Low Cation Concentrations Research Articles

Polystyrene nanoplastics are unlikely to aggregate in freshwater bodies.

The fate and toxicity of nanoplastics (NPs) in the environment is largely determined by their stability. We explored how water composition, nanoplastic size, and surface carboxyl group density influenced the aggregation of polystyrene (PS) NPs in fresh water. Unfunctionalized 200, 300, 500, and 1000 nm PS NPs and 310 nm carboxylated PS NPs with carboxyl group densities of 0.35 and 0.6 mmol.g-1 were used to simulate pristine and aged NPs. Natural water matrices tested in this study include synthetic surface water (SSW), water from the Schie canal (Netherlands) and tap water. Suwannee River Natural Organic Matter (SRNOM) was included to mimic organic matter concentrations. In CaCl2, we found PS NPs are more stable as their size increases with the increase of the critical coagulation concentration (CCC) from 44 mM to 59 mM and 77 mM for NP sizes of 200 nm, 300 nm and 500 nm. Conversely, 1000 nm PS NPs remained stable even at 100 mM CaCl2. Increasing the carboxyl group density decreased the stability of NPs as a result of the interaction between Ca2+ and the carboxyl group. These results were consistent with the mass of Ca2+ adsorbed per mass of NPs. The presence of SRNOM decreased the stability of PS NPs via particle bridging facilitated by SRNOM. However, in SSW, Schie water and tap water with low divalent cation concentrations, the hydrodynamic size of PS NPs did not change, even at prolonged durations up to one week. We concluded that PS NPs are unlikely to aggregate in water with low divalent cation concentrations, like natural freshwater bodies. Ecotoxicologists and water treatment engineers will have to consider treating PS NPs as colloidally stable particles as the lack of aggregation in fresh surface water bodies will affect their ecotoxicity and may pose challenges to their removal in water treatment.

CHARACTERIZATION AND CLASSIFICATION OF SOILS DEVELOPED ON COASTAL PLAIN SOILS FOR CROP PRODUCTION IN ORON LGA, SOUTH- SOUTH, NIGERIA

Soils are characterized and classified based on its unique properties. Detailed characterization of four representative areas of Oron coastal plain soils in South –South, Nigeria was carried out. Soil samples were collected from pedogenic horizons of soils in four sampling sites. Routine analysis of soil properties was carried out in the laboratory with standard laboratory procedures. Soil data was subjected to descriptive statistics using statistical analytical system. The soils have a deep well drafted profile of about deep 200 cm. The soil texture varied in areas ranging from loamy sand to sandy loam, sandy and sandy clay loam while bulk density increased down the natural horizons. The pH varied between moderately acidic to strongly acidic in the soils of the study area. The morphology of soils ranged in various colour matrix of hues (10-7.5) and Chroma values (1-8) in all horizons. The soils were characterized by Dark Brown (10YR3/3), Dark Greyish Brown (10YR4/2) and Yellowish Brown (10YR 5/4) to Grey (7.5YR6/2). The soils had low concentrations of exchangeable cations (Ca, Mg, Na and K). The Coefficient of variation (CV%) values ranged from 0.74 to 91.6 in Ca, Mg, Na and K. All the parameters in the soils of the study area showed low and medium mean values except soils of Esin Ufot1 and 2 which showed high mean values of Na with Esin Ufot 2 having the highest mean value of sodium to be 0.18 Cmol/kg. Suborder soils were classified as Grossarenic Kandiaqualfs (CEC > 16 Cmol/kg) for Esin Ufot1.Esin Ufot2, Esuk Oron1 while Esuk Oron 2 were classified as Typic Kandaquults (CEC < 16 Cmol/kg). A great importance in providing adequate data to enable right decision taking in the choice of site for developmental projects and crop production.

Electrochemical CO2 Reduction in Acidic Electrolytes: Spectroscopic Evidence for Local pH Gradients.

Inspired by recent advances in electrochemical CO2 reduction (CO2R) under acidic conditions, herein we leverage in situ spectroscopy to inform the optimization of CO2R at low pH. Using attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and fluorescent confocal laser scanning microscopy, we investigate the role that alkali cations (M+) play on electrochemical CO2R. This study hence provides important information related to the local electrode surface pH under bulk acidic conditions for CO2R, both in the presence and absence of an organic film layer, at variable [M+]. We show that in an acidic electrolyte, an appropriate current density can enable CO2R in the absence of metal cations. In situ local pH measurements suggest the local [H+] must be sufficiently depleted to promote H2O reduction as the competing reaction with CO2R. Incrementally incorporating [K+] leads to increases in the local pH that promotes CO2R but only at proton consumption rates sufficient to drive the pH up dramatically. Stark tuning measurements and analysis of surface water structure reveal no change in the electric field with [M+] and a desorption of interfacial water, indicating that improved CO2R performance is driven by suppression of H+ mass transport and modification of the interfacial solvation structure. In situ pH measurements confirm increasing local pH, and therefore decreased local [CO2], with [M+], motivating alternate means of modulating proton transport. We show that an organic film formed via in situ electrodeposition of an organic additive provides a means to achieve selective CO2R (FECO2R ∼ 65%) over hydrogen evolution reaction in the presence of strong acid (pH 1) and low cation concentrations (≤0.1 M) at both low and high current densities.

Rainfall Impacts Dissolved Organic Matter and Cation Export From Permafrost Catchments and a Glacial River During Late Summer in Northeast Greenland

ABSTRACTOngoing and amplified climate change in the Arctic is leading to glacier retreat and to the exposure of an ever‐larger portion of non‐glaciated permafrost‐dominated landscapes. Warming will also cause more precipitation to fall as rain, further enhancing the thaw of previously frozen ground. Yet, the impact of those perturbations on the geochemistry of Arctic rivers remains a subject of debate. Here, we determined the geochemical composition of waters from various contrasting non‐glacial permafrost catchments and investigated their impact on a glacially dominated river, the Zackenberg River (Northeast Greenland), during late summer (August 2019). We also studied the effect of rainfall on the geochemistry of the Zackenberg River, its non‐glacial tributaries, and a nearby independent non‐glacial headwater stream Grænse. We analyzed water properties, quantified and characterized dissolved organic matter (DOM) using absorbance and fluorescence spectroscopy and radiocarbon isotopes, and set this alongside analyses of the major cations (Ca, Mg, Na, and K), dissolved silicon (Si), and germanium/silicon ratios (Ge/Si). The glacier‐fed Zackenberg River contained low concentrations of major cations, dissolved Si and dissolved organic carbon (DOC), and a Ge/Si ratio typical of bulk rock. Glacial DOM was enriched in protein‐like fluorescent DOM and displayed relatively depleted radiocarbon values (i.e., old DOM). Non‐glacial streams (i.e., tributaries and Grænse) had higher concentrations of major cations and DOC and DOM enriched in aromatic compounds. They showed a wide range of values for radiocarbon, Si and Ge/Si ratios associated with variable contributions of surface runoff relative to deep active layer leaching. Before the rain event, Zackenberg tributaries did not contribute notably to the solute export of the Zackenberg River, and supra‐permafrost ground waters governed the supply of solutes in Zackenberg tributaries and Grænse stream. After the rain event, surface runoff modified the composition of Grænse stream, and non‐glacial tributaries strongly increased their contribution to the Zackenberg River solute export. Our results show that summer rainfall events provide an additional source of DOM and Si‐rich waters from permafrost‐underlain catchments to the discharge of glacially dominated rivers. This suggests that the magnitude and composition of solute exports from Arctic rivers are modulated by permafrost thaw and summer rain events. This event‐driven solute supply will likely impact the carbon cycle in rivers, estuaries, and oceans and should be included into future predictions of carbon balance in these vulnerable Arctic systems.

Ion exchange selectivity for protons by sodium ion-form crystalline silicotitanate

ABSTRACT At the Fukushima Daiichi Nuclear Power Station site, crystalline silicotitanate (CST) ion exchangers containing sodium ions (Na+) as exchange ions are used as an adsorbent to remove radioactive cesium (Cs) and strontium (Sr) from groundwater and contaminated water. The ion exchange reactions to remove Cs+ and Sr2+ compete with the reactions with other cations in the water sources. Since the groundwater and contaminated water have low concentrations of metal cations, the influence of competitive ion exchange reactions with protons (H+) is relatively large in the removal of Cs+ and Sr2+ from the water. In this paper, the H+/Na+ ion exchange property of the aqueous solution-CST system was evaluated. Results of batch tests were used to draw the isotherm and Kielland plot for the H+/Na+ ion exchange. The thermodynamic equilibrium constant K and the standard Gibbs energy ΔG 0 of the H+/Na+ ion exchange reaction were evaluated from the Kielland plot. CST exhibited high H+ selectivity in the H+/Na+ ion exchange reaction. The values of K and ΔG 0 were determined to be 7.3 × 104 and − 28 kJ mol−1, respectively. The selectivity of CST for H+ decreased with increasing H+ concentration on the ion exchange sites in CST.

The role of cations in hydrogen evolution reaction on a platinum electrode in mildly acidic media

In this work, we study the influence of cation concentration and identity on the hydrogen evolution reaction (HER) on polycrystalline platinum (Pt) electrode in pH 3 electrolytes. Our observations indicate that cations in the electrolyte do not affect proton reduction at low potentials. However, an increase in cation concentration significantly enhances water reduction. Simultaneously, we identify a non-negligible migration current under mass transport limited conditions in electrolytes with low cation concentration. To separate migration effects from specific cation-promotion effects on HER, we carried out further experiments with electrolytes with mixtures of Li+ and K+ cations. Our results show that, adding strongly hydrated cations (Li+) to a K+-containing electrolyte leads to a less negative onset potential of water reduction. Interfacial pH measurements reveal a same interfacial pH at the platinum electrode in pH 3 in the presence of 80 mM LiClO4 and KClO4, respectively, at potentials where water reduction occurs. Based on these results, we suggest that under the current conditions, the strongly hydrated cations (Li+) promote water dissociation on the Pt electrode more favorably in comparison with the more weakly hydrated cations (K+), and that this promotion is not related to a local pH effect.

Influence of Zr-doping on the structure and transport properties of rare earth high-entropy oxides

Fluorite-type ceria-based ceramics are well established as oxygen ion conductors due to their high conductivity, superseding state-of-the-art electrolytes such as yttria-stabilized zirconia. However, at a specific temperature and oxygen partial pressure they occasionally exhibit electronic conduction attributed to polaron hopping via multivalent cations (e.g. Pr and Ce). (Ce, La, Pr, Sm, Y)O2−δ is a high-entropy oxide with a fluorite-type structure, featuring low concentrations of multivalent cations that could potentially mitigate polaron hopping. However, (Ce, La, Pr, Sm, Y)O2−δ undergoes a structural transition to the bixbyite-type structure above 1000 °C. In this study, we introduce Zr doping into (Ce, La, Pr, Sm, Y)O2−δ to hinder the structural transition at elevated temperatures. Indeed, the fluorite structure at elevated temperatures is stabilized at approximately 10 at.% Zr doping. The total conductivity initially increases with doping, peaking at 5 at.% Zr doping, and subsequently decreases with further doping. Interestingly, electronic conductivity in (Ce, La, Pr, Sm, Y)1−x Zr x O2−δ under oxidizing atmospheres is not significant and is lowest at 8 at.% Zr. These results suggest that ceria-based high-entropy oxides can serve as oxygen ion conductors with a significantly reduced electronic contribution. This work paves the way for new compositionally complex electrolytes as well as protective coatings for solid oxide fuel cells.

The impact of geochemical and life-cycle variables on carbon dioxide removal by enhanced rock weathering: Development and application of the Stella ERW model

The carbon dioxide removal (CDR) potential of enhanced rock weathering (ERW) depends on dynamic interactions between several biogeochemical and life-cycle variables. This paper reports results from a systems model developed to account for key variable interactions and provide a computational tool for optimizing ERW applications. We discuss the model development, comparisons with laboratory and field test data, and results from a series of sensitivity analyses for several hypothetical ERW applications. The simulations were performed using a model developed in Stella Architect, an object-oriented systems dynamics modeling code. The model tracks the amount of carbon dioxide consumed by the weathering of a user-specified mass of rock powder in a soil environment. The primary model variables are: rock powder particle size distribution, soil pH, soil temperature, soil pore water saturation index, and a biological weathering factor. The rock bulk composition is also a key variable as it defines the enhanced weathering potential of the rock powder. Life cycle variables such as carbon emissions from mining, rock crushing, and transport are also quantified. The model predictions are consistent with measured data. It predicts CDR values ranging from 1 to 12 t CO2 ha−1 (depending on conditions) for single applications of 20–40 t of rock ha−1 over a 10-year interval. Applying the model to a hypothetical large-scale ERW campaign in which basalt rock powder is applied to 25% and 75% of Brazilian cropland results in CDR values of 0.15 and 0.5 Gt CO2 over ten years, respectively (for a single application). Model results show that combinations of suboptimal rock type (i.e., low concentrations of divalent cations and slow weathering rates for field conditions) and suboptimal life-cycle variables (i.e., high vehicle emission factors and long rock transport distances) can result in net positive CO2 emissions for some hypothetical ERW scenarios. It is, therefore, emphasized that the quantitative co-optimization of geochemical, biological, and life-cycle variables is essential in the planning stages of ERW applications.

Cation Effects on Hydrogen Oxidation Reaction on Pt Single-Crystal Electrodes in Alkaline Media.

The exact mechanism behind the cation-assisted hydrogen oxidation reaction (HOR) on platinum electrodes in alkaline media remains disputed. We show that the cation effects at platinum display a remarkable structure sensitivity: not only the H adsorption but also the HOR activity on (111) terrace sites are independent of the nature of cation and cation concentration. On (110) step sites, at low cation concentration and mildly alkaline media, cations promote the HOR, whereas at more alkaline pH and consequently higher near-surface cation concentrations, the HOR is inhibition by the cations. Moreover, the role of the cation on terrace-OHad is different from that on step-OHad, as can also be observed from the inhibition of the HOR current by terrace-OHad at higher potentials. These results suggest that near the onset potential, HOR mainly takes place on steps, but under diffusion-limited conditions at higher overpotential, HOR mainly takes place on terraces.

Response of wheat (Triticum aestivum L.) and cowpea (Vigna unguiculata L.) to foliar wetting with low pH mine waters containing acid-generating metal cations

Acid mine drainage (AMD) contains metals that have detrimental effects on crop growth if present in excess in plant-available form. The use of untreated AMD from coal mines for crop irrigation on strategically limed soils is considered a potential option for mine water management, especially in remote areas without access to water treatment infrastructure. However, leaf scorching and trace element enrichment of plant tissue are of potential concern, as these waters often contain high concentrations of potentially toxic, acid-generating metals (Al3+, Fe2+ and Mn2+) which may cause foliar damage and hyper-accumulate in plant tissue. The objectives of this trial were to quantify any foliar injury and metal accumulation in wheat (Triticum aestivum L.) and cowpea (Vigna unguiculata L.) vegetative material after foliar wetting with simulated AMD enriched with metal cations, and to ascertain if biomass production will be affected. In this trial, crop water requirements were not met through mine water irrigation, as this was only a foliar wetting investigation. Two pot experiments were set up, with wheat grown in the winter and cowpea in the summer season of 2021. Sulphuric acid was used to lower pH to 2, after the addition of low, intermediate and high concentrations of individual acid-generating metal cations, as well as a combination of all three cations. Areal foliar injury was greatest for cowpea (18.7%) with a combination of Al, Fe and Mn at the highest concentration. The crop was not able to recover at this injury level. No injury was recorded in wheat. Both crops accumulated only limited quantities of the metal cations. Calculated hazard quotient for cattle ranged from 0.022 to 0.53, indicating that such fodder would be safe to consume. It is concluded that there are large differences in crop specie susceptibility to leaf scorching after foliar wetting with acidic metal cation-rich mine waters. It is recommended, therefore, that because large volumes of mine water need to be managed, and centre pivot overhead irrigation is likely to be utilized to this end, that studies to screen more species to select crops tolerant to scorching through foliage wetting with mine water irrigation be conducted. Thereafter, studies to better understand root zone effects of irrigation with such waters need to be conducted on species that can tolerate foliar wetting with these waters.

Dilute but significant: low cation concentration affects field dependent properties of Eu2Ga11Sn35.

We investigate the temperature and magnetic field-dependent electrical and thermal properties of Eu2.2Ga11Sn35, revealing a change in electronic structure and an increase in magnetoresistance with increasing field, as well as the origin of magneto-suppressed thermal conductivity of this unconventional inorganic clathrate-I material with very low cation concentration.

Interactions of manganese oxides with natural dissolved organic matter: Implications for soil organic carbon cycling

Metal (oxyhydr)oxides are key factors for the transformation and stabilization of organic carbon (OC) in soil. While sorptive interactions between Al and Fe (oxyhydr)oxides and dissolved organic matter (DOM) are well studied, the role of Mn(IV) oxides (manganates) in DOM sorption, fractionation, and oxidation has not been extensively investigated. Therefore, we examined sorptive interactions between manganates (δ-MnO2, birnessite, cryptomelane; 5 g L−1) and different DOM types (beech litter and Oa/Oe material under pine; ∼100 mg L−1 dissolved organic carbon, DOC) at pH 4 and 7 in different background electrolytes (BGE; no salt, 0.01 M NaCl or CaCl2) for up to 32 h. Changes of DOM solutions and mineral phases were assessed by solid, liquid, and gas analyses, and statistically evaluated for the effects of manganate, DOM type, pH, and BGE on DOC sorption, fractionation, and oxidative transformation. Manganates sorbed 0.2–8.7 mg OC g−1. Per unit mass, δ-MnO2 was least effective in DOC retention due to its high DOC oxidation capacity. Manganates sorbed more DOC at acidic pH and more aromatic pine than more aliphatic beech DOC, with Ca2+ generally facilitating DOC sorption. Up to 56 % of added DOC (average: 25 %) was oxidized to CO2, which is comparable to the extent of DOC respiration by soil microorganisms. DOC oxidation by δ-MnO2 and cryptomelane exceeded that of birnessite, which had the lowest specific surface area of all manganates. However, we found no difference in the efficiency of manganates to oxidize DOC, implying a similar redox activity of phyllo- and tectomanganates. More beech than pine DOM was oxidized to CO2 and an acidic pH facilitated DOC decomposition. While the presence of Na-BGE increased DOC oxidation to CO2 relative to no-salt treatments, Ca-BGE had the opposite effect, as Ca2+ apparently impeded the electron transfer from sorbed OC to structural Mn(III/IV). Contact of DOM with manganates also produced high concentrations of dissolved low-molecular-weight organic acids (mainly formate, acetate, and oxalate), accounting for up to 19 % of the initial DOC concentration. In addition, reduced specific ultraviolet absorbance of DOM solutions at 280 nm indicated preferential sorption of aromatic moieties, especially in Ca-BGE. However, in the absence of Ca2+ and at neutral pH, manganates increased the aromaticity of beech DOM, most likely due to polymerization reactions. No mineral transformations occurred after reaction of manganates with DOM, despite reductive manganate dissolution. Our results imply that soil manganates accumulate more OC in acidic soils and in presence of more aromatic DOM. However, manganates oxidatively destabilize DOC by generating CO2 and low-molecular-weight organic compounds, which is presumably more relevant in acidic soils with low concentrations of polyvalent cations and for more aliphatic DOM. The produced low-molecular-weight organic compounds may promote microbial activity and foster mineral weathering. Our results suggest a pivotal role of manganates in soil OC cycling, including the fate and bioavailability of nutrient elements associated with DOM, and in supporting ligand-promoted mineral weathering and soil formation.

The Effects of Aminium and Ammonium Cations on the Ice Nucleation Activity of K‐Feldspar

AbstractMineral dust is one of the most abundant types of ice nucleating particles in the atmosphere. During atmospheric transport, mineral dust particles can become coated with inorganic and organic solutes, which can impact their ice nucleation activity. Aminium cations formed from amines are one type of organic solute that can coat mineral dust particles in the atmosphere, but their effects on the ice nucleation activity of mineral dust have not been studied. We investigated the effects of primary, secondary, and tertiary aminium cations with methyl and ethyl groups, as well as ammonium cations, on the ice nucleation activity of K‐feldspar, an important type of mineral dust, in the immersion freezing mode at low cation concentrations (0.2–20 mM) using a droplet‐freezing apparatus. Ammonium cations substantially increased the ice nucleation activity of K‐feldspar, consistent with previous studies. In contrast, primary aminium cations significantly reduced K‐feldspar ice nucleation activity, and secondary and tertiary aminium cations had no significant effect (the effect was less than the uncertainty of our measurements). Our combined results are consistent with the following mechanisms: ammonium cations undergo ion exchange with K‐feldspar, providing exposed N–H groups for hydrogen bonding with ice; primary aminium cations undergo ion exchange with K‐feldspar, exposing a hydrophobic tail that is not effective at nucleating ice; secondary and tertiary aminium cations do not undergo ion exchange with K‐feldspar due to steric effects caused by the multiple hydrophobic groups on the cation.

Impact of Ion-Mixing Entropy on Orientational Preferences of DNA Helices: FRET Measurements and Computer Simulations.

Biological processes require DNA and RNA helices to pack together in specific interhelical orientations. While electrostatic repulsion between backbone charges is expected to be maximized when helices are in parallel alignment, such orientations are commonplace in nature. To better understand how the repulsion is overcome, we used experimental and computational approaches to investigate how the orientational preferences of DNA helices depend on the concentration and valence of mobile cations. We used Förster resonance energy transfer (FRET) to probe the relative orientations of two 24-bp helices held together via a freely rotating PEG linker. At low cation concentrations, the helices preferred more "cross"-like orientations over those closer to parallel, and this preference was reduced with increasing salt concentrations. The results were in good quantitative agreement with Poisson-Boltzmann (PB) calculations for monovalent salt (Na+). However, PB underestimated the ability of mixtures of monovalent and divalent ions (Mg2+) to reduce the conformational preference. As a complementary approach, we performed all-atom molecular dynamics (MD) simulations and found better agreement with the experimental results. While MD and PB predict similar electrostatic forces, MD predicts a greater accumulation of Mg2+ in the ion atmosphere surrounding the DNA. Mg2+ occupancy is predicted to be greater in conformations close to the parallel orientation than in conformations close to the crossed orientation, enabling a greater release of Na+ ions and providing an entropic gain (one bound ion for two released). MD predicts an entropy gain larger than that of PB because of the increased Mg2+ occupancy. The entropy changes have a negligible effect at low Mg2+ concentrations because the free energies are dominated by electrostatic repulsion. However, as the Mg2+ concentration increases, charge screening is more effective and the mixing entropy produces readily detectable changes in packing preferences. Our results underline the importance of mixing entropy of counterions in nucleic acid interactions and provide a new understanding on the impact of a mixed ion atmosphere on the packing of DNA helices.

Methods to Improve the Stability of Nucleic Acid-Based Nanomaterials.

Nucleic acid strands can be synthesized into various nucleic acid-based nanomaterials (NANs) through strict base pairing. The self-assembled NANs are programmable, intelligent, biocompatible, non-immunogenic, and noncytotoxic. With the rapid development of nanotechnology, the application of NANs in the biomedical fields, such as drug delivery and biological sensing, has attracted wide attention. However, the stability of NANs is often affected by the cation concentrations, enzymatic degradation, and organic solvents. This susceptibility to degradation is one of the most important factors that have restricted the application of NANs. NANs can be denatured or degraded under conditions of low cation concentrations, enzymatic presence, and organic solvents. To deal with this issue, a lot of methods have been attempted to improve the stability of NANs, including artificial nucleic acids, modification with specific groups, encapsulation with protective structures, etc. In this review, we summarized the relevant methods to have a deeper understanding of the stability of NANs.

Structural and thermal properties of Eu2Ga11Sn35

Clathrates have been reported to form in a variety of different structure types; however, inorganic clathrate-I materials with a low-cation concentration have yet to be investigated. Furthermore, tin-based compositions have been much less investigated as compared to silicon or germanium analogs. We report the temperature-dependent structural and thermal properties of single-crystal Eu2Ga11Sn35 revealing the effect of structure and composition on the thermal properties of this low-cation clathrate-I material. Specifically, low-temperature heat capacity, thermal conductivity, and synchrotron single-crystal x-ray diffraction reveal a departure from Debye-like behavior, a glass-like phonon mean-free path for this crystalline material, and a relatively large Grüneisen parameter due to the dominance of low-frequency Einstein modes. Our analyses indicate thermal properties that are a direct result of the structure and composition of this clathrate-I material.

Effects of soil grain size and solution chemistry on the transport of biochar nanoparticles

Biochar nanoparticles (BC-NP) have attracted significant attention because of their unique environmental behavior, some of which could potentially limit large-scale field application of biochar. Accurate prediction of the fate and transportability of BC-NP in soil matrix is the key to evaluating their environmental influence. This study investigated the effects of soil grain size and environmentally relevant solution chemistry, such as ionic strength (cation concentration, 0.1 mM–50 mM; cation type, Na+, and Ca2+), and humic acid (HA; 0–10 mg/L), on the transport behavior of BC-NP via systematic column experiments. The transportability of BC-NP in the soil-packed column decreased with decreasing soil grain size and was inversely proportional to soil clay content. At low cation concentrations (0.1–1.0 mM), a considerable proportion of BC-NP (15.95%–67.17%) penetrated the soil columns. Compared with Na+, Ca2+ inhibited the transportability of BC-NP in the soil through a charge shielding effect. With increasing HA concentration, the transportability of BC-NP increased, likely due to an enhanced repulsion force between BC-NP and soil particles. However, at a high HA concentration (10 mg/L), Ca2+ bridging reduced the transportability of BC-NP in the soil. Breakthrough curves of BC-NP were explained by the two-site kinetic retention model. The antagonistic effects of ionic strength and HA indicated that the transport behavior of BC-NP in the soil was governed by competitive effects of some environmental factors, including soil grain size, environmental solution chemistry, and natural organic matter content.

Revealing uncommon transport in the previously unascertained very low cation clathrate-I Eu2Ga11Sn35

We report on the structure and electrical transport of single-crystal Eu2Ga11Sn35, the sole example of a very low cation concentration clathrate-I composition with atypical transport directly attributable to the structure and stoichiometry.

Evaluating acid-aluminum stress in streams of the Northeastern U.S. at watershed, fish community and physiological scales

In spite of overall improvements in air and water quality, biological stress from low pH and high concentrations of inorganic aluminum continue to impact fish and fish habitat in northeastern North America, with independent and interactive effects on individuals, populations and communities. Integrative indicators can therefore be useful in monitoring both impact and recovery across multiple scales. Using coupled water chemistry (pH, conductivity, and base cation and inorganic aluminum concentration), geographic (site elevation and watershed area) and biological (fish diversity, fish abundance, gill aluminum concentration and gill physiology) data, we developed an integrated indicator of acid-aluminum stress across the White and Green mountains in central New England, USA. As has been established in a number of previous studies, preliminary analysis clearly indicated that across all sites, inorganic aluminum concentration was consistently greatest during the spring season. Structural Equation modeling (SEM) revealed that toxic conditions (concurrent low pH and high concentrations of inorganic aluminum) were well summarized with an integrated toxicity score, related to both base cation concentrations and elevation, with sites at higher elevations more likely to experience toxic conditions as well as low base cation concentrations. Fish diversity and abundance generally trended negatively with toxicity score, with fewer cyprinids and sculpins at high toxicity score sites. In spite of considerable variation among individuals, gill aluminum was positively related to toxicity score for both Atlantic salmon and brook trout. Observed elevated gill aluminum levels associated with reduced gill metabolic activity in Atlantic salmon smolts from impacted systems likely result in impaired osmoregulatory function and seawater tolerance. Overall, our results suggest that the integrated toxicity score metric is associated with a syndrome of acute physiological stress, reduced abundance, and low species diversity for sensitive stream fishes in New England, and can likely serve as a reliable indicator of continued impairment or recovery of acid-aluminum vulnerable systems in this ecoregion.

Freshwater and Evaporite Brine Compositions on Hadean Earth: Priming the Origins of Life.

The chemical composition of aqueous solutions during the Hadean era determined the availability of essential elements for prebiotic synthesis of the molecular building blocks of life. Here we conducted quantitative reaction path modeling of atmosphere-water-rock interactions over a range of environmental conditions to estimate freshwater and evaporite brine compositions. We then evaluated the solution chemistries for their potential to influence ribonucleotide synthesis and polymerization as well as protocell membrane stability. Specifically, solutions formed by komatiite and tonalite (primitive crustal rocks) weathering and evaporation-rehydration (drying-wetting) cycles were studied assuming neutral atmospheric composition over a wide range of values of atmospheric partial pressure of CO2 (PCO2) and temperatures (T). Solution pH decreased and total dissolved concentrations of inorganic P, Mg, Ca, Fe, and C (PT, MgT, CaT, FeT, and CT) increased with increasing PCO2. The PCO2 and T dictated how the solution evolved with regard to minerals precipitated and ions left in solution. At T = 75°C and PCO2 < 0.05 atm, the concentration ratio of magnesium to calcium ion concentrations (Mg2+/Ca2+) was < 1 and predominantly metal aluminosilicates (including clays), dolomite, gibbsite, and pyrite (FeS2) precipitated, whereas at PCO2 > 0.05 atm, Mg2+/Ca2+ was > 1 and mainly magnesite, dolomite, pyrite, chalcedony (SiO2), and kaolinite (Al2Si2O5) precipitated. At T = 75°C and PCO2 > 0.05 atm, hydroxyapatite (HAP) precipitated during weathering but not during evaporation, and so, PT increased with each evaporation-rehydration cycle, while MgT, CaT, and FeT decreased as other minerals precipitated. At T = 75°C and PCO2 ∼5 atm, reactions with komatiite provided end-of-weathering solutions with high enough Mg2+ concentrations to promote RNA-template directed and montmorillonite-promoted nonenzymatic RNA polymerization, but incompatible with protocell membranes; however, montmorillonite-promoted RNA polymerization could proceed with little or no Mg2+ present. Cyclically evaporating/rehydrating brines from komatiite weathering at T = 75°C and PCO2 ∼5 atm yielded the following: (1) high PT values that could promote ribonucleotide synthesis, and (2) low divalent cation concentrations compatible with amino acid-promoted, montmorillonite-catalyzed RNA polymerization and with protocell membranes, but too low for template-directed nonenzymatic RNA polymerization. For all PCO2 values, Mg2+ and PT concentrations decreased, whereas the HCO3- concentration increased within increasing temperature, due to the retrograde solubility of the minerals controlling these ions' concentrations; Fe2+ concentration increased because of prograde pyrite solubility. Tonalite weathering and cyclical wetting-drying reactions did not produce solution compositions favorable for promoting prebiotic RNA formation. Conversely, the ion concentrations compatible with protocell emergence, placed constraints on PCO2 of early Earth's atmosphere. In summary: (1) prebiotic RNA synthesis and membrane self-assembly could have been achieved even under neutral atmosphere conditions by atmosphere-water-komatiite rock interactions; and (2) constraints on element availability for the origins of life and early PCO2 were addressed by a single, globally operating mechanism of atmosphere-water-rock interactions without invoking special microenvironments. The present results support a facile origins-of-life hypothesis even under a neutral atmosphere as long as other favorable geophysical and planetary conditions are also met.