A Self-Supported CuO/Cu Nanowire Electrode as Highly Efficient Sensor for COD Measurement.

A self-supported CuO/Cu nanowire electrode (CuO/CuNWE), which was prepared by annealing Cu nanowires to form a porous Cu nanowire electrode (CuNWE) and then anodizing the as-prepared CuNWE in alkaline medium to generate Cu(OH)2 nanowires followed by calcination, was employed for chemical oxygen demand (COD) determination using cyclic voltammetry (CV). The structure and electrochemical behavior of the CuO/CuNWE were investigated by scanning electron microscopy, X-ray diffraction, and CV. The results indicated that the as-synthesized CuO/CuNWE, in which CuO nanowires with a length of several micrometers and a diameter of 100 to 300 nm could be found, was stable in alkaline medium and more electrocatalytically active for oxidizing a wide range of organic compounds in comparison with the CuNWE. Under optimized alkaline concentration and scan rate, the CuO/CuNWE exhibited a good performance for COD measurement, with a linear range of 5 to 1153 mg L-1, a sensitivity of 2.46× 10-2 mA /(mg L-1), and a detection limit of about 2.3 mg L-1. In addition, an excellent correlation was observed in COD values obtained by our method and the classic dichromate method (r = 0.9995, p < 0.01, n = 11). Finally, our method was successfully used to measure the COD values in real water samples, showing great potential for practical application in water pollution control.

Implementation of an automatic and miniature on-line multi-parameter water quality monitoring system and experimental determination of chemical oxygen demand and ammonia-nitrogen.

An automatic, miniature and multi-parameter on-line water quality monitoring system based on a micro-spectrometer is designed and implemented. The system is integrated with the flow-batch analysis and spectrophotometric detection method. The effectiveness of the system is tested by measuring chemical oxygen demand (COD) and ammonia-nitrogen in water. The results show that the modified system provides a cost-effective, sensitive, reproducible and reliable way to measure COD and ammonia-nitrogen in water samples with automatic operation and low toxic chemical consumption. In addition, the experiment results show that the relative error of the system is less than 10%, the limit of detection is 2 mg/L COD and 0.032 mg/L ammonia-nitrogen, respectively, and the relative standard deviation was 6.6% at 15.0 mg/L COD (n = 7) and 5.0% at 0.300 mg/L ammonia-nitrogen (n = 7). Results from the newly designed system are consistent with the data collected through the Chinese national standard analysis methods.

A Novel Thermal Sensor for the Sensitive Measurement of Chemical Oxygen Demand.

A novel rapid methodology for determining the chemical oxygen demand (COD) based on a thermal sensor with a flow injection analysis system was proposed and experimentally validated. The ability of this sensor to detect and monitor COD was based on the degree of enthalpy increase when sodium hypochlorite reacted with the organic content in water samples. The measurement results were correlated with COD and were compared against the conventional method using potassium dichromate. The assay required only 5-7 min rather than the 2 h required for evaluation by potassium dichromate. The linear range was 5-1000 mg/L COD, and the limit of detection was very low, 0.74 mg/L COD. Moreover, this method exhibited high tolerance to chloride ions; 0.015 mol/L chloride ions had no influence on the response. Finally, the sensor was used to detect the COD of different water samples; the results were verified by the standard dichromate method.

Yeast-based Biochemical Oxygen Demand Sensors Using Gold-modified Boron-doped Diamond Electrodes.

A gold nanoparticle modified boron-doped diamond electrode was developed as a transducer for biochemical oxygen demand (BOD) measurements. Rhodotorula mucilaginosa UICC Y-181 was immobilized in a sodium alginate matrix, and used as a biosensing agent. Cyclic voltammetry was applied to study the oxygen reduction reaction at the electrode, while amperometry was employed to detect oxygen, which was not consumed by the microorganisms. The optimum waiting time of 25 min was observed using 1-mm thickness of yeast film. A comparison against the system with free yeast cells shows less sensitivity of the current responses with a linear dynamic range (R(2) = 0.99) of from 0.10 mM to 0.90 mM glucose (equivalent to 10 - 90 mg/L BOD) with an estimated limit of detection of 1.90 mg/L BOD. However, a better stability of the current responses could be achieved with an RSD of 3.35%. Moreover, less influence from the presence of copper ions was observed. The results indicate that the yeast-immobilized BOD sensors is more suitable to be applied in a real condition.

Dissolved Oxygen Sensor in Animal-Borne Instruments: An Innovation for Monitoring the Health of Oceans and Investigating the Functioning of Marine Ecosystems.

The current decline in dissolved oxygen concentration within the oceans is a sensitive indicator of the effect of climate change on marine environment. However the impact of its declining on marine life and ecosystems' health is still quite unclear because of the difficulty in obtaining in situ data, especially in remote areas, like the Southern Ocean (SO). Southern elephant seals (Mirounga leonina) proved to be a relevant alternative to the traditional oceanographic platforms to measure physical and biogeochemical structure of oceanic regions rarely observed. In this study, we use a new stage of development in biologging technology to draw a picture of dissolved oxygen concentration in the SO. We present the first results obtained from a dissolved oxygen sensor added to Argos CTD-SRDL tags and deployed on 5 female elephant seals at Kerguelen. From October 2010 and October 2011, 742 oxygen profiles associated with temperature and salinity measurements were recorded. Whether a part of the data must be considered cautiously, especially because of offsets and temporal drifts of the sensors, the range of values recorded was consistent with a concomitant survey conducted from a research vessel (Keops-2 project). Once again, elephant seals reinforced the relationship between marine ecology and oceanography, delivering essential information about the water masses properties and the biological status of the Southern Ocean. But more than the presentation of a new stage of development in animal-borne instrumentation, this pilot study opens a new field of investigation in marine ecology and could be enlarged in a near future to other key marine predators, especially large fish species like swordfish, tuna or sharks, for which dissolved oxygen is expected to play a crucial role in distribution and behaviour.

A new flat sheet membrane bioreactor hybrid system for advanced treatment of effluent, reverse osmosis pretreatment and fouling mitigation.

This paper introduces a new hybrid electro membrane bioreactor (HEMBR) for reverse osmosis (RO) pretreatment and advanced treatment of effluent by simultaneously integrating electrical coagulation (EC) with a membrane bioreactor (MBR) and its performance was compared with conventional MBR. Experimental results and their statistical analysis showed removal efficiency for suspended solids (SS) of almost 100% for both reactors. HEMBR removal of chemical oxygen demand (COD) improved by 4% and membrane fouling was alleviated according to transmembrane pressure (TMP). The average silt density index (SDI) of HEMBR permeate samples was slightly better indicating less RO membrane fouling. Moreover, based on the SVI comparison of two reactor biomass samples, HEMBR showed better settling characteristics which improved the dewaterability and filterability of the sludge. Analysis the change of membrane surfaces and the cake layer formed over them through field emission scanning electron microscopy (FESEM) and X-ray fluorescence spectrometer (XRF) were also discussed.

Effect of reactor configuration on performance during anaerobic treatment of low strength wastewater.

The efficiency of the up-flow anaerobic sludge blanket (UASB) reactor is quite low for the treatment of low strength wastewaters (LSWs) due to less biogas production leading to poor mixing. LSW may be treated efficiently by providing adequate mixing in the UASB reactor when gas production is low, and sufficient mixing can be achieved by modifying reactor geometry. Hence, modifying UASB reactor geometry for enhanced mixing and evaluating its performance for the treatment of LSWs would be a worthwhile effort. In the present study, UASB reactor configuration was modified by providing a vertical baffle along the height to promote mixing of reactor contents, and is termed as modified UASB (MUASB). The performance of an on-site pilot-scale MUASB reactor was evaluated for 375 days under ambient condition for the treatment of municipal sewage as LSW and compared with that of the conventional UASB and hybrid UASB (HUASB) reactors. The MUASB reactor showed better performance in terms of chemical oxygen demand (COD) removal efficiency as compared with UASB and HUASB reactors during this study. At 4 h hydraulic retention time, the total COD removal efficiency of UASB and HUASB reactors was 53.7% and 61%, respectively, which were much lower than the total COD removal efficiency of the MUASB reactor (72.7%). The better performance observed in the MUASB reactor is possibly due to improved mixing. Depth-wise analysis of reactor liquid showed that better mixing in the MUASB reactor enhances the contact of wastewater with biomass, which contributes to the improved treatment efficiency. It seems that MUASB holds promise for LSW treatment.

Development and testing of a fully gravitational submerged anaerobic membrane bioreactor for wastewater treatment.

A gravity-operated submerged anaerobic membrane bioreactor (SAnMBR) was set up in order to test its principle of operation as an alternative to conventional pumped permeation of the membrane. This operating mode allowed the membrane flux rate to be measured accurately whilst maintaining a constant transmembrane pressure (TMP), and allowed small transient variations in the flux rate to be observed. The reactor was operated at 36°C for a period of 115 days using a nutrient-balanced synthetic substrate with a high suspended solids concentration. Membrane cleaning was in situ by a gas scouring system using recirculation of headspace biogas. With an initial TMP of 7.0 kPa, the membrane flux slowly decreased due to membrane fouling and had not reached a constant value by day 71. The results indicated that the system was still acclimatizing up to 50 days after start-up; but from that point onwards, performance parameters became much more stable. A constant flux of 2.2 L m(-2) h(-1) was achieved over the last 45 days after the TMP was reduced to 2.3 kPa. The stable flux was maintained over this period and the loading raised to 1 g COD L(-1) d(-1) by increasing the influent strength. Under these conditions, the average chemical oxygen demand removal efficiency was 96% and the specific methane potential was 0.31 L CH4 g(-1) COD removed.

One-pot synthesis of 3-dimensional reduced graphene oxide-based hydrogel as support for microbe immobilization and BOD biosensor preparation.

We report a hydrothermal method to prepare reduced graphene oxide (rGO)-based hydrogel (Gel(rGONR)), using neutral red (NR) to mediate the assembly of rGO sheets and tune the pore size of Gel(rGONR). A series of techniques including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy and BET were employed to characterize the physico-chemical properties of Gel(rGONR). A large pore size of up to 20 µm and interconnected porous structure of Gel(rGONR) were obtained. Gel(rGONR) was used as a support for immobilizing microbe (denoted as Gel(rGONR-M)), which showed ~3.3 times more load mass of microbe than commonly used supports (i.e., activated carbon and carbon fiber felt) and 2.5 times higher biodegradation efficiency (BE) than carbon fiber felt. Further use of Gel(rGONR-M) as a biocatalyst for establishing a BOD biosensor exhibits a linear range of 2-64 mg O L(-1) and a detection limit 0.4 mg O L(-1) for glucose-glutamic acid (GGA). Moreover, our proposed BOD detection strategy shows a long-term viability over one year and stability up to 2 months with a relative standard deviation of 2.1%. Our results demonstrated the great potential of employing Gel(rGONR) as a microbe-immobilization support for biosensor development.

Analytical applications of microbial fuel cells. Part I: Biochemical oxygen demand.

Microbial fuel cells (MFCs) are bio-electrochemical devices, where usually the anode (but sometimes the cathode, or both) contains microorganisms able to generate and sustain an electrochemical gradient which is used typically to generate electrical power. In the more studied set-up, the anode contains heterotrophic bacteria in anaerobic conditions, capable to oxidize organic molecules releasing protons and electrons, as well as other by-products. Released protons could reach the cathode (through a membrane or not) whereas electrons travel across an external circuit originating an easily measurable direct current flow. MFCs have been proposed fundamentally as electric power producing devices or more recently as hydrogen producing devices. Here we will review the still incipient development of analytical uses of MFCs or related devices or set-ups, in the light of a non-restrictive MFC definition, as promising tools to asset water quality or other measurable parameters. An introduction to biological based analytical methods, including bioassays and biosensors, as well as MFCs design and operating principles, will also be included. Besides, the use of MFCs as biochemical oxygen demand sensors (perhaps the main analytical application of MFCs) is discussed. In a companion review (Part 2), other new analytical applications are reviewed used for toxicity sensors, metabolic sensors, life detectors, and other proposed applications.

Effects of Operating Parameters on Measurements of Biochemical Oxygen Demand Using a Mediatorless Microbial Fuel Cell Biosensor.

The conventional Biochemical Oxygen Demand (BOD) method takes five days to analyze samples. A microbial fuel cell (MFC) may be an alternate tool for rapid BOD determination in water. However, a MFC biosensor for continuous BOD measurements of water samples is still unavailable. In this study, a MFC biosensor inoculated with known mixed cultures was used to determine the BOD concentration. Effects of important parameters on establishing a calibration curve between the BOD concentration and output signal from the MFC were evaluated. The results indicate monosaccharides were good fuel, and methionine, phenylalanine, and ethanol were poor fuels for electricity generation by the MFC. Ions in the influent did not significantly affect the MFC performance. CN(-) in the influent could alleviate the effect of antagonistic electron acceptors on the MFC performance. The regression equation for BOD concentration and current density of the biosensor was y = 0.0145x + 0.3317. It was adopted to measure accurately and continuously the BOD concentration in actual water samples at an acceptable error margin. These results clearly show the developed MFC biosensor has great potential as an alternative BOD sensing device for online measurements of wastewater BOD.

Application of an online-biomass sensor in an optical multisensory platform prototype for growth monitoring of biotechnical relevant microorganism and cell lines in single-use shake flasks.

In the context of this work we evaluated a multisensory, noninvasive prototype platform for shake flask cultivations by monitoring three basic parameters (pH, pO2 and biomass). The focus lies on the evaluation of the biomass sensor based on backward light scattering. The application spectrum was expanded to four new organisms in addition to E. coli K12 and S. cerevisiae [1]. It could be shown that the sensor is appropriate for a wide range of standard microorganisms, e.g., L. zeae, K. pastoris, A. niger and CHO-K1. The biomass sensor signal could successfully be correlated and calibrated with well-known measurement methods like OD600, cell dry weight (CDW) and cell concentration. Logarithmic and Bleasdale-Nelder derived functions were adequate for data fitting. Measurements at low cell concentrations proved to be critical in terms of a high signal to noise ratio, but the integration of a custom made light shade in the shake flask improved these measurements significantly. This sensor based measurement method has a high potential to initiate a new generation of online bioprocess monitoring. Metabolic studies will particularly benefit from the multisensory data acquisition. The sensor is already used in labscale experiments for shake flask cultivations.

A new highly sensitive method to assess respiration rates and kinetics of natural planktonic communities by use of the switchable trace oxygen sensor and reduced oxygen concentrations.

Oxygen respiration rates in pelagic environments are often difficult to quantify as the resolutions of our methods for O2 concentration determination are marginal for observing significant decreases during bottle incubations of less than 24 hours. Here we present the assessment of a new highly sensitive method, that combine Switchable Trace Oxygen (STOX) sensors and all-glass bottle incubations, where the O2 concentration was artificially lowered. The detection limit of respiration rate by this method is inversely proportional to the O2 concentration, down to <2 nmol L(-1) h(-1) for water with an initial O2 concentration of 500 nmol L(-1). The method was tested in Danish coastal waters and in oceanic hypoxic waters. It proved to give precise measurements also with low oxygen consumption rates (∼7 nmol L(-1) h(-1)), and to significantly decrease the time required for incubations (≤14 hours) compared to traditional methods. This method provides continuous real time measurements, allowing for a number of diverse possibilities, such as modeling the rate of oxygen decrease to obtain kinetic parameters. Our data revealed apparent half-saturation concentrations (Km values) one order of magnitude lower than previously reported for marine bacteria, varying between 66 and 234 nmol L(-1) O2. Km values vary between different microbial planktonic communities, but our data show that it is possible to measure reliable respiration rates at concentrations ∼0.5-1 µmol L(-1) O2 that are comparable to the ones measured at full air saturation.

The potential applications of real-time monitoring of water quality in a large shallow lake (Lake Taihu, China) using a chromophoric dissolved organic matter fluorescence sensor.

This study presents results from field surveys performed over various seasons in a large, eutrophic, shallow lake (Lake Taihu, China) using an in situ chromophoric dissolved organic matter (CDOM) fluorescence sensor as a surrogate for other water quality parameters. These measurements identified highly significant empirical relationships between CDOM concentration measured using the in situ fluorescence sensor and CDOM absorption, fluorescence, dissolved organic carbon (DOC), chemical oxygen demand (COD) and total phosphorus (TP) concentrations. CDOM concentration expressed in quinine sulfate equivalent units, was highly correlated with the CDOM absorption coefficient (r(2) = 0.80, p < 0.001), fluorescence intensities (Ex./Em. 370/460 nm) (r(2) = 0.91, p < 0.001), the fluorescence index (r(2) = 0.88, p < 0.001) and the humification index (r(2) = 0.78, p < 0.001), suggesting that CDOM concentration measured using the in situ fluorescence sensor could act as a substitute for the CDOM absorption coefficient and fluorescence measured in the laboratory. Similarly, CDOM concentration was highly correlated with DOC concentration (r(2) = 0.68, p < 0.001), indicating that in situ CDOM fluorescence sensor measurements could be a proxy for DOC concentration. In addition, significant positive correlations were found between laboratory CDOM absorption coefficients and COD (r(2) = 0.83, p < 0.001), TP (r(2) = 0.82, p < 0.001) concentrations, suggesting a potential further application for the real-time monitoring of water quality using an in situ CDOM fluorescence sensor.

WO3/W nanopores sensor for chemical oxygen demand (COD) determination under visible light.

A sensor of a WO3 nanopores electrode combined with a thin layer reactor was proposed to develop a Chemical Oxygen Demand (COD) determination method and solve the problem that the COD values are inaccurately determined by the standard method. The visible spectrum, e.g., 420 nm, could be used as light source in the sensor we developed, which represents a breakthrough by limiting of UV light source in the photoelectrocatalysis process. The operation conditions were optimized in this work, and the results showed that taking NaNO3 solution at the concentration of 2.5 mol·L(-1) as electrolyte under the light intensity of 214 µW·cm(-2) and applied bias of 2.5 V, the proposed method is accurate and well reproducible, even in a wide range of pH values. Furthermore, the COD values obtained by the WO3 sensor were fitted well with the theoretical COD value in the range of 3-60 mg·L(-1) with a limit value of 1 mg·L(-1), which reveals that the proposed sensor may be a practical device for monitoring and controlling surface water quality as well as slightly polluted water.

Inoculum selection to enhance performance of a microbial fuel cell for electricity generation during wastewater treatment.

Experiments were designed to evaluate the influence of various anaerobic inoculums to enhance microbial fuel cell (MFC) performance utilizing tannery wastewater as substrate. Three bacterial electrogenic strains, tolerant to tannery environment, were isolated from soil contaminated with tannery waste and tannery wastewater was inoculated with these monotypes and mixed consortia of three bacterial strains in different MFCs. Comparative analysis was made by treating the tannery wastewater with foreign microbial consortia (activated sludge inoculum) and with only natural habitat microbes already present in plain wastewater. It was observed that inoculum contributes great effect on the MFC performance. Among the studied inoculation strategies, mixed electrogenic strain inocula enabled higher current yield along with concurrent substrate removal efficiency. On the contrary, plain wastewater resulted in relatively low efficiency.

Factors affecting the performance of a single-chamber microbial fuel cell-type biological oxygen demand sensor.

Microbial fuel cells (MFCs) are devices that exploit microorganisms as biocatalysts to degrade organic matter or sludge present in wastewater (WW), and thereby generate electricity. We developed a simple, low-cost single-chamber microbial fuel cell (SCMFC)-type biochemical oxygen demand (BOD) sensor using carbon felt (anode) and activated sludge, and demonstrated its feasibility in the construction of a real-time BOD measurement system. Further, the effects of anodic pH and organic concentration on SCMFC performance were examined, and the correlation between BOD concentration and its response time was analyzed. Our results demonstrated that the SCMFC exhibited a stable voltage after 132 min following the addition of synthetic WW (BOD concentration: 200 mg/L). Notably, the response signal increased with an increase in BOD concentration (range: 5-200 mg/L) and was found to be directly proportional to the substrate concentration. However, at higher BOD concentrations (>120 mg/L) the response signal remained unaltered. Furthermore, we optimized the SCMFC using synthetic WW, and tested it with real WW. Upon feeding real WW, the BOD values exhibited a standard deviation from 2.08 to 8.3% when compared to the standard BOD5 method, thus demonstrating the practical applicability of the developed system to real treatment effluents.

Bioelectronic tongue and multivariate analysis: a next step in BOD measurements.

Seven biosensors based on different semi-specific and universal microorganisms were constructed for biochemical oxygen demand (BOD) measurements in various synthetic industrial wastewaters. All biosensors were calibrated using OECD synthetic wastewater and the resulting calibration curves were used in the calculations of the sensor-BOD values for all biosensors. In addition, the output signals of all biosensors were analyzed as a bioelectronic tongue and comprehensive multivariate data analysis was applied to extract qualitative and quantitative information from the samples. In the case of individual biosensor measurements, most accurate result was gained when semi-specific biosensor was applied to analyze sample specific to that biosensor. Universal biosensors or biosensors semi-specific to other samples underestimated the BOD7 of the sample 10-25%. PLS regression method was used for the multivariate calibration of the biosensor array. The calculated sensor-BOD values differed from BOD7 less than 5.6% in all types of samples. By applying PCA and using three first principal components, giving 99.66% of variation, it was possible to differentiate samples by their compositions.

Investigation on the application of titania nanorod arrays to the determination of chemical oxygen demand.

In the present paper, the TiO2 nanorod arrays electrode was developed as a sensor for the determination of chemical oxygen demand (COD) based on a photoelectrochemical degradation principle. Effects of common parameters, such as applied potential, light intensity and pH on its analytical performance were investigated. Under the optimized conditions, the nanorod arrays electrode was successfully applied in the COD determination for both synthetic and real samples. In the COD determination, the proposed method can achieve a practical detection limit of 18.3mgL(-1) and a linear range of 20-280mgL(-1). Furthermore, the results obtained by the proposed method were well correlated with those obtained using the conventional (i.e., dichromate) COD determination method. The main advantages of this COD determination method were its simplicity, long term stability and environmental friendly (corrosive and toxic reagents not consumed). This work would open a new application area (COD determination) of the TiO2 nanorod arrays.

Sustainable power generation in continuous flow microbial fuel cell treating actual wastewater: influence of biocatalyst type on electricity production.

Microbial fuel cells (MFCs) have the potential to simultaneously treat wastewater for reuse and to generate electricity. This study mainly considers the performance of an upflow dual-chambered MFC continuously fueled with actual domestic wastewater and alternatively biocatalyzed with aerobic activated sludge and strain of Bacillus Subtilis. The behavior of MFCs during initial biofilm growth and characterization of anodic biofilm were studied. After 45 days of continuous operation, the biofilms on the anodic electrode were well developed. The performance of MFCs was mainly evaluated in terms of COD reductions and electrical power output. Results revealed that the COD removal efficiency was 84% and 90% and the stabilized power outputs were clearly observed achieving a maximum value of 120 and 270 mW/m(2) obtained for MFCs inoculated with mixed cultures and Bacillus Subtilis strain, respectively.