Mineral composition, major element oxides and trace element concentration of sediments from ODP Leg 180 sites

Middle Miocene to Holocene fine-grained argillaceous sediments (clays, claystones/muds, and mudstones), which volumetrically dominated the sediment recovery in the Woodlark Basin during Leg 180, were chemically analyzed for major elements, trace elements, and some rare earth elements by X-ray fluorescence. Selected samples also underwent X-ray diffraction (XRD) analysis for mineral determination. The results shed light on sediment provenance when combined with shipboard sediment descriptions, smear slide study, and XRD. The oldest sediments recovered (Site 1108) of middle-late Miocene age include volcanogenic muds with distinctive high MgO and K2O, indicative of a relatively basic calc-alkaline source related to an inferred Miocene forearc succession. The forearc basement, composed of diabase and basalt, was locally exposed (Site 1109) and eroded in the late Miocene (<5.4-9.93 Ma), giving rise to fluvial conglomerates (Sites 1109, 1115, and 1118). Chemically distinctive fine-grained claystones and siltstones (with relatively high Ti, low K) are compatible with derivation from tropically weathered basic igneous rocks, correlated with the Paleogene Papuan ophiolite. Overlying latest Miocene-Pleistocene fine-grained sediments throughout the Woodlark Basin were partly derived from calc-alkaline volcanic sources. However, relatively high abundances of Al2O3 and related element oxides (K2O and Na2O) and trace elements (e.g., Rb and Y) reflect an additional terrigenous input throughout the basin, correlated with pelitic metamorphic rocks exposed on Papua New Guinea and adjacent areas. In addition, sporadic high abundances of Cr and Ni, some other trace metals, and related minerals (talc, crysotile, and chlorite) reflect input from an ophiolitic terrain dominated by ultramafic rocks, correlated with the Paleogene Papuan ophiolite. The source areas possibly included serpentinized ultramafic ophiolitic rocks exposed in the Papua New Guinea interior highlands. Chemical evidence further indicates that fine-grained terrigenous sediment reached the Woodlark Basin throughout its entire late Miocene-Holocene history. Distinctive high-K volcanogenic muds rich in tephra and volcanic ash layers that appear at <2.3 Ma (Sites 1109 and 1115) are indicative of high-K calc-alkaline volcanic centers, possibly located in the Dawson Strait, Moresby Strait, or Dobu Seamount area. Chemical diagenesis of fine-grained sediments within the Woodlark Basin is reflected in clay neomorphism and localized formation of minerals including dolomite, ankerite, and zeolite but has had little effect on the bulk chemical composition of most samples.

Fossil pollen record of composite sediment core TMD from Tso Moriri, analysis of modern surface pollen samples, mean annual precipitation reconstruction, and digitisation and recalibration of different discussed palaeoclimate proxy records

This paper presents a new fossil pollen record from Tso Moriri (32°54'N, 78°19'E, 4512 m a.s.l.) and seeks to reconstruct changes in mean annual precipitation (MAP) during the last 12,000 years. This high-alpine lake occupies an area of 140 km**2 in a glacial-tectonic valley in the northwestern Himalaya. The region has a cold climate, with a MAP <300 mm, and open vegetation. The hydrology is controlled by the Indian Summer Monsoon (ISM), but winter westerly-associated precipitation also affects the regional water balance. Results indicate that precipitation levels varied significantly during the Holocene. After a rapid increase in MAP, a phase of maximum humidity was reached between ca. 11 to 9.6 cal ka BP, followed by a gradual decline in MAP. This trend parallels the reduction in the Northern Hemisphere summer insolation. Comparison of different palaeoclimate proxy records reveal evidence for a stronger Holocene decrease in precipitation in the northern versus the southern parts of the ISM domain. The long-term trend of ISM weakening is overlaid with several short periods of greater dryness, which are broadly synchronous with the North Atlantic cold spells, suggesting reduced amounts of westerly-associated winter precipitation. Compared to the mid and late Holocene, it appears that westerlies had a greater influence on the western parts of the ISM domain during the early Holocene. During this period, the westerly-associated summer precipitation belt was positioned at Mediterranean latitudes and amplified the ISM-derived precipitation. The Tso Moriri pollen record and moisture reconstructions also suggest that changes in climatic conditions affected the ancient Harappan Civilisation, which flourished in the greater Indus Valley from approximately 5.2 to 3 cal ka BP. The prolonged Holocene trend towards aridity, punctuated by an interval of increased dryness (between ca. 4.5 to 4.3 cal ka BP), may have pushed the Mature Harappan urban settlements (between ca. 4.5 to 3.9 cal ka BP) to develop more efficient agricultural practices to deal with the increasingly acute water shortages. The amplified aridity associated with North Atlantic cooling between ca. 4 to 3.6 and around 3.2 cal ka BP further hindered local agriculture, possibly causing the deurbanisation that occurred from ca. 3.9 cal ka BP and eventual collapse of the Harappan Civilisation between ca. 3.5 to 3 cal ka BP.

(Table 4) Estimated surface water phosphate concentrations for the past 200 kyr at the location of sediment core GeoB1016-3

We compared ocean atlas values of surface water [PO4]3- and [CO2(aq)] against the carbon isotopic fractionation (ep) of alkenones obtained from surface sediments of the South Atlantic and the central Pacific (Pacific data are from Pagani et al. 2002, doi:10.1029/2002PA000756). We observed a positive correlation between ep and 1/[CO2(aq)], which is opposite of what would be expected if the concentration of CO2(aq) were the major factor controlling the carbon isotopic fractionation of C37:2 alkenones. Instead, we found inverse relationships between ep and [PO4]3- for the two ocean basins (for the Atlantic, ep = -4.6*[PO4]3- + 15.1, R = 0.76; for the Pacific, ep = -4.1*[PO4]3- + 13.7, R = 0.64), suggesting that ep is predominantly controlled by growth rate, which in turn is related to nutrient concentration. The similarity of the slopes implies that a general relationship between both parameters may exist. Using the relationship obtained from the South Atlantic, we estimated surface water nutrient concentrations for the past 200,000 years from a deep-sea sediment core recovered off Angola. Low ep values, indicating high nutrient concentrations, coincide with high contents of total organic carbon and C37 alkenones, low surface water temperatures, and decreased bulk d15N values, suggesting an increased upwelling of nutrient-rich cool subsurface waters as the main cause for the observed ep decrease.

Ladderane lipid analysis and pore water and sediment chemistry of sediment cores from the continental shelf and slope off northwest Africa

The presence and abundance of anaerobic ammonium-oxidizing (anammox) bacteria was investigated in continental shelf and slope sediments (300-3000 m water depth) off northwest Africa in a combined approach applying quantitative polymerase chain reaction (q-PCR) analysis of anammox-specific 16S rRNA genes and anammox-specific ladderane biomarker lipids. We used the presence of an intact ladderane monoether lipid with a phosphocholine (PC) headgroup as a direct indicator for living anammox bacteria and compared it with the abundance of ladderane core lipids derived from both living and dead bacterial biomass. All investigated sediments contained ladderane lipids, both intact and core lipids, in agreement with the presence of anammoxspecific 16S rRNA gene copies, indicating that anammox occurs at all sites. Concentrations of ladderane core lipids in core top sediments varied between 0.3 and 97 ng g**-1 sediment, with the highest concentrations detected at the sites located on the shelf at shallower water depths between 300 and 500 m. In contrast, the C20 [3]-ladderane monoether-PC lipid was most abundant in a core top sediment from 1500 m water depth. Both anammox-specific 16S rRNA gene copy numbers and the concentration of the C20 [3]-ladderane monoether-PC lipid increased downcore in sediments located at greater water depths, showing highest concentrations of 1.2 x 10**8 copies g**-1 sediment and 30 pg g**-1 sediment, respectively, at the deepest station of 3000 m water depth. This suggests that the relative abundance of anammox bacteria is higher in sediments at intermediate to deep water depths where carbon mineralization rates are lower but where anammox is probably more important than denitrification.

Chemical composition of sediment core GeoB12309-5 from the northern Arabian Sea, its pore water profile and age depth relationship as well as CTD data obtained during cruise M74/3

The Arabian Sea off the Pakistan continental margin is characterized by one of the world's largest oxygen minimum zones (OMZ). The lithology and geochemistry of a 5.3 m long gravity core retrieved from the lower boundary of the modern OMZ (956 m water depth) were used to identify late Holocene changes in oceanographic conditions and the vertical extent of the OMZ. While the lower part of the core (535 - 465 cm, 5.04 - 4.45 cal kyr BP, Unit 3) is strongly bioturbated indicating oxic bottom water conditions, the upper part of the core (284 - 0 cm, 2.87 cal kyr BP to present, Unit 1) shows distinct and well-preserved lamination, suggesting anoxic bottom waters. The transitional interval from 465 to 284 cm (4.45 - 2.87 cal kyr BP, Unit 2) contains relicts of lamination which are in part intensely bioturbated. These fluctuations in bioturbation intensity suggest repetitive changes between anoxic and oxic/suboxic bottom-water conditions between 4.45 - 2.87 cal kyr BP. Barium excess (Baex) and total organic carbon (TOC) contents do not explain whether the increased TOC contents found in Unit 1 are the result of better preservation due to low BWO concentrations or if the decreased BWO concentration is a result of increased productivity. Changes in salinity and temperature of the outflowing water from the Red Sea during the Holocene influenced the water column stratification and probably affected the depth of the lower boundary of the OMZ in the northern Arabian Sea. Even if we cannot prove certain scenarios, we propose that the observed downward shift of the lower boundary of the OMZ was also impacted by a weakened Somali Current and a reduced transport of oxygen-rich Indian Central Water into the Arabian Sea, both as a response to decreased summer insolation and the continuous southward shift of the Intertropical Convergence Zone during the late Holocene.

Influence of sediment acidification and water flow on sediment acceptance and dispersal of juvenile soft-shell clams (Mya arenaria L.)

Although ocean acidification is expected to reduce carbonate saturation and yield negative impacts on open-ocean calcifying organisms in the near future, acidification in coastal ecosystems may already be affecting these organisms. Few studies have addressed the effects of sedimentary saturation state on benthic invertebrates. Here, we investigate whether sedimentary aragonite saturation (Omega aragonite) and proton concentration ([H+]) affect burrowing and dispersal rates of juvenile soft-shell clams (Mya arenaria) in a laboratory flume experiment. Two size classes of juvenile clams (0.5-1.5 mm and 1.51-2.5 mm) were subjected to a range of sediment Omega aragonite and [H+] conditions within the range of typical estuarine sediments (Omega aragonite 0.21-1.87; pH 6.8-7.8; [H+] 1.58 × 10**-8-1.51 × 10**- 7) by the addition of varying amounts of CO2, while overlying water pH was kept constant ~ 7.8 (Omega aragonite ~ 1.97). There was a significant positive relationship between the percent of juvenile clams burrowed in still water and Omega aragonite and a significant negative relationship between burrowing and [H+]. Clams were subsequently exposed to one of two different flow conditions (flume; 11 cm/s and 23 cm/s) and there was a significant negative relationship between Omega aragonite and dispersal, regardless of clam size class and flow speed. No apparent relationship was evident between dispersal and [H+]. The results of this study suggest that sediment acidification may play an important role in soft-shell clam recruitment and dispersal. When assessing the impacts of open-ocean and coastal acidification on infaunal organisms, future studies should address the effects of sediment acidification to adequately understand how calcifying organisms may be affected by shifting pH conditions.

Bacteriohopanepolyol data of sediment cores GeoB3918-2 and GeoB1514-6 from the Amazon River

We have investigated the delivery of terrestrial organic carbon (OC) to the Amazon shelf and deep sea fan based on soil marker bacteriohopanepolyols (BHPs; adenosylhopane and related compounds) and branched glycerol dialkyl glycerol tetraethers (GDGTs), as well as on 14C dating of bulk organic matter. The microbial biomarker records show persistent burial of terrestrial OC, evidenced by almost constant and high BIT values (0.6) and soil marker BHP concentration [80-230 µg/g TOC (total OC)] on the late Holocene shelf and even higher BIT values (0.8-0.9), but lower and more variable soil-marker BHP concentration (40-100 µg/g TOC), on the past glacial deep sea fan. Radiocarbon data show that OC on the shelf is 3-4 kyr older than corresponding bivalve shells, emphasizing the presence of old carbon in this setting. We observe comparable and unexpectedly invariant BHP composition in both marine sediment records, with a remarkably high relative abundance of C-35 amino BHPs including compounds specific for aerobic methane oxidation on the shelf (avg. 50% of all BHPs) and the fan (avg. 40%). Notably, these marine BHP signatures are strikingly similar to those of a methane-producing floodplain area in one of the Amazonian wetland (várzea) regions. The observation indicates that BHPs in the marine sediments may have initially been produced within wetland regions of the Amazon basin and may therefore document persistent export from terrestrial wetland regions, with subsequent re-working in the marine environment, both during recent and past glacial climate conditions.

Pollen analyses of sediment core GeoB9508-5

Millennial-scale dry events in the Northern Hemisphere monsoon regions during the last Glacial period are commonly attributed to southward shifts of the Intertropical Convergence Zone (ITCZ) associated with an intensification of the northeasterly (NE) trade wind system during intervals of reduced Atlantic meridional overturning circulation (AMOC). Through the use of high-resolution last deglaciation pollen records from the continental slope off Senegal, our data show that one of the longest and most extreme droughts in the western Sahel history, which occurred during the North Atlantic Heinrich Stadial 1 (HS1), displayed a succession of three major phases. These phases progressed from an interval of maximum pollen representation of Saharan elements between ~19 and 17.4 kyr BP indicating the onset of aridity and intensified NE trade winds, followed by a millennial interlude of reduced input of Saharan pollen and increased input of Sahelian pollen, to a final phase between ~16.2 and 15 kyr BP that was characterized by a second maximum of Saharan pollen abundances. This change in the pollen assemblage indicates a mid-HS1 interlude of NE trade wind relaxation, occurring between two distinct trade wind maxima, along with an intensified mid-tropospheric African Easterly Jet (AEJ) indicating a substantial change in West African atmospheric processes. The pollen data thus suggest that although the NE trades have weakened, the Sahel drought remained severe during this time interval. Therefore, a simple strengthening of trade winds and a southward shift of the West African monsoon trough alone cannot fully explain millennial-scale Sahel droughts during periods of AMOC weakening. Instead, we suggest that an intensification of the AEJ is needed to explain the persistence of the drought during HS1. Simulations with the Community Climate System Model indicate that an intensified AEJ during periods of reduced AMOC affected the North African climate by enhancing moisture divergence over the West African realm, thereby extending the Sahel drought for about 4000 years.

The number of plastic particles found in estuarine sediment and water samples of five estuaries, Durban, KwaZulu-Natal, South Africa

Widespread disposal of plastics negatively affects biotic and abiotic components of marine systems. Monitoring plastics transitioning through estuaries is vital in assessing terrestrial inputs to oceanic environments. Data on microplastics (particles <= 5mm) in estuaries are scant. This study determined microplastic levels within five estuaries along the Durban coastline and on intervening beaches. Plastics were isolated from estuarine sediment, beach sediment and the surface water of each estuary and characterised. Sediment at the Bayhead area of Durban Harbour was found to contain the highest average plastic concentrations (745.40 ± 129.72 particles per 500ml). Overall an attenuating concentration trend away from the city center was found. Fragments composed the largest percent of plastics (59 %) found in Bayhead, whereas fibers dominated other estuaries (Mdloti - 66 %, uMgeni - 38 %, Isipingo - 45 % and iLovu - 53 %). Plastic particle concentration in estuarine sediment generally increased from larger to smaller size classes. If high input and high retention in the harbour is coupled with high organic and metal pollutant loads, this area can become (if not already) a major environmental hazard.

Bulk rock magnetic measurements and thermomagnetic analyses of sediment core GeoB4901-8 from the southeastern flank of the Niger deep-sea fan

Diagenesis has extensively affected the magnetic mineral inventory of organic-rich late Quaternary sediments in the Niger deep-sea fan. Changes in concentration, grain size, and coercivity document modifications of the primary magnetic mineral assemblages at two horizons. The first front, the modern iron redox boundary, is characterized by a drastic decline in magnetic mineral content, coarsening of the grain size spectrum, and reduction in coercivity. Beneath a second front, the transition from the suboxic to the sulfidic anoxic domain, a further but less pronounced decrease in concentration and bulk grain size occurs. Finer grains and higher coercive magnetic constituents substantially increase in the anoxic environment. Low- and high-temperature experiments were performed on bulk sediments and on extracts which have also been examined by X-ray diffraction. Thermomagnetic analyses proved ferrimagnetic titanomagnetites of terrigenous provenance as the principal primary magnetic mineral components. Their broad range of titanium contents reflects the volcanogenic traits of the Niger River drainage areas. Diagenetic alteration is not only a grain size selective process but also critically depends on titanomagnetite composition. Low-titanium compounds are less resistant to diagenetic dissolution. Intermediate titanium content titanomagnetite thus persists as the predominant magnetic mineral fraction in the sulfidic anoxic sediments. At the Fe redox boundary, precipitation of authigenic, possibly bacterial, magnetite is documented. The presence of hydrogen sulfide in the pore water suggests a formation of secondary magnetic iron sulfides in the anoxic domain. Grain size-specific data argue for a gradual development of a superparamagnetic and single-domain iron sulfide phase in this milieu, most likely greigite.

Paleomagnetic analysed of two sediment cores off Cape Ghir

Holocene records documenting variations in direction and intensity of the geomagnetic field during the last about seven and a half millennia are presented for Northwest Africa. High resolution paleomagnetic analyses of two marine sediment sequences recovered from around 900 meter water depth on the upper continental slope off Cape Ghir (30°51'N, 10°16'W) were supplemented by magnetic measurements characterizing composition, concentration, grain size and coercivity of the magnetic mineral assemblage. Age control for the high sedimentation rate deposits (~60 cm/kyr) was established by AMS radiocarbon dates. The natural remanent magnetization (NRM) is very predominantly carried by a fine grained, mostly single domain (titano-)magnetite fraction allowing the reliable definition of stable NRM inclinations and declinations from alternating field demagnetization and principal component analysis. Predictions of the Korte and Constable (2005) geomagnetic field model CALS7K.2 for the study area are in fair agreement with the Holocene directional records for the most parts, yet noticeable differences exist in some intervals. The magnetic mineral inventory of the sediments reveals various climate controlled variations, specifically in concentration and grain size. A very strong impact had the mid-Holocene environmental change from humid to arid conditions on the African continent which also clearly affects relative paleointensity (RPI) estimates based on different remanence normalizers. To overcome this problem the pseudo-Thellier RPI technique has been applied. The results represent the first Holocene record of Earth's magnetic field intensity variations in the NW Africa region. It displays long term trends similar to those of model predictions, but also conspicuous millennium scale differences.