Microphysical explanation of the RH-dependent water affinity of biogenic organic aerosol and its importance for climate.

A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH-dependent SOA water-uptake with solubility and phase separation; (2) show that laboratory data on IP- and MT-SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single-parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.

Impact of Spironolactone on Longitudinal Changes in Health-Related Quality of Life in the Treatment of Preserved Cardiac Function Heart Failure With an Aldosterone Antagonist Trial.

BACKGROUND: Heart failure (HF) with preserved ejection fraction patients have equally impaired health-related quality of life (HRQL) compared with those with HF with reduced ejection fraction, but limited studies have evaluated the impact of therapies on changes in HRQL. METHODS AND RESULTS: Patients ≥50 years of age, with symptomatic HF and left ventricular ejection fraction ≥45%, were enrolled in Treatment of Preserved Cardiac Function Heart Failure With an Aldosterone Antagonist (TOPCAT) and randomized to spironolactone or placebo. Patients completed the Kansas City Cardiomyopathy Questionnaire (KCCQ), which was the primary HRQL instrument, and EQ5D visual analog scale at baseline, 4 months, 12 months, and annually thereafter. McMaster Overall Treatment Evaluation was assessed at 4 and 12 months to assess global change scores. Change scores (+SD) were calculated to determine between-group differences, and multivariable repeated-measures models were created to identify other factors associated with change scores. Paired KCCQ data were available for 91.7% of 3445 TOPCAT patients. By 4 months, the mean change in KCCQ was 7.7±16 and mean change in EQ5D visual analog scale was 4.7±16. Adjusted mean changes in KCCQ for the spironolactone group were significantly better than those for the placebo group at 4-month (1.54 better; P=0.002), 12-month (1.35 better; P=0.02), and 36-month (1.86 better; P=0.02) visits. No between-group differences in EQ5D visual analog scale change scores or McMaster Overall Treatment Evaluation were noted. Older age, obesity, current smoking, New York Heart Association class III/IV, and comorbid illnesses were associated with declines in KCCQ scores. Use of spironolactone was an independent predictor of improved KCCQ scores. CONCLUSIONS: In symptomatic HF with preserved ejection fraction patients, use of spironolactone was associated with an improvement in HF-specific HRQL. Several modifiable risk factors were associated with HRQL deterioration. CLINICAL TRIAL REGISTRATION: URL: http://www.clinicaltrials.gov. Unique identifier: NCT00094302.

Extraordinary capture of a Randall's snapper Randallichthys filamentosus in the temperate south-eastern Indian Ocean and its molecular phylogenetic relationship within the Etelinae.

The capture of a rarely encountered Randall's snapper Randallichthys filamentosus (female, 587 mm fork length) from the upper continental slope (c. 350 m) off the south coast of Western Australia (c. 34·5° S; 122·5° E) in January 2014 represents its first record from the temperate Indian Ocean and a southern range extension. This record suggests that spawning of this predominantly tropical species may probably be occurring in the eastern Indian Ocean, considering the extensive, and unlikely, distance the progeny would have otherwise travelled from its typical distribution in the western and central Pacific Ocean.

Diagnóstico precoce de pênfigo vulgar: relato de caso / Early diagnosis of penphigus vulgaris: case report

Relatamos um caso de pênfigo vulgar diagnosticado precocemente na consulta odontológica. Indivíduo de 42 anos apresenta-se com lesões bolhosas na mucosa bucal, com tempo de evolução aproximado de quatro meses. O laudo da biopsia incisional foi compatível com pênfigo vulgar. Imediatamente foi encaminhado para realização de exames complementares num centro especializado e, iniciou o tratamento. Geralmente, as lesões em mucosa oral precedem a aquelas em pele, dai a importância do cirurgião dentista no diagnóstico precoce desta doença potencialmente mortal.

We report a case of pemphigus vulgaris diagnosed early in a dental appointment. Male, 42 years-old, presented with bullous lesions in the oral mucosa, which developed within the last four months. The report of incisional biopsy was consistent with pemphigus vulgaris. He was immediately referred to further tests in a specialized center and started treatment. Generally, lesions in the oral mucosa precede those in the skin, hence the importance of the participation of the dentist in the early diagnosis of this potentially deadly disease.

Immersion freezing of supermicron mineral dust particles: freezing results, testing different schemes for describing ice nucleation, and ice nucleation active site densities.

Ice nucleation on mineral dust particles is known to be an important process in the atmosphere. To accurately implement ice nucleation on mineral dust particles in atmospheric simulations, a suitable theory or scheme is desirable to describe laboratory freezing data in atmospheric models. In the following, we investigated ice nucleation by supermicron mineral dust particles [kaolinite and Arizona Test Dust (ATD)] in the immersion mode. The median freezing temperature for ATD was measured to be approximately -30 °C compared with approximately -36 °C for kaolinite. The freezing results were then used to test four different schemes previously used to describe ice nucleation in atmospheric models. In terms of ability to fit the data (quantified by calculating the reduced chi-squared values), the following order was found for ATD (from best to worst): active site, pdf-α, deterministic, single-α. For kaolinite, the following order was found (from best to worst): active site, deterministic, pdf-α, single-α. The variation in the predicted median freezing temperature per decade change in the cooling rate for each of the schemes was also compared with experimental results from other studies. The deterministic model predicts the median freezing temperature to be independent of cooling rate, while experimental results show a weak dependence on cooling rate. The single-α, pdf-α, and active site schemes all agree with the experimental results within roughly a factor of 2. On the basis of our results and previous results where different schemes were tested, the active site scheme is recommended for describing the freezing of ATD and kaolinite particles. We also used our ice nucleation results to determine the ice nucleation active site (INAS) density for the supermicron dust particles tested. Using the data, we show that the INAS densities of supermicron kaolinite and ATD particles studied here are smaller than the INAS densities of submicron kaolinite and ATD particles previously reported in the literature.

[Differences in the selenium supply of cattle across Europe]. / Saisonale und überregionale Unterschiede im Selenversorgungsstatus von Rindern.

OBJECTIVE: Evaluation of differences in the selenium supply of cattle across Europe. MATERIAL AND METHODS: A total of 35,722 serum samples from cattle throughout Europe (unknown clinical status), which had been sent by veterinarians to the IDEXX Vet Med Lab Ludwigsburg, Germany between January 1st, 2006, and June 30th, 2013, were analyzed routinely for the selenium concentration using ICP-analysis. RESULTS: The collective data of the selenium concentration in cattle serum display seasonal variations, with a lower concentration during summer when compared to the winter. In recent years, the selenium supply has decreased. The farm size, husbandry conditions, economic situation, soil selenium concentration and the countries' specific feeding together play a key role in the selenium supply of the herd. Hungary and the Scandinavian countries Sweden and Denmark show the best selenium supply in Europe. A very poor situation exists in France and Luxembourg (> 50% of the cattle samples are undersupplied). CONCLUSION AND CLINICAL RELEVANCE: An optimal selenium supply for cattle is very important; a trace element deficiency can cause negative health effects and impair herd performance. The selenium concentration varies considerably, depending upon feeding and husbandry conditions. Therefore, a serum selenium analysis in cattle is essential and should be performed annually.

Occurrence and molecular typing of Giardia isolates in pet rabbits, chinchillas, guinea pigs and ferrets collected in Europe during 2006-2012.

A total of 1180 faecal samples (528 from rabbits, 531 from chinchillas and 121 from guinea pigs) collected during 2006-2012 by veterinarians in Germany and in other European countries were submitted to a diagnostic laboratory for Giardia testing by means of coproantigen ELISA. Of these samples, 40 rabbits (7.6 per cent), 326 chinchillas (61.4 per cent) and five guinea pigs (4.1 per cent ) were found to be positive. To gain insights into the genetic identity of Giardia in small mammals, ELISA-positive samples from 23 chinchillas, five ferrets, a rabbit, and a Desmarest's hutia were investigated by PCR and sequencing of fragments of the small subunit ribosomal DNA (ssu), the triose phosphate isomerase (tpi) and the ß-giardin (bg) genes. At the ssu locus, assemblage B was identified in 28 of 30 isolates, whereas assemblage A and D were each detected in one sample. The majority of isolates from chinchillas and those from ferrets had Giardia duodenalis sequences identical to sub-assemblages AI or BIV, based on either a single locus (tpi or bg) or multiple loci (tpi and bg). As sub-assemblages AI or BIV are associated with human infection, these results indicate that small mammals can act as reservoirs of cysts potentially infectious to humans.

Lemierre's syndrome: a serious complication of a routine dental procedure.

Lemierre's syndrome is the clinical presentation characterized by oropharyngeal or tonsillar infection, anaerobic septicaemia often with distant septic emboli, and clinical or radiological evidence of thrombosis of the internal jugular vein. We report a case of Lemierre's syndrome in a 44-year-old type II diabetic male. This case is unique for two reasons. Firstly, we believe it is the first reported iatrogenic case following a routine dental procedure. Secondly, the internal jugular vein thrombosis was found to occur on the contralateral side to the primary infection.

Out-of-hours maxillofacial trauma surgery: a risk factor for complications?

Recent literature from general and orthopaedic surgery as well as anaesthetic viewpoints has identified that operations performed outside normal work hours pose potential risks for both patients and healthcare workers. This is in contrast to the increasing pressure for 24h surgical availability for the public and the desire to reduce waiting times for patients. Further, there is evidence of the effects of fatigue on reducing performance. The authors aim to compare outcomes of maxillofacial trauma surgery performed in and out of normal work hours. Retrospective analysis was carried out on all maxillofacial trauma surgery under general anaesthesia at a tertiary referral hospital over a 14-month period. Outcomes of patient mortality, injury severity, patient demographics and operation duration were analysed with reference to two groups: in-hours (0800-1700 Monday to Friday) and out-of-hours (1700-0800 Monday to Friday as well as all operations performed Saturday and Sunday). 134 patients/procedures met the inclusion criteria, 53 out-of-hours and 81 in-hours. A statistically significant (p=0.05) higher complication rate (13%) was found in the out-of-hours cases compared to the in-hours cases (4%). The potential implications for this result on the need for increased availability of dedicated in-hours maxillofacial trauma operating lists at major hospitals are discussed.

[Seasonal and national differences in the selenium supply of horses across Europe]. / Saisonale und überregionale Unterschiede der Selenversorgung bei Pferden.

OBJECTIVE: Evaluation of the differences in the selenium supply to horses across Europe. MATERIAL AND METHODS: Serum samples from 137,152 horses all over Europe, which had been sent by veterinarians to IDEXX Vet Med Labor between January 1st 2006 and December 31st 2011, were routinely analyzed for the selenium concentration by means of ICP-analytic. RESULTS: The selenium content of the soil appears to play a key role in the selenium supply to horses. Countries closer to the ocean provided a better selenium supply than countries in central Europe. The best selenium supply can be seen in Denmark and in the Netherlands. The lowest values are obtained from Austria and Luxembourg. Furthermore, very large differences exist in the selenium supply in different regional areas within a country. This is particularly obvious across the German federal states, with a very good supply in the western areas and a very poor supply in the eastern states. The north-south divide is less obvious, similar to the selenium content of the soil. A very poor situation exists for central Austria, where more than 50% of the equine samples revealed an undersupply. CONCLUSION AND CLINICAL RELEVANCE: Individual horse-keeping and feeding represent key points in the selenium supply. Because of the differences in the selenium concentrations in pasture, silage and hay, and due to the lack of routinely performed analysis of the mineral content of food, it is extremely difficult from a management point of view to precisely adapt the intake of minerals. Hence, serum analyses of selenium in horses are very important and should be performed annually. In the case of an undersupply, selenium has to be supplemented with mineral food.

Myoepithelial cell differentiation markers in prepubertal bovine mammary gland: effect of ovariectomy.

We reported previously that ovariectomy alters prepubertal development of mammary myoepithelial cells (MC) by mechanisms that are not well understood. Therefore, in the present study, we analyzed expression of 2 myoepithelial differentiation markers, α-smooth muscle actin (SMA) and the common acute lymphoblastic leukemia antigen (CD10), in mammary parenchymal tissue from intact (INT) and ovariectomized (OVX) heifers. On d 40, Holstein heifers underwent either an ovariectomy (OVX; n=16) or a sham (INT; n=21) operation. At 55, 70, 85, 100, 130, and 160 d of age, tissues were collected, and multispectral imaging was used to quantify immunofluorescent staining for myoepithelial cell (MC) markers. Fluorescent intensity (FI) of the markers was normalized against a control sample. In the basal epithelial layer, CD10 FI was less and SMA FI was greater in OVX than INT. The ratio of SMA to CD10 FI, as a proxy indicator for MC differentiation, was greater in tissue from OVX compared with INT heifers after 55 d of age. The staining for SMA was frequently more intense along the basal aspect of cells, whereas CD10 expression was localized on the apical surface of the MC. In mammary tissue from both INT and OVX heifers, we observed basal cells that were negative for both CD10 and SMA, some of which appeared to span the distance from basement membrane to the ductal lumen. Interestingly, we also observed CD10+ cells adjacent to the ductal lumen, a situation that was more prevalent in OVX than in INT heifers. Also, ovariectomy affects MC expression of both SMA and CD10, as well as the pattern of MC development. Myoepithelial cells are known to limit parenchymal growth in other species. Involvement of MC as regulators of prepubertal bovine mammary development is worthy of further investigation.

Maxillary tuberosity fracture: a life-threatening haemorrhage following simple exodontia.

Maxillary tuberosity fracture is a potential complication of routine exodontia of posterior maxillary teeth. On rare occasions, such a complication can result in torrential haemorrhage due to the close proximity of significant vessels to the area. We present a case of life-threatening haemorrhage complicating a tuberosity fracture during simple extraction of a maxillary posterior tooth. The local anatomy of the region is discussed and we provide guidelines for general dental practitioners for the management of the complication of a tuberosity fracture during routine exodontia.

Reactive uptake kinetics of NO3 on multicomponent and multiphase organic mixtures containing unsaturated and saturated organics.

We investigated the reactive uptake of NO(3) (an important night-time oxidant in the atmosphere) on binary mixtures containing an unsaturated organic (methyl oleate) and saturated molecules (diethyl sebacate, dioctyl sebacate, and squalane) which we call matrix molecules. These studies were carried out to better understand the reactivity of unsaturated organics in multicomponent and multiphase atmospheric particles. For liquid binary mixtures the reactivity of methyl oleate depended on the matrix molecule. Assuming a bulk reaction, H(matrix)√(D(matrix)k(oleate)) varied by a factor of 2.7, and assuming a surface reaction H(matrix)(S)K(matrix)(S)k(oleate)(S) varied by a factor of 3.6, where H(matrix)√(D(matrix)k(oleate) and H(matrix)(S)K(matrix)(S)k(oleate)(S) are constants extracted from the data using the resistor model. For solid-liquid mixtures, the reactive uptake coefficient depended on exposure time: the uptake decreased by a factor of 10 after exposure to NO(3) for approximately 90 min. By assuming either a bulk or surface reaction, the atmospheric lifetime of methyl oleate in different matrices was estimated for moderately polluted atmospheric conditions. For all liquid mixtures, the lifetime was in the order of a few minutes (with an upper limit of 35 min). These lifetimes can be used as lower limits to the lifetimes in semi-solid mixtures. Our studies emphasize that the lifetime of unsaturated organics (similar to methyl oleate) is likely short if the particle matrix is in a liquid state.

Observations of high-density ferroelectric ordered water in kaolinite trenches using Monte Carlo simulations.

Grand canonical Monte Carlo simulations are employed to investigate the structure of water adsorbed on kaolinite surfaces with trenchlike defects. The results obtained for two water models (SPC/E and TIP5P-E) at 235 K are essentially the same. Calculation of water density profiles in all three dimensions shows that a dense ordered state is present in our trench systems. The narrowest trenches have the highest water density and display clearly layered structures along the width and depth of a trench. The water within a trench shows distinct proton order and is strongly ferroelectric. These ordered structures might be important in the initial stages of nucleation and growth of ice on kaolinite surfaces.

Inhibition of efflorescence in mixed organic-inorganic particles at temperatures less than 250 K.

It is now well recognized that mixed organic-inorganic particles are abundant in the atmosphere. While there have been numerous studies of efflorescence of mixed organic-inorganic particles close to 293 K, there are only a few at temperatures less than 273 K. Understanding the efflorescence properties of these particles at temperatures less than 273 K could be especially important for predicting ice nucleation in the upper troposphere. We studied the efflorescence properties of mixed citric acid-ammonium sulfate particles as a function of temperature to better understand the efflorescence properties of mixed organic-inorganic particles in the middle and upper troposphere. Our data for 293 K illustrate that the addition of citric acid decreases the ERH of ammonium sulfate, which is consistent with the trends observed with other systems containing highly oxygenated organic compounds. At low temperatures the trend is qualitatively the same, but efflorescence can be inhibited by smaller concentrations of citric acid. For example at temperatures <250 K an organic mass/(organic mass + sulfate mass) of only 0.33 is needed to inhibit efflorescence of ammonium sulfate. In the upper troposphere the organic mass/(organic mass + sulfate mass) can often be larger than this value. As a result, particles in the upper troposphere may be more likely to remain in the liquid state than previously thought and solid ammonium sulfate may be less likely to participate in heterogeneous ice nucleation in the upper troposphere. Additional studies are required on other model organic systems.

Water adsorption on kaolinite surfaces containing trenches.

Recent laboratory studies of water adsorption on kaolinite at 296 K, and at relative humidity (RH) values relevant for the atmosphere, have reported coverages ranging up to tens of monolayers. In contrast, recent simulations have suggested that atomistically smooth kaolinite surfaces uptake only monolayers (some slightly overgrown) at similar RH values. In an effort to possibly explain the laboratory data, we have performed water adsorption calculations on kaolinite surfaces containing trenchlike structures using the grand canonical Monte Carlo simulation method at 298 K. The results obtained show that the granularity of the surfaces can play a major role in the adsorption of multiple layers of water. For all trenches considered, multilayers of water were observed over a large range of RH. The narrowest trench investigated remained filled with water even in the very low RH regime (

Simulation of water adsorption on kaolinite under atmospheric conditions.

Grand canonical Monte Carlo calculations are employed to investigate water adsorption on kaolinite at 298 and 235 K. Both basal planes (the Al and Si surfaces) as well as two edge-like surfaces are considered. The general force field CLAYFF is used together with the SPC/E and TIP5P-E models for water. Problems that occur in single slab simulations due to arbitrary truncation of the point charge lattice are identified, and a working remedy is discussed. The edges and the Al surface adsorb water at subsaturation in the atmospherically relevant pressure range. The Si surface remains dry up to saturation. Both edges have a very strong affinity for water and adsorb continuously up to monolayer coverage. The Al surface has a weaker affinity for water but forms a subsaturation monolayer. On the Al surface, the monolayer is formed in an essentially sharp transition, and strong hysteresis is observed upon desorption. This indicates collective behavior among the water molecules which is not present for the edges. Binding energies of singly adsorbed water molecules at 10 K were determined to understand the differences in water uptake by the four kaolinite surfaces. Binding energies (SPC/E) of -21.6, -46.4, -73.5, and -94.1 kJ/mol, were determined for the Si surface, Al surface, unprotonated edge, and protonated edge, respectively. The water monolayer on the Al surface, particularly at 235 K, exhibits hexagonal patterns. However, the associated lattice parameters are not compatible with ice Ih. Water density and hydrogen bonding in the monolayers at both 298 and 235 K were also determined to better understand the structure of the adsorbed water.

Adsorption and structure of water on kaolinite surfaces: possible insight into ice nucleation from grand canonical monte carlo calculations.

Grand canonical Monte Carlo calculations are used to determine water adsorption and structure on defect-free kaolinite surfaces as a function of relative humidity at 235 K. This information is then used to gain insight into ice nucleation on kaolinite surfaces. Results for both the SPC/E and TIP5P-E water models are compared and demonstrate that the Al-surface [(001) plane] and both protonated and unprotonated edges [(100) plane] strongly adsorb at atmospherically relevant relative humidities. Adsorption on the Al-surface exhibits properties of a first-order process with evidence of collective behavior, whereas adsorption on the edges is essentially continuous and appears dominated by strong water lattice interactions. For the protonated and unprotonated edges no structure that matches hexagonal ice is observed. For the Al-surface some of the water molecules formed hexagonal rings. However, the a o lattice parameter for these rings is significantly different from the corresponding constant for hexagonal ice ( Ih). A misfit strain of 14.0% is calculated between the hexagonal pattern of water adsorbed on the Al-surface and the basal plane of ice Ih. Hence, the ring structures that form on the Al-surface are not expected to be good building-blocks for ice nucleation due to the large misfit strain.

Reactive uptake of N2O5 on aqueous H2SO4 solutions coated with 1-component and 2-component monolayers.

Reactive uptake of N(2)O(5) on aqueous sulfuric acid solutions was studied in the presence of 1-component (octadecanol) and 2-component (octadecanol + phytanic acid) monolayers. In the 1-component monolayer experiments, the reactive uptake coefficient depended strongly on the molecular surface area of the surfactant. Also, the 1-component monolayer showed significant resistance to mass transfer even when the fractional surface coverage of the surfactant was less than 1. For example, a monolayer of 1-octadecanol with a fractional surface coverage of 0.75 decreased the reactive uptake coefficient by a factor of 10. This is consistent with previous studies. In the 2-component monolayer experiments, the reactive uptake coefficient depended strongly on the composition of the monolayer. When the monolayer contained only straight-chain molecules (1-octadecanol), the reactive uptake coefficient decreased by a factor of 42 due to the presence of the monolayer. However, when the monolayer contained 0.20 mole fraction of a branched surfactant (phytanic acid) the reactive uptake coefficient only decreased by a factor of 2. Hence, a small amount of branched surfactant drastically changes the overall resistance to reactive uptake. Also, our results show that the overall resistance to reactive uptake of 2-component monolayers can be predicted reasonably accurately by a model that assumes the resistances to mass transfer can be combined in parallel.

N2O5 reactive uptake on aqueous sulfuric acid solutions coated with branched and straight-chain insoluble organic surfactants.

A flow reactor coupled to a chemical ionization mass spectrometer was used to study the reactive uptake coefficients at 273 K of N2O5 on aqueous 60 wt % sulfuric acid solutions coated with insoluble organic monolayers. Both straight-chain surfactants (1-hexadecanol, 1-octadecanol, and stearic acid) and a branched surfactant (phytanic acid) were studied. The reactive uptake coefficient decreased dramatically for straight-chain surfactants. The decrease ranged from a factor of 17 to a factor of 61 depending on the type of straight-chain surfactant. In contrast to the straight-chain data, the presence of phytanic acid did not have a significant effect on the N2O5 reactive uptake coefficient (the decrease was less than the uncertainty in the data) compared to the uncoated solution. In addition to measuring the reactive uptake coefficients, we also investigated the relationship between properties of the monolayers and the reactive uptake coefficients. The reactive uptake coefficients measured on aqueous sulfuric acid subphases showed a relationship to the surface area occupied by the surfactant molecules. However, data obtained with other subphases did not overlap with this trend.