In silico ecotoxicity assessment of pharmaceutical residues in wastewater following oxidative treatment.

Advanced oxidation processes such as thermal plasma activation and UV-C/H2O2 treatment are considered as applications for the degradation of pharmaceutical residues in wastewater complementary to conventional wastewater treatment. It is supposed that direct oxidative treatment can lower the toxicity of hospital sewage water (HSW). The aim of this study was to predict the ecotoxicity for three aquatic species before and after oxidative treatment of 10 quantified pharmaceuticals in hospital sewage water. With the application of oxidative chemistry, pharmaceuticals are degraded into transformation products before reaching complete mineralization. To estimate the potential ecotoxicity for fish, Daphnia and green algae ECOSAR quantitative structure-activity relationship software was used. Structure information from pristine pharmaceuticals and their oxidative transformation products were calculated separately and in a mixture computed to determine the risk quotient (RQ). Calculated mixture toxicities for 10 compounds found in untreated HSW resulted in moderate-high RQ predictions for all three aquatic species. Compared to untreated HSW, 30-min treatment with thermal plasma activation or UV-C/H2O2 resulted in lowered RQs. For the expected transformation products originating from fluoxetine, cyclophosphamide and acetaminophen increased RQs were predicted. Prolongation of thermal plasma oxidation up to 120 min predicted low-moderate toxicity in all target species. It is anticipated that further degradation of oxidative transformation products will end in less toxic aliphatic and carboxylic acid products. Predicted RQs after UV-C/H2O2 treatment turned out to be still moderate-high. In conclusion, in silico extrapolation of experimental findings can provide useful predicted estimates of mixture toxicity. However due to the complex composition of wastewater this in silico approach is a first step to screen for ecotoxicity. It is recommendable to confirm these predictions with ecotoxic bioassays.

Thermal plasma activation and UV/H2O2 oxidative degradation of pharmaceutical residues.

The aquatic environment becomes increasingly contaminated by anthropogenic pollutants such as pharmaceutical residues. Due to poor biodegradation and continuous discharge of persistent compounds in sewage water samples, pharmaceutical residues might end up in surface waters when not removed. To minimize this pollution, onsite wastewater treatment techniques might complement conventional waste water treatment plants (WWTPs). Advanced oxidation processes are useful techniques, since reactive oxygen species (ROS) are used for the degradation of unwanted medicine residues. In this paper we have studied the advanced oxidation in a controlled laboratory setting using thermal plasma and UV/H2O2 treatment. Five different matrices, Milli-Q water, tap water, synthetic urine, diluted urine and synthetic sewage water were spiked with 14 pharmaceuticals with a concentration of 5 µg/L. All compounds were reduced or completely decomposed by both 150 W thermal plasma and UV/H2O2 treatment. Additionally, also hospital sewage water was tested. First the concentrations of 10 pharmaceutical residues were determined by liquid chromatography mass spectrometry (LC-MS/MS). The pharmaceutical concentration ranged from 0.08 up to 2400 µg/L. With the application of 150 W thermal plasma or UV/H2O2, it was found that overall pharmaceutical degradation in hospital sewage water were nearly equivalent to the results obtained in the synthetic sewage water. However, based on the chemical abatement kinetics it was demonstrated that the degree of degradation decreases with increasing matrix complexity. Since reactive oxygen and nitrogen species (RONS) are continuously produced, thermal plasma treatment has the advantage over UV/H2O2 treatment.

Oxidative degradation of cyclophosphamide using thermal plasma activation and UV/H2O2 treatment in tap water.

There is a growing concern about pharmaceuticals entering the aquatic environment. Many of these compounds cannot be removed completely in sewage treatment plants. To remove these unwanted medicines from water, oxidative degradation techniques may complement the current purification steps. In this paper we studied the effect of advanced oxidation on the cytostatic drug cyclophosphamide (CP) by comparing thermal plasma activation with UV/H2O2 treatment. Plasma activated water (PAW) contains highly reactive oxygen and nitrogen species (RONS) as a result of electric gas discharges in air over water. CP solutions in tap water were oxidized over a period of 120 min and subsequently analyzed by LC-MS/MS to measure the compound degradation. Plasma activation was applied at 50, 100, or 150 W electric power input and UV/H2O2 treatment was carried out by the addition of H2O2 and placing an UV-C source above the test solution for immediate irradiation. The oxidative degradation of CP in PAW resulted in a complete degradation within 80 min at 150 W. CP was also completely degraded within 60 min applying UV/H2O2 oxidation. Both treatment techniques do induce different structural changes, demonstrating that CP is completely degraded in tap water.

Preparation of Free-Surface Hyperbolic Water Vortices.

Free surface vortices are present in industry in flow regulation, energy dissipation, and energy generation. Although investigated extensively, detailed experimental data regarding free surface vortices are lacking, particularly regarding the turbulence at the interface. The present paper reports on a special type of free surface vortex first proposed by Walter Schauberger in the 1960s that has an oxygen volumetric mass transfer coefficient exceeding the value of similar systems. This special type of vortex forms in a hyperbolic funnel. Different stable regimes can be stabilized with different hydraulic characteristics. Other advantages of this technology are its energy efficiency, simple design, and scalability. The flow in this hyperbolic funnel is characterized by strong turbulence and an increased surface area of the air-water interface. The local pressure strongly varies along the surface, resulting in a pronounced wavey air-water boundary layer. Due to the helical flow, these perturbations move inward, pulling the boundary layer with them. The resultant pressure gradient draws a certain air volume into the water vortex. The construction of the basic hyperbolic funnel setup and operational examples, including high-speed visualization for three different stable regimes, are presented in this work.

Determination of cytotoxicity following oxidative treatment of pharmaceutical residues in wastewater.

Pharmaceutical residues are released in the aquatic environment due to incomplete removal from wastewater. With the presence of multiple chemicals in sewage waters, contaminants may adversely affect the effectiveness of a wastewater treatment plant (WWTP). In certain cases, discharged metabolites are transformed back into their pristine structure and become bioactive again. Other compounds are persistent and can withstand conventional wastewater treatment. When WWTP effluents are released in surface waters, pristine and persistent chemicals can affect the aquatic environment. To complement WWTPs and circumvent incomplete removal of unwanted chemicals or pharmaceuticals, on-site wastewater treatment can contribute to their removal. Advanced oxidation processes (AOPs) are very powerful techniques for the abatement of pharmaceuticals, however, under certain circumstances reactive toxic by-products can be produced. We studied the application of on-site AOPs in a laboratory setting. It is expected that treatment at the contamination source can eliminate the worst polluters. Thermal plasma and UV/H2O2 oxidation were applied on simulation matrices, Milli-Q and synthetic sewage water spiked with 10 different pharmaceuticals in a range of 0.1 up to 2400 µg/L. In addition, untreated end-of-pipe hospital effluent was also subjected to oxidative treatment. The matrices were activated for 180 min and added to cultured HeLa cells. The cells were 24 h and 48 h exposed at 37 °C and subsequently markers for oxidative stress and viability were measured. During the UV/H2O2 treatment periods no toxicity was observed. After thermal plasma activation of Milli-Q water (150 and 180 min) toxicity was observed. Direct application of thermal plasma treatment in hospital sewage water caused elimination of toxic substances. The low cytotoxicity of treated pharmaceutical residues is likely to become negligible if plasma pre-treated on-site wastewater is further diluted with other sewage water streams, before reaching the WWTP. Our study suggests that AOPs may be promising technologies to remove a substantial portion of pharmaceutical components by degradation at the source. Further studies will have to be performed to verify the feasibility of upscaling this technology from the benchtop to practice.