Biodegradation of two persistent aromatic compounds by using oil shale.

Low-cost oil shale was investigated as a biodegradation promoter material, in order to exploit its potential for more widespread and efficient usage in the elimination of pollution. Degradation of two model pollutants, 4-nitrophenol and phenol, was examined in the presence of oil shale in a batch system. In order to investigate the role of the natural microflora of the oil shale in degradation, sodium azide was added to inhibit microbial growth. The effect of metal ions was also investigated. In the sodium azide-free solutions the model pollutants were completely degraded up to 2000 µmol/L concentration in a dose-dependent way, while the addition of sodium azide delayed greatly but did not stop the degradation. Manganese(II) ions increased the rate of the degradation of 4-nitrophenol, and given quantities of iron(II), manganese(II) or zinc(II) ions were also effective in degradation of phenol. Our results suggest that oil shale is not only an adsorbent but has an active role in the degradation of pollutants by its natural microflora. Utilizing these features of oil shale, it is a suitable candidate as an ameliorating agent, which can also be used in industrial size.

Investigation of the vulnerability of a partly covered karst feature in Veszprém, Hungary.

Karst aquifers represent the most important renewable sources of drinking water. Because anthropogenic influences threaten the integrity of karst aquifers, it is important to determine the soil erosion and karst denudation rates. In order to study the complex signs of degradation processes of the karst, a paleodoline (paleo-polje) was selected near to the county seat Veszprém, Hungary. It was found that gamma radiation measurements can be a useful tool to detect the level of soil erosion since the low gamma radiation indicates the surface proximity of the carbonate bedrock. The level of gamma radiation also predicts the potential agricultural usability of a site. Both the patterns of contamination and the erosion attack zone are strongly defined by the relief. The gullies and the deepest parts of the karstic landscape are the traps of organic materials and pollutants. The amounts of 40K and its decay products originate from the covering sediment and negatively correlate with the soil depth. In the case of covered karsts, the measuring of the concentration of radionuclides and field gamma-ray dose measurement together can characterize the general horizontal and vertical trends of soil erosion, the potential land use, and the vegetation.

Study of sorption of two sulfonylurea type of herbicides and their additives on soils and soil components.

The sorption of two sulfonylurea type herbicides (chlorsulfuron: (1-(2-chlorophenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea; tribenuron methyl: (methyl-2-[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-3-(methyl-ureido)-sulfonyl]-benzoate) was studied on sand and chernozem soil adsorbents. Experimental results for solutions prepared from the pure ingredients were compared to those prepared from the appropriate formulated commercial products. At small concentrations, the extent of adsorption of the active ingredient was higher than from the formulation containing solutions. Environmental fate and effects of the forming agents are less investigated because they rarely have concentration limits recommended by authorities. In addition to the adsorption of active ingredients, therefore, the sorption behavior of a widely used additive Supragil WP (sodium diisopropyl naphthalene sulphonate) was also studied. This dispersant is an anionic forming agent applied in a lot of pesticide formulations. Using three different soils (sand, brown forest, chernozem) as adsorbents two-step isotherms were obtained. The role of the soil organic matter (OM) was significant in the adsorption mechanism because the adsorbed amounts of the dispersant correlated with the specific surface area as well as with the total organic carbon (TOC) content of the soils. The sorption behavior indicates the operation of hydrophobic interaction mechanism between the soil OM and the dispersant. These results are supported by our further sorption experiments on clays, too. Zeta potential measurements seem to be promising for the interpretation of multi-step isotherms. The application of this technique proved that higher concentrations of the anionic forming agent assisted the peptization of soil organic matter (SOM) resulting in stable colloidal solution dominated by negative charges. Since the pesticides investigated are also anionic at the studied pH (7 and 8.3) the dissolved organics lead to the enhancement of the mobility of both the sulfonylureas and dispersant.

The effect of alginite on the decomposition of the herbicide propisochlor.

The catalytic effect of an oil shale rock "alginite" was studied under laboratory conditions on the decomposition of herbicide propisochlor. The breakdown process was followed in four parallel experiments: buffered solution (pH = 7), in buffer solutions containing alginite or bentonite (a common rock) and also in the solution obtained from the extraction of the alginite (alginite/buffer = 1/10). In the aqueous phase, the decomposition of the herbicide was followed by using HPLC-UV and the metabolites of degradation were identified by GC-MS techniques. For the phenomenological description of the experimental decay curves two parallel reactions with first-order kinetics were taken into account. During the time of experiments, no significant decomposition was observed either in the pure buffer solution or in the presence of bentonite. When, however, alginite was added to the system the degradation of propisochlor was accelerated dramatically: after 5 days, its concentration dropped below 50 % of the initial value. The identified degradation products indicate both reductive as well as oxidative biological mechanisms operating under anoxic conditions. It was proved earlier that the sulfenic and sulfinic acid ester derivatives of the propisochlor appeared in the metabolic pathways of animals and plants but they were not detected yet in the degradation process occurring in the soil environment. Among the degradation products a dehydrochlorinated derivative is a new metabolite identified in our experiments. Our results corroborate the algae-related origin of the alginite rock and forecast its application as a soil ameliorating agent.

Effect of pH and the role of organic matter in the adsorption of isoproturon on soils.

Equilibrium measurements were carried out with the herbicide isoproturon on natural adsorbents (brown forest-, chernozem-, sandy soils and quartz) in different buffered media (pH 5, 7, 8 phosphate buffer). Adsorption isotherms were fitted by a multi-step adsorption equation providing numerical information used in the environmental propagation models and risk assessment works. In the adsorption of the slightly polar isoproturon the dissolved organic matter of the soil and the pH play an important role. At molecular level, results are interpreted by taking into consideration the hydrophobic interaction and the formation of hydrogen bonds between the surface and the solute. The observed adsorption behavior indicates that the organic matter content of the soils and its soluble fulvic acid, alkaline soluble humic acid and insoluble humin fractions were considerable different. The chernozem soil containing the highest amount of insoluble organic fraction proved to be a very efficient adsorbent. The brown forest and the sandy soils exhibit rather similar adsorbent properties but at pH 7 the latter containing more fulvic acid adsorbs less isoproturon due to the enhanced solubility of the soil organic matter. In alkaline conditions the negatively charged solute and the surface repel each other and the hydrophobic interactions are also weaker than in neutral media.

Acetochlor as a soil pollutant.

Acetochlor is a widely used herbicide all over the world. Similarly to other organic pollutants, the environmental fate of the acetochlor is strongly related to its adsorption properties. Static adsorption equilibrium measurements were carried out at 25 degrees C on different types of Hungarian soils characterized by varying amounts of organic matter and pH values. Isotherms obtained under different conditions, as well as on various soils, exhibit a similar shape, thus indicating a two-step adsorption process. The plots cannot be interpreted according to the classes of isotherms suggested by Giles. The adsorption coefficients (K) were estimated from the initial slope of the curves. These values were determined not only by the type of the soil, but also by the composition of the aqueous media. The organic matter adsorption coefficients (Kom) were also calculated and they were approximately identical for soils of high organic matter. Due to the low value of the adsorption coefficients, the acetochlor is a rather mobile pollutant of the soil posing a potential danger to the aquatic environment. For soils with high organic content, the Kom values are similar to each other and, due to the significant coverage of the inorganic surfaces, the adsorption is controlled by the solute-organic substance interactions. The adsorption of weakly polar compounds, however, is remarkable even on those soils where the organic content is low. In this case, the binding is governed by the solute-inorganic surface interactions. This conclusion is nicely proved by the adsorption of the acetochlor on quartz. According to our hypothesis, the second part of the adsorption step is controlled by the solute-adsorbed solute interactions. The role of the organic matter in this region of the isotherm is probably negligible. As the organic matter content of the soils plays an important role in the acetochlor adsorption, humic substances must have a strong influence upon the transport of this compound. Experiments to obtain adsorption isotherms of further pesticides and the development of a quantitative model are in progress.

Adsorption of propisochlor on soils and soil components equation for multi-step isotherms.

Static equilibrium measurements were performed for the study of propisochlor on three different kinds of soils at pH = 7.0 at 25 degrees C. The concentration of herbicide was changed from 30 to 300 mumol/l. The obtained two-step adsorption isotherms cannot be evaluated by using the Freundlich or Langmuir equations. New equation has been derived by making use of the usual mass balance and equilibrium relationships of the adsorption and by considering the possibility of the formation of associates of the hydrophobic solute molecules. The characteristic model parameters of each step of the adsorption isotherm were estimated for the studied systems by a non-linear least square regression. The calculated curves fit well to the experimentally obtained two-step isotherms and the parameters of the model can be used for the characterization of the pesticide-soil interactions and consequently the mobility of the propisochlor in soil/water systems.