Abstract
The accuracy and detection limit of the oxygen technique is an actual problem in studying the processes that occur in the redox zone. The formal accuracy of the Winkler technique is 1 μM (0.02 mL L−1) and its detection limit is about 3.0 μM (0.06 mL L−1). These values are significantly higher than the similar characteristics (in molar concentrations) for such parameters as the hydrogen sulphide, nitrates, manganese, and others. In this work, we describe some recommendations for increasing the accuracy of the Winkler technique. The results of the application of these recommendations for the suboxic zone of the Black Sea are presented. During the 100th cruise of the R/V Professor Shtokman, argon-filled balloons were attached to the upper valves of Niskin bottles during the sampling, which allowed protecting the samples from contamination with atmospheric oxygen. The titration was performed with an automatic Metrohm Titrino burette with potentiometric end point detection. That allowed us to significantly increase the accuracy and decrease the detection limit compared with the visual techniques. The oxidized forms of metals present in the sea water (Mn(IV), Mn(III); Fe(III)) were measured, which allowed us to correct the Winkler technique calculations for the oxidizers. The studies performed during the 100th cruise of the R/V Professor Shtokman confirmed the absence of a layer of the coexistence of oxygen and hydrogen sulphide.
Similar content being viewed by others
References
O. Bashtyurk, I. I. Volkov, S. Gekmen, et al., “International Expedition on Board R/V Bilim in July 1997 in the Black Sea,” Oceanology 38(3), 429–432 (1998).
A. A. Bezborodov and V. N. Eremeev, Black Sea. The Zone of Interaction Between the Aerobic and Anaerobic Waters (Marine Hydrophys. Inst. Akad. Sci. Ukraine, Sevastopol, 1993) [in Russian].
A. A. Bezborodov and A. A. Novoselov, New Data on the Distribution of Oxygen on the Border of Aerobic Waters in the Black Sea: Revision of Ideas (MGI ANU, Sevastopol, 1989) [in Russian].
I. I. Volkov, E. A. Kontar’, Yu. F. Lukashev, et al., “Upper Boundary of Hydrogen Sulfide: Implications for the Nepheloid Redox Layer in Waters of the Caucasian Slope of the Black Sea,” Geochem. Int. 35(6), 540–550 (1997).
I. I. Volkov, A. G. Rozanov, and T. P. Demidova, “Inorganic Reduced Sulfur Compounds and Dissolved Manganese in Black Sea Waters,” in Winter Ecosystem State of the Open Black Sea (Inst. Oceanol. Rus. Acad. Sci., Moscow, 1992, pp. 38–50.
P. T. Danil’chenko and N. I. Chigirin, “On the Origin of Hydrogen Sulfide in the Black Sea,” Tr. Osob. Zool. Lab. and Sevastop. Biol. St., Ser. 1., No. 5010, 141–187 (1926).
S. V. Pakhomova, A. G. Rozanov, and E. G. Yakushev, “Dissolved and Particulate Forms of Iron and Manganese in the Redox Zone of the Black Sea,” Oceanology 49(6), 773–787 (2009).
Guidelines for Chemical Analysis of Sea Water. RD 52.10.243-92 (GMI, St. Petersburg, 1993) [in Russian].
B. A. Skopintsev, Formation of the Modern Chemical Composition of Black Sea Water (Gidrometeoizdat, Leningrad, 1975) [in Russian].
Modern Methods of Hydrochemical Studies of the Ocean, Ed. by O. K. Bordovskii and A. M. Chernyakova (IO RAN, Moscow, 1992) [in Russian].
P. A. Stunzhas, “On the Structure of the Zone of Interaction of Aerobic and Anaerobic Waters of the Black Sea on the Basis of Measurements with a Membrane-Free Sensor of Oxygen,” Oceanology 40(4), 503–509 (2000).
P. A. Stunzhas and E. V. Yakushev, “Fine Hydrochemical Structure of the Redox Zone in the Black Sea according to the Results of Measurements with an Open Oxygen Sensor and with Bottle Samplers,” Oceanology 46(5), 629–641 (2006).
A. M. Chernyakova, Determination of Dissolved Oxygen. Modern Methods of Hydrochemical Studies of the Ocean, Ed. by O. K. Bordovskii and A. M. Chernyakova (IO RAN, Moscow, 1992) [in Russian].
E. V. Yakushev, Yu. F. Lukashev, V. K. Chasovnikov, and V. P. Chzhu, “Current View of the Vertical Hydrochemical Structure of the Redox Zone of the Black Sea,” in Integrated Study of the Northeastern Part of the Black Sea, Ed. by A. G. Zatsepin and M.V. Flint (Nauka, Moscow, 2002), pp. 119–132 [in Russian].
W. W. Broenkow and J. D. Cline, “Colorimetric Determination of Dissolved Oxygen at Low Concentrations,” Limnol. Oceanogr. 14(3), 450–454 (1969).
J. H. Carpenter, “The Chesapeak Bay Institute Technique for the Winkler Dissolved Oxygen Method,” Limnol. Oceanogr., No. 10, 141–143 (1965).
J. H. Carpenter, “The Accuracy of the Winkler Method for Dissolved Oxygen Analysis,” Limnol. Oceanog, No. 10, 135–141 (1965).
L. Codispoti, One Man Advise on Determination of Dissolved Oxygen in Seawater, www.ocean.washington.edu/courses/oc201/OxygenProtocol.pdf
L. A. Codispoti, G. E. Friederich, J. W. Murray, and C. Sakamoto, “Chemical Variability in the Black Sea: Implications of Data Obtained with a Continuous Vertical Profiling System That Penetrated the Oxidanoxic Interface,” Deep-Sea Res. 38(Suppl.), S691–S710 (1991).
C. H. Culberson, “Dissolved Oxygen,” in WHP Operations and Methods July 1–15 (1991).
B. T. Glazer, G. W. Luther, S. K. Konovalov, et al., “Documenting the Suboxic Zone of the Black Sea via High-Resolution Realtime Redox Profiling,” Deep-Sea Res. II: Topical Studies in Oceanography 53, 1740–1755 (2006a).
W. Granéli and E. Granéli, “Automatic Potentiometric Determination of Dissolved Oxygen,” Mar. Biol. 108, 341–348 (1991).
K. Grashoff, K. Kremling, and M. Ehrhard, Methods of Seawater Analysis. 3d, Completely Revised and Extended Edition (WILEY-VCH, Weinheim, 1999).
K. Grasshoff, “Determination of Dissolved Oxygen,” in Methods of Seawater Analysis, Second, Revised and Extended Edition, Ed. by K. Grasshoff et al. (Verlag Chemie, Basel, 1983).
K. Furuya and K. Harada, “An Automated Precise Winkler Titration for Determining Dissolved Oxygen on Board Ship,” J. Oceanogr. 51, 375–383 (1995).
H. P. Hansen, “Determination of Oxygenin Methods of Seawater Analysis, 3d, Completely Revised and Extended Edition, Ed. by K. Grasshoff et al. (WILEY-VCH, Weinheim, 1999), pp. 75–90.
H. P. Hansen and F. Koroleff, “Determination of Nutrients,” in Methods of Seawater Analysis, 3d, Completely Revised and Extended Edition, Ed. by K. Grashoff et al. ((WILEY-VCH, Weinheim, 1999), pp. 149–228.
Hawaii Ocean Time-series (HOT) Field & Laboratory Protocols DISSOLVED OXYGEN. http://hahana.soest.hawaii.edu/hot/hot-jgofs.html
J. Horibe, Y. Kodama, and K. Shigehara, “Errors in Sampling Procedure for the Determination of Dissolved Oxygen by Winkler Method,” J. Oceanogr. Soc. Japan, 203–206 (1972).
D. J. Hydes, M. C. Hartman, S. E. Hartman, et al., Evaluation of the Aanderaa Oxygen Optode in Continuous Use in the Noc Portsmouth Bilbao Ferrybox System 2005, 2006, with an Assessment of the Likely Errors in the Estimation of Oxygen Concentration Anomalies (National Oceanography Centre, Southampton, 2007).
IOC Manuals and Guides No. 29. Protocols for the Joint Global Ocean Flux Study (JGOFS) Core Measurements, Ed. by A. Knap et al. (UNESCO, 1994).
J. A. Kamyshny, “Solubility of Cyclooctasulfur in Pure Water and Sea Water at Different Temperatures,” Geochim. Cosmochim. Acta, 6022–6028 (2009).
Yu. F. Lukashev and E. V. Yakushev, “Dissolved Oxygen Content Measurements on the Border of the Sulfide Zone of the Black Sea,” in Abstr. Pacon-99 Symposium. June 23–25, 1999, Russian Academy of Sciences, Moscow, Russia (Moscow, 1999), p. 167.
J. W. Murray, H. W. Jannash, S. Honjo, et al., “Unexpected Changes in the Oxic/Anoxic Interface in the Black Sea,” Nature 338, 411–413 (1989).
J. W. Murray, L. A. Codispoti, and G. E. Friederich, “Oxidation-Reduction Environments. The Suboxic Zone in the Black Sea,” in Aquatic Chemistry: Interfacial and Interspecies Processes, ACS Advances in Chemistry Series, Ed. by C. P. Huang et al. 244 157–176 (1995).
J. W. Murray, S. K. Konovalov, A. Romanov, et al., “R/V Knorr Cruise: New Observations and Variations in the Structure of the Suboxic Zone,” in Oceanography of the Eastern Mediterranean and Black Sea. Similarities and Differences of Two Interconnected Basins, Ed. by A. Yilmaz (Tubitak Publ., Ankara, 2003), pp. 545–557.
E. C. Potter, “The Microdetermination of Dissolved Oxygen in Water,” J. Appl. Chem. 7, 285–328 (1957).
R. E. Trouwborst, B. G. Clement, B. M. Tebo, et al., “Soluble Mn(III) in Suboxic Zones,” Science 313, 1955–1957 (2006).
S. Turgul, O. Basturk, C. Saydam, and A. Yilmaz, “Changes in the Hydrochemistry of the Black Sea Inferred from Water Density Profiles,” Nature 359, 137–139 (1992).
S. M. Webb, G. J. Dick, J. R. Bargar, and B. M. Tebo, “Evidence for the Presence of Mn(III) Intermediates in the Bacterial Oxidation of Mn(II),” Proc. Natl. Acad. Sci. U.S.A. 102, 5558–5563 (2005).
L. S. Winkler, “The Determination of Dissolved Oxygen,” Ber. Dtsche. Chem. GES 21, 2843–2855 (1888).
E. V. Yakushev, V. K. Chasovnikov, E. I. Debolskaya, et al., “The Northeastern Black Sea Redox Zone: Hydrochemical Structure and Its Temporal Variability,” Deep-Sea Res. II 53, 1764–1786 (2006).
E. V. Yakushev and E. I. Debolskaya, “Particulate Manganese As a Main Factor of Oxidation of Hydrogen Sulfide in Redox Zone of the Black Sea,” in Oceanic Fronts and Related Phenomena. K. Fedorov Memorial Symposium, Pushkin, St.-Petersburg, Russia, 18–22 May, 1998. Proceedings IOC Workshop Report No. 159 (Kluwer Acad. Publ., 2000), pp. 592–597.
E. V. Yakushev, F. Pollehne, G. Jost, et al., “Analysis of the Water Column Oxic/Anoxic Interface in the Black and Baltic Seas with a Redox-Layer Model,” Mar. Chem. 107, 388–410 (2007).
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © E.V. Yakushev, E.L. Vinogradova, A.V. Dubinin, A.V. Kostyleva, N.M. Men’shikova, S.V. Pakhomova, 2012, published in Okeanologiya, 2012, Vol. 52, No. 1, pp. 131–138.
Rights and permissions
About this article
Cite this article
Yakushev, E.V., Vinogradova, E.L., Dubinin, A.V. et al. On determination of low oxygen concentrations with Winkler technique. Oceanology 52, 122–129 (2012). https://doi.org/10.1134/S0001437012010201
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0001437012010201