72 research outputs found
Influence of particle-phase state on the hygroscopic behavior of mixed organic-inorganic aerosols
Recent work has demonstrated that organic and mixed organic–inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle-phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic–inorganic aerosol systems with physical states ranging from well-mixed liquids to phase-separated particles to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40 to 90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids; (2) forcing a single phase but accounting for non-ideal interactions through activity coefficient calculations; and (3) a Zdanovskii–Stokes–Robinson-like calculation in which complete separation of the inorganic and organic components is assumed at all RH values, with water uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid–liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF measurements. The performances of the simplified modeling approaches, however, differ for particles with differing phase states. This suggests that no single simplified modeling approach can be used to capture the water-uptake behavior for the diversity of particle-phase behavior expected in the atmosphere. Errors in HGFs calculated with the simplified models are of sufficient magnitude to produce substantial errors in estimates of particle optical and radiative properties, particularly for the assumption that water uptake is driven by absorptive equilibrium partitioning with ideal particle-phase mixing
Influence of particle-phase state on the hygroscopic behavior of mixed organic-inorganic aerosols
Recent work has demonstrated that organic and mixed organic–inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle-phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic–inorganic aerosol systems with physical states ranging from well-mixed liquids to phase-separated particles to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40 to 90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids; (2) forcing a single phase but accounting for non-ideal interactions through activity coefficient calculations; and (3) a Zdanovskii–Stokes–Robinson-like calculation in which complete separation of the inorganic and organic components is assumed at all RH values, with water uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid–liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF measurements. The performances of the simplified modeling approaches, however, differ for particles with differing phase states. This suggests that no single simplified modeling approach can be used to capture the water-uptake behavior for the diversity of particle-phase behavior expected in the atmosphere. Errors in HGFs calculated with the simplified models are of sufficient magnitude to produce substantial errors in estimates of particle optical and radiative properties, particularly for the assumption that water uptake is driven by absorptive equilibrium partitioning with ideal particle-phase mixing
Evidence for ambient dark aqueous SOA formation in the Po Valley, Italy
Laboratory experiments suggest that water-soluble products from the gas-phase oxidation of volatile organic compounds can partition into atmospheric waters where they are further oxidized to form low volatility products, providing an alternative route for oxidation in addition to further oxidation in the gas phase. These products can remain in the particle phase after water evaporation, forming what is termed as aqueous secondary organic aerosol (aqSOA). However, few studies have attempted to observe ambient aqSOA. Therefore, a suite of measurements, including near-real-time WSOC (water-soluble organic carbon), inorganic anions/cations, organic acids, and gas-phase glyoxal, were made during the PEGASOS (Pan-European Gas-AeroSOls-climate interaction Study) 2012 campaign in the Po Valley, Italy, to search for evidence of aqSOA. Our analysis focused on four periods: Period A on 19–21 June, Period B on 30 June and 1–2 July, Period C on 3–5 July, and Period D on 6–7 July to represent the first (Period A) and second (Periods B, C, and D) halves of the study. These periods were picked to cover varying levels of WSOC and aerosol liquid water. In addition, back trajectory analysis suggested all sites sampled similar air masses on a given day. The data collected during both periods were divided into times of increasing relative humidity (RH) and decreasing RH, with the aim of diminishing the influence of dilution and mixing on SOA concentrations and other measured variables. Evidence for local aqSOA formation was only observed during Period A. When this occurred, there was a correlation of WSOC with organic aerosol (R2 = 0.84), aerosol liquid water (R2 = 0.65), RH (R2 = 0.39), and aerosol nitrate (R2 = 0.66). Additionally, this was only observed during times of increasing RH, which coincided with dark conditions. Comparisons of WSOC with oxygenated organic aerosol (OOA) factors, determined from application of positive matrix factorization analysis on the aerosol mass spectrometer observations of the submicron non-refractory organic particle composition, suggested that the WSOC differed in the two halves of the study (Period A WSOC vs. OOA-2 R2 = 0.83 and OOA-4 R2 = 0.04, whereas Period C WSOC vs. OOA-2 R2 = 0.03 and OOA-4 R2 = 0.64). OOA-2 had a high O ∕ C (oxygen ∕ carbon) ratio of 0.77, providing evidence that aqueous processing was occurring during Period A. Key factors of local aqSOA production during Period A appear to include air mass stagnation, which allows aqSOA precursors to accumulate in the region; the formation of substantial local particulate nitrate during the overnight hours, which enhances water uptake by the aerosol; and the presence of significant amounts of ammonia, which may contribute to ammonium nitrate formation and subsequent water uptake and/or play a more direct role in the aqSOA chemistry
Climate change litigation: a review of research on courts and litigants in climate government
Studies of climate change litigation have proliferated over the past two decades, as lawsuits across the world increasingly bring policy debates about climate change mitigation and adaptation, as well as climate change‐related loss and damage to the attention of courts. We systematically identify 130 articles on climate change litigation published in English in the law and social sciences between 2000 and 2018 to identify research trajectories. In addition to a budding interdisciplinarity in scholarly interest in climate change litigation we also document a growing understanding of the full spectrum of actors involved and implicated in climate lawsuits and the range of motivations and/or strategic imperatives underpinning their engagement with the law. Situating this within the broader academic literature on the topic we then highlight a number of cutting edge trends and opportunities for future research. Four emerging themes are explored in detail: the relationship between litigation and governance; how time and scale feature in climate litigation; the role of science; and what has been coined the “human rights turn” in climate change litigation. We highlight the limits of existing work and the need for future research—not limited to legal scholarship—to evaluate the impact of both regulatory and anti‐regulatory climate‐related lawsuits, and to explore a wider set of jurisdictions, actors and themes. Addressing these issues and questions will help to develop a deeper understanding of the conditions under which litigation will strengthen or undermine climate governance. This article is categorized under: Policy and Governance > Multilevel and Transnational Climate Change Governanc
An efficient algorithm for the stochastic simulation of the hybridization of DNA to microarrays
<p>Abstract</p> <p>Background</p> <p>Although oligonucleotide microarray technology is ubiquitous in genomic research, reproducibility and standardization of expression measurements still concern many researchers. Cross-hybridization between microarray probes and non-target ssDNA has been implicated as a primary factor in sensitivity and selectivity loss. Since hybridization is a chemical process, it may be modeled at a population-level using a combination of material balance equations and thermodynamics. However, the hybridization reaction network may be exceptionally large for commercial arrays, which often possess at least one reporter per transcript. Quantification of the kinetics and equilibrium of exceptionally large chemical systems of this type is numerically infeasible with customary approaches.</p> <p>Results</p> <p>In this paper, we present a robust and computationally efficient algorithm for the simulation of hybridization processes underlying microarray assays. Our method may be utilized to identify the extent to which nucleic acid targets (e.g. cDNA) will cross-hybridize with probes, and by extension, characterize probe robustnessusing the information specified by MAGE-TAB. Using this algorithm, we characterize cross-hybridization in a modified commercial microarray assay.</p> <p>Conclusions</p> <p>By integrating stochastic simulation with thermodynamic prediction tools for DNA hybridization, one may robustly and rapidly characterize of the selectivity of a proposed microarray design at the probe and "system" levels. Our code is available at <url>http://www.laurenzi.net</url>.</p
The effect of secondary inorganic aerosols, soot and the geographical origin of air mass on acute myocardial infarction hospitalisations in Gothenburg, Sweden during 1985–2010: a case-crossover study
Discontinuities in hygroscopic growth below and above water saturation for laboratory surrogates of oligomers in organic atmospheric aerosols
Discontinuities in apparent hygroscopicity below and above water saturation
have been observed for organic and mixed organic–inorganic aerosol particles
in both laboratory studies and in the ambient atmosphere. However,
uncertainty remains regarding the factors that contribute to observations of
low hygroscopic growth below water saturation but enhanced cloud condensation
nuclei (CCN) activity for a given aerosol population. Utilizing laboratory
surrogates for oligomers in atmospheric aerosols, we explore the extent to
which such discontinuities are influenced by organic component molecular mass
and viscosity, non-ideal thermodynamic interactions between aerosol
components, and the combination of these factors. Measurements of hygroscopic
growth under subsaturated conditions and the CCN activity of aerosols
comprised of polyethylene glycol (PEG) with average molecular masses ranging
from 200 to 10 000 g mol−1 and mixtures of PEG with ammonium sulfate
(AS) were conducted. Experimental results are compared to calculations of
hygroscopic growth at thermodynamic equilibrium conducted with the Aerosol
Inorganic Organic Mixtures Functional groups Activity Coefficients (AIOMFAC)
model, and the potential influence of kinetic limitations on observed water
uptake was further explored through estimations of water diffusivity in the
PEG oligomers. Particle-phase behavior, including the prevalence of
liquid–liquid phase separation (LLPS), was also modeled with AIOMFAC. Under
subsaturated relative humidity (RH) conditions, we observed little
variability in hygroscopic growth across PEG systems with different molecular
masses; however, an increase in CCN activity with increasing PEG molecular
mass was observed. This effect is most pronounced for PEG–AS mixtures, and,
in fact, an enhancement in CCN activity was observed for the PEG10000–AS
mixture as compared to pure AS, as evidenced by a 15 % reduction in
critical activation diameter at a supersaturation of 0.8 %. We also
observed a marked increase in apparent hygroscopicity for mixtures of higher
molecular mass PEG and AS under supersaturated conditions as compared to
subsaturated hygroscopic growth. AIOMFAC-based predictions and estimations of
water diffusivity in PEG suggest that such discontinuities in apparent
hygroscopicity above and below water saturation can be attributed, at least
in part, to differences in the sensitivity of water uptake behavior to
surface tension effects. There is no evidence that kinetic limitations to
water uptake due to the presence of viscous aerosol components influenced
hygroscopic growth. For the systems that display an enhancement in apparent
hygroscopicity above water saturation, LLPS is predicted to persist to high
RH. This indicates a miscibility gap and is likely to influence
bulk-to-surface partitioning of PEG at high RH, impacting droplet surface
tension and CCN activity. This work provides insight into the factors likely
to be contributing to discontinuities in aerosol water-uptake behavior below
and above water saturation that have been observed previously in the ambient
atmosphere
- …