Abelardo Gómez-Parra

Influence of the Aznalcóllar mining spill on the vertical distribution of heavy metals in sediments from the Guadalquivir estuary (SW Spain)

The Natural Park of Doñana and the Guadalquivir estuary were impacted by the release of 6 million cubic meters of acid waste after the mine-tailing spill in Aznalcóllar (Andalusia, SW, Spain). Here is presented the monitoring of the accidental spill on vertical distribution of heavy metals in the estuarine sediments. The total concentration of six metals (Fe, Mn, Zn, Cd, Pb, Cu), their chemical speciation and the organic carbon concentration were analyzed in sediment vertical profiles. The results obtained determine background levels similar to previously reported in the area. The analysis catalogues the impact of the accident on the estuary as acute and mainly associated with high concentrations of Zn and Cd. The recent enrichment in Zn and Cd and their geochemical association with the more mobile fractions of the sediment determine an environmental risk associated with the acute impact and detected in some of the areas of the estuary.

Determining contamination sources in marine sediments using multivariate analysis

Abstract The problem of identifying sources of anthropogenic pollutants in a local marine environment has been intensively studied during the last two decades. An approach is descibed for tracing anthropogenic pollutant sources, and for characterizing various geochemical and chemical processes related to contamination by anthropogenic heavy metals and surfactants in the marine coastal environment, which uses a multivariate technique of principal components analysis (PCA). This approach was applied to study two selected littoral ecosystems in the Gulf of Cadiz. The multivariate analysis approach can be used successfully for contamination source assessments. From this information, it was possible to identify current superficial sources of contamination and it might be possible to determine the areas where further toxicological testing is required.

Sources, transport and reactivity of anionic and non-ionic surfactants in several aquatic ecosystems in SW Spain: a comparative study.

Presence, distribution and transport mechanisms of the four major synthetic surfactants--linear alkylbenzene sulfonates (LAS), alkyl ethoxysulfates (AES), nonylphenol ethoxylates (NPEOs) and alcohol ethoxylates (AEOs)--have been simultaneously studied in different aquatic ecosystems. Urban wastewater discharges and industrial activities were identified as the main sources for these compounds and their metabolites. LAS, AES and carboxylic metabolites remained in the dissolved form (87-99%). However, NPEOs and AEOs were mostly associated with particulate matter (65-86%), so their degradation in the water column was limited due to their lower bioavailability. It was also observed that sorption to the particulate phase was more intense for longer homologs/ethoxymers for all surfactants. With respect to surface sediments, AES levels were considerably below (<0.25 mg/kg) the values detected for LAS and NPEOs. Concentrations of AEOs, however, were occasionally higher (several tens of ppm) than those found for the rest of the target compounds in several sampling stations.

Heavy metal fluxes at the sediment–water interface of three coastal ecosystems from south-west of the Iberian Peninsula

Concentrations of the heavy metals Cr, Cu, Fe and Mn were measured in sediments and porewater samples collected in three coastal ecosystems southwest of the Iberian Peninsula: the Odiel and Barbate River Salt Marshes and the Bay of Cadiz. Both the sediment and the porewater metal concentrations in the Odiel River Salt Marshes are higher than the values found in the Bay of Cadiz and Barbate River Salt Marsh, particularly for copper, a metal associated with mining activity. In porewater, the profiles were not the same as those in the solid phase and reflect the different behaviours of the elements in relation to the redox conditions. The heavy metals Cr and Cu show a typical enrichment in the porewater of the oxic zone. The heavy metals Mn and Fe show an increase in the porewater at the depths where the maximum nitrate and phosphate concentrations occur, respectively. Significant differences between background levels for each heavy metal in the various studied zones exist. Iron and Cu showed larger background levels in the Odiel River Salt Marshes than those in the Cadiz Bay and the Barbate River Salt Marshes. In the Bay of Cadiz the background levels are also high, particularly for Cr. At the Odiel River Salt Marshes the diffusive flux of Cu is high (1.3-230.1 microg cm(-2) year(-1)), which suggests that the Odiel River Salt Marshes are subject to strong contamination by Cu, which is presumably introduced to the sediment in particulate form. In the Bay of Cadiz, Cr is the only metal with positive diffusive flux (2.15 microg cm(-2) year(-1)). It is higher than those obtained in other coastal ecosystems including the Odiel River Salt Marshes. The positive diffusive flux of Cr has been associated with the input of this metal by the naval industry and the manufacturing of car and aircraft components.

The influence of pH and salinity on the toxicity of heavy metals in sediment to the estuarine clam Ruditapes philippinarum

An approach is presented for determining the influence of two key variables, pH and salinity (S), on the toxicity of four common heavy metals bound to sediments in estuaries. Two samples of environmental sediment taken from two estuaries in southern Spain (the Huelva estuary and the Guadalquivir River estuary), together with a dilution of toxic mud from the Aznalcóllar (Spain) mining spill (April 1998) were used to determine their toxicity at different values of pH (6.5, 7.5, and 8.5) and salinity (10, 20, and 30) on the estuarine clam Ruditapes philippinarum. Two different endpoints, sublethal, indicated by clam reburial (median effective burial time [ET50]), and relative mortality (median lethal concentration [LC50]), were used to quantify the toxicity associated with the heavy metals. Neither salinity nor pH was found to influence the toxic responses measured by the behavioral endpoint (ET50). However, a strong effect on the LC50 related to pH and salinity was detected, with the toxicity of the heavy metals being increased at low values of both variables (pH = 6.5 and S = 10). The mechanism of heavy metals uptake through water may explain this influence of pH and salinity on the lethal toxicity detected. The results show differences in the toxicity of these heavy metals bound to sediments depending on whether the origin of metal contamination is chronic or acute.

Occurrence and distribution of linear alkylbenzene sulfonates and sulfophenylcarboxylic acids in several Iberian littoral ecosystems

The distribution of linear alkylbenzene sulfonates (LAS) and sulfophenylcarboxylic acids (SPC) has been characterized in water and sediment of five Iberian estuaries and a saltmarsh channel. The highest concentrations of LAS and SPC were detected in shallow zones close to discharge points of untreated urban effluent, and decreased sharply with increasing distance from these. SPC homologues of between 3 and 12 carbon atoms were detected, although their concentrations were several orders of magnitude lower than the corresponding LAS. The highest SPC concentrations found were of medium carboxylic chain lengths (C6-C8) in water, and of longer chain lengths (C9-C11) in particulate material. LAS homologues were associated preferentially with the particulate material. The vertical distribution of LAS in the water column was not homogeneous, in contrast to that presented by the SPC homologues. In the case of the Sancti Petri Channel, there was a net flow of LAS exportation into the Bay of Cádiz, of -38.6 kg day(-1), and a net flow for SPC of -6.0 kg day(-1). The daily mass input of LAS and their biodegradation intermediates from the Sancti Petri Channel to Cadiz Bay was 44.6 kg.

Seasonality of contamination, toxicity, and quality values in sediments from littoral ecosystems in the Gulf of Cádiz (SW Spain)

To seasonally evaluate littoral contamination, toxicity and quality values of sediments from the Gulf of Cádiz, we measured chemical concentrations and conducted toxicity tests in winter and summer and linked these results by means of multivariate analysis. Sediment samples were subjected to two separate, replicated sediment toxicity tests (Microdeutopus gryllotalpa amphipod survival, and Ruditapes philippinarum clam reburial), and to comprehensive sediment chemistry analyses (grain size, organic carbon, 14 heavy metals, and the surfactant linear alkylbenzenesulfonate (LAS)). Only sediments associated with an untreated urban discharge were toxic and related to high levels of surfactant LAS, Ag, and Pb. Multivariate analysis indicated that variables and chemicals associated with geochemical matrix and background levels (specific surface, Fe, Zn, Cu, V, Ni, and Co), chemicals associated with untreated urban discharge sources, and toxicity effects showed no seasonal variability. Only copper concentrations showed seasonal differences, being toxic during the winter and not toxic during summer. Multivariate analysis permits us to derive sediment quality values (SQVs); in terms of concentrations at or below which biological effects were not measured (mg kg(-1) dry sediment), are: LAS, 2.6; lead, 66.8; silver, 0.78; copper, 69.6.

ANALYSIS OF MACROBENTHIC COMMUNITY STRUCTURE IN RELATION TO DIFFERENT ENVIRONMENTAL SOURCES OF CONTAMINATION IN TWO LITTORAL ECOSYSTEMS FROM THE GULF OF CADIZ (SW SPAIN)

Selected chemicals in sediments and the abundances and biomasses of macrobenthic species were determined at seven stations from two littoral ecosystems in the Gulf of Cádiz. The marine macrobenthic communities were described in both ecosystems that are subjected to different sources and levels of contamination. A qualitative relationship between source of contamination and biological effects for each station is proposed and the results of the univariate and multivariate analysis used are discussed. Univariate analyses using conventional community descriptive parameters (number of species, abundance and richness, Shanon–Weaver and evenness indices) and the numerial contribution of major taxonomic groups (i.e., Polychaeta, Oligochaeta, Mollusca and Crustacea) could not be used as a means of classifying the sites as clean or polluted with respect to the contamination measured. The results showed that multivariate methods are much more sensitive than univariate techniques. Abundance/biomass comparison (ABC) plots classified the macrobenthic communities into different classes mainly related to organic contamination. However, this analysis did not reflect the alteration due to inorganic sources of contamination. This kind of analysis is valuable for the evaluation of alteration of effects but it cannot discriminate between two different phenomena: pollution (adverse effect associated with chemical concentrations) and alteration (adverse effect associated with chemical concentrations or with natural variations).

Handling of marine and estuarine samples for the determination of linear alkylbenzene sulfonates and sulfophenylcarboxylic acids

Due to the physicochemical properties of linear alkylbenzene sulfonates (LAS), an anionic surfactant, it is difficult to obtain representative samples from sampling sites. Further, the high biodegradability of these compounds makes it necessary to study their biodegradation intermediates, sulfophenylcarboxylic acids (SPC) that do not have a surfactant character and show a different behavior. A procedure for determining and quantifying LAS and SPC in different environmental matrices by Soxhlet and solid-phase extractions and high-performance liquid chromatography is presented. The recoveries varied in the range from 85 to 102% for the water samples, and from 75 to 105% for sediment samples, with a standard deviation of between 1 and 7, and 2 and 11, respectively. Detection limits obtained were in the range from 5 to 10 microg kg(-1) for sediment samples (10 g) and from 0.2 to 0.4 microg l(-1) for water samples (250 ml). The method was applied to the simultaneous determination of LAS (C10-C13) and SPC (C4-C13) homologues in water, sediment and interstitial water collected from different areas of Spain.

Anaerobic degradation pathway of linear Alkylbenzene sulfonates (LAS) in sulfate-reducing marine sediments.

Linear alkylbenzene sulfonates (LAS) are among the principal synthetic surfactants used worldwide. Their presence in the environment has been reported in a significant number of studies, and it has been generally assumed that LAS are not biotransformed in the absence of oxygen. However, laboratory experiments performed by our group using anoxic marine sediments have reported LAS degradation percentages that can reach up to 79% in 165 days. Here, we show for the first time the initial reaction metabolites (generated via fumarate addition to the LAS molecules), their biotransformation into sulfophenyl carboxylic acids (SPC), and the progressive degradation of these by successive beta-oxidation reactions. Advanced mass spectrometry has been used to carry out the identification of these compounds. This is the first time that an anaerobic degradation pathway for LAS is described, and these results represent a significant advance in understanding the final fate of these and other similar compounds in anoxic environments.