Chemical observations in the Red Sea and the inner Gulf of Aden during the International Indian Ocean Expedition 1964/65

The Red Sea has a special place among the adjacent seas of the world. High evaporation, exclusion of its deep water from contact with the Indian Ocean proper and complete absence of continental drainage may result special conditions of the chemistry of the Red Sea. This paper aims to describe and explain the peculiarity of the hydrochemical situation. The influence of the topography, of the inflow and outflow through the straights of Bab el Mandeb, of the evaporation, of the stability of the water layers, and of the circulation will be studied. An attempt is made to estimate the apparent oxygen ultilisation in order to obtain an indication of the biological activity. A further attempt is made toward the quantitative estimation of the circulation of the nutrients and also to obtain some information about transport, dissolution, and precipitation of calcium carbonate. The basis of these investigations are mainly observations of R. V. "Meteor" during the International Indian Ocean Expedition 1964/65. The determination of dissolved oxygen, dissolved inorganic phosphate, nitrate, nitrite, ammonia, pH, alkalinity, silicate as well as salinity and temperature forms the necessary basis for such an investigation of the chemical conditions. In the first chapter the methods and some modifications for the determination of the chemical properties as applied during the I.I.O.E. cruise of R. V. "Meteor" are described. The new methods, as worked out and tested under sea going conditions during several years by the author, are described in more detail. These are the methods for nitrate, silicate, the automatic determination of dissolved inorganic phosphate and silicate, the automated determination of total phosphorus, the in situ recording of the oxygen tension, and the modification for the determination of ammonia, calcium, and dissolved oxygen. With these revised methods more than 18,000 determinations have been carried out during the Indian Ocean cruise. The complete working up of the chemical data of the Indian Ocean Expedition of R. V. "Meteor" is devided into four sections: Contributions 1) to the Chemistry of the Red Sea and the Inner Gulf of Aden, 2) to the Gulf of Aden and the Somali Coast Region, 3) to the Western Indian Coast Region, and 4) to the Persian Gulf and the Straits of Oman. This paper presents the first contribution. The special hydrographical conditions are discussed. It can be shown, that the increase of salinity in the surface waters from the south to the north of the Red Sea is only to about 30 % due to evaporation. The remaining increase is presumed to be due to the admixture of deep water to the surface layers. A special rate for the consumption of oxygen (0.114 ml/ l/a) is derived for the deep water of the Red Sea at 1500 m. Based upon the distribution of the dissolved oxygen along the axii of the Red Sea, a chematic model for the longitudinal circulation of the Red Sea is constructed. This model should be considered as a first approximation and may explain the special distribution of phosphate, nitrate, and silicate. Based upon the evaluation of the residence time of the deep water a dissolution rate for silicate is estimated as 1 mygat/a. It seems possible to calculate residence times of water masses outside the Red Sea from the silicate content. The increase of silicate and the consumption of oxygen lead to residence times of the water below the thermocine of 30 to 48 years. The distribution of oxygen in the Straits of Bab el Mandeb is described and discussed. The rate of consumption of the oxygen in the outflowing Red Sea water is estimated to 8.5 ml/ l/a. This rather high rate is explained with reference to the special conditions in the outflowing water. The Red Sea water is characterized initially by a relative high content of oxygen and a low content of nutrients. The increase in nutrients and the decrease in the oxygen content is a secondary process of the Red Sea water on its way to the Arabian Sea. Based upon the vertical distribution of the dissolved inorganic phosphate vertical exchange coefficients of 1 - 4 g/cm/sec and vertical current speeds of 10**-5 to 10**-4 cm/sec are calculated for some stations in the Red Sea. The distribution of phosphate, silicate, nitrate, nitrite and ammonia for the Red Sea and the Straits of Bab el Mandeb are discussed. The special circulation is evaluated and the balance of the nutrients is estimated by means of the brutto transport. The nutrient deficit is assumed to be balanced by sporadic inflow of intermediate water from the Gulf of Aden. An example for such an inflow has been observed and is demonstrated. The silicate-salinity relationships are a suitable way for characterizing water masses in the Red Sea. Equations for the calculation of the different components from the carbonate system, the ion activities, and the calcium carbonate saturation are evaluated. The influence of temperature and pressure is taken into account. The carbonate saturation is calculated from the determined concentrations of calcium, alkalinity, and the hydrogen ion activity. Saturation values of 320 % are found for the surface layer and of 100% ± 1 for the deep water. The extraordinary equilibrium conditions may explain the constant Ca/Cl ratio and also the sedimentation of undissolved carbonate skelecons even in greater depths. A main sedimentation rate of 2 * 10**-3cm/year is evaluated from a total sedimentation of 10 * 106 to/a of calcium carbonate in the Red Sea. The appendix contains those data, which are not published in the data volume of the I.I.O.E. expedition of R. V. "Meteor".

Sea surface temperture reconstruction and planktonic foraminifera of ODP Hole 117-723A

In the western Arabian Sea (WAS), the highest seasonal sea surface temperature (SST) difference presently occurs between May and August. In order to gain an understanding on how monsoonal upwelling modulates the SST difference between these two months, we have computed SST for the months of May and August based on census counts of planktonic foraminifers by using the artificial neural network (ANN) technique. The SST difference between May and August exhibits three distinct phases: i) a moderate SST difference in the late Holocene (0-3.5 ka) is attributable to intense upwelling during August, ii) a minimum SST difference from 4 to 12 ka is due to weak upwelling during the month of August, and iii) the highest SST difference during the last glacial interval (19 to 22 ka) with high Globigerina bulloides % could have been caused by the occurrence of a prolonged upwelling season (from May through July) and maximum difference in the incoming solar radiation between May and August. Overall, variations in the SST difference between May and August show that the timing of intense upwelling in the Western Arabian Sea over the last 22 kyr has been variable over the months of June, July and August.

Geochemistry of Globigerinoides ruber from ODP Hole 130-806B

A sea surface temperature (SST) record based on planktonic foraminiferal magnesium/calcium ratios from a site in the western equatorial Pacific warm pool reveals that glacial-interglacial oscillations in SST shifted from a period of 41,000 to 100,000 years at the mid-Pleistocene transition, 950,000 years before the present. SST changes at both periodicities were synchronous with eastern Pacific cold-tongue SSTs but preceded changes in continental ice volume. The timing and nature of tropical Pacific SST changes over the mid-Pleistocene transition implicate a shift in the periodicity of radiative forcing by atmospheric carbon dioxide as the cause of the switch in climate periodicities at this time.

Calcareous nannofossils in Neogene sediments of ODP Leg 117 holes

Calcareous nannofossils were studied in 574 Neogene samples recovered from eight sites drilled in block-faulted basins on the continental margin of Oman. This portion of the Arabian Sea experiences seasonal upwelling associated with the southwest monsoon. Not surprisingly, some of the more typical Neogene warm-water nannoplankton are either missing entirely or are extremely rare in these sediments. Coccolithus pelagicus, a typical cold-water indicator, is extremely abundant in many samples of late Pliocene to early Pleistocene age. These intervals correspond to periods of Northern Hemisphere glaciation. Reworked Late Cretaceous and Cenozoic nannofossils are found in a majority of the samples. They were probably carried from the Arabian Peninsula or the continent of Africa on strong southwest summer winds. Ages for the various nannofossil events were calculated by projecting the nannofossil datums onto the magnetostratigraphic scale for Sites 724, 727, and 728. These are the first ages for the various nannofossil datums derived from Oman Margin sediments. The following ages have been calculated for these nannofossil events: FAD Emiliania huxleyi, 0.23 Ma; LAD Pseudoemiliania lacunosa, 0.38 Ma; FAD Helicosphaera inversa, 0.42 Ma; top of acme of Reticulofenestra sp. A, 0.70 Ma; FAD Gephyrocapsaparallela, 0.85 Ma; LAD Gephyrocapsa spp. (large), 1.07 Ma; LAD Helicosphaera sellii, 1.34 Ma; LAD Calcidiscus macintyrei, 1.47 Ma; FAD Gephyrocapsa oceanica, 1.53 Ma; FAD Gephyrocapsa caribbeanica, 1.80 Ma; LAD Discoaster brouweri, 2.03 Ma; LAD Discoasterpentaradiatus, 2.31 Ma; LAD Discoaster surculus, 2.42; LAD Discoaster tamalis, 2.77 Ma; LAD Sphenolithus abies, 3.44 Ma; and LAD Reticulofenestra pseudoumbilica, 3.44 Ma.

(Table 2) Age determination of sediment core NIOP-C2_929

In this study we present a sea surface temperature (SST) record from the western Arabian Sea for the last 20,000 years. We produced centennial-scale d18O and Mg/Ca SST time series of core NIOP929 with focus on the glacial-interglacial transition. The western Arabian Sea is influenced by the seasonal NE and SW monsoon wind systems. Lowest SSTs occur during the SW monsoon season because of upwelling of cold water, and highest SSTs can be found in the low-productivity intermonsoon season. The Mg/Ca-based temperature record reflects the integrated SST of the SW and NE monsoon seasons. The results show a glacial-interglacial SST difference of ~2°C, which is corroborated by findings from other Arabian Sea cores. At 19 ka B.P. a yet undescribed warm event of several hundred years duration is found, which is also reflected in the d18O record. A second centennial-scale high SST/low d18O event is observed at 17 ka B.P. This event forms the onset of the stepwise yet persistent trend toward Holocene temperatures. Highest Mg/Ca-derived SSTs in the NIOP929 record occurred between 13 and 10 ka B.P. Interglacial SST is ~24°C, indicating influence of upwelling. The onset of Arabian Sea warming occurs when the North Atlantic is experiencing minimum temperatures. The rapid temperature variations at 19, 17, and 13 ka B.P. are difficult to explain with monsoon changes alone and are most likely also linked to regional hydrographic changes, such as trade wind induced variations in warm water advection.

(Table 1) Age determination of sediment core SO139-74KL

A multiproxy record has been acquired from a piston core (SO139-74KL) taken offshore southern Sumatra, an area which is situated in the southwestern sector of the tropical Indo-Pacific Warm Pool. The high-resolution data sets (X-ray fluorescence, total organic carbon, and C37 alkenones) were used to track changes in paleoproductivity, freshwater budget, and sea surface temperature (SST) of the tropical climate system at orbital time scales over the past 300 ka. Our paleoclimatic data show that enhanced marine paleoproductivity was directly related to strengthening of coastal upwelling during periods of increased boreal summer insolation and associated SE monsoon strength with a precessional cyclicity. Changes in freshwater supply were primarily forced by precession-controlled changes in boreal NW winter monsoon rainfall enclosing an additional sea level component. SST variations of 2°-5°C occurred at eccentricity and precessional cyclicity. We suggest that the sea surface temperature variability off southern Sumatra is predominantly related to three major causes: (1) variations in upwelling intensity; (2) an elevated freshwater input into the southern Makassar Strait leading to reduced supply of warmer surface waters from the western Pacific and increased subsurface water transport via the Indonesian Throughflow into the Indian Ocean; and (3) long-term changes in the intensity or frequency of low-latitude climate phenomena, such as El Niño-Southern Oscillation.

Climatic variability in the southwest Pacific during the Last Termination (20-10 kyr BP)

The degree to which palaeoclimatic changes in the Southern Hemisphere co-varied with events in the high latitude Northern Hemisphere during the Last Termination is a contentious issue, with conflicting evidence for the degree of 'teleconnection' between different regions of the Southern Hemisphere. The available hypotheses are difficult to test robustly, however, because there are few detailed palaeoclimatic records in the Southern Hemisphere. Here we present climatic reconstructions from the southwestern Pacific, a key region in the Southern Hemisphere because of the potentially important role it plays in global climate change. The reconstructions for the period 20-10 kyr BP were obtained from five sites along a transect from southern New Zealand, through Australia to Indonesia, supported by 125 calibrated C-14 ages. Two periods of significant climatic change can be identified across the region at around 17 and 14.2 cal kyr BP, most probably associated with the onset of warming in the West Pacific Warm Pool and the collapse of Antarctic ice during Meltwater Pulse-1A, respectively. The severe geochronological constraints that inherently afflict age models based on radiocarbon dating and the lack of quantified climatic parameters make more detailed interpretations problematic, however. There is an urgent need to address the geochronological limitations, and to develop more precise and quantified estimates of the pronounced climate variations that clearly affected this region during the Last Termination. (c) 2005 Elsevier Ltd. All rights reserved.

Compilation of planktonic foraminiferal census counts from the Southern Hemisphere Oceans

We present an improved database of planktonic foraminiferal census counts from the Southern Hemisphere Oceans (SHO) from 15°S to 64°S. The SHO database combines 3 existing databases. Using this SHO database, we investigated dissolution biases that might affect faunal census counts. We suggest a depth/[DCO3]2- threshold of ~3800 m/[DCO3]2- = ~-10 to -5 µmol/kg for the Pacific and Indian Oceans, and ~4000 m/[DCO3]2- = ~0 to 10 µmol/kg for the Atlantic Ocean, under which core-top assemblages can be affected by dissolution and are less reliable for paleo-sea surface temperature (SST) reconstructions. We removed all core-tops beyond these thresholds from the SHO database. This database has 598 core-tops and is able to reconstruct past SST variations from 2° to 25.5°C, with a root mean square error of 1.00°C, for annual temperatures. To inspect dissolution affects SST reconstruction quality, we tested the data base with two "leave-one-out" tests, with and without the deep core-tops. We used this database to reconstruct Summer SST (SSST) over the last 20 ka, using the Modern Analog Technique method, on the Southeast Pacific core MD07-3100. This was compared to the SSST reconstructed using the 3 databases used to compile the SHO database. Thus showing that the reconstruction using the SHO database is more reliable, as its dissimilarity values are the lowest. The most important aspect here is the importance of a bias-free, geographic-rich, database. We leave this dataset open-ended to future additions; the new core-tops must be carefully selected, with their chronological frameworks, and evidence of dissolution assessed.

(Table 1) Comparison between bulk ICP-OES measurements and LA-ICP-MS analyses for Mg/Ca and Sr/Ca ratios of Globigerinoides sacculifer from ODP Hole 165-1000A

We constructed a high-resolution Mg/Ca record on the planktonic foraminifer Globigerinoides sacculifer in order to explore the change in sea surface temperature (SST) due to the shoaling of the Isthmus of Panama as well as the impact of secondary factors like diagenesis and large salinity fluctuations. The study covers the latest Miocene and the early Pliocene (5.6-3.9 Ma) and was combined with d18O to isolate changes in sea surface salinity (SSS). Before 4.5 Ma, SSTMg/Ca and SSS show moderate fluctuations, indicating a free exchange of surface ocean water masses between the Pacific and the Atlantic. The increase in d18O after 4.5 Ma represents increasing salinities in the Caribbean due to the progressive closure of the Panamanian Gateway. The increase in Mg/Ca toward values of maximum 7 mmol/mol suggests that secondary influences have played a significant role. Evidence of crystalline overgrowths on the foraminiferal tests in correlation with aragonite, Sr/Ca, and productivity cyclicities indicates a diagenetic overprint on the foraminiferal tests. Laser ablation inductively coupled plasma-mass spectrometry analyses, however, do not show significantly increased Mg/Ca ratios in the crystalline overgrowths, and neither do calculations based on pore water data conclusively result in significantly elevated Mg/Ca ratios in the crystalline overgrowths. Alternatively, the elevated Mg/Ca ratios might have been caused by salinity as the d18O record of Site 1000 has been interpreted to represent large fluctuations in SSS, and cultivating experiments have shown an increase in Mg/Ca with increasing salinity. We conclude that the Mg/Ca record <4.5 Ma can only reliably be considered for paleoceanographical purposes when the minimum values, not showing any evidence of secondary influences, are used, resulting in a warming of central Caribbean surface water masses after 4.5 Ma of ~2°C.

Isotope and Mg/Ca measurements from Cores ME0005A-43JC and 202-1242 of tropical Pacific

Multiproxy geologic records of d18O and Mg/Ca in fossil foraminifera from sediments under the Eastern Pacific Warm Pool (EPWP) region west of Central America document variations in upper ocean temperature, pycnocline strength, and salinity (i.e., net precipitation) over the past 30 kyr. Although evident in the paleotemperature record, there is no glacial-interglacial difference in paleosalinity, suggesting that tropical hydrologic changes do not respond passively to high-latitude ice sheets and oceans. Millennial variations in paleosalinity with amplitudes as high as 4 practical salinity units occur with a dominant period of 3-5 ky during the glacial/deglacial interval and 1.0-1.5 ky during the Holocene. The amplitude of the EPWP paleosalinity changes greatly exceeds that of published Caribbean and western tropical Pacific paleosalinity records. EPWP paleosalinity changes correspond to millennial-scale climate changes in the surface and deep Atlantic and the high northern latitudes, with generally higher (lower) paleosalinity during cold (warm) events. In addition to Intertropical Convergence Zone (ITCZ) dynamics, which play an important role in tropical hydrologic variability, changes in Atlantic-Pacific moisture transport, which is closely linked to ITCZ dynamics, may also contribute to hydrologic variations in the EPWP. Calculations of interbasin salinity average and interbasin salinity contrast between the EPWP and the Caribbean help differentiate long-term changes in mean ITCZ position and Atlantic-Pacific moisture transport, respectively.

Dinocyst-derived sea-surface characteristics, palynomorph abundances, ice-rafted debris, and planktonic foraminifera abundances and d18O of the 35-41 ka BP interval of core MD99-2285

The last glacial millennial climatic events (i.e. Dansgaard-Oeschger and Heinrich events) constitute outstanding case studies of coupled atmosphere-ocean-cryosphere interactions. Here, we investigate the evolution of sea-surface and subsurface conditions, in terms of temperature, salinity and sea ice cover, at very high-resolution (mean resolution between 55 and 155 years depending on proxies) during the 35-41 ka cal BP interval covering three Dansgaard-Oeschger cycles and including Heinrich event 4, in a new unpublished marine record, i.e. the MD99-2285 core (62.69°N; -3.57s°E). We use a large panel of complementary tools, which notably includes dinocyst-derived sea-ice cover duration quantifications. The high temporal resolution and multiproxy approach of this work allows us to identify the sequence of processes and to assess ocean-cryosphere interactions occurring during these periodic ice-sheet collapse events. Our results evidence a paradoxical hydrological scheme where (i) Greenland interstadials are marked by a homogeneous and cold upper water column, with intensive winter sea ice formation and summer sea ice melting, and (ii) Greenland and Heinrich stadials are characterized by a very warm and low saline surface layer with iceberg calving and reduced sea ice formation, separated by a strong halocline from a less warm and saltier subsurface layer. Our work also suggests that this stadial surface/subsurface warming started before massive iceberg release, in relation with warm Atlantic water advection. These findings thus support the theory that upper ocean warming might have triggered European ice-sheet destabilization. Besides, previous paleoceanographic studies conducted along the Atlantic inflow pathways close to the edge of European ice-sheets suggest that such a feature might have occurred in this whole area. Nonetheless, additional high resolution paleoreconstructions are required to confirm such a regional scheme.

Extractions and analyses of reactive phosphorus in the Bering Sea from IODP Holes 323-U1341A and 323-U1341B

To reconstruct the cycling of reactive phosphorus (P) in the Bering Sea, a P speciation record covering the last ~ 4 Ma was generated from sediments recovered during Integrated Ocean Drilling Program (IODP) Expedition 323 at Site U1341 (Bowers Ridge). A chemical extraction procedure distinguishing between different operationally defined P fractions provides new insight into reactive P input, burial and diagenetic transformations. Reactive P mass accumulation rates (MARs) are ~ 20-110 µmol/cm2/ka, which is comparable to other open ocean locations but orders of magnitude lower than most upwelling settings. We find that authigenic carbonate fluorapatite (CFA) and opal-bound P are the dominant P fractions at Site U1341. An overall increasing contribution of CFA to total P with sediment depth is consistent with a gradual "sink switching" from more labile P fractions (fish remains, Fe oxides, organic matter) to stable authigenic CFA. However, the positive correlation of CFA with Al content implies that a significant portion of the supposedly reactive CFA is non-reactive "detrital contamination" by eolian and/or riverine CFA. In contrast to CFA, opal-bound P has rarely been studied in marine sediments. We find for the first time that opal-bound P directly correlates with excess silica contents. This P fraction was apparently available to biosiliceous phytoplankton at the time of sediment deposition and is a long-term sink for reactive P in the ocean, despite the likelihood for diagenetic re-mobilisation of this P at depth (indicated by increasing ratios of excess silica to opal-bound P). Average reactive P MARs at Site U1341 increase by ~ 25% if opal-bound P is accounted for, but decrease by ~ 25% if 50% of the extracted CFA fraction (based on the lowest CFA value at Site U1341) is assumed to be detrital. Combining our results with literature data, we present a qualitative perspective of terrestrial CFA and opal-bound P deposition in the modern ocean. Riverine CFA input has mostly been reported from continental shelves and margins draining P-rich lithologies, while eolian CFA input is found across wide ocean regions underlying the Northern Hemispheric "dust belt". Opal-bound P burial is important in the Southern Ocean, North Pacific, and likely in upwelling areas. Shifts in detrital CFA and opal-bound P deposition across ocean basins likely occurred over time, responding to changing weathering patterns, sea level, and biogenic opal deposition.