Large quantities of methane are stored in hydrates and permafrost within shallow marine sediments in the Arctic Ocean. These reservoirs are highly sensitive to climate warming, but the fate of methane released from sediments is uncertain. Here, we review the principal physical and biogeochemical processes that regulate methane fluxes across the seabed, the fate of this methane in the water column, and potential for its release to the atmosphere. We find that, at present, fluxes of dissolved methane are significantly moderated by anaerobic and aerobic oxidation of methane. If methane fluxes increase then a greater proportion of methane will be transported by advection or in the gas phase, which reduces the efficiency of the methanotrophic sink. Higher freshwater discharge to Arctic shelf seas may increase stratification and inhibit transfer of methane gas to surface waters, although there is some evidence that increased stratification may lead to warming of sub-pycnocline waters, increasing the potential for hydrate dissociation. Loss of sea-ice is likely to increase wind speeds and seaair exchange of methane will consequently increase. Studies of the distribution and cycling of methane beneath and within sea ice are limited, but it seems likely that the sea-air methane flux is higher during melting in seasonally ice-covered regions. Our review reveals that increased observations around especially the anaerobic and aerobic oxidation of methane, bubble transport, and the effects of ice cover, are required to fully understand the linkages and feedback pathways between climate warming and release of methane from marine sediments.

The efficiency of transfer of gases and particles across the air-sea interface is controlled by several physical, biological and chemical processes in the atmosphere and water which are described here (including waves, large-and small-scale turbulence, bubbles, sea spray, rain and surface films). For a deeper understanding of relevant transport mechanisms, several models have been developed, ranging from conceptual models to numerical models. Most frequently the transfer is described by various functional dependencies of the wind speed, but more detailed descriptions need additional information. The study of gas transfer mechanisms uses a variety of experimental methods ranging from laboratory studies to carbon budgets, mass balance methods, micrometeorological techniques and thermographic techniques. Different methods resolve the transfer at different scales of time and space; this is important to take into account when comparing different results. Air-sea transfer is relevant in a wide range of applications, for example, local and regional fluxes, global models, remote sensing and computations of global inventories. The sensitivity of global models to the description of transfer velocity is limited; it is however likely that the formulations are more important when the resolution increases and other processes in models are improved. For global flux estimates using inventories or remote sensing products the accuracy of the transfer formulation as well as the accuracy of the wind field is crucial. IntroductionThe transfer of gases and particles across the air-sea interface depends not only on the concentration difference between the water and the air, but also on the efficiency of the transfer process. The efficiency of the transfer is controlled by complex interaction of a variety of processes in the air and in the water near the interface. Here we treat both gases and particles since the transfer, to some extent, is governed by similar mechanisms. Studies of transfer across the air-sea interface include a variety of methods and techniques ranging from laboratory studies, modeling and large-scale field studies. Various methods reach somewhat different conclusions, due to representation of different

The contemporary air‐sea flux of CO2 is investigated by the use of an air‐sea flux equation, with particular attention to the uncertainties in global values and their origin with respect to that equation. In particular, uncertainties deriving from the transfer velocity and from sparse upper ocean sampling are investigated. Eight formulations of air‐sea gas transfer velocity are used to evaluate the combined standard uncertainty resulting from several sources of error. Depending on expert opinion, a standard uncertainty in transfer velocity of either ~5% or ~10% can be argued and that will contribute a proportional error in air‐sea flux. The limited sampling of upper ocean fCO2 is readily apparent in the Surface Ocean CO2 Atlas databases. The effect of sparse sampling on the calculated fluxes was investigated by a bootstrap method, that is, treating each ship cruise to an oceanic region as a random episode and creating 10 synthetic data sets by randomly selecting episodes with replacement. Convincing values of global net air‐sea flux can only be achieved using upper ocean data collected over several decades but referenced to a standard year. The global annual referenced values are robust to sparse sampling, but seasonal and regional values exhibit more sampling uncertainty. Additional uncertainties are related to thermal and haline effects and to aspects of air‐sea gas exchange not captured by standard models. An estimate of global net CO2 exchange referenced to 2010 of −3.0 ± 0.6 Pg C/year is proposed, where the uncertainty derives primarily from uncertainty in the transfer velocity.

[1] Sea spray emission fluxes were calculated on the basis of vertical gradients of the aerosol concentration data collected with a laser particle counter during four polar scientific cruises carried out in the summers of 2000, 2001, 2002, and 2003. The calculated flux values are the first obtained with a gradient method from data measured on the open ocean; such a method has a much better physical basis than any involving calculating fluxes from concentrations measured at one level only. The sea spray generation function we obtained was compared with other functions from the literature. We show that most literature sea spray generation functions are underestimated for the 1-8 mm radius range, some of them by a factor of 6.Citation: Petelski, T., and J. Piskozub (2006), Vertical coarse aerosol fluxes in the atmospheric surface layer over the North Polar

We present an approach based on three-dimensional Monte Carlo radiative transfer simulations for estimating scattering error in measurements of light absorption by aquatic particles with a typical laboratory double-beam spectrophotometer. The scattering error is calculated by combining the weighting function describing the angular distribution of photon losses that are due to scattering on suspended particles with the volume scattering function of particles. We applied this method to absorption measurements made on marine phytoplankton, a diatom Thalassiosira pseudonana and a cyanobacterium Synechococcus. Assuming that the scattering phase function is described by the Henyey-Greenstein formula, we determined the backscatter probability of phytoplankton, which yields the best correction for scattering error at a light wavelength of 750 nm, where true absorption is null. The backscattering ratio estimated for both phytoplankton species is significantly higher than previously reported data based on Mie-scattering calculations for homogeneous spheres. Depending on the type of particles, the corrected absorption spectra obtained with our method may be similar or significantly different from spectra obtained with the null-point correction based on wavelength-independent scattering error.

The performance of several scattering correction schemes for reflecting-tube absorption and beam attenuation measurements is evaluated with data collected in European shelf seas. Standard scattering correction procedures for absorption measurements perform poorly because of nonzero absorption in the near infrared and wavelength-dependent scattering phase functions. A previously described iterative correction procedure based on Monte Carlo simulations of the Western Environmental Technologies Laboratories (WET Labs) ac-9 and independent estimates of particle backscattering initially performs poorly, but is greatly improved when realistic losses at flow-tube walls are incorporated into the model. The updated Monte Carlo scattering correction provides excellent agreement with independent absorption and attenuation measurements made with a point-source integrating-cavity absorption meter (PSICAM) and a Laser In Situ Scattering and Transmissometer (LISST, Sequoia Scientific), respectively. Implications for historic datasets and requirements for application to future datasets are discussed.

Using three-dimensional Monte Carlo radiative transfer simulations, we examine the effect of beam transmissometer geometry on the relative error in the measurement of the beam-attenuation coefficient in an aquatic environment characterized by intense light scattering, especially within submerged bubble clouds entrained by surface-wave breaking. We discuss the forward-scattering error associated with the detection of photons scattered at small angles (< 1 degrees) and the multiple-scattering error associated with the detection of photons scattered more than once along the path length of the instrument. Several scattering phase functions describing bubble clouds at different bubble void fractions in the water are considered. Owing to forward-scattering error, a beam-attenuation meter (beam transmissometer) with a half-angle of receiver acceptance of 1.0 degrees and a path length of 0.1 m can underestimate the true beam attenuation within the bubble cloud by more than 50%. For bubble clouds with a beam attenuation of as much as 100 m(-1), the multiple-scattering error is no more than a few percent. These results are compared with simulations for some example phase functions that are representative of other scattering regimes found in natural waters. The forward-scattering error for the Petzold phase function of turbid waters is 16% for a typical instrument geometry, whereas for the Henyey-Greenstein phase function with the asymmetry parameter of 0.7 and 0.9 the error range is 8-28%.

The water-leaving radiance field above a sea surface polluted by an oil film has been modelled using a Monte Carlo radiative transfer technique with large numbers of photons incident at a selected zenith angle. The calculated radiance was recorded for each of the 240 sectors of equal solid angle the upper hemisphere had been divided into. The results are presented in the form of a bi-directional reflectance distribution function (BRDF) and as a contrast function parameterised by observation angle for various angles of incident sunlight and for various states of the sea surface roughness. The conditions for observing maximal and minimal contrast are described.