composition of lipids from the first lusatian lignite seam of the … › egu2020 ›...
TRANSCRIPT
Composition of lipids from the First Lusatian lignite seam of the Konin Basin (Poland): relations to vegetation, climate and carbon cycling during the mid-Miocene Climatic Optimum
1 2 3A. Bechtel , M. Widera , M. Woszczyk 1 Applied Geosciences & Geophysics, Montanuniversität Leoben, Peter-Tunner-Strasse 5, A-8700 Leoben, Austria
2 Adam Mickiewicz University, Institute of Geology, 12 Krygowski Street, 61-680 Poznań, Poland3 Adam Mickiewicz University, Laboratory of Biogeochemistry,10 Krygowski Street, 61-680 Poznań, Poland
The positive correlation between d13C and di-/(di + tri-)terpenoid ratios of lignite indicates the role of varying gymnosperm/angiosperm contributions on the carbon isotopic composition (Fig. 7). The C-isotope data of long-chain n-alkanes, diterpenods, and angiosperm-derived triterpenoids show parallel fluctuations within the profiles, arguing for the role of minor variations in d13C of atmospheric CO2 on d13C of plant lipids during the Mid-Miocene Climatic Optimum (Fig. 8). However, the influence of local variations in ambient CO2 (e.g., the canopy effect) cannot be excluded. Fluctuations in d13C values of individual compounds may also be related to changes in humidity, air temperature, and carbon cycling within the peat (Fig. 8).
Geological Setting and Samples
The Adamów, Jóźwin IIB and Tomisławice lignite mines cover fault-bounded, relatively shallow tectonic depressions. They are located ~20–35 km of Konin in central Poland (Fig. 1a). The Grey Clays Member of the Miocene Poznań Fm. contains the examined First Lusatian lignite seam. It is up to several meters thick, on average 6.3–8.1 m (Fig. 1b-d). The seam formed in the middle part of the mid-Miocene (~15 Ma), during the last peak of the mid-Miocene Climatic Optimum.
Acknowledgement: This poster, presented at the EGU General Assembly 2020 in Vienna, is a contribution to the Research Project No. 2017/27/B/ST10/00001, funded by the National Science Centre, Poland.
Bulk geochemistry and molecular composition of lipids
Bulk geochemistry and molecular composition of lipids
Sample AD-02 Hydrocarbons (F1)
30 35 40 45 50 55 60 65 70 75 80 85 90
Time (min)
0
10
20
30
40
50
60
70
80
90
100
Rela
tive
Abundance
Std
.
23
25
Dehydro
abie
tane
Sim
onellite
a-P
hyllocla
dane
b-P
hyllocla
dane
Pim
ara
ne
Isonorp
imara
ne
Norp
imara
ne
Isopim
ara
die
ne
des-A
-Lupane
des-A
-Ole
anenes
27
29
31
Din
oro
leana-t
etr
aene
Din
orlupa-t
riene
ab-C
31-H
opane (
22R
)
bb-C
31-H
opane
des-A
-8,1
4-s
eco-n
oro
leana-p
enta
ene
a)
Cad
alen
e
19
C30 H
op-1
7(2
1)-
ene
Alcohols (F3)
30 35 40 45 50 55 60 65 70 75 80 85 90
Time (min)
0
10
20
30
40
50
60
70
80
90
100
Rela
tive
Abundance
C24 n
-Alk
anol
C26 n
-Alk
anol
C28 n
-Alk
anol
C22 n
-Alk
anol
Std
.
C18 n
-Alk
anol
C16 n
-Alk
anol
C14 n
-Alk
anol
C12 n
-Alk
anol
C23 n
-Alk
anol
C25 n
-Alk
anol
Cam
peste
rol
b-S
itoste
rol
b-A
myrin
a-A
myrin
Lupeol
Friedelin
c)
Carboxylic Acids (FA)
30 35 40 45 50 55 60 65 70 75 80 85 90
Time (min)
0
10
20
30
40
50
60
70
80
90
100
Rela
tive
Abundance
C16:0
n-F
AC
16:1
n-F
A
C15:0
n-F
AC
15:0
i-F
A
C14:0
n-F
A
C12:0
n-F
A
C10:0
n-F
A
Std
.
C18:0
n-F
AC
18:1
n-F
A
C17:0
n-F
AC
17:0
i-F
A C20:0
n-F
A
C22:0
n-F
A
C24:0
n-F
A C26:0
n-F
A
C28:0
n-F
A
C30:0
n-F
A
C23:0
n-F
A
C25:0
n-F
A
C27:0
n-F
A
C21:0
n-F
A
Hopanoic
acid
s
d)
Ketones + PAHs (F2)
30 35 40 45 50 55 60 65 70 75 80 85 90
Time (min)
0
10
20
30
40
50
60
70
80
90
100
Rela
tive
Abundance
Std
.
Dehydro
ferr
ugin
ol
Ferr
ugin
ol
Labdan-1
5-o
ic a
cid
, M
ER
ete
ne6,1
0,1
4 T
rim
eth
yl-penta
decan-2
-one
C25 n
-Alk
an-2
-one
C27 n
-Alk
an-2
-one
C29 n
-Alk
an-2
-one
C31 n
-Alk
an-2
-one
C29 n
-Alk
an-1
0-o
ne
Tetr
am
eth
yl-octa
hydro
-pic
enes
C31 n
-Alk
an-1
6-o
ne
Squale
ne
b)
Trim
eth
yl-dih
ydro
-pic
ene
Friedelin
C20 n
-Alk
anol
Fig. 5: Total ion current chromatograms of the (a) hydrocarbon fraction, (b) the ketone fraction, (c) the alcohol fraction, and (d) the carboxylic acids obtained from the lignite sample AD-02, Std. = Internal Standard (deuterated tetracosane (F1), 1,1´-binaphthyl (F2), 1-nonadecanol (F3), nonadecanoic acid (FA), respectively).
Fig. 6: Relative percentages of source specific plant lipids within the samples.
Elevated ash yields and low sulfur contents indicate peat formation in topogenous mires under freshwater conditions (Figs. 2, 3, 4). The molecular composition of the extracted lipids is highly variable, including leaf-wax n-alkanes in the C23 to C31 range, diterpenoids, hopanoids, and angiosperm-derived triterpenoids, as well as saturated fatty acids, long-chain n-alkanols and n-alkan-2-ones (Figs. 2, 3. 4). The enhanced abundances of short-chain n-FAs in several lignite samples argue for the contribution of algae and microorganisms to the biomass during periods of raised water table. Low bb/(bb+ab) hopane ratios imply acidic conditions during peatification. High concentrations of plant wax derived lipids are found in samples of detrital lignite (Fig. 5). The relative abundances (Paq = 0.08–0.51; Figs. 2d, 3d, 4d) of mid-chain (C23, C25) n-alkanes argue for a minor contribution of macrophytes (graminoids, etc.), enhanced during periods of raised water level. Terpenoid biomarker ratios (Fig. 6) argue for mixed vegetation, including gymnosperms (i.e. conifers) and angiosperms. From the sesqui- and diterpenoids present in the lignite (Fig. 5), a significant contribution of species of the coniferales families Cupressaceae and Pinaceae is concluded. High relative abundances of triterpenoids of the oleanane and ursane structural types in several parts of the seam indicate angiosperm domination in the peat-forming vegetation (Fig. 6). The input from Betulaceae is suggested from the occurrence of lupeol and its derivatives.
Stable Isotope Analyses
Texture of lignite lithotypes: DL - detritic, XDL - xylodetritic, DXL - detroxylitic,
WDL - weathered Structure of lignite lithotypes: m - massive, h - horizontal stratification, fr - fractured
F - fines (silt and clay), S - sand
- fractures (cleats)
- horizontal stratification
- xylites (fossilised wood)
Adamów mine
S DL XDL DXLF61
62
63
64
65
66
67
68
AD-02
AD-03
AD-04
AD-05
AD-06
AD-07
AD-08
AD-09
AD-01
WDLm
WDLm
DXLm(fr)
XDLm(fr)
XDLm
DLm
AD-10
Jóźwin IIB mine
S DL XDL DXLF
40
39
41
42
43
44
45
46
JD-01
JD-02
JD-03
JD-04
JD-05
JD-05 - sample position
JD-06
JD-00
XDLm(fr)
DLm(fr)
DLm(fr)
JD-07
47
Tomisławice mine
S DL XDL DXLF
TD-02
TD-03
TD-04
TD-05
TD-06
TD-07
TD-08
TD-09
TD-01
XDLm(fr)
XDLh
XDLm
DXLm
XDLh
DLm
DLm
TD-10
First Lusatia
n li
gnite
seam
Gre
y C
lays (
Mid
-Polis
h)
Mem
ber
Kozmin Formation
Po
zna
n F
orm
atio
n
Wielkopolska Member
53
54
55
56
57
58
59
60
61
62
63m a.s.l. samplesedimentary
logm a.s.l. samplesedimentary
logm a.s.l. sample lithostratigraphysedimentary
log
POLAND
WarsawPoznan
KONIN
TUREK
N
5 km
200 km
Jóźwin IIB
lignite
deposit Tomisławice
lignite
deposit
Adamów
lignite
deposit
- studied section
a)
b) c) d)
Fig. 1: (a) Location of the studied lignite opencast mines in the Konin Basin (Poland); and lignite lithotypes, structural elements, and position of detrital lignite samples in the profiles from the (b) Adamów, (c) Jóźwin IIB, and (d) Tomisławice opencast mines.
Alt
itu
de
(m
a.s
.l.)
Adamów mine
S DL XDL DXLF61
62
63
64
65
66
67
68
AD-05
AD-06
AD-07
AD-08
AD-09
AD-01
WDLm
WDLm
DXLm(fr)
XDLm(fr)
XDLm
DLm
AD-10
samplesedimentarylog
AD-02
AD-03
AD-04
Alt
itu
de (
m a
.s.l.)
Legend see Fig. 1 60
61
62
63
64
65
66
67
68
0 50 100 150 200 250
long-chain FAs
short-chain FAs
60
61
62
63
64
65
66
67
68
0 25 50 75 100
Steroids
Hopanoids
0 100 200 300
Diterpenoids
Triterpenoids
0.0 0.2 0.4 0.6 0.8 1.0 0 10 20 30
unsat. FAs
branched FAs
a) b)c)
0 10 20 30 40 50 60
TOC, Ash (wt%)
0.0 0.5 1.0 1.5
TIC, S (wt%)
0 50 100 150 200 250
Conc. (mg/g TOC)
TOC
Ash
TIC
S
n-Alkanes
n-Alkan-2-ones
n-Alkanols
Conc. (mg/g TOC) Conc. (mg/g TOC)Di-/(Di- + Tri-)-
terpenoidsConc. (mg/g TOC) Conc. (mg/g TOC)
e) f) g) h) i)
0.0 0.2 0.4 0.6 0.8 1.0
Paq
d)
Fig. 2: Sampling position and variation of concentrations and concentration ratios of lipids within the First Lusatian lignite seam at the Adamów mine.
TOC, Ash (wt%) TIC, S (wt%)
Alt
itu
de
(m
a.s
.l.)
Jóźwin IIB mine
S DL XDL DXLF
40
39
41
42
43
44
45
46
JD-01
JD-02
JD-03
JD-04
JD-05
JD-06
JD-00
XDLm(fr)
DLm(fr)
DLm(fr)
JD-07
47samplesedimentary
log
Alt
itu
de
(m
a.s
.l.)
Legend see Fig. 1
Conc. (mg/g TOC)
Di-/(Di- + Tri-)-terpenoids
Conc. (mg/g TOC) Conc. (mg/g TOC) Conc. (mg/g TOC) Conc. (mg/g TOC)
38
39
40
41
42
43
44
45
46
47
0 10 20 30 40 50 60 0.0 0.5 1.0 1.5 2.0 2.5 0 50 100 150 200 250
0 50 100 150 200 250
long-chain FAs
short-chain FAs
38
39
40
41
42
43
44
45
46
47
0 25 50 75 100
Steroids
Hopanoids
0 100 200 300
Diterpenoids
Triterpenoids
0.0 0.2 0.4 0.6 0.8 1.0 0 5 10 15 20
unsat. FAs
branched FAs
TOC
Ash
TIC
S
n-Alkanes
n-Alkan-2-ones
n-Alkanols
a) b) c)
e) f) g) h) i)
0.0 0.2 0.4 0.6 0.8 1.0
Paq
d)
Fig. 3: Sampling position and variation of concentrations and concentration ratios of lipids within the First Lusatian lignite seam at the Jóźwin IIB mine.
Alt
itu
de (
m a
.s.l
.)
Tomisławice mine
Di-/(Di- + Tri-)-terpenoids
Conc. (mg/g TOC) Conc. (mg/g TOC) Conc. (mg/g TOC) Conc. (mg/g TOC)
S DL XDLDXLF
TD-02
TD-03
TD-04
TD-05
TD-06
TD-07
TD-08
TD-09
TD-01
XDLm(fr)
XDLh
XDLm
DXLm
XDLh
DLm
DLm
TD-10
53
54
55
56
57
58
59
60
61
62
63samplesedimentary
log
Alt
itu
de
(m
a.s
.l.)
Legend see Fig. 1 51
52
53
54
55
56
57
58
59
60
61
62
63
0 20 40 60 80 0.0 1.0 2.0 3.0 0 200 400 600
0 100 200 300 400
long-chain FAs
short-chain FAs
51
52
53
54
55
56
57
58
59
60
61
62
63
0 20 40 60 80 100 120
Steroids
Hopanoids
0 50 100 150 200
Diterpenoids
Triterpenoids
0.0 0.2 0.4 0.6 0.8 1.0 0 10 20 30 40
unsat. FAs
branched FAs
TOC
Ash
TIC
S
n-Alkanesn-Alkan-2-onesn-Alkanols
Conc. (mg/g TOC)TOC, Ash (wt%) TIC, S (wt%)
a) b) c)
e) f) g) h) i)
0.0 0.2 0.4 0.6 0.8 1.0
Paq
d)
Fig. 4: Sampling position and variation of concentrations and concentration ratios of lipids within the First Lusatian lignite seam at the Tomisławice mine.
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
-26.5 -26.3 -26.1 -25.9 -25.7 -25.5 -25.3 -25.1 -24.9 -24.7 -24.5
Adamów
Jóźwin IIB
Tomisławice
13C (o/oo, PDB)d
Di-
/(D
i- +
Tri
-)te
rpe
no
ids
Fig. 7: Cross-correlation of d13C of total organic carbon versus the ratios of diterpenoids to the sum of di- plus triterpenoids concentrations of lignite samples.
S DL XDL DXLF61
62
63
64
65
66
67
68
AD-05
AD-06
AD-07
AD-08
AD-09
AD-01
WDLm
WDLm
DXLm(fr)
XDLm(fr)
XDLm
DLm
AD-10
samplesedimentarylog
AD-02
AD-03
AD-04
Alt
itu
de
(m a
.s.l.
)
S DL XDL DXLF
40
39
41
42
43
44
45
46
JD-01
JD-02
JD-03
JD-04
JD-05
JD-06
JD-00
XDLm(fr)
DLm(fr)
DLm(fr)
JD-07
47samplesedimentary
log
Alt
itu
de
(m a
.s.l.
)
Adamów mine
S DL XDLDXLF
TD-02
TD-03
TD-04
TD-06
TD-07
TD-08
TD-09
TD-01
XDLm(fr)
XDLh
XDLm
DXLm
XDLh
DLm
DLm
TD-10
53
54
55
56
57
58
59
60
61
62
63samplesedimentary
log
Alt
itu
de (
m a
.s.l.)
Legend see Fig. 1
TD-07
Tomisławice mine
-32 -31 -30 -29 -28 -28 -27 -26 -25 -24 -30 -29 -28 -27 -26
13C (o/oo, PDB)d 13C (o/oo, PDB)d 13C (o/oo, PDB)d
a) b) c)
n-C23
n-C29
n-C31
NorabietanePimaranea-PhyllocladaneFerruginol
Monoarom. OleaneneMonoarom. LupeneTriarom. OleaneneTetraarom. Oleanene
-32 -31 -30 -29 -28 -27 -26 -25 -24 -30 -29 -28 -27 -2613C (o/oo, PDB)d 13C (o/oo, PDB)d 13C (o/oo, PDB)d
Jóźwin IIB mine
n-C23
n-C29
n-C31
NorabietanePimaranea-PhyllocladaneFerruginol
Monoarom. OleaneneMonoarom. LupeneTriarom. OleaneneTetraarom. Oleanene
a) b) c)
-32 -31 -30 -29 -28 -27 -26 -25 -24 -30 -29 -28 -27 -26
13C (o/oo, PDB)d 13C (o/oo, PDB)d 13C (o/oo, PDB)d
a) b) c)
n-C23
n-C29
n-C31
NorabietanePimaranea-PhyllocladaneFerruginol
Monoarom. OleaneneMonoarom. LupeneTriarom. OleaneneTetraarom. Oleanene
Fig. 8: Depth trends of carbon isotopic compositions of (a) C23, C29, and C31 n-alkanes, (b) diterpenoids, and (c) triterpenoids within the studied profiles.