493 research outputs found
Molecular dynamics simulations of the dipolar-induced formation of magnetic nanochains and nanorings
Iron, cobalt and nickel nanoparticles, grown in the gas phase, are known to
arrange in chains and bracelet-like rings due to the long-range dipolar
interaction between the ferromagnetic (or super-paramagnetic) particles. We
investigate the dynamics and thermodynamics of such magnetic dipolar
nanoparticles for low densities using molecular dynamics simulations and
analyze the influence of temperature and external magnetic fields on two- and
three-dimensional systems. The obtained phase diagrams can be understood by
using simple energetic arguments.Comment: 6 pages, 6 figure
Secondary aerosol formation from atmospheric reactions of aliphatic amines
Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase
Intestinal parasites from public and private latrines and the harbour canal in Roman Period Ephesus, Turkey (1st c. BCE to 6th c. CE)
To improve our knowledge of the parasite species affecting the inhabitants of Roman period Asia Minor, we analysed faecal material from Ephesus, Turkey. Mineralised material from the drain from a private house latrine (3rd c. CE), sediment samples from the sewer drain of a public communal latrine (6th c. CE), and sediment from the harbour canal (ca. 1st c. BCE to ca. 6th c. CE) were studied for the presence of intestinal parasites. Samples were viewed by light microscopy for helminth eggs, and commercial enzyme-linked immunosorbent assay (ELISA) kits were used to test for protozoal parasites that cause dysentery. Eggs of roundworm were found in the public latrine, whipworm in the house latrine, and both whipworm and roundworm in the harbour canal. Sequential sampling of the harbour core suggests that whipworm was by far the most common parasite throughout the Roman period, and there was no clear evidence for change in parasite species over the centuries. Whipworm and roundworm are both spread by the contamination of food and drink by human faeces. Despite the large number of travellers to Ephesus, as the capital of its province and a major port city in the Roman Empire, there was a surprising lack of diversity in parasite species found. This is especially apparent when we consider that ten species of intestinal parasite have been found across the Roman Empire. This is the first Roman site to be directly assessed for differences between infection in individuals using private latrines, public latrines, and mixed town effluent (in the harbour) at the same site.This research was supported by a doctoral award from the Social Sciences and Humanities Research Council of Canada [752-2016-2085] and a Tidmarsh Cambridge Scholarship from the Cambridge Commonwealth, European and International Trust and Trinity Hall Colleg
Characterization and Quantification of Isoprene-Derived Epoxydiols in Ambient Aerosol in the Southeastern United States
Isoprene-derived epoxydiols (IEPOX) are identified in ambient aerosol samples for the first time, together with other previously identified isoprene tracers (i.e., 2-methyltetrols, 2-methylglyceric acid, C5-alkenetriols, and organosulfate derivatives of 2-methyltetrols). Fine ambient aerosol collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS) was analyzed using both gas chromatography/quadrupole mass spectrometry (GC/MS) and gas chromatography/time-of-flight mass spectrometry (GC/TOFMS) with prior trimethylsilylation. Mass concentrations of IEPOX ranged from ~1 to 24 ng m^(−3) in the aerosol collected from the two sites. Detection of particle-phase IEPOX in the AMIGAS samples supports recent laboratory results that gas-phase IEPOX produced from the photooxidation of isoprene under low-NO_x conditions is a key precursor of ambient isoprene secondary organic aerosol (SOA) formation. On average, the sum of the mass concentrations of IEPOX and the measured isoprene SOA tracers accounted for about 3% of the organic carbon, demonstrating the significance of isoprene oxidation to the formation of ambient aerosol in this region
Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene
The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS)
Intrinsic solidification behaviour of basaltic to rhyolitic melts: a cooling rate experimental study
Dynamic cooling-induced solidification experiments were run using six silicate glasses
along the basalt - rhyolite join (B100= 100 wt % of basalt, R100= 100 wt % of rhyolite), i.e.
B100, B80R20, B60R40, B40R60, B20R80 and R100; the glasses directly quenched from 1300 °C
after a dwell of 120 minutes (experiment E0) contain 50-400 ppm H2O, << 1 area% μm-sized
bubble, and Fe2+/Fetot between 0.34 and 0.46. Experiments were performed in Pt capsules at
room pressure and fO2 of air, between 1300 and 800 °C using three different cooling rates of
0.0167, 3 and 30 °C/min; these cooling rates were run two times: E1-E2 experiments at
0.0167°C/min, S1-E3 at 3 °C/min, and E4-E5 at 30 °C/min. In experiments E1 to E5, samples
were annealed for 120 minutes at 1300 °C, whereas in the experiment S1 the samples were
firstly heated for 30 minutes at 1400 °C followed by a dwell time of 2400 minutes at 1300°C
before cooling. In the experiments a preferential crystallization was not observed at the
melt/gas interface. B100, B80R20 and B60R40 run-products have a low tendency to preferentially
crystallize on Pt walls, while B40R60, B20R80 and R100 are not affected by the presence of Pt
substrata. All run-products show very homogeneous textures, except for B60R40 and B40R60 at
0.0167°C/min in the E1 experiment. The duplicates of B40R60 and B60R40 at 0.0167°C/min
and B100 at 30 °C/min show relatively large differences in crystal content (> 4 and < 14
area%). B40R60 and B60R40 duplicated run-products have the same amount of earlycrystallized
clinopyroxene and spinel, but different contents in lately-formed plagioclase. The
run-products with the same starting composition from E3-S1 (3 °C/min) show a high
reproducibility in terms of crystal shape, size, and amount (< 4 area%). This demonstrates
that the crystallization path is not affected by the different heat treatment above the liquidus
temperature, i.e. the time scale of structural re-equilibration (relaxation) and chemical rehomogenization
are shorter than our experimental time scale. Possible chemicalheterogeneities on a length scale of several micrometers for R100 and several hundreds of
micrometers for B100 can be removed at 1300 °C within 120 minutes. A heat treatment at
1300 °C for 120 minutes significantly reduces the amount of μm-sized bubbles, potentially
responsible for the onset of nucleation and unreveals the intrinsic solidification of silicate
melts. The experimental reproducibility is low when the cooling path intersects the tip of the
time-temperature-transformation (TTT) curves, i.e. when the nucleation rate is near its
maximum (Imax). In that case, even small thermal variations in cooling rate and local
composition can have large effects on phase abundance and crystal size. Dynamic
crystallization experiments can be properly interpreted and compared only if they are
texturally homogeneous and the physico-chemical state of the superheated silicate liquid is
known. The solidification conditions used in this study mirror those of aphyric lavas and
dikes emplaced at shallower crustal levels
Rinikerfeld Palaeolake (Northern Switzerland) – a sedimentary archive of landscape and climate change during the penultimate glacial cycle
While timing and ice extent of the last glacial maximum are generally well known, the courses of earlier glaciations have remained poorly constrained, with one of the main reasons being the scarcity of sedimentary archives. This study introduces a new palaeolake record from a Mid‐Pleistocene glaciofluvial channel system in the Lower Aare Valley (Northern Switzerland). The record of Rinikerfeld comprises a >40 m long succession of Quaternary deposits that are targeted by multi‐method sedimentological analysis. Sedimentary facies together with geochemical and geotechnical parameters, pollen content, as well as luminescence ages allow the reconstruction of the establishment, evolution and infilling of the early Marine Isotope Stage 6‐aged Rinikerfeld Palaeolake. A drastic change in lake sediment composition and structure indicates cessation of the initial glacially derived input, which is explained by landscape modification and drainage rerouting during the Penultimate (Beringen) Glaciation. Geochemical and palynological data further reveal cold, initially periglacial but slightly ameliorating, climate conditions, while the lake was progressively filled up by local runoff, before being buried by periglacial colluvial diamicts, and potentially overridden by ice. It is therefore concluded that the onset of the Beringen Glaciation was an environmentally as well as geomorphically dynamic time period in the Northern Alpine Foreland
Seasonal characterization of submicron aerosol chemical composition and organic aerosol sources in the southeastern United States: Atlanta, Georgia,and Look Rock, Tennessee
A year-long near-real-time characterization of non-refractory submicron aerosol (NR-PM1) was conducted at an urban (Atlanta, Georgia, in 2012) and rural (Look Rock, Tennessee, in 2013) site in the southeastern US using the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) collocated with established air-monitoring network measurements. Seasonal variations in organic aerosol (OA) and inorganic aerosol species are attributed to meteorological conditions as well as anthropogenic and biogenic emissions in this region. The highest concentrations of NR-PM1 were observed during winter and fall seasons at the urban site and during spring and summer at the rural site. Across all seasons and at both sites, NR-PM1 was composed largely of OA (up to 76 %) and sulfate (up to 31 %). Six distinct OA sources were resolved by positive matrix factorization applied to the ACSM organic mass spectral data collected from the two sites over the 1 year of near-continuous measurements at each site: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), semi-volatile oxygenated OA (SV-OOA), low-volatility oxygenated OA (LV-OOA), isoprene-derived epoxydiols (IEPOX) OA (IEPOX-OA) and 91Fac (a factor dominated by a distinct ion at m∕z 91 fragment ion previously observed in biogenic influenced areas). LV-OOA was observed throughout the year at both sites and contributed up to 66 % of total OA mass. HOA was observed during the entire year only at the urban site (on average 21 % of OA mass). BBOA (15–33 % of OA mass) was observed during winter and fall, likely dominated by local residential wood burning emission. Although SV-OOA contributes quite significantly ( ∼ 27 %), it was observed only at the urban site during colder seasons. IEPOX-OA was a major component (27–41 %) of OA at both sites, particularly in spring and summer. An ion fragment at m∕z 75 is well correlated with the m∕z 82 ion associated with the aerosol mass spectrum of IEPOX-derived secondary organic aerosol (SOA). The contribution of 91Fac to the total OA mass was significant (on average 22 % of OA mass) at the rural site only during warmer months. Comparison of 91Fac OA time series with SOA tracers measured from filter samples collected at Look Rock suggests that isoprene oxidation through a pathway other than IEPOX SOA chemistry may contribute to its formation. Other biogenic sources could also contribute to 91Fac, but there remains a need to resolve the exact source of this factor based on its significant contribution to rural OA mass.</html
Особенности трансформации символа креста на территории средневековой Таврики
BACKGROUND: Cow's milk-derived whey hydrolysates are nutritional substitutes for allergic infants. Safety or residual allergenicity assessment of these whey hydrolysates is crucial. Currently, rat basophilic leukemia RBL-2H3 cells expressing the human IgE receptor α-chain (huFcεRIα-RBL-2H3), sensitized with serum IgE from cow's milk allergic children, are being employed to assess in vitro residual allergenicity of these whey hydrolysates. However, limited availability and inter-lot variation of these allergic sera impede standardization of whey hydrolysate safety testing in degranulation assays. OBJECTIVE: An oligoclonal pool of chimeric human (chu)IgE antibodies against bovine β-lactoglobulin (a major allergen in whey) was generated to increase sensitivity, specificity, and reproducibility of existing degranulation assays. METHODS: Mice were immunized with bovine β-lactoglobulin, and subsequently the variable domains of dissimilar anti-β-lactoglobulin mouse IgG antibodies were cloned and sequenced. Six chimeric antibodies were generated comprising mouse variable domains and human constant IgE/κ domains. RESULTS: After sensitization with this pool of anti-β-lactoglobulin chuIgEs, huFcεRIα-expressing RBL-2H3 cells demonstrated degranulation upon cross-linking with whey, native 18 kDa β-lactoglobulin, and 5-10 kDa whey hydrolysates, whereas a 3 kDa whey hydrolysate and cow's milk powder (mainly casein) showed no degranulation. In parallel, allergic serum IgEs were less sensitive. In addition, our pool anti-β-lactoglobulin chuIgEs recognized multiple allergenic immunodominant regions on β-lactoglobulin, which were also recognized by serum IgEs from cow's milk allergic children. CONCLUSION: Usage of our 'unlimited' source and well-defined pool of β-lactoglobulin-specific recombinant chuIgEs to sensitize huFcεRIα on RBL-2H3 cells showed to be a relevant and sensitive alternative for serum IgEs from cow's milk allergic patients to assess safety of whey-based non-allergic hydrolyzed formula
Investigating the influences of SO2 and NH3 levels on isoprene-derived secondary organic aerosol formation using conditional sampling approaches
Filter-based PM2.5 samples were chemically analyzed to investigate secondary organic aerosol (SOA) formation from isoprene in a rural atmosphere of the southeastern US influenced by both anthropogenic sulfur dioxide (SO2) and ammonia (NH3) emissions. Daytime PM2.5 samples were collected during summer 2010 using conditional sampling approaches based on pre-defined high and low SO2 or NH3 thresholds. Known molecular-level tracers for isoprene SOA formation, including 2-methylglyceric acid, 3-methyltetrahydrofuran-3,4-diols, 2-methyltetrols, C5-alkene triols, dimers, and organosulfate derivatives, were identified and quantified by gas chromatography coupled to electron ionization mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS). Mass concentrations of six isoprene low-NOx SOA tracers contributed to 12–19% of total organic matter (OM) in PM2.5 samples collected during the sampling period, indicating the importance of the hydroxyl radical (OH)-initiated oxidation (so-called photooxidation) of isoprene under low-NOx conditions that lead to SOA formation through reactive uptake of gaseous isoprene epoxydiols (IEPOX) in this region. The contribution of the IEPOX-derived SOA tracers to total organic matter was enhanced by 1.4% (p = 0.012) under high-SO2 sampling scenarios, although only weak associations between aerosol acidity and mass of IEPOX SOA tracers were observed. This suggests that IEPOX-derived SOA formation might be modulated by other factors simultaneously, rather than only aerosol acidity. No clear associations between isoprene SOA formation and high or low NH3 conditional samples were found. Positive correlations between sulfate aerosol loadings and IEPOX-derived SOA tracers for samples collected under all conditions indicates that sulfate aerosol could be a surrogate for surface accommodation in the uptake of IEPOX onto preexisting aerosols
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