Major components and major and trace elements from ODP Site 175-1085

We have analyzed 33 Pliocene bulk sediment samples from Ocean Drilling Program Site 1085 in the Cape Basin, located offshore of western Africa in the Angola-Benguela Current system, for 17 major and trace elements, and interpreted their associations and temporal variations in the context of an allied data set of CaCO3, opal, and Corg. We base our interpretations on elemental ratios, accumulation rates, inter-element correlations, and several multi-element statistical techniques. On the basis of qualitative assessment of downhole changes in the distributions of P and Ba, utilized as proxies of export production, we conclude that highs in bulk and biogenic accumulation that occur at 3.2 Ma, 3.0 Ma, 2.4 Ma, and 2.25 Ma were caused by increases in export production as well as terrigenous flux, and record a greater sequestering of organic matter during these time periods. Studies of refractory elements and other indicator proxies (SiO2, Al2O3, TiO2, Fe2O3, MgO, V, Cr, Sr, and Zr) strongly suggest that the terrigenous component of the bulk sediment is composed of two compositional end-members, one being 'basaltic' in composition and the other similar to an 'average shale'. The basaltic end-member comprises approximately 10-15% of the total bulk sediment and its presence is consistent with the local geology of source material in the drainage basin of the nearby Orange River. The increase in bulk accumulation at 2.4 Ma appears to reflect a greater relative increase in basaltic input than the relative increase in shale-type input. Although studies such as this cannot precisely identify the transport mechanisms of the different terrigenous components, these results are most consistent with variations in sea level (and associated changes in shelf geometry and fluvial input) being responsible for the changing depositional conditions along the Angolan Margin during this time period.

(Table 1) Age, fork length, and tissue d15N and element concentration of arctic char (Salvelinus alpinus) from Lake Hazen

Arctic char (Salvelinus alpinus L.), the top predator in High Arctic lakes, often is used as a bioindicator of Hg contamination in Arctic aquatic ecosystems. The present study investigated effects of trophic position, size, and age of Arctic char in Lake Hazen, the largest lake in the Canadian High Arctic (81°50'N, 70°25'W), on Hg bioaccumulation. In addition, several essential (Se, K) and nonessential elements (Tl, Cs) in char muscle tissue were examined to compare their behavior to that of Hg. Trophic position of Arctic char was identified by stable isotope (d15N) signature. Temporal trends of Hg from seven sampling campaigns over a 16-year period (1990-2006) were investigated for the overall data and for one trophic class. Concentrations of Hg were not correlated with age but were positively related to fork length and trophic position. Large char with greater d15N signatures (>12 per mil) had larger Hg concentrations (0.09-1.63 µg/g wet wt) than small char with smaller d15N signatures (<12 per mil, 0.03-0.32 µg/g wet wt), indicating that Hg concentrations increased with trophic position. Nonessential Cs and Tl showed relationships to age, length, and trophic position similar to those of Hg, indicating their potential to bioaccumulate and biomagnify. Essential Se and K did not show these relationships. Concentrations of Hg were adjusted using d15N, leading to less within-year variability and a more consistent temporal trend. The d15N-adjusted trend showed no decline of Hg in Arctic char from Lake Hazen (1990-2006) in the overall data set and in the small morphotype. Trends for the same period before the adjustment were not significant for the overall data set, but a slight decrease was apparent in the small morphotype. The results confirm the need to consider trophic position and fish size when monitoring temporal trends of Hg, particularly for species with different morphotypes.

(Table 1) Platinum group element abundanves in ODP Leg 135 samples

Ocean Drilling Program Leg 135 backarc basin lavas are characterized by anomalously high Au contents (1.0-11.4 ppb) and strongly fractionated relative platinum group element (PGE) abundances (Pd/Ir ratio, approximately 100). The Rh and Ir contents are very low, ranging from below detection (approximately 0.02 ppb) to 0.08 ppb. The Pd and Pt contents range from <0.3 to 4 ppb. Rh, Pd, and Pt values are consistently and significantly higher in Site 836 and 839 samples relative to those from Sites 834 and 835. Major, trace, and rare earth element (REE) data suggest Sites 836 and 839 have a more pronounced arc signature than Sites 834 and 835. No correlation exists between noble metal abundance and indices of alteration or fractionation (e.g., loss on ignition (LOI), Mg#, and Cr or Ni contents), suggesting that measured values and ratios are primary and reflect characteristics of the mantle source. The evaluation of Leg 135 noble metal data with respect to potential mantle-source components is hindered by the lack of data on magmas derived from such sources. However, analyses of the limited available data for the different magma types suggest that the characteristic enrichment of Leg 135 lavas in Au, relative to Pd and Cu, cannot be derived solely from simple MORB-type or ocean-island-type mantle, or mantle depleted by a previous melt extraction event. The Au-enriched signature of the Lau basin lavas could, however, be produced through the addition of a sedimentary component from the downgoing slab. Separation of Au from the PGE occurs within oceanic hydrothermal systems and gold values of the resultant precipitates are 2-3 orders of magnitude higher than other oceanic crustal components. Even small additions of this component from the downgoing oceanic crust to a supra-subduction zone mantle melt could account for the high mean Au/Pd ratios of the Leg 135 samples (Sites 834 and 835, Au/Pd = 5.04; Sites 836 and 839, Au/Pd = 2.26).

Solid phase analysis of sediment core GeoB9309-1 from the Zambezi (or Mozambique) deep-sea fan

The Zambezi deep-sea fan, the largest of its kind along the east African continental margin, is poorly studied to date, despite its potential to record marine and terrestrial climate signals in the southwest Indian Ocean. Therefore, gravity core GeoB 9309-1, retrieved from 1219 m water depth, was investigated for various geophysical (magnetic susceptibility, porosity, colour reflectance) and geochemical (pore water and sediment geochemistry, Fe and P speciation) properties. Onboard and onshore data documented a sulphate/methane transition (SMT) zone at ~ 450-530 cm sediment depth, where the simultaneous consumption of pore water sulphate and methane liberates hydrogen sulphide and bi-carbonate into the pore space. This leads to characteristic changes in the sediment and pore water chemistry, as the reduction of primary Fe (oxyhydr)oxides, the precipitation of Fe sulphides, and the mobilization of Fe (oxyhydr)oxide-bound P. These chemical processes also lead to a marked decrease in magnetic susceptibility. Below the SMT, we find a reduction of porosity, possibly due to pore space cementation by authigenic minerals. Formation of the observed geochemical, magnetic and mineralogical patterns requires a fixation of the SMT at this distinct sediment depth for a considerable time-which we calculated to be ~ 10 000 years assuming steady-state conditions-following a period of rapid upward migration towards this interval. We postulate that the worldwide sea-level rise at the last glacial/interglacial transition (~ 10 000 years B.P.) most probably caused the fixation of the SMT at its present position, through drastically reduced sediment delivery to the deep-sea fan. In addition, we report an internal redistribution of P occurring around the SMT, closely linked to the (de)coupling of sedimentary Fe and P, and leaving a characteristic pattern in the solid P record. By phosphate re-adsorption onto Fe (oxyhydr)oxides above, and formation of authigenic P minerals (e.g. vivianite) below the SMT, deep-sea fan deposits may potentially act as long-term sinks for P.

Geochemistry measured on sediment core GeoB12309-5

Laminated sediment records from the oxygen minimum zone in the Arabian Sea offer unique ultrahigh-resolution archives for deciphering climate variability in the Arabian Sea region. Although numerous analytical techniques are available it has become increasingly popular during the past decade to analyze relative variations of sediment cores' chemical signature by non-destructive X-ray fluorescence (XRF) core scanning. We carefully selected an approximately 5 m long sediment core from the northern Arabian Sea (GeoB12309-5: 24°52.3' N; 62°59.9' E, 956 m water depth) for a detailed, comparative study of high-resolution techniques, namely non-destructive XRF core scanning (0.8 mm resolution) and ICP-MS/OES analysis on carefully selected, discrete samples (1 mm resolution). The aim of our study was to more precisely define suitable chemical elements that can be accurately analyzed and to determine which elemental ratios can be interpretated down to sub-millimeter-scale resolutions. Applying the Student's t-test our results show significantly correlating (1% significance level) elemental patterns for all S, Ca, Fe, Zr, Rb, and Sr, as well as the K/Ca, Fe/Ti and Ti/Al ratios that are all related to distinct lithological changes. After careful consideration of all errors for the ICP analysis we further provide respective factors of XRF Core Scanner software error's underestimation by applying Chi-square-tests, which is especially relevant for elements with high count rates. As demonstrated by these new, ultra-high resolution data core scanning has major advantages (high-speed, low costs, few sample preparation steps) and represents an increasingly required alternative over the time consuming, expensive, elaborative, and destructive wet chemical analyses (e.g., by ICP-MS/OES after acid digestions), and meanwhile also provides high-quality data in unprecedented resolution.

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.

Seawater carbonate chemistry and physiological and mechanical properties of the starfish Asterias rubens in a laboratory experiment

The increase in atmospheric CO2 due to anthropogenic activity results in an acidification of the surface waters of the oceans. Its impact will depend on the considered organisms and ecosystems. The intertidal may harbor organisms pre-adapted to the upcoming changes as they face tidal pH and temperature fluctuations. However, these environments will be more affected as shallow waters will face the highest decrease in seawater pH. In this context, the effects of reduced environmental pH on the physiology and tube feet mechanical properties of the intertidal starfish Asterias rubens, a top predator, were investigated during 15 and 27 days. A. rubens showed a respiratory acidosis with its coelomic fluid pH always lower than that of seawater. This acidosis was most pronounced at pH 7.4. Notwithstanding, the starfish showed no significant variations in RNA/DNA ratio of different tissues and in tube feet strength. However, respiration rates were significantly lower for individuals maintained at reduced seawater pH. Within the ocean acidification context, the present results suggest that A. rubens withstands the effects of reduced seawater pH, at least for medium term exposures.

(Supplement) Groundwater quality in Lahore Pakistan: emphasis on Arsenic and Fluoride levels

The dataset provides detailed information on the study that was conducted in Lahore's 7 major towns. The sample was taken from 472 tubewells and analyzed for major cations and anions using APHA 2012 techniques as explained herein. Besides, E.coli determination was done to check for microbial contamination. The data includes results from PHREEQC modeling of As(III)/ As(V) species and saturation indices as well as Aquachem's computed hydrochemical water facies. The WHO (2011) and EPA standards included in Aquachem identified the parameters that where in violation. Bicarbonates dominated the groundwater types with 50.21% of the samples exceeding the EPA maximum permissible limit of 250 mg/L in drinking water. Similarly, 30.51% of the samples had TDS values greater than 500 mg/L while 85.38 % of the samples exceed 10 µg/L threshold limit value of arsenic. Also, instances of high magnesium hazard values were observed which requires constant assessment if the groundwater is used for irrigation. Higher than 50% MH values are detrimental to crops which may reduce the expected yields. The membrane filtration technique using m-Endo Agar indicated that 3.59% samples had TNC (too numerous to count) values for E.coli while 5.06% showed values higher than 0 cfu/ 100 ml acceptable value in drinking water. Any traces of E-coli in a groundwater sample indicate recent fecal contamination. Such outcomes signify presence of enteric pathogens. If the groundwater is not properly dosed with disinfectants it may cause harm to human health. It is concluded that more studies are needed and proper groundwater management implement to safeguard the lives of communities that depend solely on groundwater in the city.

Magnesium/calcium ratio of the foraminifera Oridorsalis umbonatus in surface sediment samples off Namibia

A laser ablation system connected to an inductively coupled plasma mass spectrometer was used to determine Mg/Ca ratios of the benthic foraminifera Oridorsalis umbonatus. A set of modern core top samples collected along a depth transect on the continental slope off Namibia (320-2300 m water depth; 2.9° to 10.4°C) was used to calibrate the Mg/Ca ratio against bottom water temperature. The resulting Mg/Ca-bottom water temperature relationship of O. umbonatus is described by the exponential equation Mg/Ca = 1.528*e**0.09*BWT. The temperature sensitivity of this equation is similar to previously published calibrations based on Cibicidoides species, suggesting that the Mg/Ca ratio of O. umbonatus is a valuable proxy for thermocline and deep water temperature.

Calcareous dinoflagellate cysts and geochemistry of Mediterranean Sea sediments

Comparison of calcareous dinoflagellate cyst assemblages with Ba, Al, Mn, and Fe records from three sediment cores collected in the eastern Mediterranean Sea indicate that calcareous dinoflagellate cysts are generally resistant to postdepositional dissolution. Cyst association changes during and after sapropel S1 formation can therefore be closely related to variability in surface water productivity. Two groups of cysts are defined: those having highest abundances within the sapropelic and postsapropelic sediments. The temporal cyst distributions suggest increased freshwater input mainly from the Nile and a shallowing of the pycnocline as the most important processes increasing nutrient concentration in the photic zone, thus leading to increased productivity and organic carbon fluxes during sapropel formation. Furthermore, a general warming trend at the beginning of S1 formation and a slight salinity decrease are reconstructed.

Rare earth elements of ROV sample GeoB12338-2 from the Makran accretionary complex

Authigenic carbonates forming at an active methane-seep on the Makran accretionary prism mainly consist of aragonite in the form of microcrystalline, cryptocrystalline, and botryoidal phases. The d13Ccarbonate values are very negative (-49.0 to -44.0 per mill V-PDB), agreeing with microbial methane as dominant carbon source. The d18Ocarbonate values are exclusively positive (+ 3.0 to + 4.5 per mill V-PDB) and indicate precipitation in equilibrium with seawater at bottom water temperatures. The content of rare earth elements and yttrium (REE + Y) determined by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and solution ICP-MS varies for each aragonite variety, with early microcrystalline aragonite yielding the highest, cryptocrystalline aragonite intermediate, and later botryoidal aragonite the lowest REE + Y concentrations. Shale-normalised REE + Y patterns of different types of authigenic carbonate reflect distinct pore fluid compositions during precipitation: Microcrystalline aragonite shows high contents of middle rare earth elements (MREE), reflecting REE patterns ascribed to anoxic pore water. Cryptocrystalline aragonite exhibits a seawater-like REE + Y pattern at elevated total REE + Y concentrations, indicating higher concentrations of REEs in pore waters, which were influenced by seawater. Botryoidal aragonite is characterised by seawater-like REE + Y patterns at initial growth stages followed by an increase of light rare earth elements (LREE) with advancing crystal growth, reflecting changing pore fluid composition during precipitation of this cement. Conventional sample preparation involving micro-drilling of carbonate phases and subsequent solution ICP-MS does not allow to recognise such subtle changes in the REE + Y composition of individual carbonate phases. To be able to reconstruct the evolution of pore water composition during early diagenesis, an analytical approach is required that allows to track the changing elemental composition in a paragenetic sequence as well as in individual phases. High-resolution analysis of seep carbonates from the Makran accretionary prism by LA-ICP-MS reveals that pore fluid composition not only evolved in the course of the formation of different phases, but also changed during the precipitation of individual phases.

Geochemistry on sapropel deposition in the eastern Mediterranean from cores TTR-GL94 and M25/4-KL11

The geochemistry of the youngest Mediterranean sapropel layer suggests changes in productivity and water column oxygen conditions during sapropel deposition. The Ba-enriched interval is broader than the organic-carbon-rich interval of this sapropel. We suggest that the Ba-enriched horizon records the original thickness of the sapropel prior to subsequent partial oxidation. The main carrier of Ba is barite, as microcrystals (0.5-5 µm ) having a morphology characteristic of marine barite, particularly abundant beneath high productivity regions. Ba concentrations do not change at the sapropel layer oxidation front and diagenetic barite crystals are absent, thus the Ba-enriched layer reflects original oceanic conditions of increased biological productivity during sapropel deposition and not diagenetic Ba remobilization. Paleoredox indicators point to restricted oxygenated bottom water but not to fully anoxic conditions. Detrital elements within this layer indicate a lower eolian terrigenous input, enhanced humidity, and increased precipitation/runoff, thus likely higher nutrient supply.