ALBERT

Description: The concentrations of dissolved and suspended particulate Cd, Cu and Zn have been determined in water samples obtained during two axial transects of the Rio Tinto-Huelva Ria system in south-west Spain, which is severely impacted by acid mine drainage. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and, in the upper estuary, constituted 〉99 of total metal in the water column. Dissolved metals behaved non-conservatively on each transect, with maximum concentrations in the low salinity region. There was no evidence of metal adsorption within the turbidity maximum zone, despite the high specific surface areas of resuspending particles. Measurements of electrophoretic mobility showed that the suspended particulate matter (SPM) had a positive surface charge in the salinity range 0-4, where the waters had a pH〈3. Desorption experiments were carried out in which SPM from the turbidity maximum zone was resuspended in coastal seawater. The desorption of the metals was monitored for 24 h, using anodic stripping voltammetry (ASV) to detect the variation in total dissolved Cd, Cu and Zn and the species of Cu and Zn. Total dissolved Cd concentrations doubled during the incubation period, whereas the concentration of total dissolved Cu declined and that of Zn remained rather constant. The ASV-labile fraction of dissolved Cu and Zn showed an initial sharp release followed by a slower uptake. However, desorption was shown to be a minor source of dissolved metals and made little contribution to the non-conservative behaviour in the low salinity zone. The results are used to predict the effects of acid mine drainage on estuarine ecology. © 2002 Elsevier Science Ltd. All rights reserved.

Description: Progress in marine chemistry has been driven by improved sampling and sample handling techniques, and developments in analytical chemistry. Consequently, during the last 20 years our understanding of marine trace metal biogeochemistry has improved a great deal. Stripping voltammetric techniques (anodic stripping voltammetry and adsorptive cathodic stripping voltammetry) have made an important contribution to this understanding. The selectivity and extremely low detection limits have made stripping voltammetry a widely used technique for trace metal speciation and trace metal distribution measurements in seawater. Stripping voltammetry is very suitable for ship-board and in-situ applications because of the portability, low cost and capability for automation of the voltammetric instrumentation. Future developments in stripping voltammetry can be expected in the field of stand-alone submersible voltammetric analysers, capable of continuous trace metal measurements. Future applications of stripping voltammetry can be found in the interactions between trace metal speciation and growth and the functioning of organisms in pristine and metal polluted marine waters. Copyright (C) 1999 Elsevier Science B.V.

Description: This work presents the optimisation, validation and field deployment of a voltammetric in situ profiling (VIP) system for the simultaneous determinations of dynamic Cd(II), Cu(II) and Pb(II) in estuarine and coastal waters. Systematic studies in NaNO3 (as a supporting electrolyte) and seawater, indicated that variations in ionic strength, pH and dissolved oxygen did not affect the response of the instrument, whereas an Arrhenius type temperature response was observed. The VIP instrument allows the determination of 2-3 samples h-1, and has a detection limit (defined as 3σ) in seawater for Cd(II): 23 pM, Cu(II): 1.13 nM, and Pb(II): 23 pM. The VIP system accurately measured the total dissolved concentrations of Cd(II), Cu(II) and Pb(II) in two certified reference materials; SLRS-3, a river water, and SLEW-2, an estuarine water. Field evaluation of the instrumentation and analytical methods was achieved through a series of surveys in the Plym Estuary (Devon, UK), from which environmental data are presented.

Description: Geochemical processes in estuarine and coastal waters often occur on temporally and spatially small scales, resulting in variability of metal speciation and dissolved concentrations. Thus, surveys, which are aimed to improve our understanding of metal behaviour in such systems, benefit from high-resolution, interactive sampling campaigns. The present paper discusses a high-resolution approach to coastal monitoring, with the application of an automated voltammetric metal analyser for on-line measurements of dissolved trace metals in the Gulf of Cadiz, south-west Spain. This coastal sea receives metal-rich inputs from a metalliferous mining area, mainly via the Huelva estuary. On-line measurements of dissolved Cu, Zn, Ni and Co were carried out on-board ship during an eight-day sampling campaign in the study area in June 1997. A pumping system operated continuously underway and provided sampled water from a depth of ca. 4m. Total dissolved metal concentrations measured on-line in the Gulf of Cadiz ranged between 〈5nM Cu (〈3nM Ni) ca. 50km off-shore and 60-90nM Cu (5-13nM Ni) in the vicinity of the Huelva estuary. The survey revealed steep gradients and strong tidal variability in the dissolved metal plume extending from the Huelva estuary into the Gulf of Cadiz. Further on-line measurements were carried out with the automatic metal monitor from the bank of the Odiel estuary over a full tidal cycle, at dissolved metal concentrations in the μM range. The application confirmed the suitability of the automated metal monitor for coastal sampling, and demonstrated its adaptability to a wide range of environmental conditions in the dynamic waters of estuaries and coastal seas. The near-real time acquisition of dissolved metal concentrations at high resolution enabled an interactive sampling campaign and therefore the close investigation of tidal variability in the development of the Huelva estuary metal plume. Copyright (C) 1998 Elsevier Science B.V.

Description: Cathodic stripping voltammetry (CSV) is an analytical technique used for the analysis of low levels of analytes (principally trace metals and sulfur containing organic compounds) in aqueous solutions, and is based on the measurement of a reductive current response as a function of a potential scan towards more negative potentials. The technique is highly sensitive (limits of detection of 10− 10–10− 12 mol l− 1) because of the application of a preconcentrations step prior to the stripping step. During the preconcentration the analyte is collected on the surface of the working electrode (typically a mercury drop), often in the presence of an added electro-active ligand. The CSV technique has been used for automated measurements of trace metals in marine waters, but a key strength of CSV is in its use in trace metal speciation measurements in natural waters, in particular dissolved iron in marine waters.

Description: This paper presents the results of an inter-comparison exercise undertaken to test the reliability and performance of a voltammetric in situ profiling system (VIP system) and carried out by partners based in Italy, Sweden, Switzerland and the UK. The VIP system was designed to allow in situ simultaneous monitoring of the dynamic fractions (i.e. the maximum potentially bioavailable fractions) of Cu(II), Pb(II) and Cd(II) in natural waters at a frequency of 2-3 analyses h - 1. The four participating groups used the VIP systems under laboratory conditions to determine dissolved concentrations of Cu, Pb and Cd in river, estuarine and coastal water reference materials (SLRS-3/4, SLEW-2/3 and CASS3/4, respectively). The accuracy of the VIP method was comparable to that of established methodologies, including inductively coupled plasma mass spectrometry and voltammetric methods using mercury-electrodes. The VIP systems were also applied to determine the dynamic fractions of the target analytes in freshly collected samples ex situ, as well as in situ in contrasting European marine waters. There was good agreement between the concentrations of the dynamic metal fractions determined in laboratory analyses, and observed during the simultaneous deployment of up to five VIP instruments for periods of several hours in coastal waters. The simultaneous in situ deployment of two VIP instruments in an estuary showed a consistent analytical performance over several days of continuous operation. The results of this inter-comparison exercise show that the VIP system is a reliable submersible probe for accurate, sensitive and high resolution in situ monitoring of dissolved metal fractions in the picomolar (Cd, Pb) and nanomolar (Cu) concentration ranges. © 2009 Elsevier B.V. All rights reserved.

Description: Four surveys of the Huelva Estuary in southwest Spain and its sources, the Tinto and the Odiel Rivers, were carried out between 1996 and 1998. The surveys investigated the impact of metalliferous mining of sulfide-rich ores in the catchment area on metal speciation, metal concentrations in a macrophyte, and phytoplankton diversity and abundance. Chemical speciation measurements in the lower Tinto Estuary showed that metals were predominantly electrochemically labile (>99 of total dissolved Cu, Co, and Ni at 10 μM Cu, 424 nM Co, and 500 nM Ni, S = 28). Concentrations of Cu complexing ligands and free cupric ions Cu2+ in the Gulf of Cádiz ranged between 5.3 and 38 nM and 0.2-7.9 pM, respectively, with conditional stability constants of the ligands of log K′CuL = 11.7-12.6. At enhanced dissolved Cu concentrations in the lower Huelva Estuary, Cu complexing ligands were saturated with Cu, resulting in nanomolar Cu2+, which increased upstream. Metal tissue concentrations of the macrophyte Blindingia marginata were high, and a clear relationship between dissolved labile Cu and macrophyte tissue Cu concentrations was observed. A low biodiversity was observed in the Huelva system (Shannon-Wiener indices (H) typically 〈0.2). Nevertheless, the maximum biomass was observed in the lower Tinto Estuary, which showed high labile metal and nutrient concentrations and a low biodiversity (H 〈 0.02), thereby suggesting adaptation through evolutionary processes of the phytoplankton community to the harsh conditions. © 2007 American Chemical Society.