Atmospheric organic matter in clouds: exact masses and molecular formula identification using ultrahigh-resolution FT-ICR mass spectrometry

Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gas- and particulate-phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at the Storm Peak Laboratory near Steamboat Springs, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh-resolution mass spectra of the samples after using a reversed-phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS and CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of ∼0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NOxoxidation. Multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite were observed, indicating the significance of nitrate radical reactions on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur-containing compounds) were also observed; however further investigation is needed to determine the origin of the reduced sulfur-containing compounds. Overall, the molecular composition determined using ultrahigh-resolution Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic anion composition in the Rocky Mountain area that could help to improve the understanding of aqueous-phase processes

Mixed-phase orographic cloud microphysics during StormVEx and IFRACS

Wintertime mixed-phase orographic cloud (MPC) measurements were conducted at the Storm Peak Laboratory (SPL) during the Storm Peak Lab Cloud Property Validation Experiment (StormVEx) and Isotopic Fractionation in Snow (IFRACS) programs in 2011 and 2014, respectively. The data include 92&thinsp;h of simultaneous measurements of supercooled liquid cloud droplet and ice particle size distributions (PSDs). Average cloud droplet number concentration (CDNC), droplet size (NMD), and liquid water content (LWC) were similar in both years, while ice particle concentration (Ni) and ice water content (IWC) were higher during IFRACS. The consistency of the liquid cloud suggests that SPL is essentially a cloud chamber that produces a consistent cloud under moist, westerly flow during the winter. A variable cloud condensation nuclei (CCN)-related inverse relationship between CDNC and NMD strengthened when the data were stratified by LWC. Some of this variation is due to changes in cloud base height below SPL. While there was a weak inverse correlation between LWC and IWC in the data as a whole, a stronger relationship was demonstrated for a case study on 9 February 2014 during IFRACS. A minimum LWC of 0.05&thinsp;g m−3 showed that the cloud was not completely glaciated on this day. Erosion of the droplet distribution at high IWC was attributed to the Wegener–Bergeron–Findeisen process as the high IWC was accompanied by a 10-fold increase in Ni. A relationship between large cloud droplet concentration (25–35&thinsp;µm) and small ice particles (75–200&thinsp;µm) under cold (&lt;-8&thinsp;∘C) but not warm (&gt;-8&thinsp;∘C) conditions during IFRACS suggests primary ice particle production by contact or immersion freezing. The effect of blowing snow was evaluated from the relationship between wind speed and Ni and by comparing the relative (percent) ice particle PSDs at high and low wind speeds. These were similar, contrary to expectation for blowing snow. However, the correlation between wind speed and ice crystal concentration may support this explanation for high crystal concentrations at the surface. Secondary processes could have contributed to high crystal concentrations but there was no direct evidence to support this. Further experimental work is needed to resolve these issues.</p

Atmospheric Radiation Measurements Aerosol Intensive Operating Period: Comparison of aerosol scattering during coordinated flights

Journal of Geophyshysical Research, Vol. 111, No. D5, D05S09The article of record as published may be located at http://dx.doi.org/10.1029/2005JD006250In May 2003, a Twin Otter airplane, equipped with instruments for making in situ measurements of aerosol optical properties, was deployed during the Atmospheric Radiation Measurements (ARM) Program’s Aerosol Intensive Operational Period in Oklahoma. Several of the Twin Otter flights were flown in formation with an instrumented light aircraft (Cessna 172XP) that makes routine in situ aerosol profile flights over the site. This paper presents comparisons of measured scattering coefficients at 467 nm, 530 nm, and 675 nm between identical commercial nephelometers aboard each aircraft. Overall, the agreement between the two nephelometers decreases with longer wavelength. During the majority of the flights, the Twin Otter flew with a diffuser inlet while the Cessna had a 1 mm impactor, allowing for an estimation of the fine mode fraction aloft. The fine mode fraction aloft was then compared to the results of a ground-based nephelometer. Comparisons are also provided in which both nephelometers operated with identical 1 mm impactors. These scattering coefficient comparisons are favorable at the longer wavelengths (i.e., 530 nm and 675 nm), yet differed by approximately 30% at 467 nm. Mie scattering calculations were performed using size distribution measurements, made during the level flight legs. Results are also presented from Cadenza, a new continuous wave cavity ring-down (CW-CRD) instrument, which compared favorably (i.e., agreed within 2%) with data from other instruments aboard the Twin Otter. With this paper, we highlight the significant implications of coarse mode (larger than 1 mm) aerosol aloft with respect to aerosol optical properties

Measurements of ice water content in tropopause region Arctic cirrus during

[1] A new instrument, the closed-path laser hygrometer (CLH), was flown on the NASA DC-8 aircraft during the Stratospheric Aerosol and Gas Experiment (SAGE) III Ozone Loss and Validation Experiment (SOLVE) campaign in 1999-2000 to measure condensed-phase water. The ice water content (IWC) of Arctic cirrus was determined from in situ measurements of condensed-and gas-phase water. The IWC values obtained from the CLH observations are compared to those determined by integrating particle size distributions measured by a Forward Scattering Spectrometer Probe (FSSP) also flown on the DC-8. The considerably greater IWC seen by the CLH implies the presence of particles with diameters greater than the FSSP&apos;s upper limit of 20 mm. The evidence for and implications of the presence of large ice crystals in Arctic cirrus is discussed

Optical and Physical Properties from Primary On-Road Vehicle ParticleEmissions And Their Implications for Climate Change

During the summers of 2004 and 2006, extinction and scattering coefficients of particle emissions inside a San Francisco Bay Area roadway tunnel were measured using a combined cavity ring-down and nephelometer instrument. Particle size distributions and humidification were also measured, as well as several gas phase species. Vehicles in the tunnel traveled up a 4% grade at a speed of approximately 60 km h{sup -1}. The traffic situation in the tunnel allows the apportionment of emission factors between light duty gasoline vehicles and diesel trucks. Cross-section emission factors for optical properties were determined for the apportioned vehicles to be consistent with gas phase and particulate matter emission factors. The absorption emission factor (the absorption cross-section per mass of fuel burned) for diesel trucks (4.4 {+-} 0.79 m{sup 2} kg{sup -1}) was 22 times larger than for light-duty gasoline vehicles (0.20 {+-} 0.05 m{sup 2} kg{sup -1}). The single scattering albedo of particles - which represents the fraction of incident light that is scattered as opposed to absorbed - was 0.2 for diesel trucks and 0.3 for light duty gasoline vehicles. These facts indicate that particulate matter from motor vehicles exerts a positive (i.e., warming) radiative climate forcing. Average particulate mass absorption efficiencies for diesel trucks and light duty gasoline vehicles were 3.14 {+-} 0.88 m{sup 2} g{sub PM}{sup -1} and 2.9 {+-} 1.07 m{sup 2} g{sub PM}{sup -1}, respectively. Particle size distributions and optical properties were insensitive to increases in relative humidity to values in excess of 90%, reinforcing previous findings that freshly emitted motor vehicle particulate matter is hydrophobic

Molecular Variation at a Candidate Gene Implicated in the Regulation of Fire Ant Social Behavior

The fire ant Solenopsis invicta and its close relatives display an important social polymorphism involving differences in colony queen number. Colonies are headed by either a single reproductive queen (monogyne form) or multiple queens (polygyne form). This variation in social organization is associated with variation at the gene Gp-9, with monogyne colonies harboring only B-like allelic variants and polygyne colonies always containing b-like variants as well. We describe naturally occurring variation at Gp-9 in fire ants based on 185 full-length sequences, 136 of which were obtained from S. invicta collected over much of its native range. While there is little overall differentiation between most of the numerous alleles observed, a surprising amount is found in the coding regions of the gene, with such substitutions usually causing amino acid replacements. This elevated coding-region variation may result from a lack of negative selection acting to constrain amino acid replacements over much of the protein, different mutation rates or biases in coding and non-coding sequences, negative selection acting with greater strength on non-coding than coding regions, and/or positive selection acting on the protein. Formal selection analyses provide evidence that the latter force played an important role in the basal b-like lineages coincident with the emergence of polygyny. While our data set reveals considerable paraphyly and polyphyly of S. invicta sequences with respect to those of other fire ant species, the b-like alleles of the socially polymorphic species are monophyletic. An expanded analysis of colonies containing alleles of this clade confirmed the invariant link between their presence and expression of polygyny. Finally, our discovery of several unique alleles bearing various combinations of b-like and B-like codons allows us to conclude that no single b-like residue is completely predictive of polygyne behavior and, thus, potentially causally involved in its expression. Rather, all three typical b-like residues appear to be necessary

Current Status of a Model System: The Gene Gp-9 and Its Association with Social Organization in Fire Ants

The Gp-9 gene in fire ants represents an important model system for studying the evolution of social organization in insects as well as a rich source of information relevant to other major evolutionary topics. An important feature of this system is that polymorphism in social organization is completely associated with allelic variation at Gp-9, such that single-queen colonies (monogyne form) include only inhabitants bearing B-like alleles while multiple-queen colonies (polygyne form) additionally include inhabitants bearing b-like alleles. A recent study of this system by Leal and Ishida (2008) made two major claims, the validity and significance of which we examine here. After reviewing existing literature, analyzing the methods and results of Leal and Ishida (2008), and generating new data from one of their study sites, we conclude that their claim that polygyny can occur in Solenopsis invicta in the U.S.A. in the absence of expression of the b-like allele Gp-9b is unfounded. Moreover, we argue that available information on insect OBPs (the family of proteins to which GP-9 belongs), on the evolutionary/population genetics of Gp-9, and on pheromonal/behavioral control of fire ant colony queen number fails to support their view that GP-9 plays no role in the chemosensory-mediated communication that underpins regulation of social organization. Our analyses lead us to conclude that there are no new reasons to question the existing consensus view of the Gp-9 system outlined in Gotzek and Ross (2007)

Atmospheric organic matter in clouds: exact masses and molecular formula identification using ultrahigh-resolution FT-ICR mass spectrometry

Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gas- and particulate-phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at the Storm Peak Laboratory near Steamboat Springs, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh-resolution mass spectra of the samples after using a reversed-phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS and CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of &sim;0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NO_x oxidation. Multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite were observed, indicating the significance of nitrate radical reactions on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur-containing compounds) were also observed; however further investigation is needed to determine the origin of the reduced sulfur-containing compounds. Overall, the molecular composition determined using ultrahigh-resolution Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic anion composition in the Rocky Mountain area that could help to improve the understanding of aqueous-phase processes

Comparison of in situ aerosol extinction and scattering coefficient measurements made during the Aerosol Intensive Operating Period

Journal of Geophysical Research, Vol. 111, No. D5, D05S03The article of record as published may be located at http://dx.doi.org/10.1029/2005JD006056.In May 2003, the Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Program sponsored the Aerosol Intensive Operating Period (AIOP) which was conducted over the ARM Climate Research Facility (ACRF) in central Oklahoma. One new instrument that flew in the AIOP, called Cadenza, employed a cavity ring-down technique to measure extinction coefficient and a reciprocal nephelometer technique to simultaneously measure scattering coefficient. This instrument is described in this paper, and measurements are compared to those of conventional instrumentation. Agreement between Cadenza extinction coefficient and that derived from combining nephelometer scattering and PSAP absorption (Neph + PSAP) was excellent, about 2%. Agreement between Cadenza scattering coefficient and TSI nephelometer scattering was also excellent, about 2%, well within the uncertainty of the nephelometer and Cadenza scattering measurements. Comparisons between these instruments, made for the special case of plumes, showed that Cadenza measured extinction and scattering several percent higher on average than the Neph + PSAP and nephelometer alone. This difference is likely due to differences in the instrument response time: The response time for Cadenza is 1 s while that for the nephelometer is a minimum of 8 s. Plumes, identified as originating from Siberian biomass burning, are characterized. Composite size distributions from wing-mounted probes showed that two of the plumes had significant large particle modes that resulted in high values of the effective radius. The effect of the large particle mode was not seen in the A ° ngstro¨m coefficient calculated from the in-cabin scattering measurements because of the characteristics of the aircraft inlet

Contributions of dust and biomass burning to aerosols at a Colorado mountain-top site

Visible Multifilter Rotating Shadowband Radiometer (vis-MFRSR) data were collected at Storm Peak Laboratory (SPL), a mountain-top facility in northwest Colorado, from 1999 to 2011 and in 2013. From 2011 to 2014, in situ measurements of aerosol light scattering were also obtained. Using these data sets together, the seasonal impact of dust and biomass burning is considered for the western USA. Analysis indicates that the median contributions to spring and summer aerosol optical depth (AOD) from dust and biomass-burning aerosols across the data set are comparable. The mean AOD is slightly greater in the summer, with significantly more frequent and short-duration high AOD measurements due to biomass-burning episodes than in the spring. The Ångström exponent showed a significant increase in the summer for both the in situ and vis-MFRSR data, suggesting an increase in combustion aerosols. Spring dust events are less distinguishable in the in situ data than the column measurement, suggesting that a significant amount of dust may be found above the elevation of SPL, 3220 m a.s.l. <br><br> Twenty-two known case studies of intercontinental dust, regional dust, and biomass-burning events were investigated. These events were found to follow a similar pattern, in both aerosol loading and Ångström exponent, as the seasonal mean signal in both the vis-MFRSR and ground-based nephelometer. This data set highlights the wide-scale implications of a warmer, drier climate on visibility in the western USA