Fate of 14C-labelled ionic organic chemicals in a water-sediment system and surface water.

The persistence assessment of organic chemicals is based on neutral reference substances. Therefore, our study aimed at investigating the influence of a chemical charge on the degradation of organic compounds in a water-sediment system (OECD 308) and surface water (OECD 309). We used radiolabelled 4-n-dodecylbenzenesulfonic acid sodium salt (14C-DS-, anionic), 4-n-dodecylbenzyltrimethylammonium chloride (14C-DA+, cationic) and 4-n-dodecylphenol (14C-DP, non-ionic) which are structurally similar except their charges. After 120 days of incubation in a water-sediment system, 68% (14C-DS-), 6% (14C-DA+) and 63% (14C-DP) of the applied radioactivity (AR) were mineralized. The formation of non-extractable residues (NER) after 120 days was highest for 14C-DA+ (33% AR), followed by 14C-DS- (19% AR) and 14C-DP (14% AR). Dissipation half-lives (DT50) at 12 °C decreased as follows: 14C-DA+ (346 days) ≫ 14C-DS- (47 days) > 14C-DP (30 days). After 60 days of incubation in surface water with suspended sediment, mineralization of 14C-DS-, 14C-DA+ and 14C-DP accounted for 63%, 7% and 58% AR, respectively. Highest NER formation was observed for 14C-DP (21% AR), followed by 14C-DA+ (14% AR) and 14C-DS- (9% AR). DT50 (12 °C) decreased as follows: 14C-DA+ (45 days) > 14C-DP (3 days) > 14C-DS- (2 days). We showed that a positive charge reduces the degradability of organic chemicals in both test systems. From a scientific point of view, simulation studies following OECD 309 should always be complimented by tests with high sorption capacity, e.g. OECD 308 and OECD 307 tests in order to assess the degradation of a compound, especially in case of cationic organic compounds.

Influence of chemical charge on the fate of organic chemicals in sediment particle size fractions.

In order to investigate the influence of differently sized particle fractions on the fate of ionic chemicals in water-sediment systems, we performed simulation studies following OECD guideline 308. We used 14C-labelled anionic (4-n-dodecylbenzenesulfonic acid sodium salt, '14C-DS-'), cationic (4-n-dodecylbenzyltrimethyl ammonium chloride, '14C-DA+') and non-ionic (4-n-dodecylphenol, '14C-DP') organic chemicals. The sediment was subjected to particle size fractionation. For each particle fraction and test compound, water-sediment systems were prepared and incubated for 14 days. Across all particle fractions, higher amounts of applied radioactivity (AR) of 14C-DS- (in sand 60.1%, in silt 45.1%, in clay 57.0%) and of 14C-DP (sand: 31.8%, silt: 24.4%, clay: 29.2%) were mineralised compared to 14C-DA+ (sand: 5.1% AR, silt: 3.5% AR, clay: 2.4% AR). The highest bioavailability was observed for 14C-DS- followed by 14C-DP and 14C-DA+ across all particle fractions. Formation of non-extractable residues (NER) of 14C-DS- did not substantially differ between the particle fractions, whereas NER formation of 14C-DA+ was higher in the clay fraction (24.3% AR) than in silt (15.9% AR) and sand (8.4% AR). The same trend was observed for 14C-DP. We showed that differently sized particle fractions have an influence on the fate of ionic chemicals in water-sediment systems and conclude that this should be considered when simulation studies in soils and sediments with different textural compositions are performed. Since a positive charge of organic chemicals tends to form higher portions of NER in the clay fraction of sediments, these NER should be further investigated in terms of their nature and types of binding.

Comparison of different versions of simulation studies following OECD 309 using 14C-labelled ionic compounds - Does it make a difference?

Simulation studies following OECD guideline 309 (Aerobic Mineralisation in Surface Water - Simulation Biodegradation Test) are performed to determine the biodegradation of chemicals in surface water. The aim of our study was to perform different versions of this test to identify possible shortcomings. In order to investigate the influence of a chemical charge on the degradation, we used 14C-labelled 4-n-dodecylbenzenesulfonic acid sodium salt (14C-DS-), 4-n-dodecylbenzyltrimethylammonium chloride (14C-DA+) and 4-n-dodecylphenol (14C-DP) Additionally, abiotic degradation of these compounds and the effectiveness of different sterilization methods was assessed. The sampling technique of withdrawing sub-samples provided insufficient recoveries for 14C-DS- and 14C-DP which were mainly below 80% of applied radioactivity (AR). Therefore, the suspended sediment test was repeated using 14C-DS-, 14C-DA+ and 14C-DP and whole flasks were harvested at each sampling time resulting in superior recoveries. For 14C-DS- and 14C-DP, mineralisation was the major route of dissipation with 14CO2 evolution of 75.3% and 69.0% AR, respectively, after 62 days. Mineralisation of 14C-DA+ accounted for only 6.7% AR. Non-extractable residues (NER) of all compounds were similar after 62 days (7.3% - 9.2% AR). Sterile test conditions were best achieved using γ-irradiated sediment and autoclaved water treated with sodium azide. Under sterile conditions, mineralisation of the test compounds as well as NER formation of 14C-DS- and 14C-DP were negligible, whereas small amounts of NER were formed for 14C-DA+ (5.5% AR). We showed that OECD guideline 309 provides too much scope for the experimental setup which affects the outcome of the test and thus, needs further refinement.