Charlotte B. Braungardt

Stripping voltammetry for the determination of trace metal speciation and in-situ measurements of trace metal distributions in marine waters

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.

Metal geochemistry in a mine-polluted estuarine system in Spain

The Rio Tinto and Rio Odiel drain the Iberian Pyrite Belt, an important metal-rich sulphide deposit. The rivers are highly acidic (pH 2.2-3.6) and have milli-molar SO4 and Fe concentrations and micro-molar Co, Cu, Mn and Zn concentrations. Observed dissolved metal levels were at a maximum during autumn and early winter surveys (e.g. Rio Tinto: 460-856 μM Cu), and lower in late winter, spring and summer (121-175 μM Cu). This variability is attributed to the production of concentrated acid mine drainage (AMD) during periods of enhanced microbial activity at higher temperatures in summer, and a subsequent run-off of the AMD into the rivers with the first rain in the autumn. Lower temperatures and dilution by winter floods resulted in a reduction of river metal concentration towards the end of the wet season. Metal distributions in the estuarine mixing zones of the Tinto and Odiel were governed by the acidity. The lack of metal transfer from the dissolved to the particulate phase in the low salinity region is attributed to the electrostatic repulsion between the metal cations and positive charges on particle surfaces, and/or to the protonation of adsorption sites at low pH. Dissolved Pb was an exception and showed marked removal in the low salinity zone at low pH (pH 2.5), due to its particle reactive nature. The gross metal fluxes from the Rio Tinto and Rio Odiel are important on a global scale, for example amounting to 8.1 and 1.6 of the estimated global riverine dissolved Zn and Cu fluxes. The fluxes of metals from the estuary contribute to enhanced dissolved metal concentrations observed in the Gulf of Cadiz.

Metal biogeochemistry in the Tinto-Odiel rivers (Southern Spain) and in the Gulf of Cadiz: A synthesis of the results of TOROS project

TOROS (Tinto-Odiel-River-Ocean Study) has been studying the biogeochemical processes which control metals and nutrients cycling in the mixing zone of the Tinto and Odiel rivers (SW Spain) and has established the fate of metals in the Gulf of Cadiz in relation to hydrodynamics and biological activity. The Tinto and Odiel rivers are small, with a combined mean discharge of 18m 3/s. They drain the largest sulphide mineralisation in the world. Predominantly, Zn-Cu-Pb mineralisation has been worked since 2500yr BC. The estuarine zone includes both an extensive area of salt marsh and an intensively industrialised urban area. As a consequence of pyrite oxidation, the Tinto and Odiel rivers are strongly acidic (pH<3) with extremely high and variable metal concentrations. Transition metals are poorly removed from the water column in the mixing zone. Moreover, drainage from large phosphogypsum waste deposits contributes to As, Hg, U and phosphate contamination of the estuary. The collapse of the tailing reservoir at los Frailes in 1998 had not impacted the chemistry of the coastal waters up to 6 months later. A large plume of metal-rich waters due to the Tinto and Odiel discharges occurs along the coast of the Gulf of Cadiz. This plume affects seasonally the Atlantic inflow through the Strait of Gibraltar. The dispersion of the metal discharges has been simulated by injection of a tracer in the 3-D hydrodynamical model. Both model and field study clearly show the inflow of metal contaminated Spanish Shelf Water through the Strait of Gibraltar.

Trace metal and nutrient distribution in an extremely low pH (2.5) river–estuarine system, the Ria of Huelva (South–West Spain)

Nutrient (nitrate, phosphate, silica) and dissolved metal (Al, Cu, As, Cd, Ni, Zn, Fe, U) distributions were studied in the mixing zones of the Tinto and Odiel rivers which drain the South Iberian pyrite belt. Phosphate distribution is strongly influenced by discharges from the fertiliser industry, especially in the Tinto mixing zone. The increase of silica content in this zone is related to a release of biogenic silica from diatoms. Nitrate concentrations which are influenced by urban and industrial effluents showed an important maximum in the early stages of mixing in the Tinto (as do the metals). Compared to the Odiel river, the metal concentrations in the Tinto river reached higher values in relation to more intensive mining activities. Dissolved Fe, Mn, Al, Cu, Cd and Zn concentrations were correlated in the mixing zones of both rivers. This suggests that they have the same source and are subjected to the same controlling processes in the estuary. A maximum concentration for these metals was observed in the early stage of mixing in the Tinto and reflects a decrease of redox in a low pH (<3) environment. Downstream in the Odiel system, metals showed a slight removal. Dissolved uranium, present at a low level (0.05 μmol l-1) in the rivers, is introduced by the phosphate fertiliser industry in the estuary and trapped in sedimentation areas. As a consequence, waters of the Gulf of Cadiz have a U content similar to that of the open seawater. Copyright (C) 1999 Elsevier Science B.V. All rights reserved.

Metal behaviour in an estuary polluted by acid mine drainage: The role of particulate matter

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.

Influence of sorption processes by iron oxides and algae fixation on arsenic and phosphate cycle in an acidic estuary (Tinto river, Spain)

Inorganic arsenic and phosphate distributions have been studied in the acidic mixing zone of the Tinto river in November 1996, June 1997, and April 1998. This mixing zone receives high inputs of As, PO4/3- and Fe in relation with acid mine drainage and run-off from phosphogypsum waste. In the early stage of mixing the dissolution of detritic Fe phases (pyrite and oxides) releases Fe and As to water. This process is counterbalanced by removal due to precipitation of Fe-oxides and Fe-organic complexes and algae fixation. In autumn, the amount of algae is negligible and a release of As, Fe and PO4/3- to the dissolved phase was observed. As a consequence, high As and PO4/3- concentrations are registered in the water (up to 43 nM for As and 330 μM for PO4/3-). In spring, the removal dominates in relation with high algae productivity. As a result As and PO4/3- are depleted in the dissolved phase in spring compared to autumn and high concentrations of As (up to 1530 μg g-1 and 700 μg g-1 in June and in April, respectively) were observed in the suspended particulate matter. In autumn dissolved As is correlated with Fe whilst in spring As behaves in a similar way as PO4/3-

UV digestion of seawater samples prior to the determination of copper using flow injection with chemiluminescence detection

A purpose built UV digestion system was successfully used for the breakdown of Cu complexing organic ligands in seawater samples, prior to total dissolved Cu determination using flow injection with chemiluminescence detection (FI-CL) and on-line micro-column preconcentration/matrix removal. Residual dissolved organic carbon (DOC) was quantified using a DOC analyser. Humic acid (1.8-7.2 mg l-1C) in ultra high purity (UHP) water was completely broken down within 4h in all batch experiments (125 and 400 W lamps; with and without 15 mM H2O2 and, as expected, was more rapid with the 400 W lamp, in the presence of H2O2, and for lower humic acid concentrations. UV digestion experiments with seawater showed that the residual DOC concentration after batch UV treatment (4h) was 0.32 mg l-1C after on-line irradiation (residence time 11.2 min). Therefore, the batch method was more efficient than on-line UV digestion at breaking down added humic acid and naturally present organic compounds in seawater. However, the release of Cu from metal complexing organic matter in seawater and estuarine water was the same using both on-line and batch UV digestion (sample irradiation residence time: 5.6 min and 8h, respectively). UV digestion is, therefore, a contamination-free approach for seawater pretreatment prior to micro-column preconcentration and FI-CL determination of total dissolved Cu and should also be applicable to the selective determination of the total dissolved fractions of other trace metals in seawater (e.g. Co, Fe, Mn).

Determination of dissolved organic nitrogen in natural waters using high-temperature catalytic oxidation

Studies on nitrogen in natural waters have generally focussed on dissolved inorganic nitrogen (DIN), primarily because of relative ease of analysis and the important influence of DIN on water quality. Advances in analytical techniques now permit the systematic study of dissolved organic nitrogen (DON), and this work has shown that DON is quantitatively significant in many waters. This article describes the sampling and analytical protocols required for rapid, precise and reliable determinations of DON, involving high-temperature catalytic oxidation (HTCO), coupled to chemiluminescence detection. This approach simultaneously determines dissolved organic carbon (DOC) and total dissolved nitrogen (TDN), and DON is derived by subtraction of DIN measured by colorimetry. The DON determination is simple to perform, exhibits excellent precision (<1% for C and 1.5% for N) and is applicable to a wide range of natural waters.

Impact of Los Frailes mine spill on riverine, estuarine and coastal waters in southern Spain

On April 25, 1998, a spill at the Los Frailes mine in southern Spain resulted in a very high input of metals (including Ag, As, Cd, Cu, Fe, Pb, Tl and Zn) into the river Guadiamar. Calculations indicate that the discharges into the Guadiamar of Cu (5100t), Pb (24,700t), Zn (26,200t) and Ag (138t, based on mud only) were higher than the annual production by the Los Frailes mine for Ag and Pb, and ca. two times less for Cu and Zn. For many metals, the increase in concentration in the affected river (Guadiamar), 2days after the initial discharge, was by several orders of magnitude. However, 6months after the incident, no evidence of the spill could be observed in the plume of the river (Guadalquivir) which discharged the mine waters into the coastal waters of the Gulf of Cadiz. This observation can possibly be explained by low rainfall, natural metal removal processes in the river and estuarine environments and by human interventions. Copyright (C) 1999 Elsevier Science Ltd. On April 25, 1998, a spill at the Los Frailes mine in southern Spain resulted in a very high input of metals (including Ag, As, Cd, Cu, Fe, Pb, Tl and Zn) into the river Guadiamar. Calculations indicate that the discharges into the Guadiamar of Cu (5100 t), Pb (24,700 t), Zn (26,200 t) and Ag (138 t, based on mud only) were higher than the annual production by the Los Frailes mine for Ag and Pb, and ca. two times less for Cu and Zn. For many metals, the increase in concentration in the affected river (Guadiamar), 2 days after the initial discharge, was by several orders of magnitude. However, 6 months after the incident, no evidence of the spill could be observed in the plume of the river (Guadalquivir) which discharged the mine waters into the coastal waters of the Gulf of Cadiz. This observation can possibly be explained by low rainfall, natural metal removal processes in the river and estuarine environments and by human interventions.

Dissolved silver in European estuarine and coastal waters

Silver is one of the most toxic elements for the marine microbial and invertebrate community. However, little is known about the distribution and behaviour of dissolved silver in marine systems. This paper reports data on dissolved and sediment-associated silver in European estuaries and coastal waters which have been impacted to different extents by past and present anthropogenic inputs. This is the first extended dataset for dissolved silver in European marine waters. Lowest dissolved silver concentrations were observed in the Gullmar Fjord, Sweden (8.9 +/- 2.9 pM; x +/- 1sigma), the Tamar Estuary, UK (9.7 +/- 6.2 pM), the Fal Estuary, UK (20.6 +/- 8.3 pM), and the Adriatic Sea (21.2 +/- 6.8 pM). Enhanced silver concentrations were observed in Atlantic coastal waters receiving untreated sewage effluent from the city of A Corũna, Spain (243 +/- 195 pM), and in the mine-impacted Restronguet Creek, UK (91 +/- 71 pM). Anthropogenic wastewater inputs were a source of dissolved silver in the regions studied, with the exception of the Gullmar Fjord. Remobilisation of dissolved silver from historically contaminated sediments, resulting from acid mine drainage or sewage inputs, provided an additional source of dissolved silver to the estuaries. The ranges in the log particle-water partition coefficient (K(d)) values of 5-6 were similar for the Tamar and Mero estuaries and agreed with reported values for other estuaries. These high K(d) values indicate the particle reactive nature of silver with oxic sediments. In contrast, low K(d) values (1.4-2.7) were observed in the Fal system, which may have been due to enhanced benthic inputs of dissolved silver coupled to limited scavenging of silver on to sediments rich in Fe oxide.