Dejan Krčmar

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.

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.

Distribution of organic and inorganic substances in the sediments of the “Great Bačka Canal”, a European environmental hotspot

The Great Bačka Canal in Serbia is one of the most polluted waterways in Europe. Surface sediments from the canal were subject to systematic annual monitoring between 2007 and 2014 at 33 representative sampling sites. Eight heavy metals (Ni, Zn, Cd, Cr, Cu, Pb, As and Hg), mineral oils, 16 EPA PAHs and selected pesticides and polychlorinated biphenyls (PCB) were monitored. This study aims to evaluate the quality of the sediments and determine the potential ecological risks in order to establish pollutants of interest. The spatial and temporal influence of different and intense sources of pollution are investigated. The analysis includes multivariate statistical methods (factor analysis of principal component analysis (PCA/FA)) in order to assess the extent and origin (anthropogenic or natural, geogenic sources) of the contaminants detected in the sediment samples and the risks the present to the environment. Various sources, predominantly the food industry, were found to be responsible for most of the contamination by Cd, Cu, Cr and Zn, the mineral oils and PAHs (dibenzo[a,h]anthracene and benzo[a]pyrene contributed 86.0% of the total between 2007 and 2014). In contrast, the As was convincingly of geogenic origin, and the Hg, Pb and Ni present exhibit dual origins. Cd and Cu significantly raise the levels of potential ecological risk at all sampling locations, demonstrating the long-term effects of bioaccumulation and biomagnification. Significantly, the results of this work indicate that Cu, As and dibenzo[a,h]anthracene should be added to the EU watch list of emerging contaminants. This is supported by significant national and similar environmental data from countries in the region.

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.

Priority substances in sediments of the “Carska Bara” special nature reserve, a natural scientific research area on the UNESCO list

Surface sediments were subject to systematic long-term monitoring (2002-2014) in the Republic of Serbia (Province of Vojvodina). Eight heavy metals (Ni, Zn, Cd, Cr, Cu, Pb, As and Hg), mineral oils (total petroleum hydrocarbons), 16 EPA PAHs, selected pesticides and polychlorinated biphenyls (PCB) were monitored. As part of this research, this paper presents a sediment contamination spatial and temporal trend study of diverse pollution sources and the ecological risk status of the alluvial sediments of Carska Bara at three representative sampling sites (S1S3), in order to establish the status of contamination and recommend substances of interest for more widespread future monitoring. Multivariate statistical methods including factor analysis of principal component analysis (PCA/FA), Pearson correlation and several synthetic indicators were used to evaluate the extent and origin of contamination (anthropogenic or natural, geogenic sources) and potential ecological risks. Hg, Cd, As, mineral oils and PAHs (dominated by dibenzo(a,h)anthracene and benzo(a)pyrene, contributing 85.7% of the total) are derived from several anthropogenic sources, whereas Ni, Cu, Cr and Zn are convincingly of geogenic origin, and exhibit dual origins. Cd and Hg significantly raise the levels of potential ecological risk for all sampling locations, demonstrating the effect of long-term bioaccumulation and biomagnification. Pb is isolated from the other parameters, implying unique sources. This research suggests four heavy metals (Zn, Cr, Cu and As) and dibenzo(a,h)anthracene be added to the list of priority pollutants within the context of the application of the European Water Framework Directive (WFD), in accordance with significant national and similar environmental data from countries in the region.

Preremedial assessment of the municipal landfill pollution impact on soil and shallow groundwater in Subotica, Serbia

Most regional municipal solid waste landfills in Serbia are operated without control of landfill leachate and gas or with no regard for implementation of national and European legislation. For the first time in Serbia, groundwater and soil at a landfill were subject to systematic annual monitoring according to national, European legislation and adopted methodologies. Characterisation of the groundwater and soil samples from the landfill included ten metals (Fe, Mn, As, Zn, Cd, Pb, Ni, Cr, Cu and Hg), 16 EPA PAHs, nutrients and certain physicochemical parameters, in order to assess the risks such poorly controlled landfills pose to the environment. This impact assessment was performed using specially adapted pollution indices: LWPI, the Single factor pollution index and the Nemerow index for groundwater, and geo-accumulation index, ecological risk factor and selected rations of PAHs for soil. The data analysis included multivariate statistical methods (factor analysis of principal component analysis (PCA/FA)) in order to assess the extent of the contaminants detected in the groundwater and soil samples. The pollution indices (LWPI: 3.56-8.89; Nemerow index: 2.02-3.78) indicate the quality of the groundwater at the landfill is degrading over time, with PAH16, TOC, Cr, Cu, Pb and Zn as the substances of greatest concern. Heavy metals Hg (Igeo≤3.14), Pb (Igeo≤2.22), Cr (Igeo≤3.31) and Cu (Igeo≤2.16) represent the worst soil contamination. Hg has moderate (52.9) to very high (530.0) potential ecological risk, demonstrating the long-term potential effects of bioaccumulation and biomagnification. The results of this work indicate that Cr and Cu should possibly be added to the EU Watch List of emerging substances. This proposition is substantiated by relevant state and alike environmental information from nations in the region. This study demonstrates the need to develop a model for prioritization of landfill closure and remediation based on environmental risk assessment.

Evaluating the necessity for thermal treatment in clay-based metal immobilization techniques as an environmentally acceptable sediment remediation process

PurposeThe objective of this research was to apply the same immobilization (stabilization/solidification) clay-based treatments to sediment contaminated with different metals (Pb, Cd, Ni, Zn, Cu, Cr) with different distributions and availabilities in sediment. We also examined the possibility of using clay as an immobilization agent without the application of thermal treatment, in order to reduce the economic cost of this expensive remediation procedure.Materials and methodsClay from a canal in Vojvodina, Republic of Serbia, was used as the immobilization agent in a stabilization/solidification treatment to remediate metal-contaminated sediment. Semi-dynamic and toxicity characteristic leaching tests were conducted to assess the effectiveness of the nonthermal and thermal immobilization treatments with clay, and the long-term leaching behavior of these metals was determined using the following parameters: cumulative percentage of metals leached; diffusion coefficients; leachability indices; and toxicity characteristic leaching test concentration.Results and discussionBased on these parameters, both clay-based treatments were effective in immobilizing metals in the contaminated sediment. Results suggest that both heating temperature and clay proportion in the sediment–clay mixture impact the degree of metal immobilization.ConclusionsClay-based products are potentially good immobilization materials for metal-contaminated sediments, with the distribution of metals in the original sediment not influencing the efficacy of the treatments. Even without the thermal treatment, the metals were effectively immobilized. The leaching of metals was largely inside the regulatory limits and the treated samples can be regarded as nonhazardous materials. This justifies the choice of not applying the more expensive thermal treatment during remediation, especially when treating sediments containing a mixture of pollutants.

Distribution and ecological risk assessment of organic and inorganic pollutants in the sediments of the transnational Begej canal (Serbia-Romania)

This research is designed to determine the level and types of pollution in the highly contaminated sediments of the international Begej canal in Timiş district, Romania and north-eastern Serbia. The cross-border canal stretch investigated is currently not navigable, but represents an important waterway between the Danube River in Serbia and the city of Timisoara. Surface sediments were monitored annually from 2008 to 2016 at 36 representative sampling locations, with a wide range of analyses, including eight heavy metals of long-term monitoring concern (Ni, Zn, Cd, Cr, Cu, Pb, As and Hg) and the 16 USEPA PAHs. The purpose of this study was to determine the diversity and impact of anthropogenic and natural sources of pollution at the pollution hot spots on the canal: at the Itebej lock (near the border with Romania) and downstream at the Klek lock. Sediment quality and ecological risk were assessed in order to determine pollutants of concern. Several multi-proxies were applied (e.g. geo-accumulation index (Igeo), ecological risk index (RI) and total benzo[a]pyrene equivalent (B[a]Peq)). To determine and predict trends, multivariate statistical methods (factor analysis of principal component analysis (PCA/FA)) were carried out on the organic and inorganic parameters analysed. In the near-border region, acute and significant ecological impacts were observed. The heavy metals Hg, Cr, Pb, Cu and Zn, and the carcinogenic PAH dibenzo[a,h]anthracene, were historically the most frequently detected harmful substances to biota in this and the wider Pannonia region. This is the first long-term study to quantify and derivate the most frequently detected harmful substances of concern for this and similar sites in the wider region, and is additionally supported by significant national and similar environmental data from previous studies in the region.

Remediation of Toxic Metal Contaminated Sediment Using Three Types of nZVI Supported Materials

Due to nZVI effectiveness in the removal of toxic metals as well as low-cost regarding its production, kaolinite, bentonite and carboxymethyl cellulose supported nZVI were chosen for in-situ remediation of river sediment. Small-scale laboratory studies have shown that the percentage of removed metal (Ni, Zn and Pb) ranged up to 80% depending on the nanomaterial used. The metal mobility in sediments was investigated using single extraction, which is proved to be better for quick estimation of metal mobility, and for highly contaminated sites both single and sequential extraction needs to be used. Risk assessment code indicated medium risk for Ni and high risk for Pb and Zn in untreated sediment. In-situ treatment in laboratory proved to be very effective, providing the choice of optimal doses of three different nanomaterials used towards the concentration of toxic metals in the sediment.