Mónika Molnár

Enhanced biodegradation of transformer oil in soils with cyclodextrin--from the laboratory to the field.

The use cyclodextrins for the intensification of bioremediation by improving the mobility and bioavailability of contaminants has recently been studied. In this work, the role of randomly methylated β-cyclodextrin in the bioremediation of soils contaminated with transformer oil was studied both in bench scale bioreactors and through field experiments. The aims of this research were to (a) establish the scientific background of a cyclodextrin-based soil bioremediation technology, (b) demonstrate its feasibility and effectiveness in the field, and (c) develop an integrated methodology, consisting of a combination of physical, chemical, biological and ecotoxicological analytical methods, for efficiently monitoring the technology performances. The stepwise increasing scale of the experiments and the application of the integrated analytical methodology supported the development of a scientifically established new technology and the identification of the advantages and the limitations of its application in the field. At each phase of the study, randomly methylated β-cyclodextrin was found to significantly enhance the bioremediation and detoxification of the transformer oil-contaminated soils employed by increasing the bioavailability of the pollutants and the activity of indigenous microorganisms.

Removal of emerging micropollutants from water using cyclodextrin

Small scale laboratory experiment series were performed to study the suitability of a cyclodextrin-based sorbent (ß-cyclodextrin bead polymer, BCDP) for modelling the removal of micropollutants from drinking water and purified waste water using simulated inflow test solutions containing target analytes (ibuprofen, naproxen, ketoprofen, bisphenol-A, diclofenac, β-estradiol, ethinylestradiol, estriol, cholesterol at 2-6 μg/L level). This work was focused on the preliminary evaluation of BCDP as a sorbent in two different model systems (filtration and fluidization) applied for risk reduction of emerging micropollutants. For comparison different filter systems combined with various sorbents (commercial filter and activated carbon) were applied and evaluated in the filtration experiment series. The spiked test solution (inflow) and the treated outflows were characterized by an integrated methodology including chemical analytical methods gas chromatography-tandem mass spectrometry (GC-MS/MS) and various environmental toxicity tests to determine the efficiency and selectivity of the applied sorbents. Under experimental conditions the cyclodextrin-based filters used for purification of drinking water in most cases were able to absorb more than 90% of the bisphenol-A and of the estrogenic compounds. Both the analytical chemistry and toxicity results showed efficient elimination of these pollutants. Especially the toxicity of the filtrate decreased considerably. Laboratory experiment modelling post-purification of waste water was also performed applying fluidization technology by ß-cyclodextrin bead polymer. The BCDP removed efficiently from the spiked test solution most of the micropollutants, especially the bisphenol-A (94%) and the hormones (87-99%) The results confirmed that the BCDP-containing sorbents provide a good solution to water quality problems and they are able to decrease the load and risk posed by micropollutants to the water systems.

Acidic sandy soil improvement with biochar - A microcosm study.

Biochar produced from a wide range of organic materials by pyrolysis has been reported as a means to improve soil physical properties, fertility and crop productivity. However, there is a lack of studies on the complex effects of biochar both on the degraded sandy soil physico-chemical properties and the soil biota as well as on toxicity, particularly in combined application with fertilizer and compost. A 7-week microcosm experiment was conducted to improve the quality of an acidic sandy soil combining variations in biochar types and amounts, compost and fertilizer application rates. The applied biochars were produced from different feedstocks such as grain husks, paper fibre sludge and wood screenings. The main purpose of the microcosm experiment was to assess the efficiency and applicability of different biochars as soil amendment prior to field trials and to choose the most efficient biochar to improve the fertility, biological activity and physical properties of acidic sandy soils. We complemented the methodology with ecotoxicity assessment to evaluate the possible risks to the soil as habitat for microbes, plants and animals. There was clear evidence of biochar-soil interactions positively affecting both the physico-chemical properties of the tested acidic sandy soil and the soil biota. Our results suggest that the grain husk and the paper fibre sludge biochars applied to the tested soil at 1% and 0.5 w/w% rate mixed with compost, respectively can supply a more liveable habitat for plants and soil living animals than the acidic sandy soil without treatment.

Potential use of cyclodextrins in soil bioremediation

Bioavailability and toxic effect of contaminants are the main limitations during soil bioremediation. Cyclodextrins may influence bioavailability of the contaminants during biodegradation and also toxicity of the pollutant on soil microbes and plants since their ability to form inclusion complei with organic compounds. The effect of cyclodextrins on bioremediation and on toxic effect of hydrocarbons was investigated by testing the activity of hydrocarbon degrading microflora and of plant growth. The effect of cyclodextrins could be demonstrated in both cases: biodegradation of hydrocarbons could be enhanced and toxic effect of hydrocarbons on plants and soil microbes could be decreased by adding cyclodextrins.

Effects of RAMEB on Bioremediation of Different Soils Contaminated with Hydrocarbons

The limiting factor of soil remediation is often the low accessibility of the pollutants.Laboratory experiments have been carried out to investigate the effect of the randomlymethylated cyclodextrin (RAMEB) on bioremediation of various types of soils spikedwith Diesel and transformer oil and also on actual site soils contaminated with poorlydegradable mazout. The contaminated soil in the aerobic solid phase microcosm-experiments was amended with nutrients and supplemented with different amounts of RAMEB. An integrated chemical-biological-ecotoxicological methodology was applied to follow the bioremediation. The laboratory study proved the bioremediation enhancing effect of RAMEB both on artificially contaminated soils and on actual site mazout contaminated soils. RAMEB activated soil microbes by improving the bioavailability of the contaminants and accelerating biodegradation. Efficacy of RAMEB was influenced both by contaminantand environment related factors, such as the type and concentration of the pollutinghydrocarbons and characteristics of the soil.

The potential application of red mud and soil mixture as additive to the surface layer of a landfill cover system

Red mud, the by-product of aluminum production, has been regarded as a problematic residue all over the world. Its storage involves risks as evidenced by the Ajka red mud spill, an accident in Hungary where the slurry broke free, flooding the surrounding areas. As an immediate remediation measure more than 5cm thick red mud layer was removed from the flooded soil surface. The removed red mud and soil mixture (RMSM) was transferred into the reservoirs for storage. In this paper the application of RMSM is evaluated in a field study aiming at re-utilizing waste, decreasing cost of waste disposal and providing a value-added product. The purpose was to investigate the applicability of RMSM as surface layer component of landfill cover systems. The field study was carried out in two steps: in lysimeters and in field plots. The RMSM was mixed at ratios ranging between 0 and 50% w/w with low quality subsoil (LQS) originally used as surface layer of an interim landfill cover. The characteristics of the LQS+RMSM mixtures compared to the subsoil (LQS) and the RMSM were determined by physical-chemical, biological and ecotoxicological methods. The addition of RMSM to the subsoil (LQS) at up to 20% did not result any ecotoxic effect, but it increased the water holding capacity. In addition, the microbial substrate utilization became about triple of subsoil (LQS) after 10months. According to our results the RMSM mixed into subsoil (LQS) at 20% w/w dose may be applied as surface layer of landfill cover systems.

Quantitative and Qualitative Analysis of RAMEB in Soil

An HPLC method has been developed for determination of RAMEB in soil samplescontaminated with hydrocarbons. The extraction efficiency of RAMEB from soils wasfound to depend on the soil properties. The extraction method elaborated results in agood recovery from sandy and loamy soils, but only a poor recovery was obtained from soils of high clay content.A SPE method was worked out to remove the components disturbing the HPLCanalysis, and a one-peak method has been developed for the quantitative analyses.The isomer distribution of RAMEB was characterized by fingerprint chromatograms.The new methods have been applied for determination of RAMEB content in soilsamples from field treatment.

Stabilization of nanosized titanium dioxide by cyclodextrin polymers and its photocatalytic effect on the degradation of wastewater pollutants

Advanced oxidation processes (AOPs) are considered highly competitive water treatment technologies for the removal of organic pollutants. Among AOP techniques, photocatalysis has recently been the most widely studied. Our aims were to investigate how the dispersion of nanosized titanium dioxide (nanoTiO2) applied in photodegradation-based procedures can be stabilized with cyclodextrins in order to obtain a new, more efficient photocatalyst for the purification of waters polluted by xenobiotics applying UV irradiation. During our work, on the one hand, we studied the behavior and stability of nanoTiO2 in cyclodextrin solutions. On the other hand, we used various monomer and polymer cyclodextrin derivatives, and assessed the options for nanoTiO2 stabilization in the presence of various salts and tap water on the basis of turbidity tests. The physical stability of nanoTiO2 dispersions is diminished in the presence of the salts found in tap water (and occurring also in surface waters and ground water) and they are precipitated immediately. This colloidal instability can be improved by cyclodextrin derivatives. Based on the results of our studies we have selected carboxymethyl β-cyclodextrin polymer (CMBCD-P) for stabilization of nanoTiO2 dispersions. The photocatalytic degradation of methylene blue and ibuprofen as model organic pollutants in various media (distilled water, NaCl solution and tap water) has been studied using nanoTiO2 as catalyst stabilized by CMBCD-P. CMBCD-P itself showed a catalytic effect on the UV degradation of methylene blue. In addition to enhancing the colloid stability of nanoTiO2 CMBCD-P showed also synergistic effects in catalyzing the photodecomposition process of the dye. On the other hand, ibuprofen as a model pharmaceutical, a pollutant of emerging concern (EP), was protected by CMBCD-P against the photocatalytic degradation showing that inclusion complex formation can result in opposite effects depending on the structure of the host–guest complex.

Tiered Approach for the Evaluation of Environmental Impacts of Triclosan on Aquatic Ecosystems

The synthetic broad-spectrum antibacterial agent triclosan is one of the most commonly encountered emerging micro-pollutant in the aquatic environment due to the extensive use since 1968 mainly in cosmetics and household cleaning products and the partial elimination from wastewater. Its low water solubility, high sorption coefficient to organic matter, accumulation potential in fatty tissues and its low acute toxicity determined by conventional ecotoxicological tests suggest that its risk is more related to chronic effects requiring risk assessment based on more sensitive ecotoxicological methods. In this paper the shortand midterm ecotoxicological effects of triclosan were investigated using various test systems taking into account ecological complexity and environmental relevance. Acute single-species, simplified microcosm experiments and complex multi-species microcosm experiments were conducted with the determination of sublethal physiological and behavioral endpoints including the Daphnia magna heartbeat rate and feeding activity, the Heterocypris incongruens movement parameters and the Lemna minor chlorophyll content and root length. All physiological and behavioral endpoints indicated sensitively the adverse effect of triclosan in the concentration range of 4–25.6 μg/L. In some cases, responses of selected organisms in single-species laboratory tests did not correspond to those of the higher levels of test systems. Daphnia sensitivity increased with the level of the test system for all chosen endpoints except the heartbeat rate. Considering the varying ecological complexity of the assembled test systems, according to our results the exposure time and the different combinations of exposure routes were the most decisive parameters in terms of triclosan ecotoxicity and endpoint sensitivity.

Re-using bauxite residues: benefits beyond (critical raw) material recovery: Re-using bauxite residues

Abstract Since the world economy has been confronted with an increasing risk of supply shortages of critical raw materials (CRMs), there has been a major interest in identifying alternative secondary sources of CRMs. Bauxite residues from alumina production are available at a multi‐million tonnes scale worldwide. So far, attempts have been made to find alternative re‐use applications for bauxite residues, for instance in cement / pig iron production. However, bauxite residues also constitute an untapped secondary source of CRMs. Depending on their geological origin and processing protocol, bauxite residues can contain considerable amounts of valuable elements. The obvious primary consideration for CRM recovery from such residues is the economic value of the materials contained. However, there are further benefits from re‐use of bauxite residues in general, and from CRM recovery in particular. These go beyond monetary values (e.g. reduced investment / operational costs resulting from savings in disposal). For instance, benefits for the environment and health can be achieved by abatement of tailing storage as well as by reduction of emissions from conventional primary mining. Whereas certain tools (e.g. life‐cycle analysis) can be used to quantify the latter, other benefits (in particular sustained social and technological development) are harder to quantify. This review evaluates strategies of bauxite residue re‐use / recycling and identifies associated benefits beyond elemental recovery. Furthermore, methodologies to translate risks and benefits into quantifiable data are discussed. Ultimately, such quantitative data are a prerequisite for facilitating decision‐making regarding bauxite residue re‐use / recycling and a stepping stone towards developing a zero‐waste alumina production process.