A reconciliation of empirical and mechanistic models of the air-sea gas transfer velocity

Models of the air-sea transfer velocity of gases may be either empirical or mechanistic. Extrapolations of empirical models to an unmeasured gas or to another water temperature can be erroneous if the basis of that extrapolation is flawed. This issue is readily demonstrated for the most well-known empirical gas transfer velocity models where the influence of bubble-mediated transfer, which can vary between gases, is not explicitly accounted for. Mechanistic models are hindered by an incomplete knowledge of the mechanisms of air-sea gas transfer. We describe a hybrid model that incorporates a simple mechanistic view—strictly enforcing a distinction between direct and bubble-mediated transfer—but also uses parameterizations based on data from eddy flux measurements of dimethyl sulphide (DMS) to calibrate the model together with dual tracer results to evaluate the model. This model underpins simple algorithms that can be easily applied within schemes to calculate local, regional, or global air-sea fluxes of gases.

A reconciliation of empirical and mechanistic models of the air-sea gas transfer velocity

Models of the air-sea transfer velocity of gases may be either empirical or mechanistic. Extrapolations of empirical models to an unmeasured gas or to another water temperature can be erroneous if the basis of that extrapolation is flawed. This issue is readily demonstrated for the most well-known empirical gas transfer velocity models where the influence of bubble-mediated transfer, which can vary between gases, is not explicitly accounted for. Mechanistic models are hindered by an incomplete knowledge of the mechanisms of air-sea gas transfer. We describe a hybrid model that incorporates a simple mechanistic view—strictly enforcing a distinction between direct and bubble-mediated transfer—but also uses parameterizations based on data from eddy flux measurements of dimethyl sulphide (DMS) to calibrate the model together with dual tracer results to evaluate the model. This model underpins simple algorithms that can be easily applied within schemes to calculate local, regional, or global air-sea fluxes of gases.

Estimativa do fluxo de amônia na interface ar-mar na Baía de Guanabara: estudo preliminar

In the begining of April 2004, concentrations of NHx (NH3 + NH4+) were measured in surface waters of the Guanabara Bay. Concentrations varied from 2 to 143 mmol L-1. Ammonia exchange at the air-sea interface was quantified using a numerical model. No measurement of NH3 concentration in air (c air) was performed. Thus, calculations of NH3 flux were based on the assumptions of c air = 1 and 5 µg m-3. Fluxes were predominantly from the water to the atmosphere and varied from -20 to almost 3500 µg N m-2 h-1.

Fluxos de óxido nitroso na interface ar-mar na Baía de Guanabara

In Surface water concentrations of N2O were measured at 37 stations in Guanabara Bay and fluxes estimated across the air-sea interface. Concentrations averaged 8.2 ± 2.2 nmol L-1 and 90% of the stations showed supersaturation averaging 33%. N2O fluxes were estimated using a two-film model which is given by the product of the concentration difference across the film and the gas transfer coefficient (k w). Two parametrizations of k w were used which provided average fluxes of 0.3 and 3.0 µg N m-2 h-1. Flux measurements using floating chambers (not reported here) seem to agree with the upper limit of these estimates.

Química entre a microcamada superficial oceânica e os aerossóis marinhos

The sea surface microlayer (SML), although poorly understood, is important in biogeochemical cycling and sea - air exchanges; it is a source or a sink for a range of pollutants. In this paper, an overview of sampling techniques and the role of SML in biogeochemical cycles and climate is presented. The chemical and biological nature of the ocean surface film and its interaction with atmospheric aerosols are discussed. Special attention is given to organic constituents, gel-like compounds, surfactants, halogenated compounds, and metals. Estimates of air - sea exchange fluxes-with focus on organic carbon, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls-are compiled. In addition, research gaps in the chemical composition of marine aerosols and their relationship with SML are described.

Concentration of floating biogenic material in convergence zones

Some organisms that live just below the sea surface (the neuston) are known more as a matter of curiosity than as critical players in biogeochemical cycles. The hypothesis of this work is that their existence implies that they receive some food from an upward flux of organic matter. The behaviour of these organisms and of the associated organic matter, hereafter mentioned as floating biogenic material (FBM) is explored using a global physical-biogeochemical coupled model, in which its generation is fixed to 1% of primary production, and decay rate is of the order of I month. The model shows that the distribution of FBM should depart rapidly from that of primary production.. and be more sensitive to circulation patterns than to the distribution of primary production. It is trapped in convergence areas, where it reaches concentrations larger by a factor 10 than in divergences, thus enhancing and inverting the contrast between high and low primary productivity areas. Attention is called on the need to better understand the biogeochemical processes in the first meter of the ocean, as they may impact the distribution of food for fishes, as well as the conditions for air-sea exchange and for the interpretation of sea color.

Multi-parameter observations from coastal waters to the deepest trenche: challenges studying the carbón system with optode technology

[EN]This presentation will give examples on how multi-parameter platforms have been used in a variety of applications ranging from shallow coastal on-line observatories down to measuring in the deepest Ocean trenches. Focus will be on projects in which optode technology (primarily for CO2 and O2) has served to study different aspects of the carbon system including primary production/consumption, air-sea exchange, leakage detection from underwater storage of CO2 and measurements from moving platforms like gliders and ferries. The performance of recently developed pH optodes will als

Surface carbon dioxide measurements between 1994 and 2004 at site Estoc

Seasonal patterns in hydrography, partial pressure of CO2, fCO2, pHt, total alkalinity, AT, total dissolved inorganic carbon, CT, nutrients, and chlorophyll a were measured in surface waters on monthly cruises at the European Station for Time Series in the Ocean at the Canary Islands (ESTOC) located in the northeast Atlantic subtropical gyre. With over 5 years of oceanographic data starting in 1996, seasonal and interannual trends of CO2 species and air-sea exchange of CO2 were determined. Net CO2 fluxes show this area acts as a minor source of CO2, with an average outgassing value of 179 mmol CO2/m**2 yr controlled by the dominant trade winds blowing from May to August. The effect of short-term wind variability on the CO2 flux has been addressed by increasing air-sea fluxes by 63% for 6-hourly sampling frequency. The processes governing the monthly variations of CT have been determined. From March to October, when CT decreases, mixing at the base of the mixed layer (11.5 ± 1.5 mmol/m**3) is compensated by air-sea exchange, and a net organic production of 25.5 ± 5.7 mmol/m**3 is estimated. On an annual scale, biological drawdown accounts for the decrease in inorganic carbon from March to October, while mixing processes control the CT increase from October to the end of autumn. After removing seasonality variability, fCO2sw increases at a rate of 0.71 ± 5.1 µatm/yr, and as a response to the atmospheric trend, inorganic carbon increases at a rate of 0.39 ± 1.6 µmol/kg yr.

Seawater carbonate chemistry and community calcification during Shiraha coral reef (Ishigaki Island, Japan) studies, 1995

Only about half of all the CO_2 that has been produced by the burning of fossil fuels now remains in the atmosphere. The CO_2 "missing" from the atmosphere is the subject of an important debate. It was thought that the great majority of the missing CO_2 has invaded the ocean, for this system naturally acts as a giant chemical regulator of the atmosphere. Although it is clear that ocean processes have a major role in the regulation of the carbon dioxide content of the atmosphere through air-sea exchange processes, recent studies of the oceanic carbon cycle and air-sea interaction indicate that oceanic carbon is in a quasi-steady state via the system of biological and physical processes in the ocean interior. It is difficult to determine whether the ocean has the capacity to take up the increasing air-born CO_2 released by human activities over the past five or six decades. To understand this enigma, we need a better understanding of the natural variability of the oceanic carbon cycle.

(Table 2) Trace metal ratios of various benthic foraminifera shells

Benthic foraminiferal d13C and Cd/Ca studies suggest that deep Atlantic circulation during the Last Glacial Maximum was very different from today, with high-nutrient (low d13C, high Cd) deep Southern Ocean Water (SOW) penetrating far into the North Atlantic. However, if some glacial d13C values are biased by productivity artifacts and/or air-sea exchange processes, then the existing d13C data may be consistent with the continual dominance of North Atlantic Deep Water (NADW). Cibicidoides wuellerstorfi Cd/Ca results presented here indicate that the glacial North Atlantic was strongly enriched in dissolved Cd below ~2500 m depth. If NADW formation was still vigorous relative to SOW formation, these data could be explained by either increased preformed nutrient levels in the high-latitude North Atlantic or by increased organic matter remineralization within lower NADW. High glacial Zn/Ca values in the same samples, however, are best explained by a substantially increased mixing with Zn-rich SOW. The cause was most likely a partial replacement of NADW by less dense Glacial North Atlantic Intermediate Water. This reorganization also lowered deep North Atlantic [CO3]2- concentrations by perhaps 10 to 15 µmol/kg.

Biogenic halocarbons from the Peruvian upwelling region during METEOR cruise M91

Halocarbons, halogenated short-chained hydrocarbons, are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling obtained during the M91 cruise onboard the research vessel Meteor in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group as likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L-1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L-1 and diiodomethane (CH2I2) of up to 32.4 pmol L-1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. The enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels.

The South Atlantic carbon isotope record of planktic foraminifera

We reviewed the paleoceanographic application of the carbon isotope composition of planktic foraminifera. Major controls on the distribution of d13C of dissolved CO2 (d13CSCO2) in the modern ocean are photosynthesis-respiration cycle, isotopic fractionation during air-sea exchange, and circulation. The carbon isotope composition of surface waters is not recorded without perturbations by planktic foraminifera. Besides d13CSCO2 of the surrounding seawater, the d13C composition of planktic foraminifera is affected by vital effects, the water depth of calcification and postdepositional dissolution. We compared several high-resolution (>10cm/ka) carbon isotope records from the Southern Ocean, the Benguela upwelling system, and the tropical Atlantic. In the Southern Ocean, carbon isotope values are about 1.2 per mil lower during the LGM and up to 1.7 per mil lower during the last deglaciation, when compared to the Holocene. These depletions might be explained with a combination of a subsurface nutrient enrichment and reduced air-sea exchange due to an increased stratification of surface waters. In the Benguela Upwelling system, waters originating in the south are upwelled. While the deglacial minimum is transferred and recorded in its full extent in the d13C record of Globigerina bulloides, glacial values show only little changes. This might suggest, that the lower glacial d13C values of high-latitude surface waters are not upwelled off Namibia, or that G. bulloides records post-upwelling conditions, when increased seasonal production has already increased surface-water d13C. Synchronous to the d13C depletions in high latitudes, low d13C values were recorded in Globigerinoides sacculifer during the LGM and during the last deglaciation in the nutrient-depleted western equatorial Atlantic. Hence, part of the glacial-interglacial variability presumably transferred from high to low latitudes seems to be related to changes in thermodynamic fractionation. The variability in d13C is lowest in the northernmost core M35003-4 from the eastern Caribbean, implying that the Antarctic Intermediate Water might have acted as a conduit to transfer the deglacial minimum to tropical surface waters.

Underway measurements of dissolved gases along POLARSTERN cruise track ANT-XXVII/2

We present measurements of pCO2, O2 concentration, biological oxygen saturation (Delta O2/Ar) and N2 saturation (Delta N2) in Southern Ocean surface waters during austral summer, 2010-2011. Phytoplankton biomass varied strongly across distinct hydrographic zones, with high chlorophyll a (Chla) concentrations in regions of frontal mixing and sea-ice melt. pCO2 and Delta O2 /Ar exhibited large spatial gradients (range 90 to 450 µatm and -10 to 60%, respectively) and co-varied strongly with Chla. However, the ratio of biological O2 accumulation to dissolved inorganic carbon (DIC) drawdown was significantly lower than expected from photosynthetic stoichiometry, reflecting the differential time-scales of O2 and CO2 air-sea equilibration. We measured significant oceanic CO2 uptake, with a mean air-sea flux (~ -20 mmol m-2 d-1) that significantly exceeded regional climatological values. N2 was mostly supersaturated in surface waters (mean Delta N2 of +2.5 %), while physical processes resulted in both supersaturation and undersaturation of mixed layer O2 (mean Delta O2phys = 2.1 %). Box model calculations were able to reproduce much of the spatial variability of Delta N2 and Delta O2phys along the cruise track, demonstrating significant effects of air-sea exchange processes (e.g. atmospheric pressure changes and bubble injection) and mixed layer entrainment on surface gas disequilibria. Net community production (NCP) derived from entrainment-corrected surface Delta O2 /Ar data, ranged from ~ -40 to > 300 mmol O2 m-2 d-1 and showed good coherence with independent NCP estimates based on seasonal mixed layer DIC deficits. Elevated NCP was observed in hydrographic frontal zones and regions of sea-ice melt with shallow mixed layer depths, reflecting the importance of mixing in controlling surface water light and nutrient availability.

Studies on energy exchange between sea and atmosphere from the indian ocean with special reference to arabian sea and bay of bengal

There are only a few attempts in the Indian ocean to evolve reliable climatic models of energy exchange fluxes and to study their inter annul variations. Large space scale and time history of the flux fields could be estimated by the bulk aerodynamic exchange and radiation equation, making use of the climatic normal’s of the related parameters derived from the remarkably good amount of surface marine observations compiled and made available on magnetic tape TDF II by the national climatic centre of NOAA for the period of years 1854 –early 1973. In this thesis the author has made an attempt to calculate the thermal energy exchange fluxes in a meaningful way, using the bulk aerodynamic coefficients which depend on the changes in the wind speed. The spatial and temporal distribution of the exchanges of energy between the ocean and atmosphere , are presented and their impact on the climatic variations of the Indian ocean are discussed from the point of view of predominating air sea interaction processes.

An event of stratospheric air intrusion and its associated secondary surface cyclogenesis over the South Atlantic Ocean

This work presents an analysis of a lowermost stratospheric air intrusion event over the coast of Brazil, which may have been responsible for a secondary surface cyclogenesis over the southwestern Atlantic Ocean. The surface cyclone initiated at 0600 UTC 17 April 1999 in a cold air mass in the rear of a cold front after a primary cyclone developed over the same region. The analysis of the secondary cyclone revealed the presence of lowermost stratospheric air intrusion characterized by anomalous potential vorticity (PV), dry air, and high concentration of ozone in atmospheric column. The system developed on the eastern side of an upper level core of PV anomaly, which induced a cyclonic wind circulation at lower levels and favored the onset of the secondary cyclone. In midlevels (500 hPa), the cutoff low development contributed to reduce the propagation speed of the wave pattern. This feature seemed to (1) allow the low-level cold/dry air to heat/moisten associated with sensible and latent fluxes transferred from the ocean to the atmosphere, which intensified a baroclinic zone parallel to the coast, and (2) contribute to the long duration of the system. The present analysis indicates that this secondary cyclone development could be the result of the coupling between the PV anomaly in the upper levels and low-level air-sea interaction.