Physical and Biological Controls on the Latitudinal Asymmetry of Surface Nutrients and pCO(2) in the Central and Eastern Equatorial Pacific

Surface nutrients and dissolved inorganic carbon (DIC) in the central (CEP) and eastern equatorial Pacific (EEP) show much higher concentrations to the south than to the north of the equator. In this study, the physical and biological controls on this asymmetry are investigated using a coupled physical-biogeochemical model. Two numerical experiments are conducted to examine the effects of asymmetrical photosynthetic efficiency (a) due to asymmetrical iron supply about the equator. The experiment with asymmetrical photosynthesis produces improved results as compared with historical observations. A nitrate budget analysis suggests that in the EEP the divergence of upwelling waters controls the surface nitrate asymmetry with additional contribution from the South Equatorial Current (SEC) carrying nutrient-rich Peru upwelling water. The changes of a affect the surface nitrate distribution but not the overall asymmetry. The SEC further carries excess nitrate to the west and thus extends the asymmetry in the east to the CEP. In the CEP, however, stronger northward than southward transport tends to reduce the nitrate asymmetry, while the asymmetrical photosynthesis would help to maintain it. Similar processes also control the distributions of surface silicate and DIC in the equatorial Pacific, which is also affected by the air-sea CO(2) exchange. The asymmetrical photosynthesis influences the distribution of surface DIC, pCO(2), and the air-sea CO(2) flux, by redistributing about 20% CO(2) flux from the north to the south of the equator. Owing to the adjustment of air-sea CO(2) flux, however, the net surface DIC change is smaller than the direct change associated with primary production.

Stable isotope ratios of foraminifera and sea surface temperature estimation of sediment core W2804A-14

Carbon isotopically based estimates of CO2 levels have been generated from a record of the photosynthetic fractionation of 13C (epsilon p) in a central equatorial Pacific sediment core that spans the last ~255 ka. Contents of 13C in phytoplanktonic biomass were determined by analysis of C37 alkadienones. These compounds are exclusive products of Prymnesiophyte algae which at present grow most abundantly at depths of 70-90 m in the central equatorial Pacific. A record of the isotopic compostion of dissolved CO2 was constructed from isotopic analyses of the planktonic foraminifera Neogloboquadrina dutertrei, which calcifies at 70-90 m in the same region. Values of epsilon p, derived by comparison of the organic and inorganic delta values, were transformed to yield concentrations of dissolved CO2 (c e) based on a new, site-specific calibration of the relationship between epsilon p and c e. The calibration was based on reassessment of existing epsilon p versus c e data, which support a physiologically based model in which epsilon p is inversely related to c e. Values of PCO2, the partial pressure of CO2 that would be in equilibrium with the estimated concentrations of dissolved CO2, were calculated using Henry's law and the temperature determined from the alkenone-unsaturation index UK 37. Uncertainties in these values arise mainly from uncertainties about the appropriateness (particularly over time) of the site-specific relationship between epsilon p and 1/c e. These are discussed in detail and it is concluded that the observed record of epsilon p most probably reflects significant variations in Delta pCO2, the ocean-atmosphere disequilibrium, which appears to have ranged from ~110 µatm during glacial intervals (ocean > atmosphere) to ~60 µatm during interglacials. Fluxes of CO2 to the atmosphere would thus have been significantly larger during glacial intervals. If this were characteristic of large areas of the equatorial Pacific, then greater glacial sinks for the equatorially evaded CO2 must have existed elsewhere. Statistical analysis of air-sea pCO2 differences and other parameters revealed significant (p < 0.01) inverse correlations of Delta pCO2 with sea surface temperature and with the mass accumulation rate of opal. The former suggests response to the strength of upwelling, the latter may indicate either drawdown of CO2 by siliceous phytoplankton or variation of [CO2]/[Si(OH)4] ratios in upwelling waters.

Radium concentration in water samples from the Northeast Atlantic

We present field measurements of air-sea gas exchange by the radon deficit method that were carried out during JASIN 1978 (NE Atlantic) and FGGE 1979 (Equatorial Atlantic). Both experiments comprised repeated deficit measurements at fixed position over periods of days or longer, using a previously descibed precise and fast-acquiaition, automatic radon measuring system. The deficit time series exhibit variations that only partly reflect the expected changes in gas transfer. By evaluating averages over each time series we deduce the following gas transfer velocities (average wind velocity and water temperature in parentheses): JASIN phase 1: 1.6 ± 0.8 m/d (at ~6 m/s, 13°C) JASIN phase 2: 4.3 ± 1.2 m/d (at ~8 m/s, 13°C) FGGE: 1.2 ± 0.4 m/d (at ~5 m/s, 28°C) 0.9 ± 0.4 m/d (at ~7 m/s, 28°C) 1.5 ± 0.4 m/d (at ~7 m/s, 28°C) The large difference betwen the JASIN phase 2 and FGGE values despite quite similare average wind velocity becomes even larger when the values are, however, fully compatible with the range of gas transfer velocities observed in laboratory experiments and the conclusion is suggested that their difference is caused by the highly different wind variability in JASIN and FGGE. We conclude that in gas exchange parameterization it is not sufficinent to consider wind velocity only. A comparison of our observations with laboratory results outlines the range of variations of air-sea gas transfer velocities with wind velocity and sea state. We also reformulate the radon deficit method, in the light of our observed deficit variations, to account explicitely for non-stationary and horizontal inhomogeneity in previous radon work introduces considerable uncertainty in deduced gas transfere velocity. We furthermore discuss the observational rewuirements that have to be met for an adequate exploitation of the radon deficit method, of which an observation area of minimum horizontal inhomogeneity and monitoring of the remaining inhomogeneities are thought to be the most stringent ones.

Carbonate properties and oxygen concentrations at time series station DYFAMED

Monthly measurements of pH, alkalinity and oxygen over two years (February 1998-February 2000) at the Dyfamed site in the central zone of the Ligurian-Provençal Basin of the Mediterranean made it possible to assess the vertical distributions (5-2000 m) and the seasonal variations of these properties. Alkalinity varies linearly with salinity between surface water and the Levantine Intermediate Water (marked by a maximum of temperature and salinity). In deep water, total alkalinity is also correlated linearly to salinity, but the slope of the regression line is 15% less. In surface water, the pH at 25°C varies between 7.91 and 8.06 on the total proton scale depending upon the season. The lowest values are observed in winter, the highest in spring and in summer. These variations are primarily due to biological production. The pH goes through a minimum around 150-200 m and a small maximum below the intermediate water. The total dissolved inorganic carbon content (deduced from pH and alkalinity) is variable in surface water (2205-2310 ?mol/kg) and has a maximum in intermediate water, which is related to the salinity maximum. Normalized total inorganic carbon at a constant salinity is strongly negatively correlated with pH at 25°C. The fugacity of CO2, (fCO2) varies between 320 and 430 ?atm in surface water, according to the season. Below the seasonal thermocline, the maximum fCO2 (about 410 ?atm) is located around 150-200 m. The presence of a minimum of oxygen in the intermediate water of this area has been observed for several years, but our measurements made it possible to specify the relationship between oxygen and salinity in deep water. Data from the intense vertical mixing during the winters of 1999 and 2000 were used to calculate the oxygen quantity exchanged with the atmosphere during these periods. The estimated quantity of oxygen entering the Mediterranean Sea exceeds that deduced from exchange coefficients calculated with the formula of Wanninkhof and McGillis. During the vertical mixing in the 1999 winter, fCO2 in surface water was on average below equilibrium with atmospheric fCO2, thus implying that CO2 was entering the sea. However, on this time scale, even with high exchange coefficients, the estimated CO2 uptake had no significant influence on the inorganic carbon content in the water column.

On the fine structure of oxygen distribution in surface water layers in the area between Iceland and Faroe Islands

During the international "Overflow-Expedition'' 1973 on R.V. "Meteor" oxygen concentrations in surface layers were measured in order to determine the oxygen gradients within the first two meters and to add some informations to the mechanisms of oxygen exchange at the air-sea interface. These investigations may be interesting also with regard to longterm- observations of the oxygen distribution in the Atlantic, especially the problem of the A.O.U. (apparent oxygen utilization) determination. To measure oxygen gradients a special sampler was built which is able to take water samples each 20 cm of the first 2 meters. These data were supplemented by further samples down to 150 m, taken by conventional water samplers, from which samples were also taken to measure N2/O2-relations. By comparing these relations with theoretical relations in air-saturated water the influence of biological production and consumption on the oxygen contents in water could be estimated. A simple glass apparatus was built to extract gas from the water samples, and hereafter the N2/O2-relations were determined by mass spectrometry. Most distributions of the oxygen anomaly show a negative oxygen balance which varies largely, probably due to strong mixing processes in the Iceland-Faroe ridge area. The distribution of surface oxygen saturation values are of two different types. The values of the stations 260, 262 and 270 stem from mixed water and show homogeneous supersaturations, as can be found instantly when whitecaps appear. The values of 9 other stations are from water, sampled during calm periods which has been mixed and supersaturated before. They show a decreasing oxygen saturation towards the sea surface and often undersaturation in the upper decimeters up to 98 % and even 91 %. So at the air-sea interface even less initial oxygen saturation than 100 % can be found after supersaturation during heavy weather periods.

Hexachlorocyclohexanes concentration in air and ocean water

Hexachlorocyclohexanes (HCHs) are ubiquitous organic pollutants derived from pesticide application. They are subject to long-range transport, persistent in the environment, and capable of accumulation in biota. Shipboard measurements of HCH isomers (a-, b- and g-HCH) in surface seawater and boundary layer atmospheric samples were conducted in the Atlantic and the Southern Ocean in October to December of 2008. SumHCHs concentrations (the sum of a-, g- and b-HCH) in the lower atmosphere ranged from 12 to 37 pg/m**3 (mean: 27 ± 11 pg/m**3) in the Northern Hemisphere (NH), and from 1.5 to 4.0 pg/m**3 (mean: 2.8 ± 1.1 pg/m**3) in the Southern Hemisphere (SH), respectively. Water concentrations were: a-HCH 0.33-47 pg/l, g-HCH 0.02-33 pg/l and b-HCH 0.11-9.5 pg/l. Dissolved HCH concentrations decreased from the North Atlantic to the Southern Ocean, indicating historical use of HCHs in the NH. Spatial distribution showed increasing concentrations from the equator towards North and South latitudes illustrating the concept of cold trapping in high latitudes and less interhemispheric mixing process. In comparison to concentrations measured in 1987-1999/2000, gaseous HCHs were slightly lower, while dissolved HCHs decreased by factor of 2-3 orders of magnitude. Air-water exchange gradients suggested net deposition for a-HCH (mean: 3800 pg/m**2/day) and g-HCH (mean: 2000 pg/m**2/day), whereas b-HCH varied between equilibrium (volatilization: <0-12 pg/m**2/day) and net deposition (range: 6-690 pg/m**2/day). Climate change may significantly accelerate the release of "old" HCHs from continental storage (e.g. soil, vegetation and high mountains) and drive long-range transport from sources to deposition in the open oceans. Biological productivities may interfere with the air-water exchange process as well. Consequently, further investigation is necessary to elucidate the long term trends and the biogeochemical turnover of HCHs in the oceanic environment.

Gel particles in the sea-surface microlayer during an experimental study

Since the early 80's, the sea-surface microlayer (SML) has been hypothesized as being a gelatinous film. Recent studies have confirmed this characteristic, which confers properties that mediate mass and energy fluxes between ocean and atmosphere, including the emission of primary organic aerosols from marine systems. We investigated SML thickness and composition in five replicate indoor experiments between September and December 2010. During each experiment, the SML and underlying seawater were sampled from four seawater tanks: one served as control, and three were inoculated with Thalassiosira weissflogii grown in chemostats at 180, 380 and 780 ppm pCO2. We examined organic material enrichment factors in each tank, paying particular attention to gel particles accumulation such as polysaccharidic Transparent Exopolymer Particles (TEP) and the proteinaceous Coomassie Stainable Particles (CSP). While previous studies have observed carbohydrates and TEP enrichment in the microlayer, little is yet known about proteinaceous gel particles in the SML. Our experiments show that CSP dominate the gelatinous composition of the SML. We believe that the enrichment in CSP points to the importance of bacterial activity in the microlayer. Bacteria may play a pivotal role in mediating processes at the air-sea interface thanks to their exudates and protein content that can be released through cell disruption.

Noble gases sampled from three cruises in the eastern tropical Atlantic in September 2005 and June/July 2006

Upwelling velocities w in the equatorial band are too small to be directly observed. Here, we apply a recently proposed indirect method, using the observed helium isotope (3He or 4He) disequilibria in the mixed layer. The helium data were sampled from three cruises in the eastern tropical Atlantic in September 2005 and June/July 2006. A one-dimensional two-box model was applied, where the helium air-sea gas exchange is balanced by upwelling from 3He-rich water below the mixed layer and by vertical mixing. The mixing coefficients Kv were estimated from microstructure measurements, and on two of the cruises, Kv exceeded 1 x 10**-4 m**2/s, making the vertical mixing term of the same order of magnitude as the gas exchange and the upwelling term. In total, helium disequilibrium was observed on 54 stations. Of the calculated upwelling velocities, 48% were smaller than 1.0 x 10**-5 m/s, 19% were between 1.0 and 2.0 x 10**-5 m/s, 22% were between 2.0 and 4.0 x 10**-5 m/s, and on 11% of upwelling velocities exceeded this limit. The highest upwelling velocities were found in late June 2006. Meridional upwelling distribution indicated an equatorial asymmetry with higher vertical velocities between the equator and 1° to 2° south compared to north of the equator, particularly at 10°W. Associated heat flux into the mixed layer could be as high as 138 W/m**2, but this depends strongly on the chosen depths where the upwelled water comes from. By combining upwelling velocities with sea surface temperature and productivity distributions, a mean monthly equatorial upwelling rate of 19 Sv was estimated for June 2006 and a biweekly mean of 24 Sv was estimated for September 2005.