article highlights the opportunities that MOFs may offer also for some gas-phase reactions, particularly for the selective CO2 hydrogenation to CH3 OH. It is commented that there is a temperature compatibility window that combines the thermal stability of some MOFs with the temperature required in the CO2 hydrogenation to CH3 OH that frequently ranges from 250 to 300 °C. The existing literature in this area is briefly organized according to the role of MOF as providing the active sites or as support of active metal nanoparticles (NPs). Emphasis is made to show how the flexibility in design and synthesis of MOFs can be used to enhance the catalytic activity by adjusting the composition of the nodes and the structure of the linkers. The influence of structural defects and material crystallinity, as well as the role that should play theoretical calculations in models have also been highlighted.

Climate forcing on estuarine zooplanktonic production.

Estuaries are among the most valuable aquatic systems in the world and resolving how there are impacted by climate change is fundamental to their management under global change scenarios. In this study, a ten-year time series (2003-2013) of zooplankton in an estuarine area (Mondego estuary, Portugal) is used to determine the impact of climate variability on estuarine zooplanktonic secondary production. For that, a trend analysis of seasonal zooplankton production was applied and their link with large-scale, regional, and local environment was tested by Distance-based multivariate multiple regression (DistLM). The annual integrated production of zooplankton varied between 34.27 mg C m-3 (2003) and 179.804 mg C m-3 (2013). Results showed that estuarine and marine zooplanktonic production increased in the estuary, mostly during summer/autumn and spring/summer, respectively. Local and regional environmental forcing drove copepod production in the estuary, with large-scale regime shifts affecting both directly and indirectly.

Short and long-term temperature variations drive recruitment variability in marine and estuarine juvenile fishes.

Understanding the long-term effects of climatic factors on key species' recruitment is crucial to species management and conservation. Here, we analysed the recruitment variability of key species (Dicentrarchus labrax, Platichthys flesus, Solea solea, Pomatoschistus microps and Pomatoschistus minutus) in an estuary between 2003 and 2019, and related it with the prevailing local and large-scale environmental factors. Using a dynamic factor analysis (DFA), juvenile abundance data were grouped into three common trends linked to different habitat uses and life cycle characteristics, with significant effect of temperature-related variables on fish recruitment: Sea surface temperature and the Atlantic Multidecadal Oscillation. In 2010, a regime shift in the North Atlantic coincided with a shift in the common trends, particularly a decline in P. flesus and S. solea trend. This work highlights the thermophilic character of fish recruitment and the necessity to investigate key biological processes in the context of species-specific responses to climate change.

Interannual variability in early life phenology is driven by climate and oceanic processes in two NE Atlantic flatfishes.

Early life phenology is a crucial factor for population dynamics in a climate change scenario. As such, understanding how the early life cycle of marine fishes is influenced by key oceanic and climate drivers is of chief importance for sustainable fisheries. This study documents interannual changes in early life phenology of two commercial flatfishes: European flounder (Platichthys flesus) and common sole (Solea solea) from 2010 to 2015 based on otolith microstructure. Using GAMs, we looked for correlations of the North Atlantic Oscillation (NAO), Eastern Atlantic pattern (EA), sea surface temperature (SST), chlorophyl a concentration (Chla) and upwelling (Ui) variation with the onset of hatch, metamorphosis, and benthic settlement day. We concluded that higher SST, more intensive upwelling, and EA were coincident with a later the onset of each stage, while increasing NAO induces an earlier onset of each stage. Although similar to S. solea, P. flesus showed a more complex interaction with the environmental drivers, most possibly because it is at its southern limit of its distribution. Our results highlight the complexity of the relationship between climate conditions and fish early life history, particularly those with complex life cycles that include migrations between coastal areas and estuaries.

Green, HF-Free Synthesis of MXene Quantum Dots and their Photocatalytic Activity for Hydrogen Evolution.

A general methodology to prepare MXene quantum dots (MxQDs) with yields over 20% by liquid-phase laser ablation of the MAX phase is reported. Mechanical and thermal shock by 532 nm laser pulses (7 ns fwhp, 50 mJ × pulse-1 , 1 Hz pulse frequency) produces MAX etching and exfoliation to form MXene QDs, avoiding the use of HF. The process can be followed by absorption and emission spectroscopy and by dynamic laser scattering and it appears to be general, being applied to Ti3 AlC2 , Ti2 AlC, Nb2 AlC, and V2 AlC MAX phases. Density functional theory calculations indicate that, depending on the surface terminal groups, the diminution of the MXene size to the nanometric scale makes it possible to control the band gap of the MXene. The photocatalytic activity of these MXene QDs for hydrogen evolution has been observed, reaching an H2 production for the most efficient Ti3 C2 QDs as high as 2.02 mmol × g-1 × h-1 .

Promotional Effects on the Catalytic Activity of Co-Fe Alloy Supported on Graphitic Carbon for CO2 Hydrogenation.

Starting from the reported activity of Co-Fe nanoparticles wrapped onto graphitic carbon (Co-Fe@C) as CO2 hydrogenation catalysts, the present article studies the influence of a series of metallic (Pd, Ce, Ca, Ca, and Ce) and non-metallic (S in various percentages and S and alkali metals) elements as Co-Fe@C promoters. Pd at 0.5 wt % somewhat enhances CO2 conversion and CH4 selectivity, probably due to H2 activation and spillover on Co-Fe. At similar concentrations, Ce does not influence CO2 conversion but does diminish CO selectivity. A 25 wt % Fe excess increases the Fe-Co particle size and has a detrimental effect due to this large particle size. The presence of 25 wt % of Ca increases the CO2 conversion and CH4 selectivity remarkably, the effect being attributable to the CO2 adsorption capacity and basicity of Ca. Sulfur at a concentration of 2.1% or higher acts as a strong poison, decreasing CO2 conversion and shifting selectivity to CO. The combination of S and alkali metals as promoters maintain the CO selectivity of S but notably increase the CO2 conversion. Overall, this study shows how promoters and poisons can alter the catalytic activity of Co/Fe@C catalysts, changing from CH4 to CO. It is expected that further modulation of the activity of Co/Fe@C catalysts can serve to drive the activity and selectivity of these materials to any CO2 hydrogenation products that are wanted.

Synergistic effect of Cu and Fe small nanoparticles supported on porous N-doped graphitic framework for selective electrochemical CO2 reduction at low overpotential.

Electrochemical CO2 reduction is an appealing approach to diminish CO2 emissions, while obtaining valuable chemicals and fuels from renewable electricity. However, efficient electrocatalysts exhibiting high selectivity and low operating potentials are still needed. Herein it is reported that Cu and Fe nanoparticles supported on porous N-doped graphitic carbon matrix are efficient and selective electrocatalysts for CO2 reduction to CO at low overpotentials. XRD and Raman spectroscopy confirmed independent Cu and Fe metals as the main phases. HRSEM and HRTEM images show the coral-like morphology of the porous N-doped graphitic carbon matrix supporting Cu and Fe metal nanoparticles (about 10 wt%) homogeneously distributed with an average size of 1.5 nm and narrow size distribution. At the optimum Fe/Cu ratio of 2, this material present high activity for CO2 reduction to CO at -0.3 V vs. RHE with a faradaic efficiency of 96%. Moreover, at -0.5 V vs. RHE this electrocatalyst produces 27.8 mmol of CO gcat-1 h-1, the production rate being stable for 17 h. A synergy between Cu and Fe nanoparticles due to their close proximity in comparison with independent Cu or Fe electrocatalysts was observed.

All-carbon microporous graphitic photocatalyst-promoted reduction of CO2 to CO in the absence of metals or dopant elements.

Microporous graphitic carbon (mp-C) derived from the pyrolysis of α-, ß-, and γ-cyclodextrins exhibited photocatalytic activity in CO2-saturated acetonitrile-water upon irradiation with UV-Vis light and in the presence of triethanolamine, forming H2 (19 µmol h-1) and CO (23 µmol h-1) accompanied by a lesser proportion of CH4 (4 µmol h-1). The most efficient was the mp-C material derived from α-cyclodextrin (mp-Cα) and having a pore dimension of 0.68 nm. The process also occured, although to a much lesser extent, under simulated sunlight or with UV-Vis irradiation in the absence of a sacrificial agent, with H2O being the electron donor. The origin of the CO was proved by isotopic 13C labelling experiments. Photocurrent measurements proved the occurrence of charge separation and the increase in photocurrent intensity in the presence of CO2. Transient absorption spectroscopy was used to detect the charge separate state decay in the microsecond time scale and proved that a fraction of the photogenerated electrons were able to react with CO2.

High C2-C4 selectivity in CO2 hydrogenation by particle size control of Co-Fe alloy nanoparticles wrapped on N-doped graphitic carbon.

A catalyst based on first-row Fe and Co with a record of 51% selectivity to C2-C4 hydrocarbons at 36% CO2 conversion is disclosed. The factors responsible for the C2+ selectivity are a narrow Co-Fe particle size distribution of about 10 nm and embedment in N-doped graphitic matrix. These hydrogenation catalysts convert CO2 into C2-C4 hydrocarbons, including ethane, propane, n-butane, ethylene and propylene together with methane, CO. Selectivity varies depending on the catalyst, CO2 conversion, and the operation conditions. Operating with an H2/CO2 ratio of 4 at 300°C and pressure on 5 bar, a remarkable combined 30% of ethylene and propylene at 34% CO2 conversion was achieved. The present results open the way to develop an economically attractive process for CO2 reduction leading to products of higher added value and longer life cycles with a substantial selectivity.

Tridimensional N, P-Codoped Carbon Sponges as Highly Selective Catalysts for Aerobic Oxidative Coupling of Benzylamine.

Two tridimensional N-doped porous carbon sponges (3DC-X) have been prepared by using cetyltrimethylammonium chloride (CTAC) and cetyltrimethylammonium bromide (CTAB) as soft templates and alginate to replicate the liquid crystals formed by CTA+ in water. Alginate is a filmogenic polysaccharide of natural origin having the ability to form nanometric defectless films around objects. Subsequent pyrolysis at 900 °C under an Ar flow of the resulting CTA+-polysaccharide assemblies result in 3DC-1 and 3DC-2, with the N percentages of 0.48 and 0.36 wt % for the materials resulting from CTAC and CTAB, respectively. Another four 3DC materials were obtained via pyrolysis of the adduct of phytic acid and chitosan, rendering an amorphous, N and P-codoped carbon sample (3DC-3 to 3DC-6). The six 3DC samples exhibit a large area (>650 m2 × g-1) and porosity, as determined by Ar adsorption. The catalytic activity of these materials in promoting the aerobic oxidation of benzylamine increases with the specific surface area and doping, being the largest for 3DC-4, which is able to achieve 73% benzylamine conversion to N-benzylidene benzylamine in solventless conditions at 70 °C in 5 h. Quenching studies and hot filtration tests indicate that 3DC-4 acts as a heterogeneous catalyst rather than an initiator, triggering the formation of hydroperoxyl and hydroxyl radicals as the main reactive oxygen species involved in the aerobic oxidation.

Influences of Climate Change and Variability on Estuarine Ecosystems: An Impact Study in Selected European, South American and Asian Countries.

It is well-known that climate change significantly impacts ecosystems (at the macro-level) and individual species (at the micro-level). Among the former, estuaries are the most vulnerable and affected ecosystems. However, despite the strong relations between climate change and estuaries, there is a gap in the literature regarding international studies across different regions investigating the impacts of climate change and variability on estuaries in different geographical zones. This paper addresses this need and reviews the impacts of climate change, variability and extreme weather on estuaries. It emphasises the following: (i) a set of climate parameters governing estuarine hydrology and processes; and (ii) a sample of countries in Asia (Bangladesh), Europe (Portugal) and South America (Uruguay). We reviewed the influences of the climatic drivers of the estuarine hydrology, ecological processes and specific species in estuarine communities across the selected geographical regions, along with an analysis of their long-term implications. The key results from the three estuaries are as following: (i) Hilsa fish, of which the catches contribute to 10% of the total earnings of the fishery sector (1% of GDP), are affected by climate-forced hydrological and productivity changes in the Meghna; (ii) extreme droughts and short-term severe precipitation have driven the long-term abundance and spatial distribution of both fish larvae and juveniles/adults in the Mondego; and (iii) the river inflow and fluctuations increases since the early 1970s have contributed to variations in the salinity, the stratification, the oxygen, nutrient and trophic levels and the spatial pattern for the life stages of planktonic species, fish biomass and captures in the Rio de la Plata. The results suggested that immediate action is needed to reduce the vulnerability of estuaries to climate stressors, mainly the changing river flows, storms and sea-level rise. As a contribution to addressing current problems, we described a set of adaptation strategies to foster climate resilience and adaptive capacity (e.g., early-warning systems, dam management to prevent overflows and adaptive fisheries management). The implications of this paper are two-fold. Firstly, it showcases a variety of problems that estuaries face from changing climate conditions. Secondly, the paper outlines the need for suitable adaptive management strategies to safeguard the integrity of such vital ecosystems.

Band Engineering of Semiconducting Microporous Graphitic Carbons by Phosphorous Doping: Enhancing of Photocatalytic Overall Water Splitting.

Carbon-based solar photocatalysts for overall water splitting could provide H2 as an energy vector in a clean and sustainable way. Band engineering to align energy levels can be achieved, among other ways, by doping. Herein, it is shown that phosphorous doping of microporous graphitic carbons derived from pyrolysis of α-, ß-, and γ-cyclodextrin increases the valence band edge energy of the material, and the energy value of the conduction band decreases with the P content. In this way, P doping increases the activity of these metal-free materials in photocatalytic overall water splitting under simulated sunlight and visible-light illumination. The optimal P-doped photocatalyst in the absence of any metal as a cocatalyst affords, after 4 h of irradiation with simulated sunlight, a H2 production of 2.5 mmol of H2 × gcatalyst-1 in the presence of methanol as the sacrificial agent or 225 µmol of H2 × gcatalyst-1 from pure H2O.

Fe clusters embedded on N-doped graphene as a photothermal catalyst for selective CO2 hydrogenation.

In comparison with the Co analog, small Fe clusters incorporated in a graphene matrix exhibit a photo-assisted increase of 110% in reverse water gas shift CO2 hydrogenation under UV-Vis light irradiation. Available data indicate that the photo-assistance derives from light absorption by the N-doped graphene followed by charge recombination at the Fe clusters, increasing their local temperature.

Function of estuaries and coastal areas as nursery grounds for marine fish early life stages.

The present study describes the larval and juvenile fish fauna of an estuary and its adjacent coastal area (Mondego estuary, Northwest coast of Portugal) and evaluates their function as nurseries for marine fish. For this, larvae and juveniles were sampled in both systems. The temporal and spatial patterns of the ichthyoplankton community were described for each system and related to the influence of environmental factors. Additionally, the recruitment pattern was evaluated based on the composition of juveniles. Results show a seasonal variation of larval density and community structure between and within systems, indicating a degree of segregation according to their ecological functional classification. Temperature was the most important environmental factor structuring the communities. The juvenile recruitment patterns observed show a different nursery function of the estuary and coastal area for early life stages of different species, reinforcing the need to integrate larval and juvenile stages to better understand fish life cycles and the connectivity between systems.

Co-Fe Nanoparticles Wrapped on N-Doped Graphitic Carbons as Highly Selective CO2 Methanation Catalysts.

Pyrolysis of chitosan containing various loadings of Co and Fe renders Co-Fe alloy nanoparticles supported on N-doped graphitic carbon. Transmission electron microscopy (TEM) images show that the surface of Co-Fe NPs is partially covered by three or four graphene layers. These Co-Fe@(N)C samples catalyze the Sabatier CO2 hydrogenation, increasing the activity and CH4 selectivity with the reaction temperature in the range of 300-500 °C. Under optimal conditions, a CH4 selectivity of 91% at an 87% CO2 conversion was reached at 500 °C and a space velocity of 75 h-1 under 10 bar. The Co-Fe alloy nanoparticles supported on N-doped graphitic carbon are remarkably stable and behave differently as an analogous Co-Fe catalyst supported on TiO2.

Porous Graphitic Carbons Containing Nitrogen by Structuration of Chitosan with Pluronic P123.

Using Pluronic P123 as a structure-directing agent and chitosan as a carbon precursor, different porous carbons with remarkable morphologies such as orthohedra or spheres with diametrically opposite holes are obtained. These particles of micrometric size are constituted by the stacking of thin sheets (60 nm) that become increasingly bent in the opposite sense, concave in the upper and convex in the bottom hemispheres, as the chitosan proportion increases. TEM images, after dispersion of the particles by sonication, show that besides micrometric graphene sheets, the material is constituted by nanometric onion-like carbons. The morphology and structure of these porous carbons can be explained based on the ability of Pluronic P123 to undergo self-assembly in aqueous solution due to its amphoteric nature and the filmogenic properties of chitosan to coat Pluronic P123 nanoobjects undergoing structuration and becoming transformed into nitrogen-doped graphitic carbons. XPS analysis reveals the presence of nitrogen in their composition. These porous carbons exhibit a significant CO2 adsorption capacity of above 3 mmol g-1 under 100 kPa at 273 K attributable to their large specific surface area, ultraporosity, and the presence of basic N sites. In addition, the presence of dopant elements in the graphitic carbons opening the gap is responsible for the photocatalytic activity for H2 generation in the presence of sacrificial electron donors, reaching a H2 production of 63 µmol g-1 in 24 h.

Superior Electrocatalytic Activity of MoS2-Graphene as Superlattice.

Evidence by selected area diffraction patterns shows the successful preparation of large area (cm × cm) MoS2/graphene heterojunctions in coincidence of the MoS2 and graphene hexagons (superlattice). The electrodes of MoS2/graphene in superlattice configuration show improved catalytic activity for H2 and O2 evolution with smaller overpotential of +0.34 V for the overall water splitting when compared with analogous MoS2/graphene heterojunction with random stacking.