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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