Auxiliary Material for Paper 2011GB004156
Model design, input parameters, and additional information for a quantitative
geochemical model along a transect off Peru
1. Regional setting
1.1 Shelf sites 680, 681 and Site 679
The shelf sites 680 and 681 are located in the Salaverry Basin (Figure S1.1). Sediments
recovered from the shelf sites conform with basically upwelling-related deposits. They contain
total organic carbon-rich (TOC-rich) diatomaceous ooze and mud accumulated throughout the
Pleistocene and Holocene periods. Older sediments from the Miocene and Pliocene ages have
lower TOC content, contain more clastic components, and are coarser grained (Emeis and Morse,
1990). TOC content in the upper 150 mbsf varies between 1 and 10 wt. % (cf. Figure 2a of the
main text; Suess et al., 1988). The mixing of seawater-derived pore water and a hypersaline, subsurface brine have caused strong positive chloride and sodium concentration gradients in the
pore water profiles from Sites 680 and 681 (Figure S3.2 and Kastner et al., 1990). Sulphate,
calcium, and magnesium concentration profiles are also characterised by brine reflux.
Site 679 is located at the seaward edge of the outer shelf at a water depth of 450 m. A structural
ridge separates this site from the sub-surface brine. Thus, this site is geochemically characterised
by seawater chloride concentrations as high as 200 mbsf. Below, in the section from the middle
Miocene period, chloride concentrations decrease to 62 % of seawater chloride (Kastner et al.,
1990). Suess et al. (1988) proposed dilution with middle to late Miocene period fresh water
while the ridge was subaerially exposed, restricting the Salaverry Basin.
Quaternary and late Pliocene sediments from Site 679 consist of TOC-rich, alternately laminated
and bioturbated diatomaceous mud. Units from the middle Miocene to early Pliocene periods
contain coarser-grained sediments of terrigenous origin, as is also the case at Sites 680 and 681.
Sediments contain sparse diatoms and low-angle, cross-bedded silts and fine-grained sands. This
indicates exposure of the Salaverry basin area to high-energy bottom currents prior to at least 4-5
Ma. At this time, Sites 679, 680, and 681 were probably located inshore of the centres of present
day upwelling in a shallow water environment (Suess and von Huene, 1988).
1
Figure S1.1. Map indicating the study sites. ODP Leg 112, Sites 679, 680, 681, 682, and ODP
Leg 201, Site 1231 (modified after Shipboard Scientific Party, 1988).
1.2 Lower slope sites 682 and 688
Site 688 is located at a water depth of 3,820 m in the secondary depositional centre of the lower
slope (Figure S1.1) with material derived from resuspension on the shelf and upper slope. TOCrich diatomaceous ooze and mud accumulated throughout the Quaternary period. The TOC
content in Quaternary and Pliocene sediments is between 2 and 10 wt.%. Sediments from the
Miocene and early Pliocene ages consist of laminated, organic carbon-rich mud with TOC
contents up to 4 wt.% (cf. Figure 2a of the main text; Suess et al., 1988). The deposition of these
upwelling sediments at the lower slope is consistent with the inferred seaward shift of the
upwelling zone during this time and with the subsidence history of the Lima basin. Sediments
from Sites 682 and 688 at the lower slope have been subject toprogressive subsidence since the
Eocene period and were located underneath a coastal upwelling cell throughout the upper
Miocene period (Suess and von Huene, 1988; von Huene and Suess, 1988). At Site 682
sediments from the Pleistocene to middle Eocene periods were recovered. Sediments at Site 688
reflect progressively deeper water sedimentation from early Eocene to Pleistocene times
(Kvenvolden and Kastner, 1990).
Gas hydrates were recovered at Site 688. On the other hand, geophysical data from Site 682
yielded strong evidence that gas hydrates were present but direct observations are lacking
2
(Kvenvolden and Kastner, 1990). Bottom-simulating reflectors (BSRs) were detected at both
sites (Suess et al., 1988). In much of the sediment column of Site 688 gas hydrates are probably
present, between depths of about 20 m and the bottom of the gas hydrate stability zone at about
500 mbsf (Kvenvolden and Kastner, 1990).
1.3 Open ocean site 1231
Site 1231 is located within the Peru Basin at a water depth of 4,827 m. Sediments from the
Holocene to late Eocene ages were recovered. The sequence mostly consists of diatom-rich clay
with TOC contents between 0.1 and 0.7 wt.% (cf. Figure 5a of the main text; Suess et al., 1988).
Iron- and manganese-rich nannofossile ooze occurs in the late Eocene to early Oligocene
sediments (Shipboard Scientific Party, 1976; Shipboard Scientific Party, 2003b).
Iron and manganese concentrations in the pore waters are about one order of magnitude higher in
the upper 45 metres of the sediments than in the lower section. Also pore water sulphate
concentrations are higher in the upper part of the section. Concentration profiles of the other
dissolved species lack evidence of post-depositional reactions (Brady and Gieskes, 1976;
Shipboard Scientific Party, 2003a).
2. Explanation of the PHREEQC (version 2) model
The latest version of PHREEQC can be downloaded from the USGS website:
http://wwwbrr.cr.usgs.gov/projects/GWC_coupled/phreeqc/. The user’s guide (Parkhurst &
Appelo, 1999), containing a description of data input, can be downloaded from the same website.
The effect of varying total pressure on aqueous species distribution and associated solid phases is
minor (Table S2.1). Calculations are of the calcite solubility in pure water at 7°C and pressures
of 1 atm (calculated with PHREEQC and wateq4f.dat dataset) and 92 atm (log KCalcite is
calculated with SUPCRIT92 and DPRONS92.dat dataset; Johnson et al., 1992).
Table S2.1. Effect of the different pressure of 1 atm (calculated with PHREEQC and wateq4f.dat
dataset) and 92 atm (calculated with SUPCRT92 and DPRONS92.dat dataset, Johnson et al.,
1992) on an equilibrium constant of Calcite (log KCc), calcium-equilibrium concentration
[mmolkgw-1) and pH [-]. FeCO3 = Fe2+ + CO32-.
p = 1.0 atm
p = 92 atm
3
T
[°C]
log KCc
[-]
7
-8.40
Ca-equilibrium
concentration
[mmol kgw-1]
0.1329
pH
[-]
log KCc
[-]
9.934
-8.30
Ca-equilibrium
concentration
[mmol kgw-1]
0.1471
pH
[-]
9.965
4
The clay mineral content of the sediments (Tables S2.2–S2.7) (Clayton and Kemp, 1990) also
enables estimation of its cation exchange capacity (Jasmund and Lagaly, 1993). Calculations
assume a sediment mass of 1.89 kg per cell and meq = mmol gives 1.2 mol of exchangers
(expressing the cation exchange capacity in PHREEQC) in each cell of the PHREEQC model.
The initial occupancy of exchange sites is defined by equilibration with seawater prior to
diagenetic processes.
Table S2.2. PHREEQC model setup and input parameters of Site 679. RV: representative
volume, SI: saturation index, CEC: cation exchange capacity.
model setup parameters
number of RVs
height RV
Vtot RV
Vaq RV
time per shift a
total time modelled b
total sediment depth b
diffusion boundary conditions
database
50
10 m
1.7 L
1.0 L
357,143 yrs
17,857,150 yrs
495 m
constant (top)
closed (bottom)
wateq4f.datc
physical parameters
bottom water temperature d
geothermal gradient d
sedimentation rate d
pressure (constant)
12.5°C
20°C km–1
2.8 cm kyr–1
70.05 atm
geochemical parameters
starting solutions
primary phases f
SiO2(amorph)
Illite
Chlorite14A
Kaolinite
Goethite
Calcite
Pyrolusite
secondary phases
Calcite
Dolomite
Siderite
Ca-Rhodochrosite
Greigite
CFA
Sepiolite(d)
gas phases
CEC g
transport
diffusion coefficient h
sea water e
mol/RV
(SI)
x
y
z
10 / 10 / 10
(0)
0.82 / 0.35 / 0.26
(0)
0.10 / 0.09 / 0.03
(0)
0.13 /0.15 / 0.07
(0)
0.41 / 0.41 / 0.41
(0)
0.60 / 0.60 / 0.60
(0)
0.05 / 0.05 / 0.05
(0)
mol/RV
(SI)
0
(0)
0
(1.3)
0
(0.3)
0
(0.85)
0
(0)
0
(0)
0
(0)
CO2(g), CH4(g), N2(g)
1.2 mol/RV
diffusion
0.86E–09 m2s–1
a
: calculated from sedimentation rate and height of RVs
: calculated from sedimentation rate, number and height of RVs
c
: Parkhurst and Appelo (1999)
d
: from Suess et al. (1988)
e
: after Nordstrom et al. (1979)
f
: according to Suess et al. (1988) and Clayton and Kemp (1990)
g
: cation exchange capacity, depends on the clay mineral content, estimated according to Jasmund and
Lagaly (1993)
h
: mean value for all dissolved species, calculated according to diffusion coefficients given in Giambalvo
et al. (2002)
x
: cells 50 to 46
y
: cells 45 to 27
b
5
z
: cells 26 to 1
Table S2.3. PHREEQC model setup and input parameters of Site 680. RV: representative
volume, SI: saturation index, CEC: cation exchange capacity.
model setup parameters
geochemical parameters
number of RVs
50
starting solutions
height RV
Vtot RV
Vaq RV
time per shift a
total time modelled b
total sediment depth b
diffusion boundary conditions
10 m
1.7 L
1.0 L
384,615 yrs
19,230,750 yrs
495 m
constant (top)
constant
(bottom)
wateq4f.datc
primary phases g
SiO2(amorph)
Illite
Chlorite14A
Kaolinite
Goethite
sea water e
subsurface brinef
mol/RV
(SI)
10y / 10z
(0)
0.70 / 0.14
(0)
0.11 / 0.04
(0)
0.11 /0.02
(0)
0.41 / 0.41
(0)
secondary phases
Calcite
Dolomite
Siderite
Greigite
CFA
mol/RV
0
0
0
0
0
gas phases
CEC h
transport
diffusion coefficient i
CO2(g), CH4(g), N2(g)
1.2 mol/RV
diffusion
0.86E–09 m2s–1
database
physical parameters
bottom water temperature d
geothermal gradient d
sedimentation rate d
pressure (constant)
13°C
54°C km–1
2.6 cm kyr–1
50.25 atm
(SI)
(0)
(1.3)
(0.3)
(0)
(0)
a
: calculated from sedimentation rate and height of RVs
: calculated from sedimentation rate, number and height of RVs
c
: Parkhurst and Appelo (1999)
d
: from Suess et al. (1988)
e
: after Nordstrom et al. (1979)
f
: after Kastner et al. (1990)
g
: according to Suess et al. (1988) and Clayton and Kemp (1990)
h
: cation exchange capacity, depends on the clay mineral content, estimated according to Jasmund and
Lagaly (1993)
i
: mean value for all dissolved species, calculated according to diffusion coefficients given in Giambalvo
et al. (2002)
y
: cells 50 to 45
z
: cells 44 to 1
b
6
Table S2.4. PHREEQC model setup and input parameters of Site 681. RV: representative
volume, SI: saturation index, CEC: cation exchange capacity.
model setup parameters
geochemical parameters
number of RVs
50
starting solutions
height RV
Vtot RV
Vaq RV
time per shift a
total time modelled b
total sediment depth b
diffusion boundary conditions
10 m
1.7 L
1.0 L
125,000 yrs
6,250,000 yrs
495 m
constant (top)
constant
(bottom)
wateq4f.datc
primary phases g
SiO2(amorph)
Illite
Chlorite14A
Kaolinite
Goethite
sea water e
subsurface brinef
mol/RV
(SI)
10z
(0)
0.33
(0)
0.07
(0)
0.07
(0)
0.41
(0)
secondary phases
Calcite
Dolomite
Siderite
Greigite
CFA
mol/RV
0
0
0
0
0
gas phases
CEC h
transport
diffusion coefficient i
CO2(g), CH4(g), N2(g)
1.2 mol/RV
diffusion
0.86E–09 m2s–1
database
physical parameters
bottom water temperature d
geothermal gradient d
sedimentation rate d
pressure (constant)
13.5°C
32.5°C km–1
8 cm kyr–1
40.05 atm
(SI)
(0)
(1.3)
(0.85)
(0)
(0)
a
: calculated from sedimentation rate and height of RVs
: calculated from sedimentation rate, number and height of RVs
c
: Parkhurst and Appelo (1999)
d
: from Suess et al. (1988)
e
: after Nordstrom et al. (1979)
f
: after Kastner et al. (1990)
g
: according to Suess et al. (1988) and Clayton and Kemp (1990)
h
: cation exchange capacity, depends on the clay mineral content, estimated according to Jasmund and
Lagaly (1993)
i
: mean value for all dissolved species, calculated according to diffusion coefficients given in Giambalvo
et al. (2002)
z
: cells 50 to 1
b
7
Table S2.5. PHREEQC model setup and input parameters of Site 682. RV: representative
volume, SI: saturation index, CEC: cation exchange capacity.
model setup parameters
number of RVs
height RV
Vtot RV
Vaq RV
time per shift a
total time modelled b
total sediment depth b
diffusion boundary conditions
database
50
10 m
1.7 L
1.0 L
571,429 yrs
28,571,450 yrs
495 m
constant (top)
closed (bottom)
wateq4f.datc
physical parameters
bottom water temperature d
geothermal gradient d
sedimentation rate d
pressure (constant)
1.5°C
42.5°C km–1
1.75 cm kyr–1
403.85 atm
geochemical parameters
starting solutions
primary phases f
SiO2(amorph)
Illite
Chlorite14A
Kaolinite
Goethite
Calcite
Pyrolusite
secondary phases
Calcite
Dolomite
Siderite
Ca-Rhodochrosite
Greigite
CFA
CH4Hydrate
gas phases
CEC g
transport
diffusion
coefficient h
sea water e
mol/RV
(SI)
10w / 10x / 10y / 10z
(0)
1.02 / 0.51 / 0.14 / 0.11 (0)
0.12 / 0.07 / 0.02 /0.003 (0)
0.16 /0.15 / 0.05 / 0.01 (0)
0.68 / 0.68 / 0.68 / 0.68 (0)
0.75 / 0.75 / 0.75 / 0.75 (0)
0.01 / 0.01 / 0.01 / 0.01 (0)
mol/RV
(SI)
0
(0)
0
(1.3)
0
(0.3)
0
(0.85)
0
(0)
0
(0)
0
(0)
CO2(g), CH4(g), N2(g)
1.2 mol/RV
diffusion
0.86E–09 m2s–1
a
: calculated from sedimentation rate and height of RVs
: calculated from sedimentation rate, number and height of RVs
c
: Parkhurst and Appelo (1999)
d
: from Suess et al. (1988)
e
: after Nordstrom et al. (1979)
f
: according to Suess et al. (1988) and Clayton and Kemp (1990)
g
: cation exchange capacity, depends on the clay mineral content, estimated according to Jasmund and
Lagaly (1993)
h
: mean value for all dissolved species, calculated according to diffusion coefficients given in Giambalvo
et al. (2002)
w
: cells 50 to 40
x
: cells 39 to 20
y
: cells 19 to 11
z
: cells 10 to 1
b
8
Table S2.6. PHREEQC model setup and input parameters of Site 688. RV: representative
volume, SI: saturation index, CEC: cation exchange capacity.
model setup parameters
number of RVs
height RV
Vtot RV
Vaq RV
time per shift a
total time modelled b
total sediment depth b
diffusion boundary conditions
database
50
10 m
1.7 L
1.0 L
33,333 yrs
1,666,650 yrs
495 m
constant (top)
closed (bottom)
wateq4f.datc
physical parameters
bottom water temperature d
geothermal gradient d
sedimentation rate d
1.8°C
47°C km–1
30 cm kyr–1
pressure (constant)
406.98 atm
geochemical parameters
starting solutions
primary phases f
SiO2(amorph)
Illite
Chlorite14A
Kaolinite
Goethite
Calcite
Pyrolusite
secondary phases
Calcite
Siderite
Ca-Rhodochrosite
Greigite
CFA
FCO3Apatite
Struvite
CH4Hydrate
gas phases
CEC g
transport
diffusion coefficient h
sea water e
mol/RV
(SI)
10x / 10y / 10z
(0)
0.47 / 0.87 / 0.28
(0)
0.07 / 0.13 / 0.05
(0)
0.11 /0.19 / 0.11
(0)
0.68 / 0.68 / 0.68
(0)
0.60 / 0.60 / 0.60
(0)
0.00 / 0.75 / 0.00
(0)
mol/RV
(SI)
0
(0)
0
(0.3)
0
(0.85)
0
(0)
0
(0)
0
(0)
0
(0)
0
(0)
CO2(g), CH4(g), N2(g)
1.2 mol/RV
diffusion
0.86E–09 m2s–1
a
: calculated from sedimentation rate and height of RVs
: calculated from sedimentation rate, number and height of RVs
c
: Parkhurst and Appelo (1999)
d
: from Suess et al. (1988)
e
: after Nordstrom et al. (1979)
f
: according to Suess et al. (1988)
g
: cation exchange capacity, depends on the clay mineral content, estimated according to Jasmund and
Lagaly (1993)
h
: mean value for all dissolved species, calculated according to diffusion coefficients given in Giambalvo
et al. (2002)
x
: cells 50 to 38
y
: cells 37 to 18
z
: cells 17 to 1
b
9
Table S2.7. PHREEQC model setup and input parameters of Site 1231. RV: representative
volume, SI: saturation index, CEC: cation exchange capacity.
model setup parameters
number of RVs
height RV
Vtot RV
Vaq RV
time per shift a
total time modelled b
total sediment depth
diffusion boundary conditions
database
50
10 m
1.7 L
1.0 L
666,667 yrs
33,333,350 yrs
495 m
constant (top)
closed (bottom)
wateq4f.datc
physical parameters
bottom water temperature d
geothermal gradient d
sedimentation rate d
pressure (constant)
1.9°C
62.5°C km–1
1.5 cm kyr–1
407.7 atm
geochemical parameters
starting solutions
primary phases f
SiO2(amorph)
Illite
Chlorite14A
Kaolinite
Goethite
Pyrolusite
sea water e
mol/RV
10x / 10y / 10z
0.58 / 0.73 / 0.44
0.11 / 0.14 / 0.09
0.11 /0.13 / 0.08
0.68 / 0.68 / 0.68
0.02 / 0.02 / 0.02
secondary phases
Calcite
Dolomite
Siderite
Ca-Rhodochrosite
Greigite
CFA
CH4Hydrate
gas phases
CEC g
transport
diffusion coefficient h
mol/RV
(SI)
0
(0)
0
(1.3)
0
(0.3)
0
(0.85)
0
(0)
0
(0)
0
(0)
CO2(g), CH4(g), N2(g)
1.2 mol/RV
diffusion
0.86E–09 m2s–1
(SI)
(0)
(0)
(0)
(0)
(0)
(0)
a
: calculated from sedimentation rate and height of RVs
: calculated from sedimentation rate, number and height of RVs
c
: Parkhurst and Appelo (1999)
d
: from Shipboard Scientific Party (2003b); Shipboard Scientific Party (1976)
e
: after Nordstrom et al. (1979)
f
: according to Suess et al. (1988) and Clayton and Kemp (1990)
g
: cation exchange capacity, depends on the clay mineral content, estimated according to Jasmund and
Lagaly (1993)
h
: mean value for all dissolved species, calculated according to diffusion coefficients given in Giambalvo
et al. (2002)
x
: cells 50 to 48
y
: cells 47 to 46
z
: cells 45 to 1
b
10
Table S2.8. Equilibrium phases, mass-action equations and equilibrium constants (log K, at
25°C and 1bar pressure). Equilibrium constants are from the “wateq4f.dat” data set (Parkhurst
and Appelo, 1999).
Equilibrium
Phase
Equilibrium Reaction
log K
–2.71
18.66
SiO2(a)
Sepiolite(d)
SiO2 + 2H2O = H4SiO4
Mg2Si3O7.5OH:3H2O + 0.5H2O + 4H+ = 2Mg+2 + 3H4SiO4
Illite
K0.6Mg0.25Al2.3Si3.5O10(OH)2 + 11.2H2O = 0.6K+ + 0.25Mg+2 +
2.3Al(OH)4– + 3.5H4SiO4 + 1.2H+
–40.267
Al2Si2O5(OH)4 + 6H+ = 2Al+3 + 2H4SiO4 + H2O
Mg5Al2Si3O10(OH)8 + 16H+ = 5Mg+2 + 2Al+3 + 3H4SiO4 + 6H2O
FeOOH + 3H+ = Fe+3 + 2H2O
MnO2 + 4H+ + 2e– = Mn+2 + 2H2O
CaCO3 = Ca+2 + CO3–2
FeCO3 = Fe+2 + CO3–2
CaMg(CO3)2 = Ca+2 + Mg+2 + 2CO3–2
7.435
68.38
–1.0
41.38
–8.48
–10.75
–17.09
Mn0.9Ca0.1CO3 = 0.1Ca+2 + 0.9 Mn+2 +CO3–2
–10.39a
Kaolinite
Chlorite14A
Goethite
Pyrolusite
Calcite
Siderite
Dolomite
CaRhodochrosite
Greigite
Fe3S4 + 4H+ = 2Fe+3 + Fe+2 + 4HS–
–45.035
Ca9.316Na0.37Mg0.144(PO4)5.63(CO3)1.2 = 9.316Ca+2 + 0.37Na+ + 0.144Mg+2
CFA
–114.4b
+ 5.63PO4–3 + 1.2CO3–2
Ca9.316Na0.36Mg0.144(PO4)4.8(CO3)1.2F2.48 = 9.316Ca+2 + 0.36Na+ +
FCO3Apatite
–114.4
0.144Mg+2 + 4.8PO4–3 + 1.2CO3–2 + 2.48F–
Struvite
MgNH4PO4:6H2O = Mg+2 + NH4+ + PO4–3 + 6H2O
–13.26c
CH4Hydrate
CH4:6H2O = CH4 + 6H2O
–1.073d
CO2(g)
CO2 = CO2
–1.468
CH4(g)
CH4 = CH4
–2.860
N2(g)
N2 = N2
–3.260
a
: obtained from Rhodochrosite.
b
: obtained from FCO3Apatite.
c
: defined after Ronteltap et al.(2007).
d
: calculated from Gibb’s free energy (ΔG = 5.736 kJ mol1), pressure (P = 10MPa), and temperature (T =
279.55 K) after Lu et al. (2008).
11
3. Model results and measured data
Figure S3.1. A) Modelled and measured inorganic carbon (IC) content (wt. %) of the shelf and
lower slope sites.B) Modelled dissolved CO2 concentration (mM) profiles of the shelf and lower
slope sites. C) Modelled and measured pH (-) profiles of the shelf and lower slope sites. Grey
dots: modelled data, diamonds: measured data. Measured TOC contents and pore water
concentration data are taken from Suess et al. (1988). Red numbering indicates sedimentary units
according to Suess et al. (1988).
12
Figure S3.2. A) Modelled and measured chlorinity (mM) profiles of the shelf and lower slope
sites. B) Modelled and measured calcium concentration (mM) profiles of the shelf and lower
slope sites. C) Modelled and measured magnesium concentration (mM) profiles of the shelf and
13
lower slope sites. D) Modelled and measured iron concentration (mM) profiles of the shelf and
lower slope sites. Grey dots: modelled data, diamonds: measured data. Measured pore water
concentration data are taken from Suess et al. (1988) and the Shipboard Scientific Party (2003a).
Red numbering indicates sedimentary units according to Suess et al. (1988).
Figure S3.3. Modelled and measured inorganic carbon (IC) content (wt. %) and modelled and
measured concentration (mM) and pH (-) profiles of the open ocean site 1231. Grey dots:
modelled data, diamonds: measured data. Measured pore water concentration data are taken from
the Shipboard Scientific Party (2003b). Red numbering indicates sedimentary units according to
the Shipboard Scientific Party (2003b).
14
References
Arning, E.T., Y. Fu, W. van Berk and H.-M. Schulz (2011) Organic carbon remineralization and
complex, early diagenetic solid – aqueous solution – gas interactions: Case study ODP
Leg 204, Site 1246 (Hydrate Ridge), Mar. Chem., 126, 120–131,
doi:10.1016/j.marchem.2011.04.006.
Brady, S., and J. M. Gieskes (1976) Interstitial water studies, Leg 34, in Initial Reports of the
Deep Sea Drilling Project, Vol. 34 edited by R. S. Yeats, S. R. Hart and et al., pp. 625628, U.S. Govt. Printing Office, Washington, D.C.
Clayton, T., and A. E. S. Kemp (1990) Clay mineralogy of Cenozoic sediments from the
Peruvian continental margin: Leg 112, in: Proceedings of the Ocean Drilling Program,
Scientific Results, Vol. 112, edited by E. Suess, R. von Huene and et al., pp. 1-28, Ocean
Drilling Program, College Station, Texas.
Emeis, K.-C., and J. W. Morse (1990) Organic carbon, reduced sulfur, and iron relationships in
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