Acquiring an evolutionary perspective in marine ecotoxicology to tackle emerging concerns in a rapidly changing ocean.

Tens of thousands of anthropogenic chemicals and wastes enter the marine environment each year as a consequence of the ever-increasing anthropogenic activities and demographic growth of the human population, which is majorly concentrated along coastal areas. Marine ecotoxicology has had a crucial role in helping shed light on the fate of chemicals in the environment, and improving our understanding of how they can affect natural ecosystems. However, chemical contamination is not occurring in isolation, but rather against a rapidly changing environmental horizon. Most environmental studies have been focusing on short-term within-generation responses of single life stages of single species to single stressors. As a consequence, one-dimensional ecotoxicology cannot enable us to appreciate the degree and magnitude of future impacts of chemicals on marine ecosystems. Current approaches that lack an evolutionary perspective within the context of ongoing and future local and global stressors will likely lead us to under or over estimations of the impacts that chemicals will exert on marine organisms. It is therefore urgent to define whether marine organisms can acclimate, i.e. adjust their phenotypes through transgenerational plasticity, or rapidly adapt, i.e. realign the population phenotypic performances to maximize fitness, to the new chemical environment within a selective horizon defined by global changes. To foster a significant advancement in this research area, we review briefly the history of ecotoxicology, synthesis our current understanding of the fate and impact of contaminants under global changes, and critically discuss the benefits and challenges of integrative approaches toward developing an evolutionary perspective in marine ecotoxicology: particularly through a multigenerational approach. The inclusion of multigenerational studies in Ecological Risk Assessment framework (ERA) would provide significant and more accurately information to help predict the risks of pollution in a rapidly changing ocean.

Sunscreens as a New Source of Metals and Nutrients to Coastal Waters.

Studies detailing the environmental impact of sunscreen products on coastal ecosystems are considered a high priority. In the present study, we have determined the release rate of dissolved trace metals (Al, Cd, Cu, Co, Mn, Mo, Ni, Pb, and Ti) and inorganic nutrients (SiO2, P-PO43-, and N-NO3-) from a commercial sunscreen in seawater, and the role of UV radiation in the mobilization of these compounds. Our results indicate that release rates are higher under UV light conditions for all compounds and trace metals except Pb. We have developed a kinetic model to establish the release pattern and the contribution to marine coastal waters of dissolved trace metals and inorganic nutrients from sunscreen products. We conservatively estimate that sunscreen from bathers is responsible for an increase of dissolved metals and nutrients ranging from 7.54 × 10-4 % for Ni up to 19.8% for Ti. Our results demonstrate that sunscreen products are a significant source of metals and inorganic nutrients to coastal waters. The normally low environmental concentrations of some elements (e.g., P) and the toxicity of others (e.g., Pb) could be having a serious adverse effect on marine ecology in the Mediterranean Sea. This risk must not be ignored.

Estuarine sediment resuspension and acidification: Release behaviour of contaminants under different oxidation levels and acid sources.

Carbon dioxide (CO2) Capture and Storage (CCS) is a technology to reduce the emissions of this gas to the atmosphere by sequestering it in geological formations. In the case of offshore storage, unexpected CO2 leakages will acidify the marine environment. Reductions of the pH might be also caused by anthropogenic activities or natural events such as acid spills and dredging operations or storms and floods. Changes in the pH of the marine environment will trigger the mobilisation of elements trapped in contaminated shallow sediments with unclear redox boundary. Trace element (As, Cd, Cr, Cu, Ni, Pb and Zn) release from anoxic and oxic estuarine sediment is analysed and modelled under different laboratory acidification conditions using HNO3 (l) and CO2 (g): acidification at pH = 6.5 as worst-case scenario in events of CO2 leakages and acid spills, and acidification at pH = 7.0 as a seawater scenario under CO2 leakages, acid spills, as well as sediment resuspension. The prediction of metal leaching behaviour appear to require sediment specific and site specific tools. In the present work it is demonstrated that the proposed three in-series reactions model predicts the process kinetics of the studied elements under different simulated environmental conditions (oxidation levels and acid sources). Differences between HNO3 and CO2 acidification are analysed through the influence of the CO2 gas on the ionic competition of the medium. The acidification with CO2 provokes higher released concentrations from the oxic sediment than from the anoxic sediment, except in the case of Zn, which influences the release of the other studied elements. Slight acidification can endanger the aquatic environment through an important mobilisation of contaminants. The obtained prediction of the contaminant release from sediment (kinetic parameters and maximum concentrations) can contribute to the exposure assessment stage for risk management and preincidental planning in accidental CO2 leakages and chemical spills scenarios.

Analysis and modelling of predation on biofilm activated sludge process: Influence on microbial distribution, sludge production and nutrient dosage.

The influence of predation on the biofilm activated sludge (BAS) process is studied using a unified model that incorporates hydrolysis and predation phenomena into the two stages of the BAS system: moving bed biofilm reactor pre-treatment (bacterial-predator stage) and activated sludge (predator stage). The unified model adequately describes the experimental results obtained in a cellulose and viscose full-scale wastewater plant and has been used to evaluate the role and contribution of predator microorganisms towards removal of COD, nutrient requirements, sludge production and microbial distribution. The results indicate that predation is the main factor responsible for the reduction of both nutrient requirements and sludge production. Furthermore, increasing the sludge retention time (SRT) does not influence the total biomass content in the AS reactor of a BAS process in two different industrial wastewater treatments.

An integrated mathematical model for chemical oxygen demand (COD) removal in moving bed biofilm reactors (MBBR) including predation and hydrolysis.

An integrated mathematical model is proposed for modelling a moving bed biofilm reactor (MBBR) for removal of chemical oxygen demand (COD) under aerobic conditions. The composite model combines the following: (i) a one-dimensional biofilm model, (ii) a bulk liquid model, and (iii) biological processes in the bulk liquid and biofilm considering the interactions among autotrophic, heterotrophic and predator microorganisms. Depending on the values for the soluble biodegradable COD loading rate (SCLR), the model takes into account a) the hydrolysis of slowly biodegradable compounds in the bulk liquid, and b) the growth of predator microorganisms in the bulk liquid and in the biofilm. The integration of the model and the SCLR allows a general description of the behaviour of COD removal by the MBBR under various conditions. The model is applied for two in-series MBBR wastewater plant from an integrated cellulose and viscose production and accurately describes the experimental concentrations of COD, total suspended solids (TSS), nitrogen and phosphorous obtained during 14 months working at different SCLRs and nutrient dosages. The representation of the microorganism group distribution in the biofilm and in the bulk liquid allow for verification of the presence of predator microorganisms in the second reactor under some operational conditions.

Metal release from contaminated estuarine sediment under pH changes in the marine environment.

The contaminant release from estuarine sediment due to pH changes was investigated using a modified CEN/TS 14429 pH-dependence leaching test. The test is performed in the range of pH values of 0-14 using deionised water and seawater as leaching solutions. The experimental conditions mimic different circumstances of the marine environment due to the global acidification, carbon dioxide (CO2) leakages from carbon capture and sequestration technologies, and accidental chemical spills in seawater. Leaching test results using seawater as leaching solution show a better neutralisation capacity giving slightly lower metal leaching concentrations than when using deionised water. The contaminated sediment shows a low base-neutralisation capacity (BNCpH 12 = -0.44 eq/kg for deionised water and BNCpH 12 = -1.38 eq/kg for seawater) but a high acid-neutralisation capacity when using deionised water (ANCpH 4 = 3.58 eq/kg) and seawater (ANCpH 4 = 3.97 eq/kg). Experimental results are modelled with the Visual MINTEQ geochemical software to predict metal release from sediment using both leaching liquids. Surface adsorption to iron- and aluminium-(hydr)oxides was applied for all studied elements. The consideration of the metal-organic matter binding through the NICA-Donnan model and Stockholm Humic Model for lead and copper, respectively, improves the former metal release prediction. Modelled curves can be useful for the environmental impact assessment of seawater acidification due to its match with the experimental values.

Evaluation through column leaching tests of metal release from contaminated estuarine sediment subject to CO2 leakages from Carbon Capture and Storage sites.

The pH change and the release of organic matter and metals from sediment, due to the potential CO(2) acidified seawater leakages from a CCS (Carbon Capture and Storage) site are presented. Column leaching test is used to simulate a scenario where a flow of acidified seawater is in contact with recent contaminated sediment. The behavior of pH, dissolved organic carbon (DOC) and metals As, Cd, Cr, Cu, Ni, Pb, Zn, with liquid to solid (L/S) ratio and pH is analyzed. A stepwise strategy using empirical expressions and a geochemical model was conducted to fit experimental release concentrations. Despite the neutralization capacity of the seawater-carbonate rich sediment system, important acidification and releases are expected at local scale at lower pH. The obtained results would be relevant as a line of evidence input of CCS risk assessment, in an International context where strategies to mitigate the climate change would be applied.

Potential influence of CO2 release from a carbon capture storage site on release of trace metals from marine sediment.

One of the main risks of CCS (Carbon Capture and Storage) is CO(2) leakage from a storage site. The influence of CO(2) leakage on trace metals leaching from contaminated marine sediment in a potential storage area (Northern Spain) is addressed using standardized leaching tests. The influence of the pH of the leaching solution on the leachates is evaluated using deionized water, natural seawater and acidified seawater at pH = 5, 6 and 7, obtained by CO(2) bubbling. Equilibrium leaching tests (EN 12457) were performed at different liquid-solid ratios and the results of ANC/BNC leaching test (CEN/TS 15364) were modeled using Visual Minteq. Equilibrium tests gave values of the final pH for all seawater leachates between 7 and 8 due to the high acid neutralization capacity of the sediment. Combining leaching test results and geochemical modeling provided insight in the mechanisms and prediction of trace metals leaching in acidified seawater environment.

Biomarker responsiveness in different tissues of caged Ruditapes philippinarum and its use within an integrated sediment quality assessment.

Biomarkers comprising activities of biotransformation enzymes (ethoxyresorufin-O-deethylase -EROD-, dibenzylfluorescein dealkylase -DBF-, glutathione S-transferase -GST), antioxidant enzymes (glutathione reductase -GR- and glutathione peroxidase -GPX), lipid peroxidation -LPO- and DNA strand breaks were analyzed in the clam Ruditapes philippinarum caged at Cádiz Bay, Santander Bay and Las Palmas de Gran Canaria (LPGC) Port (Spain). Sediments were characterized. Digestive gland was the most sensitive tissue to sediment contamination. In Cádiz Bay, changes in LPO regarding day 0 were related with metals. In LPGC Port, DBF, EROD, and GST activity responses suggested the presence of undetermined contaminants which might have led to DNA damage. In Santander Bay, PAHs were related with EROD activity, organic and metal contamination was found to be associated with GR and GST activities and DNA damage presented significant (p < 0.05) induction. R. philippinarum was sensitive to sediment contamination at biochemical level. Biomarkers allowed chemical exposure and sediment quality assessment.

Sediment-quality assessment using the polychaete Arenicola marina: contamination, bioavailability, and toxicity.

The sediment quality of Cádiz Bay, Las Palmas de Gran Canaria (LPGC) Port, Santander Bay, Algeciras Bay, and Huelva Estuary (Spain) was evaluated by analysing a battery of biochemical biomarkers-activities of biotranformation enzymes ethoxyresorufin O-deethylase [EROD], dibenzylflourescein dealkylase [DBF], and glutathione S-transferase [GST]; activity of antioxidant enzyme glutathione reductase [GR]; and lipid peroxidation [LPO]-in the polychaete Arenicola marina after laboratory sediment exposure. Huelva Estuary polychaetes showed significantly (p < 0.05) enhanced LPO, GST, and EROD activities compared with control lugworms related to metals and presumably polychlorinated biphenyls. EROD activity significant (p < 0.05) induction was associated polycyclic aromatic hydrocarbons after Santander Bay sediment exposure. Nickel appeared to significantly (p < 0.05) induce GR activity and LPO in LPGC Port sediment-exposed organisms. DBF activity significantly (p < 0.05) increased in polychaetes exposed to sediments from sewage-contaminated areas. A. marina was sensitive at the biochemical level. Integration of sediment characterization and biomarker results allowed the identification of polluted sites as well as the cause of possible sediment toxicity.

Prioritization of sediment management alternatives using stochastic multicriteria acceptability analysis.

Decision-making for sediment management is a complex task that requires the consideration of temporal and spatial impacts of several remedial alternatives as well as the associated economic, social and political impact. Multicriteria decision analysis (MCDA) is becoming increasingly recognized as an important environmental management tool that can be used to support the selection of suitable remediation alternatives and prioritization of management units in space and time. This paper proposes an MCDA framework for prioritizing sediment management alternatives. This framework involves identifying of a set of feasible options, as well as defining and evaluating criteria which integrate relevant technical, economic, social and environmental aspects of remedies. The methodology allows an explicit consideration of uncertainty in criteria scores and weights by assigning probability distributions and analyzing subsequent Monte-Carlo simulations. The consideration of different stakeholder simulated values is used to assess the robustness of alternative rankings and to guide the selection of remediation options. An application of this methodology to a case study in the Bay of Santander, Spain, is presented. An assessment is conducted for the case of unknown preferences as well as for hypothetical preferences profiles for four types of stakeholders: Idealist, Politician, Environmentalist and Balanced. The results are used to visualize stakeholder positions and potential disagreements, allowing for the identification of a group of least preferred alternatives for each stakeholder. Stakeholder involvement has the potential to ease the remedy selection process during all stages of the decision-making process and to eventually remedy implementation.

Development of models for predicting toxicity from sediment chemistry by partial least squares-discriminant analysis and counter-propagation artificial neural networks.

There is strong interest in developing tools to link chemical concentrations of contaminants to the potential for observing sediment toxicity that can be used in initial screening-level sediment quality assessments. This paper presents new approaches for predicting toxicity in sediments, based on 10-day survival tests with marine amphipods, from sediment chemistry, by means of the application of Partial Least Squares-Discriminant Analysis (PLS-DA) and Counter-propagation Artificial Neural Networks (CP-ANNs) to large historical databases of chemical and toxicity data. The exploration of the internal structure of the developed models revealed inherent limitations of predicting toxicity from common chemical analyses of bulk contaminant concentrations. However, the results obtained in the validation of these models combined relevant values of non-error classification rate, sensitivity and specificity of, respectively, 76, 87 and 73% with PLS-DA and 92, 75 and 97% with CP-ANNs, outperforming the results reported for previous approaches.

A multicriteria-based methodology for site prioritisation in sediment management.

Decision-making for sediment management is a complex task that incorporates the selections of areas for remediation and the assessment of options for any mitigation required. The application of Multicriteria Analysis (MCA) to rank different areas, according to their need for sediment management, provides a great opportunity for prioritisation, a first step in an integrated methodology that finally aims to assess and select suitable alternatives for managing the identified priority sites. This paper develops a methodology that starts with the delimitation of management units within areas of study, followed by the application of MCA methods that allows ranking of these management units, according to their need for remediation. This proposed process considers not only scientific evidence on sediment quality, but also other relevant aspects such as social and economic criteria associated with such decisions. This methodology is illustrated with its application to the case study area of the Bay of Santander, in northern Spain, highlighting some of the implications of utilising different MCA methods in the process. It also uses site-specific data to assess the subjectivity in the decision-making process, mainly reflected through the assignment of the criteria weights and uncertainties in the criteria scores. Analysis of the sensitivity of the results to these factors is used as a way to assess the stability and robustness of the ranking as a first step of the sediment management decision-making process.

Assessment of Self-Organizing Map artificial neural networks for the classification of sediment quality.

The application of mathematical tools in initial steps of sediment quality assessment frameworks can be useful to provide an integrated interpretation of multiple measured variables. This study reveals that the Self-Organizing Map (SOM) artificial neural network can be an effective tool for the integration of multiple physical, chemical and ecotoxicological variables in order to classify different sites under study according to their similar sediment quality. Sediment samples from 40 sites of 3 estuaries of Cantabria (Spain) were classified with respect to 13 physical, chemical and toxicological variables using the SOM. Results obtained with the SOM, when compared to those of traditional multivariate statistical techniques commonly used in the field of sediment quality (principal component analysis (PCA) and hierarchical cluster analysis (HCA)), provided a more useful classification for further assessment steps. Especially, the powerful visualization tools of the SOM, which offer more information and in an easier way than HCA and PCA, facilitate the task of establishing an order of priority between the distinguished groups of sites depending on their need for further investigations or remediation actions in subsequent management steps.

Sediment quality assessment and dredged material management in Spain: Part I, application of sediment quality guidelines in the Bay of Santander.

Sediments are an essential component of aquatic ecosystems that must be assessed and managed properly. The use of quantitative environmental quality standards derived from consideration of sediment quality guidelines (SQGs) can be effective as part of a tiered risk assessment approach. In Part I of this 2-part paper addressing sediment quality assessment and dredged material management in Spain, different SQG methods are used to evaluate sediment quality in the Bay of Santander, located in the Cantabric Sea along the northern coast of Spain, and to guide development of empirically derived SQGs for marine sediments. The results of the study indicate a great heterogeneity of SQGs, both with regard to the numeric values for a particular chemical and the number of substances for which SQGs have been derived. The analysis highlights the scarce development of empirical SQGs for priority substances identified in current European Union water policy. Nonetheless, the application of SQGs makes it possible to classify different zones of sediment quality in the Bay of Santander. Part II of this 2-part paper considers the environmental impacts of dredged material disposal. Legislation and criteria used to regulate dredged material disposal at sea in different European countries are reviewed, and action levels derived by different countries were used to evaluate management of dredged sediments from Cádiz Bay, located on the South Atlantic coast of Spain.

Sediment quality assessment and dredged material management in Spain: Part II, analysis of action levels for dredged material management and application to the Bay of Cádiz.

When sediments are removed from aquatic bottoms, they turn into dredged material that must be managed, taking into account its environmental impact. In Part II of this 2-part paper addressing sediment quality assessment and dredged material management in Spain, legislation and criteria used to regulate dredged material disposal at sea in different European countries are reviewed, as are action levels (ALs) derived by different countries used to evaluate management of dredged sediments from Cádiz Bay located on the South Atlantic coast of Spain. Comparison of ALs established for dredged material disposal by different countries reveals orders of magnitude differences in the values established for the same chemical. In Part I of this 2-part paper, review of different sediment quality guideline (SQG) methods used to support sediment quality assessments indicated a great heterogeneity of SQGs, both with regard to the numeric values for a particular chemical and the number of substances for which SQGs have been derived. The analysis highlighted the absence of SQGs for priority substances identified in current European Union water policy. Here, in Part II, the ALs are applied to dredged sediments from Cádiz Bay (South Atlantic coast of Spain), evidencing that the heterogeneity of ALs implemented in the reviewed countries could determine different management strategies. The application of other measurements such as bioassays might offer information useful in identifying a cost-effective management option in a decision-making framework, especially for dredged material with intermediate chemical concentrations.

Influence of the organic compounds on the ecotoxicity in the treatment of foundry sludge and olive mill waste.

The study of the ecotoxicity in two industrial waste materials and the relationships with the organic parameters has been conducted. Foundry sludge and olive mill waste have been used as industrial waste materials with organic or mixed character. Stabilisation/solidification (S/S) and advanced oxidation (AOP) processes have been carried out in order to treat both foundry sludge and olive mill waste. Analysis of ecotoxicity, total organic carbon, COD and phenol index have been evaluated in the untreated waste and end-products. The results of the treated samples allow obtaining the best formulations in both processes. The best formulations in the immobilisation process have been obtained with Portland cement and black carbon, activated carbon or foundry sand ashes. In the AOP process, ozone concentrations above 35 mg/l and reaction times equal to 120 minutes have been the optimal variables. The relationships between the organic parameters and the ecotoxicity of the samples have been studied in this paper. Furthermore, the global organic parameters have been studied in relation to the phenolic compounds. Lineal and logarithmic expressions have been obtained between the total organic carbon and phenol index and the ecotoxicity of the samples related to the organic parameters, respectively. Ecotoxicity of the samples with Vibrio fischeri is recommended as a very promising biotest for the study of the characterisation and the evaluation of the treatment of organic and mixed character waste and total organic carbon is recommended as global organic parameter in the treatment of foundry sludge.

Validated analytical strategy for the determination of polycyclic aromatic compounds in marine sediments by liquid chromatography coupled with diode-array detection and mass spectrometry.

The aim of this work was to optimise and validate the experimental conditions for the analysis of 20 polycyclic aromatic compounds (PACs) [19 polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophene as polycyclic aromatic sulphur heterocycle (PASH)] in marine sediments by reversed-phase high-performance liquid chromatography (LC) coupled to photodiode array detection (DAD) and to mass spectrometry (MS). The LC-MS interface used was atmospheric pressure chemical ionization (APCI) in the positive ion mode. The operational parameters of the APCI interface and MS detection, such as organic modifier, fragmentation voltage, gain, vaporizer temperature, corona current, capillary voltage, drying gas (N2) and nebulizer pressure, were studied. The sediments were subjected to microwave-assisted solvent extraction (MAE) and clean-up by solid-phase extraction (SPE). The relevance of the selected PACs lies in the fact that 16 PACs are classified by the US Environmental Protection Agency as priority pollutants; 17 PACs are detected in the Prestige oil spill; and 8 PACs are included in the priority substance list of the EU water policy. Recoveries from 47% to 102% were obtained for SRM 1944 certified reference sediment. The limits of quantitation were lower than 100 ngg(-1) dry weight for most PACs, and good precision was achieved.