ENVS 433 assessed practical Name: Amir Mustofa Irawan

Interpretation of Stable Isotope Data.

NB you only need complete the sections covered in the taught session -
PART 1- Oxygen Isotopes and Climate Change

The use of oxygen stable isotope geochemistry to estimate ancient temperatures relies on the assumption that we can identify
minerals or shells that are likely to have precipitated in equilibrium with their surroundings. In modern environments we find, for
example, that many brachiopods, molluscs and foraminifera precipitate in equilibrium whereas algae and corals do not. Oxygen
stable isotope values in marine carbonates precipitated under equilibrium conditions depend on

1. Temperature and
2. The isotopic composition of the water

In studying sediment cores we can measure the isotopic composition of carbonates but have to estimate the composition of
the waters in which the carbonate precipitated. Today seawater has a relatively uniform composition (around 0 SMOW) in
comparison to meteoric (rain) water, which varies with latitude and temperature. In the relatively recent past the oxygen
isotopic composition of seawater may have changed in response to glaciation (+/- ~1 ). However ancient oceans may have had
more different 18O values: depending on ice-volume and ocean circulation.
1.Oxygen Isotopes Marine palaeotemperature calculations.
There is considerable debate about the climate of the Pliocene (immediately before the onset of northern Hemisphere
glaciation. The aim of this exercise is for you to interpret data from some Pliocene shells from the UK and N America. The data
from N America and Suffolk is from a paper by Mark Williams, et al . 2009. (Phil Trans Roc Soc. A 367, 85-108.
The data from New Location supposedly in Scotland is for you to critically assess!

Locality Modern Mollusc (mineral Mollusc 18O Modelled Mid Pliocene Winter
Temp Range Arag or Calcite) (Range) Mid Pliocene Temperature difference
(winter- w (range) (Plio-
summer) oC Modern)
Virginia 4.4 -25.5 Chesapecten 1.6 to -1.9 1.1 14.0 to 9.6
jeffersonius(C 29.6
Florida 16 - 27 Mercenaria 1.8 to -0.25 1.02 16.3 to 0.3
campechiensis(A 25.2
Suffolk 4 -17 Aequipecten 2.4 to 0.7 0.14 7.3 13.7 3.3
E. England opercularis (C
New Location 1. 4 - 15 Oyster -4.5 0.14 39.8 35.8
Scotland Clyde
(Aragonite)
Estuary
New Location 1. 4 - 15 Oyster -4.5 0.14 38.0 34.0
Scotland Clyde
(Calcite)
Estuary
New Location 2. 4 -15 Sea Urchin in -3.5 0.14 32.8 28.8
Scotland Clyde
beach deposits
Estuary

The modelled mid Pliocene water isotope compositions are from OAGCMs assuming reduced glacial ice and enhanced
northward moisture transport following closure of the Panama Canal ( Lunt, D.J et al. Clim Dyn, 30, 1-18)

The palaeotemperature equation for biogenic calcite (Craig (1965) equation as expressed by Anderson and Arthur 1983) is
T = 16.0 - 4.14 ( c- w)+ 0.13 ( c- w)2
Where
T= temperature (oC)
c is the 18O of the calcite with respect to the PDB international standard
and w is 18O of the water with respect to the SMOW international standard.

The equation for aragonite ( Grossman and Ku, 1986) is similarly T (oC) = 19.7- 4.34 ( a- w)

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Your job is to calculate palaeotemperatures assuming the modelled local sea water or a reasonable assumed value.
And comment on the suitability of the data and from the new site

A. Complete the table above for the data for Virginia, Florida and Suffolk.

What do the values tell us about the Pliocene Climate in the USA and in the UK (values and seasonality)?

As it can be seen from the table, Mid Pliocene temperature both during winter and summer is warmer than modern temperature
in all sites across the UK and US. Specifically, the data shows that the temperature during winter in the Mid Pliocene warmer than
Modern temperature for all sites across both in the UK and US. In the summer, the trend of mid Pliocene temperature generally
warmer than modern temperature except Florida and Suffolk. The modern temperature in Florida reach 27C that represent 1.8C
warmer than Mid Pliocene. The same pattern occurred in Suffolk which the modern temperature difference is 3.3C warmer than
Mid Pliocene. The higher modern temperature than the mid Pliocene temperature both in Florida and Suffolk during summer
possible because of climate change impact that make temperature increase. In addition, the calculation from the table exhibit that
Scotland has the mid Pliocene temperature warmer than all other location both in the UK and US.

In the all UK sites, the modern temperature during winter all are 4C which is lower than Mid Pliocene temperature in the UK that
has a range between 7.3C to 39.8C. As Langford and Bentham (1995) observed that, climate change predominantly affect colder
winter month. This cooling condition during winter also effect the wide temperature range in the UK, ranging from a winter value
of 4C to a summer value of 17C. Ultimately, the value shows that Suffolk is the coldest location in the UK and US.

Generally, the temperature in all sites of the US have a larger difference comparing with Mid Pliocene temperature during winter
than a summer. For instance, Virginia has a difference temperature during winter of 9.6C comparing during summer just only
4.1C. This indicates that the present temperature in US during winter decrease extremely than winter value of Mid Pliocene
period. Also, Virginia has a wider modern temperature range in the US from 4.4C to 25.5C.

B.) Assess the suitability of the shell material from the potential site from Scotland.

Try to calculate temperatures for the measured calcite from the new site

Are the temperature meaningful? If not, why not?

Consider - The location of the site, the habitat of the organisms and the mineralogy of their shells? (ask if you dont know!).

The temperature calculated it can be said not meaningfully compare to the other sites which the mid Pliocene temperature of
both new location 1 and new location 2 are extremely higher than Suffolk even Virginia and Florida. The location of Virginia and
Florida that near the coastline would be warmer than the temperature in all UK site regarding to the modern North Atlantic Ocean
surface water circulation. This circulation becoming the gulf stream and flowing northward from Florida Straits to Cape Hatteras
in North Carolina exhibit warmer water current flow. Regarding to climate condition, the northern hemisphere, particularly the
UK during mid Pliocene would have been cooler temperature rather than North America.
(Williams et al., 2009).

In term of the oyster shell, there are two components of the shells which is mainly composed of Calcite and the inner shell which
is composed of primarily aragonite (Epstein et al., 1953). However, the data that was inputted may be not source of the sound of
data. Furthermore, the quality of that the dataset might be not appropriated for dating.

The w value that used to new location 1 and new location 2 is the same to the Suffolk which is the location in England. It might
be having different isotopic composition method in Virginia and Florida. In addition, the w data input is of a sound quality and
that the material collected from is understood. The w data is 18O of the water with respect to the SMOW that must be
analysed directly by fluorination or carbon reduction techniques (Friedman and O'Neil, 1977).

2. Lacustrine and lake margin deposits from East Africa

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 The aim of this part of the exercise is for you to investigate some stable isotopic data from a famous archaeological site in E.
Africa and interpret the observed changes in terms of possible changes in temperature and/or water compositions.

Background
You are provided with a diagram showing changes in the stable isotopic composition of Pleistocene lacustrine and soil formed
carbonate from Olduvai Gorge in Tanzania about 2 million years ago when our hominid ancestors were starting to colonise the
landscape. (The data are from Bennett et al 2012 J. Human Evolution, 63, 328-341. Please refer to that paper in preparing
your answers to this section).

Figure 7 of Bennett et al 2012.

The field labelled Calcites (this study) represents soil-

formed and early diagenetic deposits from lake margin
deposits. The trend from A to B represents changes
associated with the evolution of the groundwaters which
precipitated the calcites. (See below, lecture material
and Bennett et al. for more information).

The Lacustrine calcites are very early diagenetic

crystals. from the lake clays.

Figure 8 of Bennett et al
2012.

The photograph shows a

cross section through a
carbonate nodule from
the lake margin deposits
(about 4cm in diameter)
which has been cut in
half.

The isotopic data

represent the measured
values in calcite from
sites 1 to 7

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Procedure
Write an Excel spreadsheet so that you can plot equilibrium lines for carbonates with different measured compositions (i.e. a
graph of Temperature vs 18O water (SMOW) with a curve representing equilibrium for a particular measured value of 18O calcite
(PDB)). To do this you will need to set up a spreadsheet with columns for
1. Measured - 18O calcite (PDB)
2. 18O water (SMOW) set up so you can input a range of values (say 6 to +4).
3. a calculated Equilibrium Temperature (oC) for each water composition.
4. Use Excel to plot equilibrium graphs for the range 18O calcite (PDB) values shown on the graph. (ie for values of
approximately -7 to - 4 PDB for the lake margin calcites and 0 for the lacustrine calcite). Consider 18O water (SMOW)
values from -6 (rainwater derived from mountains) to +4 SMOW (very evaporated lake water). Produce X-Y graphs of
temperature vs water composition with equilibrium curves for 18O = -7 and -4 (for the end members of the lake margin
calcites) and another equilibrium curve for 18O = 0 (to represent the middle of the range of lacustrine calcites..

Use these curves to discuss the possible options for temperature and or water composition at the site
For assessment attach a 1-page (maximum) summary to this handout (with your name on it!) containing at least
a.) a graph or graphs - formatted as a figure in a manner suitable for publication
b.) a paragraph or two of text explaining the environmental significance of both the oxygen and carbon isotope results.

Note - Carbon and oxygen values are affected by a range of environmental factors. You might like to consider
a. What does the oxygen isotopic data tell us about the temperature and/or rain or lake water composition at Olduvai in
the early Pleistocene or the evaporative state of the waters?
b. What does the Carbon Isotope Data contribute? - Previous workers have said that carbon isotopes can be used to
reconstruct the vegetation at the site (in terms of proportion of C3 and C4 plants) others suggest that evaporative
degassing may be important.

You may wish to use the paper cited above and any other other reading - to support your case.

Insert your 1 page answer here

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 3. Hawes Water N. Lancashire the little Temperate Hard Water lake with an isotope record that mirrors the
Greenland Ice Cores! We will have talked about the records from Hawes Water during the lectures other diagrams
are in the lecture Powerpoint.

Late Glacial Record (14ka to 11ka) (from Marshall et al 2002 Palaeogeog. Palaeoclim. Palaeoecol., 185 25-40)
Annotate the diagram below to highlight key relationships between the stable isotopes and the other proxies at the
site and suggest reasons for the patterns that are apparent in the data.
Onset of early Cold period
Holocene Cold period (Sharp rise in
(Increasing (Expansion of water
vegetation) grass land) chironomids)
Warm
period
(Increase
of
oxygen
isotopic)

Warm
period
(Increase
of
oxygen Onset of Warm
isotopic) Climate Onset of
short term Younger period Major
oscilation dryas is ( indicates by warming
13C=2o/oo) increasing
of juniperus

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 Early Holocene Record figures from J.D. Marshall et al. 2007 Geology, 35, 7, 639-642.

Annotate the figures below to demonstrate that you understand the significance of the isotope data and the way it has been
used to determine palaeoclimate.

Sites recording
abrupt cold events

Age model for

core HWLC1.

Isotopic composition
of contemporary
Cold event waters

Cold event Fractionation relationships

for contemporary calcite
precipitates

The offset between

Hawes water and ice
Two abrupt isotopic
core excursions
excursions indicate cold
indicate time lag of
event
cold event in
Greenland and NW
Europe or dating errors

Centennial stable
isotopes scale
pattern

At 8.2ka Abrupt At 9.3ka Abrupt

cold event cold event 50
180 years years

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 4. Ocean Sediment Records - Isotopic changes associated with the Cretaceous /Tertiary Boundary

This figure shows the isotopic composition of foraminiferal calcite and fine fraction carbonate (chalk) across the K/T boundary
from a deep sea core in the Pacific (Zachos et al 1989- Nature). Open symbols are for data from planktonic forams and the fine
fraction (mostly coccoliths) and closed (black) symbols are for benthic foraminifera. These provide signals from the surface of the
ocean and from the deep ocean.

Label the figure (add lines and boxes) to show that you understand the significance of the changes in carbon and oxygen isotope
values across the K/T boundary

a.) For the carbon - identify 3 intervals with different signals based on the separation of the lines - and interpret them.

b. ) What, if anything, does the oxygen data tell us about changes in temperature?

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Finally =->

Please tell us, in a sentence or two, what you have learned about the use of stable isotopes in (palaeo-)
environmental research. What would you need to consider if you plan to use stable isotopes in an
environmental research project?

Ultimately, stable isotopes are used to establish ancient environments of deposition and diagenesis. Also,
sub decadal oxygen isotopic records 18Oc suitable to indicate changes in either chironomid temperature or
water composition, or both that detect abrupt climate change in the Holocene. From the exercise, stable
isotopes can clearly determine the Mid Pliocene temperature warm record in all sites across the UK and US.
Application of the stable isotopes method from marine shell bearing animal such as from mollusc of
aragonite and calcite has provided great insight into climatic variation pattern during the last million years.
Furthermore, if we plan to use stable isotopes in an environmental project, the data input is of a sound
quality and that the material collected from is should be understood. interpretation of pollen, chironomid
and lithological data is work very nicely and connected with the use of isotopic record to discuss non-linear
system dynamics in the lake catchment.

Jim Marshall
March 2017.

Bibliography

Epstein, S., Buchsbaum, R., Lowenstam, H. A. and Urey, H. C. (1953) 'Revised carbonate-water isotopic
temperature scale', Geological Society of America Bulletin, 64(11), pp. 1315-1326.

Friedman, I. and O'Neil, J. R. (1977) Data of geochemistry: Compilation of stable isotope fractionation
factors of geochemical interest. US Government Printing Office.

Langford, I. H. and Bentham, G. (1995) 'The potential effects of climate change on winter mortality in
England and Wales', International journal of biometeorology, 38(3), pp. 141-147.

Williams, M., Haywood, A. M., Harper, E. M., Johnson, A. L., Knowles, T., Leng, M. J., Lunt, D. J.,
Okamura, B., Taylor, P. D. and Zalasiewicz, J. (2009) 'Pliocene climate and seasonality in North Atlantic
shelf seas', Philosophical Transactions of the Royal Society of London A: Mathematical, Physical and
Engineering Sciences, 367(1886), pp. 85-108.

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