Snežana Maletić

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.

Insight into changes during coagulation in NOM reactivity for trihalomethanes and haloacetic acids formation

Natural organic matter (NOM) in raw water can contribute in many ways to the poor quality of drinking water, including the formation of disinfection byproducts such as trihalomethanes (THM) and haloacetic acids (HAA) during disinfection. This paper investigates the role of individual NOM fractions on changes in THM and HAA formation during coagulation with iron chloride (FeCl3) and a combination of polyaluminium chloride and iron chloride (FeCl3/PACl). The dissolved organic carbon (DOC) in the raw water and after coagulation was fractionated into four fractions, based on their hydrophobicity. Fractionation showed that most of the DOC (68%) in the raw water comes from the fulvic acid fraction, yielding 41% of the total THM precursors and 21% of the total HAA precursors. Both coagulants remove the humic acid fraction, but result in different changes to the reactivity of the remaining NOM fractions towards THM and HAA formation, indicating that coagulation occurs by different pathways, depending upon the type of coagulant used. In particular, significant changes in the reactivities of the hydrophilic acidic and non-acidic fractions were observed.

Impact of hydrocarbon type, concentration and weathering on its biodegradability in soil

The objective of this research was to investigate the impact of the hydrocarbon type and concentration, as well as the total effect of the natural weathering process to hydrocarbon biodegradability in sandy soil and the environment. In this experiment, sandy soil was separately contaminated with 0.5%, 1.0%, 2.0% and 3.5% of diesel and crude oils. Oil contaminated soil was taken from the Oil Refinery dumping sites after 9 years of weathering, and its concentration was adjusted to the above-mentioned levels. The biodegradation process was monitored by measuring CO2, evolution rate, hydrocarbon degradation rate and dehydrogenase activity. The favourable concentration ranges for the soil contaminated with diesel oil were 1.0%, with concentrations at about 2.0% causing slightly adverse effects to CO2 production which was overcome after 2 weeks, and with 3.5% diesel oil causing significant toxicity. For soil contaminated with crude oil, 2.0% was found to be optimum for effective biodegradation, with 3.5% crude oil also causing adverse effects to CO2 production, although less so than the same concentration of diesel oil. No adverse effect was obtained for any concentration of the weathered oil, as after the weathering process, the remaining contaminants in the soil were mostly poorly degradable constituents like asphaltenes, resins etc. It has been proposed that such residual material from oil degradation is analogous to, and can even be regarded as, humic material. Due to its inert characteristics, insolubility and similarity to humic materials it is unlikely to be environmentally hazardous.

Response surface methodology investigation into the interactions between arsenic and humic acid in water during the coagulation process.

Interactions between arsenic and natural organic matter (NOM) are key limiting factors during the optimisation of drinking water treatment when significant amounts of both must be removed. This work uses Response Surface Methodology (RSM) to investigate how they interact during their simultaneous removal by iron chloride coagulation, using humic acid (HA) as a model NOM substance. Using a three factor Box-Behnken experimental design, As and HA removals were modelled, as well as a combined removal response. ANOVA results showed the significance of the coagulant dose for all three responses. At high initial arsenic concentrations (200μg/l), As removal was significantly hindered by the presence of HA. In contrast, the HA removal response was found to be largely independent of the initial As concentration, with the optimum coagulant dose increasing at increasing HA concentrations. The combined response was similar to the HA removal response, and the interactions evident are most interesting in terms of optimising treatment processes during the preparation of drinking water, highlighting the importance of utilizing RSM for such investigations. The combined response model was successfully validated with two different groundwaters used for drinking water supply in the Republic of Serbia, showing excellent agreement under similar experimental conditions.

Oxidation of natural organic matter with processes involving O3, H2O2 and UV light: formation of oxidation and disinfection by-products

This study investigates the effects of UV photolysis, ozonation and different advanced oxidation processes (O3/UV, H2O2/UV and O3/H2O2/UV) on the oxidation of groundwater natural organic matter (NOM) and by-product formation. Although the investigated treatments only slightly reduce the total organic carbon content (4–15%), the NOM character was changed significantly. The fulvic acid fraction decreased and the content of the hydrophilic acid fraction increased in ozone treated water and even more noticeably in water treated by O3/H2O2/UV. All treatments led to significant increases in polar oxidation by-products such as aldehydes (up to 8 times) and carboxylic acids (up to 34 times), with no clear relationship between the changes in concentrations of these by-products and the addition of H2O2 and the UV dose. Statistical analysis showed a good correlation between carboxylic acids with ozone applications and carboxylic acids and UV254. Trihalomethane and haloacetic acid formation potentials were reduced best (43% for THMFP and 68% for HAAFP) during the O3/H2O2/UV process (0.5 mg O3 per mg DOC; 10 mg H2O2 per L: 600 mL cm−2) using the lower UV dose, and were also well correlated (R = 0.847) during all water treatments. Bromate formation was observed only in the processes involving ozone.

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.

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.

Deployment of Microbial Biosensors to Assess the Performance of Ameliorants in Metal-Contaminated Soils

The remediation of metal-impacted soils requires either the enhanced mobility (and capture) of the target analytes or their effective complexation/immobilisation. In this study, a range of ameliorants (activated carbon, bonemeal, bentonite and CaSx (calcium polysulphide)) were compared to assess their effectiveness in immobilising metals in soils. In addition to chemical analysis (pH and trace element analysis), microbial biosensors were used to assess changes in the water-soluble biotoxicity of metals as a consequence of ameliorant dosing. Management of soil ameliorants requires an enhancement of Kd (solid/solution partition coefficient) if soil leachate is to meet predefined environmental quality standards. Of the ameliorants tested, CaSx was the most effective per unit added for both laboratory-amended and historically contaminated soils, regardless of the metal tested. At the ameliorant concentrations used to effectively immobilise the metals, the biosensor performance was not impaired. Microbial biosensors offered a rapid and relevant screening tool to validate the reduced toxicity associated with the ameliorant dosing and could be calibrated to complement chemical analysis. While laboratory-amended soils were a logical way to evaluate the performance of the ameliorants, they were generally associated with Kd values an order of magnitude lower than those of historically contaminated soils.

Investigation of the impact of ozone pretreatment and powdered activated carbon addition on the removal of natural organic matter by coagulation

AbstractThe main goal of this study was to investigate the effects of ozone oxidation pretreatment and powdered activated carbon (PAC) addition on the efficacy of natural organic matter (NOM) removal by coagulation. Relatively high iron chloride doses from 100 to 200 mg FeCl3/L were applied, due to the high dissolved organic carbon (DOC) content (10.27 ± 0.49 mg C/L) of the raw water investigated, with PAC used in doses of 5–30 mg/L. Preozonation was carried out at doses of 0.2–1.3 mg O3/mg DOC. Jar test results indicate that baseline coagulation with the optimal coagulant dose (200 mg FeCl3/L) achieved was 39% DOC and 54% UV254 removals. PAC addition improves coagulation efficacy in NOM removal by up to 9% DOC and 25% UV254. The best results were obtained in combination with 0.6 mg O3/mg DOC, 5 mg/L PAC and 200 mg FeCl3/L (removals of 58% DOC and 72% UV254), and were a significant improvement compared to coagulation alone.

A chemical and microbiological characterization and toxicity assessment of the Pančevo industrial complex wastewater canal sediments, Serbia

The wastewater canal Vojlovica of the Pančevo industrial area, Serbia, is the main collector of the effluents from the local industrial complex. The canal is directly connected to the Europe’s second largest river, the Danube. Here, we present a chemical and microbiological analysis of the sediment in order to determine the fate of pollutants over the years, as well as its current condition. Dry matter, clay and organic matter content, a Kjeldahl ammonia, phosphorus, metals, and polychlorinated biphenyls as well as polycyclic aromatic hydrocarbons concentrations were measured. Microbiological analysis included heterotrophic and oil-degrading bacterial counts, isolation of the phenanthrene-degrading bacteria, and identification of cyanobacteria. Generally, in comparison to the results from previous studies, concentrations of the measured pollutants have been in a decline. Specifically, the metal and polycyclic aromatic hydrocarbon concentrations were reduced whereas microbial counts and toxicity tests did not indicate significant pollution. The obtained results are probably a consequence of an improved wastewater treatment and microbial degradation of pollutants.