Marine Geology 252 (2008) 166173

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Marine Geology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a r g e o

Sealevel changes control diagenetic dolomite formation in hemipelagic sediments of the Peru Margin
Patrick Meister a,b,, Stefano M. Bernasconi b, Crisgono Vasconcelos b, Judith A. McKenzie b
a b

Max-Planck-Institute for Marine Microbiology, Celsiusstrasse 1, 28359 Bremen, Germany Geological Institute, ETH Zrich, 8092 Zrich, Switzerland

A R T I C L E

I N F O

A B S T R A C T
The rst experimentally determined temperature dependent oxygen-18 fractionation factor between dolomite and water at low temperatures [Vasconcelos, C., McKenzie, J.A., Warthmann, R., Bernasconi, S., 2005. Calibration of the 18O paleo-thermometer with dolomite formed in microbial cultures and natural environments. Geology 33, 317320] allows now the precise calculation of temperatures during early diagenetic dolomite precipitation. We use 18O values of early diagenetic dolomite beds sampled during ODP Legs 112 and 201 on the Peru continental margin (Sites 1227, 1228 and 1229) [Meister, P., McKenzie, J.A., Vasconcelos, C., Bernasconi, S., Frank, M., Gutjahr, M., Schrag, D.P., 2007. Dolomite formation in the dynamic deep biosphere, results from the Peru Margin, OPD Leg 201. Sedimentology 54, 10071032] to calculate paleo-porewater temperatures at the time of dolomite precipitation. We assumed unaltered seawater 18O values in the porewater, which is supported by 18O values of the modern porewater presented in this study. The dolomite layers in the Pleistocene part of the sedimentary columns showed oxygen isotope temperatures up to 5 C lower than today. Since Sites 1228 and 1229 are located at 150 and 250 m below sealevel, respectively, their paleo-porewater temperatures would be inuenced by considerably colder surface water during glacial sealevel lowstands. Thus, Pleistocene dolomite layers in the Peru Continental margin probably formed during glacial times. This nding is consistent with a model for dolomite precipitation in the Peru Margin recently discussed by Meister et al. [Meister, P., McKenzie, J.A., Vasconcelos, C., Bernasconi, S., Frank, M., Gutjahr, M., Schrag, D.P., 2007. Dolomite formation in the dynamic deep biosphere, results from the Peru Margin, OPD Leg 201. Sedimentology 54, 10071032], where dolomite forms episodically at the sulphate methane interface. It was shown that the sulphate methane interface migrates upwards and downwards within the sedimentary column, but dolomite layers may only form when the sulphatemethane interface stays at a xed depth for a sufcient amount of time. We hypothesize that the sulphatemethane interface persists within TOC-rich interglacial sediments, while this zone is buried by TOC-poor sedimentation during glacial times. Thus, the presented oxygen isotope data provide additional information on the timing of early diagenetic dolomite formation and a possible link between episodicity in dolomite formation and sealevel variations. A similar link between early diagenesis and oceanography may also explain spacing of dolomite layers in a Milankovitch type pattern observed in the geological record, such as in the Miocene Monterey Formation. 2008 Elsevier B.V. All rights reserved.

Article history: Received 22 March 2007 Received in revised form 16 March 2008 Accepted 5 April 2008 Keywords: dolomite oxygen isotopes deep biosphere glacial/interglacial cycles paleo-temperatures Peru Margin

1. Introduction Dolomite layers and nodules are commonly observed in the geological record in organic carbon-rich deep-sea hemipelagic sediments. They are found in the Miocene Monterey Fm. (Murata et al., 1969; Baker and Burns, 1985; Burns and Baker, 1987; Burns et al., 1988; Compton, 1988) and were rst observed in recent ocean margin sediments during drilling in the California Borderland (DSDP Leg 63; Pisciotto and Mahoney, 1981), the Gulf of California (DSDP Leg 64;
Corresponding author. Max-Planck-Institute for Marine Microbiology, Celsiusstrasse 1, 28359 Bremen, Germany. E-mail address: pmeister@mpi-bremen.de (P. Meister).

Kelts and McKenzie, 1982), and later on the Peru Margin (ODP Leg 112; Suess et al., 1988). These studies led to the formulation of the organic dolomite model, where the essential part of the inorganic carbon is delivered from organic matter degradation. Claypool and Kaplan (1974) concluded from the variable positive and negative 13C values that dolomite layers form at different depths and in different diagenetic zones. In the sulphate reduction zone, carbonate with negative 13C values is produced, and, in the methanogenic zone, carbonate with positive 13C values is produced. The diagenetic zone, in which dolomite formation occurs, was considered to depend on the sedimentation rate, which limits the downward diffusion of SO2 4 and, thus, the depth of organic matter degradation, which leads to supersaturation with respect to dolomite (Kelts and McKenzie, 1984).

0025-3227/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.margeo.2008.04.001

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Nevertheless, this model does not sufciently explain the formation of distinct hard-lithied layers of dolomite at different depths within the unlithied sediment. The recent study of dolomite layers recovered from the Peru shelf (ODP Leg 201; Meister et al., 2007) gave evidence that the formation of dolomite may be xed to certain hot spots of microbial activity, such as the sulphate methane interface (SMI). A maximum in alkalinity and minima in dissolved Mg2+ and Ca2+ concentrations coincident with the SMI indicate that alkalinity production by microbial degradation of organic matter is the driving force for dolomite precipitation. Also, the elevated microbial cell concentrations commonly counted at this geochemical interface (D'Hondt et al., 2003, 2004; Parkes et al., 2005) may play a kinetic role in dolomite precipitation, which has been experimentally demonstrated by Vasconcelos et al. (1995). In any case, if dolomite precipitation is xed to this microbially active interface, the variation in 13C values between +7 and 15 (Meister et al., 2007) is due to non-steady state conditions as a result of the upward and downward migration of the SMI and not due to precipitation in different redox zones, as suggested by Claypool and Kaplan (1974). The dynamic behavior of the redox zonation in the Peru Margin (shelf and upper slope) sediments can be at least partially ascribed to strong variations in SO2 consumption due to variations in the total 4 organic carbon (TOC) content of the shelf sediments (Meister et al., 2007). These variations are related to glacial/interglacial variations in oceanographic conditions (Wefer et al., 1990) whereby during glacial low stands, low-TOC sediments were deposited at the shelf sites of the otherwise highly productive Peru Margin (Suess, von Huene, et al., 1990). An indirect relation of dolomite formation to orbital cycles and variation in the oceanography during the Miocene was previously proposed by Compton (1988) based on frequency analysis of dolomite layers within the Monterey Formation. Even if

eustatic sealevel variations were low during the Miocene, the cyclicity in oceanographic conditions and sedimentation set the pace for variations in the diagenetic system. However, since previous geochemical studies generally assumed steady state conditions, they did not show a possible link between episodic diagenetic processes and changes in oceanography. In this paper, we use oxygen isotope data measured in the dolomite layers (18ODOL) from three Peru shelf sites (ODP Leg 201 Sites 1227, 1228, and 1229; Meister et al., 2007) to calculate paleo-porewater temperatures during the time of dolomite precipitation. For the same sites, new 18O data from modern porewater (18OW) are presented (Table 1) and compared with porewater data derived from ODP Leg 112 samples (Kastner et al., 1990). The relevant 18O data and calculated temperatures are found in the Appendix. The recently determined fractionation factor for oxygen-18 between dolomite and water at low temperatures (Vasconcelos et al., 2005) was used for calculation. Because seawater temperature showed considerable variation through the Quaternary, and isotopic fractionation is dependent on precipitation temperature, the calculated temperatures constrain the timing of dolomite formation in relation to Quaternary paleoceanography and provide a possible link between episodic formation of dolomite layers and past climatic/oceanographic changes. 2. Study area During ODP Leg 201, three sites were drilled on the shelf and upper slope of the Peru Margin (Fig. 1; D'Hondt et al., 2003), which were all reoccupied ODP Leg 112 sites. Sites 1228/680 and 1229/681 are located on the Peru shelf at 250 and 150 m below sealevel (mbsl), respectively. Site 1227/684 was drilled at 430 mbsl on the upper slope. Only the Leg 201 site numbering is used in this text. The Peru continental margin is characterized by active subduction tectonics. During major Eocene and Miocene orogenic phases, large parts of the Peruvian shelf were uplifted and exposed above sealevel (Suess et al., 1988). These tectonic events are documented by major unconformities, which were observed at the different Leg 112 sites (Suess et al., 1988). During times of tectonic uplift, hypersaline conditions prevailed in the exposed shelf areas (Thornburgh and Suess, 1990). Hypersaline brine was recovered from deep drill cores at the shelf sites (Suess et al., 1988) and was shown to be of Miocene age or older (Kastner et al., 1990; Meister et al., 2007). The shelf and upper slope is affected by normal faulting, and was subdivided into different sets of basins separated by topographic highs (Fig. 1, shaded areas). The ridges are characterized by sediment bypass and erosion where sediments containing dolomite layers as old as Miocene in age are exposed (Kulm et al., 1984). Sites 1228 and 1229 are located close to the center of the Salaverry basin (Fig. 1), which was completely lled up with hemipelagic sedimentation. Late Miocene subsidence is more pronounced south of the Mendaa fracture zone, whereas Site 1227 in the Trujillo Basin shows a condensed PliocenePleistocene stratigraphy (Suess et al., 1988) with erosion surfaces, phosphorite and glauconite layers. The Pleistocene sediments at the three drill sites consist predominantly of organic carbon-rich diatom ooze with variable amounts of detrital clay, silt and sand, and with diagenetic dolomite layers scattered throughout the sedimentary column. Site 1229 shows the greatest Pleistocene thickness, as it is located near the center of the coastal upwelling cell (Zuta and Guillen, 1970). Despite the greatest thickness, the sedimentary column at Site 1229 also shows a high amount of erosion surfaces, which often contain phosphorites (D'Hondt et al., 2003). High productivity leads to an oxygen minimum zone impinging on the seaoor at the shelf and upper slope sites at depths between 150 and 400 m water depth (Suess et al., 1988). However, sealevel variations strongly inuenced sedimentation at the shelf sites. During lowstands, upwelling cells migrated seaward with the oxygen minimum zone impinging on the seaoor further away

Table 1 18O values of porewaters at ODP Leg 201 Sites 1227, 1228, and 1229 Sample 201-1227A-11H-2, 135150 1227D-1H-1, 015 1227D-4H-6, 135150 201-1228A-2H-3, 015 1228A-2H-5, 135150 1228A-3H-1, 135150 1228A-3H-3, 135150 1228A-5H-4, 135150 1228A-6H-3, 135150 1228A-7H-5, 135150 1228A-8H-3, 135150 1228A-11H-1, 85100 201-1229A-1H-1, 135150 1229A-3H-5, 135150 1229A-4H-5, 135150 1229A-5H-3, 135150 1229A-6H-3, 015 1229A-8H-1, 135150 1229A-8H-5, 135150 1229A-9H-1, 135150 1229A-9H-4, 135150 1229A-9H-5, 135150 1229A-10H-1,135150 1229A-11H-1, 135150 1229A-11H-2, 135150 1229A-11H-5, 135150 1229A-12H-2, 135150 1229A-12H-4, 135150 1229A-13H-1, 135150 1229A-13H-3, 135150 1229A-14H-1, 135150 1229A-18H-1, 135150 1229A-22H-1, 135150 Depth (mbsf) 93.95 0.00 35.35 7.90 12.25 17.25 18.75 39.25 47.25 59.75 66.25 91.25 1.35 21.75 31.25 37.75 42.90 60.25 66.25 69.75 74.25 75.25 80.75 90.25 91.75 96.25 101.25 104.25 109.25 112.25 118.75 156.75 186.25 18O (in duplicates) ( SMOW) 0.11 0.09 0.30 0.05 0.16 0.10 0.17 0.20 0.18 0.04 0.17 0.20 0.30 0.57 0.57 0.47 0.59 0.50 0.43 0.30 0.35 0.35 0.33 0.26 0.37 0.35 0.41 0.15 0.94 0.20 0.30 0.04 0.54

0.36 0.43 0.27 0.43 0.36 0.35

0.17

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Fig. 1. Map of the Peru Margin showing locations of the three Peru shelf sites drilled during ODP Leg 201 (Sites 1227, 1228, and 1229), which were reoccupied ODP Leg 112 sites (Sites 684, 680, and 681). The sites are listed with coordinates and water depths in the table. Shaded areas on the map mark the ancient upper slope and shelf basins, which were inlled with late Tertiary and Quaternary sediments. Bathymetry is shown by isobaths with an equidistance of 500 m.

from the coast (Suess et al., 1988; Wefer et al., 1990). A 7 m-scale cyclicity in sediment composition and TOC content can be correlated to isotope stages 1 through 16 in the top 45 mbsf at Site 1228 and, thus, are due to glacialinterglacial sealevel variations (Wefer et al., 1990; Emeis and Morse, 1990). At Site 1229, a cyclicity in the range of glacial interglacial cycles can be recognized as 10 m-scale cycles in color reectance in the top 50 mbsf, but is not resolved in the TOC or bathymetry and a much stronger variability in the 30 m range is superimposed (Fig. 2; Meister et al., 2007). Paleobathymetry reconstructed by Resig (1990) as middle to lower neritic for Site 1229 follows the large-scale variations. Leg 201 porewater chemistry shows strong sulphate reducing and methanogenic activity at the studied sites. At Sites 1227 and 1229, the sulphate/methane interface (i.e. the depth at which sulphate is completely removed from the porewaters and methane concentrations start to increase) occurs around 30 mbsf. This is relatively deep for an SMI in TOC-rich upwelling sediment, but it can be explained by the interlayered TOC-poor glacial intervals, which show less sulphate reducing activity (Meister et al, 2007). The variations in TOC were shown to cause non-steady state porewater proles and periodic variations in the diffusion depth of SO2 (Meister et al., 2007). 4 Additional SO2, as well as Mg2+ and Ca2+ ions, diffuse upward from 4 the hypersaline brine (D'Hondt et al., 2003), such that a second SMI is present at Site 1229, 90 mbsf. No SMI is currently present at Site 1228, where the SO2 is not depleted throughout the sequence. 4 3. Methods

sediment were powdered and the mineralogy was determined using a Scintag XDS 2000 X-ray diffractometer. The samples were scanned continuously at 1/min from 10 to 70 with Cu-K radiation. Carbon and oxygen isotopes in powdered bulk dolomite samples, as well as microdrilled subsamples from thin section cuttings, were analysed at the Geological Institute of the ETH Zrich. Samples were dissolved using an on-line common acid method and a VG PRISM mass spectrometer. Reaction time was set to 10 min. All 18O values have been corrected for dolomitephosphoric acid fractionation at 90C using the fractionation factor of 1.0093 (Rosenbaum and Sheppard, 1986). The 13C and 18O values of the carbonates are given relative to the Vienna Pedee Belemnite Standard (VPDB). Reproducibility of repeated measurements of dolomite is 0.41 for 13C and 0.39 for 18O. The relatively low reproducibility compared to the reproducibility of standard materials ( 0.1 for both oxygen and carbon) is due to inhomogeneity of the samples. Most scatter is from microdrilled subsamples, where the small-scale mineralogy has not been checked. The full data set can be found in Meister et al. 2007, whereas the relevant 18O values are listed in the Appendix. Oxygen isotope analyses of the porewaters were determined by the CO2-equilibration method at 25 C with an automated ISOPPREP 18 device connected to a Micromass-OPTIMA, calibrated with the international SMOW and SLAP standards. The results are reported in the conventional notation relative to the Vienna Standard Mean Ocean Water standard (VSMOW). The precision is better than 0.1. The data are presented in Table 1. 4. Results

Dolomite layers and nodules from Sites 1227, 1228, and 1229 were systematically sampled onboard the JOIDES Resolution during ODP Leg 201. In addition we studied three samples from Site 681 (ODP Leg 112). A sample was always taken from the surrounding soft sediment for comparison. Bulk samples of dolomite nodules and surrounding

4.1. Description and distribution of dolomite layers The petrography of the dolomite layers recovered from the Leg 201 Peru Margin drill sites is described in detail in Meister et al.

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Fig. 2. Correlation of frequency of dolomite layers with color reectance (a; Shipboard Scientic Party, 2003), paleobathymetry reconstructed from benthic foraminifera (Resig, 1990), and TOC content (black rhombs; Meister et al., 2007) at shelf Site 1229. The color reectance is plotted in grey, and overlain with both, bathymetry and TOC. The x-axis has been slightly expanded for a on the right graph, in order to match the TOC prole. Ten-meter scale variations in color reectance are probably representing the 100 ka orbital cycles, but these are not resolved in the TOC data. The Brunhes Matuyama boundary is shown at 84 mbsf (D'Hondt, Jrgensen, Miller et al., 2003). Thirteen dolomite layers are counted in the last 0.78 Ma interval. The Pliocene/Pleistocene boundary is not precisely determined at this site, but must be at shallower depth than a Pliocene volcanic ash layer at 120 mbsf (Hart and Miller, 2006) and a nannofossil minimum age of 1.77 Ma at 124 mbsf (I. Aiello, pers. comm.).

(2006); here we only summarize the main features. Dolomite occurs as hard, lithied 2 to 5 cm-thick micritic layers within unlithied, almost carbonate-free hemipelagic sediment. Some of the layers are surrounded by unlithied friable dolomite and friable dolomite also occurs as independent laminae. In contrast, disseminated single dolomite rhombs are very rare throughout the drill cores. The lateral extent of the dolomite layers is unknown, since only broken pieces were recovered by advanced piston coring. From the study of outcrops of organic carbon-rich ocean margin sediments, such as the Miocene Monterey formation, however it is observed that such layers may extend laterally over hundreds of meters. In some cases, in the Monterey formation, they show lens shape pinch and swell morphologies or form layers of independent nodules. At Leg 201 sites, dolomite layers could not always be correlated between the different drill holes, nevertheless, layers recovered from the same site show similar thickness, but the thickness varies between the different sites. Within the Quaternary part of the sedimentary

column, Site 1229 shows the highest abundance of dolomite layers (Fig. 2), with 13 layers in the top 84 mbsf, which is younger than 0.78 Ma (Brunhes Matuyama Boundary; D'Hondt et al., 2003). The Pliocene Pleistocene boundary is not clearly constrained at this site. Correlation of volcanic ashes (Hart and Miller, 2006) indicate that it must be located shallower than 120 mbsf, i.e. shallower than indicated by the revised minimum age from Leg 112 biostratigraphy at 190 mbsf (D'Hondt et al., 2003). Also, a nannoplankton age of 1.77 Ma at 124 mbsf (I. Aiello, pers. comm.) supports a Pliocene Miocene boundary much shallower than the minimum age given in D'Hondt et al. (2003), and above the onset of diatomaceous sedimentation. As only 8 glacials occurred during the last 0.78 Ma the number of dolomite layers counted in this interval is too high, but some of the layers may have been counted twice in different drill holes, so that the total number approximately represents the number of glacials during this time. Indeed, if layers close together are counted as one, the number of layers would be

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PleistoceneHolocene column. Site 1227 does not contain any dolomite layers in the 10 m-thick condensed and probably incomplete Quaternary interval. Dolomite layers occur in the prePleistocene sediments at all sites, however, they are less common, and also TOC contents of the sediments are commonly lower. 4.2. Oxygen isotopes Dolomite 18O and 13C data are listed in Meister et al. (2007), but only the 13C results were discussed in detail. Here, the 18ODOL values of the Peru shelf Sites 1227, 1228, and 1229 (reproduced in Appendix) are plotted vs. 13CDOL in Fig. 3 and versus depth in Fig. 4. A few 18O data from dolomites of Leg 112 sites (Thornburg and Suess, 1990) are listed and plotted together with the new data in Fig. 4. The Peru shelf dolomites show relatively small variations in oxygen isotopic composition, ranging between 3 and 4.5 VPDB. No systematic variation was observed by comparing different proles across the dolomite layers. In this range, the effect of even small amounts of biogenic calcite mixed with the dolomite could be signicant, because the 18O of calcite would be approximately 2 lower than dolomite at near surface porewater temperatures (Vasconcelos et al., 2005). Therefore, great care was taken to avoid calcite rich samples. On a broad scale, these values are consistent with an early diagenetic, non-hydrothermal origin of the described dolomites, and exclude subsequent alteration by hydrothermal uids. No overall trend with depth is observed in downhole proles of the 18ODOL values. However, dolomite layers in pre-Pleistocene sediments at Sites 1228 and 1229, in general, show lower 18ODOL values. New porewater data from Sites 1227, 1228 and 1229 (Fig. 4ad, Table 1) show 18O values around 0 with values gradually decreasing to 1 at 200 mbsf at Site 1229. The slight decrease in 18O is a typical feature observed in porewaters of marine sediments and is probably related to silica diagenesis (Kastner et al., 1990). No positive isotopic anomaly at depth, which is related to diffusion of isotopically heavier residual glacial seawater (e.g. Adkins et al., 2003), is observed.

Fig. 3. Crossplot of carbon versus oxygen isotopic composition (in PDB) of early diagenetic dolomite layers recovered from Peru Margin shelf and upper slope sites 1227, 1228, and 1229. The distribution shows high variation in 13C, which was shown to be the result of variations in the microbial activity in the subsurface (Meister et al., 2007). Oxygen-18 values are on a large scale in equilibrium with seawater. However, Pleistocene dolomites (lled rhombs) seem to be shifted to more positive values compared to dolomites occurring in pre-Pleistocene sediments (open rhombs). Microdrilled subsamples inconsistent with the bulk sample, as well as values for dolomite from a previous study (Thornburg and Suess, 1990), are not included in the plot.

approximately 8. The dolomite layers (or couplets) show a 10 m spacing in the top 40 mbsf, which seems to be in phase with the cycles in color reectance. Below, the layers are not regularly spaced, and their abundance seems to correlate rather with largescale variation in TOC, color index and bathymetry than with the only weakly developed orbital cycles. At Site 1228, where the 7 m (100 ka) cycles are nicely resolved in TOC and color reectance (Meister et al., 2005), only 5 dolomite layers occur in a 56 m thick

Fig. 4. Oxygen isotopic compositions of dolomite and porewater from Sites 1227 (a), 1228 (b), and 1229 (c) in (PDB) and (SMOW), respectively, versus depth below seaoor. Values measured in ODP Leg 112 dolomite samples (Thornburg and Suess, 1990) and porewater (Kastner et al., 1990) were included in the plots. The depths of the Pliocene/Pleistocene boundaries are from D'Hondt et al. (2003), the 1.77 Ma minimum ages at Site 1229, 120 mbsf from Hart and Miller (2006) and at 124 mbsf from I. Aiello (pers. comm.), respectively. Oxygen isotope stages of Wefer et al. (1990) are shown for Site 1228, at 045 mbsf. Oxygen isotopes in the different carbonate phases also show, in general, compositions around 4 for dolomite and show a downward negative shift at the PliocenePleistocene boundary.

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Fig. 5. Reconstructed paleo-porewater temperatures correlated with in situ porewater temperature measurements (large crosses and regression line; Shipboard Scientic Party, 2003) at Leg 201/112 drill sites 1227 (a), 1228 (b), and 1229 (c). Paleo-porewater temperatures were calculated from the 18O values measured in dolomite (lled triangles). Paleoporewater temperatures were also calculated using a 18O value 1 heavier to represent glacial water (open triangles). The depths of the Pliocene/Pleistocene boundaries are from D'Hondt et al. (2003), the 1.77 Ma minimum ages at Site 1229, 120 mbsf from Hart and Miller (2006) and at 124 mbsf from I. Aiello (pers. comm.), respectively.

4.3. Calculated paleo-temperatures For the calculation of the paleo-temperatures for dolomite, the oxygen isotope fractionation factor of Vasconcelos et al. (2005) was used: 1000 ln adolomitewater 2:73T106 T 2 0:26 1

from dolomite layers of Site 1227 (Fig. 5a), which all occur in prePleistocene sediments are also between 5 and 10 C, but this deeper site at a water depth of 400 mbsl shows considerably lower modern porewater temperatures of 9 C and probably also pre-Pleistocene porewater temperatures were in this range. 5. Discussion 5.1. Depth and timing of dolomite formation The oxygen-18 values of the dolomite layers are not in isotopic equilibrium with the porewater at the depth they occur. Reconstructed temperatures of dolomite formation are low, often lower than modern bottom water temperatures at the different sites. This indicates that dolomite layers commonly form at shallow depth within the sedimentary sequence. This result is in agreement with a recent study of Sr isotopes (Meister et al., 2007), which indicate that dolomite layers form within the uppermost 30 mbsf of the sedimentary column and do not reect modern porewater Sr isotope compositions at the depth they are found. A shallow depth of precipitation is furthermore indicated by the fact that 13C values of the dolomites are not in equilibrium with 13C of dissolved carbonate in the modern porewater (Meister et al., 2007). The low paleo-temperatures are, thus, consistent with and provide further evidence for the previous conclusion that dolomite layers occurring throughout the sedimentary sequences were forming episodically in the past. The paleo-porewater temperatures reconstructed from the 18O of the Pleistocene dolomite layers recovered from Sites 1228 and 1229 are 5 to 10 C lower than modern values, as evidenced by the measured temperature gradient (Fig. 5). Lower bottom water temperatures during glacial periods could be an explanation for lower paleo-porewater temperatures. Kim et al. (2002) and Lamy et al. (2004) show that the sea-surface temperatures along the coast of Chile were about 5 C lower during glacial times. Modern sea-surface temperatures offshore Peru vary seasonally between 16 to 23 C. In the past, during sealevel lowstands, water depth at Site 1229 was less than 50 m and, thus, a dramatic decrease in surface water temperature must have occurred during glacial times, affecting the diagenetic

and the equation of Friedman and O'Neil (1977) was used for calcite: 1000 ln acalcitewater 2:78T106 T 2 2:89 2

Based on these fractionation factors, a contribution of up to 25% marine calcite with a 18O value of 2 would lower the measured value from the dolomite with a 18O of 4 by 0.5 and would thus result in calculated temperatures 2 C too high. However, calcite contributions determined by XRD analysis were lower than 10%. Some outliers are due to microdrill samples, which may have picked up a signal from other minerals, e.g. a single calcitic bioclast. Measurements from microdrill samples that were distinctly different from all others within the same dolomite layer were not used for paleotemperature calculation. The increase in 18O of seawater during glacial times has been estimated to be 1 to 1.2 . A change of this magnitude would lower calculated paleo-temperatures by up to 5 6 C and has to be taken into account for paleo-porewater temperatures (Fig. 5). At the shallow shelf Sites 1228/680 and 1229/681, the calculated temperatures range between 5 and 10 C, with an average of 7 C (Fig. 5b, c). Temperatures decrease across the Plio-Pleistocene boundary and are clearly lower than today's bottom water and near surface porewater temperatures, which are around 1314 C (D'Hondt et al., 2003). If an up to 5 C shift to higher paleo-temperatures due to glacial 18OW is taken into account, Quaternary paleo-temperatures at the shallow Sites 1228/680 and 1229/681 are still lower than modern porewater temperatures, whereas no signicant difference between paleo- and modern porewater temperature is indicated by the data from dolomite layers of pre-Pleistocene units. The paleo-temperatures

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Fig. 6. Model for the periodic formation of dolomite layers in the Peru Margin shelf sediments through the last two glacial/interglacial periods. Organic C-rich sediment is deposited in this region during eustatic sealevel highstand (Wefer et al., 1990), which leads to enhanced consumption of SO2 and the upward migration of the sulphate methane interface (SMI). 4 During glacial intervals, SO2 consumption is lower in the surface sediments and the SMI remains in place for a longer time, to allow the precipitation of a hard-lithied dolomite layer. 4

system. Based on the low paleo-temperatures, we conclude that Pleistocene dolomite layers formed primarily during glacial times. Since no altered residual porewater with a 18O signature of the last glacial maximum (LGM), as described by Adkins et al. (2003), is present at the three sites, we assume that this was also the case during the interglacials. Pre-Pleistocene layers show temperatures, which are close to modern near surface porewater temperatures and a gradual cooling occurs across the PliocenePleistocene boundary. Episodicity of dolomite formation during the pre-Pleistocene may have been triggered by oceanographic variations not related to glacial/interglacial cycles, as discussed below. 5.2. A non-actualistic model for dolomite formation The episodic growth of dolomite layers during glacial intervals can be explained with dolomite precipitation at an episodically migrating SMI (Fig. 6). Enhanced SO2 consumption during TOC-rich 4 highstand sedimentation led to an upward migration of the SMI. During sealevel lowstand, primary productivity and organic matter input were limited at the shelf sites, sediment with TOC contents less than 1% were deposited (Wefer et al., 1990; Meister et al., 2005), and as a result SO2 was only slowly consumed. As simulated in a numerical 4 model (Meister et al., 2007), this would have allowed downward diffusion of SO2 so that the SMI would have remained stationary. Since 4 Mg2+ and Ca2+ are limited by diffusion (Compton and Siever, 1986), the SMI had to remain at the same depth for a sufcient amount of time to allow enough Mg2+ and Ca2+ to diffuse to this depth. As the number of dolomite layers approximately match with the number of glacial/ interglacial cycles (8 layers or couplets in 0.78 Ma) at Site 1229 (Fig. 2), during each glacial interval, one layer was formed. The dolomite layers are not always regularly spaced, which is most likely due to the superimposed large-scale variations in sediment composition. At Site 1228 several dolomite layers are missing, probably due to the absence of the SMI for most of the time, as a SMI does not occur today. The observation of Compton (1988) that the distribution of

dolomite layers in the Monterey Formation shows a Milankovitch type pattern can be similarly explained even if no glacial/interglacial variations occurred in the Miocene. Other climatic/oceanographic variations may control the dynamics of the redox zonation in the subsurface in pre-Pleistocene sediments. The proposed mechanism supports an episodic formation of dolomite layers and each layer represents a snapshot of a specic time interval. It also explains why the actualistic approach, i.e. assuming a steady state geochemical zonation, failed to explain the distribution of dolomite layers in deepsea sediments. 6. Conclusions The observation of Compton (1988), that early diagenetic dolomite layers in organic carbon-rich upwelling sediments, such as in the Miocene Monterey Formation, occur with a Milankovitch type spacing could not be explained for a long time. This study of 18O values in Peru Margin dolomites recovered during ODP Leg 201 provides new data that allow to postulate a possible relationship between diagenetic dolomite formation and past oceanographic conditions. The reconstruction of paleo-porewater temperatures from 18ODOL indicates that dolomite layers formed predominantly during glacial episodes. Glacial lowstand sediments are TOC-poor, and allow for downward diffusion of SO2 so that the sulphatemethane interface 4 remains xed within a deeper zone with TOC-rich interglacial sediments, where high microbial activity increases the alkalinity at a focused depth. The supply of Mg2+ and Ca2+ is limited by diffusion and a dolomite layer only forms if the sulphatemethane interface remains stationary for a sufcient amount of time. This model provides a possible link between episodic dolomite formation, dynamics of the diagenetic zonation, and past oceanographic conditions. In this context, early diagenetic carbonate precipitates can be considered as episodic documents of past diagenetic systems and a dynamic deep biosphere in the geological record, such as in the Miocene Monterey Formation and other organic C-rich ocean margin sediments.

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Acknowledgements For their assistance during oxygen isotope measurements we thankfully acknowledge Nele Meckler and Maria Strasser. We thank Ruth Blake for allowing us to use her Leg 201 porewater samples for O analysis. Carolina Reyes signicantly improved the English of this 18 text. Discussions with Daniel Bernoulli, Sergio Contreras Quintana, Robert Garrison, and Lowell Stott contributed in major parts to the interpretations described in this study. We also thank the Leg 201 Shipboard Scientic Party for taking special care of sampling dolomite layers. This research used samples and data provided by the Ocean Drilling Program (ODP). ODP is sponsored by the participating countries under management of Joint Oceanographic Institutions (JOI), Inc. This study was nanced by Swiss National Science Foundation (SNF) Project No. 20-59282 and 20-67620 and ETH Zrich. The SNF also sponsors the Swiss participation in ODP.

Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.margeo.2008.04.001. References
Adkins, J.F., McIntyre, K., Schrag, D.P., 2003. The salinity, temperature, and 18O of the glacial deep ocean. Science 298, 17691773. Baker, P.A., Burns, S.J., 1985. Occurrence and formation of dolomite in organic-rich continental margin sediments. AAPG Bull. 69, 19171930. Burns, S.J., Baker, P.A., 1987. A geochemical study of dolomite in the Monterey Formation, California. J. Sediment. Petrol. 57, 128139. Burns, S.J., Baker, P.A., Showers, W.J., 1988. The factors controlling the formation and chemistry of dolomite in organic-rich sediments: Miocene Drakes Bay Formation, California. In: Shukla, V., Baker, P.A. (Eds.), Sedimentology and Geochemistry of Dolostones. SEPM Spec. Pub., Tulsa, vol. 43, pp. 310. Claypool, C.E., Kaplan, I.R., 1974. The origin and distribution of methane in marine sediments. In: Kaplan, I.R. (Ed.), Natural Gases in Marine Sediments. Plenum Press, New York, pp. 99140. Compton, J.S., Siever, R., 1986. Diffusion and mass balance of Mg during early dolomite formation, Monterey Formation. Geochim. Cosmochim. Acta 50, 125135. Compton, J.S., 1988. Sediment composition and precipitation of dolomite and pyrite in the Neogene Monterey and Sisquoc Formations, Santa Maria Basin area, California. In: Shukla, V., Baker, P.A. (Eds.), Sedimentology and Geochemistry of Dolostones. SEPM Spec. Pub., Tulsa, vol. 43, pp. 5364. D' Hondt, S., Jrgensen, B.B., Miller, J., ODP Leg 201 Shipboard Scientic Party, 2003. Controls on microbial communities in deeply buried sediments, Eastern Equatorial Pacic and Peru Margin, Sites 12251231. College Station, TX (Ocean Drilling Program). Proc. ODP, Init. Repts., vol. 201. D' Hondt, S., Jrgensen, B.B., Miller, J., Batzke, A., Blake, R., Cragg, B.A., Cypionka, H., Dickens, G.R., Ferdelman, T., Hinrichs, K.-U., Holm, N.G., Mitterer, R., Spivack, A., Wang, G., Bekins, B., Engelen, B., Ford, K., Gettemy, G., Rutherford, S.D., Sass, H., Skilbeck, C.G., Aiello, I.W., Gurin, G., House, C.H., Inagaki, F., Meister, P., Naehr, T., Niitsuma, S., Parkes, J., Schippers, A., Smith, D.C., Teske, A., Wiegel, J., Padilla, C.N., Solis Acosta, J.L., 2004. Distributions of microbial activities in deep subseaoor sediments. Science 306, 22162221. Emeis, K.-C., Morse, J.W., 1990. Organic carbon, reduced sulphur, and iron relationships in sediments of the Peru Margin, Sites 680 and 688. In: Suess, E., von Huene, R., et al. (Eds.), College Station, TX (Ocean Drilling Program). Proc. ODP, Sci. Results, vol. 112, pp. 413440. Friedman, I., O'Neil, J.R., 1977. Compilation of stable isotope fractionation factors of geochemical interest. In: Fleischer, M. (Ed.), Data of Geochemistry. . Professional Paper, vol. 440-KK. U.S. Geological Survey, p. 12. Hart, D., Miller, D.J., 2006. Analysis and correlation of volcanic ash in marine sediments from the Peru Margin, Ocean Drilling Program Leg 201: explosive volcanic cycles of

the north-central Andes. In: Jrgensen, B.B., D'Hondt, S.L., Miller, D.J. (Eds.), College Station, TX (Ocean Drilling Program). Proc. ODP, Sci. Results, vol. 201. Kastner, M., Eldereld, H., Martin, J.B., Suess, E., Kvenvolden, K.A., Garrison, R.E., 1990. Diagenesis and interstitial-water chemistry at the Peruvian Continental Margin major constituents and strontium isotopes. In: Suess, E., von Huene, R., et al. (Eds.), College Station, TX (Ocean Drilling Program). Proc. ODP, Sci. Results, vol. 112, pp. 413440. Kelts, K., McKenzie, J.A., 1982. In: Curray, J.R., Moore, D.G., et al. (Eds.), Diagenetic Dolomite Formation in Quaternary Anoxic Diatomaceous Muds of Deep Sea Drilling Project Leg 64, Gulf of California. . Initial Reports of the Deep Sea Drilling Project, vol. 46. Government Printing Ofce, Washington, U.S., pp. 553569. Kelts, K., McKenzie, J.A., 1984. A comparison of anoxic dolomite from deep-sea sediments: Quaternary Gulf of California and Messinian Tripoli Formation of Sicily. In: Garrison, R.E., Kastner, M., Zenger, D.H. (Eds.), Dolomites of the Monterey Formation and other Organic-rich Units. Pacic Section SEPM, vol. 41, pp. 1928. Kim, J.H., Schneider, R.R., Hebbeln, D., Mller, P.J., Wefer, G., 2002. Last deglacial seasurface temperature evolution in the Southeast Pacic compared to climate changes on the South American contintent. Quat. Sci. Rev. 21, 20852097. Kulm, L.D., Suess, E., Thornburg, T., 1984. Dolomites in organic-rich muds of the Peru forearc basins: analogue to the Monterey Formation. In: Garrison, R.E., Kastner, M., Zenger, D.H. (Eds.), Dolomites of the Monterey Formation and other Organic-rich Units. Pacic Section SEPM, vol. 41, pp. 2947. Lamy, F., Kaiser, J., Ninnemann, U., Hebbeln, D., Arz, H.W., Stoner, J., 2004. Antarctic timing of surface water change off Chile and Patagonian ice sheet response. Science 304, 19591961. Meister, P., Prokopenko, M., Skilbeck, C.G., Watson, M., McKenzie, J.A., 2005. Data report: compilation of total organic and inorganic carbon data from Peru Margin and Eastern Equatorial Pacic drill sites (ODP Legs 112, 138 and 201). In: Jrgensen, B.B., D'Hondt, S., Miller, J. (Eds.), College Station, TX (Ocean Drilling Program). Proc. ODP, Sci. Results., vol. 201. Meister, P., McKenzie, J.A., Warthmann, R., Vasconcelos, C., 2006. Mineralogy and petrography of diagenetic dolomite from the ODP Leg 201 Peru Margin drill sites. In: Jrgensen, B.B., D'Hondt, S., Miller, J. (Eds.), College Station, TX (Ocean Drilling Program). Proc. ODP, Sci. Results, vol. 201. Meister, P., McKenzie, J.A., Vasconcelos, C., Bernasconi, S., Frank, M., Gutjahr, M., Schrag, D.P., 2007. Dolomite formation in the dynamic deep biosphere, results from the Peru Margin, OPD Leg 201. Sedimentology 54, 10071032. Murata, K.J., Friedman, I., Madsen, B.H., 1969. Isotopic Composition of Diagenetic Carbonates in Marine Miocene Formations of California and Oregon. USGS Prof. Paper, vol. 614-B, p. 24. Parkes, R.J., Webster, G., Cragg, B.A., Weightman, A.J., Newberry, C.J., Ferdelman, T.G., Kallmeyer, J., Jrgensen, B.B., Aiello, I.W., Fry, J.C., 2005. Deep sub-seaoor prokaryotes stimulated at interfaces over geological time. Lett. Nature 436, 390394. Pisciotto, K.A., Mahoney, J.J., 1981. Isotopic survey of diagenetic carbonates. In: Yeats, R.S., Haq, B.U., et al. (Eds.), Init. Repts. DSDP US Govt Printing Ofce. Washington, DC, vol. 63, pp. 595609. Resig, J.M., 1990. Benthic foraminiferal stratigraphy and paleoenvironments off Peru. In: Suess, E., von Huene, R., et al. (Eds.), College Station, TX (Ocean Drilling Program). Proc. ODP, Sci. Results, vol. 112, pp. 263296. Rosenbaum, J., Sheppard, S.M.F., 1986. An isotopic study of siderites, dolomites and ankerites at high temperatures. Geochim. Cosmochim. Acta 50, 11471150. Suess, E., von Huene, R., ODP Leg 112 Shipboard Scientic Party, 1988. Peru continental margin. Proc. ODP, Init. Repts., College Station, TX (Ocean Drilling Program), p. 112. Thornburg, T.M., Suess, E., 1990. Carbonate cementation of granular and fracture porosity: implications for the cenozoic hydrologic development of the Peru Continental Margin. In: Suess, E., von Huene, R., et al. (Eds.), College Station, TX (Ocean Drilling Program). Proc. ODP, Sci. Results, vol. 112, pp. 95109. Vasconcelos, C., McKenzie, J.A., Bernasconi, S., Grujic, D., Tien, A.J., 1995. Microbial mediation as a possible mechanism for natural dolomite formation at low temperatures. Nature 377, 220222. Vasconcelos, C., McKenzie, J.A., Warthmann, R., Bernasconi, S., 2005. Calibration of the 18O paleo-thermometer with dolomite formed in microbial cultures and natural environments. Geology 33, 317320. Wefer, G., Heinze, P., Suess, E., 1990. Stratigraphy and sedimentation rates from oxygen isotope composition, organic carbon content, and grain-size distribution at the Peru upwelling region: holes 680B and 686B. In: Suess, E., von Huene, R., et al. (Eds.), College Station, TX (Ocean Drilling Program). Proc. ODP, Sci. Results, vol. 112, pp. 355367. Zuta, S., Guillen, O., 1970. Oceanograa de las aguas costeras del Peru. Inst. Mar. Peru, Bol. 2, 161323.