Jesús M. Forja

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.

Sediment quality in the Atlantic coast of Spain

Sediments from the Atlantic coast of Spain have been studied to evaluate environmental quality by using an integrated approach including chemical and toxicological data. Sediment samples were collected in four littoral ecosystems located in Spain, Bay of Cádiz, Guadalquivir River estuary, Ría of Huelva, and Ría of Coruña. To characterize the sediments, organic carbon, granulometric content, total sulfide, eight trace metals (Hg, Cd, Pb, Cu, Zn, As, Ni, and Cr), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) were measured. The toxicity of sediments was assessed with the amphipod Ampelisca brevicornis, the clam Ruditapes philippinarum, juveniles of the fish Solea senegalensis, populations of the estuarine rotifer Brachionus plicatilis, and populations of the bacterium Vibrio fischeri (Microtox). The results obtained show that in general, stations located in the Ría of Huelva were associated with heavy metal contamination and with the highest toxicity. Only chronic toxicity tests were capable of identifying the effects associated with PCB concentrations. The sediment quality guidelines calculated by means of a multivariate analysis approach for contaminants not associated with biological effects (mg/kg) are Hg, 0.54; Cd, 0.51; Pb, 260; Cu, 209; Zn, 513; As, 27.4; and total PCBs, 0.05.

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.

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.

Sediment quality in the Guadalquivir estuary: lethal effects associated with the Aznalcóllar mining spill.

Monitoring from 1998 to 2001 has assessed the impact of the Aznalcóllar mining spill on the sediment quality in the Guadalquivir estuary. Chemical analysis has been completed with biological effects measured in different organisms. The toxicity of sediments obtained from dilutions of toxic mud and from environmental stations affected by the accidental spill was tested using the amphipod Ampelisca brevicornis and the clam Scrobicularia plana. The results obtained show that amphipods are more sensitive to the accidental spill than the clams. A dilution of clean sediment by more than 1.8% of toxic mud produced 100% mortality of amphipods. In GR2 station is detected toxicity to amphipods but not to clams. The rest of the environmental stations show no toxicity. Toxicity to amphipods in GR2 station decreased along time (from 50% to 60% of mortality in 1998 to 10 to 15% in 2001) and it can be associated with a recovery of the areas impacted by the accidental spill.

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).

A multivariate assessment of sediment contamination in dredged materials from Spanish ports.

This paper summarises the performance of simple multivariate exploratory analyses to investigate on their potential application for dredged material characterization and management. The data from 25 sampling stations located at 7 different Spanish ports, produced a matrix consisting of 300 observations on 10 variables: the metals Cd, Cu, Cr, Hg, Ni, Pb and Zn, the metalloid As, the sum of PAHs and PCB congeners, and the proportion of fines and organic matter content. The cluster analysis was suitable to separate the sediments according to the extent of contamination while the PCA indicated that the data was defined by two principal factors: a first one that accounts for 56.4% of the total variance, describing the metallic contaminants except Ni and Cr, and a second one that accounts for 14.4% of the total variance describing the organic contaminants PAHs and PCBs. The use of these two simple and untutored multivariate techniques seems a cost-effective approach for future pre-dredging investigations in the studied areas providing useful information for dredged material characterization and management with little additional effort.

Evaluating the heavy metal contamination in sediments from the Guadalquivir estuary after the aznalcóllar mining spill (SW Spain): A multivariate analysis approach

The Doñana National Park is one of the most importantNatural Reserves in west Europe. The park and theGuadalquivir estuary were impacted by the release of 5million cubic meters of acid waste from the processing ofpyrite ore. Here are presented a multivariate analysisapproach to evaluate the extension and the magnitude of theaccidental spill on the estuarine sediments. Sediments wereused to analyze 6 different metals (Fe, Mn, Zn, Cd, Pb, Cu).Also the concentration of the metals in the differentgeochemical sediment fractions were determined as a means ofassessing the potential impact of the acid water from themine. The analysis of the results obtained permits toestablish that the impact of the accident was acute on theecosystem due to the set up of a treatment plan in June 1998and to the high hydrodynamic of the estuary that absorb theearly impact. Chronic contamination by Cu was also detectedduring the monitoring of the impact of the accident in theestuary but this did not appear to be related to theaccidental spill. Because the likelihood of long term adverseeffects from the heavy metal contamination of estuarinesediments, further ecotoxicological evaluations should becarried out for the estuary and the park using an integrated approach.

Anthropogenic effects on greenhouse gas (CH4 and N2O) emissions in the Guadalete River Estuary (SW Spain)

Coastal areas are subject to a great anthropogenic pressure because more than half of the worlds population lives in its vicinity causing organic matter inputs, which intensifies greenhouse gas emissions into the atmosphere. Dissolved concentrations of CH4 and N2O have been measured seasonally during 2013 in the Guadalete River Estuary, which flows into the Cadiz Bay (southwestern Spanish coast). It has been intensely contaminated since 1970. Currently it receives wastewater effluents from cities and direct discharges from nearby agriculture crop. Eight sampling stations have been established along 18 km of the estuary. CH4 and N2O were measured using a gas chromatograph connected to an equilibration system. Additional parameters such as organic matter, dissolved oxygen, nutrients and chlorophyll were determinate as well, in order to understand the relationship between physicochemical and biological processes. Gas concentrations increased from the River mouth toward the inner part, closer to the wastewater treatment plant discharge. Values varied widely within 21.8 and 3483.4 nM for CH4 and between 9.7 and 147.6 nM for N2O. Greenhouse gas seasonal variations were large influenced by the precipitation regime, masking the temperature influence. The Guadatete Estuary acted as a greenhouse gas source along the year, with mean fluxes of 495.7 μmol m(-2)d(-1) and 92.8 μmol m(-2)d(-1) for CH4 and N2O, respectively.