Validation of microwave acid digestion, diffusive gradients in thin-film preconcentration and inductively coupled plasma optical emission spectrometry methodology for the determination of REEs in natural zeolites.

The determination of rare earth element (REE) content in different natural minerals is of high interest due to their extensive use in modern and sustainable technologies. The REEs occurring in natural zeolites are specific to each deposit. This study presents the validation and evaluation of the measurement uncertainty for the determination of REEs (Ce, Dy, Er, Eu, Gd, La, Lu, Nd, Pr, Sm, Y, and Yb) in natural zeolites using microwave-assisted acid digestion and inductively coupled plasma optical emission spectrometry (ICP-OES) after diffusive gradients in thin-film preconcentration. A mixture of HNO3 : HCl : HF of 3 : 9 : 2 (v/v/v) and microwave digestion provided suitable recoveries for the analysis of two certified reference materials, CRM BCS-CRM 375/1 and CRM OREAS 460. Good linearity over the calibration range of 0-2 µg mL-1, with correlation coefficients of 0.9995-1.0000, was obtained for each REE by ICP-OES. The limits of quantification (LOQS), calculated considering the instrumental LOQs and the sample preparation by microwave digestion, were in the range of 0.20-0.60 mg kg-1. A supplementary step of preconcentration/matrix separation based on the passive sampling by diffusive gradients in thin-films (DGT) technique improved the LOQs by about 20 times after three days of passive accumulation, allowing the measurement of the concentrations of all studied REEs in natural zeolite samples. The proposed methodology is a suitable approach for the measurement of REEs at low concentrations in natural zeolite samples by ICP-OES, and it can be extended to other geological samples. The measurement uncertainty was calculated based on the validation data. The proposed method provides reliable results for the measurement of REEs in natural zeolites and was used to measure the specific concentrations of REEs in natural zeolite samples from three Romanian quarries. The REE concentration can be used as a fingerprint for each deposit.

A Novel Nanoporous Adsorbent for Pesticides Obtained from Biogenic Calcium Carbonate Derived from Waste Crab Shells.

A novel nanoporous adsorbent was obtained through the thermal treatment and chemical wash of the wasted crab shells (BC1) and characterized by various techniques. The structure of BC1 at the end of the treatments comprised a mixture of calcite and amorphous CaCO3, as evidenced by X-ray diffraction and Fourier transform infrared absorption. The BET surface area, BET pore volume, and pore diameter were 250.33 m2 g-1, 0.4 cm3 g-1, and <70 nm, respectively. The point of zero charge of BC1 was determined to be around pH 9. The prepared adsorbent was tested for its adsorption efficacy towards the neonicotinoid pesticide acetamiprid. The influence of pH (2-10), temperature (20-45 °C), adsorbent dose (0.2-1.2 g L-1), contact time (5-60 min), and initial pesticide concentration (10-60 mg L-1) on the adsorption process of acetamiprid on BC1 was studied. The adsorption capacity of BC1 was 17.8 mg g-1 under optimum conditions (i.e., 20 mg L-1 initial acetamiprid concentration, pH 8, 1 g L-1 adsorbent dose, 25 °C, and 15 min contact time). The equilibrium data obtained from the adsorption experiment fitted well with the Langmuir isotherm model. We developed an effective nanoporous adsorbent for the recycling of crab shells which can be applied on site with minimal laboratory infrastructure according to local needs.

The gut microbiome mediates adaptation to scarce food in Coleoptera.

Beetles are ubiquitous cave invertebrates worldwide that adapted to scarce subterranean resources when they colonized caves. Here, we investigated the potential role of gut microbiota in the adaptation of beetles to caves from different climatic regions of the Carpathians. The beetles' microbiota was host-specific, reflecting phylogenetic and nutritional adaptation. The microbial community structure further resolved conspecific beetles by caves suggesting microbiota-host coevolution and influences by local environmental factors. The detritivore species hosted a variety of bacteria known to decompose and ferment organic matter, suggesting turnover and host cooperative digestion of the sedimentary microbiota and allochthonous-derived nutrients. The cave Carabidae, with strong mandibula, adapted to predation and scavenging of animal and plant remains, had distinct microbiota dominated by symbiotic lineages Spiroplasma or Wolbachia. All beetles had relatively high levels of fermentative Carnobacterium and Vagococcus involved in lipid accumulation and a reduction of metabolic activity, and both features characterize adaptation to caves.

Assessment of mercury bioavailability in garden soils around a former nonferrous metal mining area using DGT, accumulation in vegetables, and implications for health risk.

Mercury (Hg) is a toxic, non-essential element for living organisms, frequently present in high concentrations in soils from industrial areas. The total, dissolved, and labile Hg concentrations in garden soils and their accumulation in edible vegetables (onion, garlic, lettuce, and parsley) grown on contaminated soils in localities situated a former mining area were evaluated. The labile Hg fraction was estimated by diffusive gradient in thin films (DGT). The soil-to-vegetable transfer factors, as well as the health risk by exposure to Hg, were calculated based on the labile Hg concentration in soil. The total Hg concentration in soil varied widely (0.11-3.77 mg kg-1), Hg in soil solution ranged between 2.14 and 20.2 µg L-1 and labile Hg between 1.13 and 18.6 µg L-1. About 36-96% (84% on average) of the Hg concentration in soil solution was found in labile form. Multivariate analysis revealed significant correlations between the labile Hg concentration in soil and Hg accumulated in vegetables. The hazard indices showed that, although the study area is affected by legacy pollution, exposure to soil and consumption of locally grown vegetables do not pose health risks.

Environmental Drivers of the Moonmilk Microbiome Diversity in Some Temperate and Tropical Caves.

Moonmilk is a cave deposit that was used for medical and cosmetic purposes and has lately raised interest for its antimicrobial potential. We studied five moonmilk samples from four caves with different microclimatic conditions, two temperate in north-western and northern Romania (Ferice, Fața Apei, and Izvorul Taușoarelor caves) and one tropical in Minas Gerais, Brazil (Nestor Cave). The physicochemical and mineralogical analyses confirmed the presence of calcite and dolomite as the main phase in the moonmilk. A 16S rRNA gene-based metabarcoding approach showed the most abundant bacteria phyla Proteobacteria, GAL15, Actinobacteriota, and Acidobacteriota. The investigated caves differed in the dominant orders of bacteria, with the highest distance between the Romanian and Nestor Cave samples. Climate and, implicitly, the soil microbiome can be responsible for some differences we found between all the samples. However, other factors can be involved in shaping the moonmilk microbiome, as differences were found between samples in the same cave (Ferice). In our five moonmilk samples, 1 phylum, 70 orders (~ 36%), and 252 genera (~ 47%) were unclassified, which hints at the great potential of cave microorganisms for future uses.

Developing Innovative Cement Composites Containing Vine Shoot Waste and Superplasticizers.

The expansion of the construction industry requires large quantities of construction materials; therefore, the utilization of alternative raw materials that reduce the environmental impact and enhance the quality of the construction materials has received increasing interest. The comparative performance of 1% Dynamon SR3 or Dynamon SR41 superplasticizers on the properties of cement paste with 1 wt.% vine shoot waste addition (VSW) was investigated after 28 days using Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), and solid-state 27Al and 29Si nuclear magnetic resonance (NMR) spectroscopy. VSW does not delay the formation of calcium hydroxide and C-S-H and a slight decrease of the -OH band in samples containing superplasticizers, suggesting that free lime is converted to carbonates. The highest degree of crystallinity was remarked for the samples with superplasticizers. The structure of the cement paste with VSW and superplasticizers was corroborated with mechanical properties, showing increased strength in using VSW and superplasticizers. The results showed that adding 1% VSW and superplasticizers does not change the performance of the cement paste but reduces the water-cement ratio. The combination of VSW and superplasticizers led to cement composite with improved structural and mechanical properties suitable for construction.

A Strategy for Tuning the Structure, Morphology, and Magnetic Properties of MnFe2O4/SiO2 Ceramic Nanocomposites via Mono-, Di-, and Trivalent Metal Ion Doping and Annealing.

This work presents the effect of monovalent (Ag+, Na+), divalent (Ca2+, Cd2+), and trivalent (La3+) metal ion doping and annealing temperature (500, 800, and 1200 °C) on the structure, morphology, and magnetic properties of MnFe2O4/SiO2 ceramic nanocomposites synthesized via sol-gel method. Fourier-transform infrared spectroscopy confirms the embedding of undoped and doped MnFe2O4 nanoparticles in the SiO2 matrix at all annealing temperatures. In all cases, the X-ray diffraction (XRD) confirms the formation of MnFe2O4. In the case of undoped, di-, and trivalent metal-ion-doped gels annealed at 1200 °C, three crystalline phases (cristobalite, quartz, and tridymite) belonging to the SiO2 matrix are observed. Doping with mono- and trivalent ions enhances the nanocomposite's structure by forming single-phase MnFe2O4 at low annealing temperatures (500 and 800 °C), while doping with divalent ions and high annealing temperature (1200 °C) results in additional crystalline phases. Atomic force microscopy (AFM) reveals spherical ferrite particles coated by an amorphous layer. The AFM images showed spherical particles formed due to the thermal treatment. The structural parameters calculated by XRD (crystallite size, crystallinity, lattice constant, unit cell volume, hopping length, density, and porosity) and AFM (particle size, powder surface area, and thickness of coating layer), as well as the magnetic parameters (saturation magnetization, remanent magnetization, coercivity, and anisotropy constant), are contingent on the doping ion and annealing temperature. By doping, the saturation magnetization and magnetocrystalline anisotropy decrease for gels annealed at 800 °C, but increase for gels annealed at 1200 °C, while the remanent magnetization and coercivity decrease by doping at both annealing temperatures (800 and 1200 °C).

Impact of Low Lithium Concentrations on the Fatty Acids and Elemental Composition of Salvinia natans.

The photosynthetic pigments, protein, macro and microelements concentrations, and fatty acids composition of Salvinia natans, a free-floating aquatic plant, were analyzed after exposure to Hoagland nutrient solution containing 1, 3, and 5 mg/L Li. The Li content of Salvinia natans grew exponentially with the Li concentration in the Hoagland nutrient solution. The exposure to Li did not induce significant changes in Na, Mg, K, Cu, and Zn content but enhanced the Ba, Cr, Mn, Ni and Mo absorption in Salvinia natans. The most abundant fatty acids determined in oils extracted from Salvinia natans were C16:0, C18:3(n6), C18:2(n6), and C18:3(n3). The photosynthetic pigments did not change significantly after exposure to Li. In contrast, chlorophyll and protein content decreased, whilst monounsaturated and polyunsaturated fatty acids content increased after the exposure to 1 mg/L Li. The results indicated that Salvinia natans exposed to low Li concentrations may be a good source of minerals, omega 6 and omega 3.

Screening of Mono-, Di- and Trivalent Cationic Dopants for the Enhancement of Thermal Behavior, Kinetics, Structural, Morphological, Surface and Magnetic Properties of CoFe2O4-SiO2 Nanocomposites.

CoFe2O4 is a promising functional material for various applications. The impact of doping with different cations (Ag+, Na+, Ca2+, Cd2+, and La3+) on the structural, thermal, kinetics, morphological, surface, and magnetic properties of CoFe2O4 nanoparticles synthesized via the sol-gel method and calcined at 400, 700 and 1000 °C is investigated. The thermal behavior of reactants during the synthesis process reveals the formation of metallic succinates up to 200 °C and their decomposition into metal oxides that further react and form the ferrites. The rate constant of succinates' decomposition into ferrites calculated using the isotherms at 150, 200, 250, and 300 °C decrease with increasing temperature and depend on the doping cation. By calcination at low temperatures, single-phase ferrites with low crystallinity were observed, while at 1000 °C, the well-crystallized ferrites were accompanied by crystalline phases of the silica matrix (cristobalite and quartz). The atomic force microscopy images reveal spherical ferrite particles covered by an amorphous phase, the particle size, powder surface area, and coating thickness contingent on the doping ion and calcination temperature. The structural parameters estimated via X-ray diffraction (crystallite size, relative crystallinity, lattice parameter, unit cell volume, hopping length, density) and the magnetic parameters (saturation magnetization, remanent magnetization, magnetic moment per formula unit, coercivity, and anisotropy constant) depend on the doping ion and calcination temperature.

Karst spring microbiome: Diversity, core taxa, and community response to pathogens and antibiotic resistance gene contamination.

Karst aquifers are important water resources for drinking water supplies worldwide. Although they are susceptible to anthropogenic contamination due to their high permeability, there is a lack of detailed knowledge on the stable core microbiome and how contamination may affect these communities. In this study, eight karst springs (distributed across three different regions in Romania) were sampled seasonally for one year. The core microbiota was analysed by 16S rRNA gene amplicon sequencing. To identify bacteria carrying antibiotic resistance genes and mobile genetic elements, an innovative method was applied, consisting of high-throughput antibiotic resistance gene quantification performed on potential pathogen colonies cultivated on Compact Dry™ plates. A taxonomically stable bacterial community consisting of Pseudomonadota, Bacteroidota, and Actinomycetota was revealed. Core analysis reaffirmed these results and revealed primarily freshwater-dwelling, psychrophilic/psychrotolerant species affiliated to Rhodoferax, Flavobacterium, and Pseudomonas genera. Both sequencing and cultivation methods indicated that more than half of the springs were contaminated with faecal bacteria and pathogens. These samples contained high levels of sulfonamide, macrolide, lincosamide and streptogramins B, and trimethoprim resistance genes spread primarily by transposase and insertion sequences. Differential abundance analysis found Synergistota, Mycoplasmatota, and Chlamydiota as suitable candidates for pollution monitoring in karst springs. This is the first study highlighting the applicability of a combined approach based on high-throughput SmartChip™ antibiotic resistance gene quantification and Compact Dry™ pathogen cultivation for estimating microbial contaminants in karst springs and other challenging low biomass environments.

Subterranean transport of microplastics as evidenced in karst springs and their characterization using Raman spectroscopy.

The increasing use of plastic materials has led to accumulation of large amounts of plastic waste in environment and a global challenge to be tackled with. The natural process of macro-plastics aging generates a multitude of secondary microplastic fragments accumulating in all areas of the planet. The pollution with microplastics of large water bodies, such as rivers, seas and oceans was already proven, but the presence of microplastics even in karst spring water was not reported yet. In this study, Raman micro-spectroscopy was used to confirm the presence of microplastics in the spring water samples collected from two rural karst springs in the Apuseni Mountains (Țarina and Josani), North-Western Romania. Two sets of water samples of 1000 L collected in spring time 2021 and one in autumn 2021 were filtered and analyzed. Using the Python programming language and combining two separate Raman databases, one for plastics and the other for pigments, we established a customized database to unambiguously identify the type of plastic and pigment present in the discovered micro-fragments. The generated reference pigment-plastic spectra were compared to those of potential microplastics found on filters and Pearson's coefficient was used to measure the level of similarity. The presence of microplastics in karst spring waters was confirmed and a quantitative estimation expressed as number of fragments or fibers per liter was 0.034 in Josani and 0.06 in Țarina karst spring. Five months later sampling (autumn 2021) revealed 0.05 microplastics per liter. The spectral results revealed that most microplastics found were dominated by polyethylene terephthalate (PET), followed by polypropylene and interestingly, abundant blue micro-fragments were identified according to their copper phthalocyanine pigments (pigment Blue 15) or indigo carmine (pigment Blue 63) characteristic spectral fingerprints, which surpassed the inherent spectral background level characteristic for the Raman spectra of naturally contaminated waste micro-samples. Their origin in mountain karst spring waters and potential decrease in time is discussed.

The gut microbiome mediates adaptation to scarce food in Coleoptera.

Beetles are ubiquitous cave invertebrates worldwide that adapted to scarce subterranean resources when they colonized caves. Here, we investigated the potential role of gut microbiota in the adaptation of beetles to caves from different climatic regions of the Carpathians. The beetles' microbiota was host-specific, reflecting phylogenetic and nutritional adaptation. The microbial community structure further resolved conspecific beetles by caves suggesting microbiota-host coevolution and influences by local environmental factors. The detritivore species hosted a variety of bacteria known to decompose and ferment organic matter, suggesting turnover and host cooperative digestion of the sedimentary microbiota and allochthonous-derived nutrients. The cave Carabidae, with strong mandibulae adapted to predation and scavenging of animal and plant remains, had distinct microbiota dominated by symbiotic lineages Spiroplasma or Wolbachia . All beetles had relatively high levels of fermentative Carnobacterium and Vagococcus involved in lipid accumulation and a reduction of metabolic activity, and both features characterize adaptation to caves.

Diversity, distribution and organic substrates preferences of microbial communities of a low anthropic activity cave in North-Western Romania.

Introduction: Karst caves are characterized by relatively constant temperature, lack of light, high humidity, and low nutrients availability. The diversity and functionality of the microorganisms dwelling in caves micro-habitats are yet underexplored. Therefore, in-depth investigations of these ecosystems aid in enlarging our understanding of the microbial interactions and microbially driven biogeochemical cycles. Here, we aimed at evaluating the diversity, abundance, distribution, and organic substrate preferences of microbial communities from Peștera cu Apa din Valea Leșului (Leșu Cave) located in the Apuseni Mountains (North-Western Romania). Materials and Methods: To achieve this goal, we employed 16S rRNA gene amplicon sequencing and community-level physiological profiling (CLPP) paralleled by the assessment of environmental parameters of cave sediments and water. Results and Discussion: Pseudomonadota (synonym Proteobacteria) was the most prevalent phylum detected across all samples whereas the abundance detected at order level varied among sites and between water and sediment samples. Despite the general similarity at the phylum-level in Leșu Cave across the sampled area, the results obtained in this study suggest that specific sites drive bacterial community at the order-level, perhaps sustaining the enrichment of unique bacterial populations due to microenvironmental conditions. For most of the dominant orders the distribution pattern showed a positive correlation with C-sources such as putrescine, γ-amino butyric acid, and D-malic acid, while particular cases were positively correlated with polymers (Tween 40, Tween 80 and α-cyclodextrin), carbohydrates (α-D-lactose, i-erythritol, D-mannitol) and most of the carboxylic and ketonic acids. Physicochemical analysis reveals that sediments are geochemically distinct, with increased concentration of Ca, Fe, Al, Mg, Na and K, whereas water showed low nitrate concentration. Our PCA indicated the clustering of different dominant orders with Mg, As, P, Fe, and Cr. This information serves as a starting point for further studies in elucidating the links between the taxonomic and functional diversity of subterranean microbial communities.

Influence of SiO2 Embedding on the Structure, Morphology, Thermal, and Magnetic Properties of Co0.4Zn0.4Ni0.2Fe2O4 Particles.

(Co0.4Zn0.4Ni0.2Fe2O4)α(SiO2)(100-α) samples obtained by embedding Co0.4Zn0.4Ni0.2Fe2O4 nanoparticles in SiO2 in various proportions were synthesized by sol-gel process and characterized using thermal analysis, Fourier-transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, inductively coupled plasma optical emission spectrometry, and magnetic measurements. Poorly crystalline Co-Zn-Ni ferrite at low annealing temperatures (500 °C) and highly crystalline Co-Zn-Ni ferrite together with traces of crystalline Fe2SiO4 (800 °C) and SiO2 (tridymite and cristobalite) (1200 °C) were obtained. At 1200 °C, large spherical particles with size increasing with the ferrite content (36-120 nm) were obtained. Specific surface area increased with the SiO2 content and decreased with the annealing temperature above 500 °C. Magnetic properties were enhanced with the increase in ferrite content and annealing temperature.

Mobile measurements of black carbon: Comparison of normal traffic with reduced traffic conditions during COVID-19 lock-down.

A mobile monitoring campaign was conducted (by bicycle) to assess the black carbon (BC) concentrations in Cluj-Napoca city, Romania, in 2020, before, during and after COVID-19 lock-down. Over the entire study period, the BC concentrations ranged between 1.0 and 25.9 µg/m³ (averaged per street section and period characterized by different traffic conditions). Marked spatial and temporal differences were observed. Observed differences in BC concentrations between locations are attributed to traffic intensities, with average BC concentrations, under normal circumstances, of 6.6-14.3 µg/m³ at roads with high to intense traffic, compared to 2.8-3.1 µg/m³ at areas with reduced traffic, such as residential areas, parks and pedestrian streets. The COVID-19 measures impacted traffic volumes, and hence average BC concentrations decreased from 5.9 µg/m³ to 3.0 µg/m³ during lock-down and in a lower extent to 3.4 µg/m³ and 4.4 µg/m³ in post-lockdown periods with reduced and more normalized traffic. Two approaches to account for variations in background concentrations when comparing different situations in time are assessed. Subtracting background concentrations that are measured at background sites along the monitoring route is an appropriate method to assess spatio-temporal differences in concentrations. A reduction of about 1-2 µg/m³ was observed for the streets with low to medium traffic, and up to 6 µg/m³ at high traffic locations under lockdown. The approach presented in this study, using mobile measurements, is useful to understand the personal exposure to BC along the roads in different seasons and the influence of traffic reduction on BC pollution during prolonged restrictions. All these will support policymakers to reduce pollution and achieve EU directives targets and WHO recommendations.

Impact of Ni Content on the Structure and Sonophotocatalytic Activity of Ni-Zn-Co Ferrite Nanoparticles.

The structure, morphology, and sonophotocatalytic activity of Ni-Zn-Co ferrite nanoparticles, embedded in a SiO2 matrix and produced by a modified sol-gel method, followed by thermal treatment, were investigated. The thermal analysis confirmed the formation of metal succinate precursors up to 200 °C, their decomposition to metal oxides and the formation of Ni-Zn-Co ferrites up to 500 °C. The crystalline phases, crystallite size and lattice parameter were determined based on X-ray diffraction patterns. Transmission electron microscopy revealed the shape, size, and distribution pattern of the ferrite nanoparticles. The particle sizes ranged between 34 and 40 nm. All the samples showed optical responses in the visible range. The best sonophotocatalytic activity against the rhodamine B solution under visible irradiation was obtained for Ni0.3Zn0.3Co0.4Fe2O4@SiO2.

High-Pressure Supercritical CO2 Pretreatment of Apple Orchard Waste for Carbohydrates Production Using Response Surface Methodology and Method Uncertainty Evaluation.

This study's objective was to separate cellulose, hemicellulose, and lignin after high-pressure supercritical carbon dioxide pretreatment for further valorization. The study investigated the supercritical carbon dioxide pretreatment of apple orchard waste at temperatures of 160-200 °C, for 15-45 min, at a pressure of 10 MPa. Response Surface Methodology (RSM) was used to optimize the supercritical process and to improve its efficiency. The change of functional groups during different pretreatment conditions was examined by Fourier transform infrared (FTIR) spectroscopy. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) confirmed the structural changes in the biomass structure before and after pretreatment. A new ultra-high performance liquid chromatography (UHPLC) coupled with an evaporative light scattering detector (ELSD) method was developed and validated for the determination of carbohydrates in the liquid fraction that resulted after pretreatment. The estimated uncertainty of the method ranged from 16.9 to 20.8%. The pre-treatment of high-pressure supercritical CO2 appears to be an effective and promising technique for the recovery of sugars and secondary by-products without the use of toxic solvents.

Analysis of Volatile Compounds, Composition, and Thermal Behavior of Coffee Beans According to Variety and Roasting Intensity.

This study aimed to investigate the ways in which the thermal behavior, composition, and volatile compound contents of roasted coffee beans depend on variety and roasting intensity. The thermal analysis revealed various transformations in coffee composition, namely, drying, water loss, and decomposition of polysaccharides, lipids, amino acids, and proteins. The results showed that volatile compounds are released differently in coffee depending on coffee type and degree of roasting. The most abundant volatile compounds present in the samples were 2-butanone, furan, 2-methylfuran, methyl formate, 2.3-pentanedione, methylpyrazine, acetic acid, furfural, 5-methyl furfural, and 2-furanmethanol. The total polyphenol contents ranged between 13.3 and 18.9 g gallic acid/kg, being slightly higher in Robusta than in Arabica varieties and in more intensely roasted beans compared to medium-roasted beans. The Robusta variety has higher mineral contents than Arabica, and the contents of most minerals (K, Ca, Mg, Fe, Cu, P, N, and S) increased with roasting intensity. Discrimination between coffee varieties and roasting intensities is possible based on mineral and polyphenol contents.

Lithium Accumulation in Salvinia natans Free-Floating Aquatic Plant.

The new context of the intensive use of lithium-based batteries led to increased production of Li and Li-containing wastes. All these activities are potential sources of environmental pollution with Li. However, the negative impact of Li on ecosystems, its specific role in the plants' development, uptake mechanism, and response to the induced stress are not fully understood. In this sense, the Li uptake and changes induced by Li exposure in the major and trace element contents, photosynthetic pigments, antioxidant activity, and elemental composition of Salvinia natans were also investigated. The results showed that Salvinia natans grown in Li-enriched nutrient solutions accumulated much higher Li contents than those grown in spring waters with a low Li content. However, the Li bioaccumulation factor in Salvinia natans grown in Li-enriched nutrient solutions was lower (13.3-29.5) than in spring waters (13.0-42.2). The plants exposed to high Li contents showed a decrease in their K and photosynthetic pigments content, while their total antioxidant activity did not change substantially.

Competition-cooperation in the chemoautotrophic ecosystem of Movile Cave: first metagenomic approach on sediments.

BACKGROUND: Movile Cave (SE Romania) is a chemoautotrophically-based ecosystem fed by hydrogen sulfide-rich groundwater serving as a primary energy source analogous to the deep-sea hydrothermal ecosystems. Our current understanding of Movile Cave microbiology has been confined to the sulfidic water and its proximity, as most studies focused on the water-floating microbial mat and planktonic accumulations likely acting as the primary production powerhouse of this unique subterranean ecosystem. By employing comprehensive genomic-resolved metagenomics, we questioned the spatial variation, chemoautotrophic abilities, ecological interactions and trophic roles of Movile Cave's microbiome thriving beyond the sulfidic-rich water. RESULTS: A customized bioinformatics pipeline led to the recovery of 106 high-quality metagenome-assembled genomes from 7 cave sediment metagenomes. Assemblies' taxonomy spanned 19 bacterial and three archaeal phyla with Acidobacteriota, Chloroflexota, Proteobacteria, Planctomycetota, Ca. Patescibacteria, Thermoproteota, Methylomirabilota, and Ca. Zixibacteria as prevalent phyla. Functional gene analyses predicted the presence of CO2 fixation, methanotrophy, sulfur and ammonia oxidation in the explored sediments. Species Metabolic Coupling Analysis of metagenome-scale metabolic models revealed the highest competition-cooperation interactions in the sediments collected away from the water. Simulated metabolic interactions indicated autotrophs and methanotrophs as major donors of metabolites in the sediment communities. Cross-feeding dependencies were assumed only towards 'currency' molecules and inorganic compounds (O2, PO43-, H+, Fe2+, Cu2+) in the water proximity sediment, whereas hydrogen sulfide and methanol were assumedly traded exclusively among distant gallery communities. CONCLUSIONS: These findings suggest that the primary production potential of Movile Cave expands way beyond its hydrothermal waters, enhancing our understanding of the functioning and ecological interactions within chemolithoautotrophically-based subterranean ecosystems.