Recovery Of Zinc from Scrap Steel Using Zinc-Bromine Battery Technology.

Secondary production of steel is known to significantly decrease the CO2 emissions of steelmaking, but only 40 % of steel is produced through recycling, which is made difficult by contamination of scrap resources with nonferrous metals and nonmetal debris. These contaminants include zinc, towards which blast furnace and electric arc systems have a low tolerance (<0.02 wt %). In this work, clean and efficient recovery of zinc from the surface of steel substrates was investigated using a custom-made low-cost membrane-free non-flow zinc-bromine battery (ZBB) that enabled rapid and straightforward integration and removal of steel substrates. The electrical performance of the cell was characterized by charge-discharge profiles, and zinc removal and recovery onto electrodes was characterized by using scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). Upon discharging, the cell efficiently removed >99.9 wt % zinc from steel surfaces. On recharging the cell, zinc was re-electroplated onto a carbon foam electrode in an easily recoverable form and with high purity. The process was repeated over 30 cycles to demonstrate robustness. The work shows the importance of the cutoff voltage upon discharging: if less than 0.5 V, the cell co-extracted iron into the electrolyte solution, affecting cell durability and zinc purity. A two-stage process for recovering zinc from scrap steel is proposed, illustrating how ZBB technology could enable efficient and clean recovery of zinc from complex scrap steel resources in the steel industry.

Bioelectrochemical treatment and recovery of copper from distillery waste effluents using power and voltage control strategies.

Copper recovery from distillery effluent was studied in a scalable bioelectro-chemical system with approx. 6.8 L total volume. Two control strategies based on the control of power with maximum power point tracking (MPPT) and the application of 0.5 V using an external power supply were used to investigate the resultant modified electroplating characteristics. The reactor system was constructed from two electrically separated, but hydraulically connected cells, to which the MPPT and 0.5 V control strategies were applied. Three experiments were carried out using a relatively high copper concentration i.e. 1000 mg/L followed by a lower concentration i.e. 50 mg/L, with operational run times defined to meet the treatment requirements for distillery effluents considered. Real distillery waste was introduced into the cathode to reduce ionic copper concentrations. This waste was then recirculated to the anode as a feed stock after the copper depletion step, in order to test the bioenergy self-sustainability of the system. Approx. 60-95% copper was recovered in the form of deposits depending on starting concentration. However, the recovery was low when the anode was supplied with copper depleted distillery waste. Through process control (MPPT or 0.5 V applied voltage) the amount and form of the copper recovered could be manipulated.

A new sequential injection analysis-capillary electrophoresis system with amperometric detection.

A novel and fully automated sequential injection analysis manifold coupled to a capillary electrophoresis apparatus with amperometric detection, is described. The sequential injection manifold was isolated from the high voltage by inserting an air plug into the circuit. Small buffer reservoirs were used to avoid the need to pump fresh buffer to the interface during the electrophoretic separation. No decoupling device was used to mitigate the interference from the high voltage electric field, instead the potential shift induced by the separation voltage, was accounted for. The new hydrodynamic injection method presented is based on the overpressure created in the circuit when a pinch valve is closed for a predetermined time. The injection method yields RSD values of peak height and area below 2.55 and 1.82%, respectively, at different durations of valve closure (n = 5). The capillary and working electrode alignment was achieved by adapting a commercial available capillary union. When the electrode was replaced, the alignment method proved to be very reliable, yielding RSD values of peak height and area lower than 2.64 and 2.08%, respectively (n = 8). Using this system with a gold microelectrode, dopamine, and epinephrine could be quantified within the concentration range of 1-500 µM and detected at a concentration of 0.3 µM. The methods here presented could be applied for the development of new capillary electrophoresis systems with amperometric detection and/or to the design of fully automated systems for online process monitoring purposes.

Removal and recovery of inhibitory volatile fatty acids from mixed acid fermentations by conventional electrodialysis.

Hydrogen production during dark fermentation is inhibited by the co-production of volatile fatty acids (VFAs) such as acetic and n-butyric acid. In this study, the effectiveness of conventional electrodialysis (CED) in reducing VFA concentrations in model solutions and hydrogen fermentation broths is evaluated. This is the first time CED has been reported to remove VFAs from hydrogen fermentation broths. During 60 min of operation CED removed up to 99% of VFAs from model solutions, sucrose-fed and grass-fed hydrogen fermentation broths, containing up to 1200 mg l(-1) each of acetic acid, propionic acid, i-butyric acid, n-butyric acid, i-valeric acid, and n-valeric acid. CED's ability to remove VFAs from hydrogen fermentation broths suggests that this technology is capable of improving hydrogen yields from dark fermentation.

Inhibition of methane production in microbial fuel cells: operating strategies which select electrogens over methanogens.

Methanogenesis may diminish coulombic efficiency of microbial fuel cells (MFCs), although its importance is application dependent; e.g., suppression of methanogenesis may improve MFC sensing accuracy, but may be tolerable in COD removal from wastewaters. Suppression of methanogenesis was investigated in three H-type MFCs, enriched and acclimated with acetate, propionate and butyrate substrates and subsequently operated under open and closed circuit (OC/CC) regimes. Altering the polarisation state of the electrode displaces microorganisms from the anodic biofilm and leads to observable methane inhibition. The planktonic archeal community was compared to the electrode biofilm whilst under the OC/CC regimes. Semi-quantitative DNA analyses indicate a shift in some dominant species, from the electrode to the solution, during OC operation. The effect of prolonged starvation on anodic species was also studied. The results indicate progressive inhibition of methanogenesis from OC/CC operations; and virtual cessation of methanogenesis when an MFC was starved for a significant period.

The use of NaCl addition for the improvement of polyhydroxyalkanoate production by Cupriavidus necator.

External stress factors in the form of ionic species or temperature increases have been shown to produce a stress response leading to enhanced PHA production. The effect of five different NaCl concentrations, namely 3.5, 6.5, 9, 12 and 15 g/l NaCl on PHA productivity using Cupriavidus necator has been investigated alongside a control (no added NaCl). A dielectric spectroscopy probe was used to measure PHA accumulation online in conjunction with the chemical offline analysis of PHA. The highest PHA production was obtained with the addition of 9 g/l NaCl, which yielded 30% higher PHA than the control. Increasing the addition of NaCl to 15 g/l was found to inhibit the production of PHA. NaCl addition can therefore be used as a simple, low cost, sustainable, non toxic and non reactive external stress strategy for increasing PHA productivity.

The influence of anodic helical design on fluid flow and bioelectrochemical performance.

In this study three different tubular helical anode designs are compared, for each helical design the pitch and nominal sectional area/liquid flow channel between the helicoids was varied and this produced maximum power densities of 11.63, 9.2 and 6.73Wm(-3) (small, medium and large helical flow channel cross-sections). It is found that the level of mixing and the associated shear rates present in the anodes affects both the power development and biofilm formation. The small helical flow channel carbon anode produced 40% more biofilm and this result was related to modelling data which determined a system shear rate of 237s(-1), compared to 52s(-1) and 47s(-1) for the other reactor configurations. The results from computational fluid dynamic modelling further distinguishes between convective flow conditions and supports the influence of helical structure on system performance, so establishing the importance of anodic design on the overall electrogenic biofilm activity.

Augmenting Microbial Fuel Cell power by coupling with Supported Liquid Membrane permeation for zinc recovery.

Simultaneous removal of organic and zinc contamination in parallel effluent streams using a Microbial Fuel Cell (MFC) would deliver a means of reducing environmental pollution whilst also recovering energy. A Microbial Fuel Cell system has been integrated with Supported Liquid Membrane (SLM) technology to simultaneously treat organic- and heavy metal containing wastewaters. The MFC anode was fed with synthetic wastewater containing 10 mM acetate, the MFC cathode chambers were fed with 400 mg L(-1) Zn(2+) and this then acted as a feed phase for SLM extraction. The MFC/SLM combination produces a synergistic effect which enhances the power performance of the MFC significantly; 0.233 mW compared to 0.094 mW in the control. It is shown that the 165 ± 7 mV difference between the MFC/SLM system and the MFC control is attributable to the lower cathode pH in the integrated system experiment, the consequent lower activation overpotential and higher oxygen reduction potential. The change in the substrate removal efficiency and Coulombic Efficiency (CE) compared to controls is small. Apart from the electrolyte conductivity, the conductivities of the bipolar and liquid membrane were also found to increase during operation. The diffusion coefficient of Zn(2+) through the liquid membrane in the MFC/SLM (4.26*10(-10) m(2) s(-1)) is comparable to the SLM control (5.41*10(-10) m(2) s(-1)). The system demonstrates that within 72 h, 93  ±  4% of the zinc ions are removed from the feed phase, hence the Zn(2+) removal rate is not significantly affected and is comparable to the SLM control (96  ±  1%), while MFC power output is significantly increased.

Increasing polyhydroxyalkanoate (PHA) yields from Cupriavidus necator by using filtered digestate liquors.

The production of polyhydroxyalkanoates (PHAs) using digestate liquor as culture media is a novel application to extend the existing uses of digestates. In this study, two micro-filtered digestates (0.22 µm) were evaluated as a source of complex culture media for the production of PHA by Cupriavidus necator as compared to a conventional media. Culture media using a mixture of micro-filtered liquors from food waste and from wheat feed digesters showed a maximum PHA accumulation of 12.29 g/l PHA, with 90% cell dry weight and a yield of 0.48 g PHA/g VFA consumed, the highest reported to date for C. necator studies. From the analysis of the starting and residual media, it was concluded that ammonia, potassium, magnesium, sulfate and phosphate provided in the digestate liquors were vital for the initial growth of C. necator whereas copper, iron and nickel may have played a significant role in PHA accumulation.

Control of power sourced from a microbial fuel cell reduces its start-up time and increases bioelectrochemical activity.

Microbial fuel cell (MFC) performance depends on the selective development of an electrogenic biofilm at an electrode. Controlled biofilm enrichment may reduce start-up time and improve subsequent power performance. The anode potential is known to affect start-up and subsequent performance in electrogenic bio-catalytic consortia. Control strategies varying electrical load through gradient based maximum power point tracking (MPPT) and transient poised anode potential followed by MPPT are compared to static ohmic loading. Three replicate H-type MFCs were used to investigate start-up strategies: (1) application of an MPPT algorithm preceded by poised-potential at the anode (+0.645 V vs Ag/AgCl); (2) MFC connected to MPPT-only; (3) static external load of 1 kΩ and 500 Ω. Active control showed a significant reduction in start-up time from 42 to 22 days, along with 3.5-fold increase in biocatalytic activity after start-up. Such active control may improve applicability by accelerating start-up and enhancing MFC power and bio-catalytic performance.

Microbial fuel cell type biosensor for specific volatile fatty acids using acclimated bacterial communities.

Volatile fatty acid (VFA) concentration is one of the most important parameters for monitoring bio-processes such as anaerobic digestion and microbial fuel cells. In this study the correlation between VFA concentration and current/voltage responses and electrochemical properties by using the MFC technology was evaluated. The discrimination between different species of VFA by using two methods i.e., coulombic efficiency and cyclic voltammetry was investigated. Columbic efficiency gave a slow response of greater than 20h, particularly at concentration levels of 20mgl(-1). By using cyclic voltammetry to measure the oxidation peak at a consistent scan rate showed linear correlation to VFA concentration and peak current produced, up to <40mgl(-1)) in a rapid response time of 1-2min. The results presented showed good correlations between the individual VFA species concentration and charge, and also current generated. A MFC based biosensor array was produced capable of measuring individual acetate, propionate and butyrate concentrations with sensitivity down to 5mgl(-1) and up to 40mgl(-1).

Addressing the challenge of optimum polyhydroxyalkanoate harvesting: monitoring real time process kinetics and biopolymer accumulation using dielectric spectroscopy.

In this study, dielectric spectroscopy was utilised to evaluate and define the optimum harvesting time for polyhydroxyalkanoates (PHA) production. It is essential to harvest PHA at the optimum time during fermentation for maximum yield, otherwise cells start degrading. Two carbon sources (acetic and butyric acids) were used in laboratory based experiments and a number of samples were measured ex situ for PHA production. The real-time measured capacitance in addition of identifying the cells growth phase, it correlated very well with ex situ measured PHA produced within the cells. The probe has proven to be a useful tool to assess process kinetics, to monitor real-time cell growth, PHA produced and defining the optimum harvesting time.

Operational temperature regulates anodic biofilm growth and the development of electrogenic activity.

The operational temperature of microbial fuel cell reactors influences biofilm development, and this has an impact on anodic biocatalytic activity. In this study, we compared three microbial fuel cell (MFC) reactors acclimated at 10°C, 20°C and 35°C to investigate the effect on biomass development, methanogenesis and electrogenic activity over time. The start-up time was inversely influenced by temperature, but the amount of biomass accumulation increased with increased temperatures, the 10°C, 20°C and 35°C acclimated biofilms resulted in 0.57, 0.82 and 5.43 g biomass (volatile suspended solids) per litre respectively at 56 weeks of operation. Biofilm build-up on the 35°C anode was further demonstrated by scanning electron microscopy, which showed large aggregations of biomass accumulating on the anode when compared to 10°C and 20°C biofilms. Biomass accumulation had a direct impact on biocatalytic performance, with the maximum power at 35°C after 60 weeks of operation being 2.14 W m(-3) and power densities for the 10°C and 20°C reactors being and 4.29 W m(-3). Methanogenic activity was also shown to be higher at 35°C, with a rate of 10.1 mmol CH(4) biofilm per gram of volatile suspended solid (VSS) per day, compared to 0.28 mmol CH(4) per gram of VSS per day produced at 20°C. These results demonstrate that higher MFC operating temperatures could be detrimental to the biocatalytic performance of electrochemically active bacteria in anodic biofilms due to biomass accumulation with enhanced development of non-electrogenic communities (e.g. methanogens and fermenters), meaning that, over time, psychro- or mesophilic operation can have beneficial effects for the development of electrogenically active populations in the reactor.

Spatiotemporal development of the bacterial community in a tubular longitudinal microbial fuel cell.

The spatiotemporal development of a bacterial community in an exoelectrogenic biofilm was investigated in sucrose-fed longitudinal tubular microbial fuel cell reactors, consisting of two serially connected modules. The proportional changes in the microbial community composition were assessed by polymerase chain reaction-denaturing gradient gel electrophoresis (DGGE) and DNA sequencing in order to relate them to the performance and stability of the bioelectrochemical system. The reproducibility of duplicated reactors, evaluated by cluster analysis and Jaccard's coefficient, shows 80-90% similarity in species composition. Biofilm development through fed-batch start-up and subsequent stable continuous operation results in a population shift from γ-Proteobacteria- and Bacteroidetes- to Firmicutes-dominated communities, with other diverse species present at much lower relative proportions. DGGE patterns were analysed by range-weighted richness (Rr) and Pareto-Lorenz evenness distribution curves to investigate the evolution of the bacterial community. The first modules shifted from dominance by species closely related to Bacteroides graminisolvens, Raoultella ornithinolytica and Klebsiella sp. BM21 at the start of continuous-mode operation to a community dominated by Paludibacter propionicigenes-, Lactococcus sp.-, Pantoea agglomerans- and Klebsiella oxytoca-related species with stable power generation (6.0 W/m(3)) at day 97. Operational strategies that consider the dynamics of the population will provide useful parameters for evaluating system performance in the practical application of microbial fuel cells.

Modular tubular microbial fuel cells for energy recovery during sucrose wastewater treatment at low organic loading rate.

Energy recovery while treating low organic loads has been investigated using longitudinal tubular microbial fuel cell (MFC) reactors. Duplicate reactors, each consisting of two modules, were operated with influent sucrose organic loading rates (OLRs) between 0.04 and 0.42 g COD/l/d. Most soluble COD (sCOD) removal occurred in the first modules with predominantly VFAs reaching the second modules. Coulombic efficiency (CE) in the second modules ranged from 9% to 92% which was 3-4 times higher than the first modules. The maximum energy production was 1.75 W h/g COD in the second modules at OLR 0.24 g/l/d, up to 10 times higher than the first modules, attributable to non-fermentable substrate. A simple plug flow model of the reactors, including a generic non-electrogenic reaction competing for acetate, was developed. This modular tubular design can reproducibly distribute bioprocesses between successive modules and could be scalable, acting as a polishing stage while reducing energy requirements in wastewater treatment.

Illicit drugs and pharmaceuticals in the environment--forensic applications of environmental data, Part 2: Pharmaceuticals as chemical markers of faecal water contamination.

This manuscript is part two of a two-part study aiming to provide a better understanding and application of environmental data not only for environmental aims but also to meet forensic objectives. In this paper pharmaceuticals were investigated as potential chemical indicators of water contamination with sewage. The monitoring program carried out in Wales revealed that some pharmaceuticals are particularly persistent and/or ubiquitous in contaminated river water and therefore might be considered as potential conservative or labile wastewater indicators. In particular, these include some anti-inflammatory/analgesics, antiepileptics, beta-blockers, some H2-receptor antagonists and antibacterial drugs.

Illicit drugs and pharmaceuticals in the environment--forensic applications of environmental data. Part 1: Estimation of the usage of drugs in local communities.

Pharmaceuticals and recently also illicit drugs have been recognised as emerging environmental contaminants due to their potential environmental impact: frequent occurrence, persistence and risk to aquatic life and humans. This manuscript is part one of the two-part study aiming to provide a better understanding and application of environmental data not only for environmental aims but also to meet forensic objectives. An attempt to use wastewater data is made in order to verify patterns of the usage of drugs (in particular illicit) in local communities. The average usage of cocaine in South Wales was estimated at 0.9 g day(-1) 1000 people(-1), which equals 1 tonne of this drug used or disposed of to sewage annually in Wales. The calculated usage of amphetamine denoted 2.5 g day(-1) 1000 people(-1) and is suspected to be an overestimate. Because no analysis of enantiomers of amphetamine was undertaken, no distinction between amphetamine's legal and illicit usage could be made.

The removal of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs during wastewater treatment and its impact on the quality of receiving waters.

A 5-month monitoring program was undertaken in South Wales in the UK to determine the fate of 55 pharmaceuticals, personal care products, endocrine disruptors and illicit drugs (PPCPs) in two contrasting wastewater plants utilising two different wastewater treatment technologies: activated sludge and trickling filter beds. The impact of treated wastewater effluent on the quality of receiving waters was also assessed. PPCPs were found to be present at high loads reaching 10kgday(-1) in the raw sewage. Concentrations of PPCPs in raw sewage were found to correlate with their usage/consumption patterns in Wales and their metabolism. The efficiency of the removal of PPCPs was found to be strongly dependent on the technology implemented in the wastewater treatment plant (WWTP). In general, the WWTP utilising trickling filter beds resulted in, on average, less than 70% removal of all 55 PPCPs studied, while the WWTP utilising activated sludge treatment gave a much higher removal efficiency of over 85%. The monitoring programme revealed that treated wastewater effluents were the main contributors to PPCPs concentrations (up to 3kg of PPCPsday(-1)) in the rivers studied. Bearing in mind that in the cases examined here the WWTP effluents were also major contributors to rivers' flows (dilution factor for the studied rivers did not exceed 23 times) the effect of WWTP effluent on the quality of river water is significant and cannot be underestimated.

The occurrence of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs in surface water in South Wales, UK.

The presence and fate of 56 pharmaceuticals, personal care products, endocrine disruptors and illicit drugs (PPCPs) were investigated in the South Wales region of the UK. Two contrasting rivers: River Taff and River Ely were chosen for this investigation and were monitored for a period of 10 months. The impact of the factors affecting the levels of concentration of PPCPs and illicit drugs in surface water such as surrounding area, proximity to wastewater effluent and weather conditions, mainly rainfall was also investigated. Most PPCPs were frequently found in river water at concentrations reaching single microgL(-1) and their levels depended mainly on the extent of water dilution resulting from rainfall. Discharge of treated wastewater effluent into the river course was found to be the main cause of water contamination with PPCPs. The most frequently detected PPCPs represent the group of pharmaceuticals dispensed at the highest levels in the Welsh community. These were antibacterial drugs (trimethoprim, erythromycin-H(2)O and amoxicillin), anti-inflammatories/analgesics (paracetamol, tramadol, codeine, naproxen, ibuprofen and diclofenac) and antiepileptic drugs (carbamazepine and gabapentin). Only four PPCPs out of 56 (simvastatin, pravastatin, digoxin and digoxigenin) were not quantified over the course of the study. Several PPCPs were found to be both ubiquitous and persistent in the aqueous environment (e.g. erythromycin-H(2)O, codeine, carbamazepine, gabapentin and valsartan). The calculated average daily loads of PPCPs indicated that in total almost 6 kg of studied PPCPs are discharged daily into the studied rivers. The illicit drugs studied were found in rivers at low levels of ng L(-1). Average daily loads of amphetamine, cocaine and its main metabolite benzoylecgonine were as follows: 8, 1.2 and 39 gday(-1), respectively. Their frequent occurrence in surface water is primarily associated with their high illegal usage and is strongly associated with the discharge of insufficiently treated wastewater effluent.

The effect of signal suppression and mobile phase composition on the simultaneous analysis of multiple classes of acidic/neutral pharmaceuticals and personal care products in surface water by solid-phase extraction and ultra performance liquid chromatography-negative electrospray tandem mass spectrometry.

A new multi-residue method for the determination of 25 acidic/neutral pharmaceuticals (antibiotics, anti-inflammatory/analgesics, lipid regulating agents, diuretics, triazides, H2-receptor antagonists, cardiac glicozides and angiotensin II antagonists) and personal care products (sunscreen agents and preservatives) in surface water with the usage of a new technique: ultra performance liquid chromatography-negative electrospray tandem mass spectrometry (UPLC-MS/MS) was developed and validated. The novel UPLC system with 1.7 microm particle-packed column allowed for good resolution of analytes with the application of low mobile phase flow rates (0.05 mL min(-1)) and short retention times (from 4.7 min to 13.3 min) delivering a fast and cost-effective multi-residue method. SPE with the usage of Oasis MCX strong cation-exchange mixed-mode polymeric sorbent was chosen for sample clean-up and concentration. The influence of mobile-phase composition, matrix assisted ion suppression and SPE recovery on the sensitivity of the method was identified and quantified. The instrumental limits of quantification varied from 0.2 microgL(-1) to 30mugL(-1). The method limits of quantification were at low nanogram per litre levels and ranged from 0.3 ng L(-1) to 30 ng L(-1). The instrumental and method intra-day and inter-day repeatabilities were on average less than 5%. The method was successfully applied for the determination of PPCPs in River Taff. Thirteen compounds were determined in river water at levels ranging from a single to a few hundred nanograms per litre. Among them were ten pharmaceuticals (aspirin, salicylic acid, ketoprofen, naproxen, diclofenac, ibuprofen, mefenamic acid, furosemide, sulfasalazine and valsartan) and three personal care products (methyl- and ethylparaben and 4-benzophenone).