Influence of salinity on heavy metal and oil removal from hypersaline oilfield-produced water by electrocoagulation: mechanistic insights.

The focus of the present study was to explore how and to what extent ultrahigh salinity affects the adsorption of cadmium and hydrocarbon pollutants onto aluminum hydroxide adsorbents formed in an electrocoagulation process. The changes in the nature and structure of the electro-generated aluminum particles and the possible removal mechanisms due to high salt content were investigated by using FE-SEM/EDS, FTIR, BET, and XRD analyses. The pseudo-second order and Freundlich models proved to fit the data for cadmium adsorption onto the aluminum hydroxides best. It was demonstrated that the adsorption capacities were significantly affected by the high salinity. With the rise of the salinity from 2 to 170 g/L, the cadmium and COD removal yields dropped from 81 to 60% and from 90 to 72%. The increase of the oil content led to the enhanced cadmium adsorption capacity due to surface complexation and ion exchange mechanisms. It was proved that Lagergren pseudo-first-order kinetic model could justify COD abatement trends. FTIR spectra depicted that the negative impact of high salinities on the adsorption was due to causing the formation of less stable adsorbents. According to BET analysis, the occurrence of much wider pore size distribution and smaller specific surface area in high salinity case was the main reason for the decreased adsorption capacity. Based on XRD analysis, the higher crystallinity of the produced aluminum hydroxide particles and their consequential smaller surface areas resulted in the lower adsorption capacity in the hypersaline environment. It was concluded that adsorption via inner-sphere and outer-sphere complexation and sweep flocculation were the possible removal mechanisms. Total treatment cost of 8.75 and 3.49 €/m3 were estimated for low and ultrahigh salinity conditions.

Molecularly imprinted polymer amalgamation on narrow-gapped Archimedean-spiral interdigitated electrodes: resistance to electrolyte fouling in acidic medium.

A conventional photolithography technique was used to fabricate three types of Archimedean-spiral interdigitated electrodes (AIDEs) containing concentric interlocking electrodes with different electrode and gap sizes, i.e., 150 µm (D1), 100 µm (D2), and 50 µm (D3). The precision of the fabrication was validated by surface topography using scanning electron microscopy, high power microscopy, 3D-nano profilometry, and atomic force microscopy. These AIDEs were fabricated with a tolerance of ± 6 nm in dimensions. The insignificant current variation at the pico-ampere range for all bare AIDEs further proved the reproducibility of the device. The large gap sized AIDE (D1) is insensitive to acidic medium, whereas D2 and D3 are insensitive to alkali medium. D2 was the best with regard to its electrical characterization. Furthermore, uniformly synthesized molecularly imprinted polymer (MIP) nanoparticles prepared with human blood clotting factor IX and its aptamer were in the size range 140 to 160 nm, attached on the sensing surface and characterized. The average thickness of deposited MIP film was 1.7 µm. EDX data shows the prominent peaks for silicon and aluminum substrates as 61.79 and 22.52%, respectively. The MIP nanoparticles-deposited sensor surface was characterized by applying it in electrolyte solutions, and smooth curves with the current flow were observed at pH lower than 8 and discriminated against alkali media. This study provides a new MIP amalgamated AIDE with nano-gapped fingers enabling analysis of other biomaterials due to its operation in an ideal buffer range.

Novel Composite Gold-Aluminum Electrode with Application to Neural Recording and Stimulation in Ultrahigh Field Magnetic Resonance Imaging Scanners.

Traditional electrodes used for neural recording and stimulation generate large regions of signal void (no functional MRI signal) when used in ultrahigh field (UHF) MRI scanners. This is a significant disadvantage when simultaneous neural recording/stimulation and fMRI signal acquisition is desired, for example in understanding the functional mechanisms of deep brain stimulation (DBS). In this work, a novel gold-aluminum microwire neural electrode is presented which overcomes this disadvantage. The gold-aluminum design greatly reduces the magnetic susceptibility difference between the electrode and brain tissue leading to significantly reduced regions of signal void. Gold-aluminum microwire samples are imaged at ultrahigh field 16.4 Tesla and compared with gold-only and aluminum-only microwire samples. First, B0 field mapping was used to quantify field distortions at 16.4T and compared with analytical computations in an agarose phantom. The gold-aluminum microwire samples generated substantially less field distortion and signal loss in comparison with gold-only and aluminum-only samples at 16.4T using gradient echo imaging and echo planar imaging sequences. Next, the proposed gold-aluminum electrode was used to successfully record local field potential signals from a rat cortex. The newly proposed gold-aluminum microwire electrode exhibits reduced field distortions and signal loss at 16.4T, a finding which translates to MRI scanners of lower magnetic field strengths as well. The design can be easily reproduced for widespread study of DBS using MRI in animal models. Additionally, the use of non-reactive gold and aluminum materials presents an avenue for translation to human implant applications in the future.

Electrocoagulation treatment of industrial tannery wastewater employing a modified rotating cylinder electrode reactor.

The removal of highly concentrated pollutants, presented in a wastewater mixture from industrial tannery effluents by electrocoagulation, was examined. All experiments were carried out in a rotating cylinder electrode reactor with six aluminum anodes and two sedimentation tanks. The influence of the applied current density and rotational speed on the removal efficiency of an electrocoagulation reactor was studied. Chemical oxygen demand was diminished at 70%, while total suspended solids, chromium (III) and turbidity were almost eliminated (>90%) with 6 mA cm-2 of the applied current density. Additionally, a homogeneous cathodic deposit was obtained at the end of each test. Those cathodic deposits and flocs were analyzed by SEM-EDS. Calculations of the cell energy consumption and the produced aluminum cost were estimated for 6 mA cm-2 and 100 rpm, obtaining 1.98 kWh m-3 and $0.7 USD m-3, respectively.

Removal of fluoride and hydrated silica from underground water by electrocoagulation in a flow channel reactor.

This paper concerns simultaneous removal of fluoride and hydrated silica from groundwater (4.08 mg L-1 fluoride, 90 mg L-1 hydrated silica, 50 mg L-1 sulfate, 0.23 mg L-1 phosphate, pH 7.38 and 450 µS cm-1 conductivity) by electrocoagulation (EC), using an up-flow EC reactor, with a six-cell stack in a serpentine array, opened at the top of the cell to favor gas release. Aluminum plates were used as sacrificial electrodes. The effect of current density (4 ≤ j ≤ 7 mA cm-2) and mean linear flow rate (1.2 ≤ u ≤ 4.8 cm s-1), applied to the EC reactor, on the elimination of fluoride and hydrated silica was analyzed. The removal of fluoride followed the WHO guideline (<1.5 mg L-1), while the hydrated silica was abated at 7 mA cm-2 and 1.2 cm s-1, with energy consumption of 2.48 kWh m-3 and an overall operational cost of 0.441 USD m-3. Spectroscopic analyses of the flocs by XRD, XRF-EDS, SEM-EDS, and FTIR indicated that hydrated silica reacted with the coagulant forming aluminosilicates, and fluoride replaced a hydroxide from aluminum aggregates, while sulfates and phosphates were removed by adsorption process onto the flocs. The well-engineered EC reactor allowed the simultaneous removal of fluoride and hydrated silica.

Fluoride removal from natural volcanic underground water by an electrocoagulation process: Parametric and cost evaluations.

Excessive fluoride content in groundwater can cause serious risks to human health, and sources of groundwater intended for human consumption should be treated to reduce fluoride concentrations down to acceptable levels. In the particular case of the island of Tenerife (Canary Islands, Spain), the water supply comes mainly from aquifers of volcanic origin with a high content of fluorides that make them unacceptable for human consumption without prior conditioning treatment. The treatments that generate a high rejection of water are not acceptable because water is a scarce natural resource of high value. An electrocoagulation process was investigated as a method to treat natural groundwater from volcanic soils containing a hazardously high fluoride content. The operating parameters of an electrocoagulation reactor model with parallel plate aluminum electrodes were optimized for batch and continuous flow operations. In the case of the batch operation, acidification of the water improved the removal efficiency of fluoride, which was the highest at pH 3. However, operation at the natural pH of the water achieved elimination efficiencies between 82 and 92%, depending on the applied current density. An optimum current density of 5 mA/cm2 was found in terms of maximum removal efficiency, and the kinetics of fluoride removal conformed to pseudo-second-order kinetics. In the continuous-flow operation, with the optimal residence time of 10 min and a separation of 0.5 cm between the electrodes, it was observed that the current density that would be applied would depend on the initial concentration of fluoride in the raw water. Thus, an initial fluoride concentration of 6.02 mg/L required a current density >7.5 mA/cm2 to comply with the legal guidelines in the product water, while for an initial concentration of 8.98 mg/L, the optimal current density was 10 mA/cm2. Under these operating conditions, the electrocoagulation process was able to reduce the fluoride concentration of natural groundwater to below 1.5 mg/L according to WHO guidelines with an operating cost between 0.20 and 0.26 €/m3 of treated water.

Otimização dos parâmetros operacionais de eletrocoagulação aplicada à recuperação de efluentes de lavagem de veículos / Optimization of electrocoagulation operating parameters applied to the recovery vehicle washing wastewater

RESUMO No Brasil, cerca de 32.700 postos de lavagem de veículos consomem 3,7 milhões de m3/mês-1, média de 60 L por veículo. Esse consumo poderia ser minimizado, se o efluente fosse devidamente tratado e reutilizado. Como diversos tipos de efluentes têm sido eficientemente tratados por técnicas eletroquímicas, como a eletrocoagulação (EC) e a eletroflotação (EF), o objetivo principal deste estudo foi desenvolver um sistema de tratamento de efluentes de lavagem de carros por EC, usando eletrodos de alumínio. Parâmetros como pH inicial, corrente elétrica aplicada e tempo de eletrólise foram otimizados por meio de análises físico-químicas e estatísticas. Em sua condição ótima, pH 5, corrente elétrica de 3,5 A e tempo de 20 minutos, o sistema conseguiu reduzir em 73% a demanda química de oxigênio (DQO), 58% de surfactantes e no mínimo 90% a turbidez e os sólidos suspensos totais (SST). Além da simples implantação e operação, a técnica mostrou-se eficiente na recuperação desse tipo de efluente, podendo ser utilizada em sistemas de reúso de água de lavagem de veículos.

ABSTRACT In Brazil, about 32,700 vehicle washing stations consume 3,7 million m3 per month-1, average of 60 L per vehicle. Consumption could be minimized if the effluent was properly treated and reused. As different types of effluents have been effectively treated by electrochemical techniques, such as electrocoagulation (EC) and electrocoagulation (EF), the main objective of this study was to develop a treatment system of carwash wastewater, by EC using electrodes aluminum. Parameters like the initial pH, applied electric current and electrolysis time were optimized by means of physical-chemical analysis and statistics. In its optimum condition, pH 5, electrical current of 3,5 A and time of 20 minutes, the system has managed to reduce by 73% the chemical oxygen demand (COD), 58% of surfactants and a minimum of 90% turbidity and total suspended solids (TSS). Besides the simple installation and operation, the technique was efficient in the recovery of this type of effluent and can be used in reuse system carwash water.

Surface Energy and Work Function Control of AlOx/Al Surfaces by Fluorinated Benzylphosphonic Acids.

The performance of organic electronic devices can be significantly improved by modifying metal electrodes with organic monolayers, which alter the physical and chemical nature of the interface between conductor and semiconductor. In this paper we examine a series of 12 phosphonic acid compounds deposited on the native oxide layer of aluminum (AlOx/Al), an electrode material with widespread applications in organic electronics. This series includes dodecylphosphonic acid as a reference and 11 benzylphosphonic acids, seven of which are fluorinated, including five newly synthesized derivatives. The monolayers are experimentally characterized by contact angle goniometry and by X-ray photoemission spectroscopy (XPS), and work function data obtained by low-intensity XPS are correlated with molecular dipoles obtained from DFT calculations. We find that monolayers are formed with molecular areas ranging from 17.7 to 42.9 Å(2)/molecule, and, by the choice of appropriate terminal groups, the surface energy can be tuned from 23.5 mJ/m(2) to 70.5 mJ/m(2). Depending on the number and position of fluorine substituents on the aromatic rings, a variation in the work function of AlOx/Al substrates over a range of 0.91 eV is achieved, and a renormalization procedure based on molecular density yields a surprising agreement of work function changes with interface dipoles as expected from Helmholtz' equation. The ability to adjust energetics and adhesion at organic semiconductor/AlOx interfaces has immediate applications in devices such as OLEDs, OTFTs, organic solar cells, and printed organic circuits.

Comparative study of humic acid removal and floc characteristics by electrocoagulation and chemical coagulation.

The current study aims at investigating the efficiency of electrocoagulation for the removal of humic acid from contaminated waters. In parallel, conventional chemical coagulation was conducted to asses humic acid removal patterns. The effect of varying contributing parameters (matrix pH, humic acid concentration, type of electrode (aluminum vs. iron), current density, solution conductivity, and distance between electrodes) was considered to optimize the electrocoagulation process for the best attainable humic acid removal efficiencies. Optimum removals were recorded at pH of 5.0-5.5, an electrical conductivity of 3000 µS/cm at 25 °C, and an electrode distance of 1 cm for both electrode types. With aluminum electrodes, a current density of 0.05 mA/cm2 outperformed 0.1 mA/cm2 yet not higher densities, whereas a current density of 0.8 mA/cm2 was needed for iron electrodes to exhibit comparable performance. With both electrode types, higher initial humic acid concentrations were removed at a slower rate but ultimately attained almost complete removals. On the other hand, the best humic acid removals (∼90%) by chemical coagulation were achieved at 4 mg/L for both coagulants. Also, higher removals were attained at elevated initial humic acid concentrations. Humic acid removals of 90% or higher at an initial HA concentration of 40 mg/L were exhibited, yet alum performed better at the highest experimented concentration. It was evident that iron flocs were larger, denser, and more geometrical in shape compared to aluminum flocs.

Optimization of electrocoagulation (EC) process for the purification of a real industrial wastewater from toxic metals.

In the present work, the efficiency evaluation of electrocoagulation (EC) in removing toxic metals from a real industrial wastewater, collected from Aspropyrgos, Athens, Greece was investigated. Manganese (Mn), copper (Cu) and zinc (Zn) at respective concentrations of 5 mg/L, 5 mg/L and 10 mg/L were present in the wastewater (pH=6), originated from the wastes produced by EBO-PYRKAL munitions industry and Hellenic Petroleum Elefsis Refineries. The effect of operational parameters such as electrode combination and distance, applied current, initial pH and initial metal concentration, was studied. The results indicated that Cu and Zn were totally removed in all experiments, while Mn exhibited equally high removal percentages (approximately 90%). Decreasing the initial pH and increasing the distance between electrodes, resulted in a negative effect on the efficiency and energy consumption of the process. On the other hand, increasing the applied current, favored metal removal but resulted in a power consumption increase. Different initial concentrations did not affect metal removal efficiency. The optimal results, regarding both cost and EC efficiency, were obtained with a combination of iron electrodes, at 2 cm distance, at initial current of 0.1 A and pH=6. After 90 min of treatment, maximum removal percentages obtained were 89% for Mn, 100% for Cu and 100% for Zn, at an energy consumption of 2.55 kWh/m(3).

Simultaneous removal of oil and grease, and heavy metals from artificial bilge water using electro-coagulation/flotation.

US and international regulations pertaining to the control of bilge water discharges from ships have concentrated their attention to the levels of oil and grease rather than to the heavy metal concentrations. The consensus is that any discharge of bilge water (and oily water emulsion within 12 nautical miles from the nearest land cannot exceed 15 parts per million (ppm). Since there is no specific regulation for metal pollutants under the bilge water section, reference standards regulating heavy metal concentrations are taken from the ambient water quality criteria to protect aquatic life. The research herein presented discusses electro-coagulation (EC) as a method to treat bilge water, with a focus on oily emulsions and heavy metals (copper, nickel and zinc) removal efficiency. Experiments were run using a continuous flow reactor, manufactured by Ecolotron, Inc., and a synthetic emulsion as artificial bilge water. The synthetic emulsion contained 5000 mg/L of oil and grease, 5 mg/L of copper, 1.5 mg/L of nickel, and 2.5 mg/l of zinc. The experimental results demonstrate that EC is very efficient in removing oil and grease. For oil and grease removal, the best treatment and cost efficiency was obtained when using a combination of carbon steel and aluminum electrodes, at a detention time less than one minute, a flow rate of 1 L/min and 0.6 A/cm(2) of current density. The final effluent oil and grease concentration, before filtration, was always less than 10 mg/L. For heavy metal removal, the combination of aluminum and carbon steel electrodes, flow rate of 1 L/min, effluent recycling, and 7.5 amps produced 99% zinc removal efficiency. Copper and nickel are harder to remove, and a removal efficiency of 70% was achieved.