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.

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.

Collection of human and environmental data on pesticide use in Europe and Argentina: Field study protocol for the SPRINT project.

Current farm systems rely on the use of Plant Protection Products (PPP) to secure high productivity and control threats to the quality of the crops. However, PPP use may have considerable impacts on human health and the environment. A study protocol is presented aiming to determine the occurrence and levels of PPP residues in plants (crops), animals (livestock), humans and other non-target species (ecosystem representatives) for exposure modelling and impact assessment. To achieve this, we designed a cross-sectional study to compare conventional and organic farm systems across Europe. Environmental and biological samples were/are being/will be collected during the 2021 growing season, at 10 case study sites in Europe covering a range of climate zones and crops. An additional study site in Argentina will inform the impact of PPP use on growing soybean which is an important European protein-source in animal feed. We will study the impact of PPP mixtures using an integrated risk assessment methodology. The fate of PPP in environmental media (soil, water and air) and in the homes of farmers will be monitored. This will be complemented by biomonitoring to estimate PPP uptake by humans and farm animals (cow, goat, sheep and chicken), and by collection of samples from non-target species (earthworms, fish, aquatic and terrestrial macroinvertebrates, bats, and farm cats). We will use data on PPP residues in environmental and biological matrices to estimate exposures by modelling. These exposure estimates together with health and toxicity data will be used to predict the impact of PPP use on environment, plant, animal and human health. The outcome of this study will then be integrated with socio-economic information leading to an overall assessment used to identify transition pathways towards more sustainable plant protection and inform decision makers, practitioners and other stakeholders regarding farming practices and land use policy.

Do initial concentration and activated sludge seasonality affect pharmaceutical biotransformation rate constants?

Pharmaceuticals find their way to the aquatic environment via wastewater treatment plants (WWTPs). Biotransformation plays an important role in mitigating environmental risks; however, a mechanistic understanding of involved processes is limited. The aim of this study was to evaluate potential relationships between first-order biotransformation rate constants (kb) of nine pharmaceuticals and initial concentration of the selected compounds, and sampling season of the used activated sludge inocula. Four-day bottle experiments were performed with activated sludge from WWTP Groesbeek (The Netherlands) of two different seasons, summer and winter, spiked with two environmentally relevant concentrations (3 and 30 nM) of pharmaceuticals. Concentrations of the compounds were measured by LC-MS/MS, microbial community composition was assessed by 16S rRNA gene amplicon sequencing, and kb values were calculated. The biodegradable pharmaceuticals were acetaminophen, metformin, metoprolol, terbutaline, and phenazone (ranked from high to low biotransformation rates). Carbamazepine, diatrizoic acid, diclofenac, and fluoxetine were not converted. Summer and winter inocula did not show significant differences in microbial community composition, but resulted in a slightly different kb for some pharmaceuticals. Likely microbial activity was responsible instead of community composition. In the same inoculum, different kb values were measured, depending on initial concentration. In general, biodegradable compounds had a higher kb when the initial concentration was higher. This demonstrates that Michealis-Menten kinetic theory has shortcomings for some pharmaceuticals at low, environmentally relevant concentrations and that the pharmaceutical concentration should be taken into account when measuring the kb in order to reliably predict the fate of pharmaceuticals in the WWTP. KEY POINTS: • Biotransformation and sorption of pharmaceuticals were assessed in activated sludge. • Higher initial concentrations resulted in higher biotransformation rate constants for biodegradable pharmaceuticals. • Summer and winter inocula produced slightly different biotransformation rate constants although microbial community composition did not significantly change.

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.

Intrusion of chlorinated hydrocarbons and their degradation products from contaminated soil. Measurement of indoor air quality and biomonitoring by analysis of end-exhaled air.

A historic soil contamination of chlorinated hydrocarbons from a former dry cleaning shop caused intrusion of vapors into a building currently used as bookshop. The aim of this study was to determine the indoor air quality and the uptake of soil contaminants and their degradation products. Samples of indoor air were collected over one week in the warm and one week in the cold season. Pre-shift and post-shift samples of end-exhaled air were collected from two employees. Chlorinated hydrocarbons were analyzed in indoor air and exhaled air samples using thermal desorption gas chromatography mass spectrometry (TD-GC-MS). Tetrachloroethylene (PER), and its degradation products trichloroethylene (TRI), 1,1-dichloroethylene (1,1-DCE), 1,2-cis-dichloroethylene (1,2-cis-DCE), 1,2-trans-dichloroethylene (1,2-trans-DCE), methylene chloride (MC) and vinyl chloride (VC) were determined in ambient air. PER was the prime contaminant with a week average (±sd) of 805.2 ±â€¯598.6 µg/m3 in June 2016 and 1031 ±â€¯499.3 µg/m3 in December 2017. MC, 1,2-cis-DCE and TRI were detected at concentrations below 2.3 µg/m3. 1,1-DCE and VC were not detected. In exhaled air PER, 1,1-DCE, and MC were detected in both June and December, whereas TRI, 1,2-cis-DCE and 1,2-trans-DCE were only detected on one or two days in the cold season. VC was not detected in exhaled air. For PER, the mean concentrations (±sd) in end-exhaled air increased from a five days (Mon-Fri) average pre-shift value of 22.2 ±â€¯8.0 to a post-shift value of 52.6 ±â€¯15.5 ng/L in the male shop owner (p < 0.01) and in the female cashier these values were 26.0 ±â€¯3.6 and 63.6 ±â€¯12.7 ng/L, respectively (p < 0.01). Intrusion of chlorinated soil contaminants resulted in contamination of indoor air above the current accepted indoor air level for PER of 250 µg/m3. For PER in end-exhaled air an accumulation over the workweek was not observed.

Changes in Work Practices for Safe Use of Formaldehyde in a University-Based Anatomy Teaching and Research Facility.

Anatomy teaching and research relies on the use of formaldehyde (FA) as a preservation agent for human and animal tissues. Due to the recent classification of FA as a carcinogen, university hospitals are facing a challenge to (further) reduce exposure to FA. The aim of this study was to reduce exposure to FA in the anatomy teaching and research facility. Workers participated in the development of improved work practices, both technical and organizational solutions. Over a period of 6 years mitigating measures were introduced, including improvement of a down-flow ventilation system, introduction of local exhaust ventilation, collection of drain liquid from displayed specimens in closed containers and leak prevention. Furthermore, some organizational changes were made to reduce the number of FA peak exposures. Stationary and personal air sampling was performed in three different campaigns to assess the effect of these new work practices on inhalation exposure to FA. Samples were collected over 8 h (full shift) and 15 min (task-based) to support mitigation of exposure and improvement of work practices. Air was collected on an adsorbent coated with 2,4-dinitrophenylhydrazine (DNPH) and analyzed by HPLC-UV. Geometric mean (GM) concentrations of FA in the breathing zone over a work-shift were 123 µg/m³ in 2012 and 114 µg/m³ in 2014, exceeding the workplace standard of 150 µg/m³ (8 h time-weighted average, TWA) on 46% of the workdays in 2012 and 38% of the workdays in 2014. This exposure was reduced to an average of 28.8 µg/m³ in 2017 with an estimated probability of exceeding the OEL of 0.6%. Task-based measurements resulted in a mean peak exposures of 291 µg/m³ in 2012 (n = 19) and a mean of 272 µg/m³ in 2014 (n = 21), occasionally exceeding the standard of 500 µg/m³ (15 min TWA), and were reduced to a mean of 88.7 µg/m³ in 2017 (n = 12) with an estimated probability of exceeding the OEL of 1.6%.