1 2 3 Supplemental Materials: Impact of Dissolution, Bioturbation and Winnowing on the Sedimentary Record of the Paleocene-Eocene Thermal Maximum 4 1. Quantifying dissolution during the PETM 5 In Supplemental Figure 1 we plot percent dissolution versus paleodepth for all PETM sites 6 with available CaCO3 data as compiled by Panchuk (2007), with the addition of the new data 7 from Site 690 and data from Site 401 from Cecily Palike (pers. comm., 2013) (Table 1). We 8 exclude Site 865 from the plot as the PETM section is clearly incomplete (e.g., Bralower et 9 al., 1995). These data suggest that Shatsky Rise Sites 1209-1212 were apparently 10 characterized by less intense dissolution than other sites at comparable paleodepths with the 11 exception of Sites 690 and 401 (N. Atlantic). We propose that the impact of dissolution on 12 carbonate at Site 1209 has been diminished by bioturbation as discussed in Section 4.2. 13 However, changes in the fluxes of carbonate may also have played a role. 14 15 Supplemental Materials Figure 1. Percent dissolution determined using the technique of 16 Broecker (1995). Red numbers are Pacific Sites, blue are sites in the Atlantic, Caribbean and 17 Southern Ocean. See Table 1 for data. 18 19 20 21 22 23 24 25 26 Site Latitude Depth (m) CaCO3 high CaCO3 low Percent Dissolution % Pacific 1209 1210 1211 1212 865 1220 1221 22.00 21.75 21.6 21.9 5.46 -3.08 -5 1900 2100 2400 2200 1500 2900 3200 96 92 95 98 96 90 74 84 86 78 83 93 0 3 0.84 0.86 0.78 0.83 0.93 0 0.03 78.1 46.6 81.3 90.0 44.6 100.0 98.9 Caribbean 999 1001 7.5 11 1750 1500 61 45 0 0 0 0 100.0 100.0 North Atlantic 401 527 549 1051 42.28 -35 43.79 28.90 1900 2400 2150 1500 56.65 83 51 56 27.89 0 1 52 0.28 0 0.01 0.52 70.2 100.0 99.0 14.9 South Atlantic 1262 1263 1266 1267 -34.8 -36 -36 -36.2 3600 1500 2600 3200 88 88 85 80 1 1 4 1 0.01 0.01 0.04 0.01 99.9 99.9 99.3 99.7 27 Southern Ocean 690 -65.4 1950 85 60 0.6 73.5 738 -61.98 1350 90 70 0.7 74.1 Table 1. Dissolution percent calculated from pre (high) and peak (low) CaCO3 contents after 28 Broecker (1995). 29 30 Sites 690, 1209 and 1262 and all PETM sections are characterized by predominantly 31 biogenic sediment sources (largely nannoplankton and planktic foraminifera) with minor 32 contributions from aeolian and clastic sources. In all likelihood, fluxes of carbonate and non- 33 carbonate particles changed during the PETM with variation in plankton production, 34 weathering and aeolian transport (e.g., Robert and Kennett, 1994; Ravizza et al., 2001; 35 Bralower, 2002; Kelly, 2002; Gibbs et al., 2006; Petrizzo, 2007). However, there is no way to 36 determine exactly the changes in these fluxes, nor can we estimate the loss of highly fragile 37 plankton species that are only preserved in clay-rich, hemi-pelagic deposits along continental 38 margins (e.g., Bown et al., 2008). The dissolution estimates (Figure 6 and Supplemental 39 Figure 1) are based on assuming that the fluxes from the different sources remained constant. 40 41 At the three study sites the amount of dissolution estimated from the change in percent 42 CaCO3 (Broecker, 1995, 2009; Stap et al., 2009; Stap, 2010) at the peak of the PETM is over 43 60%, over 70%, and 100% of the carbonate at Sites 690, 1209, and 1262, respectively 44 (Figures 6a,b). At Site 1262, complete dissolution is clear from the absence of CaCO3 in the 45 interval corresponding to the peak of the PETM. At Site 690, impoverished nannofossil 46 preservation supports the notion of a significant amount of dissolution, quite possibly 47 approaching 60%. However, nannofossil preservation at Site 1209 does not reveal 48 dissolution to the extent of 70% of the sediment (Plate 1). As discussed bioturbation has 49 likely masked the extent of dissolution at this site. In addition, the assumption of constant 50 production of carbonate has led to an overestimate of the calculated levels of dissolution at 51 Sites 690 and 1209. 52 53 Plankton assemblages suggest oligotrophic conditions in open-ocean locations during the 54 PETM (Bralower, 2002; Gibbs et al., 2006), and carbonate production rates at these sites are 55 likely to have decreased modestly during the initial stages of the PETM (e.g., Kelly et al., 56 2012). Gibbs et al. (2010) estimated a carbonate production rate decrease of ~15-20% at Site 57 690 and ~5% at Site 1209. 58 pump was less efficient at Site 690 than at Site 1209 where the water column was stratified in 59 the early part of the PETM (Schneider et al., 2013). Thus the decrease in carbonate supply 60 might have been more significant at Site 1209. At Site 690, clay accumulation may have 61 accelerated as a result of enhanced continental weathering on the nearby Antarctic continent 62 (Robert and Kennett, 1994). 63 64 However, GENIE model simulations suggest that the biological 65 2. Products of Dissolution 66 When sediment is chemically eroded, a significant amount of the dissolved carbonate is 67 released into pore waters. At Site 1209, the dissolved carbonate appears to have 68 reprecipitated as long 5-15 µm calcite blades (Colosimo et al., 2006) (Supplemental Plate 1). 69 Large blocks of reprecipitated carbonate hosting whole foraminiferal shells and molds of 70 foraminifera have been observed at Site 865, another site where the brevity of the PETM 71 interval is likely partially a result of burndown (Supplemental Plate 1, see similar objects in 72 Kozdon et al., 2013). At Site 1262, small rhombs of dolomite or calcite are observed in 73 samples with low or no carbonate; these rhombs are possibly precipitates of dissolved 74 carbonate. At Site 690 it is impossible to distinguish between micarb and clay in electron 75 micrographs, but at >50% CaCO3, some of the significant volume of fine grained material 76 (Plate 1) must be micarb derived from reprecipitation of the dissolved CaCO3. 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 Supplemental Materials Plate 1. Electron micrographs showing nannofossil preservation across the base of the CIE at Site 690. The micrographs can distinguish the abundance and preservation of coccolith carbonate, but cannot generally distinguish between clay and micarb. a. 170.53-170.65 mbsf; b. 170.67-170.73 mbsf; c.170.74-170.79 mbsf; d. 170.80-170.82 mbsf. Samples below 170.80 show moderate dissolution with samples dominated by coccoliths and pieces of coccoliths and a lower volume of clay/micarb. Between 170.80 and 170.75 mbsf there is a substantial decline in preservation with fewer coccoliths with more etched rims and more clay/micarb. Samples are poorly preserved up to 170.70 mbsf. Coccolith preservation is very poor from 170.69 to 170.65 mbsf with few whole coccoliths and a lot of clay/micarb. Samples from 170.64 mbsf and above have an increasing number of whole coccoliths with a lower volume of clay/micarb. Onset of the bulk CIE is at 170.70 mbsf (Figure 2). Supplemental Materials Plate 2. Electron micrographs showing nannofossil preservation across the base and lower part of the CIE at Site 1209 (Section 22H-1). a. 196.47-196.51 mbsf; b. 196.46-196.44 mbsf; c. 196.28 and 196.42 mbsf. Samples are dominated by nannofossils. For most of the section, fossil preservation is moderate. There is a slight decline in preservation between 196.46 and 196.47 mbsf. Lithologic boundary and CIE are at 196.45 mbsf (Figure 3). Supplemental Materials Plate 3. Morphology of calcite likely derived from reprecipitation of calcite dissolved in the PETM. a. and b. Calcite blades on planktonic foraminifera from Site 1209. c. and d. Blocks of reprecipitated calcite hosting foraminifera from Site 865. Scale bars in c. and d. are 100 µm. 105 106 107 3. Interpreting bioturbation and winnowing from single specimen and bulk records 108 In Section 4.3 we discuss evidence for bioturbation and winnowing, including single 109 specimen foraminiferal and bulk stable isotopes. In Supplemental Materials Figure 2a we 110 show single specimen planktonic isotope and bulk isotope records from Site 690 (data 111 from Thomas et al., 2002). As discussed in the text, the single specimen data show 10 112 specimens that are clearly out of place, two specimens of Subbotina that have been mixed 113 upwards and eight specimens of Acarinina that have been mixed downward. Any of 114 these specimens could be the result of bioturbation and winnowing. Bioturbation is most 115 likely to mix foraminiferal specimens downward while winnowing has the potential to 116 mix specimens upwards, thus the Subbotina specimens are more likely mixed via 117 winnowing and the specimens of Acarinina mixed via bioturbation. It is unlikely that 118 bioturbation has transported these specimens by 20 cm. This mixing is more likely the 119 result of downhole contamination during drilling. 120 121 122 123 Supplemental Materials Figure 2a. Distribution of single specimen and bulk carbonate 124 carbon isotope values at Site 690 (data from Thomas et al. 2002). All samples are from 125 the archive half of the core. Circles designate samples out of place potentially as a result 126 of bioturbation or winnowing. Lines indicate levels of samples with grain size 127 distributions potentially indicative of winnowing. 128 129 130 131 132 Supplemental Materials Figure 2b. Distribution of single specimen oxygen isotope 133 values at Site 690 (data from Thomas et al. 2002). All samples are from the archive half 134 of the core. Circles designate samples out of place potentially as a result of bioturbation 135 or winnowing. Lines indicate levels of samples with grain size distributions potentially 136 indicative of winnowing. 137 138 Grain size data allow us to identify samples that have distributions potentially altered by 139 winnowing (Supplemental Figure 3). We indicate these samples in Supplemental 140 Materials Figure 2. The lack of coincidence between samples with isotope values that are 141 out of place and those that have grain size distributions consistent with winnowing 142 suggests that winnowing is not the cause of displacement. Possibly, the two specimens of 143 Subbotina have been mixed downwards by drilling. 144 From the single specimen isotope data it is possible that a number of specimens that are 145 not clearly out of place have been mixed by bioturbation and winnowing, just not to the 146 extent that would distinguish them from surrounding specimens. This is particularly the 147 case close to the carbon isotope excursion. 148 149 150 151 152 153 154 155 156 157 158 159 Supplemental Materials Figure 3. Logarithmic grain size profiles for samples from across the base of the PETM at the three study sites. 10% scale bar is volume abundance of the sediment fraction. The data show unimodal and relatively homogenous distributions at Sites 1209 and 1262; both sites show a shift towards finer grain size in samples from the earliest part of the PETM (196.45-196.42 mbsf at Site 1209; 140.1-139.9 mcd at 1262). Samples at Site 690 generally show a more bimodal grain size distribution than the other two sites, with most samples possessing a very minor but still distinguishable peaks likely representing nannoplankton and foraminifera. Some samples (including 170.36, 170.45, 170.53, 170.69, 170.725, 170.755, 170.845 mbsf) show a more pronounced foraminiferal peak. 160 161 The impact of bioturbation can clearly be observed in bulk carbonate isotope data from 162 Site 690. We plot bulk carbonate isotopes data from the two halves of Section 19-1 in 163 Supplemental Materials Figure 3. The plot shows largely comparable values between 164 170.4 and 170.8 meters below sea floor with the exception of the interval between 170.62 165 and 170.69 mbsf where a burrow has clearly mixed the bulk carbonate isotope values in 166 the archive half with respect to the working half. 167 168 169 Supplemental Materials Figure 4. Bulk carbonate carbon isotope values of the archive 170 half of the PETM (Section, 690B-19H-1) (from Thomas et al., 2002) plotted against 171 values from the working half (from Bains et al., 1999). 172 173 174 175 Increase in fragmentation Benthic Foraminiferal Extinction Carbon isotope excursion (bulk CaCO3) Decrease in CaCO3 Site 690 mbsf 170.6 170.60-170.61 170.70 170.79 Site 1209 mbsf 196.525 196.45 196.45 196.465 Site 1262 mcd 140.10-140.16 140.18 Above 140.13 140.14 176 Deterioration of nannofossil preservation Base of claystone 170.75-170.80 NA 196.465 196.45 140.14 140.14 177 Supplemental Materials Table 2. Level of significant changes associated with the PETM 178 at the three study sites (See Figure 2) 179 180 181 References 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 Bains, S., Corfield, R.M., Norris, R.D., 1999. Mechanisms of climate warming at the end of the Paleocene: Science, v. 285, p. 724–727. Bown, P.R., Dunkley Jones, T., Lees, J.A., Randell, R.D., Mizzi, J.A., Pearson, P.N., Coxall, H.K., Young, J.R., Nicholas, C.J., Karega, A., Singano, J., Wade, B.S., 2008. Paleogene calcareous microfossil Konservat-Lagerstätte from the Kilwa Group of coastal Tanzania Geological Society of America Bulletin, 120, 3-12, doi:10.1130/B26261.1 Bralower, T. J., 2002. Evidence for surface water oligotrophy during the late Paleocene thermal maximum: nannofossil assemblage data from Ocean Drilling Program Site 690, Maud Rise, Weddell Sea, Paleoceanography, 17, doi 10.1029/2001PA000662. Bralower, T. J., Zachos, J.C., Thomas, E., Parrow, M., Paull, C.K., Kelly, D.C., Premoli Silva, I., Sliter, W.V., Lohmann, K.C., 1995. Late Paleocene to Eocene paleoceanography of the equatorial Pacific Ocean: stable isotopes recorded at ODP Site 865, Allison Guyot: Paleoceanography, 10, 841-865. Broecker, W., 1995. The Glacial World According to Wally. Eldigio Press. Broecker, W., 2009, Wally’s Quest to Understand the Ocean’s CaCO3 Cycle, Annual Review Marine Science, 1:1–18, doi:10.1146/annurev.marine.010908.163936 Colosimo, A., Bralower, T.J., Zachos, J. 2006. Evidence for lysocline shoaling at the Paleocene/Eocene Thermal Maximum on Shatsky Rise, Northwest Pacific. In Bralower, T. J., I. Premoli-Silva, M. J. Malone, et al. Proc. ODP Sci. Res., 198, 1-36. Gibbs, S. J., Bralower, T. J., Bown, P. R., Zachos, J. C., Bybell, L. M., 2006. Shelf-open ocean calcareous phytoplankton assemblages across the Paleocene-Eocene Thermal Maximum: Implications for global productivity gradients, Geology 34, 233-236. Gibbs, S.J., Stoll, H., Bown, P.R., Bralower, T.J., 2010. Ocean acidification and surface water carbonate production across the Paleocene-Eocene Thermal Maximum, Earth and Planetary Science Letters 295, 583-592. Kelly, D. C., 2002. Response of Antarctic (ODP Site 690) planktonic foraminifera to the Paleocene-Eocene thermal maximum: faunal evidence for ocean/climate change. Paleoceanography 17, doi 10.1029/2002PA000761. Kelly, D. C., Nielsen, T. M. J., Schellenberg, S. A., 2012. Carbonate saturation dynamics during the Paleocene-Eocene thermal maximum: bathyal constraints from ODP Sites 689 and 690 in the Weddell Sea (South Atlantic). Marine Geology, doi: 10.1016/j.margeo.2012.02.003. Kozdon, R., Kelly, D.C., Kitajima, K., Strickland, A., Fournelle, J. H., Valley, J.W., 2013. In situ δ18O and Mg/Ca analyses of diagenetic and planktic foraminiferal calcite preserved in a deep-sea record of the Paleocene-Eocene thermal maximum. Paleoceanography, DOI: 10.1002/palo.20048. 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 Panchuk, 2007. Investigating the Paleocene/Eocene carbon cycle perturbation: An Earth System model approach. Unpublished PhD thesis, The Pennsylvania State University, 83pp. Petrizzo, M.R. 2007. The onset of the Paleocene–Eocene Thermal Maximum (PETM) at Sites 1209 and 1210 (Shatsky Rise, Pacific Ocean) as recorded by planktonic foraminifera. Marine Micropaleontology (2007), doi:10.1016/j.marmicro.2006.11.007 Ravizza, G., Norris, R. N., Blusztajn, J., Aubry, M.P., 2001. An osmium isotope excursion associated with the late Paleocene thermal maximum: Evidence of intensified chemical weathering. Paleoceanography, 16, 155-163. Robert, C. Kennett, J.P., 1994. Antarctic subtropical humid episode at the Paleocene-Eocene boundary: Clay-mineral evidence. Geology, 22: 211-214. Schneider, L. J., Bralower, T.J., Kump, L.R., Patzkowsky, M.E., 2013. Calcareous nannoplankton ecology and community change across the Paleocene-Eocene Thermal Maximum, Paleobiology, 39(4), 2013, pp. 628–647 DOI: 10.1666/12050. Stap, L., Sluijs, A., Thomas, E., Lourens, L., 2009. Patterns and magnitude of deep sea carbonate dissolution during Eocene Thermal Maximum 2 and H2, Walvis Ridge, southeastern Atlantic Ocean. Paleoceanography, 24, PA1211, doi:10.1029/2008PA001655. Stap, H.L., 2010. Palaeoceanographic and biotic response during early Eocene extreme global warming events, Geologica Ultraiectina, 328. Thomas, D. J., Zachos, J. C., Bralower, T. J., Thomas, E., Bohaty, S., 2002. Warming the fuel for the fire: evidence for the thermal dissociation of methane hydrate during the Paleocene-Eocene thermal maximum. Geology 30, 1067-1070.