Bozo Dalmacija

Purification of high-salinity wastewater by activated sludge process

Abstract The objective of the present work was the enhancement of the efficiency of microbiological processes in purification of high-salinity oil-field brine by adding the powdered activated carbon (PAC) to the bioreactor and by diluting the brine with surface water. The investigation was carried out in a laboratory setup. Results show that the nature of pollutants and the high salinity (about 29 g/l) of oil-field brine had an unfavourable effect on the activated sludge process. Higher hydraulic loads (above 2.5 d −1 ) increased wash-out of the activated sludge from the bioreactor, so that an increased concentration of the suspended matter in the settler was observed. The addition of PAC to the bioreactor, combined with the dilution of oil-field brine with surface water, produced a substantial improvement in the sludge volume index. Also, under the given conditions, it was possible to maintain the given concentration of the activated carbon in the bioreactor. The procedure involving PAC and dilution with surface water resulted in an increased rate of pollutant degradation. The positive effect of PAC on the process of oil-field brine purification with the activated sludge was explained by the possibility of immobilization of microorganisms on the activated carbon surface in the form of a biofilm.

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.

Tertiary treatment of oil-field brine in a biosorption system with granulated activated carbon

Abstract This work describes the possibility of application of a biosorption system with granulated activated carbon (GAC) for the tertiary treatment of oil-field brine. In addition to the dissolved and dispersed oil, the oil-field brine contained about 29 g/l of mineral matter, mainly NaCl. The investigation was carried out on two columns, each containing 300 g of GAC. To form the biofilm on GAC use was made of the microorganisms from the setup for the purification of refinery wastewaters by activated sludge procedure. The wastewater flow-rate through the columns was 40, 70, 95 and 130 l/d. It was found that the activated carbon in the columns was capable of removing 2.6 times more organic matter than was its adsorption capacity, and its adsorption power was not thus exhausted. The results indicate that the microorganisms present in the biofilm on activated carbon oxidize the adsorbed pollutants and thus regenerate the carbon surface. The procedure employed was very efficient—the organic matter content in the effluent did not exceed 2.5 mg/l (BOD 5 ).

Effects of coagulation processes on aldehydes formation in groundwater treated with common oxidative agents.

This work is concerned with the effects of coagulation processes with two different coagulants (polyaluminum chloride (PACl) and Al2(SO4)3) on aldehydes formation during oxidation with common oxidants (ozone, chlorine and chlorine dioxide) in a particular groundwater source in Northern Banat region, Yugoslavia. Aldehydes concentrations in coagulated water were lower than in raw water. In contrast, obtained results showed that specific contents of these disinfection byproducts (microg mg(-1) TOC) showed an increase after coagulation processes in a number of samples. Results indicate that the choice of the coagulant-oxidant combination may be important as well as the type of filtration bed, retention time, and filter washing regime in the removal of aldehydes from water.

Case Study of Petroleum Contaminated Area of Novi Sad After NATO Bombing in Yugoslavia

The 1999 NATO bombing of the oil refinery in Novi Sad (Yugoslavia) has heavily contaminated the Danube River and its sediments, as well as the surrounding soil and groundwater. The destruction of the factories released 73,569 tons of crude oil of which 90% was incinerated, 560 tons reached the Danube River, and the remainder was spilled onto the soil. The contents of oil and oil derivatives in the soil were in the range of 3 to 42,000 mg/kg. The first soil layer contained an average of 67,000 mg/kg of crude oil and oil derivatives. The layers beneath it, above the groundwater table, contained 56 ml/l of free oil derivatives in the drained water. The spreading of this pollution could imperil the groundwater quality in the water supply zone because the refinery is located in the hinterland of the zone. The quality of water and sediment samples was monitored from April 1999 to November 2000 by measuring concentrations of hydrocarbons and polyaromatic hydrocarbons (PAH). The hydrocarbon content in the Danube River water in October 2000 was about 20% of the value measured at the time of the accident. Immediately after the accident the concentration of mineral oil in the surface sediment was in the range of 0.11 to 0.29 g/kg. At the same time PAH concentrations in the river sediment were up to 160 mg/kg, depending on the sampling site location. The values showed a decrease in the course of further monitoring.

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.

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.

Petroleum Hydrocarbon Biodegradability in Soil – Implications for Bioremediation

The development of human civilization throughout history has led to growing disruption of the natural balance and the occurrence of different types of pollution. The world depends on oil, and the use of oil as fuel has led to intensive economic development worldwide. The great need for this energy source has led to the gradual exhaustion of natural oil reserves. However, mankind will witness the results of oil consumption for centuries after its cessation. Environmental pollution with petroleum and petrochemical products has been recognized as a significant and serious problem (Alexander, 1995, 2000). Most components of oil are toxic to humans and wildlife in general, as it is easy to incorporate into the food chain. This fact has increased scientific interest in examining the distribution, fate and behaviour of oil and its derivatives in the environment (Alexander, 1995, 2000; Semple et al., 2001, 2003; Stroud et al., 2007, 2009). Oil spills in the environment cause long-term damage to aquatic and soil ecosystems, human health and natural resources.

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.

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.