Mediterranean-Atlantic water exchange over the Miocene-Pliocene boundary

[EN] The Mediterranean-Atlantic gateway connection plays a major role in ocean circulation. In the past during the Messinian Salinity Crisis (MSC; 5.33-5.97 Ma), water exchange between the Mediterranean Sea and the open Atlantic Ocean became restricted or intermittently absent, resulting in extensive evaporitic deposits in Mediterranean Basins. The Miocene-Pliocene boundary marks the re-establishment of Mediterranean-Atlantic exchange through the Gibraltar Strait and once exchange was initiated, Mediterranean Outflow water (MOW) developed. This thesis integrates multi-proxy records of MOW outside the Mediterranean Sea in the Gulf of Cadiz to study the termination, initiation and development of Mediterranean Outflow during the late Miocene to early Pliocene. The initiation and development of MOW was investigated in Integrated Ocean Drilling Program (IODP) Hole U1387C from 731.20 to 865.85 m below seafloor (mbsf), which is located on the upper slope in the Gulf of Cadiz (559 m water depth). Combining bio-, magneto-, and cyclostratigraphy, an age model was constructed with a time interval from about 5.0 to 5.7 Ma. The Miocene-Pliocene boundary at ~826 mbsf in this Hole is associated with a distinct and abrupt change in depositional environment. During the latest Messinian, hemipelagic sediments exhibit precession-induced carbonate cycles, in which the largest quantity of detrital input are found during Northern Hemisphere insolation minima. These cyclic patterns are likely to result from terrigenous input to the basin, while during insolation maxima, more widespread vegetation cover reduced riverine sediment load. There are no indications of bottom water currents or any other strong influence of MOW in stable isotopes or XRF scanning data in Hole U1387C during the late Miocene. Consequently, it is thought that MOW was absent or severely restricted during this time period. Just above the Miocene-Pliocene boundary, two contouritic bigradational sandy-beds and an increase and more variable XRF core scanning Zr/Al ratios with respect to the underlying sediment, indicate the activity of processes related to particle sorting. This provides the earliest evidence for the onset of bottom water current flow immediately at or just above the Miocene-Pliocene boundary. During the Pliocene, strong coupling between sedimentary variations and benthic stable isotope suggest the influence of bottom waters on the stable isotopes. When bottom water currents are stronger, stable isotopic expressions with similar values as in Hole U1387C are found in the Mediterranean benthic foraminiferal record from the Capo Rosello sections (Sicily, Italy), characterized by well-ventilated, warmer waters. However, bottom water currents are repeatedly interrupted, as indicated with more aluminosilicate rich beds with smaller grain sizes. During these intervals, benthic stable isotopes do not match the Mediterranean record, but record the influence of a colder and poorly ventilated water mass likely to derive from the Atlantic. Remarkably, sea surface d18O and relative abundances of planktic foraminifers Globigerinoides record coeval transitions, but in the opposite direction; when bottom waters become cold, warming is observed at surface. This pattern can be attributed to short episodes of estuarine circulation in the Mediterranean Sea, forcing Atlantic Inflow water over the sill of the Gibraltar Strait at depth while MOW exited at surface. Such a circulation pattern can be triggered by lower water densities at surface in the Mediterranean, what can be triggered by a heat balance that is less negative and a fresher net water budget. Alternatively, a three-layer flow through the gateway or a vertical shift of the MOW-plume towards shallower depths may have caused the observed pattern in the Gulf of Cadiz, although, the latter does not explain the quick synchronous shifts in the benthic stable isotopes with sea surface records. The origin of bottom water masses in the Gulf of Cadiz was also investigated through the use of authigenic neodymium (Nd) and lead (Pb) isotopes. Isotope ratios of Ferro-Manganese (Fe-Mn) oxyhydroxide sediment leachates of Hole U1387C are compared to ratios in sediments leachates of the Alboran Sea and in three Fe-Mn crusts of different water depths in the NE Atlantic (Abouchami et al., 1999; Muiños et al., 2008), to investigate endmember compositions of MOW and NE Atlantic water during the late Miocene to early Pliocene. Authigenic isotope ratios seem to correspond to oceanographic and deposistional settings, however, it remains unclear what exactly controls the incorporated authigenic signal. The isotopic Nd imprint does not match any endmember isotopic signatures as recorded in the Fe-Mn crusts. Therefore, this record is interpreted as mainly controlled by local processes, best explained by the release of rare earth elements with accompanied Nd isotopic compositions from suspended detrital sediments. Pb isotope ratios in the Alboran Sea sediments and NE Atlantic Fe-Mn crusts interpretations are incompatible. If however, the sediment leachate samples from the Alboran Sea provide reliable Pb isotopic compositions for MOW, then the leachate compositions match the stable isotope interpretations. This hints towards the usability of Fe-Mn oxyhydroxide Pb isotopic compositions as a reliable bottom water tracer in the marginal settings of the Gulf of Cadiz. Mediterranean-Atlantic water exchange before the MSC took place through the Betic Corridor in southern Spain and the Rifian Corridor in North West Morocco. These two gateways ceased during the late Miocene, but the actual timing of the closure of these Corridors has been under debate (Flecker et al. 2015). In the western Betic Cordilleras, upper Miocene basins nearby Ronda, Antequera and Arcos de la Frontera are adjacent to the late Miocene Guadalhorce Corridor, which has previously been described as the last remaining branch of the Betic Corridor (Martín et al., 2001). Sedimentary sequences in these basins are characterized by a transition from deeper marine sandy marls to shallow marine calcarenites or limestones. Biostratigraphic analyses of the marls indicate an age of deposition before 7.58 Ma. The overlying calcarenites and limestones were not reliably dated due to the lack of adequate material, however, based on the typical high sedimentation rates of these deposits, it seems unlikely that the calcarenites and limestones are much younger than the marls. This implies that the Guadalhorce Corridor is likely to have closed during the late Tortonian or early Messinian and thus cannot have supplied the necessary water to the Mediterranean to develop the extensive evaporite deposits. Considering similarities in timing and lithological successions, the shallowing upward sequences are linked to the same tectonic pulse that closed the remaining branches in the eastern Betics

The Gibraltar Corridor:Watergate of the Messinian Salinity Crisis

The existence and evolution of a Messinian salt giant in the Mediterranean Sea has caused much debate in the marine science community. Especially the suggestion that the Mediterranean was a deep desiccated basin during the Messinian Salinity Crisis (MSC, 5.97–5.33 Ma), triggered by a temporal disconnection from the global ocean, made it a well-known crisis beyond the scientific boundaries. Approximately ~50 years after this provocative statement, it remained unknown which Mediterranean–Atlantic seaway delivered the 5–6% of the global ocean's salt into the Mediterranean basin. Here, we review the changes in Mediterranean-Atlantic connectivity throughout the late Miocene in order to locate, date and quantify the missing Messinian gateway that provided the salt water inflow during the MSC. We conclude that all the known pre-MSC gateways through southern Spain and northern Morocco were closed, leaving the “Gibraltar Corridor” at its Messinian configuration as the sole candidate. We consider the possibility of longer and narrower straits existing at depth below the present Gibraltar region, and using strait dynamic theory we calculate its dimensions during the Messinian based on the salinity changes in the Mediterranean. A marine Messinian gateway through the Gibraltar Corridor is in agreement with growing evidence that Atlantic waters reached the Mediterranean Sea during all three stages of the MSC

Evidence of early bottom water current flow after the Messinian Salinity Crisis in the Gulf of Cadiz

Highlights • Stratigraphic framework over the Miocene-Pliocene boundary at IODP Site U1387. • Abrupt sedimentary changes over the Miocene-Pliocene boundary. • Clear hints for onset of Mediterranean Outflow after the Messinian Salinity Crisis. • Evidence of bottom water currents in contouritic sedimentation and elevated Zr/Al. • Quiet, hemipelagic sediment deposition during the Messinian in the Gulf of Cadiz. Abstract Integrated Ocean Drilling Program (IODP) Expedition 339 cored multiple sites in the Gulf of Cadiz in order to study contourite deposition resulting from Mediterranean Outflow water (MOW). One hole, U1387C, was cored to a depth of 865.6 meters below seafloor (mbsf) with the goal of recovering the Latest Miocene to Pliocene transition in order to evaluate the history of MOW immediately after the end of the Messinian Salinity Crisis. To understand this history, an accurate age model for the succession is needed, but is challenging to construct, because the Miocene-Pliocene boundary is not marked by a clear biostratigraphic event in the Atlantic and coring gaps occur within the recovered stratigraphic record. These limitations are overcome by combining a variety of chronostratigraphic datasets to construct an age-model that fits the currently available age indicators and demonstrates that coring in Hole U1387C did indeed recover the Miocene-Pliocene boundary at around 826 mbsf. This boundary is associated with a distinct and abrupt change in depositional environment. During the latest Messinian, hemipelagic sediments exhibiting precession-induced climate variability were deposited. These are overlain by Pliocene sediments deposited at a much higher sedimentation rate, with much higher and more variable XRF-scanning Zr/Al ratios than the underlying sediment, and that show evidence of winnowing, particle sorting and increasing grain size, which we interpret to be related to the increasing flow of MOW. Pliocene sedimentary cyclicity is clearly visible in both the benthic δ18O record and the Zr/Al data and is probably also precessionally controlled. Two contouritic bigradational sandy-beds are revealed above the third sedimentary cycle of the Pliocene. On the basis of these results, we conclude that sedimentation associated with weak Mediterranean-Atlantic exchange, began in the Gulf of Cadiz virtually at or shortly after the Miocene-Pliocene boundary

Table 2 - MCICPMS Pb isotope compositions bulk marginal sediment leachates

Pb isotope results of acid-reductive leaching of bulk sediments from the Sorbas and Caltanissetta Basins and the Apennine Foredeep. Uncertainties in the table are internal measurement uncertainties reported to 2 SE. Some samples were repeated; if RPT# is noted, this is a repeated measurement of the same solution. Otherwise, the repeat measurement was performed with a separate leaching of a new portion of sediment. An average value of these measurements is provided where relevant. The analytical session in which the measurement was performed is explained in the table footnote

Late Miocene marginal basin authigenic Pb isotope measurements and standards

This dataset is presented in the article "Precessional cyclicity of seawater Pb isotopes in the late Miocene Mediterranean" (accepted, Paleoceanography and Paleoclimatology). Marginal Mediterranean marine sediments from three separate basins were sampled at sub-precessional resolution (~4-10 samples per precessional cycle). Authigenic Pb isotope compositions of the bulk sediment were extracted using acid reductive leaching and measured with MC-ICP-MS. In addition, strong leaching and total dissolution was applied to a subset of samples. This dataset includes the results of all of the measurements, plus an extensive set of secondary standard measurements performed at the same periods for quality control purposes, on two different MC-ICP-MS (Nu Plasma and Thermo Neptune Plus, GEOMAR Helmholtz Institute for Ocean Research, Kiel). Finally, there is a table of alternative sample ages based on different orbital tuning options (see manuscript text)

Table 5 - MCICPMS Pb isotope compositions bulk ODP Site 978 sediment leachates

Pb isotope results of acid-reductive leaching of late Miocene bulk sediments from ODP Leg 161 Site 978. Uncertainties in the table are internal measurement uncertainties reported to 2 SE. One sample produced a strikingly different result; to confirm, a new measurement was performed on a new portion of sediment. An average value of these measurements is provided

Table 3 - MCICPMS Pb isotope compositions strong marginal sediment leachates

Pb isotope results of strong leachates performed on bulk sediments from the Sorbas Basin. Uncertainties in the table are internal measurement uncertainties, reported in 2SE format

Table 1 - MCICPMS Pb isotope measurements Secondary Standards

Pb isotope results of secondary standards and calculation of external reproducibility for measurements performed on Nu Plasma MCICPMS and Neptune Plus MCICPMS, GEOMAR. Uncertainties in the table are internal measurement uncertainties reported in 2 SE format

Table 6 - Alternative orbital tuning schemes for Falconara section

Results of alternate tuning experiments using (1) the original sapropel midpoints only, (2) sapropel mid-points and Pb isotope 'peaks' based on the 206Pb/204Pb record, and (3) based on only the 206Pb/204Pb 'peaks.