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Geography and Environmental Science




Earthworm secreted
calcium carbonate: A
new palaeothermometer
Emma Versteegh, Stuart Black and Mark Hodson

02 August 2012                    © University of Reading 2012   www.reading.ac.uk
?
Goldschmidt 2012       2
Earthworm secreted
       calcite (CaCO3) granules




Canti (2007)
       Goldschmidt 2012           3
How are the granules produced?
                   • Calciferous glands;
                   • Milky fluid;
                   • → CaCO3 concretions;
                   • → granules.




                    Darwin (1881) / Canti (1998)
Goldschmidt 2012                                   4
Why do they produce them?
                   • “It is probable that they primarily
                     serve as organs of excretion, and
                     secondarily as an aid to digestion”
                     (Darwin, 1881);
                   • Egg formation?
                   • Triturate food in gizzard?
                   • Absorption of food products?
                   • Water regulation → evolutionary
                     adaptation to terrestrial habitat?
                   • Respiratory organ / eliminate
                     excess CO2?
Goldschmidt 2012                                     5
Aim

To construct a new terrestrial isotope–temperature
  curve for application to earthworm secreted
  calcium carbonate granules.


   → Potential for granules in dating and
     palaeoenvironmental interpretation.



Goldschmidt 2012                                6
Oxygen isotopes (δ18O values)
as palaeothermometer




                     Equilibrium (synthetic calcite):
                   1000 ln αc-w = 18.03 (103T-1) - 32.42


             δ18Owater & temperature → δ18Ocalcite

            Standards: VSMOW (H2O) & VPDB (CaCO3)

Goldschmidt 2012                            Kim & O’Neil (1997)   7
Experiment

• Species: Lumbricus terrestris
• 2 soils
• 3 types of water (England,
  Fiji, Norway)
• 3 temperatures (10, 16, 20
  °C)
• 3 weeks acclimatisation
• 1 month
• 6 replicates

Goldschmidt 2012                  8
Experiment




Goldschmidt 2012
Isotope analyses

Delta V advantage IRMS
  & GasBench:
δ18Ocalcite values


Picarro L2120-I:
δ18Owater values




Goldschmidt 2012         10
Granule δ13C and δ18O values




Goldschmidt 2012               11
Influence of δ18Owater values




                   Increasing δ18Owater




Goldschmidt 2012                          12
Influence of temperature

        Decreasing T



                           ???




Goldschmidt 2012                 13
Predicted and measured δ18Ocalcite




Goldschmidt 2012                     14
Palaeotemperature relationships




Goldschmidt 2012                  15
Palaeotemperature equation

 T(°C) = 19.22 - 3.77 · (δ18OcVPDB - δ18OwVSMOW) - 0.03 ·
                 (δ18OcVPDB - δ18OwVSMOW)2
                          R² = 0.95


                             =


       T(°C) = 19.24 - 3.85 · (δ18OcVPDB - δ18OwVSMOW)
                          R² = 0.95

Goldschmidt 2012                                            16
Fractionation curves CaCO3-H2O




Goldschmidt 2012                 17
Fractionation factor



          1000 ln α = 18.47 (103 T-1) – 32.46



     α = (1000 + δ18OcVSMOW) / (1000 + δ18OwVSMOW)
       (Equilibrium: 1000 ln αc-w = 18.03 (103T-1) - 32.42)


Goldschmidt 2012                                              18
Conclusions
• Lumbricus terrestris produce calcite granules;
• These are enriched in 18O by 1.5 ‰ compared to
  equilibrium;
• δ18Ocalcite values depend on temperature and
  δ18Owater values following:
          1000 ln α = 18.47 (103 T-1) – 32.46
• Well-preserved archaeological granules can be
  used as palaeothermometers.


Goldschmidt 2012                                   19
Future work
• Influence of evaporation with depth?
• Changes of temperature with depth?
→ Analyse recent granules along soil profiles




                                       Canti (2007)
Goldschmidt 2012                                      20
Future work
• Analyse more replicates
• δ13C values: soil organic matter, DOC, earthworm tissues,
  milky fluid;
• The influence of [CO2] on granule production;
• δ18O internal structure heterogeneity: ion probe;
• Application to soil archaeological and geological
  samples:
     – Reconstruction of past temperatures;
     – Dating of samples by U/Th;
     – Comparison with pedogenic carbonate concretions and Bithynia
       tentaculata opercula.

Goldschmidt 2012                                                  21
Thank you!
                                   Questions?

                                 Acknowledgements:
                                 • NERC
                                 • Yan Gao
                                 • Matt Canti (English Heritage)
       God makes the earthworm
Goldschmidt 2012                                           22
Earthworm granules
vs. Arion slug granules




                   Canti (1998)


Goldschmidt 2012                  23
Different species – different granules




Goldschmidt 2012                     Canti & Piearce (2003)
                                                     24
δ13C values & temperature




Goldschmidt 2012            25
Archaeological and geological samples




                                  Canti (2007)
Goldschmidt 2012                        26
Goldschmidt 2012   IAEA (2001)
                         27
Goldschmidt 2012   28
EBSD crystallographic orientation




     Goldschmidt 2012
EBSD composition
Silicon
Magnesium
Calcium




      Goldschmidt 2012

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Goldschmidt 2012

  • 1. Geography and Environmental Science Earthworm secreted calcium carbonate: A new palaeothermometer Emma Versteegh, Stuart Black and Mark Hodson 02 August 2012 © University of Reading 2012 www.reading.ac.uk
  • 3. Earthworm secreted calcite (CaCO3) granules Canti (2007) Goldschmidt 2012 3
  • 4. How are the granules produced? • Calciferous glands; • Milky fluid; • → CaCO3 concretions; • → granules. Darwin (1881) / Canti (1998) Goldschmidt 2012 4
  • 5. Why do they produce them? • “It is probable that they primarily serve as organs of excretion, and secondarily as an aid to digestion” (Darwin, 1881); • Egg formation? • Triturate food in gizzard? • Absorption of food products? • Water regulation → evolutionary adaptation to terrestrial habitat? • Respiratory organ / eliminate excess CO2? Goldschmidt 2012 5
  • 6. Aim To construct a new terrestrial isotope–temperature curve for application to earthworm secreted calcium carbonate granules. → Potential for granules in dating and palaeoenvironmental interpretation. Goldschmidt 2012 6
  • 7. Oxygen isotopes (δ18O values) as palaeothermometer Equilibrium (synthetic calcite): 1000 ln αc-w = 18.03 (103T-1) - 32.42 δ18Owater & temperature → δ18Ocalcite Standards: VSMOW (H2O) & VPDB (CaCO3) Goldschmidt 2012 Kim & O’Neil (1997) 7
  • 8. Experiment • Species: Lumbricus terrestris • 2 soils • 3 types of water (England, Fiji, Norway) • 3 temperatures (10, 16, 20 °C) • 3 weeks acclimatisation • 1 month • 6 replicates Goldschmidt 2012 8
  • 10. Isotope analyses Delta V advantage IRMS & GasBench: δ18Ocalcite values Picarro L2120-I: δ18Owater values Goldschmidt 2012 10
  • 11. Granule δ13C and δ18O values Goldschmidt 2012 11
  • 12. Influence of δ18Owater values Increasing δ18Owater Goldschmidt 2012 12
  • 13. Influence of temperature Decreasing T ??? Goldschmidt 2012 13
  • 14. Predicted and measured δ18Ocalcite Goldschmidt 2012 14
  • 16. Palaeotemperature equation T(°C) = 19.22 - 3.77 · (δ18OcVPDB - δ18OwVSMOW) - 0.03 · (δ18OcVPDB - δ18OwVSMOW)2 R² = 0.95 = T(°C) = 19.24 - 3.85 · (δ18OcVPDB - δ18OwVSMOW) R² = 0.95 Goldschmidt 2012 16
  • 18. Fractionation factor 1000 ln α = 18.47 (103 T-1) – 32.46 α = (1000 + δ18OcVSMOW) / (1000 + δ18OwVSMOW) (Equilibrium: 1000 ln αc-w = 18.03 (103T-1) - 32.42) Goldschmidt 2012 18
  • 19. Conclusions • Lumbricus terrestris produce calcite granules; • These are enriched in 18O by 1.5 ‰ compared to equilibrium; • δ18Ocalcite values depend on temperature and δ18Owater values following: 1000 ln α = 18.47 (103 T-1) – 32.46 • Well-preserved archaeological granules can be used as palaeothermometers. Goldschmidt 2012 19
  • 20. Future work • Influence of evaporation with depth? • Changes of temperature with depth? → Analyse recent granules along soil profiles Canti (2007) Goldschmidt 2012 20
  • 21. Future work • Analyse more replicates • δ13C values: soil organic matter, DOC, earthworm tissues, milky fluid; • The influence of [CO2] on granule production; • δ18O internal structure heterogeneity: ion probe; • Application to soil archaeological and geological samples: – Reconstruction of past temperatures; – Dating of samples by U/Th; – Comparison with pedogenic carbonate concretions and Bithynia tentaculata opercula. Goldschmidt 2012 21
  • 22. Thank you! Questions? Acknowledgements: • NERC • Yan Gao • Matt Canti (English Heritage) God makes the earthworm Goldschmidt 2012 22
  • 23. Earthworm granules vs. Arion slug granules Canti (1998) Goldschmidt 2012 23
  • 24. Different species – different granules Goldschmidt 2012 Canti & Piearce (2003) 24
  • 25. δ13C values & temperature Goldschmidt 2012 25
  • 26. Archaeological and geological samples Canti (2007) Goldschmidt 2012 26
  • 27. Goldschmidt 2012 IAEA (2001) 27