using carbonate stable isotopes to identify …

1
Nicholas M. Ellis; Thomas S. Tobin The University of Alabama Distance along shell (mm) -0.3 -0.2 -0.1 0 0.1 0.2 Best Fit Linear 95% Bounds Distance along shell (mm) -1.5 -1 -0.5 0 0.5 1 1.5 Best Fit Sine 95% Bounds Distance along shell (mm) Best Fit Linear 95% Bounds Distance along shell (mm) -0.2 -0.1 0 0.1 0.2 0.3 δ 18 O (‰ VPDB) Best Fit Sine 95% Bounds Distance along shell (mm) -0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 Best Fit Sine 95% Bounds Distance along shell (mm) -4.5 -4 -3.5 -3 -2.5 -2 Best Fit Linear 95% Bounds Distance along shell (mm) Distance along shell (mm) 95% Bounds Best Fit Linear 393 mm 332 mm 107 mm 185 mm 62 mm 54 mm 35 mm 30 mm 60 mm 320 mm The locations represented by the ammonites studied during this investigation are projected onto a reconstruction of the WIS. CC-1 CC-2 WY-1 MT-1 0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 0 50 100 150 200 250 300 0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180 Acknowledgments Results and Conclusions Literature Cited Methods Introduction Specimen Name Specimen Length (mm) Period of Best Fit (mm) CC-1 367 ± 27 320 393 332 107 185 373 ± 47 No Sine Fit No Sine Fit No Sine Fit No Sine Fit No Sine Fit No Sine Fit No Sine Fit No Sine Fit No Sine Fit No Sine Fit 0.225 ± 0.066 1.671 ± 0.156 0.94 0.73 0.02 339 ± 69 0.8314 ± 0.340 0.3100 ± 0.108 1.2204 ± 0.224 0.07 0.43 0.52 0.33 0.44 331 ± 54 334 ± 73 0.42 0.34 Fatheree WY-1 MT-1 CC-2 Amplitude of Best Fit (‰ VPBD) Amplitude of Best Fit (‰ VPBD) Period of Best Fit (mm) δ 18 O R 2 R 2 δ 13 C Table 1 -2.4 -2.3 -2.2 -2.1 -2 -1.9 -1.8 -1.7 -1.6 -1.5 -1.4 Best Fit Linear 95% Bounds δ 18 O (‰ VPDB) δ 18 O (‰ VPDB) δ 18 O (‰ VPDB) δ 13 C (‰ VPDB) δ 13 C (‰ VPDB) δ 13 C (‰ VPDB) δ 13 C (‰ VPDB) y = (0.01684)sin(0.01473x + 0.07002) y = (0.155)sin(0.01597x + 0.1933) y = 0.001727x - 0.03637 y = (0.6102)sin(0.01856x - 1.122) y = -0.00569x + 0.4787 y = 0.005046x - 2.191 y = 0.0003414x - 0.1668 Isotope data from Baculites undatus specimen from the Coon Creek formation (35.35218 °N, 88.42043 °W) is shown. Oxygen and carbon isotope data were normalized to 0 using means: δ 18 O = 0.4294; δ 13 C = 0.3979. Isotope data from Baculites undatus specimen from the Coon Creek formation (35.35218 °N, 88.42043 °W) is shown. Carbon isotope data were normalized to 0 using mean: δ 13 C = -0.1215. A sine curve could not be extrapolated from the oxygen data series, so a linear fit was used. Isotope data from Baculites clinolobatus specimen from Northern Wyoming (44.75 °N, 108.5 °W) is shown. The unidirectional trends could represent a portion of the seasonal cycle given the shorter length of this specimen. Sine curves could not be extrapolated from the datasets, so linear fits were used. Isotope data from Baculites sp. specimen from the Bear Paw Shale at Hell Creek in Eastern Montana (47.6314 °N, -106.8688 °W) is shown. The signals in this specimen are rather noisy, and no meaningful or significant trends were identified. y = -0.004121x - 2.399 Distance along shell (mm) δ 18 O (‰ VPDB) 0 50 100 150 200 250 300 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 Best Fit Sine 95% Bounds Distance along shell (mm) δ 13 C (‰ VPDB) 0 50 100 150 200 250 300 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 Best Fit Sine 95% Bounds y = (0.8355)sin(0.0171x + 0.1562) y = (0.4157)sin(0.01879x + 1.784) Figure 2 Figure 1 Cochran, J.K., Kallenberg, K., Landman, N.H., Harries, P.J., Weinreb, D., Turekian, K.K., Beck, A.J., and Cobban, W.A., 2010, Effect of diagenesis on the Sr, O, and C isotope composition of late Cretaceous mollusks from the Western Interior Seaway of North America: American Journal of Science, v. 310, p. 69–88, doi: 10.2475/02.2010.01. Fatherree, J.W., Harries, P.J., and Quinn, T.M., 1998, Oxygen and Carbon Isotopic "Dissection" of Baculites compressus (Mollusca: Cephalopoda) from the Pierre Shale (Upper Campanian) of South Dakota: Implications for Paleoenvironmental Reconstructions: Palaios, v. 13, p. 376–385, doi: 10.2307/3515325. Grossman, E., 1986, Oxygen and carbon isotope fractionation in biogenic aragonite: Temperature effects: Chemical Geology, v. 59, p. 59–74, doi: 10.1016/0168-9622(86)90057-6. We acknowledge the generous support of the Undergraduate Creativity and Research Academy and The University of Alabama Department of Geological Sciences for providing financial assistance for this project. We thank the Alabama Stable Isotope Laboratory for processing our samples. We thank the United States Geological Survey and the Pink Palace Museum for providing specimens used in this project. We especially thank Tamara Braithwaite and Louella Weaver of the Pink Palace Museum for assistance with collections and sampling permission. Fatherree CC-1 7.84 1.06 ≥2.43 >3.33 n/a CC-2 WY-1 HC-1 Calculated Annual ∆T (°C) Specimen Name Table 2 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 Baculites specimen CC-1 and the specimen described by Fatherree et al. (1998) show sinusoidal δ 18 O signals with similar periods around 370 mm and have overlapping error ranges (see Table 1). Baculites specimens CC-1, CC-2, and the specimen described by Fatherree et al. (1998) show sinusoidal δ 13 C signals with very similar periods around 335 mm. Error ranges overlap with each other and the period lengths produced from δ 18 O (see Table 1). The consistency in period length is suggestive of common cause, which could be explained by a seasonal trend since δ 18 O is temperature dependent and δ 13 C may reflect seasonal variation in organism behavior, metabolism, and/or activity. The lengths of these periods suggest that Baculites grow at extremely fast rates (>300 mm/yr). Baculites may be r-strategists that grow rapidly, live short lives, and produce large amounts of offspring, or they may simply reach their mature size quickly and stop growing. The amplitude of the δ 18 O signal from the specimen CC-1 is small which may indicate low magnitude seasonal cycles, agreeing with a shallow subtropical shelf environment. The amplitude of the Fatheree et al. (2010) specimen’s δ 18 O signal is several times greater than that of CC-1 as expected at a much higher paleolatitude. Seasonal amplitude could be reduced due to organism behavior, such as seasonal geographic migration or vertical migration in the water column. Powdered shell samples were generated for isotopic analysis of ontogenetic sequences using a handheld Foredam drill. Carbon and oxygen isotope values were measured using a Thermo Scientific Delta V Plus isotope ratio mass spectrometer equipped with a GasBench II autosampler. Best fit sine functions (representing seasonal cyclicity) were found using the curve fitting toolbox in MATLAB. Datasets with insufficient data, such as unidirectional trends, were fit with linear functions. δ 18 O and δ 13 C data with apparent sinusoidal patterns were normalized to a mean of 0 by subtracting the mean of the sample data as required by MATLAB. Seasonal temperature differentials were calculated by assuming a constant δ 18 O for seawater and multiplying the peak-to-peak amplitude of the δ 18 O sine function by 4.69 as defined by Grossman and Ku (1986). All specimens preserve primary aragonite as indicated by their iridescence. Samples are currently being imaged with a scanning electron microscope to assess their preservation quality using the preservation index established by Cochran et al. (2010). Fatherree et al. (1998) measured δ 18 O and δ 13 C in an ontogenetic sequence on a single Baculites compressus collected from the Pierre Shale in Northern Wyoming (43.9333 °N, 102.8167 °W). A sinusoidal δ 18 O trend over the length of the shell (320 mm) was recognized to be approximately one seasonal cycle. We reanalyzed their data for sinusoidal fits with MATLAB using the same methods by which our data was processed (see Methods) to produce functions for their δ 18 O and δ 13 C signals. The periods of these functions are similar to those we were able to fit to our specimens, CC-1 and CC-2 (see Table 1). An SEM image of the the Fatherree (1998) Baculites’ well-preserved microstructure Mollusks are typically thought to precipitate carbonate shell material in equilibrium with seawater. Little is known about the lifespan or habits of extinct ammonite species. Most postulations are made based on their modern analog - the Nautlus. The uncoiled morphology of Baculites makes the genus an easy target for sclerochronological isotopic analysis. Seasonal temperature signals may be preserved in oxygen isotope content as shell material is deposited over time. Carbon isotope content may also preserve seasonal signals depending on organism behavior. Using Carbonate Stable Isotopes to Identify Seasonal Trends in Late Cretaceous Ammonites 160 320 80 0 Miles Middle Campanian Reconstruction Colorado Plateau Geosystems Inc. Western Interior Seaway (WIS) MT-1 Fatherree CC-1, CC-2 WY-1 N

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Page 1: USING CARBONATE STABLE ISOTOPES TO IDENTIFY …

Nicholas M. Ellis; Thomas S. TobinThe University of Alabama

Distance along shell (mm)

-0.3

-0.2

-0.1

0

0.1

0.2

Best Fit Linear

95% Bounds

Distance along shell (mm)

-1.5

-1

-0.5

0

0.5

1

1.5

Best Fit Sine

95% Bounds

Distance along shell (mm)

Best Fit Linear

95% Bounds

Distance along shell (mm)

-0.2

-0.1

0

0.1

0.2

0.3

δ1

8O

(‰

VP

DB

)

Best Fit Sine

95% Bounds

Distance along shell (mm)

-0.4

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0.4Best Fit Sine95% Bounds

Distance along shell (mm)

-4.5

-4

-3.5

-3

-2.5

-2 Best Fit Linear

95% Bounds

Distance along shell (mm)

Distance along shell (mm)

95% BoundsBest Fit Linear

393 mm 332 mm 107 mm 185 mm

62

mm

54

mm

35

mm

30

mm

60

mm

320 mm

The locations represented by the ammonites studied during this

investigation are projected onto a reconstruction of the WIS.

CC-1 CC-2 WY-1 MT-1

0 50 100 150 200 250 300 350 400

0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300

0 50 100 150 200 250 300 0 20 40 60 80 100

0 20 40 60 80 100

0 20 40 60 80 100 120 140 160 180

0 20 40 60 80 100 120 140 160 180

Acknowledgments

Results and Conclusions

Literature Cited

MethodsIntroduction

Specimen

Name

Specimen

Length (mm)

Period of Best Fit

(mm)

CC-1

367 ± 27320

393

332

107

185

373 ± 47

No Sine Fit

No Sine Fit

No Sine Fit No Sine Fit

No Sine Fit

No Sine Fit

No Sine Fit

No Sine Fit

No Sine Fit

No Sine Fit

0.225 ± 0.066

1.671 ± 0.156 0.94

0.73

0.02

339 ± 69

0.8314 ± 0.340

0.3100 ± 0.108

1.2204 ± 0.224

0.07

0.43

0.52

0.33

0.44

331 ± 54

334 ± 73

0.42

0.34

Fatheree

WY-1

MT-1

CC-2

Amplitude of Best Fit

(‰ VPBD)Amplitude of Best Fit

(‰ VPBD)

Period of Best Fit

(mm)

δ18O

R2 R2

δ13CTable 1

-2.4

-2.3

-2.2

-2.1

-2

-1.9

-1.8

-1.7

-1.6

-1.5

-1.4 Best Fit Linear95% Bounds

δ1

8O

(‰

VP

DB

)

δ1

8O

(‰

VP

DB

)

δ1

8O

(‰

VP

DB

)

δ1

3C

(‰

VP

DB

)

δ1

3C

(‰

VP

DB

)

δ1

3C

(‰

VP

DB

)

δ1

3C

(‰

VP

DB

)y = (0.01684)sin(0.01473x + 0.07002)

y = (0.155)sin(0.01597x + 0.1933)

y = 0.001727x - 0.03637

y = (0.6102)sin(0.01856x - 1.122)

y = -0.00569x + 0.4787

y = 0.005046x - 2.191

y = 0.0003414x

- 0.1668

Isotope data from Baculites undatus specimen from the Coon Creek formation

(35.35218 °N, 88.42043 °W) is shown. Oxygen and carbon isotope data were

normalized to 0 using means: δ18O = 0.4294; δ13C = 0.3979.

Isotope data from Baculites undatus specimen from the Coon Creek formation

(35.35218 °N, 88.42043 °W) is shown. Carbon isotope data were normalized to

0 using mean: δ13C = -0.1215. A sine curve could not be extrapolated from the

oxygen data series, so a linear fit was used.

Isotope data from Baculites clinolobatus specimen from Northern Wyoming

(44.75 °N, 108.5 °W) is shown. The unidirectional trends could represent a

portion of the seasonal cycle given the shorter length of this specimen. Sine

curves could not be extrapolated from the datasets, so linear fits were used.

Isotope data from Baculites sp. specimen from the Bear Paw Shale at Hell

Creek in Eastern Montana (47.6314 °N, -106.8688 °W) is shown. The signals in

this specimen are rather noisy, and no meaningful or significant trends were

identified.

y = -0.004121x - 2.399

Distance along shell (mm)

δ1

8O

(‰

VP

DB

)

0 50 100 150 200 250 300-1

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0.8

1Best Fit Sine

95% Bounds

Distance along shell (mm)

δ1

3C

(‰

VP

DB

)

0 50 100 150 200 250 300

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0.8

Best Fit Sine

95% Bounds

y = (0.8355)sin(0.0171x + 0.1562)

y = (0.4157)sin(0.01879x + 1.784)

Figure 2

Figure 1

Cochran, J.K., Kallenberg, K., Landman, N.H., Harries, P.J., Weinreb, D., Turekian, K.K., Beck, A.J., and Cobban, W.A., 2010, Effect of diagenesis

on the Sr, O, and C isotope composition of late Cretaceous mollusks from the Western Interior Seaway of North America: American

Journal of Science, v. 310, p. 69–88, doi: 10.2475/02.2010.01.

Fatherree, J.W., Harries, P.J., and Quinn, T.M., 1998, Oxygen and Carbon Isotopic "Dissection" of Baculites compressus (Mollusca: Cephalopoda)

from the Pierre Shale (Upper Campanian) of South Dakota: Implications for Paleoenvironmental Reconstructions: Palaios, v. 13,

p. 376–385, doi: 10.2307/3515325.

Grossman, E., 1986, Oxygen and carbon isotope fractionation in biogenic aragonite: Temperature effects: Chemical Geology, v. 59, p. 59–74,

doi: 10.1016/0168-9622(86)90057-6.

We acknowledge the generous support of the Undergraduate Creativity

and Research Academy and The University of Alabama Department of

Geological Sciences for providing financial assistance for this project. We

thank the Alabama Stable Isotope Laboratory for processing our samples.

We thank the United States Geological Survey and the Pink Palace

Museum for providing specimens used in this project. We especially thank

Tamara Braithwaite and Louella Weaver of the Pink Palace Museum

for assistance with collections and sampling permission.

Fatherree CC-1

7.84 1.06 ≥2.43 >3.33 n/a

CC-2 WY-1 HC-1

Calculated Annual ∆T (°C)

Specimen NameTable 2

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0.4

0.5

-0.4

-0.2

0

0.2

0.4

0.6

0.8

1

Baculites specimen CC-1 and the specimen described by Fatherree et al. (1998) show sinusoidal

δ18O signals with similar periods around 370 mm and have overlapping error ranges (see Table 1).

Baculites specimens CC-1, CC-2, and the specimen described by Fatherree et al. (1998) show

sinusoidal δ13C signals with very similar periods around 335 mm. Error ranges overlap with each

other and the period lengths produced from δ18O (see Table 1).

The consistency in period length is suggestive of common cause, which could be explained by a

seasonal trend since δ18O is temperature dependent and δ13C may reflect seasonal variation in

organism behavior, metabolism, and/or activity.

The lengths of these periods suggest that Baculites grow at extremely fast rates (>300 mm/yr).

Baculites may be r-strategists that grow rapidly, live short lives, and produce large amounts of

offspring, or they may simply reach their mature size quickly and stop growing.

The amplitude of the δ18O signal from the specimen CC-1 is small which may indicate low

magnitude seasonal cycles, agreeing with a shallow subtropical shelf environment.

The amplitude of the Fatheree et al. (2010) specimen’s δ18O signal is several times greater than that

of CC-1 as expected at a much higher paleolatitude.

Seasonal amplitude could be reduced due to organism behavior, such as seasonal geographic

migration or vertical migration in the water column.

Powdered shell samples were generated for isotopic analysis of ontogenetic sequences

using a handheld Foredam drill.

Carbon and oxygen isotope values were measured using a Thermo Scientific Delta V Plus

isotope ratio mass spectrometer equipped with a GasBench II autosampler.

Best fit sine functions (representing seasonal cyclicity) were found using the curve fitting

toolbox in MATLAB. Datasets with insufficient data, such as unidirectional trends, were fit

with linear functions.

δ18O and δ13C data with apparent sinusoidal patterns were normalized to a mean of 0 by

subtracting the mean of the sample data as required by MATLAB.

Seasonal temperature differentials were calculated by assuming a constant δ18O for

seawater and multiplying the peak-to-peak amplitude of the δ18O sine function by 4.69

as defined by Grossman and Ku (1986).

All specimens preserve primary aragonite as indicated by their iridescence.

Samples are currently being imaged with a scanning electron microscope to assess their

preservation quality using the preservation index established by Cochran et al. (2010).

••

Fatherree et al. (1998) measured δ18O and

δ13C in an ontogenetic sequence on a single

Baculites compressus collected from the

Pierre Shale in Northern Wyoming

(43.9333 °N, 102.8167 °W).

A sinusoidal δ18O trend over the length of

the shell (320 mm) was recognized to be

approximately one seasonal cycle.

We reanalyzed their data for sinusoidal fits

with MATLAB using the same methods by

which our data was processed (see

Methods) to produce functions for their

δ18O and δ13C signals.

The periods of these functions are similar to

those we were able to fit to our specimens,

CC-1 and CC-2 (see Table 1).

An SEM image of the the Fatherree (1998)

Baculites’ well-preserved microstructure

Mollusks are typically thought to precipitate

carbonate shell material in equilibrium with

seawater.

Little is known about the lifespan or habits of

extinct ammonite species. Most postulations are

made based on their modern analog - the Nautilus.

The uncoiled morphology of Baculites makes the

genus an easy target for sclerochronological

isotopic analysis.

Seasonal temperature signals may be preserved in

oxygen isotope content as shell material is

deposited over time.

Carbon isotope content may also preserve seasonal

signals depending on organism behavior.

Using Carbonate Stable Isotopes to Identify Seasonal Trends in Late Cretaceous Ammonites

160 320800Miles

Middle Campanian Reconstruction

Colorado Plateau Geosystems Inc.

Western Interior Seaway (WIS)

MT-1

Fatherree

CC-1, CC-2

WY-1

N