Hygroscopicity of nitrogen-containing organic carbon compounds: o-aminophenol and p-aminophenol.

Nitrogen-containing Organic Carbon (NOC) is a major constituent of atmospheric aerosols and they have received significant attention in the atmospheric science community. While extensive research and advancements have been made regarding their emission sources, concentrations, and their secondary formation in the atmosphere, little is known about their water uptake efficiencies and their subsequent role in climate, air quality, and visibility. In this study, we investigated the water uptake of two sparingly soluble aromatic NOCs: o-aminophenol (oAP) and p-aminophenol (pAP) under subsaturated and supersaturated conditions using a Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) and a Cloud Condensation Nuclei Counter (CCNC), respectively. Our results show that oAP and pAP are slightly hygroscopic with comparable hygroscopicities to various studied organic aerosols. The supersaturated single hygroscopicity parameter (κCCN) was measured and reported to be 0.18 ± 0.05 for oAP and 0.04 ± 0.02 for pAP, indicating that oAP is more hygroscopic than pAP despite them having the same molecular formulae. The observed disparity in hygroscopicity is attributed to the difference in functional group locations, interactions with gas phase water molecules, and the reported bulk water solubilities of the NOC. Under subsaturated conditions, both oAP and pAP aerosols showed size dependent water uptake. Both species demonstrated growth at smaller dry particle sizes, and shrinkage at larger dry particle sizes. The measured growth factor (Gf) range, at RH = 85%, for oAP was 1.60-0.74 and for pAP was 1.53-0.74 with increasing particle size. The growth and shrinkage dichotomy is attributed to morphological particle differences verified by TEM images of small and large particles. Subsequently, aerosol physicochemical properties must be considered to properly predict the droplet growth of NOC aerosols in the atmosphere.

Hygroscopicity and cloud condensation nucleation activities of hydroxyalkylsulfonates.

Hydroxyalkylsulfonates may contribute significantly to atmospheric particles; however, their hygroscopic properties and cloud condensation nuclei (CCN) activities remain unknown. In this study, three complementary techniques were utilized to examine the hygroscopicity of sodium hydroxymethanesulfonate (NaHMS), sodium 2-hydroxyethylsulfonate (NaHES), and ammonium 2-hydroxyethylsulfonate (NH4HES) under subsaturated and supersaturated environments. The mass changes in the three hydroxyalkylsulfonates at different relative humidities at 25 °C were examined by a vapor sorption analyzer, and the mass growth factors were measured to be 3.25 ± 0.01 for NaHMS, 3.32 ± 0.02 for NaHES, and 3.34 ± 0.04 for NH4HES at 90% RH. Their hygroscopic growth was investigated by a humidity tandem differential mobility analyzer, and hygroscopic growth factors were 1.78 ± 0.02 for NaHMS, 1.71 ± 0.02 for NaHES, and 1.68 ± 0.03 for NH4HES at 90% RH. Furthermore, the CCN activities of NaHMS, NaHES, and NH4HES were explored, and their single hygroscopicity parameters (κccn) were measured to be 0.649 ± 0.097 for NaHMS, 0.559 ± 0.069 for NaHES, and 0.434 ± 0.073 for NH4HES. In addition, the hygroscopic growth and CCN activities of binary mixtures of ammonium sulfate with one of the three hydroxyalkylsulfonates were also examined.

Reactivity of aminophenols in forming nitrogen-containing brown carbon from iron-catalyzed reactions.

Nitrogen-containing organic carbon (NOC) in atmospheric particles is an important class of brown carbon (BrC). Redox active NOC like aminophenols received little attention in their ability to form BrC. Here we show that iron can catalyze dark oxidative oligomerization of o- and p-aminophenols under simulated aerosol and cloud conditions (pH 1-7, and ionic strength 0.01-1 M). Homogeneous aqueous phase reactions were conducted using soluble Fe(III), where particle growth/agglomeration were monitored using dynamic light scattering. Mass yield experiments of insoluble soot-like dark brown to black particles were as high as 40%. Hygroscopicity growth factors (κ) of these insoluble products under sub- and super-saturated conditions ranged from 0.4-0.6, higher than that of levoglucosan, a prominent proxy for biomass burning organic aerosol (BBOA). Soluble products analyzed using chromatography and mass spectrometry revealed the formation of ring coupling products of o- and p-aminophenols and their primary oxidation products. Heterogeneous reactions of aminophenol were also conducted using Arizona Test Dust (AZTD) under simulated aging conditions, and showed clear changes to optical properties, morphology, mixing state, and chemical composition. These results highlight the important role of iron redox chemistry in BrC formation under atmospherically relevant conditions.

Cytoplasmic pH response to acid stress in individual cells of Escherichia coli and Bacillus subtilis observed by fluorescence ratio imaging microscopy.

The ability of Escherichia coli and Bacillus subtilis to regulate their cytoplasmic pH is well studied in cell suspensions but is poorly understood in individual adherent cells and biofilms. We observed the cytoplasmic pH of individual cells using ratiometric pHluorin. A standard curve equating the fluorescence ratio with pH was obtained by perfusion at a range of external pH 5.0 to 9.0, with uncouplers that collapse the transmembrane pH difference. Adherent cells were acid stressed by switching the perfusion medium from pH 7.5 to pH 5.5. The E. coli cytoplasmic pH fell to a value that varied among individual cells (range of pH 6.2 to 6.8), but a majority of cells recovered (to pH 7.0 to 7.5) within 2 min. In an E. coli biofilm, cells shifted from pH 7.5 to pH 5.5 failed to recover cytoplasmic pH. Following a smaller shift (from pH 7.5 to pH 6.0), most biofilm cells recovered fully, although the pH decreased further than that of isolated adherent cells, and recovery took longer (7 min or longer). Some biofilm cells began to recover pH and then failed, a response not seen in isolated cells. B. subtilis cells were acid shifted from pH 7.5 to pH 6.0. In B. subtilis, unlike the case with E. coli, cytoplasmic pH showed no "overshoot" but fell to a level that was maintained. This level of cytoplasmic pH post-acid shift varied among individual B. subtilis cells (range of pH, 7.0 to 7.7). Overall, the cytoplasmic pHs of individual bacteria show important variation in the acid stress response, including novel responses in biofilms.