Enlarging the Arsenal of Test Species for Sediment Quality Assessment.

Since only a few standard benthic test species are available for sediment quality, our study aimed to employ multiple test species representing different sensitivity categories in the quality assessment of contaminated sediments. To this end three macroinvertebrate species, Sericostoma personatum (caddisfly, sensitivity category 10), Asellus aquaticus (isopod, category 3) and Chironomus riparius (chironomid, category 2), were exposed to sediments originating from various contamination sources in whole sediment bioassays using intact sediment cores. The agricultural sediment caused insect mortality, the agricultural and urban sediment caused isopod growth reduction and the urban and Wastewater Treatment Plant (WWTP) sediment affected chironomid emergence time. It is concluded that the arsenal of standard species can be successfully expanded by non-standard species, reducing over- or underestimation of the risks of contaminated sediments.

Nationwide screening of surface water toxicity to algae.

According to the European Water Framework Directive (WFD), chemical water quality is assessed by monitoring 45 priority substances. However, observed toxic effects can often not be attributed to these priority substances, and therefore there is an urgent need for an effect-based monitoring strategy that employs bioassays to identify environmental risk. Algal photosynthesis is a sensitive process that can be applied to identify the presence of hazardous herbicides in surface water. Therefore, the aim of this study was to employ an algal photosynthesis bioassay to assess surface water toxicity to algae and to identify the compounds causing the observed effects. To this purpose, Raphidocelis subcapitata was exposed to surface water samples and after 4.5 h photosynthetic efficiency was determined using PAM fluorometry. In this rapid high throughput bioassay, algal photosynthesis was affected by surface water from only one of 39 locations. Single compounds toxicity confirmation elucidated that the observed effect could be solely attributed to the herbicide linuron, which occurred at 110 times the EQS concentration and which is not included in the WFD priority substances list. In conclusion, applying the algal photosynthesis bioassay enables more efficient and effective assessment of toxicity to primary producers because it: (i) identifies the presence of herbicides that would be overlooked by routine chemical WFD monitoring, and (ii) avoids redundant chemical analyses by focusing only on (non-)target screening in samples with demonstrated effects.

Predicting the phospholipophilicity of monoprotic positively charged amines.

The sorption affinity of eighty-six charged amine structures to phospholipid monolayers (log KIAM) was determined using immobilized artificial membrane high-performance liquid chromatography (IAM-HPLC). The amine compounds covered the most prevalent types of polar groups, widely ranged in structural complexity, and included forty-seven pharmaceuticals, as well as several narcotics and pesticides. Amine type specific corrective increments were used to align log KIAM data with bilayer membrane sorption coefficients (KMW(IAM)). Using predicted sorption affinities of neutral amines, we evaluated the difference (scaling factor ΔMW) with the measured log KMW(IAM) for cationic amines. The ΔMW values were highly variable, ranging from -2.37 to +2.3 log units. For each amine type, polar amines showed lower ΔMW values than hydrocarbon based amines (CxHyN+). COSMOmic software was used to directly calculate the partitioning coefficient of ionic structures into a phospholipid bilayer (KDMPC-W,cation), including quaternary ammonium compounds. The resulting root mean square error (RMSE) between log KDMPC-W,cation and log KMW(IAM) was 0.83 for all eighty-six polar amines, and 0.47 for sixty-eight CxHyN+ amines. The polar amines were then split into five groups depending on polarity and structural complexity, and corrective increments for each group were defined to improve COSMOmic predictions. Excluding only the group with sixteen complex amine structures (≥4 polar groups, Mw > 400, including several macrolide antibiotics), the resulting RMSE for corrected KDMPC-W,cation values improved to 0.45 log units for the remaining set of 138 polar and CxHyN+ amines.

Phospholipophilicity of CxHyN(+) amines: chromatographic descriptors and molecular simulations for understanding partitioning into membranes.

Using immobilized artificial membrane high-performance liquid chromatography (IAM-HPLC) the sorption affinity of 70 charged amine structures to phospholipids was determined. The amines contained only 1 charged moiety and no other polar groups, the rest of the molecule being aliphatic and/or aromatic hydrocarbon groups. We systematically evaluated the influence of the amine type (1°, 2°, 3° amines and quaternary ammonium), alkyl chain branching, phenyl ring positioning, charge positioning (terminal vs. central in the molecule) on the phospholipid-water partitioning coefficient (KPLIPW). These experimental results were compared with quantum-chemistry based three-dimensional (3D) molecular simulations of the partitioning of charged amines, including the most likely solute conformers, using a hydrated phospholipid bilayer in the COSMOmic module of COSMOtherm software. Both IAM-HPLC retention data and the simulations suggest that the molecular orientation of charged amines at the location in the bilayer with the lowest calculated Gibbs free energy exerts a strong influence over the partitioning within the membrane. The most favourable position of charged amines coincides with the region where the phosphate anions in the phospholipid bilayer are most abundant. Hydrocarbon units oriented in this layer are located more towards the aqueous phase and contribute less to the overall membrane affinity than hydrocarbon units extending into the more hydrophobic core of the bilayer. COSMOmic simulations explain most of the trends between the structural differences observed in IAM-HPLC based KPLIPW. For this set of cationic structures, the mean absolute difference between COSMOmic simulations and IAM-HPLC data, accounting only for amine type corrective increments, is 0.31 log units.