Mercury electrode as a tool/sensor for pollutants monitoring in natural waters; advantages and disadvantages regarding moving to “green” electrochemistry

Green Chemistry or Sustainable Chemistry is defined by the EPA1 as “the design of chemical products that reduce or eliminate the use of hazardous substances”. In recent years there are great expectations that chemists will produce greener and more sustainable chemical processes. In this direction, relevant benefits from “green” electrochemical activities (better control, higher selectivity, safer operations, milder conditions, and the use of electrons as a cheap reagent) were found. Some important instances of “green” electrochemistry are detectors and bio-detectors for environmental analysis (detection of pollutants). Since the invention of polarography, the Hg electrode was established as the preferred electrode for use in electrochemistry due to the high over potential for hydrogen evolution (which enables work at moderately negative potentials), as well as renewability of the electrode surface.2 The current trend of “green” chemistry, that encourages avoiding the use and generation of toxic substances, as well as recent EU regulations that have prohibited exporting and storing metallic Hg, have led to the search of competitive electrodes fabricated with minimal amount of Hg or definitely with other materials. However, in comparison to solid electrodes, Hg has many advantages which cannot easily be ignored and replaced in the move towards “green” electrochemistry by use of solid electrodes when characterizing the surface active (SA) fraction of organic matter as well as sulfur species in natural waters.2–6

[1]  T. Minkina,et al.  Voltammetry as a tool for rough and rapid characterization of dissolved organic matter in the drainage water of hydroameliorated agricultural areas in Croatia , 2016, Journal of Solid State Electrochemistry.

[2]  I. Ciglenečki,et al.  The anoxic stress conditions explored at the nanoscale by atomic force microscopy in highly eutrophic and sulfidic marine lake , 2015 .

[3]  I. Milanovic,et al.  The development of electrochemical methods for determining nanoparticles in the environment. Part II. Chronoamperometric study of FeS in sodium chloride solutions , 2014 .

[4]  G. Zangari Environmental Electrochemistry I , 2014 .

[5]  I. Milanovic,et al.  Deposition and dissolution of metal sulfide layers at the Hg electrode surface in seawater electrolyte conditions , 2014 .

[6]  I. Ciglenečki,et al.  Electrochemical and colorimetric measurements show the dominant role of FeS in a permanently anoxic lake. , 2013, Environmental science & technology.

[7]  B. Gašparović Decreased production of surface-active organic substances as a consequence of the oligotrophication in the northern Adriatic Sea , 2012 .

[8]  R. Compton,et al.  Gold nanoparticles show electroactivity: counting and sorting nanoparticles upon impact with electrodes. , 2012, Chemical communications.

[9]  G. Kiss,et al.  Surface-active substances in atmospheric aerosol: an electrochemical approach , 2012 .

[10]  B. Ćosović,et al.  Electrochemical Adsorption Study of Natural Organic Matter in Marine and Freshwater Systems. A Plea for Use of Mercury for Scientific Purposes , 2010 .

[11]  F. Graziottin,et al.  Analysis of dissolved metal fractions in coastal waters: An inter-comparison of five voltammetric in situ profiling (VIP) systems , 2009 .

[12]  Timothy M. Shank,et al.  Use of voltammetric solid-state (micro)electrodes for studying biogeochemical processes: Laboratory measurements to real time measurements with an in situ electrochemical analyzer (ISEA) , 2008 .

[13]  I. Ciglenečki,et al.  Voltammetric characterization of metal sulfide particles and nanoparticles in model solutions and natural waters. , 2007, Analytica chimica acta.

[14]  I. Ciglenečki,et al.  Voltammetry of copper sulfide particles and nanoparticles: investigation of the cluster hypothesis. , 2005, Environmental science & technology.

[15]  Jacques Buffle,et al.  Voltammetric environmental trace-metal analysis and speciation: from laboratory to in situ measureme , 2005 .

[16]  G. Luther,et al.  Iron and Sulfur Chemistry in a Stratified Lake: Evidence for Iron-Rich Sulfide Complexes , 2003 .

[17]  M. Vuković,et al.  Humic Acid Adsorption on the Au(111) and Au Polycrystalline Electrode Surface , 2001 .

[18]  B. Ćosović,et al.  Electrochemical Determination of Organic Surface Active Substances in Model and Natural Sea Water with Au(111) Monocrystal Electrode. , 2000 .

[19]  Martial Taillefert,et al.  The Application of Electrochemical Tools for In Situ Measurements in Aquatic Systems , 2000 .

[20]  E. Achterberg,et al.  Stripping voltammetry for the determination of trace metal speciation and in-situ measurements of trace metal distributions in marine waters , 1999 .

[21]  J. Buffle,et al.  Voltammetric characterization of a dissolved iron sulphide species by laboratory and field studies , 1998 .

[22]  B. Ćosović,et al.  Voltammetric Analysis of Surface Active Substances in Natural Seawater , 1998 .

[23]  I. Ciglenečki,et al.  Electrochemical determination of thiosulfate in seawater in the presence of elemental sulfur and sulfide , 1997 .

[24]  I. Ciglenečki,et al.  Electrochemical study of sulfur species in seawater and marine phytoplankton cultures , 1996 .

[25]  I. Ciglenečki,et al.  Determination of elemental sulphur, sulphide and their mixtures in electrolyte solutions by a.c. voltammetry , 1992 .

[26]  A. Giblin,et al.  Polarographic analysis of sulfur species in marine porewaters1 , 1985 .

[27]  I. Ciglenečki,et al.  The development of electrochemical methods for determining nanoparticles in the environment. Part I. Voltammetry and in-situ electrochemical scanning tunnelling microscopy (EC-STM) study of FeS in sodium chloride solutions , 2014 .

[28]  B. Ćosović,et al.  Seasonal variations of reduced sulfur species in a stratified seawater lake (Rogoznica Lake, Croatia) ; evidence for organic carriers of reactive sulfur , 2009 .

[29]  Jacques Buffle,et al.  In situ voltammetric measurement of trace elements in lakes and oceans , 1990 .