Inconsistency of ammonium–sulfate aerosol ratios with thermodynamic models in the eastern US: a possible role of organic aerosol

Thermodynamic models predict that sulfate aerosol (S(VI)  ≡  H2SO4(aq) + HSO4−+ SO42−) should take up available ammonia (NH3) quantitatively as ammonium (NH4+) until the ammonium sulfate stoichiometry (NH4)2SO4 is close to being reached. This uptake of ammonia has important implications for aerosol mass, hygroscopicity, and acidity. When ammonia is in excess, the ammonium–sulfate aerosol ratio R =  [NH4+] ∕ [S(VI)] should approach 2, with excess ammonia remaining in the gas phase. When ammonia is in deficit, it should be fully taken up by the aerosol as ammonium and no significant ammonia should remain in the gas phase. Here we report that sulfate aerosol in the eastern US in summer has a low ammonium–sulfate ratio despite excess ammonia, and we show that this is at odds with thermodynamic models. The ammonium–sulfate ratio averages only 1.04 ± 0.21 mol mol−1 in the Southeast, even though ammonia is in large excess, as shown by the ammonium–sulfate ratio in wet deposition and by the presence of gas-phase ammonia. It further appears that the ammonium–sulfate aerosol ratio is insensitive to the supply of ammonia, remaining low even as the wet deposition ratio exceeds 6 mol mol−1. While the ammonium–sulfate ratio in wet deposition has increased by 5.8 % yr−1 from 2003 to 2013 in the Southeast, consistent with SO2 emission controls, the ammonium–sulfate aerosol ratio decreased by 1.4–3.0 % yr−1. Thus, the aerosol is becoming more acidic even as SO2 emissions decrease and ammonia emissions stay constant; this is incompatible with simple sulfate–ammonium thermodynamics. A tentative explanation is that sulfate particles are increasingly coated by organic material, retarding the uptake of ammonia. Indeed, the ratio of organic aerosol (OA) to sulfate in the Southeast increased from 1.1 to 2.4 g g−1 over the 2003–2013 period as sulfate decreased. We implement a simple kinetic mass transfer limitation for ammonia uptake to sulfate aerosols in the GEOS-Chem chemical transport model and find that we can reproduce both the observed ammonium–sulfate aerosol ratios and the concurrent presence of gas-phase ammonia. If sulfate aerosol becomes more acidic as OA ∕ sulfate ratios increase, then controlling SO2 emissions to decrease sulfate aerosol will not have the co-benefit of suppressing acid-catalyzed secondary organic aerosol (SOA) formation

Gender, gender role identity, and children's reported feelings toward the same and opposite sex

The present study explored the relative importance of gender role identity, gender role attitudes, and biological gender in determining the intensity of anger, disgust, hurt, envy, fear, pity, and liking reported toward same- and opposite-sex children. Sixty male and 60 female 6–12-year-old children reported on the intensity of emotions that a hypothetical child would experience toward same- and opposite-sex children in various situations. The Children's Personal Attitudes Questionnaire, the Children's Attitudes toward Women Scale, and a self-reported toy preference measure were used to assess gender role identity and attitudes. The results indicated that girls were more angry at males than at females, and that both sexes tended to be more hurt and disgusted by opposite-sex than by same-sex children. Girls also tended to report more fear than did boys, and both sexes tended to report more fear of males than of females. Most importantly, gender role identity and attitudes accounted for more of the variance in predicting the quality of reported emotions than did biological gender. Biological gender predicted to only one feeling: pity toward males, after the variance accounted for by the gender role traits was removed. In general, both boys and girls who scored highly on feminine gender role identity were both communal and vulnerable in their reported emotions (high in reported liking, fear, and hurt). Children's reported feelings toward the same- and opposite-sex children seemed to be based on the evaluation of whether other children's biological gender differed from the children's own gender role identity characteristics.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/45596/1/11199_2004_Article_BF00289226.pd

CHEMOSENSORY RESPONSES TO AMINO ACIDS AND CERTAIN AMINES BY THE CILIATE TETRAHYMENA: A FLAT CAPILLARY ASSAY

Volume: 167Start Page: 322End Page: 33