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Abstract. Marine N2 fixing microorganisms, termed diazotrophs, are a key functional group in marine pelagic ecosystems. The biological fixation of dinitrogen (N2) to bioavailable nitrogen provides an important new source of nitrogen for pelagic marine ecosystems and influences primary productivity and organic matter export to the deep ocean. As one of a series of efforts to collect biomass and rates specific to different phytoplankton functional groups, we have constructed a database on diazotrophic organisms in the global pelagic upper ocean by compiling about 12 000 direct field measurements of cyanobacterial diazotroph abundances (based on microscopic cell counts or qPCR assays targeting the nifH genes) and N2 fixation rates. Biomass conversion factors are estimated based on cell sizes to convert abundance data to diazotrophic biomass. The database is limited spatially, lacking large regions of the ocean especially in the Indian Ocean. The data are approximately log-normal distributed, and large variances exist in most sub-databases with non-zero values differing 5 to 8 orders of magnitude. Reporting the geometric mean and the range of one geometric standard error below and above the geometric mean, the pelagic N2 fixation rate in the global ocean is estimated to be 62 (52–73) Tg N yr−1 and the pelagic diazotrophic biomass in the global ocean is estimated to be 2.1 (1.4–3.1) Tg C from cell counts and to 89 (43–150) Tg C from nifH-based abundances. Reporting the arithmetic mean and one standard error instead, these three global estimates are 140 ± 9.2 Tg N yr−1, 18 ± 1.8 Tg C and 590 ± 70 Tg C, respectively. Uncertainties related to biomass conversion factors can change the estimate of geometric mean pelagic diazotrophic biomass in the global ocean by about ±70%. It was recently established that the most commonly applied method used to measure N2 fixation has underestimated the true rates. As a result, one can expect that future rate measurements will shift the mean N2 fixation rate upward and may result in significantly higher estimates for the global N2 fixation. The evolving database can nevertheless be used to study spatial and temporal distributions and variations of marine N2 fixation, to validate geochemical estimates and to parameterize and validate biogeochemical models, keeping in mind that future rate measurements may rise in the future. The database is stored in PANGAEA (doi:10.1594/PANGAEA.774851).

E C I A L I S S U E O N C H A N G I N G O C E A N C H E M I S T R Y » A N T H R O P O C E N E : T H E F U T U R E … Sand ocean acidification. The article discusses the long-term changes in dissolved inorganic carbon (DIC), salinity-normalized DIC, and surface seawater pCO 2 (partial pressure of CO 2 ) due to the uptake of anthropogenic CO 2 and its impact on the ocean's buffering capacity. In addition, we evaluate changes in seawater chemistry that are due to ocean acidification and its impact on pH and saturation states for biogenic calcium carbonate minerals.

Atmospheric carbon dioxide (CO2) is increasing at an accelerating rate, primarily due to fossil fuel combustion and land use change. A substantial fraction of anthropogenic CO2 emissions is absorbed by the oceans, resulting in a reduction of seawater pH. Continued acidification may over time have profound effects on marine biota and biogeochemical cycles. Although the physical and chemical basis for ocean acidification is well understood, there exist few field data of sufficient duration, resolution, and accuracy to document the acidification rate and to elucidate the factors governing its variability. Here we report the results of nearly 20 years of time-series measurements of seawater pH and associated parameters at Station ALOHA in the central North Pacific Ocean near Hawaii. We document a significant long-term decreasing trend of ؊0.0019 ؎ 0.0002 y ؊1 in surface pH, which is indistinguishable from the rate of acidification expected from equilibration with the atmosphere. Superimposed upon this trend is a strong seasonal pH cycle driven by temperature, mixing, and net photosynthetic CO2 assimilation. We also observe substantial interannual variability in surface pH, influenced by climate-induced fluctuations in upper ocean stability. Below the mixed layer, we find that the change in acidification is enhanced within distinct subsurface strata. These zones are influenced by remote water mass formation and intrusion, biological carbon remineralization, or both. We suggest that physical and biogeochemical processes alter the acidification rate with depth and time and must therefore be given due consideration when designing and interpreting ocean pH monitoring efforts and predictive models.carbon cycle ͉ climate change ͉ CO2 ͉ pH ͉ Station ALOHA W hen gaseous CO 2 is dissolved in seawater, it reacts to form carbonic acid (H 2 CO 3 ), which undergoes a series of reversible dissociation reactions that release hydrogen (H ϩ ) ions:The concentration of H ϩ (in mol kg Ϫ1 seawater) approximates its activity and determines the acidity of the solution. Acidity is commonly expressed on a logarithmic scale as pH:The addition of CO 2 therefore acidifies seawater and lowers its pH. Over the past 250 years, the mean pH of the surface global ocean has decreased from Ϸ8.2 to 8.1, which is roughly equivalent to a 30% increase in [H ϩ ] (1-3). This acidification of the sea is driven by the rapidly increasing atmospheric CO 2 concentration, which results from fossil fuel combustion, deforestation, and other human activities. Models predict that surface ocean pH may decline by an additional 0.3-0.4 during the 21st century (3, 4); over time, turbulent mixing, subduction, and advection are expected to transport anthropogenic CO 2 from the seasonally mixed layer into the ocean interior, lowering the pH of these deeper waters as well (4). Crucial marine biogeochemical processes may be altered, and many marine organisms may be negatively impacted by such pH reductions (2, 3, 5). As ocean CO 2 accumulates, seawater becomes more corrosive ...

The atmospheric and deep sea reservoirs of carbon dioxide are linked via physical, chemical, and biological processes. The last of these include photosynthesis, particle settling, and organic matter remineralization, and are collectively termed the "biological carbon pump." Herein, we present results from a 13-y (1992-2004) sediment trap experiment conducted in the permanently oligotrophic North Pacific Subtropical Gyre that document a large, rapid, and predictable summertime (July 15-August 15) pulse in particulate matter export to the deep sea (4,000 m). Peak daily fluxes of particulate matter during the summer export pulse (SEP) average 408, 283, 24.1, 1.1, and 67.5 μmol·m −2 ·d −1 for total carbon, organic carbon, nitrogen, phosphorus (PP), and biogenic silica, respectively. The SEP is approximately threefold greater than mean wintertime particle fluxes and fuels more efficient carbon sequestration because of low remineralization during downward transit that leads to elevated total carbon/PP and organic carbon/PP particle stoichiometry (371:1 and 250:1, respectively). Our long-term observations suggest that seasonal changes in the microbial assemblage, namely, summertime increases in the biomass and productivity of symbiotic nitrogen-fixing cyanobacteria in association with diatoms, are the main cause of the prominent SEP. The recurrent SEP is enigmatic because it is focused in time despite the absence of any obvious predictable stimulus or habitat condition. We hypothesize that changes in day length (photoperiodism) may be an important environmental cue to initiate aggregation and subsequent export of organic matter to the deep sea. Approximately half of the photosynthesis on Earth is attributable to microscopic, single-celled phytoplankton that inhabit the sea (1). Within the marine environment, most (∼90%) of the photosynthetic carbon fixation takes place in the low-biomass, low-nutrient open ocean gyres that are grossly undersampled relative to coastal habitats (2, 3). A small but variable (typically <15% for open ocean ecosystems) portion of the organic matter produced in the sunlit (euphotic) zone is exported to the deeper, dark regions of the ocean by gravitational settling of living and nonliving particulate organic matter (POM). Most of the exported POM undergoes microbial decomposition before reaching the seabed. This POM remineralization process creates a deep sea reservoir of inorganic nutrients, including dissolved inorganic carbon (DIC), nitrate (NO 3 − ), and phosphate (PO 4 3− ). The resupply of these deep sea nutrients to the euphotic zone via turbulent diffusion and upwelling sustains surface ocean productivity over long time scales.The term "carbon pump" (4) is used to describe the oceanic processes that collectively sustain the large ∼272 μmol C·kg −1 global mean surface-to-deep sea increase of DIC in the ocean. The carbon pump ultimately sets the limit for carbon dioxide (CO 2 ) exchange between the ocean and the atmosphere (4). A stated goal of the seminal paper by Volk and Hoffert (4...

The elemental stoichiometry of dissolved and particulate matter in the sea, especially the nitrogen-tophosphorus ratio, is an important parameter for studies of the nutrient control of plankton growth and for modeling biogeochemical processes, including carbon sequestration. Nitrogen (N) and phosphorus (P) pools have been measured on approximately monthly intervals for a 9-yr period at a deep-ocean station in the North Paci"c subtropical gyre (Sta. ALOHA; 22345N, 1583W). These data sets reveal complex interactions between N and P pools, and several unexpected secular trends. Models based on steady-state assumptions will not capture these temporal variations, especially the apparently rapid response of the microbial assemblages to stochastic nutrient intrusion events and the time-varying (seasonal, interannual and decadal scale) changes in dissolved matter N : P ratios. Based on an analysis of these data, we hypothesize that the gyre is presently in a period of net "xed N sequestration and P control of plankton rate processes.

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