Artificial oxygen fluxes measured by the eddy correlation method using stirring-sensitive oxygen microsensor and oxygen optodes in a flume experiment

In the last decade, the aquatic eddy correlation (EC) technique has proven to be a powerful approach for non-invasive measurements of oxygen fluxes across the sediment water interface. Fundamental to the EC approach is the correlation of turbulent velocity and oxygen concentration fluctuations measured with high frequencies in the same sampling volume. Oxygen concentrations are commonly measured with fast responding electrochemical microsensors. However, due to their own oxygen consumption, electrochemical microsensors are sensitive to changes of the diffusive boundary layer surrounding the probe and thus to changes in the ambient flow velocity. The so-called stirring sensitivity of microsensors constitutes an inherent correlation of flow velocity and oxygen sensing and thus an artificial flux which can confound the benthic flux determination. To assess the artificial flux we measured the correlation between the turbulent flow velocity and the signal of oxygen microsensors in a sealed annular flume without any oxygen sinks and sources. Experiments revealed significant correlations, even for sensors designed to have low stirring sensitivities of ~0.7%. The artificial fluxes depended on ambient flow conditions and, counter intuitively, increased at higher velocities because of the nonlinear contribution of turbulent velocity fluctuations. The measured artificial fluxes ranged from 2 - 70 mmol m**-2 d**-1 for weak and very strong turbulent flow, respectively. Further, the stirring sensitivity depended on the sensor orientation towards the flow. Optical microsensors (optodes) that should not exhibit a stirring sensitivity were tested in parallel and did not show any significant correlation between O2 signals and turbulent flow. In conclusion, EC data obtained with electrochemical sensors can be affected by artificial flux and we recommend using optical microsensors in future EC-studies. Flume experiments were conducted in February 2013 at the Institute for Environmental Sciences, University of Koblenz-Landau Landau. Experiments were performed in a closed oval-shaped acrylic glass flume with cross-sectional width of 4 cm and height of 10 cm and total length of 54 cm. The fluid flow was induced by a propeller driven by a motor and mean flow velocities of up to 20 cm s-1 were generated by applying voltages between 0 V and 4 V DC. The flume was completely sealed with an acrylic glass cover. Oxygen sensors were inserted through rubber seal fittings and allowed positioning the sensors with inclinations to the main flow direction of ~60°, ~95° and ~135°. A Clark type electrochemical O2 microsensor with a low stirring sensitivity (0.7%) was tested and a fast-responding needle-type O2 optode (PyroScience GmbH, Germany) was used as reference as optodes should not be stirring sensitive. Instantaneous three-dimensional flow velocities were measured at 7.4 Hz using stereoscopic particle image velocimetry (PIV). The velocity at the sensor tip was extracted. The correlation of the fluctuating O2 sensor signals and the fluctuating velocities was quantified with a cross-correlation analysis. A significant cross-correlation is equivalent to a significant artificial flux. For a total of 18 experiments the flow velocity was adjusted between 1.7 and 19.2 cm s**-1, and 3 different orientations of the electrochemical sensor were tested with inclination angles of ~60°, ~95° and ~135° with respect to the main flow direction. In experiments 16-18, wavelike flow was induced, whereas in all other experiments the motor was driven by constant voltages. In 7 experiments, O2 was additionally measured by optodes. Although performed simultaneously with the electrochemical sensor, optode measurements are listed as separate experiments (denoted by the attached 'op' in the filename), because the velocity time series was extracted at the optode tip, located at a different position in the flume.

Surface time series of nitrate, silicate and chlorophyll a (1999-2011) and CTD profiles (1999) at the PhytoCly station, Bay of Calvi, Corsica, Mediterranean Sea

This work is based on a long time series of data collected in the well-preserved Bay of Calvi (Corsica island, Ligurian Sea, NW Mediterranean) between 1979 and 2011, which include physical characteristics (31 years), chlorophyll a (chl a, 15 years), and inorganic nutrients (13 years). Because samples were collected at relatively high frequencies, which ranged from daily to biweekly during the winter-spring period, it was possible to (1) evidence the key role of two interacting physical variables, i.e. water temperature and wind intensity, on nutrient replenishment and phytoplankton dynamics during the winter-spring period, (2) determine critical values of physical factors that explained interannual variability in the replenishment of surface nutrients and the winter-spring phytoplankton bloom, and (3) identify previously unrecognized characteristics of the planktonic ecosystem. Over the >30 year observation period, the main driver of nutrient replenishment and phytoplankton (chl a) development was the number of wind events (mean daily wind speed >5 m s-1) during the cold-water period (subsurface water <13.5°C). According to winter intensity, there were strong differences in both the duration and intensity of nutrient fertilization and phytoplankton blooms (chl a). The trophic character of the Bay of Calvi changed according to years, and ranged from very oligotrophic (i.e. subtropical regime, characterized by low seasonal variability) to mesotrophic (i.e. temperate regime, with a well-marked increase in nutrient concentrations and chl a during the winter-spring period) during mild and moderate winters, respectively. A third regime occurred during severe winters characterized by specific wind conditions (i.e. high frequency of northeasterly winds), when Mediterranean "high nutrient - low chlorophyll" conditions occurred as a result of enhanced crossshore exchanges and associated offshore export of the nutrient-rich water. There was no long-term trend (e.g. climatic) in either nutrient replenishment or the winter-spring phytoplankton bloom between 1979 and 2011, but both nutrients and chl a reflected interannual and decadal changes in winter intensity.

Oxygen and carbon isotopic composition of benthic and planktonic foraminifers at DSDP Site 610

A record of carbon and oxygen isotopes in benthic and planktonic foraminifers has been obtained from the interval corresponding to the last 2.4 m.y. of Site 610, Holes 610 and 610A, with a sample resolution of about 30 kyr. The record from the late Quaternary (<0.9 Ma) shows large amplitudes and high frequencies in oxygen isotopic variation. Prior to 0.9 Ma the isotopic variability record is reduced in amplitude (but not in frequency) compared with the late Quaternary, suggesting lower ice-volume and climatic fluctuations, and higher average eustatic sea level. Left-coiling (L, polar) Neogloboquadrinapachyderma were not found in samples between 1.0 and 2.2 Ma, indicating less influence of polar front migrations in the Northeast Atlantic. Both polar planktonic faunas and larger isotope fluctuations reappear in the lowermost samples (2.3 to 2.4 Ma), pointing toward a period of larger climatic variability in the late Pliocene than in the early Quaternary. The variation in benthic d13C and hence in deep-water d13C seems to have been constant through the analyzed section, reflecting a stable variability in the production of North Atlantic Deep Water (NADW) and possibly in Norwegian-Greenland Sea Overflow. Preliminary analyses of amino-acid epimerization in N. pachyderma (L) indicate a constant rate of epimerization to approximately 0.3 Ma. Beneath this level the average epimerization rate is much reduced.

Characteristics of acoustic recordings of narwhals (Monodon monoceros) north of Disko Island, April 2007 and 2009

A total of 1,690 individual narwhal nonecholocation sounds were recorded over 5 h in 2007 and 2009. Each sound was classified as either tonal (FM) or pulsed (amplitude modulated). Omnipresent in all the recordings were the songs of bearded seals, Erignathus barbatus, which were often so loud and numerous that the lower frequency ranges of narwhal sounds could not be distinguished.

(Table 1) Diatom abundance and preservation in ODP Hole 130-806B samples

We report on diatom abundance and preservation stratigraphy in the uppermost four cores of Ocean Drilling Program Hole 806B, which span the Quaternary period. Changes in diatom abundance and preservation show a rather complicated pattern, with much noise at high frequencies. However, in the cycles corresponding to eccentricity and obliquity variations, the picture is quite clear. Abundance and preservation follow glacial-interglacial cycles, with lowest abundances and poorest preservation observed in sediments that correspond to glacial stages. Seventy taxa compose the diatom assemblage of Hole 806B (from Samples 130-806B-1H-1, 8-9 cm, to -4H-7, 73-74 cm) with Azpeitia nodulifera as the dominant member. This species exhibits significant size variations related to glacial and interglacial stages during the Pleistocene. The distribution of power in the Fourier spectrum of the diatom signal (in the time domain) displays the expected Milankovitch frequencies (at 100,41, and 24-18 k.y.). It also shows concentration at various "odd" frequencies, especially at 62 k.y., suggesting a complicated response of productivity (and silicate chemistry) to climatic forcing.

Distribution of planktonic foraminifers, d18O and d13C in Globigerinoides sacculifer as well as Cibicidoides kullenbergi at DSDP Holes 90-590A and 90-590B

High biogenic sedimentation rates in the late Neogene at DSDP Site 590 (1293 m) provide an exceptional opportunity to evaluate late Neogene (late Miocene to latest Pliocene) paleoceanography in waters transitional between temperate and warm-subtropical water masses. Oxygen and carbon isotope analyses and quantitative planktonic foraminiferal data have been used to interpret the late Neogene paleoceanographic evolution of this site. Faunal and isotopic data from Site 590 show a progression of paleoceanographic events between 6.7 and 4.3 Ma, during the latest Miocene and early Pliocene. First, a permanent depletion in both planktonic and benthic foraminiferal d13C, between 6.7 and 6.2 Ma, can be correlated to the globally recognized late Miocene carbon isotope shift. Second, a 0.5 per mil enrichment in benthic foraminiferal d18O between 5.6 and 4.7 Ma in the latest Miocene to early Pliocene corresponds to the latest Miocene oxygen isotopic enrichment at Site 284, located in temperate waters south of Site 590. This enrichment in d18O coincides with a time of cool surface waters, as is suggested by high frequencies of Neogloboquadrina pachyderma and low frequencies of the warmer-water planktonic foraminifers, as well as by an enrichment in planktonic foraminiferal d18O relative to the earlier Miocene. By 4.6 Ma, benthic foraminiferal d18O values become depleted and remain fairly stable until about 3.8 Ma. The early Pliocene (~4.3 to 3.2 Ma) is marked by a significant increase in biogenic sedimentation rates (37.7 to 83.3 m/m.y.). During this time, heaviest values in planktonic foraminiferal d18O are associated with a decrease in the gradient between surface and intermediate-water d13C and d18O, a 1.0 per mil depletion in the d13C of two species of planktonic foraminifers, and a mixture of warm and cool planktonic foraminiferal elements. These data suggest that localized upwelling at the Subtropical Divergence produced an increase in surface-water productivity during the early Pliocene. A two-step enrichment in benthic foraminiferal d18O occurs in the late Pliocene sequence at Site 590. A 0.3 per mil average enrichment at about 3.6 Ma is followed by a 0.5 per mil enrichment at 2.7 Ma. These two events can be correlated with the two-step isotopic enrichment associated with late Pliocene climatic instability and the initiation of Northern Hemisphere glaciation.

Distribution of planktonic foraminifera in DSDP Hole 31-296 (Table III)

Late Neogene planktonic foraminiferal biostratigraphy of DSDP Site 296, Leg 31, reveals this site as an ideal reference section for correlation of Blow's low-latitude zonation with the mid-latitude zonation for temperate faunal assemblages developed in this paper and earlier for DSDP Site 310, Leg 31 (Keller). Abundance of temperate species of Globorotalia (G. inflata, G. puncticulata, G. crassaformis, G. conomiozea) permit correlation with the zonal subdivision developed at Site 310 based on these species. Evolutionary changes within the Globorotalia inflata group also appear to be consistent biostratigraphie markers in mid latitudes; a primitive variety of this species first appears at about 3.3-3.1 Ma, G. inflata praeinflata appears at about 2.6 Ma, and the modern form appears at about 2.2-2.1 Ma. Quantitative analyses of planktonic foraminifera at DSDP Site 296 reveal an inversely reciprocal frequency oscillation between species of Globorotalia and the Globigerina-Globigerinita group. Cool climatic periods are characterized by high frequencies in the Globigerina-Globigerinita group and low frequencies in the Globorotalia group, whereas warm intervals are marked by high frequencies in the Globorotalia group and low frequencies in the Globigerina-Globigerinita group. Five cool paleoclimatic events can be recognized between early Pliocene and late Pleistocene: 4.4 Ma, 3.2-3.1 Ma, 2.4-2.2 Ma, 1.2 Ma, and 0.7 Ma. These paleoclimatic/paleoceanographic events have also been recognized in planktonic foraminifera of the Central and Northeast Pacific DSDP Sites 310 and 173 and also correlate to cold events recognized in oxygen isotope measurements of DSDP Site 310 and in equatorial Pacific cores.

(Table 3) Reduced inorganic sulphur, d34S and nickel content of ODP Leg 165 sites

Leg 165 of the Ocean Drilling Program afforded a unique opportunity to investigate organic and inorganic geochemistry across a wide gradient of sediment compositions and corresponding chemical pathways. The solid fractions at Sites 998, 999, 1000, and 1001 reveal varying proportions of reactive carbonate species, a labile volcanic ash fraction occurring in discrete layers and as a dispersed component, and detrital fluxes that derive from continental weathering. The relative proportions and reactivities of these end-members strongly dictate the character of the diagenetic profiles observed during the pore-water work of Leg 165. In addition, alteration of the well-characterized basaltic basement at Site 1001 has provided a strong signal that is reflected in many of the dissolved components. The relative effects of basement alteration and diagenesis within the sediment column are discussed in terms of downcore relationships for dissolved calcium and magnesium. With the exception of Site 1002 in the Cariaco Basin, the sediments encountered during Leg 165 were uniformly deficient in organic carbon (typically <0.1 wt%). Consequently, rates of organic oxidation were generally low and dominated by suboxic pathways with subordinate levels of bacterial sulfate reduction and methanogenesis. The low rates of organic remineralization are supported by modeled rates of sulfate reduction. Site 1000 provided an exception to the generally low levels of microbially mediated redox cycling. At this site the sediment is slightly more enriched in organic phases, and externally derived thermogenic hydrocarbons appear to aid in driving enhanced levels of redox diagenesis at great depths below the seafloor. The entrapment of these volatiles corresponds with a permeability seal defined by a pronounced Miocene minimum in calcium carbonate concentration recognized throughout the basin and with a dramatic downcore increase in the magnitude of limestone lithification. The latter has been tentatively linked to increases in alkalinity associated with microbial oxidation of organic matter and gaseous hydrocarbons. Recognition and quantification of previously unconstrained large volumes and frequencies of Eocene and Miocene silicic volcanic ash within the Caribbean Basin is one of the major findings of Leg 165. High frequencies of volcanic ash layers manifest as varied but often dominant controls on pore-water chemistry. Sulfur isotope results are presented that speak to secondary metal and sulfur enrichments observed in ash layers sampled during Leg 165. Ultimately, a better mechanistic understanding of these processes and the extent to which they have varied spatially and temporally may bear on the global mass balances for a range of major and minor dissolved components of seawater.

Age determination and clay layer frequencies of sediments of the Black and Red Sea

Paleoenvironmental proxy data for ocean properties, eolian sediment input, and continental rainfall based on high-resolution analyses of sediment cores from the southwestern Black Sea and the northernmost Gulf of Aqaba were used to infer hydroclimatic changes in northern Anatolia and the northern Red Sea region during the last ~7500 years. Pronounced and coherent multicentennial variations in these records reveal patterns that strongly resemble modern temperature and rainfall anomalies related to the Arctic Oscillation/North Atlantic Oscillation (AO/NAO). These patterns suggest a prominent role of AO/NAO-like atmospheric variability during the Holocene beyond interannual to interdecadal timescales, most likely originating from solar output changes.