Humic acids from oxidized coals I. Elemental composition, titration curves, heavy metals in HA samples, nuclear magnetic resonance spectra of HAs and infrared spectroscopy

The formation of humic acids (HAs) from bituminous coal was verified by laboratory oxidation. In a relatively short time the oxidation by air at temperature above 150 degrees C led to the formation of HAs. These HAs were compared with those isolated from oxidized bituminous coal from the vicinity of red bed bodies, from weathered bituminous coal, oxihumolite and lignite. For this the organic and inorganic elemental composition of HAs, apparent dissociation constants, metal-binding capacities, nuclear magnetic resonance and infrared spectra were determined and evaluated. With increasing temperature of laboratory oxidation of bituminous coal the percentage of aromaticity of HAs increases. HAs prepared from coal oxidized at 150 degrees C are characterized by an aromaticity index 78% while for HAs prepared at 250 and 300 degrees C by 95% aromaticity. The same index for HAs isolated from naturally oxidized bituminous coals is of about 87% whereas it is of about 50% for oxihumolite and lignite. The apparent dissociation constants (Kapp) are much higher in HAs isolated from oxihumolite and lignite (pKapp from 3.35 to 3.80) than those from oxidized bituminous coal samples (pKapp from 4.47 to 4.85). There is a good negative correlation between Pb-binding capacity and pKapp of all samples suggesting that metallic ions are bonded to acidic groups of HAs. Also contents of inorganic elements like Fe, Al, Si are much higher in HAs isolated from lignite and oxihumolite than those in HAs from oxidized bituminous coal. Thus, it seems that the temperatures below 150 degrees C and the long oxidation time are necessary conditions for the formation of HAs in oxidative altered bituminous coal deposited deeply under the earth surface.     

Supramolecular interactions of humic acids with organic and inorganic xenobiotics studied by capillary electrophoresis

Methodology based on capillary electrophoresis (CE) to study humic acids (HAs)-xenobiotics interactions is proposed. The interactions of HAs with organic and inorganic xenobiotics like paraquat, diquat, p,p(')-DDE, p,p(')-DDT, potassium ferrocyanide, potassium ferricyanide, chloride, 4-nitrocatechol and other organic compounds were studied. They were found to be of different kind depending on the structure of the xenobiotic molecule and on its charge (neutral, positive or negative). Ion binding, hydrogen bonding, van der Waals forces, ligand exchange, hydrophobic and hydrophilic adsorption, charge-transfer complexes and sequestration are some of the different mechanisms proposed to bind inorganic and organic compounds to HAs.It was also observed that some of the pollutants are strongly complexed (bound) only with some of the HA fractions forming quite stable entities of supramolecular kind, which can migrate independently. In addition, the stability constant of HA-Cl (negatively charged species) was estimated to be logk=3.1+/-0.95. In order to explain the interaction between negatively charged HAs and inorganic anions (like Cl(-), [Fe(CN)(6)](3-) and [Fe(CN)(6)](4-)), it is proposed that macropolycyclic polyamine structures are present in HA supramolecules, and that they are responsible for such strong binding.     

Varying levels of female promiscuity in four <Emphasis Type="Italic">Apodemus</Emphasis> mice species

Sexual selection in most vertebrates is based on the evolution of fitness optimization strategies such as multiple-male mating (MMM). Several ecological correlates of MMM have been identified in bird and fish populations; however, only few studies have documented the effects of environmental change on promiscuity in mammals. In this study, the 127 pregnant females from four central European and ecologically diverse species of field mice (genus Apodemus) were studied to assess the role of ecological factors that may have shaped the evolution of particular mating systems. MMM was found in all analyzed species: in Apodemus uralensis and Apodemus flavicollis, up to two males could be identified as the fathers of a particular litter, while three males sired 9.1% of analyzed litters of Apodemus sylvaticus and 20.6% of Apodemus agrarius. Furthermore, there were obvious differences between species in relative testes size and the proportion of multiple sired litters during those seasons when the opportunity for multiple mating was high. The species with the smallest testes and the least promiscuous was A. uralensis (only 43.5% of multiple sired litters), while the species with the biggest testes and the most promiscuous was A. agrarius (69.2%). MMM was significantly associated with higher litter size in A. flavicollis, and the probability of MMM strongly increased with season in A. agrarius and with abundance in A. uralensis. These results indicate that ecological factors are associated with MMM rates in Apodemus field mice and more research is needed to fully understand the evolution of mating strategies at different levels of biological resolution.     

The acidobasic and complexation properties of Humic acids

Complexation of Humic Acids (HA) of different origin, like Fluka, and especially those extracted from bohemian brown coal, with cadmium(II) and lead(II) was studied at pH 5.0 using differential pulse anodic stripping voltammetry. Conditions close to those present in the environment were chosen with 3‐ 10^‐4 moll^‐4 for HAs and 2. 10^‐8‐l . 10^‐5 moll^‐1 for Cd(II) and Pb(II). Stability constants evaluation was done assuming the electrode process is diffusion controlled and the complexes are labile. Obtained log K values were in the range 4.49–5.25 for Cd(II) and as expected the higher log K values 6.05–6.60 were found for Pb(II). There was no significant difference between complexation properties of HA extracted from bohemian brown coal and that of Fluka. The results obtained are in good agreement with the literature and those obtained by ISE in our laboratory.     

Scale invariant measures of pattern intensity and grain: A simulation experiment

We propose new dimensionless and scale-invariant measures for detection of pattern intensity, defined as the level of aggregation of individuals regardless their kind, and pattern grain, the level of segregation among individuals of at least two different kinds in point-pattern spatial data using tessellation methodology. Both real and simulated data on spatial distribution of plants in ecological communities show that the proposed parameters can be considered fingerprints of particular point patterns. This approach allows definition of both pattern intensity and grain for any kind of tessellated plane in an operational way, rendering these available for quantification and testing.     

Decolorization of Orange G and Remazol Brilliant Blue R by the white rot fungus Dichomitus squalens: toxicological evaluation and morphological study

Dichomitus squalens efficiently decolorized both Orange G and Remazol Brilliant Blue R (RBBR) at concentrations of 0.5gl(-1) and 3gl(-1) in static and shaken culture and also on solid medium within 14d. The presence of the dyes in the culture medium mostly caused a decrease in biomass production and in growth rate, which was more significant in the case of RBBR. After 14d of cultivation, electron microscopy showed substantial morphological changes in mycelia of D. squalens growing in media containing dyes. The hyphae deformations were more intensively manifested in solid media than in liquid culture. In all the cases, the morphological changes were more prominent in the presence of RBBR. Higher concentrations of both dyes brought about more intensive changes. The toxicity of synthetic dyes Orange G and RBBR was tested using a bioassay based on the growth inhibition of duckweed Lemna minor. Two endpoints such as the number of fronds and their weight were studied during the bioassay. The results showed higher toxicity of RBBR than that of Orange G. The toxicity of both dyes decreased after the decolorization process.     

Structural alterations in rabbit spleen after bendiocarb administration

The histological structure of rabbit spleen after bendiocarb administration was studied. Bendiocarb was perorally administered for 30 days. At day 10, 20 and 30 morphometric analysis was realized. Quantitative evaluation showed that in the control group the relative spleen volume of white pulp ranged from 35.03 ± 10.94 % and the relative volume of red pulp 64.97 ± 10.94 %. In all experimental groups were detected significantly higher relative volume of red pulp and the lower relative volume of white pulp, except on day 30. The experimental groups showed a significant increase in the number of lymphocytes in comparison with the control group. On day 10 we observed a significant increase in diameter of investigated lymphocytes. The results of our study determined structural alterations in spleen structure after bendiocarb administration, which probably causes alteration in the immune system.     

Monitoring microbial biomass and respiration in different soils from the Czech Republic--a summary of results

The microbial biomass (Cbio), respiration (basal respiration (BR) and potential respiration (PR)), and derived indices for 520 independent soil samples of 117 different soils from the Czech Republic were statistically analysed. The broad range of soil samples allowed the stepwise breakdown of the database into six reasonable categories of soil: arable soils, loamy grassland soils, sandy grassland soils with weak organic matter content, sandy grassland soils with moderate organic matter content, forest soils with moderate organic matter content, and forest organic soils with rich organic matter content. Because soil microbiology lacks benchmarking values, the ranges of the microbial characteristics for these categories were stated and are presented here. The separation into soil groups narrowed the ranges enough to be useful for comparative purposes. The groups displayed significant differences in basal microbial parameters. The lowest microbial biomass was found in arable soils and grassland sandy soils with weak organic matter content. The highest microbial biomass was shown by loamy grassland soils and organic forest soils. Respiration displayed similar results to the microbial biomass. The derived indices revealed less significant differences confirming their inner-standard nature. The relationships between the soil contamination and microbial parameters were not explored because of the confounding effect of soil organic matter. However, it was not shown by the category of grassland sandy soils with weak organic matter content suggesting they could be especially suitable for the biomonitoring of harmful effects of chemicals on soil microorganisms.     

A long-term survey of heavy metals and specific organic compounds in biofilms, sediments, and surface water in a heavily affected river in the Czech Republic

To assess the long-term anthropogenic load of the Bílina River (Czech Republic), the concentrations of heavy metals and specific organic compounds in different river ecosystem matrices (water, biofilms, and sediments) were determined. Although the current concentrations of pollutants in surface water are low, frequently below the limits of the quantitative analytical methods used, the river ecosystem is still heavily loaded by anthropogenic pollution, mainly from the chemical and mining industries. This was demonstrated by analyzing biofilms and sediments. These matrices are more accurate representatives of the actual situation in the river and do not depend on hydrological conditions or random variability in water quality. The results indicate that the middle and the lower parts of the river are heavily polluted by mercury, arsenic, vanadium, polychlorinated biphenyls, hexachlorobenzene, and dichloro-diphenyl-trichloroethane. As a tributary of the Elbe River, the Bílina River represents a significant risk for the development of quality in this major European river.     

Low NOx burners--prediction of emissions concentration based on design,measurements and modelling

This paper describes possible ways of prediction of nitrogen oxides formation during combustion of hydrocarbon fuels. Mathematical model based on experimental data acquired from the testing facility has been developed. The model enables to predict--at a high probability measure--the extent of nitrogen oxides emissions. The mathematical model of nitrogen oxide formation relies on the application of simplified kinetic equations describing the formation of nitrogen oxides at so-called equivalent temperature. It is a semi-empirical model that comes out of experimental knowledge. An important role played by the burner design itself has been emphasized and therefore an important supplementary parameter of the model is the characteristic of the burner design. It has been established that there was a good agreement between experimental data and those calculated by the application of the model to various conditions marked out by different combustion parameters in the combustion chamber. The results obtained by application of the model respect the influence of parameters validated by industrial practice that control the formation of nitrogen oxides in the course of fuel combustion. Such parameters-first of all-tare the temperature in the combustion chamber and the concentration of the substances taking part in the reaction. By application of the model, it is possible to assess the consequence of, for example the surplus of combustion air, the increase of temperature of combustion air, the supply of inert gas, etc. on the nitrogen oxides emissions of the operating burner under evaluation. Efficient combining of experience and sophisticated approach together with importance of thus access for an improved design are shown.