Are All Creatures Created Equal?

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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
• Human beings as a part of nature
• Fossil carbon: black shale, coal and crude oil
• Conclusions
• Acknowledgment
Data by Bowen
(1979)
Biological standard
reference materials
(SRM)
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).
Wackett et al.
(2004)
Hydration of metal oxide surface:
O
O
Si
O
O
Si
O
Si
O
Si
O
Si
O
Si
O
Si
H H
H
O
O O O
O
Si
Si
Si
O
O
O
O
Si
Si
Si
O
Si
O
Si
O
Si
H
O O
O
Si
Si
O
O
Si
Si
+ n H 2O 
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 }
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) + Iz
A (g) + e-  A-1 (g) + I-1
For anions A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 Iz of the
central cation of oxyanion.
Me-Cl
R-Cl
O
Me-O-S-O
O
O
R-O-S-O
O
M+z + L-4 ML+z-4
 = [ML+z-4]/([M+z ][L-4]
Mean
residence time
=
M  X man
X mam
 50
F  Curine
Curine
1.0
1.0
Mn
(a)
(b)
IC
Al Mg
F2
Rb
0.0
Ca
0.5
Ba
Sr
Cu
Si
K
Ti
Zr
Sr
U
IC
Ca
OC
Ni
Zn
V
U
F4
0.5
Y
0.0
P
Mo
Co
-0.5
-0.5
Fe
-1.0
-0.5
Cretaceous
black shale
As
S
0.0
F1
0.5
1.0
-1.0
-0.5
0.0
F3
0.5
1.0
2
(c)
(d)
4
-2
F4 score
F2 score
0
-4
-6
-8
-3
OC rich
Srich
-2
-1
0
F1 score
1
2
2
0
OC rich
Srich
-2
3
-2
-1
0
1
2
F3 score
3
4
5
40
40
(a)
(b)
Blackshale
OC-rich
S-rich
30
OC (%)
OC (%)
30
20
10
20
10
0
40
50
60
0
0
70
5
10
Depth (cm)
(c)
30
ex Fe2O3 (%)
Fe2O3 (%)
30
20
10
20
25
(d)
rit
py
e
20
10
0
shale
0
5
15
S(%)
10
Al2O3 (%)
15
0
5
10
15
20
25
0.02
0.03
MnO(%)
0.04
0.05
S(%)
500
12
400
10
300
8
CaO (%)
Mo (ppm)
(e)
200
(f)
6
4
100
0
0
2
10
20
OC (%)
30
40
0
0.00
0.01
Conclusions
1. 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.
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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