Relationships between wind speed and gas transfer, combined with knowledge of the partial pressure difference of CO2 across the air-sea interface are frequently used to determine the CO2 flux between the ocean and the atmosphere. Little attention has been paid to the influence of variability in wind speed on the calculated gas transfer velocities and the possibility of chemical enhancement of CO2 exchange at low wind speeds over the ocean. The effect of these parameters is illustrated using a quadratic dependence of gas exchange on wind speed which is fit through gas transfer velocities over the ocean determined by the natural-14C disequilibrium and the bomb-14C inventory methods. Some of the variability between different data sets can be accounted for by the suggested mechanisms, but much of the variation appears due to other causes. Possible causes for the large difference between two frequently used relationships between gas transfer and wind speed are discussed. To determine fluxes of gases other than CO2 across the air-water interface, the relevant expressions for gas transfer, and the temperature and salinity dependence of the Schmidt number and solubility of several gases of environmental interest are included in an appendix.

Relationship between wind speed and gas exchange over the ocean

Marine dissolved organic matter (DOM) is a complex mixture of molecules found throughout the world's oceans. It plays a key role in the export, distribution, and sequestration of carbon in the oceanic water column, posited to be a source of atmospheric climate regulation. Biogeochemistry of Marine Dissolved Organic Matter, Second Edition, focuses on the chemical constituents of DOM and its biogeochemical, biological, and ecological significance in the global ocean, and provides a single, unique source for the references, information, and informed judgments of the community of marine biogeochemists. Presented by some of the world's leading scientists, this revised edition reports on the major advances in this area and includes new chapters covering the role of DOM in ancient ocean carbon cycles, the long term stability of marine DOM, the biophysical dynamics of DOM, fluvial DOM qualities and fate, and the Mediterranean Sea. Biogeochemistry of Marine Dissolved Organic Matter, Second Edition, is an extremely useful resource that helps people interested in the largest pool of active carbon on the planet (DOC) get a firm grounding on the general paradigms and many of the relevant references on this topic. * Features up-to-date knowledge of DOM, including five new chapters* The only published work to synthesize recent research on dissolved organic carbon in the Mediterranean Sea* Includes chapters that address inputs from freshwater terrestrial DOM

Biogeochemistry of marine dissolved organic matter

Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. Atmospheric emissions and concentrations of CH4 continue to increase, making CH4 the second most important human-influenced greenhouse gas in terms of climate forcing, after carbon dioxide (CO2). The relative importance of CH4 compared to CO2 depends on its shorter atmospheric lifetime, stronger warming potential, and variations in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in reducing uncertainties in the atmospheric growth rate arise from the variety of geographically overlapping CH4 sources and from the destruction of CH4 by short-lived hydroxyl radicals (OH). To address these challenges, we have established a consortium of multidisciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate new research aimed at improving and regularly updating the global methane budget. Following Saunois et al. (2016), we present here the second version of the living review paper dedicated to the decadal methane budget, integrating results of top-down studies (atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up estimates (including process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations).

For the 2008–2017 decade, global methane emissions are estimated by atmospheric inversions (a top-down approach) to be 576 Tg CH4 yr−1 (range 550–594, corresponding to the minimum and maximum estimates of the model ensemble). Of this total, 359 Tg CH4 yr−1 or ∼ 60 % is attributed to anthropogenic sources, that is emissions caused by direct human activity (i.e. anthropogenic emissions; range 336–376 Tg CH4 yr−1 or 50 %–65 %). The mean annual total emission for the new decade (2008–2017) is 29 Tg CH4 yr−1 larger than our estimate for the previous decade (2000–2009), and 24 Tg CH4 yr−1 larger than the one reported in the previous budget for 2003–2012 (Saunois et al., 2016). Since 2012, global CH4 emissions have been tracking the warmest scenarios assessed by the Intergovernmental Panel on Climate Change. Bottom-up methods suggest almost 30 % larger global emissions (737 Tg CH4 yr−1, range 594–881) than top-down inversion methods. Indeed, bottom-up estimates for natural sources such as natural wetlands, other inland water systems, and geological sources are higher than top-down estimates. The atmospheric constraints on the top-down budget suggest that at least some of these bottom-up emissions are overestimated. The latitudinal distribution of atmospheric observation-based emissions indicates a predominance of tropical emissions (∼ 65 % of the global budget, < 30∘ N) compared to mid-latitudes (∼ 30 %, 30–60∘ N) and high northern latitudes (∼ 4 %, 60–90∘ N). The most important source of uncertainty in the methane budget is attributable to natural emissions, especially those from wetlands and other inland waters.

Some of our global source estimates are smaller than those in previously published budgets (Saunois et al., 2016; Kirschke et al., 2013). In particular wetland emissions are about 35 Tg CH4 yr−1 lower due to improved partition wetlands and other inland waters. Emissions from geological sources and wild animals are also found to be smaller by 7 Tg CH4 yr−1 by 8 Tg CH4 yr−1, respectively. However, the overall discrepancy between bottom-up and top-down estimates has been reduced by only 5 % compared to Saunois et al. (2016), due to a higher estimate of emissions from inland waters, highlighting the need for more detailed research on emissions factors. Priorities for improving the methane budget include (i) a global, high-resolution map of water-saturated soils and inundated areas emitting methane based on a robust classification of different types of emitting habitats; (ii) further development of process-based models for inland-water emissions; (iii) intensification of methane observations at local scales (e.g., FLUXNET-CH4 measurements) and urban-scale monitoring to constrain bottom-up land surface models, and at regional scales (surface networks and satellites) to constrain atmospheric inversions; (iv) improvements of transport models and the representation of photochemical sinks in top-down inversions; and (v) development of a 3D variational inversion system using isotopic and/or co-emitted species such as ethane to improve source partitioning.

/pdf/the-global-methane-budget-2000-2017-mbxchwmkf5.pdf

The global methane budget 2000–2017

The National Oceanic and Atmospheric Administration (NOAA) advanced very high resolution radiometer (AVHRR) is an instrument on a polar orbiting satellite that provides information on global aerosol distributions. The remote sensing algorithm is based on measurements of backscattered solar radiation which yield a measure of the radiatively equivalent aerosol optical thickness τ A sat (EAOT) over the oceans. Seasonally composited EAOT data for the period July 1989 to June 1991 reveal many spatially coherent plume-like patterns that can usually be interpreted in terms of known (or reasonably hypothesized) sources in association with climatological wind fields. The largest and most persistent areas of high EAOT values are associated with wind-blown dust and biomass burning sources; especially prominent are sources in Africa, the middle East, and the Asian subcontinent. Prominent plumes over the midlatitude North Atlantic are attributed to pollution emissions from North America and Europe. Large plumes attributed to pollution aerosols and dust from sources in Asia are clearly visible over the western and central North Pacific. On a global scale the annually averaged northern hemisphere EAOT values are about 1.7 times greater than those in the southern hemisphere. Considering each hemisphere separately, EAOT values in summer are about twice those in winter. Within the midlatitude band 30°-60° (i.e., where anthropogenic emissions are greatest) the summer/winter ratio is about 3. The temporal variability of monthly mean EAOT in specific ocean regions often shows characteristic seasonal patterns that are usually consistent with aerosol measurements made in the marine boundary layer. Nonetheless, there are features in the EAOT distributions that can not be readily interpreted at this time. The AVHRR EAOT distributions demonstrate that satellite products can serve as a useful tool for the planning and implementation of focused aerosol research programs and that they will be especially important in studies of climate-related processes.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/96JD04009

Characterization of tropospheric aerosols over the oceans with the NOAA advanced very high resolution radiometer optical thickness operational product

. The global methane (CH4) budget is becoming an increasingly important component for managing realistic pathways to mitigate climate change. This relevance, due to a shorter atmospheric lifetime and a stronger warming potential than carbon dioxide, is challenged by the still unexplained changes of atmospheric CH4 over the past decade. Emissions and concentrations of CH4 are continuing to increase, making CH4 the second most important human-induced greenhouse gas after carbon dioxide. Two major difficulties in reducing uncertainties come from the large variety of diffusive CH4 sources that overlap geographically, and from the destruction of CH4 by the very short-lived hydroxyl radical (OH). To address these difficulties, we have established a consortium of multi-disciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate research on the methane cycle, and producing regular (∼ biennial) updates of the global methane budget. This consortium includes atmospheric physicists and chemists, biogeochemists of surface and marine emissions, and socio-economists who study anthropogenic emissions. Following Kirschke et al. (2013), we propose here the first version of a living review paper that integrates results of top-down studies (exploiting atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up models, inventories and data-driven approaches (including process-based models for estimating land surface emissions and atmospheric chemistry, and inventories for anthropogenic emissions, data-driven extrapolations). For the 2003–2012 decade, global methane emissions are estimated by top-down inversions at 558 Tg CH4 yr−1, range 540–568. About 60 % of global emissions are anthropogenic (range 50–65 %). Since 2010, the bottom-up global emission inventories have been closer to methane emissions in the most carbon-intensive Representative Concentrations Pathway (RCP8.5) and higher than all other RCP scenarios. Bottom-up approaches suggest larger global emissions (736 Tg CH4 yr−1, range 596–884) mostly because of larger natural emissions from individual sources such as inland waters, natural wetlands and geological sources. Considering the atmospheric constraints on the top-down budget, it is likely that some of the individual emissions reported by the bottom-up approaches are overestimated, leading to too large global emissions. Latitudinal data from top-down emissions indicate a predominance of tropical emissions (∼ 64 % of the global budget, The most important source of uncertainty on the methane budget is attributable to emissions from wetland and other inland waters. We show that the wetland extent could contribute 30–40 % on the estimated range for wetland emissions. Other priorities for improving the methane budget include the following: (i) the development of process-based models for inland-water emissions, (ii) the intensification of methane observations at local scale (flux measurements) to constrain bottom-up land surface models, and at regional scale (surface networks and satellites) to constrain top-down inversions, (iii) improvements in the estimation of atmospheric loss by OH, and (iv) improvements of the transport models integrated in top-down inversions. The data presented here can be downloaded from the Carbon Dioxide Information Analysis Center ( http://doi.org/10.3334/CDIAC/GLOBAL_METHANE_BUDGET_2016_V1.1 ) and the Global Carbon Project.

/pdf/the-global-methane-budget-2000-2012-4mc6pbm265.pdf

The global methane budget 2000–2012

Seawater and atmospheric methane (CH4) mixing ratios were measured on five cruises throughout the Pacific Ocean from 1987 to 1994 to assess the magnitude of the ocean-atmosphere flux. The results showed consistent regional and seasonal variations with surface seawater concentrations ranging from 1.6 to 3.6 nM and saturation ratios ranging from 0.95 to 1.17. The equatorial Pacific Ocean was supersaturated with respect to atmospheric CH4 partial pressures, while areas outside the tropics often were undersaturated during fall and winter. Although atmospheric CH4 mixing ratios over the North Pacific during April increased 3.4% from 1988 to 1993, the saturation ratios remained constant. Based on the concentration fields, the data were divided into two seasons and 10 latitude zones from 75°S to 75°N. Using monthly Comprehensive Ocean-Atmosphere Data Set (COADS) wind and surface seawater temperature data and the Wanninkhof [1992] wind speed/transfer velocity relationship, the calculated zonal average fluxes ranged from −0.1 to 0.4 μmol m−2 d−1. The combined seasonal and zonal fluxes result in a total global ocean-to-atmosphere flux of 25 Gmol yr−1 (0.4 Tg CH4 yr−1), which is an order of magnitude less than previous estimates [Intergovernmental Panel on Climate Change (IPCC), 1994]. The estimated uncertainty in this number is approximately a factor of 2.

A reevaluation of the open ocean source of methane to the atmosphere

A major purpose of the third joint Soviet-American Gases and Aerosols (SAGA 3) oceanographic cruise was to examine remote tropical marine O3 and photochemical cycles in detail. On leg 1, which took place between Hilo, Hawaii, and Pago-Pago, American Samoa, in February and March 1990, shipboard measurements were made of O3, CO, CH4, nonmethane hydrocarbons (NMHC), NO, dimethyl sulfide (DMS), H2S, H2O2, organic peroxides, and total column O3. Postcruise analysis was performed for alkyl nitrates and a second set of nonmethane hydrocarbons. A latitudinal gradient in O3 was observed on SAGA 3, with O3 north of the intertropical convergence zone (ITCZ) at 15–20 parts per billion by volume (ppbv) and less than 12 ppbv south of the ITCZ but never ≤3 ppbv as observed on some previous equatorial Pacific cruises (Piotrowicz et al., 1986; Johnson et al., 1990). Total column O3 (230–250 Dobson units (DU)) measured from the Akademik Korolev was within 8% of the corresponding total ozone mapping spectrometer (TOMS) satellite observations and confirmed the equatorial Pacific as a low O3 region. In terms of number of constituents measured, SAGA 3 may be the most photochemically complete at-sea experiment to date. A one-dimensional photochemical model gives a self-consistent picture of O3-NO-CO-hydrocarbon interactions taking place during SAGA 3. At typical equatorial conditions, mean O3 is 10 ppbv with a 10–15% diurnal variation and maximum near sunrise. Measurements of O3, CO, CH4, NMHC, and H2O constrain model-calculated OH to 9 × 105 cm−3 for 10 ppbv O3 at the equator. For DMS (300–400 parts per trillion by volume (pptv)) this OH abundance requires a sea-to-air flux of 6–8 × 109 cm−2 s−1, which is within the uncertainty range of the flux deduced from SAGA 3 measurements of DMS in seawater (Bates et al., this issue). The concentrations of alkyl nitrates on SAGA 3 (5–15 pptv total alkyl nitrates) were up to 6 times higher than expected from currently accepted kinetics, suggesting a largely continental source for these species. However, maxima in isopropyl nitrate and bromoform near the equator (Atlas et al., this issue) as well as for nitric oxide (Torres and Thompson, this issue) may signify photochemical and biological sources of these species.

/pdf/ozone-observations-and-a-model-of-marine-boundary-layer-4pzdzbjopy.pdf

Ozone observations and a model of marine boundary layer photochemistry during SAGA 3

Carbon monoxide (CO) is produced photochemically in the surface ocean and emitted to the atmosphere. To assess the magnitude of this ocean-atmosphere flux, seawater and atmospheric CO mole fractions were measured on six cruises throughout the Pacific Ocean from 1987 to 1994. The results showed consistent regional and seasonal variations in surface seawater CO concentrations with daily averaged concentrations ranging from 0.1 to 4.7 nM. Based on the concentration fields, the data were divided into four seasons and 10 latitude zones from 75°S to 75°N. Using monthly Comprehensive Ocean-Atmosphere Data Set wind and surface seawater temperature data and the Wanninkhof [1992] wind speed/transfer velocity relationship, the calculated zonal average fluxes ranged from 0.25 to 13 μmol/m2/d. The combined seasonal and zonal fluxes result in a total global flux of 0.46 Tmol CO/y with 2/3 of this flux in the southern hemisphere. The estimated uncertainty in this number is approximately a factor of 2.

Regional and seasonal variations in the flux of oceanic carbon monoxide to the atmosphere

Measurements of CO2 concentrations in the atmosphere and in the surface waters of the South Pacific Ocean were made by NOAA scientists between 1984 and 1989. These basin-wide measurements were all taken during austral autumn and provide data for evaluation of the seasonal flux of CO2 from this region. The sensitivity of this flux to the uncertainty in the CO2 gas exchange coefficient was evaluated using four different wind data sets and two formulations for the wind dependence of gas transfer velocity. The integrated net flux of CO2 to the atmosphere during austral autumn (February to May) ranges from −0.03 (ocean influx) to +0.09 (ocean efflux) GT of carbon depending on the combination of wind field and wind-dependent exchange coefficient used.

Kimberly C. Kelly

Papers

A reevaluation of the open ocean source of methane to the atmosphere

A reevaluation of the open ocean source of methane to the atmosphere

Ozone observations and a model of marine boundary layer photochemistry during SAGA 3

Regional and seasonal variations in the flux of oceanic carbon monoxide to the atmosphere

Assessment of the air-sea exchange of co2 in the south pacific during austral autumn