The application of electrochemical processes in oily wastewater treatment: a review.

Oily wastewater is becoming a concern worldwide due to its quantities and the presence of contaminants and its sustainable treatment should be cost-effective and meet all requirements so the contaminants are not transferred to the environment. The paper reviews the state-of-the-art in the oily wastewater treatment by electrochemical processes such as electrochemical advanced oxidation processes and electrocoagulation. Efficiency of oily wastewater treatment has been thoroughly investigated with its expression as a function of the main technological (process) parameters. Fe and Al electrodes, as well as their combination have proven to be very effective in oily wastewater treatment with slightly better performance of Al electrodes. Higher current densities and longer reaction times result with higher COD, TOC, turbidity, phenol and oil and grease removal efficiencies, but with resulting increase in wastewater temperature and energy consumption, so there is a strong need for the process optimization. There is a need for further research on the treatment efficiencies of different contaminants (heavy metals, total hydrocarbons, organic halogens, cyanides, etc.). A lack of research is presented on the treatment efficiency with electrodes of different materials as well as the analyses of the sludge production and its further treatment and use or disposal.

The Growth and Sporulation of Bacillus subtilis in Nanotesla Magnetic Fields.

The order of magnitude of increased growth, multiplication rate, and decreased sporulation of Bacillus subtilis after exposure to nanotesla magnetic fields (MFs) relative to control samples were observed experimentally. Earth's total magnetic field intensity was reduced from 47.9 ± 0.4 µT to cover the range from 97.5 ± 1.7 nT to 1115 ± 158 nT in eight subsequent experiments by using three pairs of Helmholtz coils combined with Mu-metal shielding. The growth, multiplication rate, sporulation, and potassium content were measured in the probe and control containing B. subtilis cultures after 24 h of exposure to nanotesla and Earth's magnetic fields, respectively. The observed effect is discussed with regard to its possible repercussions on Earth's living species during geomagnetic reversals that occurred when the magnetic field was much weaker than the field that exists today. In addition, effects on future manned voyages into deep space, an environment with reduced magnetic field intensity, are considered.

In-situ measurements of rare earth elements in deep sea sediments using nuclear methods.

The prospecting activities for finding new rare earth elements (REE) sources have increased greatly in recent years. One of the main discoveries was announced in 2011 by Japanese researchers who found large quantities of REE on the ocean seafloor at the sea depths greater than 4,000 m. The classic approach to investigate REE in deep sea sediments is to obtain sediment samples by drilling that is followed by laborious laboratory analysis. This is very expensive, time consuming and not appropriate for exploring vast areas. In order to efficiently explore the ocean floor for REE deposits, the further development of affordable sensors is needed. Here, we propose two nuclear techniques for exploring REE in surface deep sea sediments: i) Passive measurement of lutetium-176 radioactivity, appropriate if long-term in-situ measurements are possible, and ii) The use of the neutron sensor attached to a remotely operated vehicle for rapid in-situ measurement of gadolinium by thermal neutron-capture. Since concentrations of lutetium and gadolinium show strong linear correlation to the total REE concentrations in deep sea sediments, it is possible to deduce the total REE content by measuring Lu or Gd concentrations only.

Detoxification of polluted marine sediments using water treatment sludge.

The purpose of this study was development of the optimal conditions for the inertization of the polluted marine sediments using groundwater treatment sludge highly enriched in iron and aluminum. For that purpose fine-grained sediment (>85% clay and silt fraction) highly enriched in copper and zinc was amended with the waste sludge (from 10% to 50%). The sample with the optimum percentage of the waste sludge was further subjected the thermal treatment at 200-800°C. The efficiency of the treatment was determined by the leaching tests and toxicity testing using Hordeum vulgare L. as biosystem. The percentage of the seed germination, the root elongation, and the germination index before and following the treatment were determined. Untreated sediment leachate caused significant arrest in the percentage of the seed germination (6.7 ± 6.7%), the root elongation (1.9 ± 2.2%), and the germination index (0.2 ± 0.3%) with EC50 of 24.9%, suggesting a significant toxic potential of the sediments. After amendment with 30% of the waste sludge the concentrations of the considered micropollutants decreased below regulated values while all three toxicological parameters showed no significant difference compared to the negative control. The toxicity of the sediment was completely removed following the thermal treatment at 400°C.

Removal of arsenic, phosphates and ammonia from well water using electrochemical/chemical methods and advanced oxidation: a pilot plant approach.

The purpose of this work was to develop a pilot plant purification system and apply it to groundwater used for human consumption, containing high concentrations of arsenic and increased levels of phosphates, ammonia, mercury and color. The groundwater used was obtained from the production well in the Vinkovci County (Eastern Croatia). Due to a complex composition of the treated water, the purification system involved a combined electrochemical treatment, using iron and aluminum electrode plates with simultaneous ozonation, followed by a post-treatment with UV, ozone and hydrogen peroxide. The removal of the contaminant with the waste sludge collected during the electrochemical treatment was also tested. The combined electrochemical and advanced oxidation treatment resulted in the complete removal of arsenic, phosphates, color, turbidity, suspended solids and ammonia, while the removal of other contaminants of interest was up to 96.7%. Comparable removal efficiencies were obtained by using waste sludge as a coagulant.

Treatment of winery wastewater by electrochemical methods and advanced oxidation processes.

The aim of this research was development of new system for the treatment of highly polluted wastewater (COD = 10240 mg/L; SS = 2860 mg/L) originating from vine-making industry. The system consisted of the main treatment that included electrochemical methods (electro oxidation, electrocoagulation using stainless steel, iron and aluminum electrode sets) with simultaneous sonication and recirculation in strong electromagnetic field. Ozonation combined with UV irradiation in the presence of added hydrogen peroxide was applied for the post-treatment of the effluent. Following the combined treatment, the final removal efficiencies of the parameters color, turbidity, suspended solids and phosphates were over 99%, Fe, Cu and ammonia approximately 98%, while the removal of COD and sulfates was 77% and 62%, respectively. A new approach combining electrochemical methods with ultrasound in the strong electromagnetic field resulted in significantly better removal efficiencies for majority of the measured parameters compared to the biological methods, advanced oxidation processes or electrocoagulation. Reduction of the treatment time represents another advantage of this new approach.

Electroplating wastewater treatment by the combined electrochemical and ozonation methods.

This article presents a pilot-plant study of the electroplating wastewater treatment by the processes of electroreduction with iron electrode plates, and electrocoagulation/ozonation with aluminum electrode set, followed by the process of ozonation. The initial effluent was found to be highly enriched in heavy metals and to possess the elevated levels of organic contaminants. The values of Cr(VI), Fe, Ni, Cu, Zn, Pb, TOC, and COD exceeded the upper permissible limits of 63, 220.2, 1.1, 7, 131.3, 1.7, 12.3, and 11.4 times, respectively. The heavy metal removal was forced either by the coagulation/flocculation using Fe(II), Fe(III), and Al(III) ions released into the treated solution by the electrochemical corrosion of the sacrificial iron and aluminum electrodes, or the precipitation of the metal hydroxides as well as co-precipitation with iron and aluminum hydroxides. The principle organic matter destruction mechanisms were ozone oxidation and the indirect oxidation with chlorine/hypochlorite formed by the anodic oxidation of chloride already present in the wastewater. Following the combined treatment, the removal efficiencies of Cr(VI), Fe, Ni, Cu, Zn, Pb, TOC, and COD were 99.94%, 100.00%, 95.86%, 98.66%, 99.97%, 96.81%, 93.24%, and 93.43%, respectively, thus complying with the regulated values.

Preparation of drinking water used in water supply systems of the towns Zrenjanin and Temerin by electrochemical methods.

The aim of this work was the development and application of the pilot plant with the capacity of 1000 L/day for the purification of groundwater used for human consumption characterized with high concentration of arsenic and increased values of organic pollutants, ammonia, nitrites, color and turbidity. For that purpose, groundwater from the production wells supplying the towns Zrenjanin and Temerin (Vojvodina, Serbia) was used. Due to its complex composition, the purification system required the combination of the electroreduction/electrocoagulation, using iron and aluminum electrode plates with/without ozonation, followed by the electromagnetic treatment and the finally by the simultaneous ozonation/UV treatment. The electroreduction was used for the removal of nitrates, nitrites, and Cr(VI), while the removal of arsenic, heavy metals, suspended solids, color and turbidity required the application of the electrocoagulation with simultaneous ozonation. Organic contaminants and ammonia were removed completely in the last treatment step by applying the simultaneous ozonation/UV treatment. All measured parameters in the purified water were significantly lower compared to the regulated values. Under the optimum treatment conditions, the removal efficiencies for color, turbidity, suspended solids, total arsenic, total chromium, Ni(II), total copper, sulfates, fluorides, chemical oxygen demand, ammonia, nitrates, and nitrites were 100%. The removal efficiencies of the total manganese and iron were 85.19% and 97.44%, respectively, whilst the final concentrations were 4 and 7 µg/L, respectively.

A combined CaO/electrochemical treatment of the landfill leachate from different sanitary landfills in Croatia.

The aim of this research was development of appropriate procedure for the treatment of landfill leachate taken from the Visevac, Mraclinska Dubrava and Piskornica sanitary landfills. Due to the complex nature of the effluents a combined treatment approach was applied. The pretreatment step included simultaneous treatment with calcium oxide and electrocoagulation/electrooxidation by stainless steel electrode set. The main treatment included electrocoagulation/electrooxidation using the set of stainless steel, iron and aluminum electrodes. The pretreatment allowed the destruction and/or coagulation of the high molecular weight organic substances as well as optimization of pH values for the formation of reactive oxidative species, and the transformation of NH(4)-N into volatile NH(3)-N. In the presence of added calcium oxide and electrochemically generated coagulant the removal of the fluorides, phosphates and heavy metals occur through the formation of poorly soluble fluorapatite, hydroxyl apatite, and various hydroxides. During the main treatment electrochemically generated reactive oxidative species carried out rapid decomposition of the organic matter and ammonia, resulting in the removal of COD from 74.9% to 94.2%, color from 98.8% to 99.7%, turbidity from 98.4% to 99.3%, suspended solids from 97.1% to 99.3%, and ammonia from 99.6% to 99.7%. Slightly better results for the removal efficiency of color, turbidity and suspended solids were obtained in the case of Piskornica landfill compared with the other two landfills, while the COD removal efficiency decreases in the following order: Piskornica >Mraclinska Dubrava >Visevac. This could be related to the age of the landfill, which increases in the same order. Consequently, with the increasing age of the landfill the degree of degradability of the organic matter reduces significantly. Applied treatment approach resulted in clear, colorless and odorless effluent with the values of all measured parameters significantly lower compared to the upper permissible limit for discharge into the environment.

Boat pressure washing wastewater treatment with calcium oxide and/or ferric chloride.

The aim of this study was to investigate the efficiency of (1) chemical precipitation by calcium oxide, (2) coagulation/flocculation by ferric chloride (FC), and (3) the combination these two methods in reducing the toxicity of wastewater generated by boat pressure washing. All three methods gave satisfactory results in the removal of colour, turbidity, Cr, Fe, Cu, Zn, and Pb. The concentrations of heavy metals were lowered below national limits with 1 g of CaO, 2.54 mg of Fe3+ in the form of FeCl3x6H2O, and the combination of 0.25 g of CaO and 5.08 mg of Fe3+ per 50 mL of wastewater. Both CaO (1.50 g per 50 mL of wastewater) and FC proved efficient, but their combination yielded a significantly better performance: 99.41 %, 100.00 %, 97.87 %, 99.09 %, 99.90 %, 99.46 % and 98.33 % for colour, turbidity, Cr, Fe, Cu, Zn, and Pb respectively. For colour, Cr, Cu, Zn, and Pb removal efficiencies increased in the following order: FC

Characterization and electrochemical treatment of landfill leachate.

A combined treatment approach using advanced oxidation, electrochemical methods and microwaves was developed and applied for the treatment of landfill leachate taken from Piskornica (Koprivnica, Croatia) sanitary landfill. Due to the complex nature of the effluent and extremely low bio-degradability (BOD(5)/COD ratio = 0.01) the purification of the leachate started with pre-treatment with ozone followed by simultaneous ozonation and electrocoagulation/electrooxidation using the set of iron and aluminum electrodes, and finally, the degradation of organic residue and ammonia with microwaves. Applied treatment approach resulted in clear, colorless and odorless effluent with the values of all measured parameters significantly lower compared to the upper permissible limit for discharge into the environment. The removal percentages of the parameters: color, turbidity, suspended solids, ammonia, COD and iron following the combined treatment were 98.43%, 99.48%, 98.96%, 98.80%, 94.17% and 98.56%, respectively.

Barrel inspection utilizing a 14 MeV neutron beam and associate alpha particle method.

A multi-sensor system was evaluated for the determination of barrel content with regard to eventual pollution hazards. The proposed system is able to investigate (in situ) the interior of a barrel filled with various unknown substances ranging from chemical and radioactive waste, raw sewage sludge, municipal incinerator ashes to common household trash. The crucial part of the system is a neutron sensor, which enables the identification of substance content without actually opening the barrel at all. A comparative laboratory test with the 3″×3″ and 5″×5″×10″ NaI(Tl) gamma ray detectors was made after which 3″×3″ detector was selected and incorporated in the submarine called "Surveyor". A field test was made in the Croatian Adriatic coast on the island Losinj. Field tests show that the commercial system utilizing the described method could be constructed for barrel inspection regardless of the measurement environment (underwater, on land, dumping site, isolated location, etc.).

The electrocoagulation/advanced oxidation treatment of the groundwater used for human consumption.

The purpose of this work was development and application of the purification system suitable for the treatment of groundwater used for human consumption, satisfying following criteria: (a) no need for external addition of the chemicals; (b) simultaneous removal of wide range of contaminants present in the treated water; (c) low sensitivity to the changes in the composition of the treated water; (d) high quality of treated water with regards to all measured parameters. Therefore the well water from the 60 m deep water layer situated near the city of Osijek (Eastern Croatia) with elevated values of heavy metals, color, turbidity, suspended solids, ammonia and organic contaminants was processed. Due to the complex composition of the treated water, the purification system required the combination of electroreduction/electrocoagulation, using iron and aluminum electrode plates followed by the simultaneous ozonation/UV treatment. The electroreduction/electrocoagulation approach was used for the removal of heavy metals, suspended solids, color and turbidity, while the organic contaminants and ammonia were removed by the ozonation/UV treatment. All measured parameters in the purified water were significantly lower compared to the regulated values. Under the optimum treatment conditions, the removal efficiencies for color, turbidity, nickel and arsenic were 100%. The removal efficiencies of V, Cr, Mn, Fe, Cu, Zn, Pb, ammonia, fluorides, sulfates and COD were 94.5%, 96.0%, 98.3%, 99.6%, 99.7%, 97.8%, 96.7%, 96,7%, 93.4%, 51.4%, 72.2% and 93.8%, respectively, increasing with the increased initial concentrations.

The application of the ozonation/electrocoagulation treatment process of the boat pressure washing wastewater.

This paper provides the information on the optimum conditions of the treatment process of the boat pressure washing wastewater (BPWW) by the combination of the ozonation and electrochemical (EC) methods developed on the laboratory and pilot plant scale. The initial effluent was highly enriched in heavy metals and elevated levels of organic contaminants. The concentrations of V, Cr, Fe, Cu, Zn, TOC, and COD exceeded the upper permissible limits of 22, 20, 6, 112, 17, 4, and 2 times, respectively. The main mechanisms of the organic matter destruction were the ozone oxidation and the indirect oxidation with chlorine/hypochlorite formed by the anodic oxidation of chloride already present in the wastewater. The heavy metal removal was forced by the coagulation/flocculation using Fe(2+), Fe(3+), and Al(3+) ions released into the treated solution by electrochemical corrosion of the sacrificial stainless steel and aluminum electrodes. At the optimum conditions obtained with the pilot plant, the removal efficiencies of the parameters V, Cr, Fe, Ni, Cu, Zn, Pb, TOC, and COD were 100.00 %, 99.35 %, 99.51 %, 87.31 %, 99.83 %, 99.65 %, 100.00 %, 88.46 %, and 76.28 %, respectively. All the parameters in the final effluent were in agreement with regulated values. The advantages of this system compared to its physico-chemical counterparts are as follows: (1) no need for the external addition of flocculating agents since they are electrochemically generated inside the treatment tank; (2) minimal pH changes during the treatment process not requiring pH adjustment by acids/basis; (3) a significantly lower amount of sludge since only Fe and Al ions were released in the solution; (4) flocs formed by the electrocoagulation can be easily separated by the filtration due to their higher stability, lower content of the bound water and larger surface compared to chemical flocs; (5) the final EC effluent is clear, colourless and odourless, containing the less total dissolved solids and organics, thence more suitable for the reuse compared to the one obtained by the standard chemical treatment.

Characterization and treatment of water used for human consumption from six sources located in the Cameron/Tuba City abandoned uranium mining area.

The purpose of this research was the characterization and improvement of the quality of water used for human consumption of unregulated/regulated water sources located in the Cameron/Tuba City abandoned uranium mining area (NE Arizona, western edge of the Navajo Nation). Samples were collected at six water sources which included regulated sources: Wind Mill (Tank 3T-538), Badger Springs and Paddock Well as well as unregulated sources: Willy Spring, Water Wall and Water Hole. Samples taken from Wind Mill, Water Wall and Water Hole were characterized with high turbidity and color as well as high level of manganese, iron and nickel and elevated value of molybdenum. High level of iron was also found in Badger Spring, Willy Spring, and Paddock Well. These three water sources were also characterized with elevated values of fluoride and vanadium. Significant amounts of zinc were found in Water Wall and Water Hole samples. Water Wall sample was also characterized with high level of Cr(VI). Compared to primary or secondary Navajo Nation Environmental Protection Agency (NNEPA) water quality standard the highest enrichment was found for turbidity (50.000 times), color (up to 1.796 times) and manganese (71 times), Cr(VI) (17.5 times), iron (7.4 times) and arsenic (5.2 times). Activities of (226)Ra and (238)U in water samples were still in agreement with the maximum contaminant levels. In order to comply with NNEPA water quality standard water samples were subjected to electrochemical treatment. This method was selected due to its high removal efficiency for heavy metals and uranium, lower settlement time, production of smaller volume of waste mud and higher stability of waste mud compared to physico-chemical treatment. Following the treatment, concentrations of heavy metals and activities of radionuclides in all samples were significantly lower compared to NNEPA or WHO regulated values. The maximum removal efficiencies for color, turbidity, arsenic, manganese, molybdenum and nickel were 100.0%. Maximum removal percentage of Cu, F(-), V, Zn, (137)Cs, (226)Ra, (232)Th, (238)U were as follows: 98.0%; 82.7%; 99.9%; 95.6%; 75.0%; 76.9%; 80.0% and 99.2%. From the results presented it could be concluded that electrochemical treatment is a suitable approach for the purification of drinking water with complex mixture of contaminants, especially those with high turbidity and color.

A combined treatment of landfill leachate using calcium oxide, ferric chloride and clinoptilolite.

The aim of this research was development of appropriate procedure for treatment of landfill leachate taken from old sanitary landfill Piskornica (Koprivnica, Croatia). Due to complex nature of the effluent a combined treatment approach was applied. Samples were treated with calcium oxide followed by ferric chloride and finally with clinoptilolite. The optimum amount of treating agents and contact time were determined. Application of calcium oxide (25 g/L, 20 min. contact time) resulted in the reduction of color, turbidity, suspended solids and ammonia for 94.50%, 96.55%, 95.66% and 21.60%, respectively, while the removal efficiency of Cr (VI), Fe, Ni, Cu, Zn and Pb was 75.00%, 95.34%, 56.52%, 78.72%, 73.02% and 100.00%, respectively. After addition of ferric chloride (570 mg Fe(3+)/L, 20 min. contact time) removal efficiency of color, turbidity, suspended solids and ammonia increased to 96.04%, 99.27%, 98.61%, and 43.20%, respectively. Removal of ammonia (81.60%) increased significantly after final adsorption onto clinoptilolite (25 g/L, 4 h contact time). Removal of COD after successive treatment with calcium oxide, ferric chloride and clinoptilolite was 64.70%, 77.40% and 81.00%, respectively.

Chemical profile of Plomin Bay sediments.

Granulometric, chemical, and leaching properties of sediments dredged in the Plomin Bay (Northern Adriatic Sea, Croatia) were investigated in order to asses the risk of remobilisation of heavy metals into the water column. In total 65 samples from 65 sampling sites were taken from different sediment depths within the bay. Analysis of variance confirmed the homogeneity of granulometric and elemental composition of the investigated sediment throughout its volume. Granulometric analysis showed that all samples corresponded to a pelitic fraction (<0.063 mm). Bulk elemental mass fractions in the sediments were similar to literature data on relatively unpolluted areas of the Adriatic Sea. High sedimentation rate caused by constant inflow of material from the Boljuncica River drainage may be responsible for low levels of heavy metals and negligible influence of fly and bottom ash from a nearby disposal site on the chemical composition of the sediments. In contact with sea water only 0.29 mg kg-1 of V, 0.04 mg kg-1 of Cr, 0.07 mg kg-1 of Ni, 0.33 mg kg-1 of Cu, 0.67 mg kg-1 of Zn and 0.06 mg kg-1 of Pb could be remobilised from sediment material into the water column. However, these values increased three to ten times in case of leaching with organic acids.

Purification of electroplating wastewaters utilizing waste by-product ferrous sulfate and wood fly ash.

A new procedure for electroplating wastewater treatment using waste by-product (ferrous-sulfate) and waste (wood fly ash) is presented. Ferrous-sulfate was employed for Cr(VI) reduction whereas neutralization and heavy metal removal from electroplating wastewaters was performed using wood fly ash. Heavy metal removal efficiency varied from 97.5% for Cu to 99.973% for Zn. Satisfying results can be achieved already at the pH 8. The method is suitable for the purposes of wastewater treatment and disposal in compliance with environmental laws. Furthermore, it is technically simple, cost-efficient and requires less space compared to the classical methodology. According to the composition of its water extractable fraction remaining waste ash could be safely deposited on domestic waste repositories.

Toxicological characterization of the new water cleaning product and its waste by-product.

Water extracts genotoxicity of the coagulant produced from industrial waste (red mud and waste base) and its waste mud remained after waste water treatment by the coagulation/flocculation process were studied. Tests were conducted in order to confirm nontoxicity of this new product prior to commercial production and usage and also to recommend a safe way for a handling and disposal of the remaining waste material. The toxicity investigation included (i) determining frequency of the cell survival, (ii) the Ames assays, (iii) micronucleus assay, and (iv) cell proliferation kinetics (expressed as mitotic index). These techniques were also employed in toxicity testing of the different concentrations of metal salts, zinc chloride, and lead nitrate in this case since these two elements were present in high concentrations in the waste water intended for the purification with the new coagulant. Mixture of metal salts in the concentrations that represent maximum allowed values for water extracts of technological waste was also tested. Two strains of Salmonella typhimurium, TA98, and TA100 were used for determining cytotoxicity and for the Ames test, while the cytogenetic investigations were performed on human peripheral blood lymphocytes. Water extracts of the coagulant and its waste mud did not induce a significant increase of the micronuclei in human peripheral blood lymphocytes. They also did not disturb lymphocyte proliferation kinetics in vitro. As regards lead nitrate it proved not to be cytotoxic on bacterial strains in the tested concentration range (1-100 mg/L), whereas zinc chloride showed cytotoxic effect for the concentrations above 25 mg/L. The Ames test results for the noncytotoxic concentrations of these metals were negative. Comparing to the negative control a significantly higher number of the micronuclei was determined after the treatment of the whole blood with 100 mg/L of zinc chloride, as well as with 10 and 100 mg/L of lead nitrate. A linear, dose dependent increase was obtained for both salts. Similar results were obtained on the basis of the mitotic index.