Continuous Electrochemical Reduction of CO2 to Formate: Comparative Study of the Influence of the Electrode Configuration with Sn and Bi-Based Electrocatalysts.

Climate change has become one of the most important challenges in the 21st century, and the electroreduction of CO2 to value-added products has gained increasing importance in recent years. In this context, formic acid or formate are interesting products because they could be used as raw materials in several industries as well as promising fuels in fuel cells. Despite the great number of studies published in the field of the electrocatalytic reduction of CO2 to formic acid/formate working with electrocatalysts of different nature and electrode configurations, few of them are focused on the comparison of different electrocatalyst materials and electrode configurations. Therefore, this work aims at presenting a rigorous and comprehensive comparative assessment of different experimental data previously published after many years of research in different working electrode configurations and electrocatalysts in a continuous mode with a single pass of the inputs through the reactor. Thus, the behavior of the CO2 electroreduction to formate is compared operating with Sn and Bi-based materials under Gas Diffusion Electrodes (GDEs) and Catalyst Coated Membrane Electrodes (CCMEs) configurations. Considering the same electrocatalyst, the use of CCMEs improves the performance in terms of formate concentration and energy consumption. Nevertheless, higher formate rates can be achieved with GDEs because they allow operation at higher current densities of up to 300 mA·cm-2. Bi-based-GDEs outperformed Sn-GDEs in all the figures of merit considered. The comparison also highlights that in CCME configuration, the employ of Bi-based-electrodes enhanced the behavior of the process, increasing the formate concentration by 35% and the Faradaic efficiency by 11%.

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.