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Table 1 Types of NER, related properties, and methods for identification

From: A unified approach for including non-extractable residues (NER) of chemicals and pesticides in the assessment of persistence

NER types

I [24, 45,46,47,48]

II [34, 47, 49,50,51,52]

III [38, 40, 41, 53,54,55]

Properties

Strongly sorbed, entrapped (both = sequestered)

Covalently bound

Label incorporation into biomass

Formation from

Parent substance + transformation products

Parent substance + transformation products

Ultimate degradation and mineralisation

Evidencing

Identification of parent substance + transformation products

Identification of cleavage products, (highly difficult)

Label in biomarkers

Formation processes

van der Waals, hydrophobic interactions, ionic/ion–dipole/dipole–dipole forces, π–π interactions, ligand exchange, charge transfer, H-bonds

C–C, C–N, C–O–C, ester bonds (covalent bonds in general)

Microbial degradation

Stability

Low–high

High

Not relevant

Release probability of parent or transformation/degradation products

Low–high

Low

Not relevant

Extraction methods

‘Mild’–‘harsh’ for parent and transformation products

Cleavage methods for bonds of parent substances and transformation products

Biomarker: PLFA, amino acids, amino sugars

Analytical method

Typical methods used with radioisotope labelled derivatives include radio-HPLC–UV, radio-TLC, LSC, TopCount, radio-HPLC–MS, oxidative combustion followed by LSC; for additional, structural information, size exclusion chromatography or spectroscopic methods like NMR can be applied. Alternatively to radioisotopes, also stable isotope labeling can be applied with subsequent GC–MS or LC–MS analyses

GC–MS, HPLC–MS, 2D-thin layer chromatography

Cleavage methods

Silylation

Hydrolysis by KOH (ester-bonds), BBr3 (ether bonds), RuO4, (C–C bonds), TMAH (tetramethyl-ammonium hydroxide)

Not relevant

Assessment of remobilization potentials

For both types of NER

Physical treatments: simulation of heavy rain events, hot water extraction, freeze/thaw cycling, grinding, wet/dry cycling

Chemical treatments: pH changes, long-term Tenax extraction, changes in ionic strength, hydrolysis in the presence of Na18OH or H 182 O

Biological treatments: application of oxidative and other enzymes with release potential like peroxidases, laccases, and gluthathione-S-transferases, treatment with soil feeding organisms

Not relevant