Jelena Tričković

Using chemical desorption of PAHs from sediment to model biodegradation during bioavailability assessment.

This work compares the biodegradation potential of four polycyclic aromatic hydrocarbons (PAH) (phenanthrene, pyrene, chrysene and benzo(a)pyrene, chosen as representatives of the 3, 4 and 5 ring PAHs) with their desorption from sediment by XAD4 resin and methyl-β-cyclodextrin (MCD). The biodegradation study was conducted under various conditions (biostimulation, bioaugmentation and their combination). The results show that total PAH removal in all treatments except biostimulation gave similar results, whereby the total amount of PAHs was decreased by about 30-35%. The desorption experiment showed that XAD4 desorbed a greater fraction of phenanthrene (77% versus 52%), and benzo(a)pyrene (44% versus 25%) than MCD. The results for four ring PAHs were similar for both desorption agents (about 30%). Comparing the maximum biodegraded amount of each PAH with the rapidly desorbed XAD4 and MCD fraction, XAD4 was found to correlate better with biodegradation for the high molecular PAHs (pyrene, chrysene, benzo(a)pyrene), although it overestimated the availability of phenanthrene. In contrast, MCD showed better correlation with the biodegradation of low molecular weight PAHs.

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.

Degradation of pararosaniline dye photoassisted by visible light

Abstract The photoassisted degradation of pararosaniline dye has been investigated in aqueous solutions under illumination by visible light. Illumination of the dye solution in the presence of oxygen or argon does not degrade the dye molecule. Degradation occurs in the presence of H 2 O 2 . Pararosaniline dye can be easily decomposed in the TiO 2 suspensions using oxygen and hydrogen peroxide as electron acceptors. The degradation kinetics followed first-order type equation in all cases. Based on the data obtained the reaction mechanism was proposed.

Adsorption of chlorinated phenols on multiwalled carbon nanotubes

This work studies the adsorption of four chlorinated phenols (2,4-dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,5-tetrachlorophenol and pentachlorophenol) in aqueous solutions on multiwalled carbon nanotubes (MWCNT). To investigate the influence of oxygen containing functional groups, adsorption parameters for the phenols were determined for original MWCNT (OMWCNT) and functionally modified MWCNT (FMWCNT) by acid treatment for 3 h and 6 h. The correlation between phenol adsorption affinity and specific surface area (SSA) indicates that OMWCNT have higher adsorption affinities for larger molecules such as tetrachlorophenol and pentachlorophenol, which suggests that mesopore filling is not the dominant mechanism controlling their adsorption. Electrostatic repulsion between disassociated chlorinated phenols and disassociated functional groups on the surface of both FMWCNT lead to adsorption decreasing with increasing functionalisation under neutral pH conditions. On OMWCNT, a positive correlation between molecular hydrophobicity and adsorption affinity was obtained, indicating hydrophobic interactions control the adsorption of chlorinated phenols. To investigate the role of π–π interactions, Kd values (at 0.01 and 0.5 SW) were normalized by hydrophobicity. The Kd/KOW values for all MWCNT decreased from 2,4-dichlorophenol to pentachlorophenol and were negatively correlated with the electron-acceptor property of the molecules. The most pronounced π–π interactions were observed for 2,6-dichlorophenol on all MWCNT.

Sorption of atrazine, alachlor and trifluralin from water onto different geosorbents

The sorption behavior of the herbicides atrazine, alachlor and trifluralin on four sorbents (two modified organoclays, one model sediment, and one natural sediment) in three water matrices (synthetic water, natural groundwater and surface water) was investigated. The influence of the sorbent and water matrix characteristics was elucidated. All adsorption isotherms fitted well with the Freundlich model. Based on the Kd values, the organically modified bentonite and model sediment proved to be the most effective sorbents for the investigated herbicides. A linear correlation of Kd with the total organic carbon (TOC) concentration was found for trifluralin in the synthetic water matrix (c0 = 0.01 mg L−1). In the case of higher trifluralin concentration and for other tested herbicides at all concentrations the influence of both the sorbent organic matter quality and possible interactions with the mineral phase was indicated. Furthermore, the results showed different influence of the type and the content of dissolved organic carbon (DOC) in the water phase on the sorption of all the herbicides, depending on the herbicide concentration and the sorbent applied. It was confirmed that the comparison of sorbent efficiency should be done in native matrix since sorption coefficients vary depending on pollutant concentration, DOC concentration and DOC fraction. This finding is considered to be important for remediation of contaminated sites.

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.

Sorption Behaviour of Trichlorobenzenes and Polycyclic Aromatic Hydrocarbons in the Absence or Presence of Carbon Nanotubes in the Aquatic Environment

This work investigates the sorption behaviour of six hydrophobic organic compounds (HOCs) from the trichlorobenzenes (TCBs) and polycyclic aromatic hydrocarbons (PAHs) on Danube sediment using batch and column experiments, either in the presence or absence of carbon nanotubes (CNTs). For all HOCs investigated, nonlinear isotherms were obtained. Based on logKoc, it can be concluded that the Danube sediment has a higher sorption affinity for PAHs than TCBs. A positive correlation between HOC molecular hydrophobicity and sorption affinity was obtained, meaning that hydrophobic interactions play a significant role. There was a negative correlation between molecular hydrophobicity and the percentage of eluted HOCs, indicating that more hydrophobic molecules show less mobility in the sediment column. In the presence of CNTs in the sediment column, HOC concentrations in the column eluate decreased by factors of 2–3. Metal oxides and hydroxides on the surface of the sediment under the given experimental conditions had positively charged centres that caused the deposition of CNTs, leading to simultaneous sorption of organic compounds on both sediment organic matter (SOM) and CNTs. The increased retention of HOCs in the presence of CNTs on the sediment column reduces their mobility, which might also suggest that CNTs may be used for remediation of contaminated soils and sediments.

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.