Terbuthylazine and Deethylterbuthylazine in Rain and Surface Water – Determination by Enzyme Immunoassay and Gas Chromatography/Mass Spectrometry

Rain and surface water samples from Southern Germany were investigated from 1991 to 1995 for terbuthylazine and one of its major metabolites, deethylterbuthylazine. The concentrations observed were compared to the concentrations found for atrazine and deethylatrazine in the same water samples. Concentrations ranged from < 0.02 μg/L to 0.7 μg/L for terbuthylazine and from < 0.02 μg/L to 0.6 μg/L for deethylterbuthylazine, compared to concentrations of < 0.02 μg/L to 3 μg/L and < 0.02 μg/L to 0.5 μg/L for atrazine and deethylatrazine, respectively. The ratios of metabolite concentrations to parent compound concentrations were calculated for deethylterbuthylazine to terbuthylazine (DTR) and deethylatrazine to atrazine (DAR). In rain water, DTR of 0.8…3.0 and DAR of 0.3… 1.9 were determined with mean values of 0.9… 1.7 for DTR and 0.6…0.9 for DAR in the different years. The ratios increased during summer periods. The highest ratios were observed in samples from forest stands, showing that degradation of the herbicide has occurred during transport between the source and the sampling site. The DTR in rain water were about 50… 100% higher than the DAR. This indicates a higher degradation rate of terbuthylazine during atmospheric transport. In surface water, DTR of 0.3… 1.2 with mean values of 0.5…0.8 and DAR of 0.2…2.2 with mean values of 0.2… 1.3 were observed. The ratios increased from June to September.     

Approaches to the Immunochemical Analysis of Non-extractable Triazine Residues in Refractory Organic Substances (ROS) and Characterization of ROS

The tendency of several pesticides to form non-extractable residues requires simple and fast screening methods. Immunochemical methods can meet this demand. They are based on selective and highly sensitive antibody binding to pesticide residues exposed on refractory organic substances (ROS). s-Triazines were used as an example to show the feasibility of this approach. It was proven that under laboratory conditions atrazine was bound to ROS. Antibody recognition pointed to the availability of free ethyl and isopropyl groups exposed at the non-extractable s-triazine residue. Therefore, it is suggested on the basis of antibody selectivities that binding of atrazine to ROS may take place by substitution of the chlorine residue. In the next step, aquatic ROS isolated from surface waters located in an agricultural area were examined for non-extractable s-triazines. ROS from a lake were found to contain bound residues, whereas none were detected in the creek samples. As an outlook the feasibility of serological characterization of ROS is discussed. The novel concept of serotyping is based on the fractionation of ROS by electrophoretic techniques followed by an immunoreaction with polyclonal antibodies directed against different ROS. When immunoelectrophoresis is used, precipitation lines can be compared and checked for identity and cross-reactivity. This approach can form the basis for classifying ROS and determine similarities with unknown ROS.     

Assessing the spatial variability,level and source of organic chemical contaminants in bivalve fishing grounds on the Galician coast (NW Spain)

Polychlorinated biphenyls, organochlorine pesticides, organotin compounds and triazines were quantified in sediments and bivalves collected in four areas on the Galician coast. One or several species were analysed at each site depending on their availability, including mussels (Mytilus galloprovincialis), cockles (Cerastoderma edule), clams (Venerupis pullastra and Ruditapes decussatus) and razor shells (Ensis siliqua). The general spatial distribution of contaminants was consistent in spite of the different sources of contamination. High inter-species variability was also observed. M. galloprovincialis and V. pullastra showed the highest levels of contaminants and intra-spatial variability, which highlights them as suitable species to be used as sentinel organisms. The area of O Burgo showed some worrisome results: PCB sediment concentrations were within the range that could cause biological effects. Also the level of heptachlor observed in V. pullastra was above limits accepted on edible seafood. Finally TBT concentration in mussels correlated with concentrations causing imposex in snails.