What is the spatial-temporal behavior of a low, medium and high adsorptive compound in two contrasting natural sediments in OECD 218/219 test systems?

Artificial sediment used in studies according to OECD 218/219 (Sediment Water Chironomid Toxicity Test Using Spiked Sediment/Water) does not necessarily mirror the characteristics of natural sediments. To investigate the influence of sediment characteristics on the spatial-temporal behaviors of bixafen (KfOM = 2244 mL/g), fluopyram (KfOM = 162 mL/g) and N,N-dimethylsulfamide (KfOM ≈ 0 mL/g), experiments according to OECD 218/219 with two contrasting natural sediments were conducted. The silt loam sediment provided a high content of organic matter (OM) (13.1%), while the OM (0.45%) of the sandy sediment was low. Diffusion into (OECD 219) or out (OECD 218) of the sediment was dependent on the extent of adsorption, which is linked to the model compounds ́ adsorption affinities and the sediments ́ OM. Consequently, N,N-dimethylsulfamide showed unhindered mobility in each experimental set up, while the high adsorption affinities of fluopyram and bixafen limited the diffusion in the respective sediments. Therefore, in experiments with the silt loam sediment, both compounds revealed a limited mobility and either accumulated in the top 5 mm of the sediment (OECD 219) or remained homogenously distributed over the sediment depth (OECD 218). A greater mobility was observed within the sandy sediment.The influence of OM as found in a study using artificial sediment could be confirmed. Moreover, the applicability of a TOXSWA model was reassured to predict the measured concentrations at different sediment depths. TOXSWA is used in the regulatory exposure assessment to simulate the behavior of pesticides in surface waters. Calibration of three driving input parameters by inverse modelling (diffusion-, adsorption coefficient and OM) revealed no potential for improvement. The core sampling technique used and the model may contribute to a more realistic determination of concentration to which the Chironomid larvae are exposed to. This applies to water sediment test systems where the test organisms do not evenly inhabit the sediment.

What is the actual exposure of organic compounds on Chironomus riparius? - A novel methodology enabling the depth-related analysis in sediment microcosms.

A novel active sampling method enabled determination of sediment depth profiles revealing the spatial distribution of model compounds N,N-dimethylsulfamide, fluopyram and bixafen (low, medium, high adsorption affinity) in sediment microcosms according to OECD Test 218/219 (Sediment-Water Chironomid Toxicity Test Using Spiked Sediment/Spiked Water). After the overlying water was removed, plastic tubes were inserted into the sediment and the microcosms were frozen. For depth-related analysis, each "sediment core" was mounted in a cutting device and sawed into three 5-mm-slices, respectively (top, middle, bottom). Each slice was centrifuged for sediment and pore water separation. By various sampling dates within 28 days, we could follow the behavior of model compounds depending on sorption affinities and display specific distribution patterns within the sediment. N,N-dimethylsulfamide showing no sediment adsorption, migrated unhindered in (OECD 219) and out (OECD 218) of the sediment via pore water, resulting in homogenous distributions in both test designs. Fluopyram with moderate adsorption affinity revealed a concentration gradient with declining amounts from top to bottom layer (OECD 219) and higher amounts in the middle and bottom layer as compared to the top layer (OECD 218). Bixafen providing a strong adsorption affinity accumulated in the top layer in OECD 219, while no concentration gradients became visible in OECD 218. For establishing a Toxic Substances in Surface Waters (TOXSWA) model, we compared our measurements with simulated results revealing good agreements. The presented methodology is a useful tool to determine more realistic sediment and pore water concentrations, which the Chironomid larvae are exposed to.

Unraveling microbial turnover and non-extractable residues of bromoxynil in soil microcosms with 13C-isotope probing.

Bromoxynil is a widely used nitrile herbicide applied to maize and other cereals in many countries. To date, still little is known about bromoxynil turnover and the structural identity of bromoxynil non-extractable residues (NER) which are reported to occur in high amounts. Therefore, we investigated the microbial turnover of 13C-labeled bromoxynil for 32 days. A focus was laid on the estimation of biogenic NER based on the turnover of 13C into amino acids (AA). At the end, 25% of 13C6-bromoxynil equivalents were mineralized, 2% assigned to extractable residues and 72.5% to NER. Based on 12% in the 13C-total AA and an assumed share of AA of 50% in microbial biomass we arrived at 24% of total 13C-biogenic NER. About 33% of the total 13C-NER could thus be explained by 13C-biogenic NER; 67% was unknown and by definition xenobiotic NER with potential for toxicity. The 13C label from 13C6-bromoxynil was mainly detected in the humic acids (28.5%), but significant amounts were also found in non-humics (17.6%), fulvic acids (13.2%) and humins (12.7%). The 13C-total amino acids hydrolyzed from humic acids, humins and fulvic acids amounted to 5.2%, 6.1% and 1.2% of 13C6-bromoxynil equivalents, respectively, corresponding to total 13C-biogenic NER amounts of 10.4%, 12.2% and 2.4%. The humins contained mostly 13C-biogenic NER, whereas the humic and fulvic acids may be dominated by the xenobiotic NER. Due to the high proportion of unknown 13C-NER and particularly in the humic and fulvic acids, future studies should focus on the detailed characterization of these fractions.

Quantitative Identification of Biogenic Nonextractable Pesticide Residues in Soil by (14)C-Analysis.

Quantification of nonextractable residues (NER) of pesticides in soil is feasible by use of radioactively labeled compounds, but structural information on these long-term stabilized residues is usually lacking. Microorganisms incorporate parts of the radiolabeled ((14)C-) carbon from contaminants into microbial biomass, which after cell death enters soil organic matter, thus forming biogenic nonextractable residues (bioNER). The formation of bioNER is not yet determinable in environmental fate studies due to a lack of methodology. This paper focuses on the development of a feasible analytical method to quantify proteinaceous carbon, since proteins make up the largest mass portion of bacterial cells. The test substance (14)C-bromoxynil after 56 days forms more than 70% of NER in soil. For further characterization of NER the amino acids were extracted, purified, and separated by two-dimensional thin-layer chromatography (TLC). Visualization of the (14)C-amino acids was performed by bioimaging, unambiguous identification by GC-MS and LC-MS/MS. Our analysis revealed that after 56 days of incubation about 14.5% of the (14)C-label of bromoxynil was incorporated in amino acids. Extrapolating this content based on the amount of proteins in the biomass (55%), in total about 26% of the NER is accounted for by bioNER and thus is not environmentally relevant.

Life stage- dependent bioconcentration of a nonylphenol isomer in Daphnia magna.

Bioaccumulation is an important aspect for the fate and effects of xenobiotics in the environment. In this study we used a radiolabeled nonylphenol isomer to investigate the bioconcentration in Daphnia magna at different ages. Apart from the total radioactivity we measured the metabolism of p353-NP in D. magna, to calculate the amount of p353-NP compared to total radioactivity found within the daphnids. Bioconcentration factors, based on wet weight, calculated from the rate constants for total radioactivity in neonates and adults were 4271 kg/l and 760 kg/l respectively, leading to a 5.6 deviance in bioconcentration. This deviance was even more pronounced, nearly one order of magnitude, for the p353-NP concentration with bioconcentration factors of 302 kg/l for neonates and 31 kg/l for adults. We were able to describe the bioconcentration for all daphnids by a weight-dependent one- compartment model. These results pointed out that it is not possible to compare bioconcentration experiments conducted with different substances and different sized daphnids. Additionally it was shown that it is not possible to describe the bioconcentration by measuring the total radioactivity. Metabolism of nonylphenol occurs at a very fast rate and bioconcentration is not triggered by the partition between two phases, but by metabolism. Discrimination between the two mechanisms was achieved using radiolabeled substances and a pseudo two-compartment model to describe metabolism and elimination by two rate constants which afterwards can be compared between different substances.

Occurrence of a nitro metabolite of a defined nonylphenol isomer in soil/sewage sludge mixtures.

Uniformly [14C]-ring-labeled 4-(3,5-dimethyl-3-heptyl)phenol (353-nonylphenol) is a highly relevant isomer of the technical nonylphenol mixture. We studied the sorption, desorption, and degradation of the synthesized isomer in an agricultural sandy loam at various soil/sewage sludge ratios. Sorption of 353-nonylphenol was high and differed with the amount of suspended soil in water. log Koc values, which are used to assess the risk of nonylphenol, ranged from 3.80 to 5.75. Desorption was slow and low and resulted in constant concentrations of about 15 ng/L353-nonylphenol in water after several desorption steps. In degradation studies up to 6% of the applied 353-nonylphenol in soil was volatilized; we consider this an important source of nonylphenol in the environment. With increasing amounts of sewage sludge in the soil/sewage sludge mixtures, 353-nonylphenol was stabilized, probably because of the lack of oxygen in sludge aggregates even under oxic conditions in flow-through systems. Unexpectedly, a less-polar metabolite was detected in amounts up to 40% of the applied nonylphenol after 135 days of incubation. This novel metabolite was identified as 4-(3,5-dimethyl-3-heptyl)-2-nitrophenol. This product formation might indicate the existence of novel metabolic pathways of nonylphenol in the environment.