Estimating changes in ocean ventilation from early 1990s CFC-12 and late 2000s SF6 measurements

Transient tracer measurements can constrain the rates and pathways of ocean ventilation and act as proxies for biogeochemically relevant gases such as CO2 and oxygen. Various techniques have deduced changes in ocean ventilation over decadal timescales using transient tracer measurements made on repeat sections, but these require a priori assumptions about mixing in the ocean interior. Here, we introduce a simple, direct observational method that takes advantage of the similar atmospheric increase rates of chlorofluorocarbon-12 and sulfur hexafluoride, but with a time lag (offset) of 1415 years. Such repeat measurements can be directly compared without prior assumptions about mixing. A difference larger than similar to 2 years between modern sulfur hexafluoride and historical chlorofluorocarbon-12 tracer ages implies a change in ventilation, although lack of difference does not necessarily imply no change. Several tracer data sets are presented, which suggest changes in ventilation in the South Pacific and North Atlantic Oceans

Hydrographic data from R/V Endeavor cruise #143

Hydrographic data collected during R/V Endeavor cruise 143 is presented as a preliminary study of subduction in the northeast Atlantic south of the Azores Front. The front is clearly defined at the northern end of CTD section #1 which also shows a layer of 16-18°C water subducted to the south. Section #2, 280 km to the east, is dominated by a large cyclonic ring with characteristics similar to 'eastern' rings reported earlier . An anomalously salty parcel of Mediterranean water in this section is typical of highly saline lenses seen in the Canary Basin.Funding was provided by the National Science Foundation under grant Nos. OCE 85-15642 and OCE 85-18372

Long-term trends of temperature, salinity, density and transient tracers in the Central Greenland Sea

We present long-term observations of temperature, salinity, tritium/3He, chlorofluorocarbon-11 (CFC 11), and chlorofluorocarbon-12 (CFC 12) for the central Greenland Gyre. The time series span the periods between 1952 and 1994 (temperature), 1981 and 1994 (salinity), 1972 and 1994 (tritium/3He), and 1982 and 1994 (CFCs). The correlation between hydrographic and transient tracer data indicates that low temperatures in the deep water in the early 1950s and between 1960 and 1980 reflect periods of higher deep water formation rates whereas periods of increasing temperatures in the late 1950s and between 1980 and 1994 are related to low deep water formation rates. However, the transient tracer observations obtained in the 1980s and early 1990s indicate that even during periods of low deep water formation, some water from the upper water column contributed to deep water formation between 1980 and 1994. In 1994, the deep water reached temperatures and salinities of −1.149 °C and 34.899, respectively, and no longer fits most of the classical definitions of Greenland Sea Deep Water (−1.29°C< Θ < −1.0°C, 34.88<S<34.90). The temperature increase in the water column between 200 and 2000 m depth between 1980 and 1994 corresponds to an average heating rate of about 5 Wm−2 over this period, resulting in a decrease in density. The 13-year warming could be balanced by intensive cooling in two winters. The surface salinity steadily increased from 34.50 in 1991 to 34.85 in 1994

A comprehensive estimate for loss of atmospheric carbon tetrachloride (CCl4) to the ocean

© The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Atmospheric Chemistry and Physics 16 (2016): 10899-10910, doi:10.5194/acp-16-10899-2016.Extensive undersaturations of carbon tetrachloride (CCl4) in Pacific, Atlantic, and Southern Ocean surface waters indicate that atmospheric CCl4 is consumed in large amounts by the ocean. Observations made on 16 research cruises between 1987 and 2010, ranging in latitude from 60° N to 77° S, show that negative saturations extend over most of the surface ocean. Corrected for physical effects associated with radiative heat flux, mixing, and air injection, these anomalies were commonly on the order of −5 to −10 %, with no clear relationship to temperature, productivity, or other gross surface water characteristics other than being more negative in association with upwelling. The atmospheric flux required to sustain these undersaturations is 12.4 (9.4–15.4) Gg yr−1, a loss rate implying a partial atmospheric lifetime with respect to the oceanic loss of 183 (147–241) yr and that  ∼  18 (14–22)  % of atmospheric CCl4 is lost to the ocean. Although CCl4 hydrolyzes in seawater, published hydrolysis rates for this gas are too slow to support such large undersaturations, given our current understanding of air–sea gas exchange rates. The even larger undersaturations in intermediate depth waters associated with reduced oxygen levels, observed in this study and by other investigators, strongly suggest that CCl4 is ubiquitously consumed at mid-depth, presumably by microbiota. Although this subsurface sink creates a gradient that drives a downward flux of CCl4, the gradient alone is not sufficient to explain the observed surface undersaturations. Since known chemical losses are likewise insufficient to sustain the observed undersaturations, this suggests a possible biological sink for CCl4 in surface or near-surface waters of the ocean. The total atmospheric lifetime for CCl4, based on these results and the most recent studies of soil uptake and loss in the stratosphere is now 32 (26–43) yr.This research could not have been done without the support of our various institutions and the programs through which they support science, including funds at various times from NASA’s Upper Atmosphere Research Program, the US Department of Energy, NOAA’s Climate Program Office, the Atmospheric and Geosciences sections of the National Science Foundation, and the National Research Council of the US National Academies of Science

A comprehensive estimate for loss of atmospheric carbon tetrachloride (CCl4) to the ocean

© The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Atmospheric Chemistry and Physics 16 (2016): 10899-10910, doi:10.5194/acp-16-10899-2016.Extensive undersaturations of carbon tetrachloride (CCl4) in Pacific, Atlantic, and Southern Ocean surface waters indicate that atmospheric CCl4 is consumed in large amounts by the ocean. Observations made on 16 research cruises between 1987 and 2010, ranging in latitude from 60° N to 77° S, show that negative saturations extend over most of the surface ocean. Corrected for physical effects associated with radiative heat flux, mixing, and air injection, these anomalies were commonly on the order of −5 to −10 %, with no clear relationship to temperature, productivity, or other gross surface water characteristics other than being more negative in association with upwelling. The atmospheric flux required to sustain these undersaturations is 12.4 (9.4–15.4) Gg yr−1, a loss rate implying a partial atmospheric lifetime with respect to the oceanic loss of 183 (147–241) yr and that  ∼  18 (14–22)  % of atmospheric CCl4 is lost to the ocean. Although CCl4 hydrolyzes in seawater, published hydrolysis rates for this gas are too slow to support such large undersaturations, given our current understanding of air–sea gas exchange rates. The even larger undersaturations in intermediate depth waters associated with reduced oxygen levels, observed in this study and by other investigators, strongly suggest that CCl4 is ubiquitously consumed at mid-depth, presumably by microbiota. Although this subsurface sink creates a gradient that drives a downward flux of CCl4, the gradient alone is not sufficient to explain the observed surface undersaturations. Since known chemical losses are likewise insufficient to sustain the observed undersaturations, this suggests a possible biological sink for CCl4 in surface or near-surface waters of the ocean. The total atmospheric lifetime for CCl4, based on these results and the most recent studies of soil uptake and loss in the stratosphere is now 32 (26–43) yr.This research could not have been done without the support of our various institutions and the programs through which they support science, including funds at various times from NASA’s Upper Atmosphere Research Program, the US Department of Energy, NOAA’s Climate Program Office, the Atmospheric and Geosciences sections of the National Science Foundation, and the National Research Council of the US National Academies of Science

Global reconstruction reduces the uncertainty of oceanic nitrous oxide emissions and reveals a vigorous seasonal cycle

Assessment of the global budget of the greenhouse gas nitrous oxide ([Formula: see text]O) is limited by poor knowledge of the oceanic [Formula: see text]O flux to the atmosphere, of which the magnitude, spatial distribution, and temporal variability remain highly uncertain. Here, we reconstruct climatological [Formula: see text]O emissions from the ocean by training a supervised learning algorithm with over 158,000 [Formula: see text]O measurements from the surface ocean-the largest synthesis to date. The reconstruction captures observed latitudinal gradients and coastal hot spots of [Formula: see text]O flux and reveals a vigorous global seasonal cycle. We estimate an annual mean [Formula: see text]O flux of 4.2 ± 1.0 Tg N[Formula: see text], 64% of which occurs in the tropics, and 20% in coastal upwelling systems that occupy less than 3% of the ocean area. This [Formula: see text]O flux ranges from a low of 3.3 ± 1.3 Tg N[Formula: see text] in the boreal spring to a high of 5.5 ± 2.0 Tg N[Formula: see text] in the boreal summer. Much of the seasonal variations in global [Formula: see text]O emissions can be traced to seasonal upwelling in the tropical ocean and winter mixing in the Southern Ocean. The dominant contribution to seasonality by productive, low-oxygen tropical upwelling systems (>75%) suggests a sensitivity of the global [Formula: see text]O flux to El Niño-Southern Oscillation and anthropogenic stratification of the low latitude ocean. This ocean flux estimate is consistent with the range adopted by the Intergovernmental Panel on Climate Change, but reduces its uncertainty by more than fivefold, enabling more precise determination of other terms in the atmospheric [Formula: see text]O budget

Changes in deep-water CO2 concentrations over the last several decades determined from discrete pCO2 measurements

This paper is not subject to U.S. copyright. The definitive version was published in Deep Sea Research Part I: Oceanographic Research Papers 74 (2013): 48-63, doi:10.1016/j.dsr.2012.12.005.Detection and attribution of hydrographic and biogeochemical changes in the deep ocean are challenging due to the small magnitude of their signals and to limitations in the accuracy of available data. However, there are indications that anthropogenic and climate change signals are starting to manifest at depth. The deep ocean below 2000 m comprises about 50% of the total ocean volume, and changes in the deep ocean should be followed over time to accurately assess the partitioning of anthropogenic carbon dioxide (CO2) between the ocean, terrestrial biosphere, and atmosphere. Here we determine the changes in the interior deep-water inorganic carbon content by a novel means that uses the partial pressure of CO2 measured at 20 °C, pCO2(20), along three meridional transects in the Atlantic and Pacific oceans. These changes are measured on decadal time scales using observations from the World Ocean Circulation Experiment (WOCE)/World Hydrographic Program (WHP) of the 1980s and 1990s and the CLIVAR/CO2 Repeat Hydrography Program of the past decade. The pCO2(20) values show a consistent increase in deep water over the time period. Changes in total dissolved inorganic carbon (DIC) content in the deep interior are not significant or consistent, as most of the signal is below the level of analytical uncertainty. Using an approximate relationship between pCO2(20) and DIC change, we infer DIC changes that are at the margin of detectability. However, when integrated on the basin scale, the increases range from 8–40% of the total specific water column changes over the past several decades. Patterns in chlorofluorocarbons (CFCs), along with output from an ocean model, suggest that the changes in pCO2(20) and DIC are of anthropogenic origin.Rik Wanninkhof, Geun-Ha Park, John L. Bullister, and Richard A. Feely appreciate the support from the NOAA Office of Atmospheric and Oceanic Research and the Climate Observation Division. S.C.D. acknowledges support from NOAA Grant NA07OAR4310098. T.T. has been supported by grants from NSF and NOAA

Pacific anthropogenic carbon between 1991 and 2017

© The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Carter, B. R., Feely, R. A., Wanninkhof, R., Kouketsu, S., Sonnerup, R. E., Pardo, P. C., Sabine, C. L., Johnson, G. C., Sloyan, B. M., Murata, A., Mecking, S., Tilbrook, B., Speer, K., Talley, L. D., Millero, F. J., Wijffels, S. E., Macdonald, A. M., Gruber, N., & Bullister, J. L. Pacific anthropogenic carbon between 1991 and 2017. Global Biogeochemical Cycles, 33(5), (2019):597-617, doi:10.1029/2018GB006154.We estimate anthropogenic carbon (Canth) accumulation rates in the Pacific Ocean between 1991 and 2017 from 14 hydrographic sections that have been occupied two to four times over the past few decades, with most sections having been recently measured as part of the Global Ocean Ship‐based Hydrographic Investigations Program. The rate of change of Canth is estimated using a new method that combines the extended multiple linear regression method with improvements to address the challenges of analyzing multiple occupations of sections spaced irregularly in time. The Canth accumulation rate over the top 1,500 m of the Pacific increased from 8.8 (±1.1, 1σ) Pg of carbon per decade between 1995 and 2005 to 11.7 (±1.1) PgC per decade between 2005 and 2015. For the entire Pacific, about half of this decadal increase in the accumulation rate is attributable to the increase in atmospheric CO2, while in the South Pacific subtropical gyre this fraction is closer to one fifth. This suggests a substantial enhancement of the accumulation of Canth in the South Pacific by circulation variability and implies that a meaningful portion of the reinvigoration of the global CO2 sink that occurred between ~2000 and ~2010 could be driven by enhanced ocean Canth uptake and advection into this gyre. Our assessment suggests that the accuracy of Canth accumulation rate reconstructions along survey lines is limited by the accuracy of the full suite of hydrographic data and that a continuation of repeated surveys is a critical component of future carbon cycle monitoring.The data we use can be accessed at CCHDO website (https://cchdo.ucsd.edu/) and GLODAP website (https://www.glodap.info/). This research would not be possible without the hard work of the scientists and crew aboard the many repeated hydrographic cruises coordinated by GO‐SHIP, which is funded by NSF OCE and NOAA OAR. We thank funding agencies and program managers as follows: U.S., Australian, Japanese national science funding agencies that support data collection, data QA/QC, and data centers. Contributions from B. R. C., R. A. F., and R. W. are supported by the National Oceanic and Atmospheric Administration Global Ocean Monitoring and Observing Program (Data Management and Synthesis Grant: N8R3CEA‐PDM managed by Kathy Tedesco and David Legler). G. C. J. is supported by the Climate Observation Division, Climate Program Office, National Oceanic and Atmospheric Administration (NOAA), U.S. Department of Commerce and NOAA Research (fund reference 100007298), grant (N8R1SE3‐PGC). B. M. S was supported by the Australian Government Department of the Environment and CSIRO through the Australian Climate Change Science Programme and by the National Environmental Science Program. N. G. acknowledges support by ETH Zurich. This is JISAO contribution 2018‐0149 and PMEL contribution 4786. We fondly remember John Bullister as a treasured friend, valued colleague, and dedicated mentor, and we thank him for sharing his days with us. He is and will be dearly missed

Changes in the pool of Labrador Sea Water in the subpolar North Atlantic

Measurements of chlorofluorocarbon inventories during 1997–2003 allow the detection and quantification of significant changes in the formation rates of two modes of Labrador Sea Water (LSW): Upper (ULSW) and deep LSW, both here defined in fixed density intervals. Both modes contribute to the cold limb of the Meridional Overturning Circulation. Results reveal that the lighter ULSW formed since the mid-1990s has started to replace the large pool of the deep LSW stored in the western North Atlantic. Formation of deep LSW was absent in 1997–2003. Formation of ULSW compensated for this absence during 1998/99 (7.9 Sv), but afterwards significantly declined to 2.5 Sv. The decrease of the overall LSW formation throughout 1997–2003 correlates with a declining eastward baroclinic mass transport between the centers of the subpolar and subtropical gyres since 1997, a warming of LSW, and a gradually decreasing North Atlantic Oscillation index after 1999