Incubation experiments to examine the production and loss of CH3I in surface seawater

In order to investigate production pathways of methyl iodide and controls on emissions from the surface ocean, a set of repeated in-vitro incubation experiments were performed over an annual cycle in the context of a time-series of in-situ measurements in Kiel Fjord (54.3 N, 10.1E). The incubation experiments revealed a diurnal variation of methyl iodide in samples exposed to natural light, with maxima during day time and losses during night hours. The amplitude of the daily accumulation varied seasonally and was not affected by filtration (0.2µm), consistent with a photochemical pathway for CH3I production. The methyl iodide loss rate during night time correlated with the concentration accumulated during daytime. Daily (24 hour) net production (Pnet) was similar in magnitude between in vitro and in situ mass balances. However, the estimated gross production (Pgross) of methyl iodide ranged from -0.07 to 2.24 pmol/day and were 5 times higher in summer than Pnet calculated from the in-situ study [Shi et al., 2014]. The large excess of Pgross over Pnet revealed by the in-vitro (incubation) experiments in summer is a consequence of large losses of CH3I by as-yet uncharacterized processes (e.g. biological degradation or chemical pathways other than Cl- substitution).

Ocean acidification and the loss of phenolic substances in marine plants

Rising atmospheric CO2 often triggers the production of plant phenolics, including many that serve as herbivore deterrents, digestion reducers, antimicrobials, or ultraviolet sunscreens. Such responses are predicted by popular models of plant defense, especially resource availability models which link carbon availability to phenolic biosynthesis. CO2 availability is also increasing in the oceans, where anthropogenic emissions cause ocean acidification, decreasing seawater pH and shifting the carbonate system towards further CO2 enrichment. Such conditions tend to increase seagrass productivity but may also increase rates of grazing on these marine plants. Here we show that high CO2 / low pH conditions of OA decrease, rather than increase, concentrations of phenolic protective substances in seagrasses and eurysaline marine plants. We observed a loss of simple and polymeric phenolics in the seagrass Cymodocea nodosa near a volcanic CO2 vent on the Island of Vulcano, Italy, where pH values decreased from 8.1 to 7.3 and pCO2 concentrations increased ten-fold. We observed similar responses in two estuarine species, Ruppia maritima and Potamogeton perfoliatus, in in situ Free-Ocean-Carbon-Enrichment experiments conducted in tributaries of the Chesapeake Bay, USA. These responses are strikingly different than those exhibited by terrestrial plants. The loss of phenolic substances may explain the higher-than-usual rates of grazing observed near undersea CO2 vents and suggests that ocean acidification may alter coastal carbon fluxes by affecting rates of decomposition, grazing, and disease. Our observations temper recent predictions that seagrasses would necessarily be "winners" in a high CO2 world.

(Table 12-4, page 360) Percentage loss of water from manganese nodules (on a wet basis) at different temperatures

This chapter discusses the formation and distribution of some metals in ocean-floor manganese nodules in the light of the observed data in the literature and thermodynamic and kinetic considerations of the oxidation of metal ions in the oceanic environment. There are, in general, two major schools of thought on the mechanism of incorporation of the minor elements such as nickel, copper, and cobalt with the major elements such as manganese and iron. One is the lattice substitution mechanism and the other the adsorption mechanism. If the mechanism is lattice substitution, extraction of the metal ions is not possible unless the lattice of the major elements is first broken and exchanged with other ions from the bulk solution. Consequently, the leaching behavior of minor elements should display a very close relationship with that of major elements.

(Table 1) Mass loss of the Greenland Ice Sheet

Using satellite radar interferometry observations of Greenland, we detected widespread glacier acceleration below 66° north between 1996 and 2000, which rapidly expanded to 70° north in 2005. Accelerated ice discharge in the west and particularly in the east doubled the ice sheet mass deficit in the last decade from 90 to 220 cubic kilometers per year. As more glaciers accelerate farther north, the contribution of Greenland to sea-level rise will continue to increase.

Stable oxygen isotope record and lithogenic composition of ODP Hole 117-722B

The upper 38 m of Hole 722B sediments (Owen Ridge, northwest Arabian Sea) was sampled at 20 cm intervals and used to develop records of lithogenic percent, mass accumulation rate, and grain size spanning the past 1 m.y. Over this interval, the lithogenic component of Owen Ridge sediments can be used to infer variability in the strength of Arabian Sea summer monsoon winds (median grain size) and the aridity of surrounding dust source-areas (mass accumulation rate; MAR in g/cm**2/k.y). The lithogenic MAR has strong 100, 41, and 23 k.y. cyclicities and is forced primarily by changes in source-area aridity associated with glacial-interglacial cycles. The lithogenic grain size, on the other hand, exhibits higher frequency variability (23 k.y.) and is forced by the strength of summer monsoon winds which, in turn, are forced by the effective sensible heating of the Indian-Asian landmass and by the availability of latent heat from the Southern Hemisphere Indian Ocean. These forcing mechanisms combine to produce a wind-strength record which has no strong relationship to glacial-interglacial cycles. Discussion of the mechanisms responsible for production of primary Milankovitch cyclicities in lithogenic records from the Owen Ridge is presented elsewhere (Clemens and Prell, 1990, doi:10.1029/PA005i002p00109). Here we examine the 1 m.y. record from Hole 722B focusing on different aspects of the lithogenic components including an abrupt change in the monsoon wind-strength record at 500 k.y., core-to-core reproducibility, comparison with magnetic susceptibility, coherency with a wind-strength record from the Pacific Ocean, and combination frequencies in the wind-strength record. The Hole 722B lithogenic grain-size record shows an abrupt change at 500 k.y. possibly indicating decreased monsoon wind-strength over the interval from 500 k.y. to present. The grain-size decrease appears to be coincident with a loss of spectral power near the 41 k.y. periodicity. However, the grain-size decrease is not paralleled in the Globigerina bulloides upwelling record, an independent record of summer monsoon wind-strength (Prell, this volume). These observations leave us with competing hypotheses possibly involving: (1) a decrease in the sensitivity of monsoon windstrength to obliquity forcing, (2) decoupling of the grain size and G. bulloides records via a decoupling of the nutrient supply from wind-driven upwelling, and/or (3) a change in dust source-area or the patterns of dust transporting winds. Comparison of the lithogenic grain size and weight percent records from Hole 722B with those from a nearby core shows that the major and most minor events are well replicated. These close matches establish our confidence in the lithogenic extraction techniques and measurements. Further, reproducibility on a core-to-core scale indicates that the eolian depositional signal is regionally strong, coherent, and well preserved. The lithogenic weight percent and magnetic susceptibility are extremely well correlated in both the time and frequency domains. From this we infer that the magnetically susceptible component of Owen Ridge sediments is of terrestrial origin and transported to the Owen Ridge via summer monsoon winds. Because of the high correlation with the lithogenic percent record, the magnetic susceptibility record can be cast in terms of lithogenic MAR and used as a high resolution proxy for continental aridity. In addition to primary Milankovitch periodicities, the Hole 722B grain-size record exhibits periodicity at 52 k.y. and at 29 k.y. Both periodicities are also found in the grain-size record from piston core RC11-210 in the equatorial Pacific Ocean. Comparison of the two grain-size records shows significant coherence and zero phase relationships over both the 52 and 29 k.y. periodicities suggesting that the strengths of the Indian Ocean monsoon and the Pacific southeasterly trade winds share common forcing mechanisms. Two possible origins for the 52 and 29 k.y. periodicities in the Hole 722B wind-strength record are (1) direct Milankovitch forcing (54 and 29 k.y. components of obliquity) and (2) combination periodicities resulting from nonlinear interactions within the climate system. We find that the 52 and 29 k.y. periodicities show stronger coherency with crossproducts of eccentricity and obliquity (29 k.y.) and precession and obliquity (52 k.y.) than with direct obliquity forcing. Our working hypothesis attributes these periodicities to nonlinear interaction between external insolation forcing and internal climatic feedback mechanisms involving an interdependence of continental snow/ice-mass (albedo) and the hydrological cycle (latent heat availability).

Age models and sea-surface paleotemperature reconstruction of sediment cores from the eastern equatorial Atlantic

Based on the faunal record of planktonic foraminifers in three long gravity sediment cores from the eastern equatorial Atlantic, the sea-surface temperature history ove the last 750,000 years was studied at a resolution of 3,000 to 10,000 years. Detailed oxygen-isotope and paleomagnetic stratigraphy helped to identify the following major faunal events: Globorotaloides hexagonus and Globorotalia tumida flexuosa became extinct in the eastern tropical Atlantic at the isotope stage 4/5 boundary, now dated at 68,000 years B.P. The persistent occurrence of the pink variety of Globigerinoides ruber started during the late stage 12 at 410,000 years B.P. CARTUNE-age. This datum may provide an easily detectible faunal stratigraphic marker for the mid-Brunhes Chron. The updated scheme of the Ericson zones helped the recognition of a hiatus at the northwestern slope of the Sierra Leone Basin covering oxygen-isotope stages 10 to 12. Classifying the planktonic foraminifer counts into six faunal assemblages, according to the factor analysis derived model of Pflaumann (1985), the tropical and the tropical-upwelling communities account for 57 % at Site 16415, and 86 % at Site 13519, respectively of the variance of the faunal record. A largely continuous paleotemperature record for both winter and summer seasons was obtained from the top of the Sierra Leone Rise with the winter temperatures ranging between 20 and 25 °C, and the summer ones between 24 and 30 °C. The record of cores from greater water depths is frequently interrupted by samples with no-analogue faunal communities and/or poor preservation. Based on the seasonality signal, during cold periods the termal equator shifted to a geographically mnore asymmetrical northern position. Dissolution altering the faunal communities becomes stronger with greater water depth, the estimated mean minimum loss of specimens increases from 70 % to 80 % between 2,860 and 3,850 water depth although some species will be more susceptible than others. Enhanced dissolution occured during stage 4 but also during cold phases in the warm stage 7 and 9. Correlations between the Foraminiferal Dissolution Index and the estimated sea-surface temperatures are significant. Foraminiferal flux rates, negatively correlated to the flux rates of organic carbon and of diatoms, may be a result of enhanced dissolution during cold stages, destroying still more of the faunal signal than indicated by the calculated minimum loss. The fluctuations of the oxygen-isotope curves and the hibernal sea-surfave temperatures are fairly coherent. During warm oxygen-isotope stages the temperature maxima lag often by 5 to 15 ka behind the respective sotope minima. During cold stages, sea-surface temperature changes are partly out of phase and contain additional fluctuations.

Lithologic correlation of ODP Leg 115 holes

Whole-core (WC) measurements of low-field magnetic susceptibility (MS) provide an extremely simple, rapid, and nondestructive technique for high-resolution core logging and lithostratigraphic correlation between subsidiary holes at Ocean Drilling Program (ODP) sites. This is particularly useful for reconstructing composite, stratigraphically continuous sequences for individual ODP sites by splicing the uninterrupted records obtained from subsections of offset cores recovered from adjacent holes. Correlation between the WCMS profiles of holes drilled at different sites is also possible in some instances, especially when lithologic variations at each site are controlled by regional paleoceanographic or global (i.e., orbitally forced) paleoclimatic changes. In such circumstances, WCMS may also be used as a proxy paleoclimatic indicator, duly assisting climatostratigraphic zonation of the recovered sequence by more conventional microfossil and isotopic techniques. High-resolution WCMS profiles are also useful in detecting intervals of the recovered sequence affected by drilling disturbance, in the form of contamination by pipe rust or similar metallic artifacts as well as discontinuities related to repenetration of the corer or loss of material between successively cored intervals. Stratigraphic intervals that have been affected by early (suboxic) diagenesis resulting from a high initial organic matter content of the sediment are also readily identified by WCMS logging. The MS signal of horizons affected by suboxic diagensis is typically degraded in proportion to the duration and intensity (related to initial Corg concentration) of organic matter remineralization. The lowering of MS values during suboxic diagenesis results from "dissolution" (bacterially mediated ionic dissociation) of magnetic iron and manganese oxides and oxyhydroxides in the sediment. It is to be hoped that, on future ODP (or similar) cruises, WCMS logging will cease to be regarded as a mere adjunct to paleomagnetic measurements, but rather as a simple, yet powerful, lithostratigraphic tool, directly analogous to downhole geophysical logging tools, and complimentary to shipboard techniques for whole-core measurements of physical properties (e.g., P-wave logging, GRAPE, etc.).

Paleomagnetic of ODP Leg 133 holes

Paleomagnetic and rock-magnetic analyses from discrete samples of carbonate sites on the Queensland Plateau were used to determine magnetic polarity reversal stratigraphy and the nature of magnetization in these sediments. Magnetic polarity zones were correlated with the geomagnetic polarity time scale in the upper portions of cores at Sites 812 through 814, usually back to a late Pliocene age. Loss of reliable directional data was coincidental with a major decrease in magnetic intensity, below which, no stable polarity zones could be identified. The intensity reduction is either an in-situ alteration of magnetic grains, or an input signal representing progressive increase in the magnetic component of Queensland Plateau sediments. Although not conclusive at this point, the geochemical conditions and differing age of intensity reduction support the former hypothesis. Rock-magnetic analysis of carbonate sediments suggests that ultrafine-grained magnetite or maghemite crystals is an important carrier of remanence and may be biogenic in origin. Application of a recently calibrated anhysteretic remanent magnetization test to assess configuration of single-domain crystal within a natural matrix indicates that cementation (ooze-chalk-limestone) may be important in post-depositional changes affecting magnetostatic grain interaction.

Smear slide analysis of sediment core GeoB5836-2

Laminated sediments spanning the last 20,000 years (though not continuously) in the Shaban Deep, a brine-filled basin in the northern Red Sea, were analyzed microscopically and with backscattered electron imagery in order to determine laminae composition with emphasis on the diatomaceous component. Based on this detailed study, we present schematic models to propose paleoflux scenarios for laminae formation at different time-slices. The investigated core (GeoB 5836-2; 26°12.61'N, 35°21.56'E; water depth 1475 m) shows light and dark alternating laminae that are easily distinguishable in the mid-Holocene and at the end of the deglaciation (13-15 ka) period. Light layers are mainly composed of coccoliths, terrigenous material and diatom fragments, while dark layers consist almost exclusively of diatom frustules (monospecific or mixed assemblages). The regularity in the occurrence of coccolith/diatom couplets points to an annual deposition cycle where contrasting seasons and associated plankton blooms are represented (diatoms-fall/winter deposition, coccoliths-summer signal). We propose that, for the past ~15,000 years, the laminations represent two-season annual varves. Strong dissolution of carbonate, with the concomitant loss of the coccolith-rich layer in sediments older than 15 ka, prevents us from presenting a schematic model of annual deposition. However, the diatomaceous component reveals a marked switch in species composition between Last Glacial Maximum (LGM) sediments (dominated by Chaetoceros resting spores) and sediments somewhat younger (18-19 ka; dominated by Rhizosolenia). We propose that different diatom assemblages reflect changing conditions in stratification in the northern Red Sea: Strong stratification conditions, such as during two meltwater pulses at 14.5 and 11.4 ka, are reflected in the sediment by Rhizosolenia layers, while Chaetoceros-dominated assemblages represent deep convection conditions.