Seasonal variation of aliphatic amines in marine sub-micrometer particles at the Cape Verde islands

Monomethylamine (MA), dimethylamine (DMA) and diethylamine (DEA) were detected at non-negligible concentrations in sub-micrometer particles at the Cap Verde Atmospheric Observatory (CVAO) located on the island of São Vicente in Cape Verde during algal blooms in 2007. The concentrations of these amines in five stage impactor samples ranged from 0–30 pg m−3 for MA, 130–360 pg m−3 for DMA and 5–110 pg m−3 for DEA during the spring bloom in May 2007 and 2–520 pg m−3 for MA, 100–1400 pg m−3 for DMA and 90–760 pg m−3 for DEA during an unexpected winter algal bloom in December 2007. Anomalously high Saharan dust deposition and intensive ocean layer deepening were found at the Atmospheric Observatory and the associated Ocean Observatory during algal bloom periods. The highest amine concentrations in fine particles (impactor stage 2, 0.14–0.42 μm) indicate that amines are likely taken up from the gas phase into the acidic sub-micrometer particles. The contribution of amines to the organic carbon (OC) content ranged from 0.2–2.5% C in the winter months, indicating the importance of this class of compounds to the carbon cycle in the marine environment. Furthermore, aliphatic amines originating from marine biological sources likely contribute significantly to the nitrogen content in the marine atmosphere. The average contribution of the amines to the detected nitrogen species in sub-micrometer particles can be non-negligible, especially in the winter months (0.1% N–1.5% N in the sum of nitrate, ammonium and amines). This indicates that these smaller aliphatic amines can be important for the carbon and the nitrogen cycles in the remote marine environment

Characterisation and optimisation of a sample preparation method for the detection and quantification of atmospherically relevant carbonyl compounds in aqueous medium

Carbonyl compounds are ubiquitous in the atmosphere and either emitted primarily from anthropogenic and biogenic sources or they are produced secondarily from the oxidation of volatile organic compounds. Despite a number of studies about the quantification of carbonyl compounds a comprehensive description of optimised methods is scarce for the quantification of atmospherically relevant carbonyl compounds. The method optimisation was conducted for seven atmospherically relevant carbonyl compounds including acrolein, benzaldehyde, glyoxal, methyl glyoxal, methacrolein, methyl vinyl ketone and 2,3-butanedione. O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was used as derivatisation reagent and the formed oximes were detected by gas chromatography/mass spectrometry (GC/MS). With the present method quantification can be carried out for each carbonyl compound originating from fog, cloud and rain or sampled from the gas- and particle phase in water. Detection limits between 0.01 and 0.17 μmol L−1 were found, depending on carbonyl compounds. Furthermore, best results were found for the derivatisation with a PFBHA concentration of 0.43 mg mL−1 for 24 h followed by a subsequent extraction with dichloromethane for 30 min at pH = 1. The optimised method was evaluated in the present study by the OH radical initiated oxidation of 3-methylbutanone in the aqueous phase. Methyl glyoxal and 2,3-butanedione were found to be oxidation products in the samples with a yield of 2% for methyl glyoxal and 14% for 2,3-butanedione after a reaction time of 5 h

Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents

In the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known α-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon α-pinene ozonolysis. It was reacted with ozone in the presence and absence of an OH radical scavenger, leading to SOA formation with a yield of 0.75 and 0.8, respectively. The resulting oxidation products in the gas and particle phases were investigated employing a denuder/filter sampling combination. Gas-phase oxidation products bearing a carbonyl group, which were collected by the denuder, were derivatised by 2,4-dinitrophenylhydrazine (DNPH) followed by liquid chromatography/negative ion electrospray ionisation time-of-flight mass spectrometry analysis and were compared to the gas-phase compounds detected by online proton-transfer-reaction mass spectrometry. Particle-phase products were also analysed, directly or after DNPH derivatisation, to derive information about specific compounds leading to SOA formation. Among the detected compounds, the aldehydic precursor of terpenylic acid was identified and its presence was confirmed in ambient aerosol samples from the DNPH derivatisation, accurate mass data, and additional mass spectrometry (MS² and MS³ fragmentation studies). Furthermore, the present investigation sheds light on a reaction pathway leading to the formation of terpenylic acid, involving α-pinene, α-pinene oxide, campholenic aldehyde, and terpenylic aldehyde. Additionally, the formation of diaterpenylic acid acetate could be connected to campholenic aldehyde oxidation. The present study also provides insights into the source of other highly functionalised oxidation products (e.g. <i>m</i> / <i>z</i> 201, C₉H₁₄O₅ and <i>m</i> / <i>z</i> 215, C₁₀H₁₆O₅), which have been observed in ambient aerosol samples and smog chamber-generated monoterpene SOA. The <i>m</i> / <i>z</i> 201 and 215 compounds were tentatively identified as a C₉- and C₁₀-carbonyl-dicarboxylic acid, respectively, based on reaction mechanisms of campholenic aldehyde and ozone, as well as detailed interpretation of mass spectral data, in conjunction with the formation of corresponding DNPH derivatives

An Analysis of Mutual Communication between Qubits by Capacitive Coupling

A behavior of a two qubit system coupled by the electric capacitance has been studied quantum mechanically. We found that the interaction is essentially the same as the one for the dipole-dipole interaction; i.e., qubit-qubit coupling of the NMR quantum gate. Therefore a quantum gate could be constructed by the same operation sequence for the NMR device if the coupling is small enough. The result gives an information to the effort of development of the devices assuming capacitive coupling between qubits.Comment: 8 pages, 2 figures Revised and Replaced on Apr. 8 200

Trace metal characterization of aerosol particles and cloud water during HCCT 2010

Trace metal characterization of bulk and size-resolved aerosol and cloud water samples were performed during the Hill Cap Cloud Thuringia (HCCT) campaign. Cloud water was collected at the top of Mt. Schmücke while aerosol samples were collected at two stations upwind and downwind of Mt. Schmücke. Fourteen trace metals including Ti, V, Fe, Mn, Co, Zn, Ni, Cu, As, Sr, Rb, Pb, Cr, and Se were investigated during four full cloud events (FCEs) that fulfilled the conditions of a continuous air mass flow through the three stations. Aerosol particle trace metal concentrations were found to be lower than those observed in the same region during previous field experiments but were within a similar range to those observed in other rural regions in Europe. Fe and Zn were the most abundant elements with concentration ranges of 0.2–111.6 and 1.1–32.1 ng m−3, respectively. Fe, Mn, and Ti were mainly found in coarse mode aerosols while Zn, Pb, and As were mostly found in the fine mode. Correlation and enrichment factor analysis of trace metals revealed that trace metals such as Ti and Rb were mostly of crustal origin while trace metals such as Zn, Pb, As, Cr, Ni, V, and Cu were of anthropogenic origin. Trace metals such as Fe and Mn were of mixed origins including crustal and combustion sources. Trace metal cloud water concentration decreased from Ti, Mn, Cr, to Co with average concentrations of 9.18, 5.59, 5.54, and 0.46 μg L−1, respectively. A non-uniform distribution of soluble Fe, Cu, and Mn was observed across the cloud drop sizes. Soluble Fe and Cu were found mainly in cloud droplets with diameters between 16 and 22 μm, while Mn was found mostly in larger drops greater than 22 μm. Fe(III) was the main form of soluble Fe especially in the small and larger drops with concentrations ranging from 2.2 to 37.1 μg L−1. In contrast to other studies, Fe(II) was observed mainly in the evening hours, implying its presence was not directly related to photochemical processes. Aerosol–cloud interaction did not lead to a marked increase in soluble trace metal concentrations; rather it led to differences in the chemical composition of the aerosol due to preferential loss of aerosol particles through physical processes including cloud drop deposition to vegetative surfaces

High prevalence of multidrug-resistant Pneumococcal molecular epidemiology network clones among Streptococcus pneumoniae isolates from adult patients with community-acquired pneumonia in Japan

AbstractA total of 141 Streptococcus pneumoniae isolates from patients with community-acquired pneumonia were collected from May 2003 through October 2004. The strains were tested for antimicrobial agent susceptibility, serotype and genotype by multilocus sequence typing (MLST) and the presence of the pilus rlrA islet. MLST analysis identified 49 sequence types (STs), of which 19 were novel. eBURST analysis using the MLST database (3773 STs) grouped the isolates into 27 clonal complexes and three singletons. A total of 92 (65.2%) isolates were related to ten of the 43 international Pneumococcal Molecular Epidemiology Network (PMEN) clones; major clones found were multidrug-resistant Netherlands3-31 [clonal complex (CC) 180], Taiwan19F-14 (CC271), Taiwan23F-15 (CC242), and Colombia23F-26 (CC138) (the latter new to Asia). We adopted univariate and multiple logistic regression models to identify factors associated with PMEN CCs. Multivariate analysis showed that multidrug resistance (OR 6.3; 95% CI 2.0–22.9), carriage serogroups (OR 7.2; 95% CI 2.5–23.7), prevalence of rlrA (OR 12.6; 95% CI 3.6–59.7) and central nervous system-related disorders (OR 7.7; 95% CI 1.8–48.4) were independently associated with PMEN CCs. Our data indicate that multidrug-resistant PMEN clones are highly prevalent, contributing to the high frequency of resistance to antimicrobial agents in Japan, and suggest that certain predisposing factors in patients contribute to the high frequency of these clones

Terpenylic acid and related compounds: precursors for dimers in secondary organic aerosol from the ozonolysis of α- and β-pinene

In the present study, we have characterized the structure of a higher-molecular weight (MW) 358 α- and β-pinene dimeric secondary organic aerosol (SOA) product that received ample attention in previous molecular characterization studies and has been elusive. Based on mass spectrometric evidence for deprotonated molecules formed by electrospray ionization in the negative ion mode and chemical considerations, it is suggested that diaterpenylic acid is a key monomeric intermediate for dimers of the ester type. It is proposed that cis-pinic acid is esterified with the hydroxyl-containing diaterpenylic acid, which can be explained through acid-catalyzed hydrolysis of the recently elucidated lactone-containing terpenylic acid and/or diaterpenylic acid acetate, both first-generation oxidation products. To a minor extent, higher-MW 358 and 344 diester products are formed containing other terpenoic acids as monomeric units, i.e., diaterpenylic acid instead of cis-pinic acid, and diaterebic acid instead of diaterpenylic acid. It is shown that the MW 358 diester and related MW 344 compounds, which can be regarded as processed SOA products, also occur in ambient fine (PM2.5) rural aerosol collected at night during the warm period of the 2006 summer field campaign conducted at K-puszta, Hungary, a rural site with coniferous vegetation. This indicates that, under ambient conditions, the higher-MW diesters are formed in the particle phase over a longer time-scale than that required for gas-to-particle partitioning of their monomeric precursors in laboratory α-/β-pinene ozonolysis experiments

Trace metal characterization of aerosol particles and cloud water during HCCT 2010

Trace metal characterization of bulk and size-resolved aerosol and cloud water samples were performed during the Hill Cap Cloud Thuringia (HCCT) campaign. Cloud water was collected at the top of Mt. Schmücke while aerosol samples were collected at two stations upwind and downwind of Mt. Schmücke. Fourteen trace metals including Ti, V, Fe, Mn, Co, Zn, Ni, Cu, As, Sr, Rb, Pb, Cr, and Se were investigated during four full cloud events (FCEs) that fulfilled the conditions of a continuous air mass flow through the three stations. Aerosol particle trace metal concentrations were found to be lower than those observed in the same region during previous field experiments but were within a similar range to those observed in other rural regions in Europe. Fe and Zn were the most abundant elements with concentration ranges of 0.2–111.6 and 1.1–32.1 ng m−3, respectively. Fe, Mn, and Ti were mainly found in coarse mode aerosols while Zn, Pb, and As were mostly found in the fine mode. Correlation and enrichment factor analysis of trace metals revealed that trace metals such as Ti and Rb were mostly of crustal origin while trace metals such as Zn, Pb, As, Cr, Ni, V, and Cu were of anthropogenic origin. Trace metals such as Fe and Mn were of mixed origins including crustal and combustion sources. Trace metal cloud water concentration decreased from Ti, Mn, Cr, to Co with average concentrations of 9.18, 5.59, 5.54, and 0.46 μg L−1, respectively. A non-uniform distribution of soluble Fe, Cu, and Mn was observed across the cloud drop sizes. Soluble Fe and Cu were found mainly in cloud droplets with diameters between 16 and 22 μm, while Mn was found mostly in larger drops greater than 22 μm. Fe(III) was the main form of soluble Fe especially in the small and larger drops with concentrations ranging from 2.2 to 37.1 μg L−1. In contrast to other studies, Fe(II) was observed mainly in the evening hours, implying its presence was not directly related to photochemical processes. Aerosol–cloud interaction did not lead to a marked increase in soluble trace metal concentrations; rather it led to differences in the chemical composition of the aerosol due to preferential loss of aerosol particles through physical processes including cloud drop deposition to vegetative surfaces

Parity Violation in Neutron Resonances in 107,109Ag

Parity nonconservation (PNC) was studied in p-wave resonances in Ag by measuring the helicity dependence of the neutron total cross section. Transmission measurements on natural Ag were performed in the energy range 32 to 422 eV with the time-of-flight method at the Manuel Lujan Neutron Scattering Center at Los Alamos National Laboratory. A total of 15 p-wave neutron resonances were studied in 107Ag and ninep-wave resonances in 109Ag. Statistically significant asymmetries were observed for eight resonances in 107Ag and for four resonances in109Ag. An analysis treating the PNC matrix elements as random variables yields a weak spreading width of Γw=(2.67-1.21+2.65)×10-7 eV for107Ag and Γw=(1.30-0.74+2.49)×10-7 eV for 109Ag

Parity Violation in 232Th Neutron Resonances Above 250 eV

The analysis of parity nonconservation (PNC) measurements performed on 232Th by the TRIPLE Collaboration has been extended to include the neutron energy range of 250 to 1900 eV. Below 250 eV all ten statistically significant parity violations have the same sign. However, at higher energies PNC effects of both signs were observed in the transmission of longitudinally polarized neutrons through a thick thorium target. Although the limited experimental energy resolution precluded analysis in terms of the longitudinal asymmetry, parity violations were observed and the cross section differences for positive and negative neutron helicities were obtained. For comparison, a similar analysis was performed on the data below 250 eV, for which longitudinal asymmetries were obtained previously. For energies below 250 eV, the p-wave neutron strength functions for the J=1/2 and J=3/2 states were extracted: S1/21=(1.68±0.61)×10-4 and S3/21=(0.75±0.18)×10-4. The data provide constraints on the properties of local doorway states proposed to explain the PNC sign effect in thorium