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Simultaneous vertical measurements of in situ pH and CO2 in the sea using spectrophotometric profilers

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Abstract

We have developed new systems capable of profiling to >1000 m for measuring in situ pH and fugacity of CO2 (fCO2) in the ocean using spectrophotometric analysis (pH and CO2 profilers). The in situ pH is determined by detecting the color change of the pH indicator (m-cresol purple). It can withstand ambient pressure to 1000 m depth. The CO2 profiler analyzed in situ fCO2 by detecting the change of pH in an inner solution, equilibrated with the seawater through a gas permeable membrane. It can be operated to 2500 m depth. We used an amorphous fluoropolymer tubing form of AF-2400 for the gas permeable membrane due to its high gas permeability coefficients. The inner solution was a mixture of 2 μM bromocresol purple (BCP) and 5 μM sodium hydroxide. This system gave us a response time of 1 minute, which is twice as fast as previous systems. The precisions of pH and CO2 profilers were within 0.002 and 2.5% respectively. We have used these profilers to study the North Pacific, obtaining good agreement with the difference between the data from profilers and a discrete bottle of 0.002 ± 0.005 pH (SE, n = 25) and −0.4 ± 3 μatm (SE, n = 31).

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References

  • Bates, N. R., L. Samuels and L. Merlivat (2001): Biogeochemical and physical factors influencing seawater fCO2 and air-sea CO2 exchange on the Bermuda coral reef. Limnol. Oceanogr., 46, 833–846.

    Google Scholar 

  • Bris, L. N., P. M. Sarradin and S. Pennec (2001): A new deep-sea probe for in situ pH measurement in the environment of hydrothermal vent biological communities. Deep-Sea Res. I, 48, 1941–1951.

    Google Scholar 

  • Byrne, R. H. and J. A. Breland (1989): High precision multiwavelength pH determinations in seawater using cresol red. Deep-Sea Res., 36, 803–810.

    Article  Google Scholar 

  • Byrne, R. H., X. Liu, E. A. Kaltenbacher and K. Sell (2002): Spectrophotometric measurement of total inorganic carbon in aqueous solutions using a liquid core waveguide. Anal. Chim. Acta, 451, 221–229.

    Article  Google Scholar 

  • Cai, W. and C. E. Reimers (1993): The development of pH and pCO2 microelectrodes for studying the carbonate chemistry of pore waters near the sediment-water interface. Limnol. Oceanogr., 38, 1762–1773.

    Google Scholar 

  • Clayton, T. D. and R. H. Byrne (1993): Spectrophotometric seawater pH measurements: total hydrogen ion concentration scale calibration of m-cresol purple and at-sea results. Deep-Sea Res. I, 40, 2115–2129.

    Google Scholar 

  • Culberson, C., R. M. Pytkowitcz and J. E. Hawley (1970): Seawater alkalinity determination by the pH method. J. Mar. Res., 28, 15–21.

    Google Scholar 

  • DeGrandpre, M. D., T. R. Hammar, S. P. Smith and F. L. Sayles (1995): In situ measurements of seawater pCO2. Limnol. Oceanogr., 40, 1152–1159.

    Google Scholar 

  • DeGrandpre, M. D., M. B. Matthew and T. R. Hammar (1999): Calibration-free optical chemical sensors. Anal. Chem., 71, 1152–1159.

    Article  Google Scholar 

  • DelValls, T. A. and A. G. Dickson (1998): The pH of buffers based on 2-amino-2-hydroxymethyl-1,3-propanediol (’tris’) in synthetic seawater. Deep-Sea Res. I, 45, 1541–1554.

    Google Scholar 

  • Dickson, A. G. (1993): The measurement of sea water pH. Mar. Chem., 44, 131–142.

    Article  Google Scholar 

  • Dickson, A. G. and F. J. Millero (1987): A comparison of the equilibrium constants for the dissociation of carbonic acid in seawater media. Deep-Sea Res., 34, 1733–1743.

    Article  Google Scholar 

  • DOE edited by Dickson, A. G. and C. Goyet (1994): DOE: Handbook of Methods for the Analysis of the Various Parameters of the Carbon Dioxide System in Sea Water, Ver. 2, ORNL/CDIAC-74.

  • IPCC, 2001. Climate Change (2001): The scientific basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, http://www.ipcc.ch/

  • IRI/LDEO, Climate Data Library (2000): GEOSECS: Geochemical Ocean Sections Study, a global survey of the three-dimensional distribution of chemical, isotopic, and radiochemical tracers in the ocean, http://ingrid.ldgo.columbia.edu/SOURCES/.GEOSECS/

  • Lewis, E. and D. W. R. Wallace (1998): Program developed for CO2 system calculations. ORNL/CDIAC-105, Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, US Department of Energy, Oak Ridge, TN.

    Google Scholar 

  • Maberly, S. C. (1996): Diel, episodic and seasonal changes in pH and concentrations of inorganic carbon in a productive lake. Freshwater Biol., 35, 579–598.

    Google Scholar 

  • Martz, T. R., J. J. Carr, C. R. French and M. D. DeGrandpre (2003): A submersible autonomous sensor for spectrophotometric pH measurements of natural waters. Anal. Chem., 75, 1844–1850.

    Article  Google Scholar 

  • Merlivat, L. and P. Brault (1995): CARIOCA buoy: carbon dioxide monitor. Sea Technol., 10, 23–30.

    Google Scholar 

  • Millero, F. J. (1995): Thermodynamics of the carbon dioxide system in the oceans. Geochim. Cosmochim. Acta, 59, 661–677.

    Article  Google Scholar 

  • Mook, W. G. and B. K. S. Koene (1975): Chemistry of dissolved inorganic carbon in estuarine and coastal brackish waters. Estuar. Coast. Mar. Sci., 3, 325–336.

    Article  Google Scholar 

  • Ono, T., S. Watanabe, K. Okuda and M. Fukasawa (1998): Distribution of total carbonate and related properties in the North Pacific along 30°N. J. Geophys. Res., 103, 30873–30883.

    Google Scholar 

  • Ono, T., Y. W. Watanabe and S. Watanabe (2000): Recent increase of DIC in the western North Pacific. Mar. Chem., 72, 317–328.

    Article  Google Scholar 

  • Tabacco, M. B., M. Uttamlal, M. McAllister and D. R. Walt (1999): An autonomous sensor and telemetry system for low-level pCO2 measurements in seawater. Anal. Chem., 71, 154–161.

    Google Scholar 

  • Tsunogai, S., T. Ono and S. Watanabe (1993): Increase in the total carbonate in the western North Pacific water and a hypothesis on the missing sink of anthropogenic carbon. J. Oceanogr., 49, 305–315.

    Google Scholar 

  • Tsurushima, N., Y. Nojiri, K. Imai and S. Watanabe (2002): Seasonal variations of carbon dioxide system and nutrients in the surface mixed layer at station KNOT (44°N, 155°E) in the subarctic western North Pacific. Deep-Sea Res. II, 49, 5377–5394.

    Article  Google Scholar 

  • Wakita, M., S. Watanabe, Y. W. Watanabe, T. Ono, N. Tsurushima and S. Tsunogai (2005): Temporal change of dissolved inorganic carbon in the subsurface water at station KNOT (44°N, 155°E) in the western North Pacific subpolar region. J. Oceanogr., 61, 129–139.

    Article  Google Scholar 

  • Wang, Z. A., W.-J. Caia, Y. Wanga and B. L. Upchurch (2003): A long pathlength liquid-core waveguide sensor for real-time pCO2 measurements at sea. Mar. Chem., 84, 73–84.

    Article  Google Scholar 

  • Watanabe, Y. W., T. Ono and A. Shimamoto (2000): Increase in the uptake rate of oceanic anthropogenic carbon in the North Pacific determined by CFC ages. Mar. Chem., 72, 297–315.

    Article  Google Scholar 

  • Weiss, R. F. (1974): Carbon dioxide in water and seawater: The solubility of a non-ideal gas. Mar. Chem., 2, 203–215.

    Article  Google Scholar 

  • Winn, C. D., Y.-H. Li, F. Mackenzie and D. M. Karl (1998): Rising surface ocean dissolved inorganic carbon at the Hawaii Ocean Time-series site. Mar. Chem., 60, 33–47.

    Article  Google Scholar 

  • WOCE Hydrographic Program Office (WHPO) (2002): WHPO one-time survey. http://whpo.ucsd.edu/onetime.htm

  • Yao, W. and R. H. Byrne (2001): Spectrophotometric determination of freshwater pH using bromocresol purple and phenol red. Environ. Sci. Technol., 35, 1197–1201.

    Google Scholar 

  • Zhang, H. and R. H. Byrne (1996): Spectrophotometric pH measurements of surface seawater at in-situ conditions: absorbance and protonation behavior of thymol blue. Mar. Chem., 52, 17–25.

    Article  Google Scholar 

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Correspondence to Yoshiyuki Nakano.

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Nakano, Y., Kimoto, H., Watanabe, S. et al. Simultaneous vertical measurements of in situ pH and CO2 in the sea using spectrophotometric profilers. J Oceanogr 62, 71–81 (2006). https://doi.org/10.1007/s10872-006-0033-y

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  • DOI: https://doi.org/10.1007/s10872-006-0033-y

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