215 research outputs found
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Highly Speciated Measurements of Terpenoids Emitted from Laboratory and Mixed-Conifer Forest Prescribed Fires
Origins and composition of fine atmospheric carbonaceous aerosol in the Sierra Nevada Mountains, California
In this paper we report chemically resolved measurements
of organic aerosol (OA) and related tracers during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at the Blodgett Forest Research Station, California from 15 August–10 October 2007. OA contributed the majority of the mass to the fine atmospheric particles and was predominately oxygenated (OOA). The highest concentrations of OA were during sporadic wildfire influence when aged plumes were impacting the site. In
situ measurements of particle phase molecular markers were dominated by secondary compounds and along with gas phase compounds could be categorized into six factors or sources: (1) aged biomass burning emissions and oxidized urban emissions, (2) oxidized urban emissions (3) oxidation products of monoterpene emissions, (4) monoterpene emissions, (5) anthropogenic emissions and (6) local
methyl chavicol emissions and oxidation products. There were multiple biogenic components that contributed to OA at this site whose contributions varied diurnally, seasonally and in response to changing meteorological conditions, e.g. temperature and precipitation events. Concentrations of isoprene oxidation products were larger when temperatures were higher during the first half of the campaign (15 August–12 September) due to more substantial emissions of isoprene and enhanced photochemistry. The oxidation of methyl chavicol, an oxygenated terpene emitted by
ponderosa pine trees, contributed similarly to OA throughout the campaign. In contrast, the abundances of monoterpene oxidation products in the particle phase were greater during the cooler conditions in the latter half of the campaign (13 September–10 October), even though emissions of the precursors were lower, although the mechanism is not known. OA was correlated with the anthropogenic tracers 2-propyl nitrate and carbon monoxide (CO), consistent with previous observations, while being comprised of mostly non-fossil carbon (>75%). The correlation between OA and an anthropogenic tracer does not necessarily identify the source of the carbon as being anthropogenic but instead suggests a coupling between the anthropogenic and biogenic components in the air mass that might be related to the source of the oxidant and/or the aerosol sulfate. Observations of organosulfates of isoprene and α-pinene provided evidence for the likely importance of aerosol sulfate in spite of neutralized aerosol although acidic plumes might have played a role upwind of the site. This is in contrast to laboratory studies where strongly acidic seed aerosols were needed in order to form these compounds. These compounds together represented only a minor fraction (<1%) of the total OA mass, which may be the result of the neutralized aerosol at the site or because only a small number of organosulfates were quantified. The low contribution of organosulfates to total OA suggests that other mechanisms, e.g. NO_x enhancement of oxidant levels, are likely responsible for the majority of the anthropogenic enhancement of biogenic secondary organic aerosol observed at this site
Major components of atmospheric organic aerosol in southern California as determined by hourly measurements of source marker compounds
We report the first hourly in-situ measurements of speciated organic aerosol
(OA) composition in an urban environment. Field measurements were made in
southern California at the University of California–Riverside during the
2005 Study of Organic Aerosol at Riverside (SOAR), which included two
separate measurement periods: a summer study (15 July–15 August) and a
fall study (31 October–28 November). Hourly measurements of over 300
semivolatile and nonvolatile organic compounds were made using the thermal
desorption aerosol gas chromatograph (TAG). Positive matrix factorization
(PMF) was performed on a subset of these compounds to identify major
components contributing to submicron (i.e., PM<sub>1</sub>) OA at the site, as
measured by an aerosol mass spectrometer (AMS). PMF analysis was performed
on an 11-day focus period in each season, representing average seasonal
conditions during the summer and a period of urban influence during the
fall. As a result of this analysis, we identify multiple types of primary
and secondary OA (POA and SOA). Secondary sources contribute substantially
to fine OA mass at Riverside, which commonly receives regional air masses
that pass through metropolitan Los Angeles during the summer. Four
individual summertime SOA components are defined, and when combined, they
are estimated to contribute an average 88% of the total fine OA mass
during summer afternoons according to PMF results. These sources appear to
be mostly from the oxidation of anthropogenic precursor gases, with one SOA
component having contributions from oxygenated biogenics. During the fall,
three out of four aerosol components that contain SOA are inseparable from
covarying primary emissions, and therefore we cannot estimate the fraction
of total OA that is secondary in nature during the fall study. Identified
primary OA components are attributed to vehicle emissions, food cooking,
primary biogenics, and biomass burning aerosol. While a distinction between
local and regional vehicle emissions is made, a combination of these two
factors accounted for approximately 11% of observed submicron OA during
both sampling periods. Food cooking operations contributed ~10% of
submicron OA mass during the summer, but was not separable from SOA during
the fall due to high covariance of sources. Biomass burning aerosol
contributed a larger fraction of fine OA mass during the fall (~11%) than compared to summer (~7%). Primary biogenic aerosol
was also identified during the summer, contributing ~1% of the OA,
but not during the fall. While the contribution of both local and regional
primary vehicle OA accounts for only ~11% of total OA during both
seasons, gas-phase vehicle emissions likely create a substantial fraction of
the observed SOA as a result of atmospheric processing
Speciated and total emission factors of particulate organics from burning western US wildland fuels and their dependence on combustion efficiency
Western US wildlands experience frequent and large-scale wildfires which are predicted to increase in the future. As a result, wildfire smoke emissions are expected to play an increasing role in atmospheric chemistry while negatively impacting regional air quality and human health. Understanding the impacts of smoke on the environment is informed by identifying and quantifying the chemical compounds that are emitted during wildfires and by providing empirical relationships that describe how the amount and composition of the emissions change based upon different fire conditions and fuels. This study examined particulate organic compounds emitted from burning common western US wildland fuels at the US Forest Service Fire Science Laboratory. Thousands of intermediate and semi-volatile organic compounds (I/SVOCs) were separated and quantified into fire-integrated emission factors (EFs) using a thermal desorption, two-dimensional gas chromatograph with online derivatization coupled to an electron ionization/vacuum ultraviolet high-resolution time-of-flight mass spectrometer (TD-GC-GC-EI/VUV-HRToFMS). Mass spectra, EFs as a function of modified combustion efficiency (MCE), fuel source, and other defining characteristics for the separated compounds are provided in the accompanying mass spectral library. Results show that EFs for total organic carbon (OC), chemical families of I/SVOCs, and most individual I/SVOCs span 2-5 orders of magnitude, with higher EFs at smoldering conditions (low MCE) than flaming. Logarithmic fits applied to the observations showed that log (EFs) for particulate organic compounds were inversely proportional to MCE. These measurements and relationships provide useful estimates of EFs for OC, elemental carbon (EC), organic chemical families, and individual I/SVOCs as a function of fire conditions
Combinatorial CRISPR-Cas9 screens for de novo mapping of genetic interactions.
We developed a systematic approach to map human genetic networks by combinatorial CRISPR-Cas9 perturbations coupled to robust analysis of growth kinetics. We targeted all pairs of 73 cancer genes with dual guide RNAs in three cell lines, comprising 141,912 tests of interaction. Numerous therapeutically relevant interactions were identified, and these patterns replicated with combinatorial drugs at 75% precision. From these results, we anticipate that cellular context will be critical to synthetic-lethal therapies
Speciated and total emission factors of particulate organics from burning western US wildland fuels and their dependence on combustion efficiency
Western US wildlands experience frequent and large-scale wildfires which are
predicted to increase in the future. As a result, wildfire smoke emissions
are expected to play an increasing role in atmospheric chemistry while
negatively impacting regional air quality and human health. Understanding the
impacts of smoke on the environment is informed by identifying and
quantifying the chemical compounds that are emitted during wildfires and by
providing empirical relationships that describe how the amount and
composition of the emissions change based upon different fire conditions and
fuels. This study examined particulate organic compounds emitted from burning
common western US wildland fuels at the US Forest Service Fire Science
Laboratory. Thousands of intermediate and semi-volatile organic compounds
(I/SVOCs) were separated and quantified into fire-integrated emission factors
(EFs) using a thermal desorption, two-dimensional gas chromatograph with
online derivatization coupled to an electron ionization/vacuum ultraviolet
high-resolution time-of-flight mass spectrometer
(TD-GC × GC-EI/VUV-HRToFMS). Mass spectra, EFs as a function of
modified combustion efficiency (MCE), fuel source, and other defining
characteristics for the separated compounds are provided in the accompanying
mass spectral library. Results show that EFs for total organic carbon (OC),
chemical families of I/SVOCs, and most individual I/SVOCs span 2–5 orders of
magnitude, with higher EFs at smoldering conditions (low MCE) than flaming.
Logarithmic fits applied to the observations showed that log (EFs) for
particulate organic compounds were inversely proportional to MCE. These
measurements and relationships provide useful estimates of EFs for OC,
elemental carbon (EC), organic chemical families, and individual I/SVOCs as a
function of fire conditions.</p
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Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011
Understanding organic composition of gases and particles is essential to identifying sources and atmospheric processing leading to organic aerosols (OA), but atmospheric chemical complexity and the analytical techniques available often limit such analysis. Here we present speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) using a novel dual-use instrument (SV-TAG-AMS) deployed at Manitou Forest, CO, during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H_2O, Organics & Nitrogen – Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) 2011 campaign. This instrument provides on-line speciation of ambient organic compounds with 2 h time resolution. The species in this volatility range are complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C_(15)H_(24) (e.g., β-caryophyllene and longifolene), which were most abundant at night. A variety of other biogenic compounds were observed, including sesquiterpenoids with molecular formula C_(15)H_(22), abietatriene and other terpenoid compounds. Many of these compounds have been identified in essential oils and branch enclosure studies but were observed in ambient air for the first time in our study. Semivolatile polycyclic aromatic hydrocarbons (PAHs) and alkanes were observed with highest concentrations during the day and the dependence on temperature suggests the role of an evaporative source. Using statistical analysis by positive matrix factorization (PMF), we classify observed S/IVOCs by their likely sources and processes, and characterize them based on chemical composition. The total mass concentration of elutable S/IVOCs was estimated to be on the order of 0.7 µg m^(−3) and their volatility distributions are estimated for modeling aerosol formation chemistry
Primary cilia disappear in rat podocytes during glomerular development
Most tubular epithelial cell types express primary cilia, and mutations of primary-cilium-associated proteins are well known to cause several kinds of cystic renal disease. However, until now, it has been unclear whether mammalian podocytes express primary cilia in vivo. In this study, we determined whether primary cilia are present in the podocytes of rat immature and mature glomeruli by means of transmission electron microscopy of serial ultrathin sections. In immature glomeruli of fetal rats, podocytes express the primary cilia with high percentages at the S-shaped body (88 ± 5%, n = 3), capillary loop (95 ± 4%, n = 4), and maturing glomerulus (76 ± 13%, n = 5) stages. The percentage of ciliated podocytes was significantly lower at the maturing glomerulus stage than at the former two stages. In mature glomeruli of adult rats, ciliated podocytes were not found at all (0 ± 0%, n = 11). These findings indicate that the primary cilia gradually disappear in rat podocytes during glomerular development. Since glomerular filtration rate increases during development, the primary cilia on the podocytes are subjected to a stronger bending force. Thus, the disappearance of the primary cilia presumably prevents the entry of excessive calcium-ions via the cilium-associated polycystin complexes and the disturbance of intracellular signaling cascades in mature podocytes
Gas–particle partitioning of semivolatile organic compounds when wildfire smoke comes to town
Wildfires have become an increasingly important source of organic gases and particulate matter in the western USA. A large fraction
of organic particulate matter emitted in wildfires is semivolatile, and the
oxidation of organic gases in smoke can form lower-volatility products that
then condense on smoke particulates. In this research, we measured the gas-
and particle-phase concentrations of semivolatile organic compounds (SVOCs)
during the 2017 northern California wildfires in a downwind urban area,
using semivolatile thermal desorption aerosol gas chromatography
(SV-TAG), and measured SVOCs in a rural site affected by biomass burning
using cTAG (comprehensive thermal desorption aerosol gas chromatography mass spectrometry) in Idaho in 2018. Commonly used biomass burning markers such as levoglucosan, mannosan, and nitrocatechols were found to stay predominantly in the particle phase, even when the ambient organic aerosol (OA) was relatively low. The phase partitioning of SVOCs is observed to be dependent on their saturation vapor pressure, while the equilibrium absorption model underpredicts the particle-phase fraction of most of the compounds measured. Wildfire organic aerosol enhanced the condensation of polar compounds into the particle phase but not some nonpolar compounds, such as polycyclic aromatic hydrocarbons.</p
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