Reaction Layer Formation on MgO in the Presence of Humidity.

Mineralization by MgO is an attractive potential strategy for direct air capture (DAC) of CO2 due to its tendency to form carbonate phases upon exposure to water and CO2. Hydration of MgO during this process is typically assumed to not be rate limiting, even at ambient temperatures. However, surface passivation by hydrated phases likely reduces the CO2 capture capacity. Here, we examine the initial hydration reactions that occur on MgO(100) surfaces to determine whether they could potentially impact CO2 uptake. We first used atomic force microscopy (AFM) to explore changes in reaction layers in water (pH = 6 and 12) and MgO-saturated solution (pH = 11) and found the reaction layers on MgO are heterogeneous and nonuniform. To determine how relative humidity (R.H.) affects reactivity, we reacted samples at room temperature in nominally dry N2 (∼11-12% R.H.) for up to 12 h, in humid (>95% R.H.) N2 for 5, 10, and 15 min, and in air at 33 and 75% R.H. for 8 days. X-ray reflectivity and electron microscopy analysis of the samples reveal that hydrated phases form rapidly upon exposure to humid air, but the growth of the hydrated reaction layer slows after its initial formation. Reaction layer thickness is strongly correlated with R.H., with denser reaction layers forming in 75% R.H. compared with 33% R.H. or nominally dry N2. The reaction layers are likely amorphous or poorly crystalline based on grazing incidence X-ray diffraction measurements. After exposure to 75% R.H. in air for 8 days, the reaction layer increases in density as compared to the sample reacted in humid N2 for 5-15 min. This may represent an initial step toward the crystallization of the reaction layer. Overall, high R.H. favors the formation of a hydrated, disordered layer on MgO. Based on our results, DAC in a location with a higher R.H. will be favorable, but growth may slow significantly from initial rates even on short timescales, presumably due to surface passivation.

Armoring of MgO by a Passivation Layer Impedes Direct Air Capture of CO2.

It has been proposed to use magnesium oxide (MgO) to separate carbon dioxide directly from the atmosphere at the gigaton level. We show experimental results on MgO single crystals reacting with the atmosphere for longer (decades) and shorter (days to months) periods with the goal of gauging reaction rates. Here, we find a substantial slowdown of an initially fast reaction as a result of mineral armoring by reaction products (surface passivation). In short-term experiments, we observe fast hydroxylation, carbonation, and formation of amorphous hydrated magnesium carbonate at early stages, leading to the formation of crystalline hydrated Mg carbonates. The preferential location of Mg carbonates along the atomic steps on the crystal surface of MgO indicates the importance of the reactive site density for carbonation kinetics. The analysis of 27-year-old single-crystal MgO samples demonstrates that the thickness of the reacted layer is limited to ∼1.5 µm on average, which is thinner than expected and indicates surface passivation. Thus, if MgO is to be employed for direct air capture of CO2, surface passivation must be circumvented.

Grain boundary widening controls siderite (FeCO3) replacement of limestone (CaCO3).

The microstructure of minerals and rocks can significantly alter reaction rates. This study focuses on identifying transport paths in low porosity rocks based on the hypothesis that grain boundary widening accelerates reactions in which one mineral is replaced by another (replacement reaction). We conducted a time series of replacement experiments of three limestones (CaCO3) of different microstructures and solid impurity contents using FeCl2. Reacted solids were analyzed using chemical imaging, small angle X-ray and neutron scattering and Raman spectroscopy. In high porosity limestones replacement is reaction controlled and complete replacement was observed within 2 days. In low porosity limestones that contain 1-2% dolomite impurities and are dominated by grain boundaries, a reaction rim was observed whose width did not change with reaction time. Siderite (FeCO3) nucleation was observed in all parts of the rock cores indicating the percolation of the solution throughout the complete core. Dolomite impurities were identified to act as nucleation sites leading to growth of crystals that exert force on the CaCO3 grains. Widening of grain boundaries beyond what is expected based on dissolution and thermal grain expansion was observed in the low porosity marble containing dolomite impurities. This leads to a self-perpetuating cycle of grain boundary widening and reaction acceleration instead of reaction front propagation.

Selenite and Selenate Sequestration during Coprecipitation with Barite: Insights from Mineralization Processes of Adsorption, Nucleation, and Growth.

Coprecipitation of selenium oxyanions with barite is a facile way to sequester Se in the environments. However, the chemical composition of Se-barite coprecipitates usually deviates from that predicted from thermodynamic calculations. This discrepancy was resolved by considering variations in nucleation and growth rates controlled by ion-mineral interactions, solubility, and interfacial energy. For homogeneous precipitation, ∼10% of sulfate, higher than thermodynamic predictions (<0.3%), was substituted by Se(IV) or Se(VI) oxyanion, which was attributed to adsorption-induced entrapment during crystal growth. For heterogeneous precipitation, thiol- and carboxylic-based organic films, utilized as model interfaces to mimic the natural organic-abundant environments, further enhanced the sequestration of Se(VI) oxyanions (up to 41-92%) with barite. Such enhancement was kinetically driven by increased nucleation rates of selenate-rich barite having a lower interfacial energy than pure barite. In contrast, only small amounts of Se(IV) oxyanions (∼1%) were detected in heterogeneous coprecipitates mainly due to a lower saturation index of BaSeO3 and deprotonation degree of Se(IV) oxyanion at pH 5.6. These roles of nanoscale mineralization mechanisms observed during composition selection of Se-barite could mark important steps toward the remediation of contaminants through coprecipitation.

Synergistic Enhancement of Lead and Selenate Uptake at the Barite (001)-Water Interface.

The interactions of heavy metals with minerals influence the mobility and bioavailability of toxic elements in natural aqueous environments. The sorption of heavy metals on covalently bonded minerals is generally well described by surface complexation models (SCMs). However, understanding sorption on sparingly soluble minerals is challenging because of the dynamically evolving chemistry of sorbent surfaces. The interpretation can be even more complicated when multiple metal ions compete for sorption. In the present study, we observed synergistically enhanced uptake of lead and selenate on the barite (001) surface through two sorption mechanisms: lattice incorporation that dominates at lower coverages and two-dimensional monolayer growth that dominates at higher coverages. We also observed a systematic increase in the sorption affinity with increasing co-sorbed ion coverages, different from the assumption of invariant binding constants for individual adsorption processes in classical SCMs. Computational simulations showed thermodynamically favorable co-incorporation of lead and selenate by simultaneously substituting for barium and sulfate in neighboring sites, resulting in the formation of molecular clusters that locally match the net dimension of the substrate lattice. These results emphasize the importance of ion-ion interactions at mineral-water interfaces that control the fate and transport of contaminants in the environment.

Diagnosis of multiple sclerosis in times of MOG and AQP4 autoantibody testing - A monocentric study.

BACKGROUND: Myelin oligodendrocyte glycoprotein-IgG-associated encephalomyelitis (MOG-EM) and neuromyelitis optica spectrum disorders are challenging differential diagnoses of multiple sclerosis (MS). Hence, there is uncertainty, whether to test all MS patients for corresponding antibodies. Our objective was to provide a systematic study on the frequency of MOG and Aquaporin-4 (AQP4) autoantibodies in MS patients to evaluate a possible risk of misclassification. METHODS: Retrospective study in MS patients (including an unselected cohort of patients diagnosed with MS, a cohort of patients with PPMS and a healthy control group) for seroprevalence of MOG and AQP4 autoantibodies by cell-based assay. RESULTS: None of 241 patients with relapsing-remitting, 19 with secondary progressive and 82 with primary progressive MS revealed MOG or AQP4 autoantibodies. CONCLUSION: General testing of MOG and AQP4 autoantibodies in MS patients seems not necessary, but should be limited to selected cases only.

Wind Power Persistence Characterized by Superstatistics.

Mitigating climate change demands a transition towards renewable electricity generation, with wind power being a particularly promising technology. Long periods either of high or of low wind therefore essentially define the necessary amount of storage to balance the power system. While the general statistics of wind velocities have been studied extensively, persistence (waiting) time statistics of wind is far from well understood. Here, we investigate the statistics of both high- and low-wind persistence. We find heavy tails and explain them as a superposition of different wind conditions, requiring q-exponential distributions instead of exponential distributions. Persistent wind conditions are not necessarily caused by stationary atmospheric circulation patterns nor by recurring individual weather types but may emerge as a combination of multiple weather types and circulation patterns. This also leads to Fréchet instead of Gumbel extreme value statistics. Understanding wind persistence statistically and synoptically may help to ensure a reliable and economically feasible future energy system, which uses a high share of wind generation.

Organic-mineral interfacial chemistry drives heterogeneous nucleation of Sr-rich (Ba x , Sr1-x )SO4 from undersaturated solution.

Sr-bearing marine barite [(Ba x , Sr1-x )SO4] cycling has been widely used to reconstruct geochemical evolutions of paleoenvironments. However, an understanding of barite precipitation in the ocean, which is globally undersaturated with respect to barite, is missing. Moreover, the reason for the occurrence of higher Sr content in marine barites than expected for classical crystal growth processes remains unknown. Field data analyses suggested that organic molecules may regulate the formation and composition of marine barites; however, the specific organic-mineral interactions are unclear. Using in situ grazing incidence small-angle X-ray scattering (GISAXS), size and total volume evolutions of barite precipitates on organic films were characterized. The results show that barite forms on organic films from undersaturated solutions. Moreover, from a single supersaturated solution with respect to barite, Sr-rich barite nanoparticles formed on organics, while micrometer-size Sr-poor barites formed in bulk solutions. Ion adsorption experiments showed that organic films can enrich cation concentrations in the adjacent solution, thus increasing the local supersaturation and promoting barite nucleation on organic films, even when the bulk solution was undersaturated. The Sr enrichment in barites formed on organic films was found to be controlled by solid-solution nucleation rates; instead, the Sr-poor barite formation in bulk solution was found to be controlled by solid-solution growth rates. This study provides a mechanistic explanation for Sr-rich marine barite formation and offers insights for understanding and controlling the compositions of solid solutions by separately tuning their nucleation and growth rates via the unique chemistry of solution-organic interfaces.

Correlative Atom Probe Tomography and Transmission Electron Microscopy Analysis of Grain Boundaries in Thermally Grown Alumina Scale.

We employed correlative atom probe tomography (APT) and transmission electron microscopy (TEM) to analyze the alumina scale thermally grown on the oxide dispersion-strengthened alloy MA956. Segregation of Ti and Y and associated variation in metal/oxygen stoichiometry at the grain boundaries and triple junctions of alumina were quantified and discussed with respect to the oxidation behavior of the alloy, in particular, to the formation of cation vacancies. Correlative TEM analysis was helpful to avoid building pragmatically well-looking but substantially incorrect APT reconstructions, which can result in erroneous quantification of segregating species, and highlights the need to consider ionic volumes and detection efficiency in the reconstruction routine. We also demonstrate a cost-efficient, robust, and easy-handling setup for correlative analysis based solely on commercially available components, which can be used with all conventional TEM tools without the need to modify the specimen holder assembly.

Development of atopic sensitization in Finnish and Estonian children: A latent class analysis in a multicenter cohort.

BACKGROUND: The prevalence of atopy is associated with a Western lifestyle, as shown by studies comparing neighboring regions with different socioeconomic backgrounds. Atopy might reflect various conditions differing in their susceptibility to environmental factors. OBJECTIVE: We sought to define phenotypes of atopic sensitization in early childhood and examine their association with allergic diseases and hereditary background in Finland and Estonia. METHODS: The analysis included 1603 Finnish and 1657 Estonian children from the DIABIMMUNE multicenter young children cohort. Specific IgE levels were measured at age 3, 4, and 5 years, respectively, and categorized into 3 CAP classes. Latent class analysis was performed with the statistical software package poLCA in R software. RESULTS: Both populations differed in terms of socioeconomic status and environmental determinants, such as pet ownership, farm-related exposure, time spent playing outdoors, and prevalence of allergic diseases (all P < .001). Nevertheless, we found similar latent classes in both populations: an unsensitized class, a food class, 2 inhalant classes differentiating between seasonal and perennial aeroallergens, and a severe atopy class. The latter was characterized by high total and specific IgE levels and strongly associated with wheeze (odds ratio [OR], 5.64 [95% CI, 3.07-10.52] and 4.56 [95% CI, 2.35-8.52]), allergic rhinitis (OR, 22.4 [95% CI, 11.67-44.54] and 13.97 [95% CI, 7.33-26.4]), and atopic eczema (OR, 9.39 [95% CI, 4.9-19.3] and 9.5 [95% CI, 5.2-17.5] for Finland and Estonia, respectively). Environmental differences were reflected in the larger seasonal inhalant atopy class in Finland, although composition of classes was comparable between countries. CONCLUSION: Despite profound differences in environmental exposures, there might exist genuine patterns of atopic sensitization. The distribution of these patterns might determine the contribution of atopic sensitization to disease onset.

Impact of climate change on backup energy and storage needs in wind-dominated power systems in Europe.

The high temporal variability of wind power generation represents a major challenge for the realization of a sustainable energy supply. Large backup and storage facilities are necessary to secure the supply in periods of low renewable generation, especially in countries with a high share of renewables. We show that strong climate change is likely to impede the system integration of intermittent wind energy. To this end, we analyze the temporal characteristics of wind power generation based on high-resolution climate projections for Europe and uncover a robust increase of backup energy and storage needs in most of Central, Northern and North-Western Europe. This effect can be traced back to an increase of the likelihood for long periods of low wind generation and an increase in the seasonal wind variability.

Modeling long correlation times using additive binary Markov chains: Applications to wind generation time series.

Wind power generation exhibits a strong temporal variability, which is crucial for system integration in highly renewable power systems. Different methods exist to simulate wind power generation but they often cannot represent the crucial temporal fluctuations properly. We apply the concept of additive binary Markov chains to model a wind generation time series consisting of two states: periods of high and low wind generation. The only input parameter for this model is the empirical autocorrelation function. The two-state model is readily extended to stochastically reproduce the actual generation per period. To evaluate the additive binary Markov chain method, we introduce a coarse model of the electric power system to derive backup and storage needs. We find that the temporal correlations of wind power generation, the backup need as a function of the storage capacity, and the resting time distribution of high and low wind events for different shares of wind generation can be reconstructed.

Chorea-Acanthocytosis Presenting as Autosomal Recessive Epilepsy in a Family With a Novel VPS13A Mutation.

Chorea-acanthocytosis (ChAc) is a rare, adult-onset disease usually characterized by, hence the name, a movement disorder and acanthocytosis in the blood. It is caused by mutations of the VPS13A gene with an autosomal recessive transmission. We report a consanguineous Turkish family with a different and informative clinical and diagnostic course. Three siblings developed seizures and the index patient had been diagnosed with bilateral temporal lobe epilepsy. A key finding, however, was the basal ganglia involvement in neuroimaging although no movement disorder was present. [18F]FDG-PET showed a prominent decline in striatal glucose metabolism at 31 years of age and [123I]FP-CIT-SPECT revealed a moderate loss of striatal dopamine transporter availability. The family was referred for genetic testing and exome sequencing detected a homozygous novel truncating mutation c.4326 T>A (p.Tyr1442*) in VPS13A in all affected siblings. With this case, we present autosomal recessive epilepsy as the predominant phenotype of ChAc with a new homozygous VPS13A mutation and provide pathological structural and molecular neuroimaging findings.

The effect of cortisol on autobiographical memory retrieval depends on remoteness and valence of memories.

There is evidence that specificity of autobiographical memory (AM) retrieval is impaired by cortisol. However, it is unknown whether glucocorticoids differentially influence the retrieval of recent versus remote AMs. Therefore, the aim of the current study was to investigate the effects of cortisol on AM retrieval, in terms of memory specificity, with respect to remoteness of the retrieved memories. A placebo controlled, double blind study was conducted. Thirty female and 24 male healthy participants (mean age 24.5, SD=3.7) received either placebo or 10mg hydrocortisone before completing an autobiographical memory test. Participants showed higher memory specificity for recent memories compared to remote ones. There was no main effect of cortisol on AM retrieval. However, interaction effects suggest that cortisol affects remote, but not recent memories, which seems to depend upon valence.

Effects of hydrocortisone on false memory recognition in healthy men and women.

Most of the studies focusing on the effect of stress on false memories by using psychosocial and physiological stressors yielded diverse results. In the present study, we systematically tested the effect of exogenous hydrocortisone using a false memory paradigm. In this placebo-controlled study, 37 healthy men and 38 healthy women (mean age 24.59 years) received either 10 mg of hydrocortisone or placebo 75 min before using the false memory, that is, Deese-Roediger-McDermott (DRM), paradigm. We used emotionally charged and neutral DRM-based word lists to look for false recognition rates in comparison to true recognition rates. Overall, we expected an increase in false memory after hydrocortisone compared to placebo. No differences between the cortisol and the placebo group were revealed for false and for true recognition performance. In general, false recognition rates were lower compared to true recognition rates. Furthermore, we found a valence effect (neutral, positive, negative, disgust word stimuli), indicating higher rates of true and false recognition for emotional compared to neutral words. We further found an interaction effect between sex and recognition. Post hoc t tests showed that for true recognition women showed a significantly better memory performance than men, independent of treatment. This study does not support the hypothesis that cortisol decreases the ability to distinguish between old versus novel words in young healthy individuals. However, sex and emotional valence of word stimuli appear to be important moderators. (PsycINFO Database Record

IL-33 polymorphisms are associated with increased risk of hay fever and reduced regulatory T cells in a birth cohort.

BACKGROUND: IL-33 polymorphisms influence the susceptibility to asthma. IL-33 indirectly induces Th2-immune responses via dendritic cell activation, being important for development of atopic diseases. Furthermore, IL-33 upregulates regulatory T cells (Tregs), which are critical for healthy immune homeostasis. This study investigates associations between IL-33 polymorphisms during the development of childhood atopic diseases and underlying mechanisms including immune regulation of Tregs. METHODS: Genotyping of IL-33-polymorphisms (rs928413, rs1342326) was performed by MALDI-TOF-MS in 880 of 1133 PASTURE/EFRAIM children. In 4.5-year-old German PASTURE/EFRAIM children (n = 99), CD4+ CD25high FOXP3+ Tregs were assessed by flow cytometry following 24-h incubation of PBMCs with PMA/ionomycin, LPS or without stimuli (U). SOCS3, IL1RL1, TLR4 mRNA expression and sST2 protein levels ex vivo were measured in PASTURE/EFRAIM children by real-time PCR or ELISA, respectively. Health outcomes (hay fever, asthma) were assessed by questionnaires at the age of 6 years. RESULTS: rs928413 and rs1342326 were positively associated with hay fever (OR = 1.77, 95%CI = 1.02-3.08; OR = 1.79, 95%CI = 1.04-3.11) and CD4+ CD25high FOXP3+ Tregs (%) decreased in minor allele homozygotes/heterozygotes compared to major allele homozygotes (p(U) = 0.004; p(LPS) = 0.005; p(U) = 0.001; p(LPS) = 0.012). SOCS3 mRNA expression increased in minor allele homozygotes and heterozygotes compared with major allele homozygotes for both IL-33-polymorphisms (p(rs928413) = 0.032, p(rs1342326) = 0.019) and negatively correlated to Tregs. CONCLUSIONS: IL-33-polymorphisms rs928413 and rs1342326 may account for an increased risk of hay fever with the age of 6 years. Lower Tregs and increased SOCS3 in combined heterozygotes and minor allele homozygotes may be relevant for hay fever development, pointing towards dysbalanced immune regulation and insufficient control of allergic inflammation.

Does cortisol modulate emotion recognition and empathy?

INTRODUCTION: Emotion recognition and empathy are important aspects in the interaction and understanding of other people's behaviors and feelings. The Human environment comprises of stressful situations that impact social interactions on a daily basis. Aim of the study was to examine the effects of the stress hormone cortisol on emotion recognition and empathy. METHODS: In this placebo-controlled study, 40 healthy men and 40 healthy women (mean age 24.5 years) received either 10mg of hydrocortisone or placebo. We used the Multifaceted Empathy Test to measure emotional and cognitive empathy. Furthermore, we examined emotion recognition from facial expressions, which contained two emotions (anger and sadness) and two emotion intensities (40% and 80%). RESULTS: We did not find a main effect for treatment or sex on either empathy or emotion recognition but a sex × emotion interaction on emotion recognition. The main result was a four-way-interaction on emotion recognition including treatment, sex, emotion and task difficulty. At 40% task difficulty, women recognized angry faces better than men in the placebo condition. Furthermore, in the placebo condition, men recognized sadness better than anger. At 80% task difficulty, men and women performed equally well in recognizing sad faces but men performed worse compared to women with regard to angry faces. CONCLUSION: Apparently, our results did not support the hypothesis that increases in cortisol concentration alone influence empathy and emotion recognition in healthy young individuals. However, sex and task difficulty appear to be important variables in emotion recognition from facial expressions.

Role of Sortilin in Models of Autoimmune Neuroinflammation.

The proneurotrophin receptor sortilin is a protein with dual functions, being involved in intracellular protein transport, as well as cellular signal transduction. The relevance of the receptor for various neuronal disorders, such as dementia, seizures, and brain injury, is well established. In contrast, little is known about the role of sortilin in immune cells and inflammatory diseases. The aim of our study was to elucidate the distribution of sortilin in different immune cell types in mice and humans and to analyze its function in autoimmune CNS inflammation. Sortilin was expressed most profoundly in murine and human macrophages and dendritic cells and to a much lesser extent in B and T cells. In dendritic cells, sortilin had an impact on Ag processing. Accordingly, sortilin was highly expressed by infiltrated perivascular myeloid cells, mainly in vessel cuffs, in the CNS of patients suffering from multiple sclerosis, the most common inflammatory autoimmune disease of the CNS. Yet, sortilin gene-targeted mice (Sort1(-/-)) and chimeras deficient in sortilin in the immune system were as susceptible as wild-type littermates to T cell-dependent experimental autoimmune encephalomyelitis. Considering our results and recent data from other investigators, we conclude that the proneurotrophin receptor sortilin plays a role in innate, rather than in adaptive, immune processes and, thus, not in autoimmune neuroinflammation.