In situ removal of copper from sediments by a galvanic cell

This study dealt with in situ removal of copper from sediments through an electrokinetic (EK) process driven by a galvanic cell. Iron (Fe) and carbon (C) were placed separately and connected with a conductive wire. Polluted sediments were put between them and water was filled above the sediments. The galvanic cell was thus formed due to the different electrode potentials of Fe and C. The cell could remove the pollutants in the sediments by electromigration and/or electroosmosis. Results showed that a weak voltage less than 1V was formed by the galvanic cell. The voltage decreased with the increase of time. A slight increase of sediment pH from the anode (Fe) to the cathode (C) was observed. The presence of supernatant water inhibited the variation of sediment pH because H(+) and OH(-) could diffuse into the water. The removal of copper was affected by the sediment pH and the distribution of electrolyte in sediment and supernatant water. Lower pH led to higher removal efficiency. More electrolyte in the sediment and/or less electrolyte in the supernatant water favored the removal of copper. The major removal mechanism was proposed on the basis of the desorption of copper from sediment to pore solution and the subsequent electromigration of copper from the anode to the cathode. The diffusion of copper from sediment to supernatant water was negligible.     

Transport of cadmium and assessment of phytotoxicity after electrokinetic remediation

The use of ethylene diamine tetraacetic acid (EDTA) on the electrokinetic removal of cadmium-contaminated soil was evaluated. A total of four different tests were conducted using EDTA as a washing solution as well as a purging solution at the electrode compartments. The efficiency of electrokinetic extraction was significantly influenced by the pH of the soil medium. The results show that EDTA was effective in desorbing cadmium at a high pH, with Cd-EDTA(-) anion complexes migrating toward the anode. At low pH values near the anode area, cadmium existed as Cd(2+), migrating toward the cathode. Such contradicting directions of cadmium have resulted in its detrimental removal from the soil cell. However, accumulation of cadmium near the cathode was observed at the end of the tests due to the dominating low pH in the soil cell. The phytotoxicity after the electrokinetic process was investigated using Sorghum saccharatum, Lepidium sativum and Sinapis alba plants. The germination index was a major endpoint estimated by measuring seed germination and shoot elongation. The results obtained show that the phytotoxicity was increased after electrokinetic extraction. Despite, the extensive cadmium removal from two-thirds of the cell, the low pH of the soil was the principal parameter exhibiting the phytotoxicity.     

Fluoride removal using capacitive deionization process employing carbon electrodes

Contamination of groundwater with fluoride poses adverse health impacts for humans. This study aims to investigate the feasibility of capacitive deionization process for fluoride removal from groundwater. In this study, composition of binder content was optimized and the experiments were performed using a lab scale batch reactor. Effect of initial ionic concentration on the removal efficiency was also studied. The electrodes were also evaluated for their efficiency to remove arsenic. The maximum fluoride removal efficiency obtained was 99.1% for the PVDF content of 15% (w/w) whereas for arsenic it was only 52%. The voltage applied across the electrodes was only 1.2V. Electrodes were tested for their physical strength and their characterization was done using Scanning Electron Microscope. Sorption kinetics of the electrodes was also investigated and was found that the adsorption followed elovich model most closely.     

Intermittently aerated EMMC-Biobarrel (entrapped mixed microbial cell with Bio-barrel) process for concurrent organic and nitrogen removal

The PEMMC-Biobarrel (packed-bed of entrapped mixed microbial cells with Bio-barrel) process and MEMMC-Biobarrel (moving EMMC-Biobarrel) process were investigated for enhancing concurrent organic and nitrogen removal with applied intermittent aeration. For the PEMMC-Biobarrel process, the EMMC-Biobarrel carriers were employed at a packing ratio of 20%. In the MEMMC-Biobarrel process, the EMMC-Biobarrel carriers with a packing ratio of 10% were added along with the activated sludge (AS) in the bioreactor. Three different hydraulic retention times (HRTs) of 9, 6 and 4 h were applied. Aeration was provided intermittently at time schedules of 1 h air on/1 h air off, 1 h on/1.5 h off and 1 h on/2 h off. Nitrogen removal in the PEMMC-Biobarrel system was not improved by increasing the intermittent non-aeration time period. On the other hand, the MEMMC-Biobarrel process enhanced nitrogen removal with increasing non-aeration time even though the SCOD/N(TIN) ratio decreased from 6 to 4. Significant denitrification during the aeration cycle was observed in the MEMMC-Biobarrel process. The MEMMC-Biobarrel process demonstrated the most efficient organic and nitrogen removal at an HRT of 6 h with an intermittent aeration time schedule of 1 h on/2 h off. Nitrogen removal of 80% was achieved, which was about 15% higher compared to the AS system. TCOD and SCOD removal efficiencies were 80% and 75%, respectively.     

Use of constructed wetland for the removal of heavy metals from industrial wastewater

This study was conducted to investigate the effectiveness of a continuous free surface flow wetland for removal of heavy metals from industrial wastewater, in Gadoon Amazai Industrial Estate (GAIE), Swabi, Pakistan. Industrial wastewater samples were collected from the in-let, out-let and all cells of the constructed wetland (CW) and analyzed for heavy metals such as lead (Pb), cadmium (Cd), iron (Fe), nickel (Ni), chromium (Cr) and copper (Cu) using standard methods. Similarly, samples of aquatic macrophytes and sediments were also analyzed for selected heavy metals. Results indicate that the removal efficiencies of the CW for Pb, Cd, Fe, Ni, Cr, and Cu were 50%, 91.9%, 74.1%, 40.9%, 89%, and 48.3%, respectively. Furthermore, the performance of the CW was efficient enough to remove the heavy metals, particularly Cd, Fe, and Cu, from the industrial wastewater fed to it. However, it is suggested that the metal removal efficiency of the CW can be further enhanced by using proper management of vegetation and area expansion of the present CW.     

Rapid removal of nitrate and sulfate in freshwater wetland sediments

Anaerobic microbial processes play particularly important roles in the biogeochemical functions of wetlands, affecting water quality, nutrient transport, and greenhouse gas fluxes. This study simultaneously examined nitrate and sulfate removal rates in sediments of five southwestern Michigan wetlands varying in their predominant water sources from ground water to precipitation. Rates were estimated using in situ push-pull experiments, in which 500 mL of anoxic local ground water containing ambient nitrate and sulfate and amended with bromide was injected into the near-surface sediments and subsequently withdrawn over time. All wetlands rapidly depleted nitrate added at ambient ground water concentrations within 5 to 20 h, with the rate dependent on concentration. Sulfate, which was variably present in porewaters, was also removed from injected ground water in all wetlands, but only after nitrate was depleted. The sulfate removal rate in ground water-fed wetlands was independent of concentration, in contrast to rates in precipitation-fed wetlands. Sulfate production was observed in some sites during the period of nitrate removal, suggesting that the added nitrate either stimulated sulfur oxidation, possibly by bacteria that can utilize nitrate as an oxidant, or inhibited sulfate reduction by stimulating denitrification. All wetland sediments examined were consistently capable of removing nitrate and sulfate at concentrations found in ground water and precipitation inputs, over short time and space scales. These results demonstrate how a remarkably small area of wetland sediment can strongly influence water quality, such as in the cases of narrow riparian zones or small isolated wetlands, which may be excluded from legal protection.     

Removal of Cr(VI) from Cr-contaminated groundwater through electrochemical addition of Fe(II)

The conventional chemical reduction-precipitation technique in the removal of Cr(VI) from contaminated groundwater involves a two-step process whereby Cr(VI) is first reduced to Cr(III) at an acidic pH by a reducing agent and in a subsequent step, Cr(III) is precipitated as insoluble hydroxide at an alkaline pH. In a variation of this method, Fe(II) is added electrochemically to the Cr(VI) containing water. From a pure iron electrode, Fe(2+) ions are released into the solution and bring forth the reduction of Cr(VI). At the cathode, H(2)O is reduced whereby the OH(-) ions entering the solution keep the pH of the solution in the alkaline range. This latter fact greatly facilitates simultaneous reduction of Cr(VI) to Cr(III) and co-precipitation of hydroxides of trivalent Cr and Fe. On the basis of a set of experimental data, it is shown that this process is both thermodynamically and kinetically efficient, meaning, with the electrochemical method, rapid and nearly complete removal of Cr(VI) from a groundwater source with both high and low levels of Cr-contamination can be achieved. These factors make the electrochemical process superior to the conventional chemical process in remediation of Cr-contaminated groundwater.     

Electrochemical remediation of copper (II) from an industrial effluent Part II: three-dimensional foam electrodes

A batch recycle removal of copper ions from an industrial effluent by means of copper foam cathodes was tested. A constant current of 750 A was applied to the cell in order to perform the reduction. Copper depletion was investigated at different solution flow rates and a removal greater than 98% was obtained with a flow rate of 1000 l/h. The influence of initial metal concentration on copper deposition and current efficiency is also discussed.     

Accumulation, distribution, and toxicity of copper in sediments of catfish ponds receiving periodic copper sulfate applications

Copper sulfate (CuSO4) is applied periodically to commercial channel catfish (Ictalurus panctatus) ponds as an algicide or parasiticide. Current understanding of the chemistry of copper in soil-water systems suggests that copper may accumulate in pond sediments, although the forms and potential bioavailability of copper in catfish pond sediments are not known. This study investigated the accumulation and distribution of copper in the sediment of catfish ponds receiving periodic additions of CuSO4.5H2O. All ponds were constructed in Sharkey (very-fine, smectitic, thermic Chromic Epiaquert) soil. Nine 0.40-ha ponds received 59 applications of 2.27 kg CuSO4.5H2O per application per pond over 3 yr; no CuSO4.5H2O applications were made to nine additional ponds. Total Cu concentration in the sediments of CuSO4.5H2O-amended catfish ponds (172.5 mg kg(-1)) was four to five times higher than that in the sediments of nonamended ponds (36.1 mg kg(-1)). Copper accumulated in catfish pond sediments at a rate of 41 microg kg(-1) dry sediment for each 1 kg ha(-1) of CuSO4. 5H2O applied to ponds. Copper in the sediments of amended ponds was mainly in the organic matter-bound (30.7%), carbonate-bound (31.8%), and amorphous iron oxide-bound (22.1%) fractions with a considerable fraction (3.4%; 3 to 8 mg kg(-1)) in soluble and exchangeable fractions. This indicates that Cu accumulates differentially in various fractions, with proportionally greater initial accumulation in potentially bioavailable forms. However, toxicity bioassays with amphipods (Hyallela azteca) and common cattail (Typha latifolia L.) indicated that the effect of exposure to amended or nonamended pond sediments was not different.     

Characterization of selenate removal from drainage water using rice straw

Removal of selenium (Se) from agricultural drainage water is very important for protecting wildlife in wetland systems. We conducted a series of experiments on selenite [Se(IV)] adsorption and selenate [Se(VI)] reduction to determine Se removal from drainage water amended with 1000 microg/L of Se(VI) or Se(IV) and 5 g of rice (Oryza sativa L.) straw. Under sterile conditions, the added Se(IV) was not adsorbed to the rice straw within 2 d of the experiment and the added Se(VI) was not reduced within 14 d. In contrast, added Se(VI) in a nonsterile rice-straw solution was reduced rapidly, from 930 microg/L at Day 3 to 20 microg/L at Day 5, with an increase in unprecipitated elemental Se [Se(0)] and total Se(0). In the last several days of the experiments, unprecipitated Se(0) was the major Se form in the rice-straw solution, with a small amount of organic Se(-II). This study showed that Se removal from drainage water in the presence of rice straw involves a two-step process. The first is the microbial reduction of Se(VI) to Se(IV) and then to colloidal Se(0). The second is flocculation and precipitation of colloidal Se(0) to the bottom of the experimental flasks and the surface of rice straw.     

Fate of colloidal-particulate elemental selenium in aquatic systems

Bacterial reduction of selenate [Se(VI)] to elemental Se [Se(0)] is considered an effective bioremediation technique to remove selenium (Se) from agricultural drainage water. However, the fate of the newly formed Se(0) in aquatic systems is not known when it flows out of the treatment system. A set of laboratory experiments was conducted to determine the fate of the colloidal-particulate Se(0) in a water column and in a water-sediment system. Results showed that the newly formed colloidal-particulate Se(0) followed two removal pathways in aquatic systems: (i) flocculation-sedimentation to the bottom of the water and (ii) oxidation to selenite [Se(IV)] and Se(VI). During 58 d of the experiments, 51% of the added Se(0) was precipitated to the bottom of the water and 47% was oxidized to Se(IV) in the water column. In the water-sediment system, Se(IV) in the water accounted for 21 to 25% of the added Se(0). Adsorption of Se(IV) to the bottom sediment resulted in a relatively low amount of Se(IV) in the water. This study indicates that the newly formed Se(0) may be an available form of Se for uptake by organisms if it flows to aquatic systems from a treatment site. Therefore, an effective bioremediation system for removing Se from drainage water must reduce Se(VI) to Se(0) and remove Se(0) directly from the drainage water.     

Optimization of the electrocoagulation process for the removal of copper, lead and cadmium in natural waters and simulated wastewater

Chemical, electrochemical and flow variables were optimized to examine the effectiveness of the electrocoagulation process for the removal of copper, lead and cadmium. The electrochemical process, which uses electrodes of commercial laminate steel, was applied to simulated wastewater containing 12 mg dm(-3) of copper, 4 mg dm(-3) of lead and 4 mg dm(-3) of cadmium. The optimum conditions for the process were identified as pH=7, flow rate=6.3 cm(3) min(-1) and a current density between 31 and 54 A m(-2). When the electrode geometric area and time of electrolysis reached critical values, the copper removal reached a maximum value of 80%. A linear relationship was identified between the current density and the mass of generated sludge. In addition, a linear relationship was found between specific energy consumption and current density. The results of this investigation provide important data for the development of an industrial-scale electrolytic reactor.     

Dredging of drainage ditches increases short-term transport of soluble phosphorus

Managed drainage ditches are common in the midwestern United States. These ditches are designed to remove water from fields as quickly as possible, and sediment buildup necessitates dredging, to ensure adequate water removal. This laboratory study was conducted to determine the impact of ditch dredging on soluble phosphorus (P) transport. Ditch sediments were collected from a drainage ditch in northeastern Indiana immediately before and after dredging. The sediments were placed in a stream simulator, and stream water was loaded with 0.55 mM P for 5 d (adsorption experiment). Water was then removed, and "clean" water (no P added) was used for a desorption experiment, lasting 1 d. During the adsorption experiment, pre-dredged sediments were able to remove P from the water column quicker, and P concentrations 120 h after introduction of high P water were lower for the pre-dredged sediments (0.075 mM P) than the dredged sediments (0.111 mM P). During the desorption experiment, P was released to the water column slower in the pre-dredged treatment than the dredged treatment (instantaneous flux at t = 0 was 0.205 microM P h(-1) for pre-dredged and 0.488 microM P h(-1) for dredged). This occurred despite higher Mehlich 3-extractable P in the pre-dredged sediments than the dredged sediments. Equilibrium phosphorus concentrations (EPCo) were lower in the pre-dredged sediments during both adsorption and desorption experiments. Transport of soluble P immediately after dredging will likely increase in drainage ditches; however, dredging is a necessary management tool to ensure adequate discharge of water from surrounding fields.     

Electrokinetic extraction of lead from kaolinites: I. Numerical modeling

Experimental results obtained to date indicate electrokinetic extraction is viable in removing organic and inorganic contaminants from fine-grained soils. However, electrochemical reactions and soil-contaminant interactions that occur simultaneously may enhance or reduce the removal efficiency of the hazardous waste site remediation process. Many sites worldwide are contaminated by lead and its compounds, resulting in lead poisoning. It is difficult to remove lead from fine-grained soil because of the existence of a great variety of lead complexes and their pH-dependent and reversible physicochemical properties. The feasibility of electrokinetic extraction of lead from kaolinites is investigated theoretically, numerically, and experimentally in this study. This is the first paper of two companion papers presenting the theoretical and numerical modeling of the transport of lead species, and electrochemical reactions and soil-contaminant interactions occurring during the electrokinetic extraction process. The comparison between simulation results and experimental results is presented in the second paper.     

Removal of Fe(II) from the wastewater of a galvanized pipe manufacturing industry by adsorption onto bentonite clay

Bentonite clay has been used for the adsorption of Fe(II) from aqueous solutions over a concentration range of 80-200 mg/l, shaking time of 1-60 min, adsorbent dosage from 0.02 to 2 g and pH of 3. The process of uptake follows both the Langmuir and Freundlich isotherm models and also the first-order kinetics. The maximum removal (>98%) was observed at pH of 3 with initial concentration of 100 mg/l and 0.5 g of bentonite. The efficiency of Fe(II) removal was also tested using wastewater from a galvanized pipe manufacturing industry. More than 90% of Fe(II) can be effectively removed from the wastewater by using 2.0 g of the bentonite. The effect of cations (i.e. zinc, manganese, lead, cadmium, nickel, cobalt, chromium and copper) on the removal of Fe(II) was studied in the concentration range of 10-500 mg/l. All the added cations reduced the adsorption of Fe(II) at high concentrations except Zn. Column studies have also been carried out using a certain concentration of wastewater. More than 99% recovery has been achieved by using 5 g of the bentonite with 3M nitric acid solution.     

Solar oxidation and removal of arsenic from water: An experimental study

Arsenic poses a significant threat to both human health and the environment. Arsenic removal through solar oxidation has been investigated in a batch process. Arsenic was artificially added to both deionized and tap water to conduct the experiments. Clean, colorless, transparent, Polyethylene Terephthalate (PET) bottles were used for Solar Oxidation and Removal of Arsenic (SORAS) experiments. Various parameters including concentration of arsenic, iron, and photo-catalyst were varied during the experiments. The maximum arsenic removal efficiency obtained was 94% and 88% for deionized water and tap water respectively when ferrous ammonium sulphate and lemon juice were used. Maximum efficiency of 88% and 82% was obtained for deionized and tap water respectively when locally available ferrous alum and glacial acetic acid were used. The change in volume of the photo-catalyst (lemon juice and glacial acetic acid) also did not affect the SORAS process significantly. Therefore, the recommended volume for the photo-catalyst was 1–2 ml/L. SORAS can very well be used for areas contaminated with arsenic having concentrations less than 100 μg/L.     

The removal of lignin and phenol from paper mill effluents by electrocoagulation

This study aims to investigate the treatment of paper mill effluents using electrocoagulation. Removal of lignin, phenol, chemical oxygen demand (COD) and biological oxygen demand (BOD) from paper mill effluents was investigated at various current intensities by using different electrodes (Al and Fe) and at various electrolysis times (1.0, 2.5, 5.0 and 7.5min). It was observed that the experiments carried out at 12V, an electrolysis time of 2min and a current intensity of 77.13mA were sufficient for the removal of these pollutants with each electrode. The removal capacities of the process using an Al electrode were 80% of lignin, 98% of phenol, 70% of BOD, and 75% of COD after 7.5min. Using an Fe electrode the removal capacities were 92%, 93%, 80% and 55%, respectively. In addition, it was found that removal of lignin, phenol, BOD and COD increased with increasing current intensity. In the experiments carried out at different current intensities, higher removal can be explained through a decrease in intra-resistance of solution and consequently an increase at the transfer speed of organic species to electrodes. It was also found that Al electrode performs higher efficiency than Fe electrode except for COD removal. However, the time required for removal of BOD was more than that of COD. The results suggest that electrocoagulation could be considered as an effective alternative to paper mill effluents treatment.     

Electrokinetic extraction of lead from kaolinites: II. Experimental investigation

This is the second paper of two companion papers presenting the results of laboratory bench-scale experimental studies on electrokinetic extraction of lead from two different kaolinites. The theoretical formulation and numerical simulation of the process are presented in the first paper. Two different kaolinites were used in the study: (1) Georgia kaolinite and (2) Milwhite kaolinite. The lead spiked in Georgia kaolinite was highly mobilized and effectively extracted by the technique as the pH in the soil was significantly lowered by the electrokinetic process. Milwhite kaolinite has a much higher acid/base buffer capacity, and the required acidic environment could not be developed. As a result, removal of the lead spiked in Milwhite kaolinite was minimal. Comparison between simulations and experimental results is also presented. Factors affecting the cleanup efficiency of the process and potential enhancement techniques are also discussed.     

Electroosmotic dewatering of dredged sediments: bench-scale investigation

The Indiana Harbor (Indiana, USA) has not been dredged since 1972 due to lack of a suitable disposal site for dredged sediment. As a result of this, over a million cubic yards of highly contaminated sediment has accumulated in the harbor. Recently, the United States Army Corps of Engineers (USACE) has selected a site for the confined disposal facility (CDF) and is in the process of designing it. Although dredging can be accomplished rapidly, the disposal in the CDF has to be done slowly to allow adequate time for consolidation to occur. The sediment possesses very high moisture content and very low hydraulic conductivity, which cause consolidation to occur slowly. Consolidation of the sediment is essential in order to achieve adequate shear strength of sediments and also to provide enough air space to accommodate the large amount of sediment that requires disposal. Currently, it has been estimated that if a one 3-foot (0.9-m) thick layer of sediment was disposed of at the CDF annually, it would take approximately 10 years to dispose of all the sediment that is to be dredged from the Indiana Harbor. This study investigated the feasibility of using an electroosmotic dewatering technology to accelerate dewatering and consolidation of sediment, thereby allowing more rapid disposal of sediment into the CDF. Electroosmotic dewatering essentially involves applying a small electric potential across the sediment layer, thereby inducing rapid flow as a result of physico-chemical and electrochemical processes. A series of bench-scale electrokinetic experiments were conducted on actual dredged sediment samples from the Indiana Harbor to investigate dewatering rates caused by gravity alone, dewatering rates caused by gravity and electric potential, and the effects of the addition of polymer flocculants on dewatering of the sediments. The results showed that electroosmotic dewatering under an applied electric potential of 1.0VDC/cm could increase the rate of dewatering and consolidation by an order of magnitude as compared to gravity drainage alone. Amending the sediment with polymers at low concentrations (0.5-1% by dry weight) will enhance this dewatering process; however, the optimal polymer concentration and the cost-effectiveness of using polymers should be investigated further.