Ljiljana Rajić

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.

Spectroscopic monitoring of photocatalytic degradation of the insecticide acetamiprid and its degradation product 6-chloronicotinic acid on TiO2 catalyst

Two spectroscopic methods, 1H NMR and FTIR, were developed for the monitoring of the photocatalytic degradation of acetamiprid, a widely used pyridine-based neonicotinoid insecticide, in UV-irradiated aqueous suspensions of O2/TiO2. The 1H NMR method allowed also the identification of the intermediates such as 6-chloronicotinic and formic acids, as well as separate monitoring of the kinetics of degradation of acyclic and aromatic moieties based on the different chemical shifts of the protons belonging to the methyl group of the acyclic and selected proton of the heterocyclic aromatic moiety. The FTIR procedure enabled the monitoring of the kinetics of degradation of the cyano group of the compound. The obtained results are in good agreement with the comparative HPLC-DAD and HPLC-MS/MS measurements, which also enabled the identification of certain intermediates. To get a deeper insight into the complex photocatalytic process, the photocatalytic degradation of 6-chloronicotinic acid, a stable degradation intermediate of acetamiprid, was also investigated by 1H NMR and HPLC-DAD methods. Based on the obtained data, a tentative reaction mechanism was proposed for the photocatalytic degradation of acetamiprid.

Degradation of Anthraquinone Dye Reactive Blue 4 in Pyrite Ash Catalyzed Fenton Reaction

Pyrite ash (PA) is created by burning pyrite in the chemical production of sulphuric acid. The high concentration of iron oxide, mostly hematite, present in pyrite ash, gives the basis for its application as a source of catalytic iron in a modified Fenton process for anthraquinone dye reactive blue 4 (RB4) degradation. The effect of various operating variables such as catalyst and oxidant concentration, initial pH and RB4 concentration on the abatement of total organic carbon, and dye has been assessed in this study. Here we show that degradation of RB4 in the modified Fenton reaction was efficient under the following conditions: pH = 2.5; [PA]0 = 0.2 g L−1; [H2O2]0 = 5 mM and initial RB4 concentration up to 100 mg L−1. The pyrite ash Fenton reaction can overcome limitations observed from the classic Fenton reaction, such as the early termination of the Fenton reaction. Metal (Pb, Zn, and Cu) content of the solution after the process suggests that an additional treatment step is necessary to remove the remaining metals from the water. These results provide basic knowledge to better understand the modified, heterogeneous Fenton process and apply the PA Fenton reaction for the treatment of wastewaters which contains anthraquinone dyes.

Correlation of different pollution criteria in the assessment of metal sediment pollution.

In this article an assessment of the sediment metal pollution (cadmium, copper, chromium, lead, nickel, zinc) in the Veliki Backi canal (Serbia) was carried out using pseudo-total metal content, contamination factor (CF), pollution load index (PLI) and enrichment factor (EF). The study also encompassed pore-water metal concentrations and an assessment of sediment pollution based on the analysis of simultaneously extracted metals (SEM), acid volatile sulphides (AVS) and the sequential extraction procedure. The concentrations of metals are likely to result in harmful effects based on the comparison with sediment quality guidelines (Dutch, Canadian, US EPA - United States Environmental Protection Agency). The ratio of simultaneously extracted metals and volatile acid sulphides was found to be greater than 1 in only one location, which is already recognized as a place of high risk based on the criteria applied. Other samples had Σ[SEM]/[AVS] < 1, despite their high risk classification based on the applied criteria. According to the sequential extraction procedure, zinc and nickel exhibit high risk in most samples, whereas other metals show low and medium risk. The CF values for Cr, Cu and Zn were > 6 in most samples, which denotes very high contamination by these metals. The PLI values indicated moderate and high pollution. The EF values for all metals studied except for Cd in some cases were >1.5, suggesting anthropogenic impact. The obtained results will be invaluable for future activities regarding sediment monitoring and will facilitate the selection of appropriate criteria when evaluating sediment quality.

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.

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.

Influence of Electric Field Operation Modes on Nickel Migration during Electrokinetic Treatment

ABSTRACT Nickel-contaminated sediment can be remediated by electrokinetic techniques. In practical application, nickel may migrate into deep layers and potentially pollute unpolluted layers. In this study, the influence of different types of electric field operation modes on nickel migration in sediment layers was studied. The following experiments were conducted: without current application (NC), with horizontal electric field (HEF), with vertical electric field (VEF), and 2D electric field (horizontal and vertical). The following Ni overall removal efficacies were achieved: 48.9, 49.4, 55.7, and 58.1 after VEF, NC, 2D, and HEF, respectively. Using a vertical electric field in 2D and VEF resulted in less Ni found in the vertical sediment bed (25% and 60%, respectively). The available Ni content in a contaminated sediment bed decreased significantly after using the electrokinetic treatments: 46%, 62%, and 79% after HEF, VEF, and 2D, respectively. Vertical electric field is the most efficient for Ni removal in terms of the amount of Ni that migrated into deeper layers of sediment bed and its amount in mobile form. Thus, the vertical electric field is a promising and practical method for the remediation of nickel-contaminated sediments. Risk analysis indicated the efficiency of EK treatment as available Ni content was reduced after the applied treatments to a degree that poses no risk for the environment.

Application of the pyrite ash in the microwave Fenton process of decolorization of the synthetic color solution

The aim of this study is to investigate the possibility of fly ash and pyrite ash applications as a Fenton catalysts in the advancement of the microwave/hydrogen peroxide (MW/H2O2) treatment in the Rhodamine B decolorization process. At the same time, a comparison of the influence of these heterogenous catalysts with the homogenous Fenton catalyst on the decolorization process was conducted. The influence of the catalyst was tracked in previously optimized conditions MW/H2O2: [Rhodamine B] = 0.2 mM; pH 3.2; temperature 85oC; [H2O2] = 80 mM; power = 300 W. Under such conditions, the efficiency of 99.5% was achieved after 30 minutes of reaction time. The same efficiency was achieved through the application of MW/Fe2+/H2O2 and MW/pyrite ash/H2O2 after only 10 minutes of reaction time. The order of the tested integrated processes according to the initial reaction rate is as follows: MW/Fe2+/H2O2>MW/fly ash/H2O2>MW/H2O2. The results of this study present a basis for further research and optimization of water solution decolorization process through pyrite ash with MW and hydrogen peroxide application.

Comparative Assessment of the Photocatalytic Efficiency of TiO2 Wackherr in the Removal of Clopyralid from Various Types of Water

Many pyridine derivatives have found widespread application as herbicides. Because of their frequent use, chemical stability and resistance to biodegradation, they are encountered in waste waters, and, due to their hazardous effects on ecosystems and human health, their removal is imperative (Stapleton et al., 2006). With this in mind, we have recently paid significant attention to the study of the model compounds (Abramovic et al., 2003; Abramovic et al., 2004a, 2004b) and pyridine containing pesticides (Abramovic et al., 2007; Sojic et al., 2009; Abramovic & Sojic, 2010; Abramovic et al., 2010; Guzsvany et al., 2010; Sojic et al., 2010a, 2010b; Banic et al., 2011).