A numerical simulation study of the hydrodynamic effects caused by morphological changes in the Guadalquivir River Estuary.

This study presents an analysis of the impacts of the changes in bottom depth along the Guadalquivir Estuary on tidal dynamics. A realistic non-linear 1D numerical model, incorporating changes in both breadth and bottom depth, was employed to investigate the involved effects. The findings reveal a significant amplification of the M2 tidal wave towards the upper region of the Estuary, resulting from the gradual deepening caused by multiple dredging operations. The Estuary exhibits a pronounced tendency towards resonance, which is further enhanced by its deepening, resulting in reduced bottom friction and a smaller decrease in tidal wave amplitude as it propagates through the Estuary. The alterations in depth, particularly in breadth, along the Estuary play a crucial role in determining the magnitude of the resonant response of the M2 tidal wave.

Submarine mud volcanoes as a source of chromophoric dissolved organic matter to the deep waters of the Gulf of Cádiz.

Seafloor structures related to the emission of different fluids, such as submarine mud volcanoes (MVs), have been recently reported to largely contribute with dissolved organic matter (DOM) into the oceans. Submarine MVs are common structures in the Gulf of Cádiz. However, little is known about the biogeochemical processes that occur in these peculiar environments, especially those involving DOM. Here, we report DOM characterization in the sediment pore water of three MVs of the Gulf of Cádiz. Estimated benthic fluxes of dissolved organic carbon (DOC) and chromophoric DOM (CDOM) were higher than in other marine sediments with an average of 0.11 ± 0.04 mmol m-2 d-1 for DOC and ranging between 0.11 and 2.86 m-1 L m-2 d-1, for CDOM. Protein-like components represented ~ 70% of the total fluorescent DOM (FDOM). We found that deep fluids migration from MVs (cold seeps) and anaerobic production via sulfate-reducing bacteria represent a source of DOC and FDOM to the overlying water column. Our results also indicate that fluorescent components can have many diverse sources not captured by common classifications. Overall, MVs act as a source of DOC, CDOM, and FDOM to the deep waters of the Gulf of Cádiz, providing energy to the microbial communities living there.

Temporal and spatial variation of N2O production from estuarine and marine shallow systems of Cadiz Bay (SW, Spain).

There is still much uncertainty regarding the global oceanic emissions of N2O, and particularly emissions from coastal regions, because spatio-temporal datasets have limited coverage. The concentration of dissolved N2O in surface waters and the associated fluxes to the atmosphere have been studied in three coastal systems located near Cadiz Bay (southwestern coast of Spain) over different time scales. The three systems present different hydrodynamic characteristics (an estuary and two marine systems) that influence the distribution of N2O in the water column. Nutrients, oxygen, and particulate organic nitrogen were also measured to investigate the processes responsible for N2O production in the water column. Data on dissolved N2O has been obtained in each system from i) two-year monitoring at fixed station; ii) four seasonal samplings along the longitudinal length of the system; and iii) daily sampling in summer. The concentration of N2O ranges between 1.1 and 292.0nM indicating very high spatio-temporal variability. In general, the concentration of N2O increased during the rainy season associated with the precipitation regime that, in turn, increases the lateral inputs of organic matter and nutrients from both natural sources (discharges into rivers and adjacent marshes) and anthropogenic activities (agriculture, urban effluents and fish farming). Dissolved N2O also varied with the tides: the highest concentrations were measured during the ebb, which suggests that the systems export N2O to the Bay and adjacent Atlantic Ocean. In addition nitrification seems to be an important process for N2O formation in the water column, which also explains some of the variability in the dataset. The mean atmospheric flux of N2O reveals that entire study area was a net source of N2O to the atmosphere. The fluxes ranged between 0.5 and 313.2µmolm-2day-1 in the estuarine system, and between -7.2 and 97.8µmolm-2day-1 in the two marine systems.

An integrated approach to determine sediment quality in areas above CO2 injection and storage in agreement with the requirements of the international conventions on the protection of the marine environment.

The urgent need to reduce the greenhouse emissions to the atmosphere has leaded to study new systems to capture and store carbon dioxide (CO(2)). The sequestration of CO(2) in marine geological formations is one of these systems proposed at the international level to effectively reduce the concentration of atmospheric CO(2). Although permanent containment is expected, it is necessary to determine the risk of leakage to the marine environment. The integrated model for the evaluation of the environmental quality of the marine environment will contribute to determine the potential environmental pathways and effects that are relevant to the consideration of the potential consequences of the leakage of CO(2) and incidental associated substances from the geological formations to the marine environment. In addition, this model will satisfy the requirements for a safe CO(2) storage in sub-seabed geological formations set in the international conventions on the protection of the marine environment (1992 OSPAR Convention and 1996 London Protocol). The objective of this paper is to show how to adapt classical methodologies based on a weight-of-evidence approach to establish the impact of CO(2) leaks in the sediment quality. It is described how the classical methods should modify their application when acidification occurs related to CO(2) leaks being the main potential impact in these areas.

Toxicity and bioaccumulation of copper and lead in five marine microalgae.

On five marine microalgae with the same biovolume quantity (Tetraselmis chuii, Rhodomonas salina, Chaetoceros sp., Isochrysis galbana (T-iso) and Nannochloropsis gaditana) 72-h exposure toxicity tests with copper and lead were performed. For both metals, 72-h EC50s showed T. chuii as the most tolerant and R. salina as one of the most sensitive. Besides copper and lead EC(50) concentrations, metal concentrations in solution and accumulated on/in the cell where also analysed. T. chuii, the most tolerant species accumulated high copper concentrations (EC(50(Cu))=330 microgL(-1); EC(50(Pb))=2600 microgL(-)1), and R. salina the most sensitive to copper, accumulated the highest amount of this metal (EC(50(Cu))=50 microgL(-1)). Results of this study show that there is no specific relationship between cell tolerance and accumulated metal on/in the cell. On the other hand, due to an established evidence of the influence of cellular density in microalgae toxicity tests, this effect was also studied. Results showed reduced EC(50) values when initial cellular densities decreased. In this study, the term "toxic cellular quota" was used to express all data. This allowed, in a single expression, the combination of two parameters that clearly influence growth, cellular density and toxic concentration.

Biological adverse effects on bivalves associated with trace metals under estuarine environments.

Toxic effects of pollutants on marine organisms can be studied both by performing field measurements, and by undertaking laboratory simulation experiments. Here is described the effect of trace metals Zn, Cd, Pb and Cu on the clam Scrobicularia plana along a salinity gradient simulated in a hypothetical estuary using simulation experiments. The simulator produces a continuous entry of trace metals into the estuary through injection in the lower salinity tank of the system. The clams were exposed during two weeks to different concentration of trace metals to assess the bioaccumulation process along a salinity gradient. Bivalves were analysed for body tissue residue to determine the bioaccumulation factors related to each metal and the salinity influence was addressed. Differences among tanks were observed as a result of the salinity gradient. In the achieved assays, the mechanism of bioaccumulation of Zn and Cd in organisms was more efficient at high salinity values. Bioaccumulation factors for both metals showed a linear increase with the increase of salinity values. It seems that the mechanism of bioaccumulation of Pb and Cu in organisms was dependent on two simultaneous processes: the proximity to the input point of metals and the low salinity values.

Sediment quality in littoral regions of the Gulf of Cádiz: a triad approach to address the influence of mining activities.

To evaluate sediment quality in different areas in the Gulf of Cádiz affected by mining activities, an integrative approach to assessment was used: the Sediment Quality Triad (SQT). Sediment samples were collected at six stations and subjected to replicated sediment acute and chronic toxicity tests, and comprehensive sediment chemistry analyses. Organisms collected synoptically at the same stations were analyzed for histopathological lesions and chemical concentrations in their tissues to determine 'in situ' alteration and bioavailability, in place of benthic community structure. The results obtained for each component were linked to the SQT using different methodologies of interpretation and expression of the integrated approach: (a) multivariate analysis, (b) significant statistical differences compared to the reference stations, (c) ANOVA-based pie charts, and (d) classical methods using triangles and the SQT index of pollution. SQT results indicated that the highest pollution was mainly associated with metals from mining activities and polyaromatic hydrocarbons in the Ría of Huelva. The use of histopathological measures and bioaccumulation of metals, improved the characterization of 'gray areas' of pollution and in the determination of the bioavailability of metals.

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.

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.

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.