Temperature-Dependent Henry's Law Constants of Atmospheric Amines.

There has been growing interest in understanding atmospheric amines in the gas phase and their mass transfer to the aqueous phase because of their potential roles in cloud chemistry, secondary organic aerosol formation, and the fate of atmospheric organics. Temperature-dependent Henry's law constants (KH) of atmospheric amines, a key parameter in atmospheric chemical transport models to account for mass transfer, are mostly unavailable. In this work, we investigated gas-liquid equilibria of five prevalent atmospheric amines, namely 1-propylamine, di-n-propylamine, trimethylamine, allylamine, and 4-methylmorpholine using bubble column technique. We reported effective KH, intrinsic KH, and gas phase diffusion coefficients of these species over a range of temperatures relevant to the lower atmosphere for the first time. The measured KH at 298 K and enthalpy of solution for 1-propylamine, di-n-propylamine, trimethylamine, allylamine, and 4-methylmorpholine are 61.4 ± 4.9 mol L(-1) atm(-1) and -49.0 ± 4.8 kJ mol(-1); 14.5 ± 1.2 mol L(-1) atm(-1) and -72.5 ± 6.8 kJ mol(-1); 8.9 ± 0.7 mol L(-1) atm(-1) and -49.6 ± 4.7 kJ mol(-1); 103.5 ± 10.4 mol L(-1) atm(-1) and -42.7 ± 4.3 kJ mol(-1); and 952.2 ± 114.3 mol L(-1) atm(-1) and -82.7 ± 9.7 kJ mol(-1), respectively. In addition, we evaluated amines' characteristic times to achieve gas-liquid equilibrium for partitioning between gas and aqueous phases. Results show gas-liquid equilibrium can be rapidly established at natural cloud droplets surface, but the characteristic times may be extended substantially at lower temperatures and pHs. Moreover, our findings imply that atmospheric amines are more likely to exist in cloud droplets, and ambient temperature, water content, and pH of aerosols play important roles in their partitioning.

Temperature-dependent deliquescent and efflorescent properties of methanesulfonate sodium studied by ATR-FTIR spectroscopy.

Modeling of aerosols and cloud formation processes in the marine boundary layer (MBL) require extensive data on hygroscopic properties of relevant methanesulfonate particles, which are currently scarce. In this work, methanesulfonate sodium (CH3SO3Na, MSA-Na), the most abundant methanesulfonate salt, was selected, and its deliquescent and efflorescent properties at temperatures relevant to the lower troposphere were studied using an ATR-FTIR flow system. To validate the approach, we investigated hygroscopic properties of NaCl particles, and our measured deliquescent relative humidity (DRH) and efflorescent relative humidity (ERH) of the NaCl particles obtained from the changes in integrated absorbance of water peaks in infrared spectra agreed with literature data well. We then reported DRH and ERH of MSA-Na particles as a function of temperature for the first time using both the changes in integrated absorbance of water peaks and the changes in peak position and shape of CH3SO3(-) symmetric and asymmetric vibrational modes. Our experiments showed that MSA-Na particles present quite different temperature-dependent hygroscopic behaviors from NaCl. Both the DRH and ERH of MSA-Na particles increase with decreasing temperatures. Due to the significant differences in temperature-dependent DRH and ERH, NaCl particles, if processed in MBL by methanesulfonic acid, are expected to deliquesce slightly earlier during a hydration process but effloresce at a much earlier stage during a dehydration process, especially at lower temperatures. This could considerably influence phase, size, and water content of sea salt aerosols and consequently their reactivity, lifetime, and impacts on atmospheric chemistry and climate systems.

Temperature-dependent Henry's law constants of atmospheric organics of biogenic origin.

There have been growing interests in modeling studies to understand oxidation of volatile organic compounds in the gas phase and their mass transfer to the aqueous phase for their potential roles in cloud chemistry, formation of secondary organic aerosols, and fate of atmospheric organics. Temperature-dependent Henry's law constants, key parameters in the atmospheric models to account for mass transfer, are often unavailable. In the present work, we investigated gas-liquid equilibriums of isoprene, limonene, α-pinene, and linalool using a bubble column technique. These compounds, originating from biogenic sources, were selected for their implications in atmospheric cloud chemistry and secondary organic aerosol formation. We reported Henry's law constants (K(H)), first order loss rates (k), and gas phase diffusion coefficients over a range of temperatures relevant to the lower atmosphere (278-298 K) for the first time. The measurement results of K(H) values for isoprene, limonene, α-pinene, and linalool at 298 K were 0.036 ± 0.003; 0.048 ± 0.004; 0.029 ± 0.004; and 21.20 ± 0.30 mol L(-1) atm(-1), respectively. The fraction for these compounds in stratocumulus and cumulonimbus clouds at 278 K were also estimated in this work (isoprene, 1.0 × 10(-6), 6.8 × 10(-6); limonene, 1.5 × 10(-6), 1.0 × 10(-5); α-pinene, 4.5 × 10(-7), 3.1 × 10(-6); and linalool, 6.2 × 10(-4), 4.2 × 10(-3)). Our measurements in combination with literature results indicated that noncyclic alkenes could have smaller K(H) values than those of cyclic terpenes and that K(H) values may increase with an increasing number of double bonds. It was also shown that estimated Henry's law constants and their temperature dependence based on model prediction can differ from experimental results considerably and that direct measurements of temperature-dependent Henry's law constants of atmospheric organics are necessary for future work.