This work presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, Dlimonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NO x (to simulate an urban atmosphere). Chamber-and flow-tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3−8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NO x -generated SOA had more unique visual appearance and indicated a lower extent of product overlap. Furthermore, the fraction of nitrogen-containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NO x oxidation conditions compared to the ozone-driven oxidation. Comparison of the SOA constituents before and after photolysis showed the tendency to reduce the average number of atoms in the SOA compounds without a significant effect on the overall O/C and H/C ratios. SOA prepared by OH/NO x photooxidation of 1,3,5-trimethylbenzene and guaiacol were more resilient to photolysis despite being the most light-absorbing. The composition of SOA prepared by ozonolysis of monoterpenes changed more significantly as a result of the photolysis. The results indicate that aqueous photolysis of dissolved SOA compounds in cloud/fog water can occur in various types of SOA, and on atmospherically relevant time scales. However, the extent of the photolysis-driven change in molecular composition depends on the specific type of SOA.
Messenger RNA (mRNA) secondary structure decreases the elongation rate, as ribosomes must unwind every structure they encounter during translation. Therefore, the strength of mRNA secondary structure is assumed to be reduced in highly translated mRNAs. However, previous studies in vitro reported a positive correlation between mRNA folding strength and protein abundance. The counterintuitive finding suggests that mRNA secondary structure affects translation efficiency in an undetermined manner. Here, we analyzed the folding behavior of mRNA during translation and its effect on translation efficiency. We simulated translation process based on a novel computational model, taking into account the interactions among ribosomes, codon usage and mRNA secondary structures. We showed that mRNA secondary structure shortens ribosomal distance through the dynamics of folding strength. Notably, when adjacent ribosomes are close, mRNA secondary structures between them disappear, and codon usage determines the elongation rate. More importantly, our results showed that the combined effect of mRNA secondary structure and codon usage in highly translated mRNAs causes a short ribosomal distance in structural regions, which in turn eliminates the structures during translation, leading to a high elongation rate. Together, these findings reveal how the dynamics of mRNA secondary structure coupling with codon usage affect translation efficiency.
Intermediate volatility organic compound (IVOC) emissions from a large cargo vessel were characterized under realworld operating conditions using an on-board measurement system. Test ship fuel-based emission factors (EFs) of total IVOCs were determined for two fuel types and seven operating conditions. The average total IVOC EF was 1003 ± 581 mg•kg-fuel −1 , approximately 0.76 and 0.29 times the EFs of primary organic aerosol (POA) emissions from low-sulfur fuel (LSF, 0.38 wt % S) and high-sulfur fuel (HSF, 1.12 wt % S), respectively. The average total IVOC EF from LSF was 2.4 times that from HSF. The average IVOC EF under low engine load (15%) was 0.5−1.6 times higher than those under 36%−74% loads. An unresolved complex mixture (UCM) contributed 86.1 ± 1.9% of the total IVOC emissions. Ship secondary organic aerosol (SOA) production was estimated to be 546.5 ± 284.1 mg•kg-fuel −1 ; IVOCs contributed 98.9 ± 0.9% of the produced SOA on average. Fuel type was the dominant determinant of ship IVOC emissions, IVOC volatility distributions, and SOA production. The ship emitted more IVOC mass, produced higher proportions of volatile organic components, and produced more SOA mass when fueled with LSF than when fueled with HSF. When reducing ship POA emissions, more attention should be paid to commensurate control of ship SOA formation potential.
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