SULFUR PROXIES IN TYPE III BLACK SHALES: Fe, Mn, Co, Cu, Ni, Zn, Sc Pat WILDE Pangloss Foundation,...

SULFUR PROXIES IN TYPE III BLACK SHALES:

Fe, Mn, Co, Cu, Ni, Zn, Sc

Pat WILDE Pangloss Foundation,

1735 Highland Place; Berkeley, CA 94709 pat.wilde.td.57@aya.yale.edu

Mary S. QUINBY-HUNT Lawrence Berkeley Laboratory: Berkeley, CA 94720

mshunt@sbcglobal.net

Timothy W. LYONS Department of Earth Sciences,

University of California-Riverside: Riverside, CA 92521-0423 timothy.lyons@ucr.edu

Why Calculate Proxies for C, S, P Why Calculate Proxies for C, S, P etc.etc.??

Data enhancement for old data setsData enhancement for old data sets

Provide for elements not analyzedProvide for elements not analyzed

Useful for assessing initial reservoir conditions Useful for assessing initial reservoir conditions disguised by diagenesis and elemental transfer disguised by diagenesis and elemental transfer through geologic timethrough geologic time

Data recovery when originals not availableData recovery when originals not available

Black Shale Groups> 50,000 ppm Al, < 4000 ppm Ca

Group 1 Oxic

Group 2 Mn-

Soluble

Group 3Mn,Fe-

Soluble

Group 4V-High

Mn > 830 Mn < 730 Mn < 730 Mn < 230

Fe > 38500 Fe < 37500 Fe < 37500 Fe < 37500

V < 320 V < 320 V < 320 V > 320

Sulfur proxies using Fe, Ni, Co, and Cu Sulfur proxies using Fe, Ni, Co, and Cu

Determined with 62 Type-III Black Shales1 from

Modern Cariaco Basin2 and Devonian of New York3

Proxies developed for ODP [Cariaco] site2 used to estimate unreported S for Cariaco Basin USGS core PL07-39C4 located about 50 km E

Corresponding lithologic units and ages were compared.

Estimated values internally agreed within a range of 0.4 % Sulfur.

1.Quinby-Hunt and Wilde, 1991, 1996 2. Lyons et al.., 2003 3. Werne et al., 2002 4. Piper and Dean, 2002

Sulfur proxies using Fe, Ni, Co, and CuSulfur proxies using Fe, Ni, Co, and Cu

High correlation over ~400 million years → Sulfur-Metal relationships relatively fixed during deposition and early diagenesis.

Additional sulfur proxies with Mn, Sc and Zn, found in Cariaco Basin, but could not be reproduced for the Devonian samples.

Type III Black Shale ProxiesType III Black Shale ProxiesComposite 62 samplesComposite 62 samples

Pyrite Pyrite SulfurSulfur % = 0.000105( % = 0.000105(FeFe ppm) - 1.67 ppm) - 1.67 R square = R square = 0.920.92

Pyrite Pyrite SulfurSulfur % = 0.0179( % = 0.0179(NiNi ppm) + 0.339 ppm) + 0.339 R square = R square = 0.880.88

Pyrite Pyrite SulfurSulfur % = 0.118( % = 0.118(CoCo ppm) + .0967 ppm) + .0967 R square = R square = 0.850.85

Pyrite Pyrite SulfurSulfur % = 0.0172( % = 0.0172(CuCu ppm) + 0.877 ppm) + 0.877 R square = R square = 0.680.68

Cariaco Basin + New York Oatka Fm

Pyrite Sulfur % = 9E-05 (Fe ppm) - 1.1004

R2 = 0.8757 n = 62

0

1

2

3

4

5

6

7

0 10000 20000 30000 40000 50000 60000 70000

Fe ppm

Pyr

ite

Su

lfu

r %

FeFe

Cariaco Basin + New York Oakta Fm

Pyrite Sulfur % = 0.0174(Ni ppm) + 0.4026

R2 = 0.8684 n = 62

0

1

2

3

4

5

6

7

0 50 100 150 200 250 300 350 400

Ni ppm

Pyr

ite

Su

lfu

r %

NiNi

Cariaco Basin + New York Oatka Fm

Pyrite Sulfur % = 0.1169(Co ppm) + 0.0807

R2 = 0.8359 n= 62

0

1

2

3

4

5

6

7

0 10 20 30 40 50 60

Co ppm

Pyr

ite

Su

lfu

r %

CoCo

Cariaco Basin + New York Oatka Fm

Pyrite Sulfur % = 0.0168(Cu ppm) + 0.8088

R2 = 0.6552 n = 62

0

1

2

3

4

5

6

7

0 50 100 150 200 250 300

Cu ppm

Pyr

ite S

ulfu

r %

CuCu

Reverse correlation SReverse correlation Spypy vs Mn vs Mn Cariaco Basin vs NY Devonian Cariaco Basin vs NY Devonian Reverse correlation Spy Reverse correlation Spy vsvs MnMn

CariacoCariaco Trench Trench vsvs NY DevonianNY Devonian

Pyrite Sulfur % = 0.005(Mn ppm) + 0.3711

R2 = 0.7992 n = 30 CB

Pyrite Sulfur % = -0.0414 (Mn ppm) + 10.005

R2 = 0.6406 n = 21 Oatka Fm Devonian

0

1

2

3

4

5

6

7

100 150 200 250 300 350 400 450

Mn ppm

Pyr

ite S

ulfu

r %

Trends in Oxygen, CO2, Sulfate and Phosphate over Time

After COPSE model (Bergman et al., p. 418 2004

Evidence of Oceanic Ventilation??Evidence of Oceanic Ventilation??

Middle Devonian Oatka Creek FormationMiddle Devonian Oatka Creek Formation

Deposited during Deposited during rise in atmospheric Orise in atmospheric O22 and and development of land plantsdevelopment of land plants

Atmospheric CO2 is reduced by production of O2 Atmospheric CO2 is reduced by production of O2

thereby thereby lowering lowering CO2 concentration in seawaterCO2 concentration in seawater

[[Sulfate] in seawater Sulfate] in seawater also also increased increased

Evidence of Oceanic Ventilation??Evidence of Oceanic Ventilation??

Decrease of MnDecrease of Mn with with increased Sincreased S suggests [prior to mid- suggests [prior to mid-Devonian]Devonian]

MnCO3 MnCO3 deposition under anoxic conditions deposition under anoxic conditions Fe sulfideFe sulfide deposition under anoxic conditions deposition under anoxic conditions Lowering of Lowering of CO2CO2 ++ increased oxygenationincreased oxygenation in in

mid-Devonian seawater mid-Devonian seawater →→ Destabilization of MnCODestabilization of MnCO3 3 → Mn→ Mn++++

Mn and Fe Redox Zones – with Rhodochrosite

Evidence of Oceanic Ventilation??Evidence of Oceanic Ventilation??

AccordinglyAccordingly

MnCO3 ‘dissolved’ into MnMnCO3 ‘dissolved’ into Mn2+2+ returned to the returned to the water columnwater column

Thus Mn decreases as Pyritic S increases.Thus Mn decreases as Pyritic S increases.

Sulfate reduction continues with Fe present Sulfate reduction continues with Fe present to form additional pyriteto form additional pyrite

New York Oatka Fm - Devonian

Pyrite Sulfur % = 0.0856(As ppm) - 0.2642

R2 = 0.8621 n = 29

0

1

2

3

4

5

6

7

0 10 20 30 40 50 60 70 80

As ppm

Py

rite

Su

lfu

r %

AsAs

Cariaco Basin - Zones I & IIScSc

Pyrite Sulfur % = 0.1647 (Sc ppm) - 0.4607

R2 = 0.8958 n =32

0

0.5

1

1.5

2

2.5

3

3.5

5 7 9 11 13 15 17 19

Sc ppm

Pyr

ite S

ulfu

r %

Cariaco Basin - Zones I & IIZnZn

Pyrite Sulfur % = 0.0139 (Zn ppm) + 0.0484

R2 = 0.8654 n = 34

0

0.5

1

1.5

2

2.5

3

3.5

50 70 90 110 130 150 170 190 210

Zn ppm

Pyr

ite S

%

Sulfur proxies using Fe, Ni, Co, and Cu Sulfur proxies using Fe, Ni, Co, and Cu Determined with 51 Type-III Black Shales1 from

Modern Cariaco Basin2 and Devonian of New York3

Proxies developed for ODP [Cariaco] site2 used to estimate unreported S for Cariaco Basin USGS core PL07-39C4 located about 50 km E

Estimated values internally agreed within a range of 0.4 % Sulfur.

1.Quinby-Hunt and Wilde, 1991, 1996 2. Lyons et al.., 2003 3. Werne et al., 2002 4. Piper and Dean, 2002

Sample Sites in Cariaco BasinODP: Lyons et al. (2003) PLO7: Piper and Dean (2002)

Sulfur Proxy by MetalsCariaco Basin Comparisons

0

0.5

1

1.5

2

2.5

Depth 4 to 957 Cm: increasing to the right

Py

rite

Su

lfu

r %

via Fevia MnVia Covia Zn

via Cuvia Ni

Sulfur proxies using Fe, Ni, Co, and CuSulfur proxies using Fe, Ni, Co, and Cu

Extrapolation of sulfur proxies using Mn, Sc, and Zn over long time spans should be used with caution.

Variations among proxies with time might beused to track various sedimentary and mineralogical processes.

More data sets of varying ages, but with similar lithologies and anoxic

conditions, should be compared.

• What does this all mean??

–Ray knew!!

Siever Diagram

THANKS, RAY !!! THANKS, RAY !!! For all the wonderful For all the wonderful

MEMORIESMEMORIES

SULFUR PROXIES IN TYPE III BLACK SHALES:

Fe, Mn, Co, Cu, Ni, Zn, Sc

Pat WILDE Pangloss Foundation,

1735 Highland Place; Berkeley, CA 94709 pat.wilde.td.57@aya.yale.edu

Mary S. QUINBY-HUNT Lawrence Berkeley Laboratory: Berkeley, CA 94720

mshunt@sbcglobal.net

Timothy W. LYONS Department of Earth Sciences,

University of California-Riverside: Riverside, CA 92521-0423 timothy.lyons@ucr.edu

ReferencesReferences

Piper, D. Z. and Dean, W. E. , 2002, Trace-Element Deposition in the Cariaco Piper, D. Z. and Dean, W. E. , 2002, Trace-Element Deposition in the Cariaco Basin,Venezuela Shelf, under Sulfate-Reducing Conditions. A History of the Basin,Venezuela Shelf, under Sulfate-Reducing Conditions. A History of the Local Hydrography and Global Climate, 20 Ka to the Present: US Geological Local Hydrography and Global Climate, 20 Ka to the Present: US Geological Survey Prof. Paper 670, 1-41.Survey Prof. Paper 670, 1-41.

Quinby-Hunt. M. S. and P. Wilde, 1991, The provenance of low-calcic black Quinby-Hunt. M. S. and P. Wilde, 1991, The provenance of low-calcic black shales: Mineralium Deposita, v. 26, p. 113-121.shales: Mineralium Deposita, v. 26, p. 113-121.

Quinby-Hunt, M. S. and Wilde, P., 1996, Depositional environments of calcic Quinby-Hunt, M. S. and Wilde, P., 1996, Depositional environments of calcic marine black shales: Economic Geology, vol. 91, p. 4-13.marine black shales: Economic Geology, vol. 91, p. 4-13.

Werne, J. P., Sageman, B. B., Lyons, T. W. and Hollander, D. J., 2002, An Werne, J. P., Sageman, B. B., Lyons, T. W. and Hollander, D. J., 2002, An integrated assessment of a "type euxinic" deposit: Evidence for multiple integrated assessment of a "type euxinic" deposit: Evidence for multiple controls on black shale deposition in the Middle Devonian Oatka Creek controls on black shale deposition in the Middle Devonian Oatka Creek Formation: American Journal of Science, v. 302, p. 110-143.Formation: American Journal of Science, v. 302, p. 110-143.