54 research outputs found
Molecular insights on aging and aqueous-phase processing from ambient biomass burning emissions-influenced Po Valley fog and aerosol
To study the influence of regional biomass burning emissions and secondary processes, ambient samples of fog and aerosol were collected in the Po Valley (Italy) during the 2013 Supersito field campaign. After the extent of fresh vs. aged biomass burning influence was estimated from proton nuclear magnetic resonance (1H NMR) and high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), two samples of fog water and two samples of PM1 aerosol were selected for ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis. Molecular compositions indicated that the water-soluble organic matter was largely non-polymeric without clearly repeating units. The selected samples had an atypically large frequency of molecular formulas containing nitrogen and sulfur (not evident in the NMR composition) attributed to multifunctional organonitrates and organosulfates. Higher numbers of organonitrates were observed in aerosol, and higher numbers of organosulfates were observed in fog water. Consistent with the observation of an enhanced aromatic proton signature in the 1H-NMR analysis, the average molecular formula double-bond equivalents and carbon numbers were higher in the fresh biomass-burning-influenced samples. The average O:C and H:C values from FT-ICR MS were higher in the samples with an aged influence (O:C = 0.50–0.58, and H:C = 1.31–1.37) compared to those with fresh influence (O:C = 0.43–0.48, and H:C = 1.13–1.30). The aged fog had a large set of unique highly oxygenated CHO fragments in the HR-ToF-AMS, which reflects an enrichment of carboxylic acids and other compounds carrying acyl groups, highlighted by the NMR analysis. Fog compositions were more oxidized and SOA (secondary organic aerosol)-like than aerosols as indicated by their NMR measured acyl-to-alkoxyl ratios and the observed molecular formula similarity between the aged aerosol and fresh fog, implying that fog nuclei must be somewhat aged. Overall, functionalization with nitrate and sulfate moieties, in addition to aqueous oxidation, triggers an increase in the molecular complexity in this environment, which is apparent in the FT-ICR MS results. This study demonstrates the significance of the aqueous phase in transforming the molecular chemistry of atmospheric organic matter and contributing to secondary organic aerosol
Bone and gut microbiota crosstalk: A novel 3D in vitro approach
The present research aimed at shedding light on the interplay between the composition of the human gut microbiota and bone cells
Elastic Tensor of SrRuO
The six independent elastic constants of SrRuO were determined using
resonant ultrasound spectroscopy on a high-quality single-crystal specimen. The
constants are in excellent agreement with those obtained from pulse-echo
experiments performed on a sample cut from the same ingot. A calculation of the
Debye temperature using the measured constants agrees well with values obtained
from both specific heat and M\"{o}ssbauer measurements.Comment: 4 pages, 2 figures, 2 tables, submitted to PR
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Size-resolved aerosol composition at an urban and a rural site in the Po Valley in summertime: implications for secondary aerosol formation
The aerosol size-segregated chemical composition was analyzed at an urban (Bologna) and a rural (San Pietro Capofiume) site in the Po Valley, Italy, during June and July 2012, by ion-chromatography (major water-soluble ions and organic acids) and evolved gas analysis (total and water-soluble carbon), to investigate sources and mechanisms of secondary aerosol formation during the summer. A significant enhancement of secondary organic and inorganic aerosol mass was observed under anticyclonic conditions with recirculation of planetary boundary layer air but with substantial differences between the urban and the rural site. The data analysis, including a principal component analysis (PCA) on the size-resolved dataset of chemical concentrations, indicated that the photochemical oxidation of inorganic and organic gaseous precursors was an important mechanism of secondary aerosol formation at both sites. In addition, at the rural site a second formation process, explaining the largest fraction (22 %) of the total variance, was active at nighttime, especially under stagnant conditions. Nocturnal chemistry in the rural Po Valley was associated with the formation of ammonium nitrate in large accumulation-mode (0.42–1.2 µm) aerosols favored by local thermodynamic conditions (higher relative humidity and lower temperature compared to the urban site). Nocturnal concentrations of fine nitrate were, in fact, on average 5 times higher at the rural site than in Bologna. The water uptake by this highly hygroscopic compound under high RH conditions provided the medium for increased nocturnal aerosol uptake of water-soluble organic gases and possibly also for aqueous chemistry, as revealed by the shifting of peak concentrations of secondary compounds (water-soluble organic carbon (WSOC) and sulfate) toward the large accumulation mode (0.42–1.2 µm). Contrarily, the diurnal production of WSOC (proxy for secondary organic aerosol) by photochemistry was similar at the two sites but mostly affected the small accumulation mode of particles (0.14–0.42 µm) in Bologna, while a shift to larger accumulation mode was observed at the rural site. A significant increment in carbonaceous aerosol concentration (for both WSOC and water-insoluble carbon) at the urban site was recorded mainly in the quasi-ultrafine fraction (size range 0.05–0.14 µm), indicating a direct influence of traffic emissions on the mass concentrations of this range of particles
Structure, computational and biochemical analysis of PcCel45A endoglucanase from <i>Phanerochaete chrysosporium </i>and catalytic mechanisms of GH45 subfamily C members
Abstract The glycoside hydrolase family 45 (GH45) of carbohydrate modifying enzymes is mostly comprised of β-1,4-endoglucanases. Significant diversity between the GH45 members has prompted the division of this family into three subfamilies: A, B and C, which may differ in terms of the mechanism, general architecture, substrate binding and cleavage. Here, we use a combination of X-ray crystallography, bioinformatics, enzymatic assays, molecular dynamics simulations and site-directed mutagenesis experiments to characterize the structure, substrate binding and enzymatic specificity of the GH45 subfamily C endoglucanase from Phanerochaete chrysosporium (PcCel45A). We investigated the role played by different residues in the binding of the enzyme to cellulose oligomers of different lengths and examined the structural characteristics and dynamics of PcCel45A that make subfamily C so dissimilar to other members of the GH45 family. Due to the structural similarity shared between PcCel45A and domain I of expansins, comparative analysis of their substrate binding was also carried out. Our bioinformatics sequence analyses revealed that the hydrolysis mechanisms in GH45 subfamily C is not restricted to use of the imidic asparagine as a general base in the “Newton’s cradle” catalytic mechanism recently proposed for this subfamily
Structure, computational and biochemical analysis of PcCel45A endoglucanase from phanerochaete chrysosporium and catalytic mechanisms of GH45 subfamily C members
FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORThe glycoside hydrolase family 45 (GH45) of carbohydrate modifying enzymes is mostly comprised of β-1,4-endoglucanases. Significant diversity between the GH45 members has prompted the division of this family into three subfamilies: A, B and C, which may d8FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR10/52362-511/20505-411/21608-115/13684-0405191/2015-4303988/2016-9440977/2016-9sem informaçãoThe PcCel45A dataset was collected at the Brookhaven National Laboratory, during the RapiData course. This study was supported by the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) via grants 10/52362-5, 11/20505-4, 11/21608-1 and 15/13684
Shipborne measurements of Antarctic submicron organic aerosols: an NMR perspective linking multiple sources and bioregions
Abstract. The concentrations of submicron aerosol particles in maritime regions around
Antarctica are influenced by the extent of sea ice. This effect is two ways:
on one side, sea ice regulates the production of particles by sea spray
(primary aerosols); on the other side, it hosts complex communities of
organisms emitting precursors for secondary particles. Past studies
documenting the chemical composition of fine aerosols in Antarctica indicate
various potential primary and secondary sources active in coastal areas, in
offshore marine regions, and in the sea ice itself. In particular,
beside the well-known sources of organic and sulfur material originating
from the oxidation of dimethylsulfide (DMS) produced by microalgae, recent
findings obtained during the 2015 PEGASO cruise suggest that
nitrogen-containing organic compounds are also produced by the microbiota
colonizing the marginal ice zone. To complement the aerosol source
apportionment performed using online mass spectrometric techniques, here we
discuss the outcomes of offline spectroscopic analysis performed by nuclear
magnetic resonance (NMR) spectroscopy. In this study we (i) present the
composition of ambient aerosols over open-ocean waters across bioregions,
and compare it to the composition of (ii) seawater samples and (iii) bubble-bursting aerosols produced in a sea-spray chamber onboard the ship. Our
results show that the process of aerosolization in the tank enriches primary
marine particles with lipids and sugars while depleting them of free
amino acids, providing an explanation for why amino acids occurred only at
trace concentrations in the marine aerosol samples analyzed. The analysis of
water-soluble organic carbon (WSOC) in ambient submicron aerosol samples
shows distinct NMR fingerprints for three bioregions: (1) the open Southern
Ocean pelagic environments, in which aerosols are enriched with primary
marine particles containing lipids and sugars; (2) sympagic areas in the
Weddell Sea, where secondary organic compounds, including methanesulfonic
acid and semivolatile amines abound in the aerosol composition; and (3)
terrestrial coastal areas, traced by sugars such as sucrose, emitted by land
vegetation. Finally, a new biogenic chemical marker, creatinine, was
identified in the samples from the Weddell Sea, providing another
confirmation of the importance of nitrogen-containing metabolites in
Antarctic polar aerosols
Leaching material from Antarctic seaweeds and penguin guano affects cloud-relevant aerosol production
Within the Southern Ocean, the greatest warming is occurring on the Antarctic Peninsula (AP) where clear cryospheric and biological consequences are being observed. Antarctic coastal systems harbour a high diversity of marine and terrestrial ecosystems heavily influenced by Antarctic seaweeds (benthonic macroalgae) and bird colonies (mainly penguins). Primary sea spray aerosols (SSA) formed by the outburst of bubbles via the sea-surface microlayer depend on the organic composition of the sea water surface. In order to gain insight into the influence of ocean biology and bio-geochemistry on atmospheric aerosol, we performed in situ laboratory aerosol bubble chamber experiments to study the effect of different leachates of biogenic material - obtained from common Antarctic seaweeds as well as penguin guano - on primary SSA. The addition of different leachate materials on a seawater sample showed a dichotomous effect depending on the leachate material added - either suppressing (up to 52%) or enhancing (22–88%) aerosol particle production. We found high ice nucleating particle number concentrations resulting from addition of guano leachate material. Given the evolution of upper marine polar coastal ecosystems in the AP, further studies on ocean-atmosphere coupling are needed in order to represent the currently poorly understood climate feedback processes.The study was further supported by the Spanish Ministry of Economy through project PI-ICE (no. CTM 2017–89117-R) and the Ramon y Cajal fellowship (no. RYC-2012-11922). This work acknowledges the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S). The National Centre for Atmospheric Science (NCAS) Birmingham group is funded by the UK Natural Environment Research Council. We gratefully acknowledge the funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation, Projektnummer 268020496–TRR 172) within the Transregional Collaborative Research Center “ArctiC Amplification: Climate Relevant Atmospheric and SurfaCe Processes, and Feedback Mechanisms (AC)3” in subproject B04.Peer reviewe
Sea Ice Microbiota in the Antarctic Peninsula Modulates Cloud-Relevant Sea Spray Aerosol Production
Este artículo contiene 21 páginas, 8 figuras.Sea spray aerosol (SSA) formation plays a major role in the climate system. The Antarctic
Peninsula (AP) is affected by the greatest warming occurring in the Southern Ocean;
changes in cryospheric and biological processes are being observed. Whilst there is some
evidence that organic material produced by ice algae and/or phytoplankton in the high
Arctic contributes to SSA, less is known about Antarctic Sea ice (sympagic) regions. To gain
insight into the influence of Antarctic Sea ice biology and biogeochemistry on atmospheric
aerosol, we report simultaneous water-air measurements made by means of in situ aerosol
chamber experiments. For the first time, we present a methodology showing that the
controlled plunging jet aerosol chamber settings do not cause major cell disruption on the
studied sea ice ecosystems. Larger sea ice phytoplankton cells (>20 μm; mainly diatoms)
tend to sediment at the bottomof the chamber (during the 24h experiment) and likely have a
minor role on SSA production. When comparing four chamber experiments - we find that
the two producing more SSA are the ones with highest abundance of nanophytoplankton
cells (<20 μm; mainly nanoflagellates) as well as viruses. Our marine biogeochemical data
show two broad groups of dissolved organic carbon: one rich in carbohydrates and proteic
material and one rich in humic-like substances; the latter enhancing SSA production. This
work provides unique insights into sea ice productivity that modulates SSA production, with
potentially significant climate impacts. Further studies of these types are advised in order to
see how microbiology impacts the biogeochemical cycling of elements and how aerosols
are formed and processed in cold regions.The study was further supported by the Spanish Ministry of
Economy through project PI-ICE (no. CTM 2017–89117-R) and
the Ramon y Cajal fellowship (no. RYC-2012-11922). This work
acknowledges the ‘Severo Ochoa Centre of Excellence’
accreditation (CEX2019-000928-S). The National Centre for
Atmospheric Science (NCAS) Birmingham group is funded by
the UK Natural Environment Research Council. DOC was
analyzed by Mara Abad (ICM-CSIC) and the POC was
analyzed at the IIM-CSIC (Vigo).Peer reviewe
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