O R I G I N A L P A P E R
B. KoberÆ A. KaltÆM. HanelÆR. T. Pidgeon
SHRIMP dating of zircons from high-grade metasediments
of the Schwarzwald/SW-Germany and implications for the evolution of the Moldanubian basement
Abstract Four metasedimentary zircon populations from different tectonometamorphic units of the Central and the Northern Schwarzwald (Variscan belt, SW- Germany) were investigated using SEM, cathodolumi- nescence and SHRIMP dating. Despite partially strong modifications of primary internal morphologies during Variscan metamorphism at amphibolite (750C, 0.4–
0.6 GPa) and granulite-facies conditions (950–1,000 C, 1.4–1.8 GPa), many grains show well-preserved proto- lith ages. The detritus indicates a northern Gondwana origin and different Palaeozoic episodes of sediment deposition and consolidation. Two of the studied sedi- ments were deposited in Cambrian/early-Ordovician times and consolidated in positions close to northern Gondwana. Late Ordovician and rare Devonian detritus from sediments of two other tectonometamorphic units indicates much later sedimentation close to the leading edge of Gondwana or a terrane assemblage during northern drift towards Laurussia. Subsolidus growth of new zircon due to Variscan granulite facies metamor-
phism of one of the tectonometamorphic units is pre- cisely dated at 335±2 Ma.
Introduction
Single zircon dating is a powerful tool for investigating sediment provenances and estimating sedimentation ages (e.g. Aleinikoff et al. 1988; Lork et al. 1990; Robb et al. 1990; Davis et al. 1990; Ross et al. 1991; McLen- nan et al. 2001). Where sedimentary sources have suit- able lithological characteristics it is possible to constrain the duration of sedimentation episode(s) by evaluating the detrital zircon age distribution (e.g. Nelson 2001).
Detritus ages and times of sediment deposition are important for discussions of sediment sources and con- tinental drift models (e.g. Gebauer et al. 1989; Nance and Murphy 1996; Friedl et al. 2000). Sediment prove- nance and sedimentation ages are crucial to unravelling the orogenic and pre-orogenic history of mountain belts.
In the Variscan fold belt detritus ages have been suc- cessfully used to detect ancient terranes and to recon- struct the geodynamic and geotectonic evolution of Europe during the Palaeozoic (e.g. Franke 2000; Hegner and Kro¨ner 2000; Linnemann et al. 2000; So¨llner et al.
1997; Tichomirova et al. 2001; von Raumer et al. 2002, 2003). The contribution of detrital zircon dating is most important in the understanding of the internal parts of orogens where complex internal nappe structures and high-grade metamorphism often impede the application of palaeomagnetic, stratigraphic and palaeontological methods. In the Variscan belt, however, there are only few studies of detrital components from high-grade metasediments (e.g. Zeh et al. 2001). The present work focuses on detrital zircon ages from high-grade meta- morphic sediments of the Schwarzwald as part of the internal Variscan belt. We will show that even zircons from granulite-facies metasediments can serve to char- acterize sediment provenance and to constrain the premetamorphic evolution of these rocks.
B. Kober (&)
Institut fu¨r Umwelt-Geochemie, Ruprecht-Karls-Universita¨t, Im Neuenheimer Feld 236, 69120 Heidelberg, Germany
E-mail: bernd.kober@urz.uni-heidelberg.de A. Kalt
Institut de Ge´ologie, Universite´ de Neuchaˆtel, Rue Emile Argand 11 / CP 2,
2007 Neuchaˆtel, Switzerland M. Hanel
Mineralogisches Institut, Ruprecht-Karls-Universita¨t, Im Neuenheimer Feld 236, 69120 Heidelberg, Germany R. T. Pidgeon
Curtin University of Technology, GPO Box U1987, 6845 Perth, WA, Australia
which should be used for any reference to this work
Geodynamic and palaeogeographic context
The Variscan fold belt can be traced from the Appala- chian and Ouitchita Mountains in the west via Europe to the Caucasus in the east. It formed by Devonian to Carboniferous accretion and collision processes between Laurussia in the north, Gondwana in the south and different terranes and microcontinents in between. The latter are generally seen as derived from the northern margin of Gondwana (e.g. Franke 2000; von Raumer et al. 2002) during Palaeozoic rifting events. From the Neoproterozoic to the Ordovician, they are viewed as an EW-trending belt comprising from west to east Avalo- nia, the Amorican terrane assemblage (ATA) and the Cadomian terranes, the future Alpine realm, and parts of future Asia (e.g. Scotese and McKerrow 1990, Tait et al. 1994, 1995; Stampfli et al. 2002, von Raumer et al.
2002, 2003). In the Silurian, Avalonia had already col- lided with the northern continents, whereas the other parts of the belt remained close to Gondwana. The subsequent motion of the microplates and opening or
closure of ocean basins has been modelled by alternative concepts (e.g. Scotese and McKerrow 1990; Tait et al.
2000; Matte 2001; Cocks and Torsvik 2002; Stampfli and Borel 2002). For a critical discussion e.g. of the Armo- rica microplate concept we refer to Robardet (2003) and references therein.
In central Europe, the isolated Variscan basement outcrops found today have been divided into several EW-trending zones according to their grade of meta- morphism and their magmatic intrusions (Kossmat 1927). Within this scheme, the southern margin of the Northern Phyllite Zone is thought to represent the Rheic suture, separating the Avalonia-derived Rhenohercy- nian Zone in the north from the Armorica- or Hun-derived Mid-German Crystalline High and the Saxothuringian and Moldanubian zones in the south (Fig. 1). However, due to large-scale lateral transfer and escape along the Eurasian margin in Carboniferous times (Stampfli et al. 2002) these zones do not necessarily correspond to ancient terrane boundaries. Also, the pre- Variscan provenance of the predominantly high-grade
Fig. 1 Sketch map showinga the position of the Schwarzwald and other units in the crystalline basement rocks of Central Europe;bthe Central Schwarzwald Gneiss Complex (CSGC) and the northern Schwarzwald (Omerskopf, OGC), tectonometamorphic units of the Central Schwarzwald basement, and sample locations. (SSGC Southern Schwarzwald Gneiss Complex)
Saxothuringian and Moldanubian zones is only poorly understood. Within this context, the Schwarzwald and the Vosges in the southwestern part of the Moldanubian zone are of particular interest. Geographically, they are located between the Armorican Massif, classically con- sidered to represent the terrane Armorica, and the Moldanubian zone of the Bohemian Massif, seen as a more easterly part of the European Hunic terrane by several authors (Stampfli et al. 2002; von Raumer et al.
2002). Lithologically, apart from granites, the Sch- warzwald and Vosges are dominated by high-grade metamorphic gneisses and migmatites.
Geological setting and samples
The samples for this study were taken from the Central Schwarzwald Gneiss Complex (CSGC) and the Omers- kopf Gneiss Complex (OGC). Both complexes belong to the southwestern part of the Moldanubian zone (e.g.
Franke 2000, Fig. 1). On the basis of metamorphic grade, lithology and high-grade metamorphic relics the CSGC was divided into three different tectonometa- morphic units (Hanel and Wimmenauer 1990; Hanel et al. 1999; Fig. 1). Unit 1 of the CSGC is dominated by paragneisses and migmatites with relics of eclogite-facies and mantle-derived rocks. Unit 2 consists of more var- iegated gneisses and is devoid of high-pressure relics, but with rare evidence for an older medium-pressure med- ium-temperature stage (Rehfeld 1983). Unit 3 is char- acterized by granulite-facies relics and rare eclogites and mantle-derived rocks, and is mainly found in the northern part of the CSGC (Fig. 1, Hanel et al. 1993).
Peak equilibration conditions of the granulites were approximately 950–1,000 C and 1.4–1.8 GPa, and the entire unit is interpreted as part of the lower crust of a hanging continental plate in a convergent Variscan set- ting (Marschall et al. 2003). While Unit 1 is in the tec- tonically uppermost position, there is some evidence that Unit 3 overlies Unit 2 (Kalt et al. 2000). All three units were subjected to a final high-temperature low-pressure metamorphic event at about 330 Ma (Kalt et al. 1994;
Lippolt et al. 1994), with P–T conditions of 730–780C and 0.42–0.45 GPa (Kalt et al. 2000). The pre-meta- morphic history and the depositional conditions of the metasediments in the Schwarzwald are very roughly constrained by palynological data (Montenari 1996;
Hann and Sawatzki 1998; Hanel et al. 1999; Montenari et al. 2000), which are consistent with sediment deposi- tion in Neoproterozoic to Early Palaeozoic marine environments. The genetic relations between the me- tasediments hosted in the tectonometamorphic units, the timing of sediment deposition, and the palaeogeographic positions of the corresponding marine basins are yet unknown.
For this study, three paragneiss samples were selected to represent the tectonometamorphic Units 1–3 (Fig. 1):
St-4-1 (Unit 1), SB-22 (Unit 2), 91-1c (Unit 3). A fourth sample (OM-3-2,Fig. 1) was taken from the OGC. The
relation of the OGC to the CSGC units is unclear be- cause it is separated from the main part of the CSGC by Carboniferous granites and shear zones. While sample 91-1c is a pelitic garnet-cordierite-sillimanite gneiss, the other investigated rocks are plagioclase-biotite-quartz gneisses, probably derived from greywackes (Mu¨ller 1989).
Analytical procedures
Zircon grain size fractions were separated from 2–4 kg of each of the rock samples following routine preparation procedures. Several hundred zircon grains from the 100–200lm size fraction were embedded in epoxy resin for a comprehensive SEM and cathodo- luminescence (CL) documentation of the internal grain morpho- logies. This documentation was a prerequisite for the recognition of zircon subpopulations in the investigated rocks, for the preselection of grains representative of the distribution of zircon phases in the different zircon populations, and for the choice of suitable spot locations on the polished internal surfaces of the grains selected for ion probe analysis (SHRIMP, Compston et al. 1984). The proce- dures applied for the U-Th-Pb isotope analyses using the SHRIMP II instrument at Curtin University/Perth-Australia are described in detail e.g. by Nemchin and Pidgeon (1997) and by De Laeter and Kennedy (1998). Fragments of the gem Sri Lankan zircon CZ3 were embedded in the mounts together with the sample zircons and used as a standard reference (Pidgeon et al. 1994). A206Pb/238U value of 0.0914 corresponding to an age of 564 Ma was used for the calculation of ages. Data were reduced using the Perth in-house programs (Kinny, personal communication) and the ISOPLOT program of Ludwig (2000). Broken Hill Pb isotope composition was assumed for the common Pb correction, according to the composition of the applied gold coating of the mounts.
Reproducibility of the normalizing standard U/Pb ratio ranged between 1.5 and 2.3% for the different data sets. Errors given in Table 1 and in the data plots (Fig. 2) are overall errors on the one sigma standard deviation level, including counting statistics,204Pb- correction and the U/Pb ratio reproducibility calculated from the repeated U/Pb measurements of the standard fragments.
Results
SHRIMP results are presented in Table 1 and on con- cordia plots in Fig. 2. CL images of representative grains with SHRIMP analytical spots are shown on Fig. 3.
Morphological comparisons
It can be seen that the investigated zircon populations are complex, with subpopulations consisting of euhedral grains with characteristic oscillatory or sector zoning, and rounded or irregularly shaped grains with irregular or patchwork-like internal zoning. Many grains show core/rim associations, and/or have patchy zones with enhanced luminescence. The preservation of euhedral crystal shapes in the sedimentary subpopulations is striking. A common feature of all the investigated pop- ulations is frequent partial modification and obliteration of igneous oscillatory zoning, and the generation of secondary internal structures, showing transgressive recrystallization with recrystallization fronts and
Table1U-PbSHRIMPdataoffourmetasedimentaryzirconpopulationsfromtheSchwarzwald.IsotoperatiosarecorrectedforcommonPbusingthe204 Pb-concentration.%conc %concordance=100x(age206 Pb/238 U)/(age207 Pb/206 Pb).Errorsareatthe1sigmastandarddeviationlevel.ccore;rrim;ozoscillatoryzoning;szsectorzoning;wlweakluminescence; wilweakirregularluminescence;slstrongluminescence;spshortprismatic;lplongprismatic;rorounded SpotCommentU/ppmTh/ppmTh/UPb/ppm207/206-4+/-208/206-4+/-207/235-4+/-206/238-4+/-% concAge 206/238+/-Age 207/235+/-Age 207/206+/- SampleSt-4-1.‘‘unit1’’ st41-6-1aoc,oz,sp72200.27470.05250.00680.05960.01640.61580.08220.08510.00181725271148752306270 st41-6-1boc,oz,sp99300.30690.05770.00110.09690.00210.73360.02170.09230.0019110569115591351742 st41-6-1cr,oz77230.29870.05490.00630.07890.01510.68460.08180.09040.00201375581253049408259 st41-14-1aoz,lp1821040.572190.06030.00140.18470.00360.80070.02570.09620.001896592115971461651 st41-16-1awl,ro2,5269080.3591850.05480.00040.16040.00210.52170.01070.06910.00121074317426740318 st41-16-1bwl,ro2,1974440.2021450.05300.00080.05830.00230.47360.01210.06490.00121244057394832736 st41-16-2ac,sz,sp174620.359160.05790.00130.10930.00300.71850.02170.09000.0017106555105501352648 st41-16-3ac,oz,sp3771550.409360.05970.00080.12680.00190.77660.01830.09430.001798581105841059328 st41-17-1awl,lp9521,4461.5181170.05900.00040.46210.00170.76060.01510.09350.001710157610574956815 st41-18-1ac,sl,sz156880.563160.05930.00160.17610.00400.77980.02710.09540.0018102588115851557758 st41-18-1br,sl,oz99340.342100.06230.00260.11380.00600.82210.03920.09570.001986589116092268588 st41-18-2awl3511870.534360.06010.00100.16810.00260.79410.02100.09580.001797590105941260737 st41-18-2bil3001430.477310.05910.00100.14440.00260.79950.02130.09810.0018106603105971257138 st41-18-2cil,sp152530.349150.05670.00210.09630.00510.76650.03400.09800.0018125602115782048284 st41-19-1aoz,wl,sp1,5082,3791.5771690.05760.00030.50650.00160.65830.01270.08290.00151005149514851413 st41-19-1boz,wl,sp1,0235450.5331010.05890.00040.16260.00110.76360.01510.09400.001710357910576956415 st41-19-2aoz,lp2881290.448280.05890.00120.13700.00300.76650.02270.09430.0017103581105781356446 st41-19-2boz,lp3721410.378360.05830.00080.11400.00200.76770.01890.09550.0017109588105781154132 st41-19-3ac,wil,sp383600.158330.06120.00090.04950.00190.76250.01890.09040.001786558105751164630 st41-19-4awill,lp5521730.313530.05950.00060.09650.00130.79650.01700.09710.0017102597105951058521 st41-20-1aoz,lp2271100.483230.06040.00200.14680.00490.77700.03120.09330.001893575105841861772 st41-20-1boz,lp2391090.458270.05550.00420.14260.01010.66850.05330.08730.00171255401052032433168 st41-20-1coz,lp2261070.474230.05770.00200.13510.00480.76750.03150.09650.0018115594115781851775 st41-20-2ac,il227630.277220.05990.00140.08340.00340.80850.02590.09790.0018100602116021560152 st41-20-2boc,oz9281150.124840.05940.00040.03630.00090.78820.01590.09630.001710259210590958116 st41-20-2cr,oz,sp1891360.721210.05520.00190.21080.00490.74010.03070.09720.0018142598115621842278 st41-20-3awl4722690.570480.05900.00090.17930.00230.76040.01890.09350.0017102576105741156632 st41-20-3boz,sp4391520.346420.06060.00070.10670.00150.79850.01770.09550.001794588105961062623 st41-22-1aoz,lp7841930.247710.05770.00080.07210.00170.73190.01870.09190.0018109567115581152031 st41-22-1boz,lp523650.124460.05670.00090.03440.00210.71320.01850.09130.0016118563105471147837 st41-22-2ac,sz,sl551202.19080.05840.00390.66390.01290.74890.05520.09310.00201055741256832544148 st41-22-2br,oz1,967940.0481510.05660.00070.01170.00160.61730.01410.07900.00141034908488947827 st41-22-2cr,oz,sp706420.060620.05830.00060.01750.00120.76300.01680.09490.0017108585105761054123 st41-23-1ac,oz3581940.5411080.11700.00050.16720.00104.38590.08300.27200.0049811,551251,7101619107 st41-23-1br,wl,ro1,288470.0371270.06160.00050.00990.00090.90180.01820.10620.001999651116531065916 st41-24-1aoz,lp5212110.405480.05750.00090.12180.00210.71860.01800.09060.0016109559105501151233 st41-24-1boz,lp312610.196270.05600.00150.05070.00350.68800.02340.08910.0016122550105321445259 st41-25-1awl3872860.738420.05940.00080.22390.00220.79690.01900.09740.0018103599105951158029 st41-25-2ar,wl,sp2,0147820.3882060.06010.00040.11420.00100.82620.01630.09960.001810161210611960815 st41-25-2bc,il4833610.748640.05890.00230.21770.00590.86260.03980.10620.0020115651126322256486 st41-25-3asz,sp199630.315210.06100.00070.09480.00150.89090.02030.10600.0020102649126471163824 SampleOM-3-2.OGC om32-12-1aoz,sp6302850.452620.05810.00080.13420.00190.76180.02000.09510.0020110586125751253329 om32-12-2aoz,sp4371360.311400.05960.00070.09880.00170.74980.01920.09120.001995563115681159027 om32-14-1aoz,sp4653290.708480.05870.00070.22910.00200.74810.01910.09240.0019102570115671155727
Table1(contd.) SpotCommentU/ppmTh/ppmTh/UPb/ppm207/206-4+/-208/206-4+/-207/235-4+/-206/238-4+/-% concAge 206/238+/-Age 207/235+/-Age 207/206+/- om32-14-2aoz,sp322240.076280.05850.00080.02180.00150.75780.01970.09390.0020105579125731154928 om32-14-3aoc,oz,hl65330.500410.19850.00100.13800.001614.86060.34220.54290.0118992,796492,806222,8149 om32-14-3boc,oz,hl,sp92430.466530.19800.00090.12840.001313.87250.30950.50820.0108942,649462,741212,8107 om32-16-1asl,sp18201.12070.10360.00550.33580.01324.08400.25440.28590.0075961,621381,651511,69099 om32-17-1aoz6432540.395610.05800.00070.12630.00170.73870.01870.09230.0019107569115621153026 om32-17-1boz,sp5811520.261440.05160.00130.07480.00290.54530.02070.07660.0020177476124421426956 om32-19-1aoz,sp124810.649130.05290.00220.18480.00550.67610.03340.09270.0020177572125242032395 om32-21-1aoz4681830.391450.05810.00080.11580.00190.75690.01980.09450.0020109582125721153229 om32-21-1boz,lp1,2943940.3041200.05820.00060.09220.00130.73770.01750.09190.0019105567115611053821 om32-23-1aoc,oz,sp3882260.5831880.15350.00060.16480.00079.04200.19570.42720.0089962,293402,342202,3857 om32-23-3aoz,sp3,4782800.0812940.05870.00020.02420.00020.73500.01550.09090.00191015611155995546 om32-24-1ac,oz,sp1981160.583200.05950.00180.17880.00460.76960.03050.09390.002099578125801858466 om32-24-3ac,sz,sp168750.446160.06140.00170.13870.00400.77350.02850.09140.002086564125821665258 om32-24-4ac,il149810.544870.18520.00140.14610.001213.05500.31000.51130.0110992,662472,684222,70013 om32-24-4bc,il,sp352550.1561030.12840.00050.04630.00075.10090.11160.28810.0060791,632301,836192,0767 om32-24-6awl,sz2391000.417220.06050.00130.12780.00300.76710.02420.09190.002091567125781462345 om32-26-1ar,oz1,6074560.2841440.05800.00040.08520.00090.72710.01670.09090.0019106561115551053016 om32-28-aoz123730.595130.05970.00340.18220.00830.74860.04710.09100.0020955611256727593122 om32-28-boz109530.488100.05930.00310.15050.00750.73610.04330.09010.0020965561256025577112 om32-28-coz173440.255150.05870.00170.07500.00390.72770.02750.09000.0020100555125551655562 om32-28-doz,lp115460.400110.05580.00280.11650.00670.67950.03900.08830.00201235461252624444112 U-richOM-3-2subgroupwithweakluminescence om32-14-4ail,sp1,8497880.4261780.05880.00020.12720.00060.76400.01640.09420.00191045801157695609 om32-16-2awil,ro2,7363800.1391320.05480.00080.02520.00190.36060.00960.04780.0010753016313740233 om32-16-2bwil,ro2,4021340.0561230.05380.00070.01580.00170.38640.01000.05210.0011903277332736330 om32-17-2awil,ro2,2241350.0611420.05730.00080.03160.00170.51610.01360.06530.0014814088423950429 om32-21-2awl,ro1,1343300.2911030.05840.00040.09230.00090.73500.01650.09120.0019103563115591054615 om32-21-3awl,ro3,2031,2640.3952790.05810.00050.10950.00110.66330.01530.08280.00179651310517953318 om32-23-2awl1,7795150.2891300.05700.00030.11330.00070.57090.01240.07260.0015924529459849211 om32-23-2bwl1,3545790.4271280.05880.00030.12940.00080.74540.01650.09200.0019102567115661055812 om32-23-4awl8394150.495790.05880.00050.15430.00120.72650.01680.08960.001999553115541055918 om32-24-2awil,ro2,8041560.0561710.05330.00110.02270.00270.44480.01400.06060.001311137983741034048 om32-24-5awil,ro2,6794450.1662100.05810.00050.05800.00110.63630.01470.07950.00169349310500953318 om32-24-7awil2,0464200.2051340.05500.00040.08830.00100.50150.01150.06620.00141014138413841118 om32-24-7bwil,sp3,0501,3250.4342570.05790.00030.17730.00100.63020.01380.07900.00169349010496952511 om32-26-2awil,ro2,6643110.1171790.05670.00070.02810.00150.52950.01310.06780.0014884238431947925 om32-27-1awil4,1104350.1062490.05450.00080.03030.00180.43860.01160.05840.0012943667369839131 om32-27-1bwil2,4664690.1902050.05660.00040.06070.00100.65760.01510.08430.001711052210513947617 om32-27-1cwil,sp3,7888350.2202870.05450.00090.06030.00220.50080.01410.06670.001410741684121039038 SampleSB-22.‘‘unit2’’ sb22-1-6ac,wl,ro3,6412,0110.5523750.05980.00020.16800.00060.80060.00950.09720.0010100598659755959 sb22-2-1ac,sl177590.336140.05140.00310.08850.00750.54570.03480.07700.0010186478644223257140 sb22-2-1br,oz,sp1,8533510.1891350.05630.00040.05510.00080.58980.00780.07590.00081014725471546514 sb22-2-2aoz5671830.323520.05750.00080.09550.00180.72950.01360.09210.00101115686556850930 sb22-2-2bil,sp7751880.242540.05470.00110.01440.00260.55040.01370.07290.00081134545445940247 sb22-2-3ac,oz8654910.568810.05830.00060.17930.00160.70610.01150.08780.00101005436542754223 sb22-2-3boc,oz4071370.337370.05750.00110.10100.00260.71150.01680.08970.001010855465461051142 sb22-2-3cr,oz,lp5232050.392400.05470.00140.10880.00330.55500.01620.07360.000811545854481139957
sb22-3-1ac,il,ro7841640.209820.06040.00050.06340.00100.89580.01320.10760.00121076597649761819 sb22-3-2aoz2461460.593190.05290.00220.17270.00540.52770.02330.07230.000913845054301532693 sb22-3-2boz,sp5782130.368420.05440.00110.10680.00270.54080.01360.07210.00081164495439938747 sb22-3-3ac,sz,sp1711821.064200.05740.00190.31920.00530.75640.02810.09570.001211758975721650573 sb22-5-1ac,sl63220.35490.07120.00380.12490.00911.30270.07530.13260.0020838031284733964110 sb22-5-1br,oz,lp486220.045450.05670.00090.00930.00200.78060.01650.09980.00111276137586948236 sb22-5-2aoc,wl5842820.4843150.18430.00060.13140.000612.12180.14240.47690.0052932,514232,614112,6925 sb22-5-2boc,wl6003450.5762700.15840.00050.15650.00078.67500.10260.39720.0044882,156202,304112,4395 sb22-5-2cr,oz,sp16850.02790.05110.00220.01150.00490.42030.01920.05970.000815337453561424597 sb22-5-3ac,wl1,4321880.1311290.05930.00040.03840.00080.77800.01050.09510.00101015866584657915 sb22-9-1awl2,2632,6921.1903980.04850.00560.08090.01380.44530.05280.06660.0008332415537437125253 sb22-11-1aoz2801050.376670.10010.00080.11520.00173.10330.04630.22480.0026801,307141,434111,62615 sb22-11-1boz249580.233310.08160.00140.07900.00291.36680.02980.12150.0015607398875131,23533 sb22-11-1coz,sp1,0613970.374830.05600.00070.11270.00160.59450.01020.07700.00081064785474645126 sb22-11-2ac,sz137530.390140.05690.00270.10520.00640.76610.03840.09760.0013123600857822488103 sb22-11-2br,il,sp5601570.281430.05850.00100.09650.00230.62750.01360.07780.0009884835495854837 sb22-13-1awil2,545560.0221610.05520.00060.00500.00130.51570.00850.06770.00071004235422642125 sb22-13-3aoc,oz119520.43790.05510.00350.13000.00840.56170.03700.07400.0011111460645324415140 sb22-13-3boc,oz102390.38380.05280.00500.11620.01210.54000.05320.07410.0011143461743835322217 sb22-13-3cr,oz,sp683760.111440.05350.00280.03610.00680.42650.02370.05780.0007103362436117351120 sb22-13-2aoc,sz39230.59240.06310.00540.20240.01340.87020.07790.10010.001686615963642711184 sb22-13-2boc,il537200.036360.06360.00270.03220.00610.59330.02660.06770.00085842254731772889 sb22-13-2cr,wl,sp573190.033290.05230.00150.00780.00340.39220.01260.05440.00061143414336929865 Sample91-1c.‘‘unit3’’ 91-3-1awil3,1053590.1162310.05750.00030.04080.00050.62270.01000.07850.0012954877492651210 91-3-1bwil,sp4,2018570.2043190.05710.00020.07430.00040.61120.00960.07770.001298482748464938 91-3-2aoc,oz5403880.718510.05440.00130.21800.00350.63120.01930.08420.001313552184971238655 91-3-2boz,wl,sp1,597170.011770.05370.00050.00520.00090.39340.00710.05310.0008933345337535919 91-6-1ar,wil,sp2,102200.0091010.05350.00050.00340.00080.39050.00710.05290.0008943325335535219 91-6-1bc,wil1,2813010.235760.05450.00060.07590.00150.45800.00920.06100.0009983826383639026 91-6-1cr,wil,sp1,576150.009770.05290.00060.00190.00110.39160.00750.05370.00081033375336632624 91-6-2aoz1811040.573720.20980.00120.17770.00209.61970.16690.33250.0052641,851252,399162,9049 91-6-2boz,lp2641380.5221620.21090.00070.15360.000915.14880.24390.52090.0080932,703342,825152,9125 91-6-3aoz,ro226910.402200.05680.00200.12230.00480.68140.02750.08690.001411153785281748577 91-6-4aoz4262230.524760.13750.00080.16820.00152.99960.05060.15820.002443947131,408132,19610 91-6-4boz,lp6033080.5122110.12760.00050.14300.00095.61530.08920.31910.0048861,785231,918142,0656 91-6-5ac,oz1861280.689200.05800.00200.21290.00520.78300.03170.09790.001611360295871853177 91-6-5br,il,sp51490.018270.05260.00130.00030.00280.41630.01260.05740.00091153595353931455 91-7-1ar,wl,sp775190.025380.05240.00090.00560.00200.38260.00960.05290.00081093325329730541 91-7-1boc,wil9221000.108690.05710.00060.03490.00140.62140.01230.07890.0012994907491849624 91-7-1cr,wl,sp921240.027460.05060.00110.00380.00250.37670.01060.05400.00081523395325822450 91-7-2aoc,oz23311.35730.04770.01580.38090.04000.60700.20420.09230.00286665691748213085639 91-7-2boc,oz,sp1041801.727140.05840.00340.53970.00990.74510.04640.09250.00161045701056527546126 91-7-3awil,ro726130.018350.05370.00140.00660.00310.38560.01210.05210.0008913275331935858 91-10-1awil2,316610.0261130.05320.00040.00750.00080.39010.00680.05320.0008993345334533817 91-10-1bwil,sp1,339340.025650.05130.00080.00360.00170.37220.00840.05260.00081293305321625534 91-10-2awil4,6562,8930.6214560.05890.00020.19670.00050.73540.01130.09050.001399559856075646 91-10-2bwil,ro4,0882,1700.5313670.05780.00020.17390.00060.67200.01050.08430.0012100522752265228 91-11-1ac,oz,ro3201330.417280.05690.00130.14150.00330.65030.01950.08290.001310651485091248652 91-12-1ac,sz209760.363200.05860.00160.11080.00370.76060.02500.09420.001510558095741455158
