Organic Copper Speciation by Anodic Stripping Voltammetry in Estuarine Waters With High Dissolved Organic Matter.

Jasmin Pađan,Ana-Marija Cindrić,Saša Marcinek,Dario Omanović,Simona Retelletti Brogi,Cédric Garnier,Chiara Santinelli,Olivier Radakovitch

doi:10.3389/fchem.2020.628749

Abstract

The determination of copper (Cu) speciation and its bioavailability in natural waters is an important issue due to its specific role as an essential micronutrient but also a toxic element at elevated concentrations. Here, we report an improved anodic stripping voltammetry (ASV) method for organic Cu speciation, intended to eliminate the important problem of surface-active substances (SAS) interference on the voltammetric signal, hindering measurements in samples with high organic matter concentration. The method relies on the addition of nonionic surfactant Triton-X-100 (T-X-100) at a concentration of 1 mg L−1. T-X-100 competitively inhibits the adsorption of SAS on the Hg electrode, consequently 1) diminishing SAS influence during the deposition step and 2) strongly improving the shape of the stripping Cu peak by eliminating the high background current due to the adsorbed SAS, making the extraction of Cu peak intensities much more convenient. Performed tests revealed that the addition of T-X-100, in the concentration used here, does not have any influence on the determination of Cu complexation parameters and thus is considered "interference-free." The method was tested using fulvic acid as a model of natural organic matter and applied for the determination of Cu speciation in samples collected in the Arno River estuary (Italy) (in spring and summer), characterized by a high dissolved organic carbon (DOC) concentration (up to 5.2 mgC L−1) and anthropogenic Cu input during the tourist season (up to 48 nM of total dissolved Cu). In all the samples, two classes of ligands (denoted as L1 and L2) were determined in concentrations ranging from 3.5 ± 2.9 to 63 ± 4 nM eq Cu for L1 and 17 ± 4 to 104 ± 7 nM eq Cu for L2, with stability constants logK Cu,1 = 9.6 ± 0.2–10.8 ± 0.6 and logK Cu,2 = 8.2 ± 0.3–9.0 ± 0.3. Different linear relationships between DOC and total ligand concentrations between the two seasons suggest a higher abundance of organic ligands in the DOM pool in spring, which is linked to a higher input of terrestrial humic substances into the estuary. This implies that terrestrial humic substances represent a significant pool of Cu-binding ligands in the Arno River estuary.

Highlights

Copper (Cu) is an essential micronutrient in natural waters, required for the proper functioning of metabolic and respiratory processes for many aquatic species (Peers et al, 2005; Peers and Price, 2006; Annett et al, 2008; Glass and Orphan, 2012; Jacquot et al, 2014)
The lack of a Cu oxidation peak was rather expected because the majority of the Cu present in the samples with a high dissolved organic matter (DOM) load is predicted to be complexed by strong organic ligands, which are not reducible at the applied deposition potential
The method relies on the addition of the nonionic surfactant T-X100, which competitively inhibits the adsorption of DOM on the Hg electrode during the deposition and stripping steps

Summary

Introduction

Copper (Cu) is an essential micronutrient in natural waters, required for the proper functioning of metabolic and respiratory processes for many aquatic species (Peers et al, 2005; Peers and Price, 2006; Annett et al, 2008; Glass and Orphan, 2012; Jacquot et al, 2014). Coastal areas and estuaries are the most relevant areas for Cu speciation studies because of the high potential for anthropogenic Cu contamination (e.g., Helland and Bakke, 2002; Blake et al, 2004; Louis et al, 2009) including secondary contamination by the release from sediment during estuarine mixing (e.g., Cobelo-Garcia and Prego, 2003) These areas are usually characterized by high concentrations of DOM from both allochthonous and autochthonous sources (Fellman et al, 2011; Retelletti Brogi et al, 2020), including biogenic thiol compounds and terrestrially derived humic and fulvic acids, which all form strong Cu complexes (Tang et al, 2000; Kogut and Voelker, 2001; Laglera and van den Berg, 2003; Shank et al, 2004; Whitby et al, 2017; Dulaquais et al, 2020). Besides regulating its bioavailable concentration, binding with these organic ligands in coastal waters is an important factor in Cu transport to the ocean (Helland and Bakke, 2002)

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