Mechanistic modeling of the bioconcentration of (super)hydrophobic compounds in Hyalella azteca.

Bioconcentration tests using the freshwater amphipod Hyalella azteca as an alternative to conventional fish tests have recently received much attention. An appropriate computational model of H. azteca could help in understanding the mechanisms behind bioconcentration, in comparison to the fish as test organism. We here present the first mechanistic model for H. azteca that considers the single diffusive processes in the gills and gut. The model matches with the experimental data from the literature quite well when appropriate physiological information is used. The implementation of facilitated transport was essential for modeling. Application of the model for superhydrophobic compounds revealed binding to organic matter and the resulting decrease in bioavailable fraction as the main reason for the observed counterintuitive decrease in uptake rate constants with increasing octanol/water partition coefficient. Furthermore, estimations of the time needed to reach steady state indicated that durations of more than a month could be needed for compounds with a log Kow > 8, limiting the experimental applicability of the test. In those cases, model-based bioconcentration predictions could be a preferable approach, which could be combined with in vitro biotransformation measurements. However, our sensitivity analysis showed that the uncertainty in determining the octanol/water partition coefficients is a strong source of error for superhydrophobic compounds.

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.

Fate and behavior of 14C-labelled ionic compounds in a soil simulation test.

The influence of an ionic functional group on the fate and behavior of chemicals in the environment has so far not been systematically investigated. This study, therefore, examines the following three substances with high structural similarity but differing charge: non-charged 4-n-dodecylphenol[phenylring-14C(U)] (14C-DP), negatively charged 4-n-dodecylbenzenesulfonicacid[phenylring-14C(U)] sodium salt (14C-DS-) and positively charged 4-n-dodecylbenzyltrimethylammonium chloride[phenylring-14C(U)] (14C-DA+). They were investigated in a soil simulation study according to the OECD 307 test guideline by measuring the distribution of the applied radioactivity (AR) among volatile, mineralized, extractable and non-extractable residues (NER) in one soil after 0, 1, 7, 14, 49, 84 and 124 days of incubation. Extractable portions of 14C were examined by means of radio-TLC and -HPLC analyses. Microbial activity of the soil incubated with and without 14C-DP, 14C-DS- and 14C-DA+ was determined measuring the reduction of dimethylsulfoxide (DMSO) over time. After 124 days of incubation highest mineralization could be observed for 14C-DS- (64.5% AR). Except CO2, no volatile residues were formed over time. Besides the parent compounds, polar (14C-DP, 14C-DS- and 14C-DA+) and nonpolar (14C-DA+) transformation products were detected. Highest amounts of 14C were extracted using methanol and were thus potentially bioavailable for soil microorganisms. Microbial activity was markedly higher in soil incubated with 14C-DP and 14C-DS- compared to 14C-DA+ or soil without any treatment. Half-lives (DT50 k2) at 18 °C were as follows: DA+ (61.8 days) > DS- (18.2 days) > DP (10.0 days). In case of the cationic compound and its transformation products we conclude that a higher sorption affinity to soil particles leads to reduced bioavailability for microorganisms and thus reduced mineralization resulting in a higher persistence compared to anionic and non-charged organic compounds in soil. The impact of our findings on the persistence assessment of chemicals when performing OECD guideline tests in soil, water-sediment and surface water is discussed.

Formation, classification and identification of non-extractable residues of 14C-labelled ionic compounds in soil.

The influence of an ionic functional group on the fate of chemicals in the environment, especially the formation of non-extractable residues (NER), has not been systematically investigated. Using 4-n-dodecylphenol[phenylring-14C(U)], 4-n-dodecylbenzenesulfonicacid[phenylring-14C(U)] sodiumsalt (14C-DS-) and 4-n-dodecylbenzyltrimethylammoniumchloride[phenylring-14C(U)] (14C-DA+) all with a high structural similarity, the formation, classification and identification of NER of negatively (14C-DS-), positively (14C-DA+) and uncharged (14C-DP) chemicals were investigated in a sterilized and non-sterilized soil. After 84 days of incubation in non-sterile soil, 40.6%, 21.7% and 33.5% of the applied radioactivity (AR) of 14C-DP, 14C-DS- and 14C-DA+, respectively, were converted to NER. In contrast, in sterile soil NER formation was markedly lower. The NER were further investigated with respect to sequestered, covalently bound and biogenic residues (i.e. NER types I, II, and III). Silylation of 14C-DP, 14C-DS- and 14C-DA+ derived NER released 3.0-23.2% AR, indicating that these were sequestered, whereas the residual NER (12.9-33.1% AR) was covalently bound to the soil. Analysis of extracts derived by silylation showed that 14C-DP, but neither 14C-DS- nor 14C-DA+, were released by silylation, suggesting that DP might be part of the sequestered NER. Acid hydrolysis of the NER containing soil and subsequent analysis of soil extracts for 14C-aminoacids indicated that 2.5-23.8% AR were biogenic residues. Most DP and DS- derived NER were biogenically or covalently bound, whereas DA+ predominantly forms sequestered NER in soil. From these results we propose that chemicals forming high amounts of NER should be investigated regarding types I-III NER because sequestered parent compounds should be considered in persistence assessments.

Competitive mobilization of phosphate and arsenate associated with goethite by root activity.

Arsenate (As V) is the predominant form of arsenic in soils under aerobic conditions and competes with the major plant nutrient phosphorus (P) in the form of phosphate (PV) not only for sorption sites on mineral surfaces in soil but also for root membrane transporters. Plants have evolved several mechanisms for the mobilization of PV in soils in response to P deficiency, such as the release of organic anions and protons. The aim of the present study was to test whether these mechanisms result in a simultaneous mobilization of arsenate and what would be the consequences for As transfer from soil to plant. The compartment system approach with Zea mays as model crop was chosen as an experimental setup. The system is equipped with micro suction cups and allowed us to investigate processes occurring in the vicinity of roots. As a case study, an artificial quartz substrate with well defined soil physical properties was fertilized, spiked with As V, and amended with increasing amounts of goethite (0, 1, and 4 g kg(-1) in treatments G-0, G-1, and G-4, respectively). The addition of goethite alleviated the As V-induced growth reduction and reduced As V transfer from the substrate to the plant but induced P deficiency at the same time. When low amounts of goethite (1 g kg(-1)) were added, plants mobilized PV but not As V, which might be related to differences in surface complexation reported for PV and As V. No mobilization of PV or As V was observed with the addition of higher amounts of goethite, probably because of decreasing competition between organic anions, PV, and As V for binding sites.