Juan Santos-Echeandía

Effect of dissolved organic matter (DOM) of contrasting origins on Cu and Pb speciation and toxicity to Paracentrotus lividus larvae

Water samples of contrasting origin, including natural seawater, two sediment elutriates and sewage-influenced seawater, were collected and obtained to examine the effect of the dissolved organic matter (DOM) present on metal bioavailability. The carbon content (DOC) and the optical properties (absorbance and fluorescence) of the coloured DOM fraction (CDOM) of these materials were determined. Cu and Pb complexation properties were measured by anodic stripping voltammetry (ASV) and the effect of DOM on Cu and Pb bioavailability was studied by means of the Paracentrotus lividus embryo-larval bioassay. Sediment elutriates and sewage-influenced water (1) were enriched 1.4-1.7 times in DOC; (2) absorbed and reemitted more light; and (3) presented higher Cu complexation capacities (L(Cu)) than the natural seawater used for their preparation. L(Cu) varied from 0.08 microM in natural seawater to 0.3 and 0.5 microM in sediment elutriates and sewage-influenced water, respectively. Differences in DOC, CDOM and Cu complexation capacities were reflected in Cu toxicity. DOM enriched samples presented a Cu EC(50) of 0.64 microM, significantly higher than the Cu EC(50) of natural and artificial seawater, which was 0.38 microM. The protecting effect of DOM on Cu toxicity greatly disappeared when the samples were irradiated with high intensity UV-light. Cu toxicity could be successfully predicted considering ASV-labile Cu concentrations in the samples. Pb complexation by DOM was only detected in the DOM-enriched samples and caused little effect on Pb EC(50). This effect was contrary for both elutriates: one elutriate reduced Pb toxicity in comparison with the control artificial seawater, while the other increased it. UV irradiation of the samples caused a marked increase in Pb toxicity, which correlated with the remaining DOC concentration. DOM parameters were related to Cu speciation and toxicity: good correlations were found between DOC and Cu EC(50), while L(Cu) correlated better with the fluorescence of marine humic substances. The present results stress the importance of characterizing not only the amount but also the quality of seawater DOM to better predict ecological effects from total metal concentration data.

The relevance of defining trace metal baselines in coastal waters at a regional scale: the case of the Portuguese coast (SW Europe).

The Water Framework Directives aims a reduction in concentration of hazardous substances in the marine environment. Consequently, there is a need to distinguish between anthropogenically influenced metal concentrations from natural background levels. To better achieve this goal in the Portuguese coast, dissolved and particulate trace metal (TM) concentrations along the Portuguese coast were determined in 46 sites distance 1-3 km from the shoreline. Dissolved values ranged within the following intervals: 0.01-0.89 nM for Cd, 0.01-3.37 nM for Co, 0.90-45.4 nM for Cu, 3.30-140 pM for Hg, 1.88-15.1 nM for Ni, 0.01-0.15 nM for Pb and 1.40-62.0 nM for Zn. Whereas Cd, Co, Cu, Ni and Zn were enhanced in the southern coast, while Pb values were higher in the central part of the western coast. Mercury concentrations showed punctual increases all along the coast. Values of trace metals in suspended particulate matter varied in a broad range: 36-2902 μmol g(-1) for Al, 0.10-15.1 nmol g(-1) for Cd, 1.50-165 nmol g(-1) for Co, 50.0-990 nmol g(-1) for Cu, 2.80-76.4 nmol g(-1) for Hg, 22-1471 nmol g(-1) for Ni, 10.0-347 nmol g(-1) for Pb and 416-10,981 nmol g(-1) for Zn. Higher values for Al, Ni and Co were found in the central part of the western coast. However, Cd, Cu, Pb and Zn increased their levels from the north coast towards the central and south areas. The variability of both dissolved and particulate metals appears to be mainly associated with oceanographic conditions and continental inputs at North and central areas of the coast, and in the south coast to geological features rather than to anthropogenic pressures. On the basis of these results, regional baseline concentrations are proposed for the three typologies in Portuguese coastal waters defined under the Water Framework Directive.

Quantification of Iron in Seawater at the Low Picomolar Range Based on Optimization of Bromate/Ammonia/Dihydroxynaphtalene System by Catalytic Adsorptive Cathodic Stripping Voltammetry

A new analytical protocol for the challenging analysis of total dissolved iron at the low picomolar level in oceanic waters suitable for onboard analysis is presented. The method is based on the revision of the adsorptive properties of the iron/2,3-dihydroxynaphthalene (Fe/DHN) complexes on the hanging mercury drop electrode with catalytic enhancement by bromate ions. Although it was based on a previously proposed reagent combination, we show here that the addition of an acidification/alkalinization step is essential in order to cancel any organic complexation, and that an extra increment of the pH to 8.6-8.8 leads to the definition of a preconcentration-free procedure with the lowest detection limit described up to now. For total dissolved iron analysis, samples were acidified to pH 2.0 in the presence of 30 μM DHN and left to equilibrate overnight. A 10 mL sample was subsequently buffered to a pH of ∼8.7 in the presence of 20 mM bromate: a 60 s deposition at 0 V led to a sensitivity of 34 nA nM(-1) min(-1), a 4-fold improvement over previous methods, that translated in a limit of detection of 5 pM (2-20 fold improvement). Several tests proved that a nonreversible reaction in the time scale of the analysis, triggered by the acidification/alkalinization step, was behind the signal magnification. The new method was validated onboard via the analysis of reference material and via intercalibration against flow injection analysis-chemiluminescence on Southern Ocean surface samples.

Improving the voltammetric quantification of ill-defined peaks using second derivative signal transformation: Example of the determination of platinum in water and sediments

The determination of trace elements using stripping voltammetry may be seriously affected by the presence of intensive matrix background or interfering peaks, leading to poorer detection limits and/or inaccurate quantitative results. In this work, we have tested the use of signal transformation (e.g., second derivative) in the analysis of platinum in seawater and sediment digests by means of catalytic adsorptive stripping voltammetry. In natural waters, the limit of detection of Pt is affected by a broad background wave due to the formazone complex used in the sample matrix for its determination, while in sediment digests, the Pt peak may be interfered with due to the presence of elevated concentrations of Zn, affecting the accuracy of the determination. Results applying second derivative signal transformation revealed a significant improvement (2-3-fold) of the detection limit in water due to the minimization of background effects, therefore allowing shorter accumulation times and faster determinations. In the presence of interfering peaks, the inaccuracy resulting from erroneous baseline selection in the original signal is eliminated when the second derivative is used. Signal processing should be considered as a useful tool for other voltammetric methodologies where more accurate or faster determinations are needed.

Controls of primary production in two phytoplankton blooms in the Antarctic Circumpolar Current

The Antarctic Circumpolar Current has a high potential for primary production and carbon sequestration through the biological pump. In the current study, two large-scale blooms observed in 2012 during a cruise with R.V. Polarstern were investigated with respect to phytoplankton standing stocks, primary productivity and nutrient budgets. While net primary productivity was similar in both blooms, chlorophyll a –specific photosynthesis was more efficient in the bloom closer to the island of South Georgia (39 °W, 50 °S) compared to the open ocean bloom further east (12 °W, 51 °S). We did not find evidence for light being the driver of bloom dynamics as chlorophyll standing stocks up to 165 mg m−2 developed despite mixed layers as deep as 90 m. Since the two bloom regions differ in their distance to shelf areas, potential sources of iron vary. Nutrient (nitrate, phosphate, silicate) deficits were similar in both areas despite different bloom ages, but their ratios indicated more pronounced iron limitation at 12 °W compared to 39 °W. While primarily the supply of iron and not the availability of light seemed to control onset and duration of the blooms, higher grazing pressure could have exerted a stronger control toward the declining phase of the blooms.

Intra-annual variation and baseline concentrations of dissolved trace metals in the Vigo Ria and adjacent coastal waters (NE Atlantic Coast)

Trace metal analysis in natural waters requires the use of extremely careful procedures to avoid sample contamination. Such techniques include, for example, the use of trace metal-clean sampling and storage devices, high-purity reagents, air-filtered clean lab conditions, and certified reference materials (Howard and Statham, 1993). Accordingly, it has been shown in the decades that most trace metal concentrations reported before the 1980s were subject to a significant overestimation due to contamination (Kremling, 1983). The complexity of trace metal analysis has lead to a limited number of seasonal complete datasets along Atlantic European waters, both in shelf (Auger et al., 1999; Statham et al., 1999; Cottè-Krief et al., 2000; Elbaz-Poulichet et al., 2001) and coastal systems (Martino et al., 2002; Cobelo-García and Prego, 2003; Monbet, 2004, 2006), despite the well-known role of the coastal zone in the transfer of metals from land-based sources (e.g., rivers) to the oceans (Martin and Windom, 1991). Studies on the factors controlling the distribution of trace elements in the Iberian coast and shelf, and in particular the Galician Rias, are still limited (Prego and Cobelo-García, 2003a). Rias are estuarine–coastal systems formed by flooding of river valleys in the Pleistocene–Holocene in regions of high relief during the last interglacial transgression, and are typical of areas such as NE Iberia, SW England or SE Asia (Evans and Prego, 2003; Bianchi, 2007). Several Galician Rias (e.g., Vigo Ria) are under significant anthropogenic influence due to population and industry on their margins (Prego et al., 2008) and/or contamination events (e.g., the Prestige oil tanker shipwreck in 2002; Prego and Cobelo-García, 2003b, Santos-Echeandía et al., 2005, 2008a), which alter to some extent the natural distribution and processes of trace metals. Therefore, studies on the seasonal variability and baseline concentrations of trace elements in these coastal areas are needed. The objectives of this study were: (i) to obtain a complete dataset of dissolved trace metal concentrations in this region of the NE Atlantic Ocean based on a one-year period, providing a baseline for future research in this field; and (ii) to ascertain the anthropogenic influence in the ria waters, comparing their trace metal concentrations with those found in the adjacent coast. In order to achieve the objectives, seawater samples were collected at two stations: station 1 was located inside the Vigo Ria and station 2 at the shelf. Samples were collected on a monthly ba-

Osmium and Platinum Decoupling in the Environment: Evidences in Intertidal Sediments (Tagus Estuary, SW Europe)

Catalytic converters in automobiles have significantly increased the input of platinum group elements (PGE) to the environment, and their coupled geochemical behavior has been proposed. To check this hypothesis, Pt and Os concentrations and (187)Os/(188)Os ratios were determined in sediment cores and interstitial waters from the Tagus Estuary (SW Europe) affected by different traffic pressure. Platinum concentration in surface sediments nearby the high traffic zone (up to 40 ng g(-1)) indicated severe contamination. Although lower than Pt, Os enrichment was also observed in surface sediments, with lower (187)Os/(188)Os ratios than in deeper layers. Dissolved Pt and Os in interstitial waters, 0.1-0.7 pg g(-1) and 0.03-0.10 pg g(-1), respectively, were higher than in typical uncontaminated waters. Results indicate two sources of Pt and Os into the Tagus Estuary salt marshes: a regional input associated with industrial activities, fossil fuel combustions, and regional traffic and a local source linked to nearby traffic density emissions. Estimations of Os and Pt released by catalytic converters support this two-source model. Differences in geochemical reactivity and range of dispersion from their sources lead to a decoupled behavior of Os and Pt, questioning the use of Os isotopes as proxies of PGE sources to the environment.

First Evaluation of the Role of Salp Fecal Pellets on Iron Biogeochemistry

Planktonic grazers such as salps may have a dominant role in iron (Fe) cycling in surface waters of the Southern Ocean (SO). Salps have high ingestion rates and egest large, fast sinking fecal pellets (FPs) that potentially contribute to the vertical flux of carbon. In this study, we determined the impact of FPs from Salpa thompsoni, the most abundant salp in the SO, on Fe biogeochemistry. During the Polarstern expedition ANT-XXVII/3, salps were sampled from a large diatom bloom area in the Atlantic sector of the SO. Extensive work on carbon export and salp FPs export at the sampling location had shown that salps were a minor component of zooplankton and were responsible for only a 0.2% consumption of the daily primary production. Furthermore, at 100 m, export efficiency of salp FPs was ~2-3 fold higher than that of the bulk of sinking particulate organic carbon (POC). After collection, salps were maintained in 200 µm screened seawater and their FPs were collected for further experiments. To investigate whether the FPs release Fe and/or Fe-binding ligands into the filtered seawater (FSW) under different experimental conditions, they were either incubated in the dark or under full sunlight at in situ temperatures for 24h, or placed into the dark after a freeze/thaw treatment. We observed that none of the treatments caused release of dissolved Fe (dFe) or strong Fe ligands from the salp FPs. However, humic-substance like (HS-like) compounds, weak Fe ligands, were released at a rate of 8.2 ± 4.7 µg HS-like FP-1 d-1. Although the Fe content per salp FP was high at 0.33 ± 0.02 nmol dFe FP-1, the small contribution of salps to the zooplankton pool resulted in an estimated dFe export flux of 11.3 nmol Fe m-2 d-1 at 300 m. Since salp FPs showed an export efficiency at 100 m well above that shown by the bulk of sinking POC, our results suggest that in those areas of the SO where salps play a major role in the grazing of primary production, they could be actively contributing to the depletion of the dFe pool in surface water.

Toxicity of seabird guano to sea urchin embryos and interaction with Cu and Pb.

Guano is an important source of marine-derived nutrients to seabird nesting areas. Seabirds usually present high levels of metals and other contaminants because the bioaccumulation processes and biotic depositions can increase the concentration of pollutants in the receiving environments. The objectives of this study were to investigate: the toxicity of seabird guano and the joint toxicity of guano, Cu and Pb by using the sea urchin embryo-larval bioassay. In a first experiment, aqueous extracts of guano were prepared at two loading rates (0.462 and 1.952 g L(-1)) and toxicity to sea-urchin embryos was tested. Toxicity was low and not dependent of the load of guano used (EC50 0.42 ± 0.03 g L(-1)). Trace metal concentrations were also low either in guano or in aqueous extracts of guano and the toxicity of extracts were apparently related to dissolved organic matter. In a second experiment, the toxicity of Cu-Pb mixtures in artificial seawater and in extracts of guano (at two loadings: 0.015 and 0.073 g L(-1)), was tested. According to individual fittings, Cu added to extracts of guano showed less toxicity than when dissolved in artificial seawater. The response surfaces obtained for mixtures of Cu and Pb in artificial seawater, and in 0.015 g L(-1) and 0.073 g L(-1) of guano, were better described by Independent Action model adapted to describe antagonism, than by the other proposed models. This implied accepting that EC50 for Cu and Pb increased with the load of guano and with a greater interaction for Cu than for Pb.