External Review and Options Appraisal of the Global Fund for Community Foundations

This Strategic Review and Options Appraisal was undertaken for the Global Fund for Community Foundations (GFCF). This Report is not an evaluation of the work of the GFCF, while it nonetheless 'reviews' the work and achievements of the organisation, particularly in the light of where the organisation stands at the present time. In this sense, it is more of a 'snapshot' view of the GFCF, and the Report, recognising that the GFCF is at an important moment in its life at a time of both challenge and opportunity, then presents a set of Options for decision

Photochemical Organonitrate Formation in Wet Aerosols

Water is the most abundant component of atmospheric fine aerosol. However, despite rapid progress, multiphase chemistry involving wet aerosols is still poorly understood. In this work, we report results from smog chamber photooxidation of glyoxal and OH &ndash; containing ammonium sulfate or sulfuric acid particles in the presence of NOx and O3 at high and low relative humidity. Particles were analyzed using ultra high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). During the 3 hour irradiation, OH oxidation products of glyoxal that are also produced in dilute aqueous solutions (e.g., oxalic acids and tartaric acids) were formed in both ammonium sulfate (AS) aerosols and sulfuric acid (SA) aerosols. However, the major products were organonitrogens (CHNO), organosulfates (CHOS), and organonitrogen-sulfates (CHNOS). These were also the dominant products formed in the dark chamber indicating non-radical formation. In the humid chamber (> 70 % RH), two main products for both AS and SA aerosols were organonitrates, which appeared at m/z&minus; 147 and 226. They were formed in the aqueous phase via non-radical reactions of glyoxal and nitric acid, and their formation was enhanced by photochemistry because of the photochemical formation of nitric acid via reactions of peroxy radicals, NOx and OH during the irradiation.</html

Los Angeles Summer Midday Particulate Carbon: Primary and Secondary Aerosol

Aerosol sampling during photochemically active times across the Los Angeles Basin has provided evidence of secondary formation of organic aerosol from gas-phase precursors at midday. Ambient organic carbon/elemental carbon ratios exceeded the estimated ratio of organic carbon/elemental carbon in primary source emissions on most sampling days at all sites. The concentration of secondary organic aerosol was calculated by using ambient data and estimates of the organic carbon/elemental carbon ratio in primary source emissions. Nonparametric sign correlations comparing calculated secondary organic carbon concentrations with tracers of both primary and secondary aerosols supported the method used to quantify secondary organic carbon. Secondary organic aerosol appears to have contributed roughly half of the organic aerosol in Pasadena during midday summer conditions

Early experience with food items of differing sizes and optimal foraging in golden hamsters (Mesocricetus auratus)

The experiments in this dissertation were designed to examine the role of early experience on later food choice by golden hamsters. In Experiment 1, the profitabilities of three sizes of Noyes food pellets (20, 45, and 94 mg) were assessed. The order of profitabilities were 94&gt; 45&gt; 20. In Experiment 2, hamsters were reared, from birth to 35 days of age, on one of the three pellet sizes used in Experiment 1 and were later allowed to choose among the sizes. It was found that early experience had consistent effects on later food choice: Animals chose the size(s) most dissimilar to the size with which they were reared. This result is unexpected and fits into no extant theory of food choice. Experiment 3 was conducted in order to see whether taste preference could be induced in hamsters as they are in other rodents. Animals were reared on either unflavored (control), banana-flavored, or coconut-flavored food, and, later, given a simultaneous choice between banana- and coconut-flavored food. Control animals showed no preference for either flavor; animals in the other groups showed a preference for the familiar flavor

Volatility of methylglyoxal cloud SOA formed through OH radical oxidation and droplet evaporation

The volatility of secondary organic aerosol (SOA) formed through cloud processing (aqueous hydroxyl radical ( OH) oxidation and droplet evaporation) of methylglyoxal (MGly) was studied. Effective vapor pressure and effective enthalpy of vaporization (ΔH vap,eff ) were determined using 1) droplets containing MGly and its oxidation products, 2) a Vibrating Orifice Aerosol Generator (VOAG) system, and 3) Temperature Programmed Desorption Aerosol-Chemical Ionization Mass Spectrometry (TPD Aerosol-CIMS). Simulated in-cloud MGly oxidation (for 10–30 min) produces an organic mixture of higher and lower volatility components with an overall effective vapor pressure of (4 ± 7) × 10−7 atm at pH 3. The effective vapor pressure decreases by a factor of 2 with addition of ammonium hydroxide (pH 7). The fraction of organic material remaining in the particle-phase after drying was smaller than for similar experiments with glycolaldehyde and glyoxal SOA. The ΔH vap,eff of pyruvic acid and oxalic acid + methylglyoxal in the mixture (from TPD Aerosol-CIMS) were smaller than the theoretical enthalpies of the pure compounds and smaller than that estimated for the entire precursor/product mix after droplet evaporation. After 10–30 min of aqueous oxidation (one cloud cycle) the majority of the MGly +  OH precursor/product mix (even neutralized) will volatilize during droplet evaporation; neutralization and at least 80 min of oxidation at 10−12 M OH (or >12 h at 10−14 M) is needed before low volatility ammonium oxalate exceeds pyruvate

Los Angeles Summer Midday Particulate Carbon: Primary and Secondary Aerosol

Aerosol sampling during photochemically active times across the Los Angeles Basin has provided evidence of secondary formation of organic aerosol from gas-phase precursors at midday. Ambient organic carbon/elemental carbon ratios exceeded the estimated ratio of organic carbon/elemental carbon in primary source emissions on most sampling days at all sites. The concentration of secondary organic aerosol was calculated by using ambient data and estimates of the organic carbon/elemental carbon ratio in primary source emissions. Nonparametric sign correlations comparing calculated secondary organic carbon concentrations with tracers of both primary and secondary aerosols supported the method used to quantify secondary organic carbon. Secondary organic aerosol appears to have contributed roughly half of the organic aerosol in Pasadena during midday summer conditions

Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOA$_{AQ}$). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOA$_{AQ}$. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of watersoluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH ·) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 μM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra highresolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS– MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus, formation of pyruvate/oxalate suggests the potential for aqueous processing of these ambient mixtures to form SOA$_{AQ}$

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