Molecular modeling in environmental science∗

Quantum mechanic computer models are often used in chemistry to predict properties of molecules and to simulate reaction pathways. Such models calculate bond lengths, bond angles, dihedral angles, the energy of the molecular‐orbitals (MO's), the dipole moment, the ionisation potential, and the heat of formation. These results lead to detailed information on electronic structures like bond orders, electronic charges and levels of frontier orbitals (HOMO, LUMO).

It is possible to calculate properties of ground state molecules as well as ionic and radicalic structures, or reaction intermediates and other compounds with very short lifetimes.

From the exact knowledge of electronic structure, frontier orbitals, and reaction intermediates it is possible to predict stability of chemicals in the environment but also of fictive chemicals, which are not yet synthesized. Some authors have shown that there are correlations between electronic structure and toxicity.

The most interesting models for environmental chemistry are semiempirical models, such as MINDO, MNDO or MOPAC. Theses programs are able to handle molecules with 30 and more heavy atoms (all elements without hydrogen), and it is possible to install them on main frame computers (CPU‐time several minutes to hours) and on personal computers, with coprocessors (CPU‐time several hours to a few days).

Normally the molecule is read in from a Z‐matrix (a matrix of polar coordinates of atoms connected in the molecule) and with symmetry data. Furthermore, programs are available which create a Z‐matrix from the molecular structure plotted on the screen with a mouse.     

Characterization studies of a semi‐automated separation method for analysis of non‐ortho substituted polychlorinated biphenyl (PCB) congeners in environmental samples

Non‐ortho substituted polychlorinated biphenyl (PCB) congeners can account for the majority of the dioxin‐like toxicity in environmental samples, yet analysis for these congeners is difficult because other PCB congeners co‐elute with them in most Chromatographic methods. An automated method was developed which incorporates a porous graphitic carbon (PGC) column which is commercially available. Non‐ortho substituted congeners were successfully separated from interfering PCB congeners. Recoveries of non‐ortho substituted congeners were consistently reproducible (CV < 9%) when chicken eggs were fortified with individual congeners.     

Dissolved and dispersed petroleum hydrocarbons in the Aegean Sea

The distribution and transportation of Dissolved and Dispersed Petroleum Hydrocarbon (DDPH) were investigated in the Aegean Sea with the hydrodynamics of the water masses of the region. It is clear that distribution of this pollutant is strongly affected by physical dynamics of environment. The data were collected during cruises in November 1994, in the framework of National Marine Measurement and Monitoring Programme in the Aegean Sea. In the present study additionally the Chlorophyll‐a was measured fluorometrically and there is good correlation between petroleum hydrocarbon and chlorophyll‐a in the Aegean Sea. DDPH data was used to search origin of hydrocarbons: biogenic or non biogenic.     

Organic matter balances in anaerobic digestors

Organic carbon and COD balances in a system of 12 anaerobic units operating at organic loading levels 0.4–0.8 kg COD/m³.d and hydraulic detention times 8–20 d resulted in a mean CH₄ production of 341 ml/g COD converted and a mean CH₄ + CO₂ production 1815 ml/g OC converted. The gas retained in the liquid anaerobic effluent was mainly carbon dioxide (94–98%).     

On the role of solid NaCl in polluted marine urban areas

Last decade the reactions of gases at solid interfaces were increasingly recognized as significant in polluted marine troposphere and perhaps in remote areas as well. In this study the reactions of gases with solid NaCl at temperatures 200 K and 300 K were examined by using a recently proposed thermodynamical model (Varotsos et al., 1988) which provides the interconnection of entropy and enthalpy for various processes with well known macroscopic properties of the bulk solid.     

Persistent organochlorine contaminants in human tissues of the Czech and Slovak populations

The persistence of lipophilic organochlorine substances leads to their incorporation into the food chain and subsequent uptake by humans. Due to their use in the past, Czech and Slovak countries belong to the countries with a relatively high body burden of organochlorines. Levels of PCBs in human tissues based on the congener‐specific analysis are reported in this paper. Samples were analysed for the most abundant PCB congeners. Prevalent persistent organochlorine pesticides and their isomers/metabolites have also been included. The present study is focused on following areas: i) distribution of analysed substances in the various human tissue samples from selected regions of the Czech and Slovak Republic and ii) comparison with the results from other foreign and local studies.     

Medium ‐ pressure ‐ liquid ‐ extraction (MPLE) of selected polychlorinated biphenyls from soil (MPLE II) 1

The extraction of PCBs from spiked soils using the Medium‐Pressure Liquid‐Extraction method showed good recovery rates. Comparison of MPLE and Soxhlet extraction of naturally contaminated soil showed similar results. However, too large quantities of solvents have to be used in MPLE procedure and the elution profile makes it unlikely, that the aspired separation from PAHs would be sufficient.     

Metsulfuron‐methyl soil persistence and mobility in winter wheat and following green manure crops

A procedure has been developed for the analysis of metsulfuron‐methyl in the soil of field crops. The soil extracts are cleaned by repeated TLC, and metsulfuron‐methyl is simultaneously separated from its soil metabolites. Metsulfuron‐methyl is transformed by diazomethane into its N,N ‘‐dimethyl derivative which in the GC (electron capture detection) and GC‐MS apparatus is transformed into a benzisothiazole compound which is measured with great sensitivity. The sensitivity limit is 0.3 μg metsulfuron‐methyl kg^‐1 dry soil. The results of the chemical analyses are confirmed by bioassays using sugar beet as test plant. Metsulfuron‐methyl was measured in the soil of two winter wheat crops after post‐emergence application in the spring of 6 g metsulfuron‐methyl ha^‐1. In the 0–8 cm surface soil layer, the metsulfuron‐methyl soil half‐life was 78 days in 1997, and 67 days in 1998. During crop, metsulfuron‐methyl remained in the 0–8 cm surface soil layer. There, it was at a maximum concentration and herbicide efficiency in a 2 cm‐thick soil layer. This maximum concentration soil layer progressively moved down during crop, attaining the 4–6 cm surface soil layer at crop end. After the winter wheat harvest at the end of July, and the rotary‐tilling of the 0–10 cm surface soil layer before sowing of the green manures, 27% of the metsulfuron‐methyl initial dose still remained in the 0–10 cm surface soil layer. This residue progressively disappeared, and was no more detected at the middle of November. It had no, or only very low inhibiting effect on the growth of the green manures. Thus there is no concern about the possible phytotoxicity of persistent metsulfuron‐methyl soil residues towards the following crops, when metsulfuron‐methyl is applied at the rate of 6 g a.i.ha^‐1.     

Influence of cadmium on the storage and metabolism of HCH in rats

Male albino rats were administered Cd and HCH daily for six weeks to study the effect of Cd on storage and metabolism of HCH. The results indicated a marked inhibition of the metabolism of HCH in the group dosed with HCH + Cd. The metabolic rate of HCH in the group dosed with HCH + Cd was also significantly lower than that in the group dosed with HCH alone. The hepatic content of Cd and Zn was significantly increased whereas a marked depletion of Cu and Fe was observed in the groups exposed to Cd and HCH + Cd. A high level of free Cd and Zn or a low level of Fe and Cu in liver seemed to play an important role in the metabolic inhibition observed in this study.     

Reaction of chlorimuron‐ethyl with diazomethane

Methylation of chlorimuron‐ethyl with etheral solution of diazomethane gave ethyl‐2‐[[[[(4‐chloro‐6‐methoxy‐2‐pyrimidinyl) N‐methylamino] carbonyl] N‐methylamino] sulfonyl] benzoate (dimethyl derivative of chlorimuron‐ethyl) as the major product along with 4‐chloro‐6‐methoxy‐2‐N‐methylamino pyrimidine, 2‐aminomethyl sulfonyl benzoic acid, ethyl‐2‐[(N‐methylamino) sulfonyl] benzoate, ethyl‐2‐[N,N‐dimethylamino) sulfonyl] benzoate and o‐benzoic sulf‐N‐methylimide as the minor products.