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At least 577 records · Page 32

Fluorescence Correlation Spectroscopy at Micromolar Concentrations without Optical Nanoconfinement

Fluorescence correlation spectroscopy (FCS) is an important technique for studying biochemical interactions dynamically that may be used in vitro and in cell-based studies. It is generally claimed that FCS may only be used at nM concentrations. We show that this general consensus is incorrect and that the limitation to nM concentrations is not fundamental but due to detector limits as well as laser fluctuations. With a high count rate detector system and applying laser fluctuation corrections, we demonstrate FCS measurements up to 38 μM with the same signal-to-noise as at lower concentrations. Optical nanoconfinement approaches previously used to increase the concentration range of FCS are not necessary, and further increases above 38 μM may be expected using detectors and detector arrays with higher saturation rates and better laser fluctuation corrections. This approach greatly widens the possibilities of dynamic measurements of biochemical interactions using FCS at physiological concentrations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mercury in Active-Layer Tundra Soils of Alaska: Concentrations, Pools, Origins, and Spatial Distribution

Tundra soils serve as major sources of mercury (Hg) input to the Arctic Ocean via river runoff and coastal erosion; yet little information is available on tundra soil Hg concentrations, pool sizes, origins, and dynamics. We present a detailed investigation of Hg in the active layer (upper ~100 cm subject to seasonal thaw) of tundra soils across 11 sites in Alaska. Soil Hg concentrations in organic horizons (151 ± 7 μg/kg) were in the upper range of temperate soil organic horizons, and concentrations in mineral horizons (98 ± 6 μg/kg) were much higher than in temperate soils. Soil Hg concentrations declined from inland to coastal sites, in contrast to a hypothesized northward increase expected because of proximity to coastal atmospheric mercury depletion events. Principle component analyses and elemental ratios results show that exogenic sources dominated over geogenic sources—in A-horizons (66 ± 4%) and mineral B-horizons (51 ± 1%). 14 C age-dating suggested recent origins of Hg in surface soils but showed that mineral soils (more than 7,300 years old) must have accumulated atmospheric inputs across millennia leading to high soil concentrations and pools. We estimated a total Northern Hemisphere active-layer tundra soil Hg pool of 184 Gg (range of 136 to 274 Gg), suggesting a globally important Hg storage pool. Tundra soils are subject to seasonal thaw and freeze dynamics, thereby providing large inputs to rivers, lakes, and the Arctic Ocean. Understanding processes that mobilize Hg from tundra soils will be critical to understanding future Arctic wildlife and human Hg exposures.

54 ENVIRONMENTAL SCIENCES↗

Background Free‐Tropospheric Ice Nucleating Particle Concentrations at Mixed‐Phase Cloud Conditions

Abstract Clouds containing ice are vital for precipitation formation and are important in determining the Earth's radiative budget. However, primary formation of ice in clouds is not fully understood. In the presence of ice nucleating particles (INPs), the phase change to ice is promoted, but identification and quantification of INPs in a natural environment remains challenging because of their low numbers. In this paper, we quantify INP number concentrations in the free troposphere (FT) as measured at the High Altitude Research Station Jungfraujoch (JFJ), during the winter, spring, and summer of the years 2014–2017. INPs were measured at conditions relevant for mixed‐phase cloud formation at T = 241/242 K. To date, this is the longest timeline of semiregular measurements akin to online INP monitoring at this site and sampling conditions. We find that INP concentrations in the background FT are on average capped at 10/stdL (liter of air at standard conditions [ T = 273 K and p = 1013 hPa]) with an interquartile range of 0.4–9.6/stdL, as compared to measurements during times when other air mass origins (e.g., Sahara or marine boundary layer) prevailed. Elevated concentrations were measured in the field campaigns of 2016, which might be due to enhanced influence from Saharan dust and marine boundary layer air arriving at the JFJ. The upper limit of INP concentrations in the background FT is supported by measurements performed at similar conditions, but at different locations in the FT, where we find INP concentrations to be below 13/stdL most of the time.

54 ENVIRONMENTAL SCIENCES↗

Subseasonal Variability of Elevated Dust Concentrations Over South Florida

Dust mass concentrations have been measured daily at Miami, Florida, in the summer months, and biweekly throughout the remaining months, since 1974. The 43-year record of dust mass concentrations indicate large daily, seasonal, and interannual variations, with most of the dust arriving within 5–8 episodes each summer. On average, dust arrives to Miami, Florida, 10 days after emission from North Africa, with measured concentrations depending on characteristics of the lower free-tropospheric winds due to the vast travel distance. Daily dust mass concentrations from July and August, the months that contribute the most to the annual mean, are used to characterize the synoptic conditions most favorable for dust transport. Two key regions are linked with the highest daily dust mass concentrations above Miami: (i) easterly winds, averaged over 850–500 mb, over the Tropical West Atlantic [15–25°N, 45–80°W], and (ii) southerly winds, similarly averaged, over the Florida Peninsula [20–30°N,75–80°W]. Winds within these two regions are enhanced when the North Atlantic subtropical high is displaced south and zonally elongated, relocating the western edge over Florida. A dust-transport-efficiency index, based on the maximum potential for dust to arrive above Miami with limited loss to deposition or mixing, identifies high-dust loading cases on the subseasonal scale. Monthly dust-transport-efficiency values agree well with the monthly dust trends over the 43-year time span. While seasonal dust loadings have been decreasing over Florida in the past decade, the transport efficiency has been increasing, possibly due to trends in the North Atlantic subtropical high.

54 ENVIRONMENTAL SCIENCES↗

Sediment Records Shed Light on Drivers of Decadal Iron Concentration Increase in a Boreal Lake

Increasing iron (Fe) concentrations are found in lakes on a wide geographical scale but exact causes are still debated. The observed trends might result from increased Fe loading from the terrestrial catchment, but also from changes in how Fe distributes between the water column and the sediments. To get a better understanding of the causes we investigated whether there has been any change in the sediment formation of Fe sulfides (FeS) as an Fe sink in response to declining atmospheric sulfur (S) deposition during recent decades. For our study, we chose Lake Bolmen in southern Sweden, a lake for which we confirmed that Fe concentrations in the water column have strongly increased along with water color during 1966–2018. Our investigations showed that Fe accumulation and speciation varied independently of S accumulation patterns in the Lake Bolmen sediment record. Thus, we were not able to relate the positive trend in Fe concentrations to reduced FeS binding in the sediments. Furthermore, we found that Fe accumulation rates increased along with lake water Fe concentrations, indicating that increased catchment loading rather than a change in the distribution between the sediments and the water column has driven the increase in Fe concentrations. The increased loading may be due to land-use change in the form of an extensive expansion of coniferous forest during the past century. Altered forest management practices and increased precipitation may have led to enhanced weathering and erosion of organic soil layers under aging coniferous forest.

58 GEOSCIENCES↗

Differential Trends in Iron Concentrations of Boreal Streams Linked to Catchment Characteristics

Increasing iron (Fe) concentrations have been reported for freshwaters across northern Europe over the last decades. This increase, together with elevated concentrations of dissolved organic carbon (DOC), leads to browning of freshwaters, which affects aquatic organisms, ecosystem functioning, biogeochemical cycles, and brings challenges to drinking water production. However, how such increasing trends in stream Fe concentrations reflect the contribution of different catchment sources remains poorly resolved. Here, we explored how catchment characteristics, that is, mires and coniferous soils, regulate spatial and temporal patterns of Fe in a boreal stream network. For this, we determined Fe speciation in riparian and mire soils, and studied temporal Fe dynamics in soil-water and stream-water over a span of 18 years. Positive Fe trends were found in the solution of the riparian soil, while no long-term trend was observed in the mire. These differences were reflected in stream-water, where three headwater streams dominated by coniferous cover also displayed positive Fe trends, whereas the mire dominated stream showed no trend. Surprisingly, the majority of higher order streams showed declining Fe trends, despite long-term increases in DOC. In addition, we found that an extreme drought event led to a prolonged release of Fe and DOC from the riparian soils, that could have long-term effects on stream Fe concentrations. Our results show that riparian forest soils can be major contributors to ongoing increases in freshwater Fe concentrations and that drought can further promote the release of Fe from organic soils.

54 ENVIRONMENTAL SCIENCES↗

Concentrations and Health Implications of As, Hg, and Cd and Micronutrients in Rice and Emissions of CH 4 From Variably Flooded Paddies

Abstract The flooded soil conditions under which rice is typically grown are beneficial for boosting yield and decreasing herbicide inputs but may pose a food safety and environmental health risk. Flooded soils lead to reducing conditions and anaerobic metabolisms of soil microorganisms, which mobilizes arsenic from soil into soil solution, where it can be absorbed by rice roots and transported to grain. These conditions also promote the production and emission of methane (CH 4 )—a potent greenhouse gas. To evaluate how water management affects metal(loid) grain concentrations and CH 4 emissions, we conducted a 2‐year field study in which rice paddy water was managed under a range of soil redox conditions that spanned from flooded to non‐flooded. We observed that growing rice under less flooded conditions decreased CH 4 emissions and concentrations of grain total As, grain inorganic As, grain total Hg, and grain inorganic Hg relative to flooded conditions, with more reductions observed as conditions were drier; grain organic As and Hg (MeHg) species also decreased with drier conditions particularly in Year 1. However, the driest conditions tested led to a 50%–97% increase in grain Cd concentrations that exceeded the CODEX limit and grain yield reductions as high as 25% and 40% in Year 1 and 2, respectively. While concentrations of toxic metal(loid)s could be manipulated by water management, micronutrient concentrations were similar or decreased with drier conditions, potentially increasing grain Cd bioaccessibility to humans. Because practices for rice water management are gaining momentum, more research should monitor grain Cd levels along with micronutrients.

Environmental Sciences & Ecology↗

Quantifying concentration distributions in redox flow batteries with neutron radiography

Abstract The continued advancement of electrochemical technologies requires an increasingly detailed understanding of the microscopic processes that control their performance, inspiring the development of new multi-modal diagnostic techniques. Here, we introduce a neutron imaging approach to enable the quantification of spatial and temporal variations in species concentrations within an operating redox flow cell. Specifically, we leverage the high attenuation of redox-active organic materials (high hydrogen content) and supporting electrolytes (boron-containing) in solution and perform subtractive neutron imaging of active species and supporting electrolyte. To resolve the concentration profiles across the electrodes, we employ an in-plane imaging configuration and correlate the concentration profiles to cell performance with polarization experiments under different operating conditions. Finally, we use time-of-flight neutron imaging to deconvolute concentrations of active species and supporting electrolyte during operation. Using this approach, we evaluate the influence of cell polarity, voltage bias and flow rate on the concentration distribution within the flow cell and correlate these with the macroscopic performance, thus obtaining an unprecedented level of insight into reactive mass transport. Ultimately, this diagnostic technique can be applied to a range of (electro)chemical technologies and may accelerate the development of new materials and reactor designs.

Science & Technology - Other Topics↗

Safety and efficacy of C. muridarum vaccines adjuvanted with CpG-1826 and four concentrations of Montanide-ISA-720-VG

It is recommended that the adjuvant Montanide ISA 720 VG be used at a concentration of 70% v/v. At this concentration, Montanide causes at the site of immunization a local granuloma that can last for several weeks. To determine the safety and protective efficacy of a Chlamydia muridarum MOMP vaccine, formulated with CpG-1826 and four different concentrations of Montanide (70%, 50%, 30% and 10%), BALB/c (H-2 d ) female mice were immunized twice intramuscularly. Local reactogenicity was significant for vaccines formulated with 70% or 50% Montanide but not for those inoculated with 30% or 10% Montanide. Robust humoral and cell mediated memory immune responses were elicited by the 70%, 50% and 30% Montanide formulations. Mice were challenged intranasally with 10 4 C. muridarum inclusion forming units (IFU). Based on changes in body weight, lungs’s weight and number of IFU recovered, mice vaccinated with the 70%, 50% and 30% Montanide formulations were significantly protected, but not mice receiving 10% Montanide. To conclude, we recommend the 30% Montanide concentration to be tested in humans and animal models to determine its safety and efficacy, in comparison to the 70% Montanide concentration currently used. The 30% Montanide formulation could significantly facilitate licensing of this adjuvant for human use.

60 APPLIED LIFE SCIENCES↗

Strong stretching theory for pH-responsive polyelectrolyte brushes in large salt concentrations

Here, we develop a theory for describing the thermodynamics, configuration, and electrostatics of strongly-stretched, pH-responsive polyelectrolyte (PE) brushes in the presence of large salt concentrations. The aim of the paper, therefore, is to study the properties of a PE brush in a salt concentration regime (namely, large concentrations of several molars) that has been hitherto unexplored theoretically in the context of PE brushes but can be routinely encountered in molecular scale simulations of the problem. The brushes are modelled using our recently developed augmented Strong Stretching Theory (SST), while the effect of the presence of the large salt concentration is accounted for by including the contributions of three different types of non-Poisson–Boltzmann (non-PB) effects to the free energy description of the PE brush induced electric double layer (EDL). These non-PB effects are ionic non-mean-field ion–ion correlations, solvent polarization, and the finite size effect of the ions and water dipoles. We study the individual influences of these different effects and show that the ion–ion correlations and solvent polarization effect reduce the brush height which consequently enhances the monomer density and leads to an electrostatic potential distribution of the brush induced EDL that has a larger magnitude at near-wall locations and becomes zero at shorter distances from the wall. The finite size effect, on the other hand, increases the brush height and therefore, weakens the monomer density and leads to a smaller near-wall magnitude of the EDL potential that becomes zero at larger distances from the wall. In time, we consider the impact of all the three non-PB effects simultaneously and show that the ion–ion correlations and solvent polarization effect dominate the size effects and dictate the overall brush configuration and the EDL electrostatics. We also point out that the influence of all the three non-PB effects becomes the largest for a larger salt concentration and a smaller bulk pH. Finally, we compare our theoretical predictions with those obtained from our recently developed all-atom MD simulation model and obtain an excellent match.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced ordering in length-polydisperse carbon nanotube solutions at high concentrations as revealed by small angle X-ray scattering

Carbon nanotubes (CNTs) are stiff, all-carbon macromolecules with diameters as small as one nanometer and few microns long. Solutions of CNTs in chlorosulfonic acid (CSA) follow the phase behavior of rigid rod polymers interacting via a repulsive potential and display a liquid crystalline phase at sufficiently high concentration. Here, we show that small-angle X-ray scattering and polarized light microscopy data can be combined to characterize quantitatively the morphology of liquid crystalline phases formed in CNT solutions at concentrations from 3 to 6.5% by volume. We find that upon increasing their concentration, CNTs self-assemble into a liquid crystalline phase with a pleated texture and with a large inter-particle spacing that could be indicative of a transition to higher-order liquid crystalline phases. We explain how thermal undulations of CNTs can enhance their electrostatic repulsion and increase their effective diameter by an order of magnitude. By calculating the critical concentration, where the mean amplitude of undulation of an unconstrained rod becomes comparable to the rod spacing, we find that thermal undulations start to affect steric forces at concentrations as low as the isotropic cloud point in CNT solutions.

36 MATERIALS SCIENCE↗

A recirculation system for concentrating CO 2 electrolyzer products

Electrochemical carbon dioxide reduction represents a promising path to utilize CO 2 as a feedstock for generating valuable products such as fuels and chemicals. Faradaic efficiencies near 100% have been achieved for certain CO 2 reduction products such as CO, but the electrolyzer outlet streams usually contain large fractions of unreacted CO 2 , dropping the product concentrations below 1% in many cases. The system disclosed here recycles the unreacted CO 2 together with the products and flows them back into the CO 2 reduction reactor, enabling much higher CO 2 conversion rates without dropping the gas flow rate. However, simple recirculation is shown to accumulate significant amounts of hydrogen, impeding effective CO 2 reduction. In this looped system, an electrochemical H 2 pump is placed in series with the CO 2 reactor, which effectively removes all the H 2 from the recycled gas stream, increasing the concentrations of carbon-containing products. Here, the system was initially tested with a CO-generating catalyst and CO concentrations above 70% were achieved in the recycled gas stream, compared to a maximum CO concentration of 8% in single-pass configuration. Results with a CO 2 reactor targeting ethylene as the main product show that ethylene concentrations of at least 10% can be achieved, which is roughly 20 times higher compared to a single-pass system.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Acid–base concentration swing for direct air capture of carbon dioxide

This work demonstrates the first experimental evidence of the acid–base concentration swing (ABCS) for direct air capture of CO 2 . This process is based on the effect that concentrating particular acid–base chemical reactants will strongly acidify solution, through Le Chatelier's principle, and result in outgassing absorbed CO 2 . After collecting the outgassed CO 2 , diluting the solution will result in a reversal of the acid–base reaction, basifying the solution and allowing for atmospheric CO 2 absorption. The experimental study examines a system that includes sodium cation as the alkalinity carrier, boric acid, and a polyol complexing agent that reversibly reacts with boric acid to strongly acidify solution upon concentration. Though the tested experimental system faces absorption rate and water capacity limitations, the ABCS process described here provides a basis for further process optimization. A generalized theoretical ABCS reaction framework is developed and different reaction orders and conditions are studied mathematically. Higher order reactions yield favorable cycle output results, reaching volumetric cycle capacity above 50 mM for third-order and 80 mM for fourth-order reactions. Optimal equilibrium constants are determined in order to guide alternative chemical searches and synthetic chemistry design targets. There is a substantial energetic benefit for reaction orders above the first, with second- and third-order ABCS cycles exhibiting a thermodynamic minimum work for the concentrating and outgassing steps around 150 kJ per mole of CO 2 . A significant advantage of the ABCS is that it can be driven through well-developed and widely-deployed desalination technologies, such as reverse osmosis, with opportunities for energy recovery when recombining the concentrated and diluted streams, and extraction can occur directly from the liquid phase upon vacuum application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of graphite oxide solution concentration on the properties of multilayer graphene

This paper reports the influence of graphite oxide (GO) solution concentration on the optical and electrical properties of multilayer graphene (MLG) films. Graphene oxide (GrO) films were deposited on the glass substrates by spin coating aqueous solutions of GO with different concentrations (7, 8, 9, 10 and 11 mg/ml). The GrO films were then thermally reduced at temperature of 500°C in argon flow for half an hour to form MLG films. Both the transmittance and sheet resistance decreased with the GO concentration from 8 mg/ml to 9 mg/ml, possibly due to thicker and uniform coverage of MLG over the substrate. However, the transmittance and sheet resistance increased rapidly as the GO concentration reached 11 mg/ml, which can be attributed to poor film quality. The MLG film obtained at concentration of 10 mg/ml showed the highest transmittance/sheet resistance ratio with 69 % transmittance and sheet resistance of 292 ± 63 kΩ/sq. The optimum MLG film was utilized as counter electrode in dye sensitized solar cells based on ZnO nanorods.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Effect of the minority concentration on ion cyclotron resonance heating in presence of the ITER-like wall in JET

The most recent JET campaign has focused on characterizing operation with the 'ITER-like' wall. One of the questions that needed to be answered is whether the auxiliary heating methods do not lead to unacceptably high levels of impurity influx, preventing fusion-relevant operation. In view of its high single pass absorption, hydrogen minority fundamental cyclotron heating in a deuterium plasma was chosen as the reference wave heating scheme in the ion cyclotron domain of frequencies. The present paper discusses the plasma behavior as a function of the minority concentration X[H] in L-mode with up to 4MW of RF power. It was found that the tungsten concentration decreases by a factor of 4 when the minority concentration is increased from X[H] ≈ 5% to X[H] % 20% and that it remains at a similar level when X[H] is further increased to 30%; a monotonic decrease in Beryllium emission is simultaneously observed. The radiated power drops by a factor of 2 and reaches a minimum at X[H] ≈ 20%. It is discussed that poor single pass absorption at too high minority concentrations ultimately tailors the avoidance of the RF induced impurity influx. The edge density being different for different minority concentrations, it is argued that the impact ICRH has on the fate of heavy ions is not only a result of core (wave and transport) physics but also of edge dynamics and fueling.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Corrosion in low dielectric constant Si-O based thin films: Buffer concentration effects

Organosilicate glass (OSG) is often used as an interlayer dielectric (ILD) in high performance integrated circuits. OSG is a brittle material and prone to stress-corrosion cracking reminiscent of that observed in bulk glasses. Of particular concern are chemical-mechanical planarization techniques and wet cleans involving solvents commonly encountered in microelectronics fabrication where the organosilicate film is exposed to aqueous environments. Previous work has focused on the effect of pH, surfactant, and peroxide concentration on the subcritical crack growth of these films. However, little or no attention has focused on the effect of the conjugate acid/base concentration in a buffer. Accordingly, this work examines the “strength” of the buffer solution in both acidic and basic environments. The concentration of the buffer components is varied keeping the ratio of acid/base and therefore pH constant. In addition, the pH was varied by altering the acid/base ratio to ascertain any additional effect of pH. Corrosion tests were conducted with double-cantilever beam fracture mechanics specimens and fracture paths were verified with ATR-FTIR. Shifts in the threshold fracture energy, the lowest energy required for bond rupture in the given environment, G{sub TH}, were found to shift to lower values as the concentration of the base in the buffer increased. This effect was found to be much larger than the effect of the hydroxide ion concentration in unbuffered solutions. The results are rationalized in terms of the salient chemical bond breaking process occurring at the crack tip and modeled in terms of the chemical potential of the reactive species.

36 MATERIALS SCIENCE↗

The effect of concentration- and temperature-dependent dielectric constant on the activity coefficient of NaCl electrolyte solutions

Our implicit-solvent model for the estimation of the excess chemical potential (or, equivalently, the activity coefficient) of electrolytes is based on using a dielectric constant that depends on the thermodynamic state, namely, the temperature and concentration of the electrolyte, ε(c, T). As a consequence, the excess chemical potential is split into two terms corresponding to ion-ion (II) and ion-water (IW) interactions. The II term is obtained from computer simulation using the Primitive Model of electrolytes, while the IW term is estimated from the Born treatment. In our previous work [J. Vincze, M. Valiskó, and D. Boda, “The nonmonotonic concentration dependence of the mean activity coefficient of electrolytes is a result of a balance between solvation and ion-ion correlations,” J. Chem. Phys. 133, 154507 (2010)], we showed that the nonmonotonic concentration dependence of the activity coefficient can be reproduced qualitatively with this II+IW model without using any adjustable parameter. The Pauling radii were used in the calculation of the II term, while experimental solvation free energies were used in the calculation of the IW term. In this work, we analyze the effect of the parameters (dielectric constant, ionic radii, solvation free energy) on the concentration and temperature dependence of the mean activity coefficient of NaCl. We conclude that the II+IW model can explain the experimental behavior using a concentration-dependent dielectric constant and that we do not need the artificial concept of “solvated ionic radius” assumed by earlier studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Separation of thorium (IV) from lanthanide concentrate (LC) and water leach purification (WLP) residue

Thorium (IV) content in industrial residue produced from rare earth elements production industry is one of the challenges to Malaysian environment. Separation of thorium from the lanthanide concentrate (LC) and Water Leach Purification (WLP) residue from rare earth elements production plant is described. Both materials have been tested by sulphuric acid and alkaline digestions. Th concentrations in LC and WLP were determined to be 1289.7 ± 129 and 1952.9±17.6 ppm respectively. The results of separation show that the recovery of Th separation from rare earth in LC after concentrated sulphuric acid dissolution and reduction of acidity to precipitate Th was found 1.76-1.20% whereas Th recovery from WLP was less than 4% after concentrated acids and alkali digestion processes. Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS) was used to determine Th concentrations in aqueous phase during separation stages. This study indicated that thorium maybe exists in refractory and insoluble form which is difficult to separate by these processes and stays in WLP residue as naturally occurring radioactive material (NORM)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗