Abstract
All chemicals form non-extractable residues (NER) to various extents in environmental media like soil, sediment, plants and animals. NER can be quantified in environmental fate studies using isotope-labeled (such as 14C or 13C) tracer compounds. Previous NER definitions have led to a mismatch of legislation and state of knowledge in research: the residues are assumed to be either irreversibly bound degradation products or at least parts of these residues can be released. In the latter assumption, soils and sediments are a long-term source of slowly released residues. We here present a conceptual experimental and modeling approach to characterize non-extractable residues and provide guidance how they should be considered in the persistence assessment of chemicals and pesticides. Three types of NER can be experimentally discriminated: sequestered and entrapped residues (type I), containing either the parent substance or xenobiotic transformation products or both and having the potential to be released, which has indeed been observed. Type II NER are residues that are covalently bound to organic matter in soils or sediments or to biological tissue in organisms and that are considered being strongly bound with very low remobilization rates like that of humic matter degradation rates. Type III NER comprises biogenic NER (bioNER) after degradation of the xenobiotic chemical and anabolic formation of natural biomolecules like amino acids and phospholipids, and other biomass compounds. We developed the microbial turnover to biomass (MTB) model to predict the formation of bioNER based on the structural properties of chemicals. Further, we proposed an extraction sequence to obtain a matrix containing only NER. Finally, we summarized experimental methods to distinguish the three NER types. Type I NER and type II NER should be considered as potentially remobilizable residues in persistence assessment but the probability of type II release is much lower than that of type I NER, i.e., type II NER in soil are “operationally spoken” irreversibly bound and can be released only in minute amounts and at very slow rates, if at all. The potential of remobilization can be evaluated by chemical, physical and biological methods. BioNER are of no environmental concern and, therefore, can be assessed as such in persistence assessment. The general concept presented is to consider the total amount of NER minus potential bioNER as the amount of xenoNER, type I + II. If a clear differentiation of type I and type II is possible, for the calculation of half-life type I NER are considered as not degraded parent substance or transformation product(s). On the contrary, type II NER may generally be considered as (at least temporarily) removed. Providing proof for type II NER is the most critical issue in NER assessment and requires additional research. If no characterization and additional information on NER are available, it is recommended to assess the total amount as potentially remobilizable. We propose our unified approach of NER characterization and evaluation to be implemented into the persistence and environmental hazard assessment strategies for REACH chemicals and biocides, human and veterinary pharmaceuticals, and pesticides, irrespective of the different regulatory frameworks.
Highlights
Criteria for the assessment of chemical properties and toxicological and environmental behavior of industrial chemicals in general, and for biocidal products, plant protection products, and veterinary medicines are summarized in specific European legislations, [1,2,3] and guidelines [4,5,6], respectively
As there is no unified guidance available for the differentiation of different non-extractable residues (NER) types in the general regulatory context, here, an approach is suggested based on a thorough review of the current scientific state of the art
Previous NER definitions led to a mismatch of legislation and current state of knowledge in research and modeling; only parent compounds and primary metabolites are considered as NER, whereas remaining label conversion into natural bio-components was explicitly excluded [13]
Summary
Criteria for the assessment of chemical properties and toxicological and environmental behavior of industrial chemicals in general, and for biocidal products, plant protection products, and veterinary medicines are summarized in specific European legislations, [1,2,3] and guidelines [4,5,6], respectively. As there is no unified guidance available for the differentiation of different NER types in the general regulatory context, here, an approach is suggested based on a thorough review of the current scientific state of the art. The regulatory views on NER formation differ considerably with the two extremes of (i) assuming them as either degraded residues of no environmental concern in the regulation of pesticides [14, 15], at least if the NER are below or the mineralisation rates above certain threshold values, or (ii) as potentially bioavailable and nondegraded residues (“parent substance”) in the regulation of general industrial chemicals [7, 9, 16] if no clear indication for ultimate degradation or irreversible immobilization is available. NER in the respective matrix are valued either as ‘safe sink’ or as potential ‘hidden hazard’
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