T.A. DelValls

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.

Bioavailability of heavy metals bound to estuarine sediments as a function of pH and salinity values

Abstract The role of two key-variables such as pH and salinity in chemical speciation and bioavailability of heavy metals originated by mining activities bound to sediments was evaluated under estuarine conditions. Two sediment samples collected in two estuaries in southern Spain (Ría of Huelva and Guadalquivir estuary) together with dilution of toxic mud from the Aznalcóllar mining spill (April, 1998) were used to determine their chemical speciation and bioavailability at different pH (6.5, 7.5, 8.5) and salinity (10, 20, 35) values using the estuarine clam Ruditapes philippinarum. The chemical speciation was established by means of measurements of the mobilization of heavy metals from sediments to waters and determining in it pH, salinity, alkalinity and heavy metal concentration. The geochemical model MINTEQA2 was used to establish the thermodynamic species in the assays. To assess the bioavailability of the heavy metals the concentration of metallothioneins in the clam tissues and the mortality of this organism was measured at different pH and salinity values. The influence of both salinity and pH was detected in the chemical behavior of metals and in their associated biological responses established by metallothioneins and the percentage of mortality. At low values of both variables (pH=6.5 and S=10), the biological effects were highest, and it was related to the free ion Zn2+.

Development of site-specific sediment quality guidelines for North and South Atlantic littoral zones: comparison against national and international sediment quality benchmarks.

We aimed to develop site-specific sediment quality guidelines (SQGs) for two estuarine and port zones in Southeastern Brazil (Santos Estuarine System and Paranaguá Estuarine System) and three in Southern Spain (Ría of Huelva, Bay of Cádiz, and Bay of Algeciras), and compare these values against national and traditionally used international benchmark values. Site-specific SQGs were derived based on sediment physical-chemical, toxicological, and benthic community data integrated through multivariate analysis. This technique allowed the identification of chemicals of concern and the establishment of effects range correlatively to individual concentrations of contaminants for each site of study. The results revealed that sediments from Santos channel, as well as inner portions of the SES, are considered highly polluted (exceeding SQGs-high) by metals, PAHs and PCBs. High pollution by PAHs and some metals was found in São Vicente channel. In PES, sediments from inner portions (proximities of the Ponta do Félix ports terminal and the Port of Paranaguá) are highly polluted by metals and PAHs, including one zone inside the limits of an environmental protection area. In Gulf of Cádiz, SQGs exceedences were found in Ria of Huelva (all analysed metals and PAHs), in the surroundings of the Port of Cádiz (Bay of Cádiz) (metals), and in Bay of Algeciras (Ni and PAHs). The site-specific SQGs derived in this study are more restricted than national SQGs applied in Brazil and Spain, as well as international guidelines. This finding confirms the importance of the development of site-specific SQGs to support the characterisation of sediments and dredged material. The use of the same methodology to derive SQGs in Brazilian and Spanish port zones confirmed the applicability of this technique with an international scope and provided a harmonised methodology for site-specific SQGs derivation.

Integrated sediment quality assessment in Paranaguá Estuarine System, Southern Brazil.

Sediment quality from Paranaguá Estuarine System (PES), a highly important port and ecological zone, was evaluated by assessing three lines of evidence: (1) sediment physical-chemical characteristics; (2) sediment toxicity (elutriates, sediment-water interface, and whole sediment); and (3) benthic community structure. Results revealed a gradient of increasing degradation of sediments (i.e. higher concentrations of trace metals, higher toxicity, and impoverishment of benthic community structure) towards inner PES. Data integration by principal component analysis (PCA) showed positive correlation between some contaminants (mainly As, Cr, Ni, and Pb) and toxicity in samples collected from stations located in upper estuary and one station placed away from contamination sources. Benthic community structure seems to be affected by both pollution and natural fine characteristics of the sediments, which reinforces the importance of a weight-of-evidence approach to evaluate sediments of PES.

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.

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.

Accumulation and histopathological damage in the clam Ruditapes philippinarum and the crab Carcinus maenas to assess sediment toxicity in Spanish ports

The degree of contamination and toxicity in sediment from four Spanish ports (Cádiz, Huelva, Pasajes and Bilbao) was assessed in the present study. Two marine invertebrate species, the shore crab Carcinus maenas and the clam Ruditapes philippinarum, were exposed to the different sediments under laboratory conditions for 28 days. Relationships were developed among metal contamination (As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in sediments, metal accumulation in gill tissues and histopathological lesions in different biological tissues to assess sediment toxicity. A multivariate analysis approach was used to calculate sediment quality guidelines (SQGs) by linking metal concentration in sediments with histopathological lesions measured in the exposed organisms. The results showed significant contaminant accumulation and histopathological lesions due to As, Pb and Zn in sediments at the port of Huelva; As, Cr, Cu, Hg and Ni at the ports of Pasajes and Cádiz; and Cr and Hg at the port of Bilbao. The link between chemical concentration in sediments and histopathological lesions allowed the determination of SQGs for the chemicals As, Cd, Cu, Cr, Hg, Ni and Zn.

Harmonised framework for ecological risk assessment of sediments from ports and estuarine zones of North and South Atlantic

This paper presents a harmonised framework of sediment quality assessment and dredging material characterisation for estuaries and port zones of North and South Atlantic. This framework, based on the weight-of-evidence approach, provides a structure and a process for conducting sediment/dredging material assessment that leads to a decision. The main structure consists of “step 1” (examination of available data); “step 2” (chemical characterisation and toxicity assessment); “decision 1” (any chemical level higher than reference values? are sediments toxic?); “step 3” (assessment of benthic community structure); “step 4” (integration of the results); “decision 2” (are sediments toxic or benthic community impaired?); “step 5” (construction of the decision matrix) and “decision 3” (is there environmental risk?). The sequence of assessments may be interrupted when the information obtained is judged to be sufficient for a correct characterisation of the risk posed by the sediments/dredging material. This framework brought novel features compared to other sediment/dredging material risk assessment frameworks: data integration through multivariate analysis allows the identification of which samples are toxic and/or related to impaired benthic communities; it also discriminates the chemicals responsible for negative biological effects; and the framework dispenses the use of a reference area. We demonstrated the successful application of this framework in different port and estuarine zones of the North (Gulf of Cádiz) and South Atlantic (Santos and Paranaguá Estuarine Systems).

Identification of specific malformations of sea urchin larvae for toxicity assessment: Application to marine pisciculture effluents

Standard toxicity screening tests are useful tools in the management of impacted coastal ecosystems. To our knowledge, this is the first time that the sea urchin embryo development test has been used to evaluate the potential impact of effluents from land-based aquaculture farms in coastal areas. The toxicity of effluents from 8 land-based turbot farms was determined by calculating the percentage of abnormal larvae, according to two criteria: (a) standard, considering as normal pyramid-shaped larvae with differentiated components, and (b) skeletal, a new criterion that considers detailed skeletal characteristics. The skeletal criterion appeared to be more sensitive and enabled calculation of effective concentrations EC(5), EC(10), EC(20) and EC(50), unlike the classical criterion. Inclusion of the skeleton criterion in the sea urchin embryo development test may be useful for categorizing the relatively low toxicity of discharges from land-based marine fish farms. Further studies are encouraged to establish any causative relationships between pollutants and specific larval deformities.

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.