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Are All Creatures Created Equal? (Chemistry of biosphere)

Are All Creatures Created Equal? (Chemistry of biosphere). Yuan-Hui (Telu) Li Department of Oceanography University of Hawaii at Manoa. Outline. Chemical compositions of terrestrial and marine organisms Biophile and biophobe elements Surface complexation model

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Are All Creatures Created Equal? (Chemistry of biosphere)

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  1. Are All Creatures Created Equal?(Chemistry of biosphere) Yuan-Hui (Telu) Li Department of Oceanography University of Hawaii at Manoa

  2. Outline • Chemical compositions of terrestrial and marine organisms • Biophile and biophobe elements • Surface complexation model • Human beings as a part of nature • Fossil carbon: black shale, coal and crude oil • Conclusions • Acknowledgment

  3. Data by Bowen (1979)

  4. Biological standard reference materials (SRM)

  5. Biophile: major ions in seawater, and B-type cations (d-shell electrons 5-10; high polarizability). Biophobe: A-type cations (electron configurations of noble gases; low polarizability).

  6. Wackett et al. (2004)

  7. Hydration of metal oxide surface:O O O O O OSi Si Si Si SiO O O O O O + n H2O  Si Si Si Si Si H H H H O O O O O O O OSi Si Si Si SiO O O O O O Si Si Si Si Si

  8. Surface complexation model:Amphoteric property of oxide and organic matter surfaces:For Cations M+z : M+z + MeOH MeO‑M+z‑1 + H+Me are mostly Si, Fe, and Mn K = {MeO‑M+z‑1 }[H+ ]/[M+z ]{MeOH }= Kd [H+]/{MeOH }

  9. M+z + R-LH  R-L‑M+z‑1 + H+L are organic ligands with hydrophilic functional groups, such as R-OH, R-NH2, and R-SH, on the surface of organic particles.The relative O-M and L-M bond strengths for various cations are shown to be proportional to K, Kd, and the electron bonding energy to gaseous ions (Iz), i.e.M+z (g) + e- M+z-1 (g) + IzA(g) + e- A-1 (g) + I-1

  10. For anionsAz(e.g. Cl-, HS-; SO4-2, MoO4-2, ReO4-) Az + MeOH Me-A-z+1 + OHAz + R-OH R-A-z+1 + OH The relative Me-A and R-A bond strengths are proportional to the I-1 of simple anions, or inversely related to the Izof the central cation of oxyanion. Me-Cl R-Cl O O Me-O-S-O R-O-S-O O O

  11. M+z + L-4 ML+z-4  = [ML+z-4]/([M+z ][L-4]

  12. Mean residence time  =

  13. Conclusions1. The relative abundances of elements in marine and terrestrial living organisms, including human being, are remarkably similar.2. Enrichment of biophile elements relative to soil or pelagic clays mainly reflect the formation of extra strong bonds between highly polarizable biophile elements and organic ligands containing -NH2, -SH, and -COOH groups.3. The mean residence times of elements in the human body again can be explained by the concept of the relative bond strength between ions and organic matter.4. The enriched biophile elements in coals are mainly associated with sulfide phases.5. The enriched biophile elements in crude oils are mainly concentrated in the resin and asphaltene fractions.

  14. Acknowledgement: Many thanks are due to Professor Yoshiki Sohrin, who has graciously sponsored my visit at the Kyoto University. The pioneering works by Professor Toshio Yamamoto on seaweeds are acknowledged here.

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