Mineralogical sources of groundwater fluoride in Archaen bedrock/regolith aquifers: Mass balances from southern India and north-central Sri Lanka

STUDY REGION: The Maheshwaram and Waipally catchments of Andhra Pradesh, India, and the Plonnaruwa catchment of north-central Sri Lanka. STUDY FOCUS: The distribution of F across eight crystalline phases and between the bedrock and the regolith at eleven sites in three catchments is documented. Mineral contributions to F release during weathering and regolith development are quantified. NEW HYDROLOGICAL INSIGHTS FOR THE REGION: An estimate of weathering duration for the in situ regolith in Andhra Pradesh, 250-380 Ka, is close to a previous estimate for southern India. Partial or total destruction of the primary F-bearing bedrock minerals and consistent depletion of F in the remnant minerals result in a much reduced total F content in the regolith. Leaching experiments and field relationships, however, indicate a greater potential for F mobilisation to groundwater from the regolith than the bedrock. Schemes for managed aquifer recharge should beware the risk of mobilising additional F to groundwater

Impact of particle size, oxidation state and capping agent of different cerium dioxide nanoparticles on the phosphate-induced transformations at different pH and concentration

The potential hazard posed by nanomaterials can be significantly influenced by transformations which these materials undergo during their lifecycle, from manufacturing through to disposal. The transformations may depend on the nanomaterials’ own physicochemical properties as well as the environment they are exposed to. This study focuses on the mechanisms of transformation of cerium oxide nanoparticles (CeO$_{2}$ NPs) in laboratory experiments which simulate potential scenarios in which the NPs are exposed to phosphate-bearing media. We have experimented with the transformation of four different kinds of CeO$_{2}$ NPs, in order to investigate the effects of nanoparticle size, capping agent (three were uncapped and one was PVP capped) and oxidation state (two consisted mostly of Ce$^{4+}$ and two were a mix of Ce$^{3+}$/Ce$^{4+}$). They were exposed to a reaction solution containing KH$_{2}$PO$_{4}$, citric acid and ascorbic acid at pH values of 2.3, 5.5 and 12.3, and concentrations of 1mM and 5mM. The transformations were followed by UV-vis, zeta potential and XRD measurements, which were taken after 7 and 21 days, and by transmission electron microscopy after 21 days. X-ray photoelectron spectroscopy was measured at 5mM concentration after 21 days for some samples. Results show that for pH 5 and 5mM phosphate concentration, CePO$_{4}$ NPs were formed. Nanoparticles that were mostly Ce$^{4+}$ did not dissolve at 1mM reagent concentration, and did not produce CePO$_{4}$ NPs. When PVP was present as a capping agent it proved to be an extra reducing agent, and CePO$_{4}$ was found under all conditions used. This is the first paper where the transformation of CeO$_{2}$ NPs in the presence of phosphate has been studied for particles with different size, shapes and capping agents, in a range of different conditions and using many different characterisation methods

A review on nanomaterial-based SERS substrates for sustainable agriculture

The agricultural sector plays a pivotal role in driving the economy of many developing countries. Any dent in this economical structure may have a severe impact on a country's population. With rising climate change and increasing pollution, the agricultural sector is experiencing significant damage. Over time this cumulative damage will affect the integrity of food crops and create food security issues around the world. Therefore, an early warning system is needed to detect possible stress on food crops. Here we present a review of the recent developments in nanomaterial-based Surface Enhanced Raman Spectroscopy (SERS) substrates which could be utilized to monitor agricultural crop responses to natural and anthropogenic stress. Initially, our review delves into diverse and cost-effective strategies for fabricating SERS substrates, emphasizing their intelligent utilization across various agricultural scenarios. In the second phase of our review, we spotlight the specific application of SERS in addressing critical food security issues. By detecting nutrients, hormones, and effector molecules in plants, SERS provides valuable insights into plant health. Furthermore, our exploration extends to the detection of contaminants, chemicals, and foodborne pathogens within plants, showcasing the versatility of SERS in ensuring food safety. The cumulative knowledge derived from these discussions illustrates the transformative potential of SERS in bolstering the agricultural economy. By enhancing precision in nutrient management, monitoring plant health, and enabling rapid detection of harmful substances, SERS emerges as a pivotal tool in promoting sustainable and secure agricultural practices. Its integration into agricultural processes not only augments productivity but also establishes a robust defence against potential threats to crop yield and food quality. As SERS continues to evolve, its role in shaping the future of agriculture becomes increasingly pronounced, promising a paradigm shift in how we approach and address challenges in food production and safety

Thermal transformations of manufactured nanomaterials as a proposed proxy for ageing

Ageing is an important part of a manufactured nanomaterial\u27s life cycle and can be considered as a transformation over time. It is particularly relevant to nanomaterials (NMs) because they are more reactive than their bulk counterparts and therefore are likely to undergo more significant or faster transformations with time. The conditions upon exposure of a NM to the environment, e.g. temperature, humidity and redox, will all individually affect ageing, as well as time. In experimental simulations, time has to be substituted by a proxy that makes timescales more realistic. Thermal ageing accelerates the normal ageing processes of NMs and thus elevated temperatures can be used to simulate prolonged ageing, allowing access to information on the long-term effects of NM ageing within a shorter time. Similar approaches are utilised in experimental simulation of protein fibrillation, for example, where processes that naturally occur over decades are accelerated to days or hours. In this work, time and temperature dependent studies were carried out on a fully characterised library of laboratory synthesised comparable polyvinylpyrrolidone (PVP) capped NMs (with core compositions of ceria, copper oxide and zinc oxide) and a commercially available uncoated cerium dioxide NM, to assess their transformations. Specifically, physical and chemical changes were studied on NMs exposed to various temperatures (25, 45, 65 and 80 °C) for a period of 4 weeks. The size, zeta potential, agglomeration/aggregation and valence state of the NMs were studied through dynamic light scattering (DLS), zeta potential, ultra-violet visible light spectroscopy (UV-VIS), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), as a function of time. Results generally show a decrease in NM stability with increasing temperature and time. Changes in the NM size and core oxidation state were noted with increasing temperature/time. These changes varied depending on the NM core composition. Additionally the PVP capping, despite stabilising the NM dispersion, still allowed the NM core to be influenced by external factors, thus indicating likely ageing-related reduction in efficiency, though to a lesser extent than the uncapped particles. Overall the experiments recorded a complex picture of transformations as a function of time/temperature highlighting the complexity of NMs\u27 ageing

Hydro-biogeochemical coupling beneath a large polythermal Arctic glacier: Implications for subice sheet biogeochemistry

This article was published in the serial, Journal of Geophysical Research: Earth Surface [Wiley © American Geophysical Union]. It is also available at: http://dx.doi.org/10.1029/2009JF001602We analyze the interannual chemical and isotopic composition of runoff from a large, high Arctic valley glacier over a 5 year period, during which drainage evolved from a long-residence-time drainage system feeding an artesian subglacial upwelling (SGU) at the glacier terminus to a shorter-residence-time drainage system feeding an ice-marginal channel (IMC). Increased icemelt inputs to the SGU are thought to have triggered this evolution. This sequence of events provides a unique opportunity to identify coupling between subglacial hydrology and biogeochemical processes within drainage systems of differing residence time. The biogeochemistry of the SGU is consistent with prolonged contact between meltwaters and subglacial sediments, in which silicate dissolution is enhanced, anoxic processes (e.g., sulphate reduction) prevail, and microbially generated CO2 and sulphide oxidation drive mineral dissolution. Solute in the IMC was mainly derived from moraine pore waters which are added to the channel via extraglacial streams. These pore waters acquire solute predominantly via sulphide oxidation coupled to carbonate/silicate dissolution. We present the first evidence that microbially mediated processes may contribute a substantial proportion (80% in this case) of the total glacial solute flux, which includes coupling between microbial CO2-generation and silicate/carbonate dissolution. The latter suggests the presence of biofilms in subglacial/ice-marginal sediments, where local perturbation of the geochemical environment by release of protons, organic acids, and ligands stimulates mineral dissolution. These data enable inferences to be made regarding biogeochemical processes in longer-residence-time glacial systems, with implications for the future exploration of Antarctic subglacial lakes and other wet-based ice sheet environments

Meloneis Gen. Nov., a New Epipsammic Genus of Rhaphoneidaceae (Bacillariophyceae)

The diatom family Rhaphoneidaceae is characterized by high generic diversity and low species diversity with most genera known to have long stratigraphic ranges. The genera within this family are neritic marine, and mostly epipsammic. A new modern and epipsammic genus, Meloneis gen. nov., is described herein and is compared to all genera within Rhaphoneidaceae and especially to Rhaphoneis Ehrenberg s.l. Within Meloneis three new species and one variety are distinguished and described herein: M. mimallis sp. nov., M. mimallis var. zephyria var. nov., M. akytos sp. nov., and M. gorgis sp. nov

Genetic prediction of ICU hospitalization and mortality in COVID-19 patients using artificial neural networks

There is an unmet need of models for early prediction of morbidity and mortality of Coronavirus disease-19 (COVID-19). We aimed to a) identify complement-related genetic variants associated with the clinical outcomes of ICU hospitalization and death, b) develop an artificial neural network (ANN) predicting these outcomes and c) validate whether complement-related variants are associated with an impaired complement phenotype. We prospectively recruited consecutive adult patients of Caucasian origin, hospitalized due to COVID-19. Through targeted next-generation sequencing, we identified variants in complement factor H/CFH, CFB, CFH-related, CFD, CD55, C3, C5, CFI, CD46, thrombomodulin/THBD, and A Disintegrin and Metalloproteinase with Thrombospondin motifs (ADAMTS13). Among 381 variants in 133 patients, we identified 5 critical variants associated with severe COVID-19: rs2547438 (C3), rs2250656 (C3), rs1042580 (THBD), rs800292 (CFH) and rs414628 (CFHR1). Using age, gender and presence or absence of each variant, we developed an ANN predicting morbidity and mortality in 89.47% of the examined population. Furthermore, THBD and C3a levels were significantly increased in severe COVID-19 patients and those harbouring relevant variants. Thus, we reveal for the first time an ANN accurately predicting ICU hospitalization and death in COVID-19 patients, based on genetic variants in complement genes, age and gender. Importantly, we confirm that genetic dysregulation is associated with impaired complement phenotype

Development of scalable and versatile nanomaterial libraries for nanosafety studies: polyvinylpyrrolidone (PVP) capped metal oxide nanoparticles

The potential long-term environmental impact of manufactured nanomaterials (NMs) remains poorly understood, and the need to better predict NM fate and transformations and chronic effects is particularly urgent. Compared to their bulk counterparts, manufactured NMs can have distinct physical and chemical characteristics, which influence their behaviour, stability and toxicity. It is therefore essential to develop standard and reference NM libraries for environmental nanoscience and nano(eco)toxicology, and to facilitate a move towards computational prediction of NM fate, through quantitative structure–activity relationships for example. The aim of this work was to develop and fully characterise one such library, which included comparable NMs with a range of core chemistries, but the same capping agent and size range, for use in future studies to test the hypothesis that the core chemistry is a primary factor in controlling toxicity. The library contained the following NMs: 10k, 40k and 360k PVP capped ceria, zinc oxide and copper oxide (9 NMs in total). The work presented here upholds the underpinning hypothesis that the mechanism of NM formation is the same in all cases, suggesting that the protocol is very robust and has the potential to generate a wide range of comparable metal oxide NMs and potentially expand the library further with doped metal oxide and metal NMs. Characterisation by means of DLS (both size and zeta measurements), UV/Vis, XPS, FT-IR, TEM, STEM, EDX and EELS confirms that the tested synthesis protocol can easily and successfully be used to create stable PVP capped metal oxide NMs of reproducible sizes

Trace metal distribution in the bed, bank and suspended sediment of the Ravensbourne River and its implication for sediment monitoring in an urban river

Purpose This study aims to identify a suitable sediment compartment for sediment quality monitoring by: (a) studying the concentration of trace metals (Cd, Cu, Ni, Pb and Zn) in the bed, bank and suspended sediment compartments of the Ravensbourne River to establish any differences in trace metal concentrations with compartment; (b) determining the influence of sediment particle size fractions ( 0.05) in the concentrations of metals between the suspended sediment and the < 63 μm bed sediment fraction, but there was a significant difference (p < 0.05) between the suspended sediment and the < 63 μm bank sediment fraction. There were also significant differences between the concentrations of metals in the < 63 μm and the 63 μm–2 mm fractions. Generally, the Ravensbourne River did not comply with the draft UK sediment quality guidelines for the metals analysed. Conclusions This study shows the importance of identifying a suitable sediment compartment to sample for compliance with sediment quality standards. The bed and suspended sediments are the most widely used sediment compartments for sediment monitoring, but collecting sufficient mass of the < 63 μm sediment fraction for monitoring presents a challenge for urban gravel bed rivers like the Ravensbourne River. It seems appropriate to establish individual monitoring regimes for different rivers