Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
RESEARCH FRONT

Constant current chronopotentiometric stripping characterisation of organic matter in seawater from the northern Adriatic, Croatia

Slađana Strmečki A B , Jelena Dautović A and Marta Plavšić A

A Ruđer Bošković Institute, Division for Marine and Environmental Research, Bijenička 54, PO Box 180, 10 002 Zagreb, Croatia.

B Corresponding author. Email: strmecki@irb.hr

Environmental Chemistry 11(2) 158-166 http://dx.doi.org/10.1071/EN13122
Submitted: 3 July 2013  Accepted: 6 December 2013   Published: 25 March 2014

Environmental context. We determined seasonal changes in the organic matter content of the northern Adriatic with newly applied electrochemical techniques able to measure catalytically active organics. The inflow of the Po River and its nutrient load are responsible for the observed changes in the type and concentrations of organic matter in the area.

Abstract. Catalytically active polysaccharides (Cat PSs) and nitrogen-containing polymeric organic material (N-POM) were determined in seawater from the northern Adriatic station ST101. Catalytically active organics were measured by applying electrochemical methods of adsorptive transfer chronopotentiometric stripping with medium exchange and chronopotentiometric stripping in unmodified seawater. Their concentrations were expressed in milligrams per cubic decimetre of equivalents of the model calibrating substances, polysaccharide xanthan and protein human serum albumin. The optimal electroanalytical conditions for determination of Cat PSs in seawater were evaluated and defined. Seasonal changes of Cat PSs and N-POM were observed during the period 2011–2013. The highest values were determined in the spring–summer period and the lowest in winter. Cat PSs and N-POM were present in both the dissolved and particulate organic carbon fractions. Cat PSs and N-POM showed a statistically significant positive correlation with the concentrations of surface-active substances. A weak but statistically significant correlation was found between Cat PSs and dissolved organic carbon concentrations. Copper complexing capacities in the period 2011–2013 were in the range of 41–130 nmol dm–3.


References

[1]  X. Mari, E. Rochelle-Newall, J. P. Torreton, O. Pringault, A. Jouon, C. Migon, Water residence time: a regulatory factor of the DOM to POM transfer efficiency. Limnol. Oceanogr. 2007, 52, 808.
Water residence time: a regulatory factor of the DOM to POM transfer efficiency.CrossRef | open url image1

[2]  M. L. Wells, Marine colloids and trace metals in Biogeochemistry of Marine Dissolved Organic Matter (Eds D. A. Hansell, C. A. Carlson) 2002, pp. 367–404 (Academic Press: San Diego, CA).

[3]  M. S. Quigley, P. H. Santschi, C. C. Hung, L. D. Guo, B. D. Honeyman, Importance of acid polysaccharides for Th-234 complexation to marine organic matter. Limnol. Oceanogr. 2002, 47, 367.
Importance of acid polysaccharides for Th-234 complexation to marine organic matter.CrossRef | open url image1

[4]  N. G. A. Quiroz, C. C. Hung, P. H. Santschi, Binding of thorium(IV) to carboxylate, phosphate and sulfate functional groups from marine exopolymeric substances (EPS). Mar. Chem. 2006, 100, 337.
Binding of thorium(IV) to carboxylate, phosphate and sulfate functional groups from marine exopolymeric substances (EPS).CrossRef | open url image1

[5]  U. Passow, J. Dunne, J. W. Murray, L. Balistrieri, A. L. Alldredge, Organic carbon to Th-234 ratios of marine organic matter. Mar. Chem. 2006, 100, 323.
Organic carbon to Th-234 ratios of marine organic matter.CrossRef | open url image1

[6]  U. Passow, Transparent exopolymer particles (TEP) in aquatic environments. Prog. Oceanogr. 2002, 55, 287.
Transparent exopolymer particles (TEP) in aquatic environments.CrossRef | open url image1

[7]  X. Mari, A. Burd, Seasonal size spectra of transparent exopolymeric particles (TEP) in a coastal sea and comparison with those predicted using coagulation theory. Mar. Ecol. Prog. Ser. 1998, 163, 63.
Seasonal size spectra of transparent exopolymeric particles (TEP) in a coastal sea and comparison with those predicted using coagulation theory.CrossRef | open url image1

[8]  J. Zhou, K. Mopper, U. Passow, The role of surface-active carbohydrates in the formation of transparent exopolymer particles by bubble adsorption of seawater. Limnol. Oceanogr. 1998, 43, 1860. open url image1

[9]  B. Ćosović, Aqueous surface chemistry. Adsorption characteristics of organic solutes. Electrochemical evaluation, in Chemical Processes in Lakes (Ed. W. Stumm) 1985, pp. 55–85 (Wiley: New York).

[10]  B. Ćosović, Surface-active properties of the sea surface microlayer and consequences for pollution in the Mediterranean Sea, in The Mediterranean Sea, Vol. 5K (Ed. A. Saliot) 2005, pp. 269–296 (Springer: Berlin).

[11]  P. L. Croot, U. Passow, P. Assmy, S. Jansen, V. H. Strass, Surface active substances in the upper water column during a Southern Ocean Iron Fertilization Experiment (EIFEX). Geophys. Res. Lett. 2007, 34, L03612. open url image1

[12]  F. De Angelis, M. V. Barbarulo, M. Bruno, L. Volterra, R. Nicoletti, Chemical-composition and biological origin of dirty sea mucilages. Phytochemistry 1993, 34, 393.
Chemical-composition and biological origin of dirty sea mucilages.CrossRef | open url image1

[13]  W. C. Chin, M. V. Orellana, P. Verdugo, Spontaneous assembly of marine dissolved organic matter into polymer gels. Nature 1998, 391, 568.
Spontaneous assembly of marine dissolved organic matter into polymer gels.CrossRef | open url image1

[14]  G. G. Leppard, The characterization of algal and microbial mucilages and their aggregates in aquatic ecosystems. Sci. Total Environ. 1995, 165, 103.
The characterization of algal and microbial mucilages and their aggregates in aquatic ecosystems.CrossRef | 7754351PubMed | open url image1

[15]  N. Kovač, J. Faganeli, O. Bajt, B. Sket, B. Orel, N. Penna, Chemical composition of macroaggregates in the northern Adriatic sea. Org. Geochem. 2004, 35, 1095.
Chemical composition of macroaggregates in the northern Adriatic sea.CrossRef | open url image1

[16]  C. Panagiotopoulos, R. Sempere, Analytical methods for the determination of sugars in marine samples: a historical perspective and future directions. Limnol. Oceanogr. Methods 2005, 3, 419.
Analytical methods for the determination of sugars in marine samples: a historical perspective and future directions.CrossRef | open url image1

[17]  C. Panagiotopoulos, O. Wurl, Spectrophotometric and chromatographic analysis of carbohydrates in marine samples, in Practical Guidelines for the Analysis of Seawater (Ed. O. Wurl) 2009, pp. 49–65 (CRC Press, Taylor & Francis Group: New York).

[18]  M. Plavšić, B. Gašparović, S. Strmečki, V. Vojvodić, N. Tepić, Copper complexing ligands and organic matter characterization in the northern Adriatic Sea. Estuar. Coast. Shelf Sci. 2009, 85, 299.
Copper complexing ligands and organic matter characterization in the northern Adriatic Sea.CrossRef | open url image1

[19]  K. W. Bruland, E. L. Rue, J. R. Donat, S. A. Skrabal, J. W. Moffett, Intercomparison of voltammetric techniques to determine the chemical speciation of dissolved copper in a coastal seawater sample. Anal. Chim. Acta 2000, 405, 99.
Intercomparison of voltammetric techniques to determine the chemical speciation of dissolved copper in a coastal seawater sample.CrossRef | open url image1

[20]  B. Ćosović, V. Vojvodić, Direct determination of surface-active substances in natural-waters. Mar. Chem. 1987, 22, 363.
Direct determination of surface-active substances in natural-waters.CrossRef | open url image1

[21]  S. Strmečki, M. Plavšić, B. Ćosović, Constant current chronopotentiometric stripping analysis of ‘N-catalyst’ in sodium chloride solution and seawater. Electroanalysis 2010, 22, 91.
Constant current chronopotentiometric stripping analysis of ‘N-catalyst’ in sodium chloride solution and seawater.CrossRef | open url image1

[22]  M. Heyrovsky, Catalytic hydrogen evolution at mercury electrode from solutions of peptides and proteins, in Electrochemistry of Nucleic Acids and Proteins. Towards Electrochemical Sensors for Genomics and Proteomics, Vol. 1 (Ed. E. Paleček, F. Scheller, J. Wang) 2005, pp. 657–680 (Elsevier: Amsterdam).

[23]  S. Strmečki, M. Plavšić, Adsorptive transfer chronopotentiometric stripping of sulphated polysaccharides. Electrochem. Commun. 2012, 18, 100.
Adsorptive transfer chronopotentiometric stripping of sulphated polysaccharides.CrossRef | open url image1

[24]  E. Paleček, Adsorptive transfer stripping voltammetry - determination of nanogram quantities of DNA immobilized at the electrode surface. Anal. Biochem. 1988, 170, 421.
Adsorptive transfer stripping voltammetry - determination of nanogram quantities of DNA immobilized at the electrode surface.CrossRef | 3394940PubMed | open url image1

[25]  V. Adam, J. Petrlova, J. Wang, T. Eckschlager, L. Trnkova, R. Kizek, Zeptomole electrochemical detection of metallothioneins. PLoS ONE 2010, 5, e11441.
Zeptomole electrochemical detection of metallothioneins.CrossRef | 20625429PubMed | open url image1

[26]  E. Paleček, M. Trefulka, Electrocatalytic detection of polysaccharides at picomolar concentrations. Analyst (Lond.) 2011, 136, 321.
Electrocatalytic detection of polysaccharides at picomolar concentrations.CrossRef | open url image1

[27]  L. I. Aluwihare, D. J. Repeta, R. F. Chen, A major biopolymeric component to dissolved organic carbon in surface sea water. Nature 1997, 387, 166.
A major biopolymeric component to dissolved organic carbon in surface sea water.CrossRef | open url image1

[28]  G. Sartoni, R. Urbani, P. Sist, D. Berto, C. Nuccio, M. Giani, Benthic mucilaginous aggregates in the Mediterranean Sea: origin, chemical composition and polysaccharide characterization. Mar. Chem. 2008, 111, 184.
Benthic mucilaginous aggregates in the Mediterranean Sea: origin, chemical composition and polysaccharide characterization.CrossRef | open url image1

[29]  N. Supić, R. Kraus, M. Kuzmić, E. Paschini, R. Precali, A. Russo, I. Vilibić, Predictability of northern Adriatic winter conditions. J. Mar. Syst. 2012, 90, 42.
Predictability of northern Adriatic winter conditions.CrossRef | open url image1

[30]  C. Chavanne, I. Janeković, P. Flament, P. M. Poulain, M. Kuzmić, K. W. Gurgel, Tidal currents in the northwestern Adriatic: high-frequency radio observations and numerical model predictions. J. Geophys. Res. – Oceans 2007, 112, C03S21. open url image1

[31]  T. Djakovac, D. Degobbis, N. Supić, R. Precali, Marked reduction of eutrophication pressure in the northeastern Adriatic in the period 2000–2009. Estuar. Coast. Shelf Sci. 2012, 115, 25.
Marked reduction of eutrophication pressure in the northeastern Adriatic in the period 2000–2009.CrossRef | open url image1

[32]  M. Plavšić, D. Krznarić, M. Branica, Determination of the apparent copper complexing capacity of sea-water by anodic-stripping voltammetry. Mar. Chem. 1982, 11, 17.
Determination of the apparent copper complexing capacity of sea-water by anodic-stripping voltammetry.CrossRef | open url image1

[33]  I. Ružić, Theoretical aspects of the direct titration of natural-waters and its information yield for trace-metal speciation. Anal. Chim. Acta 1982, 140, 99.
Theoretical aspects of the direct titration of natural-waters and its information yield for trace-metal speciation.CrossRef | open url image1

[34]  C. M. G. Van Den Berg, A. L. Rebello, Organic-copper interactions in Guanabara Bay, Brazil. Sci. Total Environ. 1986, 58, 37.
Organic-copper interactions in Guanabara Bay, Brazil.CrossRef | open url image1

[35]  P. M. Berthouex, L. C. Brown, Statistics for Environmental Engineers, 2nd edn, Vol. 1 2002 (CRC Press LLC: Boca Raton, FL).

[36]  P. Mader, V. Vesela, V. Dorčak, M. Heyrovsky, The “presodium” hydrogen evolution at the dropping mercury electrode catalysed by simple cysteine peptides. Collect. Czech. Chem. Commun. 2001, 66, 397.
The “presodium” hydrogen evolution at the dropping mercury electrode catalysed by simple cysteine peptides.CrossRef | open url image1

[37]  W. Stumm, J. J. Morgan, Aquatic Chemistry, 2nd edn, 1981 (Wiley: New York).

[38]  D. C. O. Thornton, E. M. Fejes, S. F. DiMarco, K. M. Clancy, Measurement of acid polysaccharides in marine and freshwater samples using alcian blue. Limnol. Oceanogr. Methods 2007, 5, 73.
Measurement of acid polysaccharides in marine and freshwater samples using alcian blue.CrossRef | open url image1

[39]  V. Mirčeski, S. Skrzypek, W. Ciesielski, A. Sokolowski, Theoretical and experimental study of the catalytic hydrogen evolution reaction in the presence of an adsorbed catalyst by means of square-wave voltammetry. J. Electroanal. Chem. 2005, 585, 97.
Theoretical and experimental study of the catalytic hydrogen evolution reaction in the presence of an adsorbed catalyst by means of square-wave voltammetry.CrossRef | open url image1

[40]  V. Mirčeski, Š. Komorsky-Lovrić, M. Lovrić, Square-Wave Voltammetry: Theory and Application, Vol. 1 2007 (Springer: Berlin).

[41]  D. Zanchettin, P. Traverso, M. Tomasino, Po River discharges: a preliminary analysis of a 200-year time series. Clim. Change 2008, 89, 411.
Po River discharges: a preliminary analysis of a 200-year time series.CrossRef | open url image1

[42]  M. Zavatarelli, F. Raicich, D. Bregant, A. Russo, A. Artegiani, Climatological biogeochemical characteristics of the Adriatic Sea. J. Mar. Syst. 1998, 18, 227.
Climatological biogeochemical characteristics of the Adriatic Sea.CrossRef | open url image1

[43]  B. Gašparović, V. Vojvodić, B. Ćosović, Excretion of organic matter during an experimental phytoplankton bloom followed using o-nitrophenol as an electrochemical probe. Croat. Chem. Acta 1998, 71, 271. open url image1

[44]  N. Tepić, B. Gašparović, M. Ahel, Multivariate statistical analysis of the distribution patterns of carbohydrates and surface-active substances in the northern Adriatic Sea. Mar. Chem. 2009, 114, 37.
Multivariate statistical analysis of the distribution patterns of carbohydrates and surface-active substances in the northern Adriatic Sea.CrossRef | open url image1

[45]  C. Fajon, G. Cauwet, P. Lebaron, S. Terzić, M. Ahel, A. Malej, P. Mozetič, V. Turk, The accumulation and release of polysaccharides by planktonic cells and the subsequent bacterial response during a controlled experiment. FEMS Microbiol. Ecol. 1999, 29, 351.
The accumulation and release of polysaccharides by planktonic cells and the subsequent bacterial response during a controlled experiment.CrossRef | open url image1

[46]  M. Giani, T. Đakovac, D. Degobbis, S. Cozzi, C. Solidoro, S. F. Umani, Recent changes in the marine ecosystems of the northern Adriatic Sea. Estuar. Coast. Shelf Sci. 2012, 115, 1.
Recent changes in the marine ecosystems of the northern Adriatic Sea.CrossRef | open url image1

[47]  D. Marić, R. Kraus, J. Godrijan, N. Supić, T. Đakovac, R. Precali, Phytoplankton response to climatic and anthropogenic influences in the north-eastern Adriatic during the last four decades. Estuar. Coast. Shelf Sci. 2012, 115, 98.
Phytoplankton response to climatic and anthropogenic influences in the north-eastern Adriatic during the last four decades.CrossRef | open url image1

[48]  S. Cozzi, M. Giani, River water and nutrient discharges in the Northern Adriatic Sea: current importance and long term changes. Cont. Shelf Res. 2011, 31, 1881.
River water and nutrient discharges in the Northern Adriatic Sea: current importance and long term changes.CrossRef | open url image1

[49]  B. Gašparović, Decreased production of surface-active organic substances as a consequence of the oligotrophication in the northern Adriatic Sea. Estuar. Coast. Shelf Sci. 2012, 115, 33.
Decreased production of surface-active organic substances as a consequence of the oligotrophication in the northern Adriatic Sea.CrossRef | open url image1



Export Citation Cited By (1)