Pacific Neogene carbonate accumulation rates

I have compiled CaCO3 mass accumulation rates (MARs) for the period 0-25 Ma for 144 Deep Sea Drilling Project and Ocean Drilling Program drill sites in the Pacific in order to investigate the history of CaCO3 burial in the world's largest ocean basin. This is the first synthesis of data since the beginning of the Ocean Drilling Program. Sedimentation rates, CaCO3 contents, and bulk density were estimated for 0.5 Myr time intervals from 0 to 14 Ma and for 1 Myr time intervals from 14 to 25 Ma using mostly data from Initial Reports volumes. There is surprisingly little coherence between CaCO3 MAR time series from different Pacific regions, although regional patterns exist. A transition from high to low CaCO3 MAR from 23-20 Ma is the only event common to the entire Pacific Ocean. This event is found worldwide. The most likely cause of lowered pelagic carbonate burial is a rising sea-level trend in the early Miocene. The central and eastern equatorial Pacific is the only region with adequate drill site coverage to study carbonate compensation depth (CCD) changes in detail for the entire Neogene. The latitude-dependent decrease in CaCO3 production away from the equator is an important defining factor of the regional CCD, which shallows away from the equatorial region. Examination of latitudinal transects across the equatorial region is a useful way to separate the effects of changes in carbonate production ('productivity') from changes in bottom water chemistry ('dissolution') upon carbonate burial.

Benthic oxygen isotope and dust flux record from ODP Site 108-659 in the North Atlantic

High-resolution benthic oxygen isotope and dust flux records from Ocean Drilling Program site 659 have been analyzed to extend the astronomically calibrated isotope timescale for the Atlantic from 2.85 Ma back to 5 Ma. Spectral analysis of the delta18O record indicates that the 41-kyr period of Earth's orbital obliquity dominates the Pliocene record. This is shown to be true regardless of fundamental changes in the Earth's climate during the Pliocene. However, the cycles of Sahelian aridity fluctuations indicate a shift in spectral character near 3 Ma. From the early Pliocene to 3 Ma, the periodicities were dominantly precessional (19 and 23 kyr) and remained strong until 1.5 Ma. Subsequent to 3 Ma, the variance at the obliquity period (41 kyr) increased. The timescale tuned to precession suggests that the Pliocene was longer than previously estimated by more than 0.5 m.y. The tuned ages for the magnetic boundaries Gauss/Gilbert and Top Cochiti are about 6-8% older than the ages of the conventional timescale. A major phase of Pliocene northern hemisphere ice growth occurred between 3.15 Ma and 2.5 Ma. This was marked by a gradual increase in glacial Atlantic delta18O values of 1per mil and an increase in amplitude variations by up to 1.5 per mil, much larger than in the Pacific deepwater record (site 846). The first maxima occured in cold stages G6-96 between 2.7 Ma and 2.45 Ma. Prior to 3 Ma, the isotope record is characterized by predominantly low amplitude fluctuations (< 0.7 per mil). When obliquity forcing was at its minimum between 4.15 and 3.6 Ma and during the Kaena interval, delta18O amplitude fluctuations were minimal. From 4.9 to 4.3 Ma, the delta18O values decreased by about 0.5 per mil, reaching a long-term minimum at 4.15 Ma, suggesting higher deepwater temperatures or a deglaciation. Deepwater cooling and/or an increase in ice volume is indicated by a series of short-term delta18O fluctuations between 3.8 and 3.6 Ma.

Foraminifera species in the CO2 vents near Ischia, Italy, 2010

The seas around the island of Ischia (Italy) have a lowered pH as a result of volcanic gas vents that emit carbon dioxide from the sea floor at ambient seawater temperatures. These areas of acidified seawater provide natural laboratories in which to study the long-term biological response to rising CO2 levels. Benthic foraminifera (single-celled protists) are particularly interesting as they have short life histories, are environmentally sensitive and have an excellent fossil record. Here, we examine changes in foraminiferal assemblages along pH gradients at CO2 vents on the coast of Ischia and show that the foraminiferal distribution, diversity and nature of the fauna change markedly in the living assemblages as pH decreases.

(Table 1) Sea surface temperature reconstruction for eastern equatorial Pacific surface sediment samples

Significant uncertainties persist in the reconstruction of past sea surface temperatures in the eastern equatorial Pacific, especially regarding the amplitude of the glacial cooling and the details of the post-glacial warming. Here we present the first regional calibration of alkenone unsaturation in surface sediments versus mean annual sea surface temperatures (maSST). Based on 81 new and 48 previously published data points, it is shown that open ocean samples conform to established global regressions of Uk'37 versus maSST and that there is no systematic bias from seasonality in the production or export of alkenones, or from surface ocean nutrient concentrations or salinity. The flattening of the regression at the highest maSSTs is found to be statistically insignificant. For the near-coastal Peru upwelling zone between 11-15°S and 76-79°W, however, we corroborate earlier observations that Uk'37 SST estimates significantly over-estimate maSSTs at many sites. We posit that this is caused either by uncertainties in the determination of maSSTs in this highly dynamic environment, or by biasing of the alkenone paleothermometer toward El Niño events as postulated by Rein et al. (2005).

Sedimentation rates and geochemical analysis of surface sediments from the South Atlantic

Extensive investigations of sedimentary barium were performed in the southern South Atlantic in order to assess the reliability of the barium signal in Antarctic sediments as a proxy for paleoproductivity. Maximum accumulation rates of excess barium were calculated for the Antarctic zone south of the polar front where silica accumulates at high rates. The correspondence between barium and opal supports the applicability of barium as a proxy for productivity. Within the Antarctic zone north of today's average sea ice maximum, interglacial vertical rain rates of excess barium are high, with a maximum occurring during the last deglaciation and early Holocene and during oxygen isotope chronozone 5.5. During these periods, the maximum silica accumulation was supposedly located south of the polar front. Glacial paleoproductivity, instead, was low within the Antarctic zone. North of the polar front, significantly higher barium accumulation occurs during glacial times. The vertical rain rates, however, are as high as in the glacial Antarctic zone. Therefore there was no evidence for an increased productivity in the glacial Southern Ocean.

Expanded GHOST database

In this study we review a global set of alkenone- and foraminiferal Mg/Ca-derived sea surface temperatures (SST) records from the Holocene and compare them with a suite of published Eemian SST records based on the same approach. For the Holocene, the alkenone SST records belong to the actualized GHOST database (Kim, J.-H., Schneider R.R., 2004). The actualized GHOST database not only confirms the SST changes previously described but also documents the Holocene temperature evolution in new oceanic regions such as the Northwestern Atlantic, the eastern equatorial Pacific, and the Southern Ocean. A comparison of Holocene SST records stemming from the two commonly applied paleothermometry methods reveals contrasting - sometimes divergent - SST evolution, particularly at low latitudes where SST records are abundant enough to infer systematic discrepancies at a regional scale. Opposite SST trends at particular locations could be explained by out-of-phase trends in seasonal insolation during the Holocene. This hypothesis assumes that a strong contrast in the ecological responses of coccolithophores and planktonic foraminifera to winter and summer oceanographic conditions is the ultimate reason for seasonal differences in the origin of the temperature signal provided by these organisms. As a simple test for this hypothesis, Eemian SST records are considered because the Holocene and Eemian time periods experienced comparable changes in orbital configurations, but had a higher magnitude in insolation variance during the Eemian. For several regions, SST changes during both interglacials were of a similar sign, but with higher magnitudes during the Eemian as compared to the Holocene. This observation suggests that the ecological mechanism shaping SST trends during the Holocene was comparable during the penultimate interglacial period. Although this "ecology hypothesis" fails to explain all of the available results, we argue that any other mechanism would fail to satisfactorily explain the observed SST discrepancies among proxies.

Age of bottom sediments from the South Atlantic Rise as indicated by 14C data for stations of R/V Professor Shtokman

Sedimentation of pelagic biogenic coccolithic-foraminiferal sediments predominates in the section of the South Atlantic ridge between 20° and 30°S. Sedimentation rate and thickness of Late Quaternary sediments differ in the rift valley, the crestal section of the ridge, its flanks and transform faults. Holocene and layers representing the most recent and pen¬ultimate continental glaciations and the last interglacial are distinguishable in the late Quaternary profile. During their development, changes in the mean annual sea surface temperature in the tropical zone of the South Atlantic were minimal, i.e. 1-2°C.

Seasonal variations in surface metabolite composition of Fucus vesiculosus and Fucus serratus sampled at outer Kiel Fjord (August 2012 - July 2013)

The chemical composition of surface associated metabolites of two Fucus species (Fucus vesiculosus and Fucus serratus) was analysed by means of gas chromatography-mass spectrometry (GC-MS) to describe temporal patterns in chemical surface composition. Method: The two perennial brown macroalgae F. vesiculosus and F. serratus were sampled monthly at Bülk, outer Kiel Fjord, Germany (54°27'21 N / 10°11'57 E) over an entire year (August 2012 - July 2013). Per month and species six non-fertile Fucus individuals were collected from mixed stands at a depth of 0.5 m under mid water level. For surface extraction approx. 50 g of the upper 5-10 cm apical thalli tips were cut off per species. The surface extraction of Fucus was performed according to the protocol of de Nys and co-workers (1998) with minor modifications (see Rickert et al. 2015). GC/EI-MS measurements were performed with a Waters GCT premier (Waters, Manchester, UK) coupled to an Agilent 6890N GC equipped with a DB-5 ms 30 m column (0.25 mm internal diameter, 0.25 mM film thickness, Agilent, USA). The inlet temperature was maintained at 250°C and samples were injected in split 10 mode. He carrier gas flow was adjusted to 1 ml min-1. Alkanes were used for referencing of retention times. For further details (GC-MS sample preparation and analysis) see the related publication (Rickert et al. submitted to PLOS ONE).

Calcareous nannofossils and C37 alkenones at ODP Site 162-982

During the late Pliocene (~3 to 2.5 Ma), oceanic records of opal and C37 alkenone accumulation from around the world show a secular shift towards lower values in the high latitudes and higher values in the low and mid latitudes. These shifts are broadly coincident with the intensification of northern hemisphere glaciation and are suggestive of changes in export productivity, with potential implications for Pliocene atmospheric carbon dioxide concentrations. The interpretation of a global latitudinal shift in productivity, however, requires testing because of the potential uncertainties associated with site to site comparisons of records that can be influenced by highly nonlinear processes associated with production, export, and preservation. Here, we assess the inferred Pliocene latitudinal productivity shift interpretation by presenting new records of C37 alkenone accumulation from Ocean Drilling Program (ODP) Site 982 in the North Atlantic and biotic assemblages (calcareous nannoplankton) from this site and ODP Site 846 in the eastern tropical Pacific. Our results corroborate the interpretation of C37 alkenone accumulation as a proxy for gross export productivity at these sites, indicating that large-scale productivity decreases at high latitudes and increases at tropical sites are recorded robustly. We conclude that the intensification of northern hemisphere glaciation during the late Pliocene was associated with a profound reorganisation of ocean biogeochemistry.

Sea ice thickness distribution (ITD) Model for the Arctic, links to NetCDF files

Sea ice models contain many different parameterizations of which one of the most commonly used is a subgrid-scale ice thickness distribution (ITD). The effect of this model component and the associated ice strength formulation on the reproduction of observed Arctic sea ice is assessed. To this end the model's performance in reproducing satellite observations of sea ice concentration, thickness and drift is evaluated. For an unbiased comparison, different model configurations with and without an ITD are tuned with an automated parameter optimization. The original combination of ITD and ice strength parameterization does not lead to better results than a simple single category model. Yet changing to a simpler ice strength formulation, which depends linearly on the mean ice thickness across all thickness categories, allows to clearly improve the model-data misfit when using an ITD. In the original formulation, the ice strength depends strongly on the number of thickness categories, so that introducing more categories can lead to thicker albeit weaker ice on average.

Phosphorus geochemistry of eastern equatorial Pacific Ocean sediments

We determined phosphorus (P) concentrations in Leg 138 sediment samples from Sites 844, 846, and 851, using a sequential extraction technique to identify the P associated with five sedimentary components. Total concentrations of P (sum of the five components) ranged from 4 to 35 µmol P/g sediment, with mean values relatively similar between the three sites (11, 14, and 12 for Sites 844,846, and 851, respectively). Authigenic/biogenic P was the most important component in terms of percentage of total P (about 75%), with iron-bound P (13%), adsorbed P (2%-9%), and organic P (4%) of secondary importance; detrital P was a minor P sink (1%) in these sediments. Profiles of adsorbed P and iron-bound P show decreasing concentrations with age, indicating that these components have been affected by diagenesis and reorganization of P. A peak in iron-bound P may reflect higher fluxes of hydrothermally derived Fe to eastern equatorial Pacific Ocean sediments from 11 to 8 Ma. Lower detrital P values for western Site 851 reflect a greater distance of this site from a terrigenous source area, compared to that of Sites 844 and 846. Phosphorus mass accumulation rates (P-MARs; units of µmol P/cm**2/k.y.) were calculated using total P concentrations (not including the minor and oceanically unreactive detrital P component) and sedimentation rates and dry-bulk densities averaged over time intervals of 0.5 m.y. P-MARs generally decrease from 17 Ma to the present. Eastern transect Sites 844 and 846 display a decrease in P-MARs from about 30 to 10 in the interval from 17 to 8 Ma, while western transect Site 851 is highly variable during this interval. P-MARs increase to about 45 and stay relatively high from 8 to 6 Ma, then decrease toward the present to some of the lowest values of the record (about 10). The general trend of high P-MARs at about 6 Ma and decreasing values toward the present is correlated with other geochemical and sedimentary trends through this interval and may reflect (1) a change in net sediment and P burial, (2) a reorganization of fluxes with no change of net burial, or (3) a combination of the two.