• Energy Research

Reliable monitoring of microbial and water quality parameters in freshwater ecosystems (either natural or human-made) is of capital importance for improving both the management of water resources and the assessment of microbially-driven bio-geo-chemical processes. In this context, bioelectrochemical systems (BES), such as microbial three-cell electrodes (M3C), are very promising devices for their use as biosensors. However, current experiences on the use of BES-based devices for biosensing purposes are almost exclusively limited to water-saturated environments. This limitation hampers the use of this technology for a wider range of applications where the biosensor may work discontinuously (such as discontinuously saturated ecosystems). Discontinuous operation of M3C-based biosensors creates an electric current peak immediately after the reconnection of the system due to electron accumulation, in a process known as biocapacitance. The present work aimed at quantifying the bioindication potential of biocapacitance for the assessment of key ecosystem parameters such as microbial metabolic activity and biomass, as well as organic matter concentration. Significant linear regression coefficients (R2 > 0.9) were found for all combinations of parameters tested. Moreover, for most of the ecological parameters assessed, an electric charge accumulation of 1-5 min (biocapacitance elapsed time) and discharge of 5 min was enough to get reliable information. In conclusion, we have demonstrated for the first time that biocapacitance in M3C-based biosensors can be used as a proxy parameter for the assessment of microbial activity, microbial biomass and organic matter concentration in a model nature-based ecosystem.

Reliable monitoring of microbial and water quality parameters in freshwater ecosystems (either natural or human-made) is of capital importance for improving both the management of water resources and the assessment of microbially-driven bio-geo-chemical processes. In this context, bioelectrochemical systems (BES), such as microbial three-cell electrodes (M3C), are very promising devices for their use as biosensors. However, current experiences on the use of BES-based devices for biosensing purposes are almost exclusively limited to water-saturated environments. This limitation hampers the use of this technology for a wider range of applications where the biosensor may work discontinuously (such as discontinuously saturated ecosystems). Discontinuous operation of M3C-based biosensors creates an electric current peak immediately after the reconnection of the system due to electron accumulation, in a process known as biocapacitance. The present work aimed at quantifying the bioindication potential of biocapacitance for the assessment of key ecosystem parameters such as microbial metabolic activity and biomass, as well as organic matter concentration. Significant linear regression coefficients (R2 > 0.9) were found for all combinations of parameters tested. Moreover, for most of the ecological parameters assessed, an electric charge accumulation of 1-5 min (biocapacitance elapsed time) and discharge of 5 min was enough to get reliable information. In conclusion, we have demonstrated for the first time that biocapacitance in M3C-based biosensors can be used as a proxy parameter for the assessment of microbial activity, microbial biomass and organic matter concentration in a model nature-based ecosystem.

Treatment wetlands (TW) operated as bioelectrochemical systems (BES-TW) provide a higher degree of treatment than conventional TW. Yet, the fundamental processes or mechanisms for the envisaged better performance of BES-TW over conventional TW remains poorly understood. This work aimed to determine to which extent microbial activity enhancement could be the reason behind this treatment performance increase. To this purpose, pilot-scale horizontal sub-surface flow BES-TW operated under three different configurations were continuously fed with real urban wastewater. BES-TW were evaluated for COD and ammonia removal efficiency, and two techniques of microbial activity assessment were applied. Configurations, tested in duplicate, were: control TWs without electrodes (C-TW), TWs operated as microbial fuel cells (MFC-TW), and TWs operated as microbial electrolysis cells (MEC-TW). Microbial activity was assessed by measuring the enzymatic activity (EA) (FDA hydrolysis technique) and the aerobic activity (AA) (estimated through respirometry). Results showed that BES-TW outperformed C-TW in terms of both microbial activity enhancement and contaminants removal efficiency, especially in the case of MEC-TW. More precisely, this configuration showed an average improvement of 17%, and 56% in COD removal and EA efficiencies, respectively, compared to C-TW. Regarding AA activity, although MEC-TW seemed to outperform the rest of the configurations, differences were not statistically significant. This work demonstrates that TWs operated as BES increase the overall enzymatic activity of the treatment bed and this, in turn, is the leading cause to a higher degree of treatment performance.

Treatment wetlands (TW) operated as bioelectrochemical systems (BES-TW) provide a higher degree of treatment than conventional TW. Yet, the fundamental processes or mechanisms for the envisaged better performance of BES-TW over conventional TW remains poorly understood. This work aimed to determine to which extent microbial activity enhancement could be the reason behind this treatment performance increase. To this purpose, pilot-scale horizontal sub-surface flow BES-TW operated under three different configurations were continuously fed with real urban wastewater. BES-TW were evaluated for COD and ammonia removal efficiency, and two techniques of microbial activity assessment were applied. Configurations, tested in duplicate, were: control TWs without electrodes (C-TW), TWs operated as microbial fuel cells (MFC-TW), and TWs operated as microbial electrolysis cells (MEC-TW). Microbial activity was assessed by measuring the enzymatic activity (EA) (FDA hydrolysis technique) and the aerobic activity (AA) (estimated through respirometry). Results showed that BES-TW outperformed C-TW in terms of both microbial activity enhancement and contaminants removal efficiency, especially in the case of MEC-TW. More precisely, this configuration showed an average improvement of 17%, and 56% in COD removal and EA efficiencies, respectively, compared to C-TW. Regarding AA activity, although MEC-TW seemed to outperform the rest of the configurations, differences were not statistically significant. This work demonstrates that TWs operated as BES increase the overall enzymatic activity of the treatment bed and this, in turn, is the leading cause to a higher degree of treatment performance.

Sediment microbial fuel cell (sMFC) represents a variation of the typical configuration of a MFC in which energy can be harvested via naturally occurring electropotential differences. Moreover, constructed wetlands show marked redox gradients along the depth which could be exploited for energy production via sMFC. In spite of the potential application of sMFC to constructed wetlands, there is almost no published work on the topic. The main objective of the present work was to define the best operational and design conditions of sub-surface flow constructed wetlands (SSF CWs) under which energy production with microbial fuel cells (MFCs) would be maximized. To this aim, a pilot plant based on SSF CW treating domestic sewage was operated during six months. Redox gradients along the depth of SSF CWs were determined as function of hydraulic regime (continuous vs discontinuous) and the presence of macrophytes in two sampling campaigns (after three and six months of plant operation). Redox potential (EH) within the wetlands was analysed at 5, 15 and 25 cm. Results obtained indicated that the maximum redox gradient was between the surface and the bottom of the bed for continuous planted wetlands (407.7 ± 73.8 mV) and, to a lesser extent, between the surface and the middle part of the wetland (356.5 ± 76.7 mV). Finally, the maximum redox gradients obtained for planted wetlands operated under continuous flow regime would lead to a power production of about 16 mW/m(2).

Sediment microbial fuel cell (sMFC) represents a variation of the typical configuration of a MFC in which energy can be harvested via naturally occurring electropotential differences. Moreover, constructed wetlands show marked redox gradients along the depth which could be exploited for energy production via sMFC. In spite of the potential application of sMFC to constructed wetlands, there is almost no published work on the topic. The main objective of the present work was to define the best operational and design conditions of sub-surface flow constructed wetlands (SSF CWs) under which energy production with microbial fuel cells (MFCs) would be maximized. To this aim, a pilot plant based on SSF CW treating domestic sewage was operated during six months. Redox gradients along the depth of SSF CWs were determined as function of hydraulic regime (continuous vs discontinuous) and the presence of macrophytes in two sampling campaigns (after three and six months of plant operation). Redox potential (EH) within the wetlands was analysed at 5, 15 and 25 cm. Results obtained indicated that the maximum redox gradient was between the surface and the bottom of the bed for continuous planted wetlands (407.7 ± 73.8 mV) and, to a lesser extent, between the surface and the middle part of the wetland (356.5 ± 76.7 mV). Finally, the maximum redox gradients obtained for planted wetlands operated under continuous flow regime would lead to a power production of about 16 mW/m(2).

The removal of organic micropollutants (OMPs) has been investigated in constructed wetlands (CWs) operated as bioelectrochemical systems (BES). The operation of CWs as BES (CW-BES), either in the form of microbial fuel cells (MFC) or microbial electrolysis cells (MEC), has only been investigated in recent years. The presented experiment used CW meso-scale systems applying a realistic horizontal flow regime and continuous feeding of real urban wastewater spiked with four OMPs (pharmaceuticals), namely carbamazepine (CBZ), diclofenac (DCF), ibuprofen (IBU) and naproxen (NPX). The study evaluated the removal efficiency of conventional CW systems (CW-control) as well as CW systems operated as closed-circuit MFCs (CW-MFCs) and MECs (CW-MECs). Although a few positive trends were identified for the CW-BES compared to the CW-control (higher average CBZ, DCF and NPX removal by 10-17% in CW-MEC and 5% in CW-MFC), these proved to be not statistically significantly different. Mesoscale experiments with real wastewater could thus not confirm earlier positive effects of CW-BES found under strictly controlled laboratory conditions with synthetic wastewaters. Chemosphere, 38 pages, 1 figure, 4 tables (2 figures and 6 tables in Supplementary Information)