soil humic acids - masarykova univerzita · soil humic acids -review of latest results. from simple...
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SoilSoil humichumic acids acids --review of latest results. review of latest results.
From simple models to elucidation of From simple models to elucidation of supramolecularsupramolecular interactionsinteractions
Josef HAVELDepartment of Analytical Chemistry
Faculty of ScienceMASARYK UNIVERSITYBrno, Czech Republic
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SoilSoil humichumic acidsacids--review of latest results. review of latest results.
From simple models to elucidation of From simple models to elucidation of supramolecularsupramolecular interactionsinteractions
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Amount of carbon in various reservoirsReservoir Amount of C ( 1014 kg)
At Earth’sSurface
Atmospheric CO2BiomassFresh WaterMarine, above ThermoclineSoil Organic Matter
74.82.5
5 - 830 - 50
At Depthsto 16 km
Marine Organic DetritusCoal and PetroleumDeep Sea Solute CarbonSediments
30100345
200,000
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SoilSoil humichumic acidsacids
What is the M. W. ???
Composition? Chemical nature?
Structure?
Physicochemical properties ? pK, stability constants ?
Interaction with xeno-biotics ????
How they influence fate of contaminants in soil and waters?
Etc.
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HUMIC ACIDSElemental analysis
UV/VIS spectroscopy
EPR, NMR
Potentiometry (Glass, Cu-ISE, Uranyl electrodes)
Vapor Pressure Osmometry
Stripping Voltammetry
Capillary Zone &Paper Electrophoresis
MALDI/TOF MS, Pyrolysis MS, CZE-MS
Thin Layer Chromatography, TLC-MS
Instrumentation methods
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HUMIN(insoluble)
HYMATOMELANIC ACID
extract with alcohol
GRAY HUMIC ACID(precipitated)
BROWN HUMIC ACID(not precipitated)
redissolve in base and add electrolyte
HUMIC ACID(precipitated)
FULVIC ACID(not precipitated)
treat with acid
(soluble)
HUMUSSOMextract with alkali
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SOM in soils
OM in sediments
Waters
???????
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O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
Stee link molecular structure
HOHOOC COOH
OH
OH
COOH
HOO
OH
H2N
O
HO
O
O
H2 N
TNB humic acid monomer
Some HA structures proposed
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OHOH
MeO
HO
OH
OMe OMe
OH
MeO
MeO
O
O
OH
OH
HO
R
NH2
O
COOH
Humic acid building blocks
Known
Lignin
precursors
Secoisolariciresinol
Arctigenin
Proposed humic acid building block
from aminoacid precursors
G. Davies,E.A. Ghabbour,
Chem.&Industry1999, 426.
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CAPILLARY ELECTROPHORESIS
DetectorCapillary
Electrolytereservoirs Computer
HVPS
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High Voltage Supply
Thermostate
Detector
(+) (-)
capillary
Sample / BGEBackground Electrolyte
(BGE)
data acquisitionand evaluation
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High Voltage Supply
Thermostate
Detector
(+) (-)
capillary
Sample / BGEBackground Electrolyte
(BGE)
data acquisitionand evaluation
SAMPLE
SEPARATION
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4 6 80.00
0.05
0.10
0.15
Abs
orba
nce
(AU
)
Migration time (min)
Soil IHSS Std.
Peat IHSS Std.
Chemapex
Imerca HA
Humitron 60 HA
Artech HA
Brazilian HA
Argentinean4 6 8
0.00
0.05
0.10
0.15
Abs
orba
nce
(AU
)
Migration time (min)
Soil IHSS Std.
Peat IHSS Std.
Chemapex
Imerca HA
Humitron 60 HA
Artech HA
Brazilian HA
Argentinean4 6 8
Migration time (min)
Abs
orba
nce(
AU
)
0.15
0.10
0.05
0.00
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0 000
0.005
0.010
0.015
0.020
0.025
Abs
orba
nce
(AU
)* The same compounds
**
?
?
?
0 5 10 15 200.000
0.005
0.010
0.015
0.020
0.025
()
Time (min)
CZECH
CHINA
FLUKA
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HUMIC ACIDSElemental analysis
UV/VIS spectroscopy
EPR, NMR
PotentiometryVapor Pressure Osmometry
Stripping Voltammetry
MALDI/TOF MS, Pyrolysis MS
Thin Layer Chromatography, TLC-MS
Capillary Zone Electrophoresis, CZE-MS
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Model 3: CuX log β1,1 = 7.96 ± 0.05CuZ log β2,1 = 6.39 ± 0.06
0 1 2Volume 0.08215 M HCl, ml
2
4
6
8
10pH
-0.10
-0.05
0.00
0.05
0.10
pH -
pH
(c)
calc
exp
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HA COMPLEXING METAL IONS
22+
Na+, K+ … alkali, Cs+
Heavy metal ions,
Toxic metal ions
Cu(II), Cd(II), Pb(II)
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J. Patočka, J. Kassa, R. Štětina, G. Šafr, and J. Havel, Toxicological Aspects of Depleted Uranium, Journal of Applied
Biomedicine, 2: 37–42, 2004, ISSN 1214-0287.
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0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
1 1.5 2 2.5 3 3.5
Migration time (min)
Abs
orba
nce
(AU
)
UO22+
13
67
8
11
9
10
2
5
11
NeutralMarker
4
[HA]tot (mM)
1 0.5
2 1.0
3 1.2
4 1.4
5 1.6
6 1.8
7 2.0
8 2.5
9 3.0
10 3.5
11 4.0
DECREASE OF POSITIVE
CHARGE
UO2 2+
+
MIGRATION OFMIGRATION OF POSITIVELYPOSITIVELY CHARGED CHARGED UOUO222+2+--HA SPECIESHA SPECIES
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0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
1 1.2 1.4 1.6 1.8 2 2.2 2.4
Migration time (min)
Abs
orba
nce
(AU
)
UO2 2+
[HA]tot = 1 mM
[HA]tot = 2 mM
[HA]tot = 3 mM
[HA]tot = 0.5 mM
NeutralMarker
(a) Peat HA
(b) MAR 329 HA (CZ)
(c) Tehum HA (CZ)
(d) China HA
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
1 1.2 1.4 1.6 1.8 2 2.2 2.4
Migration time (min)
Abs
orba
nce
(AU
)
UO2 2+
[HA]tot = 1 mM
[HA]tot = 2 mM
[HA]tot = 3 mM
[HA]tot = 0.5 mM
NeutralMarker
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
1 1.2 1.4 1.6 1.8 2 2.2 2.4
Migration time (min)
Abs
orba
nce
(AU
)
UO2 2+
[HA]tot = 1 mM
[HA]tot = 2 mM
[HA]tot = 3 mM
[HA]tot = 0.5 mM
NeutralMarker
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
1 1.2 1.4 1.6 1.8 2 2.2 2.4
Migration time (min)
Abo
srba
nce
(AU
)
UO2 2+
[HA]tot = 1 mM
[HA]tot = 2 mM
[HA]tot = 3 mM
[HA]tot = 0.5 mM
NeutralMarker
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33--D ELECTROPHEROGRAMD ELECTROPHEROGRAM[HA]tot = 1.6 mM, [UO2
2+]tot = 0.2 mM, pH = 4.0
1.013
1.3461.679
2.0132.346
200230
260290
320350
380
-0.005
0.000
0.005
0.010
0.015
0.020
0.025
0.030
Absorba nce (AU)
M igra tion tim e (m in )
W a ve le ng ht (nm )
UO22+- HA
complex
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Potentiometricand Spectroscopic study of Uranyl Complexationwith Humic Acids
P. LUBAL, D. FETSCH, D. ŠIROKÝ, M. LUBALOVÁ, J. ŠENKÝŘ ,
and J. HAVEL*
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Equation for URANYL ion selective electrode
E const UORTFexp, . log [ ]i i= + +2 303 2
2
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The possible reaction schemes of uranylcomplexation with HA’s functional groups of polyphenols and/or phenolcarboxylic acids
O-
O
O
OH + UO 22+
OUO2
O
O
O
+ H +
O
UO2
O
OH
O-
+ UO22+ + H+
OH
O-
O
+ UO22+
OUO2
O
O
+ H+
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HUMIC ACIDSElemental analysis
UV/VIS spectroscopy
EPR, NMR
Potentiometry
Vapor Pressure Osmometry
Stripping Voltammetry
MALDI/TOF MS, Pyrolysis MS
Thin Layer Chromatography, TLC-MS
Capillary Zone Electrophoresis, CZE-MS
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Matrix Assisted Laser DesorptionTime Of Flight
Mass Spectrometry
[1] Karas M., Hillenkamp F., Anal. Chem. 1988, 60, 2299-2301.
[2] Tanaka K., Waki H., Ido Y., Akita S., Yoshida Y., Yoshida T.,Rapid Commun. Mass Spectrom. 1988, 8, 151-53.
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Depleted URANIUM?Virginia S.G. Murray, Michael R. Bailey, Brian G. Spratt,Depleted uranium: a new battlefield hazard, THE LANCET Supplement Vol
360 December 2002 www.thelancet.com 31-32.[1] Properties, use and health effects of depleted uranium (DU): a general overview, Journal of Environmental Radioactivity, Volume 64, Issues 2-3, 2003, Pages 93-112A. Bleise, P. R. Danesi and W. Burkart[2] Civil use of depleted uranium, Journal of Environmental Rad., Volume 64, Issues 2-3, 2003, p. 113-119
[3] Depleted uranium particles in selected Kosovo samples, J.Environ. Radioactivity, Vol. 64, Issues 2-3, 2003, Pages 143-154 P. R. Danesi, A. Markowicz, E. Chinea-Cano, W. Burkart, B. Salbu, D. Donohue, F. Ruedenauer, M. Hedberg, S. Vogt, P. Zahradnik and A. Ciurapinski
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2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n
pH
WO42−
H2WO4
HW6O215−
W6O216−
WO3(c)
[WO42−]TOT = 10.00 mM
2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n
pH
WO42−
H2WO4
HW6O215−
W6O216−
WO3(c)
[WO42−]TOT = 10.00 mM
COMPLEXATION of URANYL
with
C60 derived ligands
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Uranyl reacts with oxalate forming UO2(ox)n2-2n
complexes in solution.
OO
O
O
O
O
O
UOO
O
O
O
O
O
1:3 complex
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0.00
0.05
0.10
0.15
370 380 390 400 410 420 430 440 450 460 470 480
W avelength /nm
AFirst DerivativeSecond Derivative
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0
10
20
30
40
50
60
350 370 390 410 430 450 470
Uranium/Oxalate System:Spectrophotometry of the Individual Species
1:0 1:11:2
1:3
2:32:5
ε
Wavelength
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Equilibrium THISWORK
Ferri et al.
H+ + ox2− = Hox− 3.83(1) 3.81(2)2H+ + ox2− = H2ox− 4.92(1) 4.95(2)
UO22+ + ox2− = UO2ox 6.38(1) 6.39(1)
UO22+ + 2ox2− = UO2(ox)2
2− 11.46(9) 11.52(2) UO2
2+ + 3ox2− = UO2(ox)34− 14.98(1) 15.20(1)
2UO22+ + 3ox2− = (UO2)2(ox)3
2− 20.40(6)2UO2
2+ + 5ox2− = (UO2)2(ox)56− 29.64(7)*
D.Ferri et al., J. Chem. Soc. Dalton Trans. (2000) 3460.
Havel J., J. Soto-Guerrero, P. Lubal, POLYHEDRON 21: (14-15) 1411-1420 JUN 15 2002.
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2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n
pH
WO42−
H2WO4
HW6O215−
W6O216−
WO3(c)
[WO42−]TOT = 10.00 mM
2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n
pH
WO42−
H2WO4
HW6O215−
W6O216−
WO3(c)
[WO42−]TOT = 10.00 mM
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2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n
pH
WO42−
H2WO4
HW6O215−
W6O216−
WO3(c)
[WO42−]TOT = 10.00 mM
2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n
pH
WO42−
H2WO4
HW6O215−
W6O216−
WO3(c)
[WO42−]TOT = 10.00 mM
pK = ???
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Distribution Diagram of Dimalonate [C60] Fullerene Species
0.0
0.2
0.4
0.6
0.8
1.0
0 2 4 6 8
pH
FractionLH2
2- L4-LH3-
LH3-
LH4
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0.0
0.5
1.0
1.5
200 250 300 350 400Wavelength /nm
Spectrophotometric titration of Uranyl by Dimalonate [C60] Fullerene
Progressive additionof uranyl
L
A
Constant total dimalonate [C60]fullerene concentration: 2.23 × 10-5 MpH = 3.5
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Spectrophotometric titration of L with Uranyl
0.24
0.26
0.28
0.30
0.32
0 2 4 6 8 10
ModelUO2L2−
(UO2)2L296 nm
Metal to Ligand Ratio
A
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2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n
pH
WO42−
H2WO4
HW6O215−
W6O216−
WO3(c)
[WO42−]TOT = 10.00 mM
2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n
pH
WO42−
H2WO4
HW6O215−
W6O216−
WO3(c)
[WO42−]TOT = 10.00 mM
Havel J., J. Soto-Guerrero, POLYHEDRON 2002, submitted.
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2 4 6 8 10 12-12
-10
- 8
- 6
- 4
- 2
0
Log Conc.
H+
Mg2+Ca2+
F−
Cl−
SO42−
CO32−
CaCl+CaCO3
CaF+
CaHCO3+
CaHSO4+
CaOH+
CaSO4
H2CO3
H2F2
H2SO4
HCO3−
HF
HF2−
HSO4−
MgCO3
MgF+
MgHCO3+
MgOH+
MgSO4
OH−CaCO3(c
CaMg(CO3)2(c)Mg(OH)2(c
[Mg2+]TOT = 2.90 mM[Ca2+]TOT = 4.30 mM[F−]TOT = 47.00 µM
[Cl−]TOT = 12.60 mM[SO4
2−]TOT = 0.78 mM[CO3
2−]TOT = 24.60 mM
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2 4 6 8 10 12-9
-7
-5
-3
-1
1
Log C
onc.
pH
H+
UO22+
Ca2+
Mg2+
F−
CO32−
SO42−
(UO2)2(OH)22+
(UO2)2(OH)3CO3−
(UO2)2OH3+
(UO2)3(OH)5+
CaCO3CaF+
CaHCO3+
CaHSO4+
CaOH+
CaSO4
H2CO3
H2F2
H2SO4
HCO3−
HF
HSO4−
MgCO3
MgF+MgHCO3
+
MgOH+
MgSO4
OH−
UO2(CO3)22−
UO2(CO3)34−
UO2(OH)2(aq)
UO2(OH)3−
UO2(SO4)22−
UO2CO3
UO2F+
UO2F2UO2F3
−
UO2OH+
UO2SO4
CaCO3(c)
CaUO4(c)Mg(OH)2(c)
MgCO3(c)
UO2CO3(c)
[UO22+]TOT = 0.10 mM
[Ca2+]TOT = 4.30 mM[Mg2+]TOT = 2.90 mM
[F−]TOT = 47.00 µM[CO3
2−]TOT = 24.60 mM[SO4
2−]TOT = 0.78 mM
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MALDI TOF MS
and
HUMIC ACIDS
(SOM)
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Mass spectra of HAs extracted from Czech garden soil and Soil standard of IHSS
200 400 600 800 1000 1200
0
20
40
60
80
100
841.
588
1.4
788.
1 814.
780
0.8
828.
285
5.0
800.
2
854.
2 880.
7
690.
0556.
0
605.
2
661.
163
3.5
302.0
826.
8
907.
1382.9
905.
5
Soil IHSS standard
Czech garden soil
% In
tens
ity
m/z200 400 600 800 1000 1200
0
10
20
30
40
50
60
70
80
90
100
843.
5
Che ma pe x s ta nda rd
801.
481
6.1
829.
785
6.3
884.
090
8.8
% In
tens
ity
m/z
2727
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750 1000 1250 1500
0
20
40
60
80
100
1 3 4 9 .71 2 8 2 .0
1 2 6 3 .17 9 5 .5
8 2 6 .3
8 3 9 .4
8 5 7 .8
1 0 8 5 .7
9 2 6 .9
9 1 0 .3
9 5 4 .2
9 7 0 .0
1 0 1 4 .2
8 6 7 .7
1 1 7 5 .01 1 4 6 .9
1 1 3 2 .7
9 9 8 .6
1 1 0 1 .91 0 4 3 .3
1 0 5 8 .9
8 8 3 .3
F ig .1 a Ma s s s p e c tru m o f s o d iu m h u m a te (TE HUM) m e a s u re d a t th e b e la s e r e n e rg y E =1 2 0
% In
t
m /z
CZECH
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200 300 400 500 600 700 800 900 10000
20
40
60
80
100
B
799.09853.03
827.07813.09
659.01557.23
529.18501.19
473.19449.15
433.13
413.01
360.19
338.18
310.16
277.05
265.08
251.07
189.98
164.92
144.97
128.96
Inte
nsity
[%
]
Mass/Charge
750 800 850 900 950
940.09
926.47
907.01881.08
867.14853.03
841.06827.07813.09
799.09785.13
773.11757.11
745.11733.15
717.12
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0
20
40
60
80
100
%Int.
826 828 830 832 834 836 838 840Mass/Charge
829.77
827.75831.79
828.75832.80825.74
833.81836.85
C47H105O10+
C47H107O10+
C47H103O10+
C47H101O10+
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E. M. Peña-Méndez, D. Gajdošová, K. Novotná, P. Prošek and J. Havel,Chemometrics approach to thecharacterization of humic acids of different origin including Antarcticafrom MALDI TOF mass spectra, Talanta, submitted 2004, in print2005.
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plcdLps
sCAnt-5
Ant-200
pr
sCZ PtfsP LAnt-9Ant-4
Ant-100
Ant-m
cdF
sScdC
cdAAnt-2Ant-1
P
Ant-3
cdLst
PC3
PC2 PC1
4.0
2.0
0.0
-2.0
-2.5
0.01.0
-2.5
2.0
-1.5
1.0
-3.5
3.0
1.0
-1.0
-1.5
0.0
0
5
10
15
20
25
30
1 2 3 4 5 6 7 8 9 10PCs
Var
ianc
e (%
)
Principal
Component Analysis
E. M. Peña-Méndez, D. Gajdošová, K. Novotná, P. Prošek andJ. Havel, Chemometrics approach to the characterization of
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cdF
Ant
-2A
nt-1
cdC
cdA sS
Ant
-m
Ant
-100
Ant
-200
Ant
-9
Ant
-5A
nt-4 Pt
f
cdL sC
0
5
10
15
20
25
30
35
40
45Li
nkag
eD
ista
nce
A B
C D
Samples
Cluster Analysis
Ant
-3
cdLs
t
prsC
Z plsPL psP
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A
-20 -15 -10 -5 0 5PC1
psplprsS sCZsC
sP
cdL
cdLst
Ant-1
Ant-2Ant-3
Ant-4 Ant-5Ant-9Ant-100
Ant-200
Ant-m
cdAcdC
cdFLP
Ptf
-10
-5
0
5
10PC
2
∗
∗
pspl pr
sS
sCZsCsPsL
cdLst Ant-1 Ant-2
Ant-3
Ant-4
Ant-5Ant-9
Ant-100
Ant-200 Ant-m
cdAcdC
cdFL
P Ptf
-10 -5 0 5 10PC2
-10
-5
0
5
10
15
PC3
**B
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M. L. Pacheco, E.M. Pena-Mendez, J. Havel,
Supramolecular interactions of humic acids with organic and inorganic xenobiotics studied by capillary electrophoresis,
Chemosphere 51, 95-108 (2003).
xenobiotics like pesticides, toxic inorganic compounds,
ferro- and ferricyanides
nitrate, chloride, etc
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M. L. Pacheco, E.M. Pena-Mendez, J. Havel,
Supramolecular interactions of humic acids with organic and inorganic xenobiotics studied by capillary electrophoresis,
Chemosphere 51, 95-108 (2003).xenobiotics like pesticides, toxic inorganic compounds,
ferro- and ferricyanides, nitrate, chloride, etc
Methyl viologen dichlorid hydrat (paraquat)
1,1 - Bis- (4-chlorphenyl)-2, 2-dichlorethylen (p,p’-D D E )
1,1-Bis-(4-chlorphenyl)-2, 2, 2-trichlorethan (p,p’-D D T)
Deiquat monohydrate (diquat)
Fluorescein and 5-sulfosalicylic acid
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M. L. Pacheco, E.M. Pena-Mendez, J. Havel,
Supramolecular interactions of humic acids with organic and inorganic xenobiotics studied by capillary electrophoresis,
Chemosphere 51, 95-108 (2003).
Pacheco M.L. and J. Havel: New results from capillaryelectrophoresis and MALDI TOF MS studies of humic
acids interactions with various compounds andxenobiotics, in Humic Substances: Molecular Details and
Applications in Land and Water Conservation ( E. A.Ghabbour, G. Davies, Eds.), Taylor and Francis, Inc. New
York, USA, 2005.
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D. Gajdošová, K. Novotná, P. Prošekand J. Havel,
Separation and characterization of humic acids from Antarctica by capillary electrophoresis and matrix-assisted laser desorption ionisation time-of-flight mass spectrometry. Inclusion complexes
of humic acids with cyclodextrins,
J. Chromatogr. A, 1014 (2003), 117-127.O
O
HOH2C
HO OH
O
O
CH2OHHO
OH
O
O
HOH2COH
OH
O
O
HOH2C
OH
OH
O
O
CH2OH
HO
HO
O
O
CH2OH
OHOH
6
23
d1
d2
h
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WATER
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Formation of Cyclic Water Hexamer in Liquid Helium:
The Smallest Piece of IceK. Nauta and R.E. Miller
Department of Chemistry, University of North Carolina, Chapel Hill, NC 27599, USA
SCIENCE Vol 287, 14 January 2000
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Evaluation of water sorption equilibrium data on ion exchangers RX(s) + n H2O (g) RX(H2O)n (s)
kWater molecules are forming clusters:
Dowex(x% DVB) in PO4 3- cyclen k ± σ(k)
2 301.8 ± 20.3
3 815 ± 61
6 13 722 ± 20216 81 737 ± 518
44 126 696 ± 1 149
168 20 068 ± 133Havel J., Högfeldt E., Talanta, 39, 517 (1992); Scripta Fac. Sci. Nat. Univ. Masaryk Brun. 25 ;73 (1995).
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Evaluation of water sorption equilibrium data on ion exchangers RX(s) + n H2O (g) RX(H2O)n (s)
kWater molecules are forming clusters:
Dowex(x% DVB) in PO4 3- cyclen k ± σ(k)
2 301.8 ± 20.3
3 815 ± 61
6 13 722 ± 20216 81 737 ± 518
44 126 696 ± 1 149
168 20 068 ± 133Havel J., Högfeldt E., Talanta, 39, 517 (1992); Scripta Fac. Sci. Nat. Univ. Masaryk Brun. 25 ;73 (1995).
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O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
HA SUPRAMOLECULE
M1
M2
M3M3 M4
M3 M5M3
M6
R-(CH2)n -(CH2)n -(CH2)n -(CH2)n COO-
R-(CH2)n -(CH2)n -(CH2)n -(CH2)n COO-
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REVIEW of XENOBIOTICS INTERACTIONpH, salt,
metal ions, etc++HA fraction 1 HA fraction 2
HA AGGREGATES(Formation of HA supramolecules)
X-aq + P+
aq {X-,P+}aqIon associate Xenobiotics {DDE}aq
Extraction of neutral xenobioticsinto HA supramolecule
Na+
Charge neutralization
Complexation(coordination)Hydrogen bonds Hydrophilic part
(non polar)
H
HA HAO-
COO-
O-
- OOC H
MM2+2+
O-
-OOC
HAO-
COO-COO- - Na+
HA
{DDE}org{X-, P+}org
pH, salt,metal ions, etc++
HA fraction 1HA fraction 1 HA fraction 2HA fraction 2
HA AGGREGATES(Formation of HA supramolecules)
X-aq + P+
aq {X-,P+}aqIon associate Xenobiotics {DDE}aq
Extraction of neutral xenobioticsinto HA supramolecule
Na+
Charge neutralization
Complexation(coordination)Hydrogen bonds Hydrophilic part
(non polar)
H
HA HAO-
COO-
O-
- OOC H
MM2+2+
O-
-OOC
HAO-
COO-COO- - Na+
HA
{DDE}org{X-, P+}org
Complexation(coordination)Hydrogen bonds Hydrophilic part
(non polar)
H
HA HAO-
COO-
O-
- OOC H
MM2+2+
O-
-OOC
HAO-
COO-COO- - Na+
HA
{DDE}org{X-, P+}org
Hydrogen bonds Hydrophilic part(non polar)
H
HA HAO-
COO-
O-
- OOC H
MM2+2+
O-
-OOC
HAO-
COO-COO- - Na+
HA
{DDE}org{X-, P+}org
HA HAO-
COO-
O-
- OOC H
MM2+2+
O-
-OOC
HAO-
COO-COO- - Na+
HA
{DDE}org{X-, P+}org
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xenobiotics like pesticides, toxic inorganic compounds, ferro- and ferricyanides, nitrates and chloride,
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+INTERCALATION
+ +AGGREGATION
[ ]+ADSORPTION
n
+ +SUBSTITUTION
- -
+INTERCALATION
+INTERCALATION
+ +AGGREGATION
+ +AGGREGATION
[ ]+ADSORPTION
n[ ]+ADSORPTION
n
+ +SUBSTITUTION
- -+ +
SUBSTITUTION- -
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O
O
HO
O
H2N
OH
O HO
COOH
OH
OH
COOHHOOCHO
Stee link molecular structure
HOHOOC COOH
OH
OH
COOH
HOO
OH
H2N
O
HO
O
O
H2 N
TNB humic acid monomer
Some HA structures proposed
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CONCLUSIONS
* HA are low M.W. (~ 1-2 000 Da) compounds
•They strongly aggregate
•HA are complexing metal ions
•HA are also “complexing” water, organic molecules, xenobiotics, …
Forming supramolecules
SUPRAMOLECULAR entities are formed from HA or {HA-xenobiotic} which can migrate independently
HA are mixture of hundreds or thousands of various compounds ….
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ACKNOWLEDGEMENTSGrants Bestowed for ProjectsKONTAKT - BARRANDE 1999 - bilateral Czech-French cooperation project: Humic Acids and Model Ligands: Coordination Properties and Metal Transport, with Laboratory of Bioinorganic Chemistry, ECPM, Strasbourg, France. French Ministry of Foreign Affairs and Czech Ministry of Education and Youth
Ministry of Education and Youth of the Czech Republic, Programme of Intensification of Research at Universities 404/99/0427
Structure and bonding relationships, properties and analysis of synthetic and natural molecule ensembles, part „Bioanalytical Laboratory“ (Havel, J.).
Ministry of Education and Youth of the Czech RepublicCEZ J07-98, 143100011
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ACKNOWLEDGEMENTSMarta Farková (RNDr., CSc.),Jan Havliš (Mgr., Dr.)
Přemysl Lubal (Mgr., Dr.), Jiří Pazourek (RNDr., Dr.)Jan Preisler (Mgr., PhD.), since October 1999, Ing. K. Novotná
Dr.Alma L. Revilla Vazquéz (PhD), MEXICODr. Maria Gabriela Vargas(PhD.) MEXICO
Jaroslav Šenkýř (Ing., CSc.)
PhD Dr. Gaston Bocaz Beneventi, CHILEVlastimil Dohnal (Mgr.)
Dr. David V. Fetsch, PhD, FRANCEMaria L. Pacheco Hernandéz, MEXICO
Drs. Hana Chromá, Daniel Kalný, Jiří Maleček, Sabina MalovanáDr. Lenka Pokorná (Mgr.)
Julio A. Soto Guerrero , MEXICOPreeti Vashi,SOUTH AFRICA
Universidad Nacional de Cordoba, Facultad de CienciasQuímicas, Departamento de Fisicoquímica, Cordoba, Argentina
Drs S. Ceppi, M. Vazquez
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ACKNOWLEDGEMENTSMarta Farková (RNDr., CSc.),Jan Havliš (Mgr., Dr.)
Přemysl Lubal (Mgr., Dr.), Jiří Pazourek (RNDr., Dr.)Jan Preisler (Mgr., PhD.), since October 1999, Ing. K. Novotná
Dr.Alma L. Revilla Vazquéz (PhD), MEXICODr. Maria Gabriela Vargas(PhD.) MEXICO
Jaroslav Šenkýř (Ing., CSc.)
PhD Dr. Gaston Bocaz Beneventi, CHILEVlastimil Dohnal (Mgr.)
Dr. David V. Fetsch, PhD, FRANCEMaria L. Pacheco Hernandéz, MEXICO
Drs. Hana Chromá, Daniel Kalný, Jiří Maleček, Sabina MalovanáDr. Lenka Pokorná (Mgr.)
Julio A. Soto Guerrero , MEXICOPreeti Vashi,SOUTH AFRICA
Prof. Dr. E.M. PEñA-MÉNDEZ, SPAIN
Civ. Ing. Dáša GAJDOŠOVÁ
Dr. Guillermo RAMÍREZ-GALICIA, MÉXICO
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Thank you !