Evidence of O2 consumption in underway seawater lines: Implications for air-sea O2 and CO2 fluxes

We observed O2 deficits of 0.5 to 2.0% (1 to 4 mol/kg) in the underway seawater lines of three different ships. Deficits in O2/Ar and isotopic enrichments in dissolved O2 observed in underway seawater lines indicate a respiratory removal process. A 1% respiratory bias in underway lines would lead to a 2.5-5 atm (2.5-5pbar) enhancement in surface water pCO2. If an underway pCO2 bias of this magnitude affectedall measurements, the global oceanic carbon uptake based on pCO 2 climatologies would be 0.5-0.8 Pg/yr higher than the present estimate of 1.6 Pg/yr. Treatment of underway lines with bleach for several hours and thorough flushing appeared to minimize O2 loss. Given the increasing interest in underway seawater measurements for the determination of surface CO2 and O2 fluxes, respiration in underway seawater lines must be identified and eliminated on all observing ships to ensure unbiased data

CO2 fluxes in the sub-tropical and sub-arctic North Atlantic based on measurements from a Volunteer Observing Ship

Surface seawater pCO2 and related parameters were measured at high frequency onboard the volunteer observing ship M/V Falstaff in the North Atlantic Ocean between 36° and 52°N. Over 90,000 data points were used to produce monthly CO2 fluxes for 2002/2003. The air-sea CO2 fluxes calculated by two different averaging schemes were compared. The first approach used gas transfer velocity determined from wind speed retrieved at the location of the ship and called colocated winds, while for the second approach a monthly averaged gas transfer velocity was calculated from the wind for each grid pixel including the variability in wind. The colocated wind speeds determined during the time of passage do not capture the monthly wind speed variability of the grid resulting in fluxes that were 47% lower than fluxes using the monthly averaged wind products. The Falstaff CO2 fluxes were in good agreement with a climatology using averaged winds. Over the entire region they differed by 2–5%, depending on the time-dependent correction scheme to account for the atmospheric in increase in pCO2. However, locally the flux differences between the ship measurements and the climatology were greater, especially in regions north of 45°N, like the eastern sector. A comparison of two wind speed products showed that the annual CO2 sink is 4% less when using 6 hourly NCEP/NCAR wind speeds compared to the QuikSCAT wind speed data

Seasonal Patterns of Surface Inorgamic Carbon System Variables In the Gulf of Mexico Inferred From a Regional High-Resolution Ocean Biogeochemical Model

Uncertainties in carbon chemistry variability still remain large in the Gulf of Mexico (GoM), as data gaps limit our ability to infer basin-wide patterns. Here we configure and validate a regional high-resolution ocean biogeochemical model for the GoM to describe seasonal patterns in surface pressure of CO2 (pCO2), aragonite saturation state (ΩAr), and sea–air CO2 flux. Model results indicate that seasonal changes in surface pCO2 are strongly controlled by temperature across most of the GoM basin, except in the vicinity of the Mississippi–Atchafalaya river system delta, where runoff largely controls dissolved inorganic carbon (DIC) and total alkalinity (TA) changes. Our model results also show that seasonal patterns of surface ΩAr are driven by seasonal changes in DIC and TA, and reinforced by the seasonal changes in temperature. Simulated sea–air CO2 fluxes are consistent with previous observation-based estimates that show CO2 uptake during winter–spring, and CO2 outgassing during summer–fall. Annually, our model indicates a basin-wide mean CO2 uptake of 0.35 molm-2yr-1, and a northern GoM shelf (\u3c 200 m) uptake of 0.93 molm-2yr-1. The observation and model-derived patterns of surface pCO2 and CO2 fluxes show good correspondence; thus this study contributes to improved constraints of the carbon budget in the region

Variability of USA East Coast surface total alkalinity distributions revealed by automated instrument measurements

Seawater total alkalinity (TA) is one important determinant used to monitor the ocean carbon cycle, whose spatial distributions have previously been characterized along the United States East Coast via discrete bottle samples. Using these data, several regional models for TA retrievals based on practical salinity (S) have been developed. Broad-scale seasonal or interannual variations, however, are not well resolved in these models and existing data are highly seasonally biased. This study reports findings from the first long duration deployment of a new, commercially available TA titrator aboard a research vessel and the continuous underway surface TA measurements produced. The instrument, operated on seven East Coast USA cruises during six months in 2017 and for two months in 2018 on the summertime East Coast Ocean Acidification survey (ECOA-2), collected a total of nearly 11,000 surface TA measurements. Data from these efforts, along with a newly synthesized set of more than 11,000 regional surface TA observations, are analyzed to re-examine distributions of TA and S along the United States East Coast. Overall, regional distributions of S and TA generally agreed with prior findings, but linear TA:S regressions varied markedly over time and deviated from previously developed models. This variability is likely due to a combination of biological, seasonal, and episodic influences and indicates that substantial errors of ±10–20 μmol kg−1 in TA estimation from S can be expected due to these factors. This finding has likely implications for numerical ecosystem modeling and inorganic carbon system calculations. New results presented in this paper provide refined surface TA:S relationships, present more data in space and time, and improve TA modeling uncertainty

Variability and trends in surface seawater pCO2 and CO2 flux in the Pacific Ocean

Author Posting. © American Geophysical Union, 2017. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 44 (2017): 5627–5636, doi:10.1002/2017GL073814.Variability and change in the ocean sink of anthropogenic carbon dioxide (CO2) have implications for future climate and ocean acidification. Measurements of surface seawater CO2 partial pressure (pCO2) and wind speed from moored platforms are used to calculate high-resolution CO2 flux time series. Here we use the moored CO2 fluxes to examine variability and its drivers over a range of time scales at four locations in the Pacific Ocean. There are significant surface seawater pCO2, salinity, and wind speed trends in the North Pacific subtropical gyre, especially during winter and spring, which reduce CO2 uptake over the 10 year record of this study. Starting in late 2013, elevated seawater pCO2 values driven by warm anomalies cause this region to be a net annual CO2 source for the first time in the observational record, demonstrating how climate forcing can influence the timing of an ocean region shift from CO2 sink to source.NOAA, OAR, CPO, OOMD Grant Number: 100007298; NOAA, OAR, CPO, OOMD Grant Number: NA09OAR4320129; Ocean Observation and Monitoring Division (OOMD) Grant Number: NA09OAR4320129; National Oceanic and Atmospheric Administration (NOAA) Grant Number: 1000072982017-12-1

The reinvigoration of the Southern Ocean carbon sink

Several studies have suggested that the carbon sink in the Southern Ocean—the ocean’s strongest region for the uptake of anthropogenic CO2 —has weakened in recent decades. We demonstrated, on the basis of multidecadal analyses of surface ocean CO2 observations, that this weakening trend stopped around 2002, and by 2012, the Southern Ocean had regained its expected strength based on the growth of atmospheric CO2. All three Southern Ocean sectors have contributed to this reinvigoration of the carbon sink, yet differences in the processes between sectors exist, related to a tendency toward a zonally more asymmetric atmospheric circulation. The large decadal variations in the Southern Ocean carbon sink suggest a rather dynamic ocean carbon cycle that varies more in time than previously recognized

Evaluation of the National Oceanic and Atmospheric Administration/Coupled-Ocean Atmospheric Response Experiment (NOAA/COARE) air-sea gas transfer parameterization using GasEx data

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 109 (2004): C08S11, doi:10.1029/2003JC001831.During the two recent GasEx field experiments, direct covariance measurements of air-sea carbon dioxide fluxes were obtained over the open ocean. Concurrently, the National Oceanic and Atmospheric Administration/Coupled-Ocean Atmospheric Response Experiment air-sea gas transfer parameterization was developed to predict gas transfer velocities from measurements of the bulk state of the sea surface and atmosphere. The model output is combined with measurements of the mean air and sea surface carbon dioxide fugacities to provide estimates of the air-sea CO2 flux, and the model is then tuned to the GasEx-1998 data set. Because of differences in the local environment and possibly because of weaknesses in the model, some discrepancies are observed between the predicted fluxes from the GasEx-1998 and GasEx-2001 cases. To provide an estimate of the contribution to the air-sea flux of gas due to wave-breaking processes, the whitecap and bubble parameterizations are removed from the model output. These results show that moderate (approximately 15 m s−1) wind speed breaking wave gas transfer processes account for a fourfold increase in the flux over the modeled interfacial processes.This work was supported by the NOAA Office of Global Programs, under the leadership of Dr. Lisa Dilling. WHOI was supported by the National Science Foundation grant OCE-9711218

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

New and Updated Global Empirical Seawater Property Estimation Routines

We introduce three new Empirical Seawater Property Estimation Routines (ESPERs) capable of predicting seawater phosphate, nitrate, silicate, oxygen, total titration seawater alkalinity, total hydrogen scale pH (pHT), and total dissolved inorganic carbon (DIC) from up to 16 combinations of seawater property measurements. The routines generate estimates from neural networks (ESPER_NN), locally interpolated regressions (ESPER_LIR), or both (ESPER_Mixed). They require a salinity value and coordinate information, and benefit from additional seawater measurements if available. These routines are intended for seawater property measurement quality control and quality assessment, generating estimates for calculations that require approximate values, original science, and producing biogeochemical property context from a data set. Relative to earlier LIR routines, the updates expand their functionality, including new estimated properties and combinations of predictors, a larger training data product including new cruises from the 2020 Global Data Analysis Project data product release, and the implementation of a first-principles approach for quantifying the impacts of anthropogenic carbon on DIC and pHT. We show that the new routines perform at least as well as existing routines, and, in some cases, outperform existing approaches, even when limited to the same training data. Given that additional training data has been incorporated into these updated routines, these updates should be considered an improvement over earlier versions. The routines are intended for all ocean depths for the interval from 1980 to ~2030 c.e., and we caution against using the routines to directly quantify surface ocean seasonality or make more distant predictions of DIC or pHT.1,82

USE OF, SATISFACTION WITH, AND REQUIREMENTS FOR IN SITU pH SENSORS

The fundamental goal of this survey was to assess user needs and applications and to provide the focus for an Alliance for Coastal Technologies (ACT, www.act-us.info) Technology Verification of in situ pH sensors. The Customer Needs and Use Assessment strives to better understand how pH sensors are used. We hope this information can also assist manufacturers in refining pH sensor technologies to better address user priorities