(Appendix) Gephyrocapsa coccolith abundance and holocene paleotemperature assessment

A global sea surface temperature calibration based on the relative abundance of different morphotypes within the coccolithophore genus Gephyrocapsa in Holocene deep-sea sediments is presented. There is evidence suggesting that absolute sea surface temperature for a given location can be calculated from the relative abundance of Gephyrocapsa morphotypes in sediment samples, with a standard error comparable to temperature estimates derived from other temperature proxies such as planktic foraminifera transfer functions. A total of 110 Holocene sediment samples were selected from the Pacific, Indian, and Atlantic Oceans covering a mean sea surface temperature gradient from 13.6° to 29.3°C. Standard multiple linear regression analyses were applied to this data set, linking the relative abundance of Gephyrocapsa morphotypes to sea surface temperature. The best model revealed an r**2 of 0.83 with a standard residual error of 1.78°C for the estimation of mean sea surface temperature. This new proxy provides a unique opportunity for the reconstruction of paleotemperatures with a very small amount of sample material due to the minute size of coccoliths, permitting examination of thinly laminated sediments (e.g., a pinhead of material from laminated sediments for the reconstruction of annual sea surface temperature variations). Such fine-scale resolution is currently not possible with any other proxy. Application of this new paleotemperature proxy may allow new paleoenvironmental interpretations in the late Quaternary period and discrepancies between the different currently used paleotemperature proxies might be resolved.

Sea-surface temperature reconstruction of sediment cores from the Skagerrak

We attempt a reconstruction of salinity levels of the central Baltic Sea based on diatom assemblages, the isotopic composition of organic matter and sedimentological expression of anoxia over the last 10 000 years. We use the data to investigate the dependence of salinity levels on climate evolution and isostasy. Changes in salinity of surface and deep waters were most pronounced from 8400 to approximately 5000 cal. BP. Density stratification between salty deep and fresher surface waters caused the frequent development of anoxic conditions and deposition of laminated sediments on large parts of the sea floor in the central Baltic Sea, and dramatic changes in organic carbon-accumulation rates. From 5000 to 3100 cal. BP, the salinity of the basin decreased, oxygenation of deep sea floors was improved, and fertility of the sea surface was significantly reduced. This is reflected by low accumulation rates of organic carbon in bioturbated sediments. Since 2800 cal. BP, salinity rose again and anoxic periods were more common. Even though the major steps in environmental evolution in the Baltic Sea coincide with known patterns of climatic change of the North Atlantic realm over the last 10 000 years, we find no conclusive evidence for synchronous changes or linear responses on submillennial timescales. However, we note that major variations in our salinity records agree with temporal patterns of reconstructed summer warmth and winter precipitation in southern Scandinavia. Both types of record suggest that climate in the mid-Holocene was far from stable. Our data also confirm that climate evolution over the late Holocene had significant impact on environmental conditions in the Baltic Sea.

(Table S1) Opal content of sediment core OXMZ01MV-GC31

The North American monsoon (NAM), an onshore wind shift occurring between July and September, has evolved in character during the Holocene largely due to changes in Northern Hemisphere insolation. Published paleoproxy and modeling studies suggest that prior to ~8000 cal years BP, the NAM affected a broader region than today, extending westward into the Mojave Desert of California. Holocene proxy SST records from the Gulf of California (GoC) and the adjacent Pacific provide constraints for this changing NAM climatology. Prior to ~8000 cal years BP, lower GoC SSTs would not have fueled northward surges of tropical moisture up the GoC, which presently contribute most of the monsoon precipitation to the western NAM region. During the early Holocene, the North Pacific High was further north and SSTs in the California Current off Baja California were warmer, allowing monsoonal moisture flow from the subtropical Pacific to take a more direct, northwesterly trajectory into an expanded area of the southwestern U.S. west of 114°W. A new upwelling record off southwest Baja California reveals that enhanced upwelling in the California Current beginning at ~7500 cal year BP may have triggered a change in NAM climatology, focusing the geographic expression of NAM in the southwest USA into its modern core region east of ~114°W, in Arizona and New Mexico. Holocene proxy precipitation records from the southwestern U.S. and northwestern Mexico, including lakes, vegetation/pollen, and caves are reviewed and found to be largely supportive of this hypothesis of changing Holocene NAM climatology.

Geochemistry and P and Fe fractionation in anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (~94 Ma) and the Paleocene-Eocene thermal maximum (?55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO3 contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO3 can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.

Bulk sediment parameter of three sediment cores from permafrost lowlands, Alaska Arctic Coastal Plain

Arctic lowland landscapes have been modified by thermokarst lake processes throughout the Holocene. Thermokarst lakes form as a result of ice-rich permafrost degradation and they may expand over time through thermal and mechanical shoreline erosion. We studied proximal and distal sedimentary records from a thermokarst lake located on the Arctic Coastal Plain of northern Alaska to reconstruct the impact of catchment dynamics and morphology on the lacustrine depositional environment and to quantify carbon accumulation in thermokarst lake sediments. Short cores were collected for analysis of pollen, sedimentological and geochemical proxies. Radiocarbon and Pb/Cs dating, as well as extrapolation of measured historic lake expansion rates, were applied to estimate a minimum lake age of ~ 1,400 calendar years BP. The pollen record is in agreement with the young lake age as it does not include evidence of the "alder high" that occurred in the region ~ 4.0 cal ka BP. The lake most likely initiated from a remnant pond in a drained thermokarst lake basin (DTLB) and deepened rapidly as evidenced by accumulation of laminated sediments. Increasing oxygenation of the water column as shown by higher Fe/Ti and Fe/S ratios in the sediment indicate shifts in ice regime with increasing water depth. More recently, the sediment source changed as the thermokarst lake expanded through lateral permafrost degradation, alternating from redeposited DTLB sediments, to increased amounts of sediment from eroding, older upland deposits, followed by a more balanced combination of both DTLB and upland sources. The characterizing shifts in sediment sources and depositional regimes in expanding thermokarst lakes were therefore archived in the thermokarst lake sedimentary record. This study also highlights the potential for Arctic lakes to recycle old carbon from thawing permafrost and thermokarst processes.

(Table 2) Terrigenous, authigenic and biogenic composition of sediments at DSDP Hole 93-603B

Pelagic sedimentation during the Early Cretaceous at Site 603 produced alternations of laminated marly limestone and bioturbated limestone-a facies typical of the "Blake-Bahama Formation" of the western Atlantic. This limestone is a nannofossil micrite, rich in calcified radiolarians, with variable amounts of organic matter, pyritized radiolarian tests, fish debris, and micaceous silt. The laminated marly limestone layers are enriched in organic matter when compared with the intervals of bioturbated limestone. The organic carbon is predominantly terrestrial plant debris; where the organic-carbon content is in excess of 1%, there is also a significant marine-derived component. Laminations can result either from bands of alternately enriched and depleted opaque material and clay, or from bands of elongate lenses (microflasers) of micrite, which could be plastically deformed pellets or diagenetic features. The alternating intervals of laminated and bioturbated structures may have resulted from combined changes in surface productivity, in the influx of terrigenous organic matter, and in the intensity of bottom circulation, which led to episodic oxygen depletion in the bottom water and sediments. Variations in the relative proportions of laminated clay-rich and bioturbated lime-rich limestone and in the development of cycles between these structures make it possible to subdivide the Lower Cretaceous pelagic facies into several subunits which appear to be regional in extent. Bioturbated limestone is dominant in the Berriasian, laminated marly limestone in the Valanginian and Barremian-lower Aptian, and well-developed alternations between these end members in the Hauterivian. The Hauterivian to lower Aptian sediments contain abundant terrigenous clastic turbidites associated with a submarine fan complex. These changes in the general characteristics of the pelagic sediment component of the Blake-Bahama Formation at Site 603 are synchronous with those in the Blake-Bahama Basin (Sites 534 and 391) to the south. Carbonate sedimentation ended in the early Aptian, probably because of a regional shoaling of the carbonate compensation depth.

Smear slide analysis of sediment core GeoB5836-2

Laminated sediments spanning the last 20,000 years (though not continuously) in the Shaban Deep, a brine-filled basin in the northern Red Sea, were analyzed microscopically and with backscattered electron imagery in order to determine laminae composition with emphasis on the diatomaceous component. Based on this detailed study, we present schematic models to propose paleoflux scenarios for laminae formation at different time-slices. The investigated core (GeoB 5836-2; 26°12.61'N, 35°21.56'E; water depth 1475 m) shows light and dark alternating laminae that are easily distinguishable in the mid-Holocene and at the end of the deglaciation (13-15 ka) period. Light layers are mainly composed of coccoliths, terrigenous material and diatom fragments, while dark layers consist almost exclusively of diatom frustules (monospecific or mixed assemblages). The regularity in the occurrence of coccolith/diatom couplets points to an annual deposition cycle where contrasting seasons and associated plankton blooms are represented (diatoms-fall/winter deposition, coccoliths-summer signal). We propose that, for the past ~15,000 years, the laminations represent two-season annual varves. Strong dissolution of carbonate, with the concomitant loss of the coccolith-rich layer in sediments older than 15 ka, prevents us from presenting a schematic model of annual deposition. However, the diatomaceous component reveals a marked switch in species composition between Last Glacial Maximum (LGM) sediments (dominated by Chaetoceros resting spores) and sediments somewhat younger (18-19 ka; dominated by Rhizosolenia). We propose that different diatom assemblages reflect changing conditions in stratification in the northern Red Sea: Strong stratification conditions, such as during two meltwater pulses at 14.5 and 11.4 ka, are reflected in the sediment by Rhizosolenia layers, while Chaetoceros-dominated assemblages represent deep convection conditions.

Geochemical composition of ODP Site 210-1276 shales

During Ocean Drilling Program Leg 210, a greatly expanded sedimentary sequence of continuous Cretaceous black shales was recovered at Site 1276. This section corresponds to the Hatteras Formation, which has been documented widely in the North Atlantic Ocean. The cored sequence extends from the lowermost Albian, or possibly uppermost Aptian, to the Cenomanian/Turonian boundary and is characterized by numerous gravity-flow deposits and sporadic, finely laminated black shales. The sequence also includes several sedimentary intervals with high total organic carbon (TOC) contents, in several instances of probable marine origin that may record oceanic anoxic events (OAE). These layers might correspond to the Cenomanian-Turonian OAE 2; the mid-Cenomanian event; and OAE 1b, 1c, and 1d in the Albian. In addition, another interval with geochemical characteristics similar to OAE-type layers was recognized in the Albian, although it does not correspond to any of the known OAEs. This study investigates the origin of the organic matter contained within these black shale intervals using TOC and CaCO3 contents, Corg/Ntot ratios, organic carbon and nitrogen isotopes, trace metal composition, and rock-eval analyses. Most of these black shale intervals, especially OAE 2 and 1b, are characterized by low 15N values (<0) commonly observed in mid-Cretaceous black shales, which seem to reflect the presence of an altered nitrogen cycle with rates of nitrogen fixation significantly higher than in the modern ocean.

Microbialites and lipid biomarker from coral reefs off the volcanic islands Tahiti and Vanuatu and from the nonvolcanic sites Belize and the Maldives

The occurrence of microbialites in post-glacial coral reefs has been interpreted to reflect an ecosystem response to environmental change. The greater thickness of microbialites in reefs with a volcanic hinterland compared to thinner microbial crusts in reefs with a non-volcanic hinterland led to the suggestion that fertilization of the reefal environment by chemical weathering of volcanic rocks stimulated primary productivity and microbialite formation. Using a molecular and isotopic approach on reef-microbialites from Tahiti (Pacific Ocean), it was recently shown that sulfate-reducing bacteria favored the formation of microbial carbonates. To test if similar mechanisms induced microbialite formation in other reefs as well, the Tahitian microbialites are compared with similar microbialites from coral reefs off Vanuatu (Pacific Ocean), Belize (Caribbean Sea, Atlantic Ocean), and the Maldives (Indian Ocean) in this study. The selected study sites cover a wide range of geological settings, reflecting variable input and composition of detritus. The new lipid biomarker data and stable sulfur isotope results confirm that sulfate-reducing bacteria played an intrinsic role in the precipitation of microbial carbonate at all study sites, irrespective of the geological setting. Abundant biomarkers indicative of sulfate reducers include a variety of terminally-branched and mid chain-branched fatty acids as well as mono-O-alkyl glycerol ethers. Isotope evidence for bacterial sulfate reduction is represented by low d34S values of pyrite (-43 to -42 per mill) enclosed in the microbialites and, compared to seawater sulfate, slightly elevated d34S and d18O values of carbonate-associated sulfate (21.9 to 22.2 per mill and 11.3 to 12.4 per mill, respectively). Microbialite formation took place in anoxic micro-environments, which presumably developed through the fertilization of the reef environment and the resultant accumulation of organic matter including bacterial extracellular polymeric substances (EPS), coral mucus, and marine snow in cavities within the coral framework. ToF-SIMS analysis reveals that the dark layers of laminated microbialites are enriched in carbohydrates, which are common constituents of EPS and coral mucus. These results support the hypothesis that bacterial degradation of EPS and coral mucus within microbial mats favored carbonate precipitation. Because reefal microbialites formed by similar processes in very different geological settings, this comparative study suggests that a volcanic hinterland is not required for microbialite growth. Yet, detrital input derived from the weathering of volcanic rocks appears to be a natural fertilizer, being conductive for the growth of microbial mats, which fosters the development of particularly abundant and thick microbial crusts.

(Table 1) Radiocarbon ages of core AB01/94 obtained in the Tromper Wiek, western Baltic Sea

In the Tromper Wiek northeast of Rügen, acoustical investigations using Air Gun, Boomer, Chirp Sonar and Sediment-Echosounder were carried out. Together with sediment core information, it allowed the identification of five seismostratigraphic units (E1 to E5). Conventional and AMS-14C-datings supported their chronostratigraphical classification. The uppermost till (E1) was incised by late glacial channels filled with glaciolacustrine sediments (E2) of the early Baltic Ice Lake stages. These were regionally overlain with a sharp unconformity by a thick (locally >20 m) sedimentary complex (E3) of acoustically laminated silts of freshwater origin. This lower part of the E3-complex (E3a) is overlain by fluvial to coastal silty fine sands (E3b) deeper towards the Arkona Basin. Fine plant debris in the uppermost part of sub-unit E3a yielded ages of 10,100 and 10,500 14C-years B.P., representing the final phase of the Baltic Ice Lake. The fine sands of sub-unit E3b were deposited after the final drainage of the Baltic Ice Lake. In the shallower central part of the bay, the silts of sub-unit E3a were covered by a younger unit (E4) of fine sand with plant debris. A sedge peat occurring at the basis of unit E4 yielded an age of 9,590 14C-years B.P. The fine sands overlying the unit E3 in the central part of Tromper Wiek were deposited in the Ancylus Lake. Their position at about 20 m below present sea level (b.s.l.) reflects the maximum highstand in this area. The character and distribution of the Early Holocene deposits at greater depth suggest a lake water level at about 30 m b.s.l. after this highstand. Below 25 m b.s.l. muddy Littorina Sea sediments are observed. The thickness of these muds and sandy muds increases gradually towards the Arkona Basin. Locally, they are found in a channel-like structure immediately north of Jasmund.

(Table 1) Stable carbon isotope ratios of methane and carbon dioxide from ODP Leg 169S holes

Sites 1033 and 1034 of ODP Leg 169S in Saanich Inlet have an unusual diagenetic system, that has the appearance of being depth reversed, i.e. a bacterial methane accumulation zone underlain by a sulphate reduction zone. During the late Pleistocene grey, undifferentiated, glacio-marine clays were deposited with low Corg contents (<0.4 wt.%), and interstitial fluids replete in SO4 (ca. 27 mM), devoid of CH4 and low in nutrients. This indicates oxic conditions are present, reflecting the open exchange of waters with Haro Strait during the Pleistocene before the Saanich Peninsula emerged. In the earliest Holocene (ca. 11,000 years BP) the inlet was formed, severely restricting water circulation, and leading to the presence of anoxic bottom waters. The sediments are laminated and show a dramatic rise to high Corg, Norg and Stot contents (up to 2.5, 0.4, 1.4 wt.%, respectively) over a period of ca. 1000 years. The nutrient concentrations are especially high (TA, NH4, PO4 up to 115 meq/l, 20 mM and 400 µM, respectively), SO4 is exhausted and CH4 is prolific. Stable carbon isotope ratio measurements of CH4 and co-existing CO2 indicate that methanogenesis is via carbonate reduction (delta13C-CH4 ca. -60 to - 70 per mil, delta13C-CO2 ca. +10 per mil). At the sulphate-methane interfaces, both at the near-surface and at 50 mbsf (Site 1033) and 80 mbsf (Site 1034) methane consumption by sulphate reducing bacteria is intensive.

Pollen counts of sediment core MFM6

In recent years enormous success has been achieved in varve counting of the Eifel maar lakes, but a detailed correlation with the biostratigraphy has been missing. In this paper, we present new palynological results of the Lateglacial sequences from Holzmaar Lake and Meerfelder Maar Lake based on annually laminated sediments. In particular, the Meerfelder Maar has great potential, because, in contrast to the Holzmaar, the sequence between the Ulmener Maar Tephra (11 000 varve years BP) and the Laacher See Tephra (12 880 varve years BP) including the Younger Dryas is undisturbed and complete. Therefore, we currently use the Meerfelder Maar chronology (Brauer et al., 1999b) as an independent varve calendar for the biostratigraphy of the Lateglacial. The palynological signals of both maar lakes are in good agreement and can easily be correlated with one another and with type sections/type regions in northwestern Germany and Jutland. The sequences of the Eifel maar lakes have the quality of hypostratotypes with regional biozones based on an absolute time scale.