Milena Dalmacija

Removal of natural organic matter and arsenic from water by electrocoagulation/flotation continuous flow reactor.

The performance of the laboratory scale electrocoagulation/flotation (ECF) reactor in removing high concentrations of natural organic matter (NOM) and arsenic from groundwater was analyzed in this study. An ECF reactor with bipolar plate aluminum electrodes was operated in the horizontal continuous flow mode. Electrochemical and flow variables were optimized to examine ECF reactor contaminants removal efficiency. The optimum conditions for the process were identified as groundwater initial pH 5, flow rate=4.3 l/h, inter electrode distance=2.8 cm, current density=5.78 mA/cm(2), A/V ratio=0.248 cm(-1). The NOM removal according to UV(254) absorbance and dissolved organic matter (DOC) reached highest values of 77% and 71% respectively, relative to the raw groundwater. Arsenic removal was 85% (6.2 μg As/l) relative to raw groundwater, satisfying the drinking water standards. The specific reactor electrical energy consumption was 17.5 kWh/kg Al. The specific aluminum electrode consumption was 66 g Al/m(3). According to the obtained results, ECF in horizontal continuous flow mode is an energy efficient process to remove NOM and arsenic from groundwater.

A comparative study of the effects of ozonation and TiO2-catalyzed ozonation on the selected chlorine disinfection by-product precursor content and structure

This study compares the effects of ozonation (0.4-3.0 mg O(3)/mg DOC) and TiO(2)-catalyzed ozonation - TiO(2)-O(3) (0.4-3.0 mgO(3)/mg DOC; 1.0 mgTiO(2)/L) at pH 6 on the content and structure of natural organic matter (NOM) and trihalometane (THM) and haloacetonitrile (HAN) precursors in groundwater. The investigated groundwater from Northern Serbia is rich in NOM (9.85 mg/L DOC) which is mostly of hydrophobic character (65% fulvic acid and 14% humic acid fraction). It was found that the TiO(2)-catalyzed process, by favoring the radical mechanism of NOM oxidation, resulted in a more effective reduction in the content of total NOM (up to 18% DOC) compared to ozonation alone (up to 6% DOC). The use of TiO(2) also resulted in an improvement of ozonation in terms of THM precursor content removal (up to 80%). On the other hand, the application of both oxidation treatments resulted in an increase in the HANFP compared to the raw water. NOM oxidation during ozonation and TiO(2)-O(3) caused changes in their structure in the direction of an increased proportion of the hydrophilic fraction (up to 70%), which has the most reactive THM and HAN precursors, as well as the fraction with the highest content of their brominated species.

Correlation between the results of sequential extraction and effectiveness of immobilization treatment of lead- and cadmium-contaminated sediment.

The assessment of the quality of sediment from the Great Backi Canal (Serbia), based on the pseudo-total lead (Pb) and cadmium (Cd) content according to the corresponding Dutch standards and Canadian guidelines, showed its severe contamination with these two metals. A microwave-assisted BCR (Community Bureau of Reference of the Commission of the European Union) sequential extraction procedure was employed to assess their potential mobility and risk to the aquatic environment. Comparison of the results of sequential extraction and different criteria for sediment quality assessment has led to somewhat contradictory conclusions. Namely, while the results of sequential extraction showed that Cd comes under the high-risk category, Pb shows low risk to the environment, despite its high pseudo-total content. The contaminated sediment, irrespective of the different speciation of Pb and Cd, was subjected to the same immobilization, stabilization/solidification (S/S) treatments using kaolinite, montmorillonite, kaolinite-quicklime, montmorillonite-quicklime, fly ash, zeolite, or zeolite-fly ash combination. Semi-dynamic leaching tests were conducted for Pb- and Cd-contaminated sediment in order to assess the long-term leaching behavior of these metals. In order to simulate “worst case” leaching conditions, the semi-dynamic leaching test was modified using 0.014 M acetic acid (pH = 3.25) and humic acid solutions (20 mg TOC l-1) as leachants instead of deionized water. The effectiveness of S/S treatment was evaluated by determining diffusion coefficients (De) and leachability indices (LX). The standard toxicity characteristic leaching procedure (TCLP) was applied to evaluate the extraction potential of Pb and Cd. A diffusion-based model was used to elucidate the controlling leaching mechanisms. Generally, the test results indicated that all applied S/S treatments were effective in immobilizing Pb and Cd, and the treated sediments may be considered acceptable for “controlled utilization” based on LX values, irrespective of their different availability in the untreated samples. In the majority of samples, the controlling leaching mechanism appeared to be diffusion, which indicates that a slow leaching of Cd and Pb could be expected when the above S/S agents were applied. The TCLP results showed that all S/S samples were nonhazardous.

Changes in metal availability during sediment oxidation and the correlation with the immobilization potential.

Fractionation of metals (Pb, Cd, Ni, Zn, Cu and Cr) in severely contaminated sediment has been investigated to determine its speciation and eco-toxic potential at the beginning of the experiment and after 18 months of sediment oxidation. Pb, Ni and Zn showed a high risk, while Cu, Cd and Cr showed low to medium risk at the beginning. Oxidation yielded an increased mobility of all metals apart from cadmium. The ratio of the simultaneously extracted metals (SEM) and acid volatile sulfides (AVS) was found to be >1. Semi-dynamic and toxicity characteristic leaching tests were conducted to assess the effectiveness of solidification/stabilization (S/S) thermal treatment with clay and long-term leaching behavior of these metals. A diffusion-based model was used to elucidate the controlling leaching mechanisms. Applied S/S thermal treatment was effective in immobilizing metals, irrespective of their different availability in the untreated samples. The controlling leaching mechanism appeared to be diffusion.

Removal of arsenic and natural organic matter from groundwater using ferric and alum salts: A case study of central Banat region (Serbia)

This paper presents a comparison of the efficacy of three different coagulants (polyaluminium chloride (PACl), Aluminium sulphate (Al2(SO4)3) and ferrous chloride (FeCl3)) for natural organic matter and arsenic (As) removal from groundwater. Coagulation efficacy was evaluated for the coagulants alone and for combinations of them (PACl/FeCl3; Al2(SO4)3/FeCl3), on the basis of changes in dissolved organic matter (DOC) and arsenic content. For single coagulants, PACl (30 mg Al/L) showed optimal efficacy for DOC removal (57%, relative to raw water). The highest arsenic reduction (< 5 μ g As/L in coagulated water) was achieved when a very high 300 mg/L dose of FeCl3 was used. However, if PACl (30 mg Al/L) and FeCl3 (10 mg FeCl3/L) are combined, the efficacy of DOC removal increases compared to PACl and FeCl3 alone under similar doses (66% decrease in DOC relative to raw water). The DOC and As contents of the coagulated water after application of these doses were 2.26 mg C/L and 9.7 μ g/L, respectively, compared to 6.44 mg C/L and 60.5 μ g As/L measured in the raw groundwater. The combination of Al2(SO4)3 and FeCl3 did not show any improvement in DOC and As removal efficacy relative to using those coagulants alone.

Photocatalytic Degradation of Herbicide Quinmerac in Various Types of Natural Water

The efficiency of the photocatalytic degradation of the herbicide quinmerac in aqueous TiO2 suspensions was examined as a function of the type of light source, TiO2 loading, pH, temperature, electron acceptors, and hydroxyl radical (•OH) scavenger. The optimum loading of catalyst was found to be 0.25 mg mL−1 under UV light at pH 7.2, with the apparent activation energy of the reaction being 13.7 kJ mol−1. In the first stage of the reaction, the photocatalytic degradation of quinmerac (50 μM) followed approximately a pseudo-first order kinetics. The most efficient electron acceptor appeared to be H2O2 along with molecular oxygen. By studying the effect of ethanol as an •OH scavenger, it was shown that the heterogeneous catalysis takes place mainly via •OH. The results also showed that the disappearance of quinmerac led to the formation of a number of organic intermediates and ionic byproducts, whereas its complete mineralization occurred in about 120 min. The reaction intermediates (7-chloro-3-methylquinoline-5,8-dione, three isomeric phenols hydroxy-7-chloro-3-methylquinoline-8-carboxylic acids, and 7-chloro-3-(hydroxymethyl)quinoline-8-carboxylic acid) were identified and the kinetics of their appearance/disappearance was followed by LC–ESI–MS/MS. Tentative photodegradation pathways were proposed and discussed. The study also encompassed the effect of quality of natural water on the rate of removal of quinmerac.

Behavior of zinc, nickel, copper and cadmium during the electrokinetic remediation of sediment from the Great Backa Canal (Serbia)

This paper describes a bench-scale study dealing with the removal of heavy metals by electrokinetic (EK) remediation from sediment of the Great Backa Canal (Vojvodina, Republic of Serbia), with an emphasis on the dependence of removal efficacies on the physicochemical states of the heavy metals and sediment chemistry. Sediment samples were spiked with the following heavy metals (mg kg− 1): Zn 4400, Ni 900, Cu 1140 and Cd 57. In addition to determining the pseudo-total metal content in the contaminated sediment before and after EK treatment, BCR sequential extraction was also performed to examine the distribution of the contaminants in the sediment. Conventional EK remediation (EXP I) was ineffective in removing the heavy metals investigated, so two enhanced processes were developed. In both these processes, the mass of treated sediment was reduced to avoid the presence of inactive electric field areas in the sediment and increase current density. The first enhanced experiment (EXP II) used acetic acid (HAc) solution (pH 2.9) as an anolyte. Combined with the smaller sediment mass, this resulted in an increase in overall removal efficacies (9% for Zn, 15% for Ni, 10% for Cu and 15% for Cd). The second enhanced experiment (EXP III), as well as using HAc solution as an anolyte, made use of a cation exchange membrane in the cathodic chamber to minimize pH changes in the region adjacent to the cathode, which negatively influenced the removal of some heavy metals. However, no improvement in removal efficacy was achieved in EXP III. Since the redox potential of the sediment drops during the EK process, metals removal is limited by the formation of their sulfides. In conclusion, the removal of heavy metals by EK remediation is governed by a complex interplay of the complexation, precipitation and reduction processes, and the difficulties encountered in their optimization can explain the unsatisfactory effectiveness achieved by the described remediation procedure. Improved understanding of the behavior of metal ions during EK treatment can be useful in predicting and enhancing the efficacy of the process.

Immobilization of Cadmium from Contaminated Sediment Using Cardboard Mill Sludge

Abstract Sludge from cardboard mill is most commonly landfilled, but it could also be recycled on-site into production or reused in some other way. In this study the use of sludge from cardboard mill as stabilizing agent in the stabilization treatment of cadmium polluted sediment was examined. The effectiveness of treatment and long-term leaching behavior of cadmium was evaluated by determining the cumulative percentage of cadmium leached, diffusion coefficients (De) and by applying different leaching tests (semi-dynamic test, toxicity characteristic leaching procedure, waste extraction test). In order to simulate the “worst case” leaching conditions, the semi-dynamic leaching test was modified using 0.014 M acetic acid (pH = 3.25) and humic acids solution (20 mg l-1 TOC) as leachants instead of deionized water. A diffusion-based model was used to elucidate the controlling leaching mechanisms. Applied treatment was effective in immobilizing cadmium irrespective of high availability in the untreated sample. The controlling leaching mechanism appeared to be diffusion, which indicates that a slow leaching of cadmium could be expected when the cardboard mill sludge as stabilization agent is applied.

Tracking disinfection by-products and arsenic removal during various drinking water treatment trains

In the central Banat region (Northern Serbia), groundwater is used as a drinking water source. Raw water originates from a 40-80 m and 100-150 m deep layer. It contains a high amount of natural organic matter (DOC = 9.17+/-0.87 mg C/L) with a trihalomethanes formation potential of 448+/-88.2 microg/L and a haloacetic acid formation potential of 174+/-68.9 microg/L. A high amount of arsenic (86.0+/-3.4 microg/L) is also found in this water. This study used a pilot-scale system to investigate the possibilities of combining polyaluminium chloride and ferrous-chloride to remove disinfection by-products precursors and arsenic by coagulation. Two treatment trains with different pre-treatment steps were investigated (ozone vs. H2O2/O3). For the final water polishing, filtration with granulated activated carbon (GAC) was applied. Both investigated treatment lines achieved a satisfactory chemical water quality. Simulation of disinfection conditions was performed and the contents of trihalomethanes and haloacetic acids measured, to investigate whether the chemical quality of the water remained satisfactory over a 48 hour period.

Improving the Electrokinetic Remediation of Nickel-, Cadmium-, and Lead-contaminated Sediment

In this work, the simultaneous application of bipolar electrodes and a longer cathodic compartment length without agents addition was used as an enhanced electrokinetic treatment of Ni-, Cd-, and Pb-contaminated sediment. Conventional and enhanced treatments were investigated and their efficacy assessed by comparing the residual metals content in the sediment with values given by Dutch standards. After conventional treatment removals of 20%, 19%, and 31% for Ni, Cd, and Pb were achieved, whereas the enhanced treatment achieved removal efficacies of 36% for Ni, 42% for Cd, and 43% for Pb. Results indicate that the simultaneous application of the techniques mentioned is effective for removing Ni and Pb whereas Cd was not removed to the desired level. Here we show that the addition of chemicals is not necessary to increase the efficacies of electrokinetic sediment treatments, so the simultaneous application of the techniques mentioned can be described as environmentally friendly.