Strontium isotope composition of sedimentary rocks and its application to chemostratigraphy and palaeoenvironmental reconstructions - Biblioteka UMCS

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A N N A L E S

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ABSTRACT

Strontium isotope composition of seawater is homogenous in all oceans and marginal seas but KDVYDULHGWKURXJKWLPHZLWKFKDQJLQJVWURQWLXPIOX[HV6WURQWLXPLVRWRSHUDWLRRIDQFLHQWVHDZDWHU

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Because of a change in the strontium isotope ratio between sea- and freshwaters it can also be employed for the determination of palaeosalinities or the reconstruction of diagenetic processes of marine OLPHVWRQHV$UHYLHZRIPHWKRGRORJ\DQGSUDFWLFDOKLQWVFRQFHUQLQJWKHXWLOL]DWLRQRIVWURQWLXPLVR- WRSHVLQJHRORJLFDOVWXGLHVRIERWKPDULQHDQGEUDFNLVKVHGLPHQWVDUHSUHVHQWHGLQWKHFXUUHQWDUWLFOH

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of ⁸⁷Rb isotope the ⁸⁷6U⁸⁶Sr ratios of Earth crust have increased from the initial YDOXHRIFD$FKDQJHLQWKHVWURQWLXPLVRWRSHUDWLRVLVGHSHQGHQWRQWKH

URFN5E6UUDWLR6LQFHWKHFRQWLQHQWDOFUXVWLVHQULFKHGLQUXELGLXPLWV⁸⁷6U⁸⁶Sr ratios become increasingly higher and more and more dissimilar from the ratios of WKHRFHDQLFFUXVWDQGWKHPDQWOH)LJ

Strontium isotope composition of sedimentary rocks and its application to chemostratigraphy

and palaeoenvironmental reconstructions

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The seawater strontium isotope composition is uniform across modern RFHDQV GXH WR UHODWLYH ORQJ UHVLGHQFH WLPH RI VWURQWLXP ± ⁶ \HDUV DQG

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has changed through geologic history of the Earth owing to changing inputs of VWURQWLXP7KUHHPDMRULQSXWVRXUFHVLQIOXHQFHWKHVWURQWLXPLVRWRSHFRPSRVLWLRQ

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GHULYHGIURPFRQWLQHQWDOZHDWKHULQJDQGVWURQWLXPRILQWHUPHGLDWH⁸⁷6U⁸⁶Sr ratios aRULJLQDWHVIURPVXEPDULQHGLVVROXWLRQDQGUHFU\VWDOOL]DWLRQRIFDUERQDWH

VHGLPHQWVFI>@7KH⁸⁷6U⁸⁶Sr ratio of continental strontium may have varied ZLWKFKDQJLQJSURSRUWLRQVRIYDULRXVW\SHVRIURFNVH[SRVHGWRZHDWKHULQJJUDQ- LWHVEDVDOWVRUPDULQHFDUERQDWHVFI>@&KDQJLQJDUHDVRIZHDWKHUHGURFNVGR

QRWKRZHYHUDSSHDUWRKDYHKDGDFRQVLGHUDEOHHIIHFWRQVHDZDWHU⁸⁷6U⁸⁶Sr ratio LQWKH0HVR]RLF>@7KHGHSHQGHQFHRIWKHVHDZDWHUVWURQWLXPLVRWRSHUDWLRRQ

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FI>@RQHFDQGHGXFHIURP)LJWKDWWKHVWURQWLXPLVRWRSHUDWLRRIVHDZDWHU

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4.55 Ga Time Present

MORB

0.7200

0.7100

0.7050 0.7025 Continental

crust

Bulk lithosphere

8786 Sr/Sr

0.6989 Primordial Earth

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)LJ0RGHORIVHDZDWHU⁸⁷6U⁸⁶Sr ratio regarded as a mixture of strontium contributed by WKH ZHDWKHULQJ RI FRQWLQHQWV VWURQWLXP FRQWULEXWHG E\ WKH K\GURWKHUPDO DFWLYLW\ RI WKH VHDIORRU

DQGGLDJHQHWLFVWURQWLXPGHULYHGIURPGLVVROXWLRQDQGUHFU\VWDOOL]DWLRQRIFDUERQDWHV'RWWHGOLQHV

represent different ⁸⁷6U⁸⁶6UUDWLRVRIVHDZDWHU'DVKHGOLQHUHSUHVHQWVPRGHUQGLDJHQHWLFVWURQWLXP

IOX[FI>@

The temporal seawater strontium isotope curve is characterized by several PD[LPDDQGPLQLPDWZRGHHSHVWPLQLPDRFFXULQWKH/DWH3HUPLDQDQGDWWKH

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An almost continuous increase of the seawater ⁸⁷6U⁸⁶Sr ratio has occurred since WKH/DWH&UHWDFHRXV)LJ

The seawater strontium isotope curve may be used to date marine sedimen- WDU\URFNVFI>@7KHVWURQWLXPLVRWRSHFRPSRVLWLRQRIIRVVLOVGHULYHGIURP

EUDFNLVKHQYLURQPHQWVLVDQLQGLFDWRURISDODHRVDOLQLW\FI>@7KHYDULDWLRQ

in the isotope composition of strontium may also be an indicator of diagenetic DOWHUDWLRQRIPDULQHURFNVDQGPD\DOORZTXDQWLI\LQJIOXLGURFNLQWHUDFWLRQVFI

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Continental Sr Sr/Sr = 0.711

87 86

Hydr otherm

al Sr Sr/Sr

= 0.

703

87 86

Diagenetic Sr Sr/ Sr = 0.708

87 86

0 10

20 30

40 50

60 70

80 90

100% 0 10

20 30

40 50

60 70

80 90

100%

0 10 20 30 40 50 60 70 80 90 100%

0.705 0.706 0.707 0.708 0.709

Modern

diag enetic S

r flux

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The aim of the present contribution is not to repeat information and interpre- tation of the ⁸⁷6U⁸⁶Sr data given elsewhere but focus on practical aspects of using VWURQWLXPLVRWRSHIRUGDWLQJRIPDULQHURFNVDQGWKHUHFRQVWUXFWLRQRIDQFLHQW

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from 200 to 10 000_SSPFI>@6WURQWLXPLVRWRSHFRPSRVLWLRQRIDQFLHQW

waters may be studied based on analyses of strontium preserved in authigenic min- HUDOV±FDUERQDWHVSKRVSKDWHVRUHYDSRUDWHV&DUERQDWHVDUHHVSHFLDOO\XVHIXOIRU

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Cenozoic Cretaceous

Jurassic Triassic Perm.

Carbon.

Devon.

Sil.

Ordov.

Cambr.

0.7095

0.7090

0.7085

0.7080

0.7075

0.7070

0.7065

0 Ma 50

100 150 200 250 300 350 400 450 500

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>@6HOHFWLYHGLVVROXWLRQWHFKQLTXHVLQZHDNDFLGVHJDFHWLFDFLGDUHUHF- ommended by some authors for impure samples to avoid dissolution of clay con- WDPLQDQWVRUGLDJHQHWLFPLQHUDOSKDVHV>@

Strontium isotope composition is traditionally reported as ⁸⁷6U⁸⁶Sr ratio be- FDXVHWKHUDWLRLVPHDVXUHGGLUHFWO\E\WKHUPDOLRQL]DWLRQPDVVVSHFWURPHWHUV%H- fore reporting measured ⁸⁷6U⁸⁶Sr ratios are normalized to a standard ⁸⁶6U⁸⁸Sr ratio RIWRDOORZIRUWKHIUDFWLRQDWLRQEHWZHHQ6U⁸⁶6U⁸⁷Sr and⁸⁸Sr isotopes GXULQJ PDVVVSHFWURPHWU\ DQDO\VLV ,Q RUGHU WR FRUUHFW IRU LQWHUODERUDWRU\ ELDV

ZKLFKLVFDXVHGE\LQVWUXPHQWDOHIIHFWVPHDVXUHG⁸⁷6U⁸⁶Sr ratios are normalized to the recommended ratios of isotope standards analysed along with studied sam- SOHV)RUWKHVWURQWLXPLVRWRSHVWUDWLJUDSK\WKHUHFRPPHQGHGUDWLRVRI1,67

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:KHUHDVWKHH[WHUQDOSUHFLVLRQRIWKHPHDVXUHPHQWRI⁸⁶6U⁸⁸Sr ratio of ±2Â10^-5 is DWWHVWHGLQROGHUVWXGLHV>@QHZODERUDWRU\DQGPDVVVSHFWURPHWU\WHFKQLTXHV

allow better precision of replicated strontium isotope analyses of ±3Â10^-6>@

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Strontium isotope composition of sedimentary rocks may be affected by dia- JHQHWLFDOWHUDWLRQ0DULQHURFNVDUHVXVFHSWLEOHWRH[SRVXUHDQGDOWHUDWLRQE\PH- WHRULFZDWHUVGXHWRWKHLUORZVWURQWLXPFRQFHQWUDWLRQDQGDVDUXOHKLJKVWURQ- WLXPLVRWRSHUDWLRVFI>@*RRGSUHVHUYDWLRQVWDWHRILQYHVWLJDWHG

samples is therefore FRQGLFLRVLQHTXDQRQ¹ for all chemostratigraphy applications DQGSDODHRUHFRQVWUXFWLRQVEDVHGRQVWURQWLXPLVRWRSHGDWD

Skeletal calcites can be screened for the state of preservation using chemical DQDO\VHVFDWKRGROXPLQHVFHQFHVWXGLHVDQGVWDLQLQJWHFKQLTXHV'LDJHQHWLFDOWHUD- tion often causes an increase in Fe and Mn contents of calcite and a decrease in its Sr contents as concentrations of these elements drastically differ between seawater DQGGLDJHQHWLFIOXLGVLQUHGXFHGRUIUHVKZDWHUHQYLURQPHQWV>@7KH

comparison between measured element concentrations and concentrations found in modern marine shells or predicted for intact marine calcites permits an assess- PHQWRIGLDJHQHWLFDOWHUDWLRQ6RPHSUREOHPVPD\DULVHEHFDXVHYDULRXVDXWKRUV

indicate different threshold levels of element concentrations in well-preserved VNHOHWRQVRIH[WLQFWRUDQFLHQWRUJDQLVPVVHH7DEOHV

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Mn (ppm) Fe (ppm) Sr (ppm)

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Mn²⁺ ions are also an activator of orange-red cathodoluminescence that is dis- tinctive of diagenetically altered calcites but high Fe²⁺ contents may quench their OXPLQHVFHQFH>@6LQFHSULPDU\VKHOOFDOFLWHLVQRWSUHFLSLWDWHGLQUHGXFLQJ

environments where Mn²⁺LVDYDLODEOHWKHOXPLQHVFHQFHLVLQGLFDWLYHRIWKHVKHOO

UHFU\VWDOOL]DWLRQ)LJ%DUELQDQG*DVSDUG>@VKRZHGKRZHYHUWKDWOXPL- nescent bands may occur in modern brachiopod shells in areas of slow growth rate FKDUDFWHUL]HG E\ GLVWRUWLRQ RI FU\VWDO ODWWLFH 6RPH DXWKRUV DGGLWLRQDOO\ UHFRP- mend staining thin sections made from calcitic fossils with potassium ferricyanide and alizarine red-S to screen for the replacement of Ca²⁺ by Fe²⁺FI>@7KLV

is because of the fact that calcite zones with higher iron contents due to its quench- LQJSURSHUWLHVFDQQRWEHREVHUYHGXVLQJFDWKRGROXPLQHVFHQFHVWXGLHV

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brachiopod shells

Mn (ppm) Fe (ppm) Sr (ppm)

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Low-magnesium calcite is relatively insoluble therefore shows high potential IRUWKHSUHVHUYDWLRQRIRULJLQDOVWDEOHLVRWRSHUDWLRV>@:HOOSUHVHUYHGEHOHP- QLWHURVWUDR\VWHULQRFHUDPLGDQGEUDFKLRSRGVKHOOVDOORIZKLFKDUHFRPSRVHG

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GLDJHQWLFDOO\DOWHUHGVDPSOHV3UHOHDFKHGWHFKQLTXHVHOHPHQWDODQDO\VLVPLFUR- structure observation and comparisons to the ⁸⁷6U⁸⁶Sr ratios of coeval samples from different sites and localities were employed to increase the reliability of bulk URFNGDWDFI>@5HOLDEOH&HQR]RLFVWURQWLXPLVRWRSHGDWDDUHGHULYHG

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Fossil biogenic apatites can be recrystallized during early or late stages of GLDJHQHVLV'LDJHQHWLFDOO\DOWHUHGILVKWHHWKDUHUHSRUWHGWRVKRZDOWHUHGPLFUR- VWUXFWXUH>@VWURQJHQULFKPHQWLQLQWHUPHGLDWHUDUHHDUWKHOHPHQWV³EHOOVKDSHG

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REE enrichment is also reported to activate orange-brown cathodoluminescence RIWHHWK>@&RQRGRQWVFDQEHVFUHHQHGIRUWKHVWDWHRISUHVHUYDWLRQE\VWXG\LQJ

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exchange Sr isotopes with pore waters the reliability of conodont and fish tooth

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isotope composition of well-preserved dental apatitesis also found to be a proxy IRUDQFLHQWZDWHUFKHPLVWU\FI>@

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WKH⁸⁷6U⁸⁶Sr ratios of well-preserved samples may be used to date and correlate PDULQHVHGLPHQWV&RPSDULVRQRIPHDVXUHG⁸⁷6U⁸⁶Sr ratio to previously construct- HGWHPSRUDOFDOLEUDWLRQFXUYHVFDQ\LHOGVWUDWLJUDSKLFDORUQXPHULFDODJHV7KH

precision of the strontium isotope dating depends on the analytical precision of an LVRWRSHPHDVXUHPHQWFRQILGHQFHOLPLWVRIDFDOLEUDWLRQFXUYHDQGLWVVORSH)LJV

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Altered samples show higher and scattered ⁸⁷6U⁸⁶6UUDWLRV$OOYDOXHVDUHQRUPDOL]HGWRWKH650

987 ⁸⁷6U⁸⁶6UUDWLRRI

0.707434

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LateBajocian EarlyBathonian MiddleBathonian LateBathonian EarlyCallovian MiddleCallovian LateCallovian

ChronSubstage

1

1 1

1 2 22 2

1 1

1 1 8786 Sr/Sr

168.3 1.3 Ma± 166.1 1.2 Ma± 163.5 1.1 Ma±

2

95% confidence limits 1 Lowess fit dating error data from Callomon and Dietl (2000)

data from Jones et al. (1994)

data from Wierzbowski et al. (2012)

Diagenetically altered samples:

data from Jones et al. (1994) data from Podlaha et al. (1998) Well-preserved samples:

2 1 0.70715

(9)

Seawater strontium isotope curves have been constructed for several strati- JUDSKLFDOLQWHUYDOVE\YDULRXVDXWKRUVHJ>

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Strontium isotopes can be used to determine palaeosalinities of ancient brackish waters owing to differences in strontium isotope ratios and concentrations EHWZHHQHQGPHPEHUV±VHDZDWHUPRGHUQ⁸⁷6U⁸⁶6U PRGHUQ&_Sr= 90 ȝPRONJ>@DQGIUHVKZDWHUVPRGHUQDYHUDJH⁸⁷6U⁸⁶6U PRG- ern average C_Sr ȝPRONJ>@7KHULYHULQHVWURQWLXPLQSXWGHSHQGVRQ

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draining young volcanic arcs show low ⁸⁷6U⁸⁶Sr ratios and high strontium con- FHQWUDWLRQV ZKHUHDV ULYHUV GUDLQLQJ FRQWLQHQWDO EDVLQV ILOOHG ZLWK VHGLPHQWDU\

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The strontium isotope composition of brackish waters forms a hyperbolic re- ODWLRQVKLSWRVDOLQLW\DQGWKHVDOLQLW\FDQQRUPDOO\EHUHVROYHGLQWKHORZHUSDUWRI

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ZKHUH⁸⁷6U⁸⁶6U_%:⁸⁷6U⁸⁶6U_6:⁸⁷6U⁸⁶6U_): are strontium isotope ratios of brac- NLVKZDWHUVHDZDWHUDQGIUHVKZDWHUUHVSHFWLYHO\C_6: and C_): concentrations of VWURQWLXPLQVHDZDWHUDQGIUHVKZDWHUUHVSHFWLYHO\

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URFNVLQGUDLQLQJDUHD$QRPDORXVO\KLJK⁸⁷6U⁸⁶Sr ratios and Sr concentrations of Avon and Mur- FKLQVRQULYHUVUHVXOWIURPHYDSRUDWLYHFRQFHQWUDWLRQRIVWURQWLXP+LJK⁸⁷6U⁸⁶Sr ratios and Sr con- FHQWUDWLRQVLQ*DQJHVDQG%UDKPDSXWUDUHVXOWIURPODUJHVHGLPHQWORDGIURP+LPDOD\D0RXQWDLQV

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S)_%: is a salinity factor of brackish water calculated as a fraction of freshwa- WHUDQGVHDZDWHUIURPDEVROXWHVDOLQLWLHVDFFRUGLQJWRDQHT

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(11)

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C_Sr ȝPRONJDQGVHDZDWHUV⁸⁷6U⁸⁶6U DQG&_Sr= 90_ȝPRONJ on ⁸⁷6U⁸⁶6UUDWLRVRIEUDFNLVKZDWHU0HDVXUDEOHHIIHFWVDWǻ⁸⁷6U⁸⁶6URIRFFXUDWVDOLQLWLHV

EHORZÅ

The chemistry of end-members may be assumed as similar to modern ana- ORJXHV IRU UHODWLYHO\ \RXQJ VHGLPHQWV > @ DQG EH UHFRQVWUXFWHG IURP WKH

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@0HDVXUDEOHHIIHFWVRIVDOLQLW\RQ⁸⁷6U⁸⁶Sr ratios do not allow precise re- FRQVWUXFWLRQRIVDOLQLW\LQSRO\KDOLQHRUHXKDOLQHHQYLURQPHQWVZLWKVDOLQLW\

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VWURQWLXPUDWLRVFI)LJVHHDOVR:LHU]ERZVNLHWDO>@7KHVLPSOHWZRHQG

members mixing models are also not valid in evaporation-dominated basins due WRWKHHYDSRUDWLYHLQFUHDVHLQZDWHUVDOLQLW\>@

675217,80,62723(6$6$75$&(5

2)',$*(1(7,&352&(66(6

Since ⁸⁷6U⁸⁶Sr ratio of marine carbonates is affected by diagenetic fluids it can EHXVHGDVWUDFHURIWKHLUDOWHUDWLRQ'LDJHQHWLFLQWHUDFWLRQVEHWZHHQSRUHIOXLGV

and marine rocks lead to the re-equilibration of original element and isotope com-

0,707000

0.712

0

Salinity [‰]

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 0.711

0.710

0.709

0.708

8786 Sr/Sr

87Sr/ Sr86 _seawater = 0.709174

87Sr/ Sr86 _seawater = 0.708000

87Sr/ Sr86 _seawater = 0.707000

Minimal measurable effect of salinity on Sr/ Sr ratio⁸⁷ ⁸⁶

12‰

14‰

16‰

(12)

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An increase in ⁸⁷6U⁸⁶Sr ratios of aragonite ammonite shells was reported to be caused by the adsorption of diagenetic strontium on aragonite with minor altera- WLRQRIWKHRULJLQDOVKHOOFKHPLVWU\>@'HSOHWLRQVLQ⁸⁷6U⁸⁶Sr ratios of marine carbonates resulting from the non-typical alteration by hydrothermal fluids have EHHQREVHUYHGLQEHOHPQLWHURVWUDIURP&DQDGDDQG1HZ=HDODQG>@7KH

876U⁸⁶Sr ratios of the belemnite rostra have also been used as a precise and inde- SHQGHQWGLDJHQHVLVWUDFHULQWKHPLFURRUPDFURVFDOH>@

)LJ0RGHOOHGR[\JHQDQGVWURQWLXPLVRWRSHYDULDWLRQVGXULQJUHFU\VWDOOL]DWLRQRIDPDULQH

OLPHVWRQHE\IUHVKZDWHU:DWHUURFNUDWLRV1DUHVKRZQDWJLYHQVWDJHVRIWKHLQWHUDFWLRQSDWKV

7KHRULJLQDOOLPHVWRQHLVDVVXPHGWRKDYHį¹⁸2 Å93'%⁸⁷6U⁸⁶6U &_Sr SSP

SRURVLW\ WKHIUHVKZDWHUFRPSRVLWLRQLVį¹⁸2 Å9602:⁸⁷6U⁸⁶6U &_Sr

SSP7recrystallization &DIWHU%DQQHU>@ 4

0

-4

-8

ä18 O [‰]

87Sr/ Sr86

0.708 0.709 0.710

0.4

N = 410 Marine

limestone

Diagenetic limestone 50%

Water-rock interaction K = 0.15_D^Sr

Mixing of mineral end-members

1.3

į180 [‰]

(13)

&21&/86,216

The present study aims to present the most popular applications of strontium LVRWRSHVLQFKHPRVWUDWLJUDSK\VDOLQLW\UHFRQVWUXFWLRQRUVFUHHQLQJRIGLDJHQHWLF

SURFHVVHVLQPDULQHRUEUDFNLVKVHGLPHQWV7KHVXPPDU\RIWKHPHWKRGVDQDO\WL- FDOSUREOHPVDQGWKHLQWHUSUHWDWLRQVPD\EHKHOSIXOIRU3K'VWXGHQWVDQGJHROR- JLVWV,WPD\DOVRFRQWULEXWHWRWKHZLGHUXVHRIVWURQWLXPLVRWRSHVLQ(DUWKVFL- HQFHVWRVROYHGDWLQJDQGSDODHRHQYLURQPHQWDOSUREOHPV

Further less common aspects of strontium isotope geochemistry in marine URFNVLHLWVXVHWRGHFLSKHUJOREDOZHDWKHULQJDQGK\GURWKHUPDOIOX[HVWRDQD- O\VHZDWHUH[FKDQJHLQLVRODWHGEDVLQVWRWUDFHPLJUDWLRQRIGLDGURPRXVILVKHV

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