Organic Contaminants and Interactions with Micro- and Nano-Plastics in the Aqueous Environment: Review of Analytical Methods.

Micro- and nanoplastic particles are increasingly seen not only as contaminants themselves, but also as potential vectors for trace organic chemicals (TOrCs) that might sorb onto these particles. An analysis of the sorbed TOrCs can either be performed directly from the particle or TOrCs can be extracted from the particle with a solvent. Another possibility is to analyze the remaining concentration in the aqueous phase by a differential approach. In this review, the focus is on analytical methods that are suitable for identifying and quantifying sorbed TOrCs on micro- and nano-plastics. Specific gas chromatography (GC), liquid chromatography (LC) and ultraviolet-visible spectroscopy (UV-VIS) methods are considered. The respective advantages of each method are explained in detail. In addition, influencing factors for sorption in the first place are being discussed including particle size and shape (especially micro and nanoparticles) and the type of polymer, as well as methods for determining sorption kinetics. Since the particles are not present in the environment in a virgin state, the influence of aging on sorption is also considered.

Ozonation of Tamoxifen and Toremifene: Reaction Kinetics and Transformation Products.

The oxidation of the two antiestrogenic pharmaceuticals tamoxifen and toremifene with ozone in water was investigated concerning kinetics, reaction pathway, and transformation product formation. For both compounds a high dependency of second order rate constants and products on pH was determined. In case of full protonation of the amine (cation) ozone attacks with a second order rate constant of 1.57 × 104 M-1 s-1 for tamoxifen and 4.37 × 103 M-1 s-1 for toremifene. The neutral tertiary amine has an unexpected high second order rate constant of 3.17 × 108 M-1 s-1 for tamoxifen and 1.46 × 108 M-1 s-1 for toremifene. For the reaction of ozone and the tertiary amine only N-oxide formation was observed. p Ka values for tamoxifen (9.49 ± 0.22) and toremifene (9.57 ± 0.22) can be reported based on experimental data. Eight transformation products (TPs) were observed and identified based on MS/MS spectra or a reference standard. Products observed derived from Criegee reaction and hydroxylation as well as N-oxide formation. Further TPs from reactions with TAM products were combinations of N-oxides, Criegee products and hydroxylation products. Thus, reaction pathways can be derived and primary and secondary TPs distinguished for the first time.

Digest, stain and bleach: Three steps to achieving rapid microplastic fluorescence analysis in wastewater samples.

Efforts associated with common analytical techniques for microplastics including spectroscopic and thermo-analytical techniques are limiting the ability to perform large-scale monitoring of microplastics in the aquatic environment, because the analytical equipment required is costly and the analysis itself time consuming. Thus, there is a need to develop low cost, rapid alternative monitoring approaches. One possible alternative is the use of selective fluorescence staining of microplastic particles directly applied to environmental samples. However, to the best of our knowledge this has not yet been successfully implemented for wastewater samples. In this study, sludge samples are used as surrogates for wastewater alongside six different polymers to develop a combined sample preparation and staining protocol that could selectively stain microplastics without significant interference from the natural constituents of the sludge. Results confirmed that using Fenton's reagent to remove the organic matter before staining the sample with Nile red (NR) and subsequently bleaching it by sodium hypochlorite resulted in the best workflow to selectively stain microplastics and then analyze them in wastewater samples using fluorescence microscopy.

Exploring the effects of intermittent aeration on the performance of nitrifying membrane-aerated biofilm reactors.

Membrane-aerated biofilm reactors (MABRs) are an emerging technology for nutrient removal; however, a trade-off remains between their removal rate and oxygen transfer efficiency. This study compares nitrifying flow-through MABRs operated under continuous and intermittent aeration modes at mainstream wastewater ammonia levels. The intermittently-aerated MABRs maintained maximal nitrification rates, including under conditions allowing the oxygen partial pressure on the gas side of the membrane to considerably drop during the no-aeration period. Nitrous oxide emissions of all reactors were comparable and amounted to approximately 20 % of the converted ammonia. Intermittent aeration increased the transformation rate constant of atenolol, yet did not affect the removal of sulfamethoxazole. Seven additional trace organic chemicals were not biodegraded by any of the reactors. The ammonia-oxidizing bacteria in the intermittently-aerated MABRs were dominated by Nitrosospira, previously shown to be abundant at low oxygen concentrations and provide reactor stability under changing conditions. Our findings indicate that intermittently-aerated flow-through MABRs can achieve high nitrification rates and oxygen transfer efficiencies, highlighting the possible implications of air supply discontinuity on nitrous oxide emissions and trace organic chemical biotransformation.

Interaction of heavy metals and biocide/herbicide from stormwater runoff of buildings with dissolved organic matter.

Stormwater runoff from roofs and façades can be contaminated by heavy metals and biocides/herbicides. High efficiency on-site treatment methods are now urgently needed to safeguard the ecosystem. The basis for developing such treatment facilities is an in-depth understanding of their interactions with dissolved organic matter (DOM), as this affects their migration in the environment. Hence, the interactions between copper (Cu), zinc (Zn), benzyl-dimethyl-tetradecylammonium chloride dihydrate (BAC), mecoprop-P (MCPP) and DOM at pH 5 to 9 were investigated separately in this study. The evaluation of the interaction processes was achieved by applying excitation emission matrix and parallel factor analysis (EEM-PARAFAC) to titration samples; obtained data were fitted by two different models. Mechanisms involved in BAC/MCPP-DOM interactions were revealed by Fourier-transform infrared spectroscopy (FTIR) and two-dimensional correlation spectrum (2D-COS) analysis. Results showed that the applied DOM was composed of the two different fluorescent components C1 and C2. More interaction with C1 than with C2 was observed for both Cu/Zn and BAC/MCPP. Increasing the pH enhanced the interactions between Cu/Zn and DOM. At pH 5 with a maximum quencher addition, the remaining fluorescence of CuC1 and ZnC1 were 15.7% and 87.1%, respectively. Corresponding data at pH 9 decreased to 3% and 69.5%. Contrarily, interactions between BAC/MCPP and DOM were impaired by high pH conditions. The increase of pH from 5 to 9 with maximum BAC and MCPP added raised the remaining fluorescence of BAC-C1 and MCPP-C1 by 15.9% and 21.3% separately. The fitting outcomes from the Ryan-Weber equation (Cu/Zn titration) and the Stern-Volmer equation (BAC/MCPP titration) corresponded well with the titration studies. FTIR coupled with 2D-COS analysis revealed that mechanisms involved in BAC/MCPP titration include hydrogen bonding, π-π interaction, and electrostatic effect. The order of mechanisms taking effect during the interaction with DOM is affected by the molecular structure of BAC and MCPP.

A Novel Analytical Approach to Assessing Sorption of Trace Organic Compounds into Micro- and Nanoplastic Particles.

Assessing the sorption of trace organic compounds (TOrCs) into micro- and nanoplastic particles has traditionally been performed using an aqueous phase analysis or solvent extractions from the particle. Using thermal extraction/desorption-gas chromatography/mass spectrometry (TD-Pyr-GC/MS) offers a possibility to analyze the TOrCs directly from the particle without a long sample preparation. In this study, a combination of two analytical methods is demonstrated. First, the aqueous phase is quantified for TOrC concentrations using Gerstel Twister® and TD-GC/MS. Subsequently, the TOrCs on the particles are analyzed. Different polymer types and sizes (polymethyl methacrylate (PMMA), 48 µm; polyethylene (PE), 48 µm; polystyrene (PS), 41 µm; and PS, 78 nm) were analyzed for three selected TOrCs (phenanthrene, triclosan, and α-cypermethrin). The results revealed that, over a period of 48 h, the highest and fastest sorption occurred for PS 78 nm particles. This was confirmed with a theoretical calculation of the particle surface area. It was also shown for the first time that direct quantification of TOrCs from PS 78 nm nanoparticles is possible. Furthermore, in a mixed solute solution, the three selected TOrCs were sorbed onto the particles simultaneously.

Microplastic sampling from wastewater treatment plant effluents: Best-practices and synergies between thermoanalytical and spectroscopic analysis.

Wastewater treatment plants (WWTPs) may represent point sources for microplastic discharge into the environment. Quantification of microplastic in effluents of WWTPs has been targeted by several studies although standardized methods are missing to enable a comparability of results. This study discusses theoretical and practical perspectives on best practices for microplastic sampling campaigns of WWTPs. One focus of the study was the potential for synergies between thermoanalytical and spectroscopic analysis to gain more representative sampling using the complementary information provided by the different analytical techniques. Samples were obtained before and after sand filtration from two WWTPs in Germany using cascade filtration with size classes of 5,000 - 100 µm, 100 - 50 µm, and 50 - 10 µm. For spectroscopic methods samples were treated by a Fenton process to remove natural organic matter, whereas TED-GC-MS required only sample extraction from the filter cascade. µFTIR spectroscopy was used for the 100 µm and 50 µm basket filters and µRaman spectroscopy was applied to analyze particles on the smallest basket filter (10 µm). TED-GC-MS was used for all size classes as it is size independent. All techniques showed a similar trend, where PE was consistently the most prominent polymer in WWTP effluents. Based on this insight, PE was chosen as surrogate polymer to investigate whether it can describe the total polymer removal efficiency of tertiary sand filters. The results revealed no significant difference (ANOVA) between retention efficiencies of tertiary sand filtration obtained using only PE and by analyzing all possible polymers with µFTIR and µRaman spectroscopy. Findings from this study provide valuable insights on advantages and limitations of cascade filtration, the benefit of complementary analyses, a suitable design for future experimental approaches, and recommendations for future investigations.

Ecotoxicological effects prior to and after the ozonation of tamoxifen.

The endocrine disrupting micropollutant tamoxifen can induce several effects on aquatic organisms. It is introduced into the environment mainly by wastewater treatment plant effluents. To reduce the discharge of micropollutants into surface waters, ozonation can be used as additional wastewater treatment option. For only few transformation products (TPs) formed by ozonation ecotoxicological data are available. To enable an initial estimation of ecotoxicological potentials of the TPs formed after the ozonation of tamoxifen, acute toxicity (immobilization) to Daphnia magna and green algae growth inhibition using Desmodesmus subspicatus were determined for several ozone doses spiked at pH 3 and pH 7. The initial immobilization of D. magna by tamoxifen was not further observed after ozonation. In contrast, the green algae growth inhibition increased due to ozonation of tamoxifen. Overall, five transformation products were observed. For three TPs, positive correlations of green algae growth inhibition and peak area were determined, whereas two TPs do not induce the residual effects. Based on our observations, TP 270 can be assumed as most potent of the formed TPs concerning green algae growth inhibition. Since the effect is not induced by formed N-oxides, green algae growth inhibition could be reduced by sufficient ozone exposure during wastewater treatment.

Endocrine effects after ozonation of tamoxifen.

Ozonation is used as additional wastewater treatment option to remove recalcitrant micropollutants. It also removes the estrogenic activity found in wastewater but not always the anti-estrogenic activity. This can be explained by an incomplete removal of anti-estrogenic micropollutants or by formation of transformation products (TPs) which retain the activity. The present study investigates the degradation of the anti-estrogenic pharmaceutical tamoxifen in pure water, regarding TP formation and related anti-estrogenic effect using Arxula adeninivorans yeast estrogen screen (A-YES). In total, five transformation products were detected: three N-oxides and two further products (TP 270 and TP 388). For the transformation product TP 270 a correlation of the extent of formation with an increase of the anti-estrogenic activity was determined, demonstrating that transformation products from ozonation can be more active in a bioassay than the parent compounds. Our study shows also that the transformation of tamoxifen to N-oxides reduces the anti-estrogenic activity. The reactivity of amines towards ozone typically increases with pH, since only deprotonated amines react with ozone. Hence, removal of the endocrine activity by N-oxide formation may be disfavored at low pH.