First evidence for a stereoselective incorporation of nonylphenol diastereomers in soil-derived organo-clay complexes

Environmental processes can affect the stereochemical properties of organic pollutants. In particular, biotic processes like microbial transformations or membrane penetration alter the ratios of enantiomers as well as diastereomers. These effects have been intensively used not only in environmental studies but also in medicine, toxicology, pharmacy, and agricultural sciences. However, in order to identify unambiguously biotic-initiated alteration of organic compounds, the knowledge on the stereoselective effect of all relevant processes is mandatory. Therefore, here we report the first evidence for a stereospecific formation of non-extractable residues of a xeniobiotic in a highly relevant soil subfraction, the organo-clay complexes. In this study, soils were spiked with labeled and unlabeled nonylphenol isomer, and incubation experiments were performed to study its long-term incorporation behavior into soil-derived organo-clay complexes under abiotic and biotic conditions. Besides the extractable particle-associated proportion especially the humic fractions comprising the bound residues have been analyzed by GC/MS. Our results from biotic experiments revealed alterations of the diastereomeric composition of the contaminant in the different soil humic subfractions. A depletion of the first eluting diastereomer as expressed by diastereomeric ratios around 0.6 has been observed for the extractable fraction, whereas the non-extractable proportion was enriched in the first diastereomer (diasteremoric ratio around 1.0). On the contrary, the diastereomeric ratios remained unaffected during the abiotic experiments (diasteremoric ratio around 0.8). These systematic observations give clear evidence that the process of microbial-assisted incorporation of nonylphenol into soil organo-clay complexes is a stereoselective process. To our knowledge, this is the first report on a stereoselective incorporation process of organic substances forming non-extractable residues. Consequently, the formation of non-extractable residues has to be considered in environmental studies dealing with stereoselective analysis of organic pollutants in soils to study their microbial transformation.     

Investigation on the chemical structure of nonextractable residues of the fungicide cyprodinil in spring wheat using 13C-C1-phenyl-cyprodinil on 13C-depleted plants-an alternative approach to investigate nonextractable residues

13C-labelled cyprodinil was applied on 13C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of 14C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The 13C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.     

Nativ-basierte Grundöle für die Produktion von Kühlschmierstoffen

Aims and Scope

Compared to mineral oil products, cooling lubricants based on fatty acid esters have technological advantages. Moreover, they are more environmentally compatible and make a contribution to a sustainable economy. Nevertheless, they are rarely applied in practice, because of their comparably high price, that is based on raw-material and synthesis costs. Alternatives concerning raw-materials and synthesis pathways are considered and properties of resulting ester products are compared.

Methods

The investigations aimed at three fatty acid-2-ethyl-hexylesters that were synthesized in an enzymatic-catalytic routine based on peanut oil, suet, and waste edible fat and at esters that were conventionally produced from animal and plant fats and 2-ethyl-1-hexanol. Physical properties, fatty acid patterns, contents of free fatty acids, as well as oxidative and hydrolytic stabilities were determined. Thermolysis experiments were performed.

Results

The physical properties of the seven esters, density, viscosity, pourpoint, and flash point, were comparable and gave reason for the assumption, that the products could be used as basis oils in lubricant formulations. Hydrolysis stabilities of the esters were high and thermal stress did not point at high potential of hazardous compounds formation. Especially the enzymatic-catalytically produced esters showed deficits concerning oxidation stabilities and free fatty acid contents.

Outlook

For practice it will be necessary to define minimum qualities for raw-materials and resulting ester oils to be used as lubricant basis oils. Moreover, processes have to be developed, that yield high quality ester products from waste edible and animal fats without loosing the advantage of low-cost raw-materials by high production and refinement costs. Surely, one contribution is the further development of the energy-saving enzymtic alcoholysis for ester production.