Biomineraliza+onPupaGilbert

DepartmentsofPhysics(100%),Chemistry(0%),Materials

Science(0%),Geoscience(0%)UW-Madison

RadcliffeIns+tuteforAdvancedStudy,HarvardUniversity

worksupportedbyNSF-DMR-BMAT DOE-BES-Geosciences US-IsraelBSF RadcliffeIns+tute,Harvard 1

hSp://www.lovethisp

ic.com

/image/14

196/colorful-seashells

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3pngimg.comCopyright©2013-2017

4hSp://paulmerriman.com/facing-fears/

5hSp://www.playbuzz.com/radio+mes10/40-fascina+ng-facts-about-jaws

6hSp://3.bp.blogspot.com/-kHCZ-0PidgQ/Ve_geFe342I/AAAAAAAAQOw/RU6Y5C5pUyQ/s1600/pf3267_majung2_h.jpg

7hSp://www.mnn.com/earth-maSers/animals/photos/28-commonly-confused-animals/turtles-and-tortoises

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Yangetal.Nanoscale2011

seaurchinspinediffractslikeasinglecrystalofcalcite

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calcitesinglecrystal

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100µm

Yangetal.Nanoscale2011

seaurchinspinediffractslikeasinglecrystalofcalcite

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calcitesinglecrystal

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biominerals

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biomineraliza+on=forma+onmechanisms

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biomineraliza+on

•  whyisitimportant?

•  becauseitisawidespreadnaturalphenomenon

•  usefulforsleuthingintodeep+me(500,000Myrs)

•  mechanismscanbeapplied

•  largecrystalsforsolarenergy•  amorphousdrugs•  3Dprin+ng•  boneimplants•  …

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biomineraliza+onmechanisms

amorphouspar+cles(~100nm)infresh,formingbiominerals

PNAS2012 JACS2015 Science2017underreview

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•  crystalsgrowbypar+cleaSachment(Science2015)

biomineraliza+onmechanisms

•  crystalsgrowbypar+cleaSachment

•  orienta+onofcrystalschangesasthebiomineralgrows

Mc Pm HmCalciteprismsinmussel Aragoniteinapearl Vateriteinseasquirtspicule

DeVoletal.2014 25

calciteunitcell

Ca

C

O

aragoniteunitcell

vateriteunitcell

DeVoletal.2014 26

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RebeccaMetzleretal.,PRL2007………

DeVoletal.2014

x-raylineardichroisminOK-edgeXASspectra

Mc Pm HmCalciteprismsinmussel Aragoniteinapearl Vateriteinseasquirtspicule

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PIC-mappingPolariza+on-dependentImagingContrast-mapping

color=c-axisorienta3onin3D

RebeccaMetzleretal.,PRL2007………

DeVoletal.2014

•  linestheinsideofmanymolluskshells•  iswidelystudiedbecauseofitsmechanicalproper+es•  isiridescent

nacre(mother-of-pearl)

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SEMofnacreHr

2µmHrf4-5-042 30

photobyGailBissonhSp://quotesgram.com/quotes-on-soap-bubbles/#8QXy4UUHoZ

iridescenceorthin-layerinterference

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PIC-mapsofnacre(PIC=Polariza+on-dependentImagingContrast)

ICOlsonetal.2013

sheetnacre(bivalves) columnarnacre(gastropods,cephalopods)Pm Hrb

PIC-mappingrevealedthatnacregraduallyorders,andgrowsepitaxially(PRL2007,JACS2008,JACS2012)

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nacregraduallyorders,andgrowsepitaxially

Pf

Gilbertetal.JACS2008Olsonetal.JSB2013

Checaetal.JSB2011

PIC-map(Polariza+on-dependentImagingContrast)TEM

Gu

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Atrinarigidashell,Florida

whatcontrolstabletthicknessinnacre?

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ques+onatHarvard2014-15:doesnacreTTrecordenvironmentaltemperature?

AndrewH.Knoll

CorinneE.MyersnowatNM

Kris+nD.BergmannnowatMIT 36

Pfo1 Ps8

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Ps PIC-mapofnacrePolariza+on-dependentImagingContrastobtainedwithPhotoEmissionElectronMicroscopy(PEEM)attheBerkeley-AdvancedLightSource

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test of fossil preservation

0 Ma 13 Ma

53 Ma 66 Ma

PIC-maps (PIC=Polarization-dependent Imaging Contrast) 39

3Recent+7Fossilshells822PIC-maps,partlyoverlappingtoensurecon+nuityinposi+on/+me.

=interiorofshell,recent

Ar5-1

=exteriorofshell,old

Pn1-1 Ah2-1 Ah4-1 Px1-1 Px2-1Ps5-1Ps6-1

20µm

Ah3-1Pc2-1

Ps8-2

Pfo1-3

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linear fit, with error bars NOT taken into account

0.0

0.2

0.4

0.6

0.8

1.0

0 5 10 15 20 25 30

y = 0.30954 + 0.014267x R= 0.945

y = 0.34874 + 0.0099511x R= 0.74803

y = 0.2454 + 0.016353x R= 1

y = 0.29194 + 0.015107x R= 0.97939

mea

n TT

in e

ach

shel

l (µm

)

T(°C)

nacre tablet thickness (TT) vs temperature (T)

Ah213Ma

Ah413Ma

Px253Ma

Ps666Ma

Px1 53Ma

Pn10Ma

Ps566MaPc2

0MaAh3

13Ma

R = 0.979

Y = M0 + M1*x + ... M8*x8 + M9*x9

0.39471M00.0075674M10.0003083M2

0.99986R

Y = M0 + M1*x + ... M8*x8 + M9*x9

0.10527M00.025387M1

-0.00029935M20.99998R

PUPAGilbert,KDBergmann,CEMyers,MAMarcus,RTDeVol,C-YSun,AZBlonsky,JZhao,EAKaran,ETamre,NTamura,AJGiuffre,SLemer,GGiribet,JMEiler,AHKnoll.Nacretabletthicknessrecordsforma+ontemperatureinmodernandfossilshells.EPSL2017. 41

bootstrapping: fit 9 pts (1 per

shell) displaced within the errors, repeat 105 times.

PUPAGilbert,KDBergmann,CEMyers,MAMarcus,RTDeVol,C-YSun,AZBlonsky,JZhao,EAKaran,ETamre,NTamura,AJGiuffre,SLemer,GGiribet,JMEiler,AHKnoll.Nacretabletthicknessrecordsforma+ontemperatureinmodernandfossilshells.EPSL2017.

0.0

0.2

0.4

0.6

0.8

1.0

0 5 10 15 20 25 30

avg

TT in

eac

h im

age

(µm

)

T(°C)

nacre tablet thickness (TT) vs temperature (T)

TT = 0.2830 +0.0144 T

90% CL

line

9 pts fit

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0.0

0.2

0.4

0.6

0.8

1.0

0 5 10 15 20 25 30

y = 0.30954 + 0.014267x R= 0.945

y = 0.34874 + 0.0099511x R= 0.74803

y = 0.28301 + 0.014433x R= 1 av

g TT

in e

ach

imag

e (µ

m)

T(°C)

nacre tablet thickness (TT) vs temperature (T)

Ah213Ma

Ah413Ma

Px253Ma

Ps666Ma

Px153Ma

Pn10Ma

Ps566MaPc20Ma

Ah313Ma

TT = 0.2830 +0.0144 T

Y = M0 + M1*x + ... M8*x8 + M9*x9

0.10527M00.025387M1

-0.00029935M20.99998R

90% CL

50% CLline

this version, Feb 2016, has no Ar4 or Ar5 data

Matthew's most probable fit line and CL lines take into account all errors in TT and T on all 633 data points. The line has the avg slope and intercept of all 100,000 simulated lines, and is therefore the most probable line. I plotted all data, CL lines not p2 fit, then extrapolated to margins with lines. The line is a lin fit, exptrapolated to the edges of the plot.

(mean,median,mode)

PUPAGilbert,KDBergmann,CEMyers,MAMarcus,RTDeVol,C-YSun,AZBlonsky,JZhao,EAKaran,ETamre,NTamura,AJGiuffre,SLemer,GGiribet,JMEiler,AHKnoll.Nacretabletthicknessrecordsforma+ontemperatureinmodernandfossilshells.EPSL2017. 43

usingthenacreTTproxyforJurassicPinnawithextensivediagenesisnotaccessibletoelementalorisotopicanalysis

PIC-maps (PIC=Polarization-dependent Imaging Contrast)

Pfo1, 187 Ma Ps8-2, 187 Ma

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3Recent+9Fossilshells842PIC-maps,partlyoverlappingtoensurecon+nuityinposi+on/+me.

=interiorofshell,lastdeposited

Ar5

=exteriorofshell,firstdeposited

Pn1 Ah2 Ah4 Px1 Px2 Ps5 Ps6

20µm

Ah3Pc2

Ps8

Pfo1

0.0

0.2

0.4

0.6

0.8

1.0

0 5 10 15 20 25 30

y = 0.30954 + 0.014267x R= 0.945

y = 0.34874 + 0.0099511x R= 0.74803

y = 0.28301 + 0.014433x R= 1

avg

TT in

eac

h im

age

(µm

)

T(°C)

nacre tablet thickness (TT) vs temperature (T)

Ah213Ma

Ah413Ma

Px253Ma

Ps666Ma

Px153Ma

Pn10Ma

Ps566MaPc20Ma

Ah313Ma

Y = M0 + M1*x + ... M8*x8 + M9*x9

0.10527M00.025387M1

-0.00029935M20.99998R

Ps8187Ma

Pfo1187Ma

90% CL

50% CLline

this version, Feb 2016, has no Ar4 or Ar5 data

Matthew's most probable fit line and CL lines take into account all errors in TT and T on all 633 data points. The line has the avg slope and intercept of all 100,000 simulated lines, and is therefore the most probable line. I plotted all data, CL lines not p2 fit, then extrapolated to margins with lines. The line is a lin fit, exptrapolated to the edges of the plot.

TT = 0.2830 +0.0144 T

measuring Jurassic T from TT:

sample T(°C) 50% CL(°C)

90% CL(°C)

Pfo1,T1 23 21-27 18-34Pfo1,T2 21 19-24 16-31

Ps8 14 12-14 8-20

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conclusions

•  biominerals,fewforma+onmechanisms

•  PIC-mapping

•  TTvs.Tcorrela+onprovidesthefirstphysical-structureproxy

•  environmentdrivesstructure:

metabolism–kine+cs–thermodynamicsbiology–chemistry–physics

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thankstomygroup

Chang-YuSunUW-MaterialsScience

ElizabethKaranHarvardCollegeOEB

AudraL.Amasinograduatestudent

MIT

Dr.AnthonyJ.GiuffreUW-Physics

RebeccaA.MetzlerAssociateProfessor

ColgateU

JessicaZhaoHarvardCollege

ApplMathMaSJ.FrazierUW-Physics

AnnieWhissonUW-MaterialsScience

CaylaS+flerUW-Physics

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manythankstoexcellentcollaborators

AlexNavrotskyUC-Davis

MicheleParrinelloETH

JohnW.ValleyUW-Madison

MaShewA.MarcusBerkeley-ALS

AndrewH.KnollKris+nBergmannCorinneE.MyersHarvardU

GonzaloGiribetSarahLemerOEB-Harvard

NobumichiTamuraBerkeley-ALS

Sa+shC.B.MyneniPrinceton

SteveWeiner YaelPoli+Weizmann,nowatMPILiaAddadi

Weizmann,Israel

SusanN.CoppersmithUW-Madison

FredWiltUC-Berkeley

BoazPokroyTechnion,Israel

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