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McLaughlin, K, Nezlin NP, Weisberg SB, Dickson AG, Booth JAT, Cash CL, Feit A, Gully JR, Howard MDA, Johnson S, Latker A, Mengel MJ, Robertson GL, Steele A, Terriquez L.  2018.  Seasonal patterns in aragonite saturation state on the southern California continental shelf. Continental Shelf Research. 167:77-86.   10.1016/j.csr.2018.07.009   AbstractWebsite

Shoaling of the saturation horizon for aragonite in the California Current System has been well-documented; however, these reports are based primarily on surveys conducted in waters off the continental shelf. Here we characterize, for the first time, regional spatial and seasonal patterns in aragonite saturation state (Omega(arag)) in the shallow, nearshore waters of the southern California continental shelf through a series of synoptic surveys. Spectrophotometric pH and total alkalinity samples were collected quarterly from 72 sites along the shelf for two years. Samples were collected using Niskin bottles deployed at 2-3 depths per station (surface, mixed layer, and near-bottom) to characterize site extremes in Omega(arag) (highest values near the surface, lowest at depth). Omega(arag) in bottle samples ranged between 3.0 and 0.54 and was strongly associated with density; average Omega(arag) from samples collected in the top 10 m was 2.5 compared to an average of 1.1 in samples below 100 m. The average depth of corrosive waters (Omega(arag) < 1) was interpolated for the shelf from the bottle data and was estimated to be an average of 100 m regionally, though there were instances when the saturation horizon rose to less than 20 m depth, primarily in the northern part of the coast during the spring. Omega(arag) was strongly correlated with dissolved inorganic carbon and dissolved oxygen indicating that patterns in Omega(arag) were linked to biological processes. The seasonality and spatial patterns we observed on the continental shelf were comparable to those observed by the California Cooperative Fisheries Investigations (CalCOFI) and West Coast Ocean Acidification (WCOA) programs in offshore southern California waters, suggesting that oceanic forcing is a strong driver defining broad patterns in aragonite saturation state on the shelf.

Carter, BR, Feely RA, Williams NL, Dickson AG, Fong MB, Takeshita Y.  2018.  Updated methods for global locally interpolated estimation of alkalinity, pH, and nitrate. Limnology and Oceanography-Methods. 16:119-131.   10.1002/lom3.10232   AbstractWebsite

We have taken advantage of the release of version 2 of the Global Data Analysis Project data product (Olsen et al. ) to refine the locally interpolated alkalinity regression (LIAR) code for global estimation of total titration alkalinity of seawater (A(T)), and to extend the method to also produce estimates of nitrate (N) and in situ pH (total scale). The updated MATLAB software and methods are distributed as Supporting Information for this article and referred to as LIAR version 2 (LIARv2), locally interpolated nitrate regression (LINR), and locally interpolated pH regression (LIPHR). Collectively they are referred to as locally interpolated regressions (LIRs). Relative to LIARv1, LIARv2 has an 18% lower average A(T) estimate root mean squared error (RMSE), improved uncertainty estimates, and fewer regions in which the method has little or no available training data. LIARv2, LINR, and LIPHR produce estimates globally with skill that is comparable to or better than regional alternatives used in their respective regions. LIPHR pH estimates have an optional adjustment to account for ongoing ocean acidification. We have used the improved uncertainty estimates to develop LIR functionality that selects the lowest-uncertainty estimate from among possible estimates. Current and future versions of LIR software will be available on GitHub.

Williams, NL, Juranek LW, Feely RA, Johnson KS, Sarmiento JL, Talley LD, Dickson AG, Gray AR, Wanninkhof R, Russell JL, Riser SC, Takeshita Y.  2017.  Calculating surface ocean pCO(2) from biogeochemical Argo floats equipped with pH: An uncertainty analysis. Global Biogeochemical Cycles. 31:591-604.   10.1002/2016gb005541   AbstractWebsite

More than 74 biogeochemical profiling floats that measure water column pH, oxygen, nitrate, fluorescence, and backscattering at 10 day intervals have been deployed throughout the Southern Ocean. Calculating the surface ocean partial pressure of carbon dioxide (pCO(2sw)) from float pH has uncertainty contributions from the pH sensor, the alkalinity estimate, and carbonate system equilibrium constants, resulting in a relative standard uncertainty in pCO(2sw) of 2.7% (or 11 mu atm at pCO(2sw) of 400 mu atm). The calculated pCO(2sw) from several floats spanning a range of oceanographic regimes are compared to existing climatologies. In some locations, such as the subantarctic zone, the float data closely match the climatologies, but in the polar Antarctic zone significantly higher pCO(2sw) are calculated in the wintertime implying a greater air-sea CO2 efflux estimate. Our results based on four representative floats suggest that despite their uncertainty relative to direct measurements, the float data can be used to improve estimates for air-sea carbon flux, as well as to increase knowledge of spatial, seasonal, and interannual variability in this flux. Plain Language Summary The Southern Ocean is a key player in the global flow of carbon, yet it is hard to reach, and there are relatively few measurements there, especially in winter. Measuring the amount of carbon dioxide gas in seawater is key to advancing our understanding of the Southern Ocean. More than 74 robotic floats that use sensors to measure seawater properties have been deployed throughout the Southern Ocean, and each has a lifetime of around 5 years. It is currently not possible to directly measure carbon dioxide gas from these floats; however, it is possible to estimate carbon dioxide from things that the float can measure, like pH, a measure of ocean acidity. Here surface ocean carbon dioxide is estimated from several floats and compared to two ship-based estimates. In some locations, the floats closely match the existing estimates, but in other locations the floats see significantly higher surface ocean carbon dioxide in the wintertime, reinforcing the idea that the Southern Ocean's role in the global carbon cycle needs a closer look. Our results show that despite not measuring carbon dioxide directly, these floats will help scientists learn a lot about the Southern Ocean's part in the global flow of carbon.

Carter, BR, Feely RA, Mecking S, Cross JN, Macdonald AM, Siedlecki SA, Talley LD, Sabine CL, Millero FJ, Swift JH, Dickson AG, Rodgers KB.  2017.  Two decades of Pacific anthropogenic carbon storage and ocean acidification along Global Ocean Ship-lebased Hydrographic Investigations Program sections P16 and P02. Global Biogeochemical Cycles. 31:306-327.   10.1002/2016gb005485   AbstractWebsite

A modified version of the extended multiple linear regression (eMLR) method is used to estimate anthropogenic carbon concentration (C-anth) changes along the Pacific P02 and P16 hydrographic sections over the past two decades. P02 is a zonal section crossing the North Pacific at 30 degrees N, and P16 is a meridional section crossing the North and South Pacific at similar to 150 degrees W. The eMLR modifications allow the uncertainties associated with choices of regression parameters to be both resolved and reduced. Canth is found to have increased throughout the water column from the surface to similar to 1000 m depth along both lines in both decades. Mean column Canth inventory increased consistently during the earlier (1990s-2000s) and recent (2000s-2010s) decades along P02, at rates of 0.53 +/- 0.11 and 0.46 +/- 0.11 mol Cm-2 a(-1), respectively. By contrast, Canth storage accelerated from 0.29 +/- 0.10 to 0.45 +/- 0.11 mol Cm-2 a(-1) along P16. Shifts in water mass distributions are ruled out as a potential cause of this increase, which is instead attributed to recent increases in the ventilation of the South Pacific Subtropical Cell. Decadal changes along P16 are extrapolated across the gyre to estimate a Pacific Basin average storage between 60 degrees S and 60 degrees N of 6.1 +/- 1.5 PgC decade(-1) in the earlier decade and 8.8 +/- 2.2 PgC decade(-1) in the recent decade. This storage estimate is large despite the shallow Pacific Canth penetration due to the large volume of the Pacific Ocean. By 2014, Canth storage had changed Pacific surface seawater pH by -0.08 to -0.14 and aragonite saturation state by -0.57 to -0.82.

Takeshita, Y, Martz TR, Coletti LJ, Dickson AG, Jannasch HW, Johnson KS.  2017.  The effects of pressure on pH of Tris buffer in synthetic seawater. Marine Chemistry. 188:1-5.   10.1016/j.marchem.2016.11.002   AbstractWebsite

Equimolar Tris (2-amino-2-hydroxymethyl-propane-1,3-diol) buffer prepared in artificial seawater media is a widely accepted pH standard for oceanographic pH measurements, though its change in pH over pressure is largely unknown. The change in volume (Delta V) of dissociation reactions can be used to estimate the effects of pressure on the dissociation constant of weak acid and bases. The Delta V of Tris in seawater media of salinity 35 (Delta V-Tris*) was determined between 10 and 30 degrees C using potentiometry. The potentiometric cell consisted of a modified high pressure tolerant Ion Sensitive Field Effect Transistor pH sensor and a Chloride-Ion Selective Electrode directly exposed to solution. The effects of pressure on the potentiometric cell were quantified in aqueous HCl solution prior to measurements in Tris buffer. The experimentally determined Delta V-Tris* were fitted to the equation Delta V-Tris*= 4528 +0.04912t where t is temperature in Celsius; the resultant fit agreed to experimental data within uncertainty of the measurements, which was estimated to be 0.9 cm(-3) mol(-1). Using the results presented here, change in pH of Tris buffer due to pressure can be constrained to better than 0.003 at 200 bar, and can be expressed as: DpH(Tris) = -(4.528 + 0.04912t)p/ln(10)RT. where T is temperature in Kelvin, R is the universal gas constant (83.145 cm(3) bar K-1 mol(-1)), and Pis gauge pressure in bar. On average, pH of Tris buffer changes by approximately -0.02 at 200 bar. (C) 2016 Elsevier B.V. All rights reserved.

Alin, SR, Feely RA, Dickson AG, Hernandez-Ayon JM, Juranek LW, Ohman MD, Goericke R.  2012.  Robust empirical relationships for estimating the carbonate system in the southern California Current System and application to CalCOFI hydrographic cruise data (2005-2011). Journal of Geophysical Research-Oceans. 117   10.1029/2011jc007511   AbstractWebsite

The California Current System (CCS) is expected to experience the ecological impacts of ocean acidification (OA) earlier than most other ocean regions because coastal upwelling brings old, CO2-rich water relatively close to the surface ocean. Historical inorganic carbon measurements are scarce, so the progression of OA in the CCS is unknown. We used a multiple linear regression approach to generate empirical models using oxygen (O-2), temperature (T), salinity (S), and sigma theta (sigma(theta)) as proxy variables to reconstruct pH, carbonate saturation states, carbonate ion concentration ([CO32-]), dissolved inorganic carbon (DIC) concentration, and total alkalinity (TA) in the southern CCS. The calibration data included high-quality measurements of carbon, oxygen, and other hydrographic variables, collected during a cruise from British Columbia to Baja California in May-June 2007. All resulting empirical relationships were robust, with r(2) values >0.92 and low root mean square errors. Estimated and measured carbon chemistry matched very well for independent data sets from the CalCOFI and IMECOCAL programs. Reconstructed CCS pH and saturation states for 2005-2011 reveal a pronounced seasonal cycle and inter-annual variability in the upper water column. Deeper in the water column, conditions are stable throughout the annual cycle, with perennially low pH and saturation states. Over sub-decadal time scales, these empirical models provide a valuable tool for reconstructing carbonate chemistry related to ocean acidification where direct observations are limited. However, progressive increases in anthropogenic CO2 content of southern CCS water masses must be carefully addressed to apply the models over longer time scales.

Pavlova, GY, Tishchenko PY, Volkova TI, Dickson A, Wallmann K.  2008.  Intercalibration of Bruevich's method to determine the total alkalinity in seawater. Oceanology. 48:438-443.   10.1134/s0001437008030168   AbstractWebsite

In 2000, the Carbon Dioxide in the Ocean working group of the North Pacific Marine Science Organization (PICES) performed an international experiment on the intercalibration of the measurements of the total alkalinity in seawater using certified reference materials (CRM). Taking part in this experiment, Russian specialists presented the method by Bruevich. The results of the intercalibration showed that the alkalinity values obtained by Bruevich's method using modern burettes, an Na2CO3 reactant of high purity as a standard to ascertain the acid titre, and corrections for the acid density and for the weights of the acid and seawater samples in vacuum are in agreement with the standard within +/- 1 mu M/kg.

Hernandez-Ayon, JM, Zirino A, Dickson AG, Camiro-Vargas T, Valenzuela-Espinoza E.  2007.  Estimating the contribution of organic bases from microalgae to the titration alkalinity in coastal seawaters. Limnology and Oceanography-Methods. 5:225-232. AbstractWebsite

This study reports the potential contribution of organic bases to the alkalinity of seawater samples. The concentration of organic bases in these samples was inferred from the difference between the measured alkalinity and that calculated from a knowledge of pH and concentrations of the various inorganic acid- bases species such as total carbon, total boron, and so on. Significant concentrations of such organic bases were measured in cultures of the marine microalgae Rhodomonas sp. ( 800 mu mol kg (-1)) and Isochrysis aff. Galbana ( 400 mu mol kg (-1)), as well as in three marine environments ( northern gulf of California, mexico; San Quintin Bay, B. C., Mexico; and San Diego Bay). These three sites are characterized by significant biological activity and restricted mixing, and the organic bases were found at concentrations greater than 50 mu mol kg(-1) in each of these three locations.

Lee, K, Tong LT, Millero FJ, Sabine CL, Dickson AG, Goyet C, Park GH, Wanninkhof R, Feely RA, Key RM.  2006.  Global relationships of total alkalinity with salinity and temperature in surface waters of the world's oceans. Geophysical Research Letters. 33   10.1029/2006gl027207   AbstractWebsite

A simple function of sea surface salinity (SSS) and temperature (SST) in the form A(T) = a + b (SSS - 35) + c (SSS - 35)(2) + d (SST - 20) + e (SST - 20)(2) fits surface total alkalinity (A(T)) data for each of five oceanographic regimes within an area-weighted uncertainty of +/- 8.1 mu mol kg(-1) (1 sigma). Globally coherent surface A(T) data (n = 5,692) used to derive regional correlations of A(T) with SSS and SST were collected during the global carbon survey in the 1990s. Such region-specific A(T) algorithms presented herein enable the estimation of the global distribution of surface A(T) when observations of SSS and SST are available.

Watanabe, A, Kayanne H, Nozaki K, Kato K, Negishi A, Kudo S, Kimoto H, Tsuda M, Dickson AG.  2004.  A rapid, precise potentiometric determination of total alkalinity in seawater by a newly developed flow-through analyzer designed for coastal regions. Marine Chemistry. 85:75-87.   10.1016/j.marchem.2003.09.004   AbstractWebsite

A flow-through analyzer has been developed for the rapid, potentiometric determination of total alkalinity (TA) in seawater in order to capture large temporal and spatial variations of the CO2 system in coastal zones, where the carbon cycle is still not well understood despite the potential large contribution of such areas to the global carbon cycle. This analyzer requires small amounts of seawater (3 ml min(-1)), and has realized continuous measurements of TA with a response time of 4-5 min, with long-term precision of about 0.1% (ca. 2 mumol kg(-1)), and accuracy of a similar level over a range of TA (more than 200 mumol kg(-1)) when appropriate standard solutions are used. This analyzer is fully automated and can achieve stable measurements (within 0.15%; 3 mumol kg(-1)) over 1-2 days without regular recalibration for drift, which will enable us to carry out continuous, in situ measurements of TA in coastal waters. (C) 2003 Elsevier B.V. All rights reserved.

Millero, FJ, Dickson AG, Eischeid G, Goyet C, Guenther P, Johnson KM, Key RM, Lee K, Purkerson D, Sabine CL, Schottle RG, Wallace DWR, Lewis E, Winn CD.  1998.  Assessment of the quality of the shipboard measurements of total alkalinity on the WOCE Hydrographic Program Indian Ocean CO2 survey cruises 1994-1996. Marine Chemistry. 63:9-20.   10.1016/s0304-4203(98)00043-7   AbstractWebsite

In 1995, we participated in a number of WOCE Hydrographic Program cruises in the Indian Ocean as part of the Joint Global Ocean flux Study (JGOFS) CO, Survey sponsored by the Department of Energy (DOE). Two titration systems were used throughout this study to determine the pH, total alkalinity (TA) and total inorganic carbon dioxide (TCO2) of the samples collected during these cruises. The performance of these systems was monitored by making closed cell titration measurements on Certified Reference Materials (CRMs). A total of 962 titrations were made on six batches of CRMs during the cruises. The reproducibility calculated from these titrations was +/-0.007 in pH, +/-4.2 mu mol kg(-1) in TA, and +/-4.1 mu mol kg(-1) in TCO2. The at-sea measurements on the CRMs were in reasonable agreement with laboratory measurements made on the same batches. These results demonstrate that the CRMs can be used as a reference standard for TA and to monitor the performance of titration systems at sea. Measurements made on the various legs of the cruise agreed to within 6 mu mol kg(-1) at the 15 crossover points. The overall mean and standard deviation of the differences at all the crossovers are 2.1 +/- 2.1 mu mol kg(-1). These crossover results are quite consistent with the overall reproducibility of the CRM analyses for TA (+/-4 mu mol kg(-1)) over the duration of the entire survey, The TA results for the Indian Ocean cruises provide a reliable data set that when combined with TCO2 data can completely characterize the carbonate system. (C) 1998 Elsevier Science B.V. All rights reserved.