Chemically Influenced Self-Preservation Kinetics of CH4 Hydrates below the Sub-Zero Temperature

The self-preservation property of CH4 hydrates is beneficial for the transportation and storage of natural gas in the form of gas hydrates. Few studies have been conducted on the effects of chemicals (kinetic and thermodynamic promoters) on the self-preservation properties of CH4 hydrates, and most of the available literature is limited to pure water. The novelty of this work is that we have studied and compared the kinetics of CH4 hydrate formation in the presence of amino acids (hydrophobic and hydrophilic) when the temperature dropped below 0 °C. Furthermore, we also investigated the self-preservation of CH4 hydrate in the presence of amino acids. The main results are: (1) At T < 0 ℃, the formation kinetics and the total gas uptake improved in the presence of histidine (hydrophilic) at concentrations greater than 3000 ppm, but no significant change was observed for methionine (hydrophobic), confirming the improvement in the formation kinetics (for hydrophilic amino acids) due to increased subcooling; (2) At T = −2 °C, the presence of amino acids improved the metastability of CH4 hydrate. Increasing the concentration from 3000 to 20,000 ppm enhanced the metastability of CH4 hydrate; (3) Metastability was stronger in the presence of methionine compared to histidine; (4) This study provides experimental evidence for the use of amino acids as CH4 hydrate stabilizers for the storage and transportation of natural gas due to faster formation kinetics, no foam during dissociation, and stronger self-preservation.

Transport of isoprene and its oxidation products by deep convective clouds in the Amazon

&lt;p&gt;Transport of organic trace gases by deep convective clouds plays an important role for new particle formation (NPF) and particle growth in the upper atmosphere. Isoprene accounts for a major fraction of the global volatile organic vapor emissions and a significant fraction is emitted in the Amazon. We examined transport and chemical processing of isoprene and its oxidation products in a deep convective cloud over the Amazon using a box model. Trajectories of individual air parcels of the cloud derived from a large eddy simulation are used as input to the model. Our results show that there exist two main pathways for NPF from isoprene associated with deep convection. The first one is when the gas transport occurs through a cloud with low lightning activity and with efficient gas uptake of low-volatile oxidation products by ice particles. Some of the isoprene will reach the cloud outflow where it is further aged and produces low volatile species capable of forming and growing new particles. The second way is via transport through clouds with high lightning activity and with low gas uptake by ice. For this case, low volatile oxidation products will reach the immediate outflow in concentrations close to the values observed in the boundary layer. The efficiency of gas condensation on ice particles is still uncertain and further research in this direction is needed.&lt;/p&gt;

Surface-Promoted Redox Reactions Occurs Spontaneously on Solvating Salt Surfaces

&lt;p&gt;Gas-particle interfaces play essential roles in the atmosphere and directly influence many atmospheric processes, including gas uptake, halogen chemistry, ozone depletion, and heterogeneous ice nucleation. However, because interfacial processes take place on molecular scales, classical bulk thermodynamic theories are often insufficient to describe interfaces. Also, interfacial processes are challenging to characterize and are often overlooked in current atmospheric chemistry.&lt;/p&gt;&lt;p&gt;For this study, ambient pressure X-ray photoelectron spectroscopy (APXPS) experiments were performed. A surface-promoted sulfate-reducing ammonium oxidation reaction is discovered to spontaneously take place on common inorganic aerosol surfaces undergoing solvation. Several key intermediate species including, S&lt;sup&gt;0&lt;/sup&gt;, HS&lt;sup&gt;-&lt;/sup&gt;, HONO, and NH&lt;sub&gt;3(aq)&lt;/sub&gt;&amp;#160;are identified as reaction components associated with the solvation process. Depth profiles of relative species abundance show the surface propensity of key species. The species assignments and depth profile features are supported by classical and first-principle molecular dynamics calculations. A detailed mechanism is proposed to describe the processes that lead to unexpected products during salt solvation. This discovery reveals novel chemistry that is uniquely linked to a solvating surface and has great potential to illuminate current puzzles within heterogeneous chemistry. Lastly, natural salts sampled from saline lakes and playas are examined for this behavior, and provide further evidence of the important roles this surface-promoted redox mechanism may play in nature.&lt;/p&gt;