Microplastic assessment in remote and high mountain lakes of Gilgit Baltistan, Pakistan.

Microplastic (MP) pollution is a critical environmental challenge worldwide, however limited research is reported in remote lakes of Pakistan. This study assessed MPs (>5 mm) prevalence, distribution and risk perspective in water and sediment of eight remote and high-altitude lakes (>1500 m above sea level) of Gilgit Baltistan, Pakistan. The lakes exhibited an average abundance of 152.6 ± 104.6 to 12.1 ± 7 MP/kg of dry sediments and 2 ± 0.9 to 17.1 ± 17.2 MP/L of surface water. MPs <200 µm dominated in both matrices. Surface water predominantly contained polyester and polypropylene, while polypropylene and polyethylene dominated in sediments. The gradient of elevation did not show any pronounced impact on the fiber loading or MP count in both matrices. Backward air mass trajectory revealed that air masses vastly travelled from western-Asia, Arabian sea and Bay of Bengal with an average transmission distance of 2500-3500 km (500 m a.s.l) that can be a potential deposition MP source in the area. Pollution Load Index of the lakes were >1 exhibiting pollution. All other lakes except Batura and Borith manifested a moderate hazard index. Naltar lake along with aforementioned two lakes also manifested high polymer toxicity. Further research should emphasize understanding the mechanisms and biotic interactions in high-mountain ecosystems.

Application of Silk Light Chain on a Graphene Composite Surface: A Molecular Dynamics and Electrochemical Experiment.

The surface functionalization of pristine graphene (PG) with beneficial biocomposites is important for biomedical and tissue engineering. This study introduces silk light chain as novel biocomposites to increase the biocompatibility of PG. We explored the supramolecular structures of the silk heavy and light chains. Through molecular dynamics, we compared and analyzed the structural effects and binding mechanisms of these domains in their interaction with PG. Our results highlighted a significant hydrophobic interaction between the silk light chain and PG, without structural collapse. The supramolecular structure of the silk light chain was identified by analyzing the amino acids bound to PG. Moreover, using the silk light chain, the hydrophobic surface of PG has changed to a hydrophilic surface, and the silk light-chain-PG electron transfer rate was evaluated for the graphene congeners: graphene oxide (GO) and reduced graphene oxide. Therefore, we are confident that the dispersibility and biocompatibility of PG can be increased using silk light chains, which will contribute to broadening the field of application of PG-based materials.

Interface Engineering by Unsubstituted Pristine Nickel Phthalocyanine as Hole Transport Material for Efficient and Stable Perovskite Solar Cells.

Lead halide perovskite solar cells (PSCs) have been rapidly developed in the past decade. With the development of a PSC, interface engineering plays an increasingly important role in maximizing device performance and long-term stability. We report a simple and effective interface engineering method for achieving improvement of PSCs up to 20% by employing unsubstituted pristine nickel phthalocyanine (NiPc). Thermal annealing of NiPc improves the interface between NiPc and perovskite because of the incorporation of NiPc molecules into the perovskite grain boundaries, which creates improvements in hole extraction from the perovskite absorber layer, as evidenced by time-resolved photoluminescence measurements. This significantly improves the charge transfer and collection efficiency, which are closely related to the improvement of the interface between perovskite and NiPc.

The microbial community structure and nitrogen cycle of high-altitude pristine saline lakes on the Qinghai-Tibetan plateau.

The nitrogen (N) cycle is the foundation of the biogeochemistry on Earth and plays a crucial role in global climate stability. It is one of the most important nutrient cycles in high-altitude lakes. The biogeochemistry of nitrogen is almost entirely dependent on redox reactions mediated by microorganisms. However, the nitrogen cycling of microbial communities in the high-altitude saline lakes of the Qinghai-Tibet Plateau (QTP), the world's "third pole" has not been investigated extensively. In this study, we used a metagenomic approach to investigate the microbial communities in four high-altitude pristine saline lakes in the Altun mountain on the QTP. We observed that Proteobacteria, Bacteroidota, and Actinobacteriota were dominant in these lakes. We reconstructed 1,593 bacterial MAGs and 8 archaeal MAGs, 1,060 of which were found to contain nitrogen cycle related genes. Our analysis revealed that nitrite reduction, nitrogen fixation, and assimilatory nitrate reduction processes might be active in the lakes. Denitrification might be a major mechanism driving the potential nitrogen loss, while nitrification might be inactive. A wide variety of microorganisms in the lake, dominated by Proteobacteria, participate together in the nitrogen cycle. The prevalence of the dominant taxon Yoonia in these lakes may be attributed to its well-established nitrogen functions and the coupled proton dynamics. This study is the first to systematically investigate the structure and nitrogen function of the microbial community in the high-altitude pristine saline lakes in the Altun mountain on the QTP. As such, it contributes to a better comprehension of biogeochemistry of high-altitude saline lakes.

How loss of nature through clear-cutting forestry affects well-being.

The United Nations declares that the global degradation of ecosystems represents a danger to human health. Deterioration of forests is one of several threats against the natural systems. The aim of this exploratory study was to investigate people's experiences with clear-cutting and how it had affected their health and well-being. Qualitative data from six people who valued forest ecosystems were collected through semi-structured interviews and analyzed in accordance with Graneheim and Lundman's qualitative content analysis (Graneheim, U. H. and Lundman, B. (2004) Qualitative content analysis in nursing research: concepts, procedures and measures to achieve trustworthiness. Nurse Education Today, 24, 105-112). Clear-cutting was not regarded as an environment-friendly forestry method. The interviewees described emotional reactions such as grief and poor mental well-being when beloved forests were clear-felled. The grief was partly because of a personal loss of place and recreation area that was important for their physical and emotional well-being. Another part was grief on behalf of nature itself, that is, the loss of habitats of animals and plants and a worsening of the global climate. The interviewees held that emotions related to loss of nature were insufficiently communicated in public discourse. They felt powerless and unable to influence forestry because of what they experienced as an impenetrable industry. Clear-cutting of forests may result in poor well-being among people who value forest ecosystems. More focus on planetary health is needed, including healthy public policy promoting forest management that considers people's need for nature experiences and possible ecological grief when forests are totally and abruptly cleared.

Phonon transport in vacancy induced defective stanene/hBN van der Waals heterostructure.

In this study, Non-Equilibrium Molecular Dynamics (NEMD) simulation is employed to investigate the phonon thermal conductivity (PTC) of Sn/hBN van der Waals heterostructures with different vacancy-induced defects. We deliberately introduce three types of vacancies in Sn/hBN bilayer point vacancies, bivacancies, and edge vacancies at various concentrations ranging from 0.25% to 2%, to examine their effects on PTC across temperatures from 100 K to 600 K. The key findings of our work are (i) PTC declines monotonically with increasing vacancy concentration for all types of vacancies, with a maximum reduction of ∼62% observed at room temperature compared to its pristine form. (ii) The position of defects has an impact on PTC, with a larger decrease observed when defects are present in the hBN layer and a smaller decrease when defects are in the Sn layer. (iii) The type of vacancy also influences PTC, with point vacancies causing the most substantial reduction, followed by bivacancies, and edge vacancies having the least effect. A 2% defect concentration results in a ∼62% decrease in PTC for point vacancies, ∼51% for bivacancies, and ∼32% for edge vacancies. (iv) Finally, our results indicate that for a given defect concentration, PTC decreases as temperature increases. The impact of temperature on thermal conductivity is less pronounced compared to the effect of vacancies for the defective Sn/hBN bilayer. The presence of vacancies and elevated temperatures enhance phonon-defect and phonon-phonon scattering, leading to changes in the phonon density of states (PDOS) profile and the distribution of phonons across different frequencies of Sn/hBN bilayer, thus affecting its thermal conductivity. This work offers new insights into the thermal behavior of vacancy-filled Sn/hBN heterostructures, suggesting potential pathways for modulating thermal conductivity in bilayer van der Waals heterostructures for applications in thermoelectric, optoelectronics, and nanoelectronics in future.

Influence of algal-extracellular polymeric substances (EPS) on the pristine and combined toxicity of TiO2 NPs and PSNPs in Artemia salina: Eco-corona enhances the toxic effects.

The study on the influence of Natural Organic Matter (NOM) over the individual and combined effects of different nanomaterials on marine species is pertinent. The current study explores the role of Extracellular Polymeric Substances (EPS) in influencing the individual and combined toxic effects of polystyrene nanoplastics (PSNPs) viz. aminated (NH2-PSNPs), carboxylated (COOH-PSNPs), and plain PSNPs and TiO2 NPs in the marine crustacean, Artemia salina. A. salina was interacted with pristine PSNPs, pristine TiO2 NPs, EPS incubated PSNPs, EPS incubated TiO2 NPs, binary mixture of PSNPs and TiO2 NPs, and EPS adsorbed binary mixture of PSNPs and TiO2 NPs for 48 h. The present study proves that, when compared to the pristine toxicity of PSNPs and TiO2 NPs, the coexposure of TiO2 NPs with PSNPs resulted in increased toxicity. The adsorption of algal EPS on the NMs (both in their pristine and combined forms) significantly increased the toxic nature of the NMs against A. salina. It was observed that with an increase in the hydrodynamic diameter of the particles, the mortality, oxidative stress, and ingestion of the NMs by A. salina increased. The uptake of Ti by A. salina from 8 mg/L TiO2 NPs, EPS adsorbed 8 mg/L TiO2 NPs, 8 mg/L TiO2 NPs + NH2-PSNPs and the EPS adsorbed mixture of 8 mg/L TiO2 NPs, 8 mg/L TiO2 NPs + NH2-PSNPs was observed to be 0.043, 0.047, 0.186, and 0.307 mg/g of A. salina. The adsorption of algal EPS on the NMs (both in their pristine and combined forms) significantly increased the toxic nature of the NMs against A. salina. The major outcomes from the current study highlight the role of EPS in exacerbating the toxicity of NMs in marine crustaceans.

Environmentally relevant concentrations of microplastics from agricultural mulch and cadmium negatively impact earthworms by triggering neurotoxicity and disrupting homeostasis.

Recent research has highlighted the ecological risk posed by microplastics (MPs) from mulching film and heavy metals to soil organisms. However, most studies overlooked real environmental levels of MPs and heavy metals. To address this gap, pristine and aged polyethylene (PE) mulching film-derived MPs (PMPs, 500 mg/kg; AMPs, 500 mg/kg) were combined with cadmium (Cd, 0.5 mg/kg) to assess the acute toxicity to earthworms and investigate associated molecular mechanisms (oxidative stress, osmoregulation pressure, gut microbiota, and metabolic responses) at environmentally relevant concentrations. Compared to Cd alone and Cd + PMPs treatments (11.15 ± 4.19 items/g), Cd + AMPs treatment resulted in higher MPs bioaccumulation (23.73 ± 13.14 items/g), more severe tissue lesions, and increased cell membrane osmotic pressure in earthworms' intestines. Cd + AMPs induced neurotoxicity through elevated levels of glutamate and acetylcholinesterase. Earthworm intestines (0.98 ± 0.49 to 3.33 ± 0.37 mg/kg) exhibited significantly higher Cd content than soils (0.19 ± 0.01 to 0.51 ± 0.06 mg/kg) and casts (0.15 ± 0.01 to 0.25 ± 0.05 mg/kg), indicating PE-MPs facilitated Cd transport in earthworms' bodies. Metabolomic analysis showed Cd + AMPs exposure depleted energy and nucleotide metabolites, disrupted cell homeostasis more profoundly than Cd and Cd + PMPs treatments. Overall, co-exposure to AMPs + Cd induced more severe neurotoxicity and disruption of homeostasis in earthworm than Cd and PMPs + Cd treatments. Our study, using Cd and MPs with environmental relevance, underscores MPs' role in amplifying Cd accumulation and toxicity in earthworms.

Large Fermi surface in pristine kagome metal CsV3Sb5 and enhanced quasiparticle effective masses.

The kagome metal CsV[Formula: see text]Sb[Formula: see text] is an ideal platform to study the interplay between topology and electron correlation. To understand the fermiology of CsV[Formula: see text]Sb[Formula: see text], intensive quantum oscillation (QO) studies at ambient pressure have been conducted. However, due to the Fermi surface reconstruction by the complicated charge density wave (CDW) order, the QO spectrum is exceedingly complex, hindering a complete understanding of the fermiology. Here, we directly map the Fermi surface of the pristine CsV[Formula: see text]Sb[Formula: see text] by measuring Shubnikov-de Haas QOs up to 29 T under pressure, where the CDW order is completely suppressed. The QO spectrum of the pristine CsV[Formula: see text]Sb[Formula: see text] is significantly simpler than the one in the CDW phase, and the detected oscillation frequencies agree well with our density functional theory calculations. In particular, a frequency as large as 8,200 T is detected. Pressure-dependent QO studies further reveal a weak but noticeable enhancement of the quasiparticle effective masses on approaching the critical pressure where the CDW order disappears, hinting at the presence of quantum fluctuations. Our high-pressure QO results reveal the large, unreconstructed Fermi surface of CsV[Formula: see text]Sb[Formula: see text], paving the way to understanding the parent state of this intriguing metal in which the electrons can be organized into different ordered states.

Protective and Flame-Retardant Bifunctional Epoxy-Based Nanocomposite Coating by Intercomponent Synergy between Modified CaAl-LDH and rGO.

Extensive utilization in various settings poses extra requirements of coatings beyond just anticorrosion properties. Herein, 8-hydroxyquinoline (8-HQ) intercalated CaAl-based layered double hydroxide (CaAl-8HQ-LDH) was loaded on reduced GO (rGO) through a one-pot hydrothermal reaction, which was employed as the nanofiller endowing the epoxy (EP/CaAl-8HQ LDH@rGO) with excellent flame-retardancy while ensuring efficient protection for mild steel. Results of electrochemical impedance spectroscopy (EIS) demonstrated the durability of the EP/CaAl-8HQ LDH@rGO-coated specimen, with the impedance at the lowest frequency (|Z|0.01Hz) maintained as 1.84 × 1010 Ω cm2 after 120 days of immersion in a 3.5 wt % NaCl solution. Even for the scratched EP/CaAl-8HQ LDH@rGO system, only a slight decline in |Z|0.01Hz was observed during 180 h of exposure to the NaCl solution, indicating a self-healing feature supported by salt spray tests. UL-94 burning tests revealed the V-0 rating for EP/CaAl-8HQ LDH@rGO with improved thermostability. Strong physical barrier from two-dimensional rGO and the release of 8-HQ from LDH interlayers accounted for the anticorrosive and self-healing properties. However, O2-concentration dilution and charring-layer promotion governed the flame-retardant behavior of the nanocomposite coating. The intercomponent synergy of nanofillers achieved in this work may provide a useful reference for designing multifunctional coatings.

Pristine cobalt humic acid xerogels embedded with ultrafine cobalt sulfide for enhanced and stable lithium-ion storage.

The electrochemical performance of pristine metal-organic xerogels as anodes in lithium-ion batteries is reported for the first time. We propose a novel synthesis approach for the in situ generation of highly dispersed, ultrafine cobalt sulfide nanoparticles on humic acid gels (CoSHA). The CoS nanoparticles in CoSHA have an average diameter of approximately 3 nm. CoSHA electrodes demonstrate enhanced lithium storage capacity, delivering a capacity of 662 mAh g-1 at 0.1 A g-1. They also show stable long-term cycling performance, with no capacity decay after 900 cycles at 1.0 A g-1. Furthermore, our experiments indicate that the improved lithium-ion adsorption results from the oxygen-containing functional groups in humic acid and the ultrafine CoS active sites. This study offers a practical methodology for synthesizing ultrafine metal sulfides and new insights into using pristine gel-based electrodes for energy storage and conversion.

Shallow water foraminifera from Niue and Beveridge Reef (South Pacific): insights into ecological significance and ecosystem integrity.

Niue represents one of many important steppingstones facilitating the dispersal of marine organisms across the tropical Pacific Ocean. This study is part of a collaborative expedition involving National Geographic Pristine Seas, the government of Niue, Oceans 5, and the Pacific Community. We present the first survey documenting the species richness of foraminiferal communities in Niue and nearby Beveridge Reef and explore their significance for ecosystem integrity. A substantial portion (59%) of Niue's foraminiferal assemblages is Large Benthic Foraminifera (LBF), a symbiont-bearing group known as ecosystem engineers and indicators of coral reef regime shifts. LBF species reported here reflect the gradual decrease of tropical diversity from the Coral Triangle towards the central Pacific Ocean. Calcarinidae, an LBF family represented in this study by two species, is the easternmost ever recorded in published literature, and the biogeographical dispersal of this temperature-controlled group is of great importance to future global warming related studies. Foraminifera are an important component of beach development in Niue, with a close relationship between source and depositional zones. These essential ecological-sedimentary linkages highlight the importance of habitat conservation not only as a means to safeguard biodiversity, but also for its role in the island's physical framework.

Recent Advances in Pristine Iron Triad Metal-Organic Framework Cathodes for Alkali Metal-Ion Batteries.

Pristine iron triad metal-organic frameworks (MOFs), i.e., Fe-MOFs, Co-MOFs, Ni-MOFs, and heterometallic iron triad MOFs, are utilized as versatile and promising cathodes for alkali metal-ion batteries, owing to their distinctive structure characteristics, including modifiable and designable composition, multi-electron redox-active sites, exceptional porosity, and stable construction facilitating rapid ion diffusion. Notably, pristine iron triad MOFs cathodes have recently achieved significant milestones in electrochemical energy storage due to their exceptional electrochemical properties. Here, the recent advances in pristine iron triad MOFs cathodes for alkali metal-ion batteries are summarized. The redox reaction mechanisms and essential strategies to boost the electrochemical behaviors in associated electrochemical energy storage devices are also explored. Furthermore, insights into the future prospects related to pristine iron triad MOFs cathodes for lithium-ion, sodium-ion, and potassium-ion batteries are also delivered.

Risk implications induced by behaviors of artificial and pavement-generated TWPs in river water: Role of particle-self properties and incubation aging.

Here, we investigated the pristine properties of three typical tire wear particles (TWPs) and their aging properties after incubation in runoff (primary aging) and sewage (further aging), and captured the differences in the behavioral characteristics of nine TWPs in river water, with a view to paving the way for revealing the intrinsic mechanism of the hydroecological effects of TWPs. Our results highlight that the generation modes of three pristine tire wear particles (TWPs), stemming from typical tire and road wear processes-specifically, rolling friction (R-TWPs) and sliding friction (S-TWPs), alongside cryogenically milled tire treads (C-TWPs)-significantly impact their pristine physicochemical properties. This impact encompasses surface structure, particle size (D [4,3]: 8.5-121.3 µm), surface potential (-10.4 âˆ¼ -1.8 mV), contact angle (95.2-129.8°), density (1.09-1.75 kg/m3), etc., consequently, these differences significantly influence their migration capability and sorption capacity during the incubation and aging in runoff and sewage. Interestingly, after incubation and aging in the migrating aqueous phase, particularly with additional aging in sewage, not only do distinctions in the aforementioned physicochemical properties (namely, particle size (5.6-6.6 µm), surface potential (-18.4 âˆ¼ -18.1 mV), contact angle (124.5-125.4°), density (1.05-1.16 kg/m3)) among various types of TWPs diminish, but the environmental behaviors (encompassing, desorption capacity, aggregation kinetics, photochemical activity-formation of persistent free radicals, and exudation-derivative (6PPD-Quinone) of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine: 6PPD) exhibited by this array of TWPs demonstrate a remarkable coherence within the downstream river water. Concerningly, the aforementioned features of aquatic system behaviors appear to be predisposed towards exacerbating the heightened toxicity of TWPs, for example, the leaching concentration of 6PPD-Q increased by two to three times after aging, aligning with established precedents regarding the toxicological causes associated with the quinone derivatives of antioxidants in rubber contaminants.

Microplastics - Back to Reality: Impact of Pristine and Aged Microplastics in Soil on Earthworm Eisenia fetida under Environmentally Relevant Conditions.

Recently, studies have highlighted the potential danger for soil organisms posed by film-derived microplastics (MPs). However, the majority of those does not accurately reflect the field conditions and the degree of MP contamination that can be found in actual settings. To fill the gap between laboratory and field scenarios, the polyethylene (PE) plastic film was made into PE-MPs and aged. Toxicity and molecular mechanisms of pristine PE-MPs (PMPs) and aged PE-MPs (AMPs) with the concentration at 500 mg/kg of dry weight were determined after 14 days of exposure by measuring the oxidative stress, osmoregulation pressure, gut microbiota, and metabolic responses in earthworms under environmentally relevant conditions. Our research showed that, when compared to PMPs (13.13 ± 1.99 items/g), AMPs accumulated more (16.19 ± 8.47 items/g), caused more severe tissue lesions, and caused a higher increase of cell membrane osmotic pressure in earthworms' intestines. Furthermore, the proportion of probiotic bacteria Lactobacillus johnsonii in the gut bacterial communities was 24.26%, 23.26%, and 12.96%, while the proportion of pathogenic bacteria of the phylum Verrucomicrobia was 2.28%, 4.79%, and 10.39% in the control and PMP- and AMP-exposed earthworms, indicating that the decrease in number of probiotic bacteria and the increase in number of pathogenic bacteria were more pronounced in the gut of AMP- rather than PMP-exposed earthworms. Metabolomic analysis showed that AMP exposure reduced earthworm energy metabolites. Consequently, the constant need for energy may result in protein catabolism, which raises levels of some amino acids, disturbs normal cell homeostasis, causes changes of cell membrane osmolarity, and destroys the cell structure. Our studies showed that aged MPs, with the same characteristics as those found in the environment, have greater toxicity than pristine MPs. The results of this study broaden our understanding of the toxicological effects of MPs on soil organisms under environmentally relevant conditions.

Making of the "Pristine Vegetables": Soil-Transmitted Parasites and U.S. Military Procurement in Korea.

In the twenty-first century Korea, "Pristine Vegetables(청정채소)" refers to organic products grown without the use of pesticides and chemical fertilizers. However, the meaning of "Pristine" was radically different until 1970s. After the Korean War, the infection rate of intestinal parasite reached almost 100 percent in Korean population. Disruption in chemical fertilizers manufacturing pressured farmers to use night-soil, which was contaminated with parasite eggs, causing the vicious cycle of infection. At the same time, rapid urbanization increased the demands of fresh vegetables in the city, leading to a large amount of semi-urban agricultural practices. This was closely linked with the national economy; as most of Korean vegetable products were contaminated with parasites, they were deemed unsuitable for export. In 1957, US Army stationed in Seoul issued a guideline for producing local vegetables acceptable for US troop consumption. This gave rise to the concept of "Pristine Vegetables" that were free of any infectious materials. These practices continued well into the 1970s. Due to the lack of sewage treatment system, the waste of urban population provided necessary fertilizer for these farmers without much cost. In order to secure public health, the Korean government actively encouraged the use of chemical fertilizers, naming the vegetables "Pristine." This effort included the ban of night-soil in urban and semi-urban farms and the establishment of Pristine Vegetable Shops. However, the rapid decline of parasitic diseases in the population and the rising concerns of environmental pollutions reshaped Pristine Vegetables from chemical to organic in the 1980s. Thus, Pristine Vegetable in Korea during late twentieth century exemplifies rapid transformation of the urban environment, showing shifted concept of cleanness and contaminants among the public and policymakers, as well as acceptable risk of the urban environment in Korea.

Laboratory Studies about Microplastic Aging and Its Effects on the Adsorption of Chlorpyrifos.

The constant change in microplastics (MP) due to exposure to environmental conditions leads to physical and chemical changes that enhance their ability to transport other pollutants, increasing the concern about their widespread presence in the environment. This work aimed to simulate the aging process of six MP (polyamide 6, unplasticized polyvinyl chloride, low-density polyethylene, polystyrene, polyethylene-co-vinyl acetate, polypropylene) in freshwater and seawater ecosystems at laboratory scale and evaluate its effects through optical microscope observation, Fourier transform infrared spectroscopy-Attenuated Total Reflectance (FTIR-ATR), Raman spectroscopy, and thermal gravimetric analysis (TGA). Through a combined experimental study of aged MP, the degradation by UV interaction was evidenced by the appearance of new infrared bands in the FTIR spectra assigned to ketones and hydroxyl groups. While Raman analysis and microscope images reveal the appearance of pores, wrinkles, and roughness in the MP surfaces. Variations in the temperature of the maximum weight loss of the MP were observed in the TGA analysis. The adsorption of chlorpyrifos (CPF), a common pesticide widely used in agriculture, by the pristine and aged MP was also studied. The highest affinity for CPF was observed for pristine LDPE and the lowest for PP. The batch adsorption studies revealed an increase in adsorption capacity as a consequence of the aging process for both MP. These results proved that the weathering effects caused changes in the behavior of MP, namely in the interaction with other pollutants.

Pure Graphene Acts as an "Entropic Surfactant" at the Octanol-Water Interface.

Graphene oxide (GO) has proved itself as a nanomaterial capable of acting as a surfactant by lowering the interfacial tension of the oil-water interface due to its polar oxygen groups. However, the surfactant behavior of the pure graphene sheet─since prevention of edge oxidation in experimental setups is nontrivial─is still an unresolved issue in graphene research despite significant progress in the field in recent years. Here, we conduct both atomistic and coarse-grained simulations to demonstrate that─surprisingly─even pristine graphene, which only consists of hydrophobic carbon atoms, is attracted to the octanol-water interface and consequently reduces its surface tension by 2.3 kBT/nm2 or about 10 mN/m. Interestingly, the location of the free energy minimum is not precisely at the oil-water interface itself but is rather buried about two octanol layers into the octanol phase, being about 0.9 nm from the water phase. We demonstrate that the observed surfactant behavior is purely entropically driven and can be attributed to the unfavorable lipid-like structuring of octanol molecules at the free octanol-water interface. In essence, graphene enhances the inherent lipid-like behavior of octanol at the water interface rather than directly acting as a surfactant. Importantly, graphene does not display surfactant-like behavior in corresponding Martini coarse-grained simulations of the octanol-water system since the free liquid-liquid interface loses essential structure at the lower coarse-grained resolution. However, a similar surfactant behavior is recovered in coarse-grained simulations of longer alcohols such as dodecan-1-ol and hexadecan-1-ol. The observed discrepancies at different model resolutions enable us to construct a comprehensive model of the surfactant behavior of graphene at the octanol-water interface. The here-gained insights may facilitate the broader utilization of graphene in numerous domains of nanotechnology. Furthermore, since a drug's octanol-water partition coefficient is a crucial physicochemical parameter in rational drug discovery, we also believe that the universality of the here-illustrated entropic surfactant behavior of planar molecules deserves special attention in the drug design and development field.

An impressive pristine biochar from food waste digestate for arsenic(V) removal from water: Performance, optimization, and mechanism.

Anaerobic digestion has become a global practice for valorizing food waste, but the recycling of the digestate (FWD) remains challenging. This study aimed to address this issue by utilizing FWD as a low-cost feedstock for Ca-rich biochar production. The results demonstrated that biochar pyrolyzed at 900 °C exhibited impressive As(V) adsorption performance without any modifications. Kinetic analysis suggested As(V) was chemisorbed onto CDBC9, while isotherm data conformed well to Langmuir model, indicating monolayer adsorption with a maximum capacity of 76.764 mg/g. Further analysis using response surface methodology revealed that pH value and adsorbent dosage were significant influencing factors, and density functional theory (DFT) calculation visualized the formation of ionic bonds between HAsO42- and CaO(110) and Ca(OH)2(101) surfaces. This work demonstrated the potential of using FWD for producing Ca-rich biochar, providing an effective solution for As(V) removal and highlighting the importance of waste material utilization in sustainable environmental remediation.

Recent developments in metallic-nanoparticles-loaded biochars synthesis and use for phosphorus recovery from aqueous solutions. A critical review.

Phosphorus (P) represents a major pollutant of water resources and at the same time a vital element for human and plants. P recovery from wastewaters and its reuse is a necessity in order to compensate the current important depletion of P natural reserves. The use of biochars for P recovery from wastewaters and their subsequent valorization in agriculture, instead of synthetic industrial fertilizers, promotes circular economy and sustainability concepts. However, P retention by pristine biochars is usually low and a modification step is always required to improve their P recovery efficiency. The pre- or post-treatment of biochars with metal salts seems to be one of the most efficient approaches. This review aims to summarize and discuss the most recent developments (from 2020- up to now) in: i) the role of the feedstock nature, the metal salt type, the pyrolysis conditions, and the experimental adsorption parameters on metallic-nanoparticles-loaded biochars properties and effectiveness in recovering P from aqueous solutions, as well as the dominant involved mechanisms, ii) the effect of the eluent solutions nature on the regeneration ability of P-loaded biochars, and iii) the practical challenges facing the upscaling of P-loaded biochars production and valorization in agriculture. This review shows that the synthesized biochars through slow pyrolysis at relatively high temperatures (up to 700-800 °C) of mixed biomasses with Ca- Mg-rich materials or impregnated biomasses with specific metals in order to from layered double hydroxides (LDHs) biochars composites exhibit interesting structural, textural and surface chemistry properties allowing high P recovery efficiency. Depending on the pyrolysis's and adsorption's experimental conditions, these modified biochars may recover P through combined mechanisms including mainly electrostatic attraction, ligand exchange, surface complexation, hydrogen bonding, and precipitation. Moreover, the P-loaded biochars can be used directly in agriculture or efficiently regenerated with alkaline solutions. Finally, this review emphasizes the challenges concerning the production and use of P-loaded biochars in a context of circular economy. They concern the optimization of P recovery process from wastewater in real-time scenarios, the reduction of energy-related biochars production costs and the intensification of communication/dissemination campaigns to all the concerned actors (i.e., farmers, consumers, stakeholders, and policymakers) on the benefits of P-loaded biochars reuse. We believe that this review is beneficial for new breakthroughs on the synthesis and green application of metallic-nanoparticles-loaded biochars.