Evolution of the complex refractive index in the UV spectral region in ageing secondary organic aerosol

The chemical and physical properties of secondary organic aerosol (SOA) formed by the photochemical degradation of biogenic and anthropogenic volatile organic compounds (VOC) are as yet still poorly constrained. The evolution of the complex refractive index (RI) of SOA, formed from purely biogenic VOC and mixtures of biogenic and anthropogenic VOC, was studied over a diurnal cycle in the SAPHIR photochemical outdoor chamber in Jülich, Germany. The correlation of RI with SOA chemical and physical properties such as oxidation level and volatility was examined. The RI was retrieved by a newly developed broadband cavity-enhanced spectrometer for aerosol optical extinction measurements in the UV spectral region (360 to 420 nm). Chemical composition and volatility of the particles were monitored by a high-resolution time-of-flight aerosol mass spectrometer, and a volatility tandem differential mobility analyzer. SOA was formed by ozonolysis of either (i) a mixture of biogenic VOC (α-pinene and limonene), (ii) biogenic VOC mixture with subsequent addition of an anthropogenic VOC (<i>p</i>-xylene-d₁₀), or (iii) a mixture of biogenic and anthropogenic VOC. The SOA aged by ozone/OH reactions up to 29.5 h was found to be non-absorbing in all cases. The SOA with <i>p</i>-xylene-d₁₀ showed an increase of the scattering component of the RI correlated with an increase of the O / C ratio and with an increase in the SOA density. There was a greater increase in the scattering component of the RI when the SOA was produced from the mixture of biogenic VOCs and anthropogenic VOC than from the sequential addition of the VOCs after approximately the same ageing time. The increase of the scattering component was inversely correlated with the SOA volatility. Two RI retrievals determined for the pure biogenic SOA showed a constant RI for up to 5 h of ageing. Mass spectral characterization shows the three types of the SOA formed in this study have a significant amount of semivolatile components. The influence of anthropogenic VOCs on the oxygenated organic aerosol as well as the atmospheric implications are discussed

Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

High molecular weight (300–650 Da) naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C&lt;sub&gt;10&lt;/sub&gt;H&lt;sub&gt;16&lt;/sub&gt;) oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC). The ions were identified as clusters of the nitrate ion (NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt;) and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7–1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt; (Hyytiälä) and C&lt;sub&gt;3&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt; (JPAC). The most abundant products in the ion spectra were identified as C&lt;sub&gt;10&lt;/sub&gt;H&lt;sub&gt;14&lt;/sub&gt;O&lt;sub&gt;7&lt;/sub&gt;, C&lt;sub&gt;10&lt;/sub&gt;H&lt;sub&gt;14&lt;/sub&gt;O&lt;sub&gt;9&lt;/sub&gt;, C&lt;sub&gt;10&lt;/sub&gt;H&lt;sub&gt;16&lt;/sub&gt;O&lt;sub&gt;9&lt;/sub&gt;, and C&lt;sub&gt;10&lt;/sub&gt;H&lt;sub&gt;14&lt;/sub&gt;O&lt;sub&gt;11&lt;/sub&gt;. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C&lt;sub&gt;9&lt;/sub&gt; compounds which were not observed in Hyytiälä, where β-pinene on average is 4–5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1–1 ppt (~10&lt;sup&gt;6&lt;/sup&gt;–10&lt;sup&gt;7&lt;/sup&gt; molec cm&lt;sup&gt;−3&lt;/sup&gt;). This is in a similar range as the amount of gaseous H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; in Hyytiälä during day-time. As these highly oxidized organics are roughly 3 times heavier, likely with extremely low vapor pressures, their role in the initial steps of new aerosol particle formation and growth may be important and needs to be explored in more detail in the future

Environmental conditions regulate the impact of plants on cloud formation

The terrestrial vegetation emits large amounts of volatile organic compounds (VOC) into the atmosphere, which on oxidation produce secondary organic aerosol (SOA). By acting as cloud condensation nuclei (CCN), SOA influences cloud formation and climate. In a warming climate, changes in environmental factors can cause stresses to plants, inducing changes of the emitted VOC. These can modify particle size and composition. Here we report how induced emissions eventually affect CCN activity of SOA, a key parameter in cloud formation. For boreal forest tree species, insect infestation by aphids causes additional VOC emissions which modifies SOA composition thus hygroscopicity and CCN activity. Moderate heat increases the total amount of constitutive VOC, which has a minor effect on hygroscopicity, but affects CCN activity by increasing the particles’ size. The coupling of plant stresses, VOC composition and CCN activity points to an important impact of induced plant emissions on cloud formation and climate

The formation, properties and impact of secondary organic aerosol: current and emerging issues

Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed

Cloud condensation nuclei activity, droplet growth kinetics, and hygroscopicity of biogenic and anthropogenic secondary organic aerosol (SOA)

© 2016 Author(s).Interaction of biogenic volatile organic compounds (VOCs) with Anthropogenic VOC (AVOC) affects the physicochemical properties of secondary organic aerosol (SOA). We investigated cloud droplet activation (CCN activity), droplet growth kinetics, and hygroscopicity of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Selected monoterpenes and aromatics were used as representative precursors of BSOA and ASOA, respectively. We found that BSOA, ASOA, and ABSOA had similar CCN activity despite the higher oxygen to carbon ratio (O/C) of ASOA compared to BSOA and ABSOA. For individual reaction systems, CCN activity increased with the degree of oxidation. Yet, when considering all different types of SOA together, the hygroscopicity parameter, κ$_CCN$, did not correlate with O/C. Droplet growth kinetics of BSOA, ASOA, and ABSOA were comparable to that of (NH$_4$)$_2$SO$_4$, which indicates that there was no delay in the water uptake for these SOA in supersaturated conditions. In contrast to CCN activity, the hygroscopicity parameter from a hygroscopic tandem differential mobility analyzer (HTDMA) measurement, κ$_HTDMA$, of ASOA was distinctively higher (0.09-0.10) than that of BSOA (0.03-0.06), which was attributed to the higher degree of oxidation of ASOA. The ASOA components in mixed ABSOA enhanced aerosol hygroscopicity. Changing the ASOA fraction by adding biogenic VOC (BVOC) to ASOA or vice versa (AVOC to BSOA) changed the hygroscopicity of aerosol, in line with the change in the degree of oxidation of aerosol. However, the hygroscopicity of ABSOA cannot be described by a simple linear combination of pure BSOA and ASOA systems. This indicates that additional processes, possibly oligomerization, affected the hygroscopicity. Closure analysis of CCN and HTDMA data showed κ$_HTDMA$ was lower than κ$_CCN$ by 30-70 %. Better closure was achieved for ASOA compared to BSOA. This discrepancy can be attributed to several reasons. ASOA seemed to have higher solubility in subsaturated conditions and/or higher surface tension at the activation point than that of BSOA.EUROCHAMP2 European Commission 7th framework, NordForsk, VILLUM Foundatio

Phase partitioning and volatility of secondary organic aerosol components formed from alpha-pinene ozonolysis and OH oxidation : the importance of accretion products and other low volatility compounds

We measured a large suite of gas- and particle-phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas and particle phases, the latter being detected by temperature-programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO-HR-ToF-CIMS are highly correlated with, and explain at least 25-50% of, the organic aerosol mass measured by an Aerodyne aerosol mass spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from high molecular weight organics and/or oligomers (i.e., multi-phase accretion reaction products). Approximately 50% of the HR-ToF-CIMS particle-phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption-temperature-based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas-particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.Peer reviewe

Using viral vectors as gene transfer tools (Cell Biology and Toxicology Special Issue: ETCS-UK 1 day meeting on genetic manipulation of cells)

In recent years, the development of powerful viral gene transfer techniques has greatly facilitated the study of gene function. This review summarises some of the viral delivery systems routinely used to mediate gene transfer into cell lines, primary cell cultures and in whole animal models. The systems described were originally discussed at a 1-day European Tissue Culture Society (ETCS-UK) workshop that was held at University College London on 1st April 2009. Recombinant-deficient viral vectors (viruses that are no longer able to replicate) are used to transduce dividing and post-mitotic cells, and they have been optimised to mediate regulatable, powerful, long-term and cell-specific expression. Hence, viral systems have become very widely used, especially in the field of neurobiology. This review introduces the main categories of viral vectors, focusing on their initial development and highlighting modifications and improvements made since their introduction. In particular, the use of specific promoters to restrict expression, translational enhancers and regulatory elements to boost expression from a single virion and the development of regulatable systems is described

ROTATIONALLY RESOLVED, MOLECULAR BEAM, OVERTONE SPECTROSCOPY OF HYDROGEN-BONDED COMPLEXES: 2ν1OF(HCN)22\nu_{1} OF (HCN)_{2} AND HCN-HF

Author Institution: Department of Chemistry, Princeton UniversityWe have used a $1.5 \mu m$ color-center laser, with the optothermal detection method, to study the vibrational predissociation in the $2\nu_{1}$ hands of HCN dimer and HCN-HF. For HCN dimer the complexation-induced redshift of -6.3923(5) $cm^{-1}$ is nearly exactly equal to twice the fundamental redshift, indicating a very small (0.1\%) increase in the anharmonicity of the CH stretch potential. However, the much smaller than twice the fundamental redshift (-1.2905(5) $cm^{-1}$), observed in the overtone of HCN-HF, indicates a relatively large (1\%) decrease in the anharmonicity. The linewidths of the HCN dimer spectrum are instrument limited, giving a lower limit of 11 ns to the lifetime. The upper limit is given by the $90\mu{s}$ time-of-flight from laser crossing to detector. In the case of HCN-HF we find linewidths broader than the 22 MHz instrumental width. The homogeneous contribution to the overall linewidth is roughly 15 MHz, which compares to a 9.9 MHz Lorentzian component that was needed to fit the fundamental transitions. Presently, efforts are underway to measure the overtone linewidths at improved resolution."

A novel method for online analysis of gas and particle composition: description and evaluation of a Filter Inlet for Gases and AEROsols (FIGAERO)

We describe a novel inlet that allows measurement of both gas and particle molecular composition when coupled to mass spectrometric, chromatographic, or optical sensors: the Filter Inlet for Gases and AEROsols (FIGAERO). The design goals for the FIGAERO are to allow unperturbed observation of ambient air while simultaneously analyzing gases and collecting particulate matter on a Teflon® (hereafter Teflon) filter via an entirely separate sampling port. The filter is analyzed periodically by the same sensor on hourly or faster timescales using temperature-programmed thermal desorption. We assess the performance of the FIGAERO by coupling it to a high-resolution time-of-flight chemical-ionization mass spectrometer (HRToF-CIMS) in laboratory chamber studies of α-pinene oxidation and field measurements at a boreal forest location. Low instrument backgrounds give detection limits of ppt or lower for compounds in the gas-phase and in the picogram m−3 range for particle phase compounds. The FIGAERO-HRToF-CIMS provides molecular information about both gases and particle composition on the 1 Hz and hourly timescales, respectively for hundreds of compounds. The FIGAERO thermal desorptions are highly reproducible (better than 10%), allowing a calibrated assessment of the effective volatility of desorbing compounds and the role of thermal decomposition during the desorption process. We show that the often multi-modal desorption thermograms arising from secondary organic aerosol (SOA) provide additional insights into molecular composition and/or particle morphology, and exhibit changes with changes in SOA formation or aging pathways