Electronic Supplementary Material

Benthic anoxia, intermittent photic zone euxinia and elevated productivity during

deposition of the Lower Permian, post-glacial fossiliferous black shales of the Paraná

Basin, Brazil

Lucas D. Mouroa,b, Michał Rakocińskic, Leszek Marynowskic, Agnieszka Pisarzowskad,

Sabiela Musabelliuc, Michał Zatońc*, Marcelo A. Carvalhoe, Antonio C. S. Fernandese

& Breno L. Waichelb

a Programa de Pós-Graduação em Geologia, Instituto de Geociências, Universidade Federal

do Rio de Janeiro, 21941-901, Rio de Janeiro, Brazil.b Departamento de Geociências, Universidade Federal de Santa Catarina, PFRH-PB 240,

88040-970, Florianópolis, Santa Catarina, Brazil.c Faculty of Earth Sciences, University of Silesia, Będzińska 60, 41-200 Sosnowiec, Poland.d Institute of Geological Sciences, Polish Academy of Sciences, Senacka 1, 31-002 Kraków,

Poland.e Departamento de Geologia e Paleontologia, Museu Nacional, Universidade Federal do Rio

de Janeiro, 20940-040, Rio de Janeiro, Brazil.

*Correspondin author: e-mail: mzaton@wnoz.us.edu.pl

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ESM Table 1. Inorganic geochemical data - major elements in the samples from the Campáleo section. MDL - Minimum detection limit.

Sample

SiO2

[wt.%]

Al2O3

[wt.%]

Fe2O3

[wt.%]

MgO

[wt.%]

CaO

[wt.%]

Na2O

[wt.%]

K2O

[wt.%]

TiO2

[wt.%]

P2O5

[wt.%]

MnO

[wt.%]

Cr2O3

[wt.%]

Cr

[ppm]

MDL 0.01 0.01 0.04 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.002 20

4A 47.29 14.13 7.06 1.67 0.09 0.38 3.16 0.57 0.46 0.04 0.039 266.84

3D 48.50 14.31 6.66 1.57 0.06 0.30 3.09 0.55 0.19 0.02 0.054 369.47

3C 49.49 13.69 6.41 1.46 0.12 0.33 3.17 0.59 0.40 0.03 0.037 253.16

3B 51.15 14.10 5.23 1.53 0.10 0.35 3.27 0.61 0.55 0.02 0.038 260.00

3A 49.08 13.62 7.41 1.92 0.43 0.86 3.35 0.60 0.40 0.03 0.037 253.16

2B 53.56 15.01 5.99 2.24 0.20 0.70 3.71 0.61 0.18 0.03 0.024 164.21

2A 54.05 14.65 6.89 2.28 0.67 0.87 3.66 0.61 0.49 0.03 0.024 164.21

1D 59.29 13.95 5.78 2.13 0.41 1.41 3.50 0.62 0.18 0.04 0.016 109.47

1C 57.02 14.89 5.25 2.23 0.36 1.28 3.76 0.64 0.16 0.04 0.019 130.00

1B 53.86 13.38 5.52 1.93 0.39 1.24 3.25 0.61 0.19 0.03 0.028 191.58

1A 54.29 13.12 4.94 1.83 0.39 1.37 3.18 0.63 0.16 0.03 0.028 191.58

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ESM Table 2. Inorganic geochemical data - selected trace elements in the Lontras black shales of the Campáleo section. MDL - Minimum detection limit.

Sample

Ba

[ppm]

Co

[ppm]

Rb

[ppm]

Sr

[ppm]

Th

[ppm]

U

[ppm]

V

[ppm]

Zr

[ppm]

Mo

[ppm]

Cu

[ppm]

Pb

[ppm]

Zn

[ppm]

Ni

[ppm]

As

[ppm]

Cd

[ppm]

Ag

[ppm]

Sb

[ppm]

Ce

[ppm]

MDL 1 0.2 0.1 0.5 0.2 0.1 8 0.1 0.1 0.1 0.1 1 0.1 0.5 0.1 0.1 0.1 0.1

4A 1261 25.2 156.9 230.0 10.9 22.5 512 152.4 11.8 116.7 526.3 >10000# 127.7 87.1 81.6 1.5 3.3 102.9

3D 566 15.7 150.1 99.8 11.4 22.6 574 143.0 7.8 76.8 760.4 9766 93.6 83.5 49.9 1.6 1.8 61.2

3C 1827 15.9 150.5 232.5 11.4 20.7 401 148.1 9.2 99.2 682.2 9883 93.1 74.2 45.4 1.7 2.6 73.4

3B 2707 14.1 150.8 300.3 11.8 21.4 400 152.3 5.5 71.6 574.5 4922 93.3 53.1 27.5 1.3 1.8 71.5

3A 560 12.2 158.8 109.9 12.1 20.1 348 154.0 4.4 90.1 1026.2 2963 87.3 80.8 16.1 1.5 2.6 65.9

2B 768 13.8 174.2 101.7 12.6 17.0 333 148.5 3.4 47.4 491.4 1428 80.4 49.8 9.8 0.8 2.8 50.2

2A 718 15.2 167.7 90.8 12.7 16.3 315 152.2 3.7 47.1 496.1 658 96.2 51.9 4.9 0.9 2.6 49.1

1D 395 19.8 155.5 93.3 11.9 13.2 248 135.7 6.3 47.0 433.6 1278 142.5 53.2 6.3 0.5 3.1 60.6

1C 410 19.0 168.5 102.8 12.9 15.1 259 149.0 6.7 38.8 345.8 962 135.2 37.7 3.6 0.5 1.7 67.4

1B 390 19.4 146.9 108.0 11.7 17.7 234 160.1 9.5 37.3 550.7 1622 176.1 45.5 8.4 0.8 1.3 70.9

1A 390 16.9 141.4 108.1 11.8 17.5 222 184.3 10.7 38.6 463.5 3645 175.7 30.6 19.8 0.6 1.4 69.9

# - value above max. detection limit was taken as 10000 ppm to EFZn calculation; in fact it can be higher.

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ESM Table 3. Kerogen components found in the Lontras black shales of the Campáleo section. AOM - amorphic organic matter; opaq. equi - opaque-equidimensional; opaq. lath - opaque – lath; opaq. corrod. – opaque-corroded; non-opaq. non-biostr. non-degr. – non-opaque – non-biostructured – non-degraded; non-opaq. non-biostr.-degr. – non-opaque – non-biostructured – degraded; non-opaq. biostr.-degr. – non-opaque – biostructured – degraded; unrecog. palyno. – unrecognized palynomorphs.

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AOM PHYTOCLASTS PALYNOMORPHS

Samples AOM opaq.equi.

opaq.lath

opaq.corrod

.

non-opaq.non-biostr.non-degr.

non-opaq.non-biostr.-

degr.

non-opaq.biostr.-degr. pollen spore

s Portalites fungi acritarchs prasinophytes unrecog.

palyno. Total

4A 50.7% 5.6% 7.5% 22.9% 0.0% 9.6% 0.5% 0.0% 0.5% 0.5% 0.0% 0.3% 0.5% 1.3% 100%3D 66.9% 4.3% 4.0% 15.5% 0.0% 6.9% 0.3% 0.0% 0.5% 0.0% 0.0% 0.0% 0.0% 1.6% 100%3C 71.1% 1.9% 2.7% 12.3% 0.0% 8.3% 0.3% 0.0% 1.1% 0.3% 0.0% 0.3% 1.6% 0.3% 100%3B 85.8% 1.1% 1.3% 6.7% 0.3% 2.7% 0.3% 0.0% 0.5% 0.0% 0.0% 0.0% 0.3% 1.1% 100%3A 90.4% 0.3% 1.3% 3.2% 0.0% 2.9% 0.3% 0.3% 0.3% 0.0% 0.0% 0.0% 0.0% 1.1% 100%2B 76.5% 0.8% 4.8% 5.9% 0.0% 9.4% 0.5% 0.3% 0.5% 0.0% 0.0% 0.0% 0.3% 1.1% 100%2A 77.5% 0.8% 4.8% 3.5% 0.0% 10.2% 0.0% 0.0% 0.5% 0.0% 0.0% 0.0% 1.6% 1.1% 100%1D 69.0% 0.8% 5.9% 6.1% 0.0% 13.9% 0.3% 0.0% 0.3% 0.0% 0.0% 0.0% 1.6% 2.1% 100%1C 66.3% 4.3% 6.1% 6.1% 0.3% 11.5% 1.1% 0.0% 0.0% 0.0% 0.3% 0.0% 0.0% 4.0% 100%1B 76.5% 1.9% 2.4% 13.1% 0.0% 2.4% 1.1% 0.5% 0.0% 0.3% 0.3% 0.3% 1.1% 0.3% 100%1A 87.7% 0.3% 2.9% 4.3% 0.0% 2.7% 0.3% 0.3% 0.8% 0.0% 0.0% 0.0% 0.5% 0.3% 100%

Total 74.4% 2.0% 4.0% 9.1% 0.0% 7.3% 0.4% 0.1% 0.5% 0.1% 0.0% 0.1% 0.7% 1.3% 100%

ESEM Table 4. General organic geochemical characteristics of the Lontras black shales of the Campáleo section.

Sample TOC TS EOM Al Ar Pol CPI(25-31) Pr/Ph SCh/LCh Ster/Hop C31 22S/(22S+22R) 30M/(M+H) C29 20S/(20S+20R) C27 C28 C29 C30

4A 11.4 1.5 39 30 24 46 1.9 1.2 2.3 1.6 0.50 0.29 0.25 37 26 28 9

3D 11.6 2.0 43 33 23 44 2.0 1.5 2.1 1.3 0.55 0.29 0.24 37 27 27 8

3C 11.1 2.7 58 13 43 44 1.9 2.0 2.0 2.3 0.56 0.30 0.41 37 26 27 10

3B 11.6 4.5 37 20 25 55 2.0 1.5 1.6 1.9 0.55 0.30 0.22 37 26 27 10

3A 11.9 1.7 15 23 18 58 1.9 2.2 2.0 1.5 0.53 0.30 0.24 32 23 34 11

2B 8.6 1.2 39 29 25 46 1.9 2.5 1.6 1.1 0.56 0.31 0.24 35 23 34 8

2A 7.1 1.7 24 22 25 53 1.9 2.4 13.7 1.2 0.59 0.28 0.28 45 24 26 6

1D 5.5 4.0 10 20 15 65 1.8 2.7 2.3 0.6 0.58 0.31 0.25 38 18 38 6

1C 7.2 3.7 10 15 26 59 2.4 2.0 2.0 1.0 0.49 0.32 0.25 36 22 34 8

1B 11.9 1.7 22 20 28 52 1.9 2.1 2.2 1.7 0.50 0.30 0.24 35 24 33 8

1A 12.4 2.6 28 19 29 53 1.8 2.0 2.0 1.8 0.56 0.31 0.24 28 16 44 12TOC = total organic carbon [%]TS = total sulphur [%]EOM = extractable organic matter [mg/gTOC]Al = aliphatic fraction [%]Ar = aromatic fraction [%]Pol = polar fraction [%]CPI(25-31) = carbon preference index counted as (C25 + C27 + C29) + (C27 + C29 + C31)/2(C26 + C28 + C30)Pr/Ph = pristane to phytane ratioSCh/LCh = short chain n-alkanes (C17 – C19) to long chain n-alkanes (C27 – C29) ratioSter/Hop = sum of C27 – C29 steranes and diasteranes to sum of C27 – C33 hopanes ratioC31 22S/(22S+22R) = C31 22S 17α-homohopane to (sum of 22S and 22R 17α-homohopane) ratio30M/(M+H) = C30 17β21α(H)-moretane to (sum of C30 17α21β(H)-hopane and C30 17β21α(H)-moretane) ratioC29 20S/(20S+20R) = C29-5α,14α,17α(H)-stigmastane 20S to a sum of its diastereomers 20S and 20R,C27, C28, C29, C30 = regular steranes with 27 to 30 carbon atoms [%]

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ESM Table 5. Concentration of compounds characteristic for photic zone euxinia and maleimide ratios.

Sample Aryl isoprenoids TMeEBi TMeEBi + TMP Me,i-Bu/Me,Et Me, i-Bu/Me, n-Bu4A 0.57 3.63 5.21 4.96 0.183D 0.61 3.52 5.28 2.86 0.123C 1.73 6.05 7.39 2.84 0.123B 0.15 1.17 1.75 4.09 0.063A 0.00 0.61 0.97 1.48 0.022B 0.60 2.76 4.20 3.60 0.152A 0.17 1.50 2.45 0.00 0.001D 0.00 0.88 1.37 0.00 0.001C 0.00 1.13 1.68 0.00 0.001B 0.68 1.93 2.92 1.85 0.101A 0.39 1.79 2.74 2.80 0.18

Aryl isoprenoids = concentration of aryl isoprenoids compounds in g/gTOCTMeEBi = 3,4,5,5’-tetramethyl, 2’-ethyl biphenyl in g/gTOCTMeEBi + TMP = 3,4,5,5’-tetramethyl, 2’-ethyl biphenyl + trimethylphenantrene in g/gTOCMe,i-Bu/Me,Et = methyl, iso-butyl to methyl, ethyl maleimides ratio x 1000 (see Grice et al., 1996)Me, i-Bu/Me, n-Bu = methyl, iso-butyl to methyl, n-buthyl maleimides ratio

ESM Fig. 1. Composite plot of the Campáleo section showing paleoproductivity and redox sensitive elements normalizes to Al.

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ESM Fig. 2. TOC vs. TN for the Lontras black shales of the Campáleo section.

ESM Fig. 3. Plots showing good correlation between TOC and Ster/Hop as well as 3,4,5,5’-tetramethyl, 2’-ethyl biphenyl and aryl isoprenoids concentration in the Lontras black shales of the Campáleo section.

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ESM Fig. 4. U-EF vs. Mo-EF for the Lontras black shales of the Campáleo section. According to Tribovillard et al. (2012).

ESM Fig. 5. Cross-plots of maturity related biomarker parameters [C30 hopane structural isomer ratio C30 /(+ ) vs. C31 hopane epimer ratio C31 22S/(22S + 22R)] showing low maturity of the analyzed samples of the Lontras black shales of the Campáleo section.

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ESM Fig. 6. Cross plot of aryl isoprenoid ratio vs. Pr/Ph ratio showing episodic rather than persistent photic zone euxinia during deposition of the Lontras black shales.

References

Grice, K., Gibbson, R., Atkinson, J.E., Schwark, L., Eckardt, C.B., Maxwell, J.R., 1996.

Maleimides (1H-pyrrole-2,5-diones) as molecular indicators of anoxygenic

photosynthesis in ancient water column. Geochimica et Cosmochimica Acta 60, 3913–

3924.

Tribovillard, N., Algeo, T.J., Baudin, F., Riboulleau, A., 2012. Analysis of marine

environmental conditions based on molybdenum–uranium covariation - Applications to

Mesozoic paleoceanography. Chemical Geology 324-325, 46–58.

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