Fate of pharmaceutical residue in two Romanian rivers receiving treated water: Occurrence, distribution and risk assessment.

This study presents the first set of data on the removal of proton pump inhibitors (PPIs) and histamine H2 receptor antagonists (HRAs) and their transformation products in two Romanian wastewater treatment plants (WWTPs), as well as the impact of these organic pollutants on freshwater receiving effluents. The research investigated eight target pharmaceuticals and three metabolites using a newly developed and validated Liquid Chromatography - Mass Spectrometry (LC-MS/MS) method. The combined determination had a range of quantification limits varying from 0.13 ng/L to 0.18 ng/L for surface water and from 0.28 ng/L to 0.43 ng/L for wastewater. All analytes except cimetidine and 5-hydroxy-omeprazole were identified in water samples. The study found similar overall removal efficiencies for both WWTPs (43.2 % for Galati and 51.7 % for Ramnicu-Valcea). The research also showed that ranitidine and omeprazole could pose a low to high ecological risk to aquatic organisms. The findings suggest that the treatment stages used in the two Romanian WWTPs are insufficient to remove the target analytes completely, leading to environmental risks associated with the occurrence of pharmaceutical compounds in effluents and freshwater.

Perfluoroalkyl substances in Romanian wastewater treatment plants: Transfer to surface waters, environmental and human risk assessment.

The current study aimed to determine the concentration levels of nine perfluoroalkyl substances (PFAS) in the five most significant Romanian wastewater treatment plants (WWTPs) and their transfer to natural receivers. The analytes were concentrated using a solid-phase extraction/ultrasonic-assisted extraction procedures and then selectively quantified by liquid chromatography-tandem mass spectrometry (LC-MS/MS) using electrospray ionization. In most of the wastewater samples investigated, the dominant compounds were perfluoropentanoic acid (PFPeA), perfluorooctanoic acid (PFOA), and perfluorooctansulfonate acid (PFOS), with the maximum concentration range between 105 and 316 ng/L in influents, 14.8-31.3 ng/L in effluents and removal efficiencies higher than 80 % for all selected PFAS compounds. In sewage sludge samples, PFOA and PFOS were the majority substances, with values up to 35.8 ng/g dw for PFOA and 27.8 ng/g dw for PFOS. PFOA and PFOS achieved the maximum levels by estimating mass loading and emission levels. As a result, 237 mg/day/1000 people of PFOA and 95.5 mg/day/1000 people of PFOS are entering daily in the WWTPs, while up to 31 mg/day/1000 people of PFOA and up to 13.6 mg/day/1000 people of PFOS are discharged daily into the natural emissaries. Human risk assessment shows that PFOA and PFOS are low to high risk for all age and gender categories. Children are the most exposed to PFOA and PFOS contamination in drinking water. Environmental risk assessment reveals that PFOA exhibits a low risk for some insect species, PFOS - a low risk for freshwater shrimps and a medium risk for midges, while perfluoroundecanoic acid (PFNuDA) could have a low to medium risk for midges. No assessment studies regarding the environmental and human risk of PFAS have been performed in Romania.

An Initial Survey on Occurrence, Fate, and Environmental Risk Assessment of Organophosphate Flame Retardants in Romanian Waterways.

Organophosphate ester flame retardants (OPFRs) are ubiquitous organic pollutants in the environment and present an important preoccupation due to their potential toxicity to humans and biota. They can be found in various sources, including consumer products, building materials, transportation industry, electronic devices, textiles and clothing, and recycling and waste management. This paper presents the first survey of its kind in Romania, investigating the composition, distribution, possible sources, and environmental risks of OPFRs in five wastewater treatment plants (WWTPs) and the rivers receiving their effluents. Samples from WWTPs and surface waters were collected and subjected to extraction processes to determine the OPFRs using liquid chromatography with mass spectrometric detection. All the target OPFRs were found in all the matrices, with the average concentrations ranging from 0.6 to 1422 ng/L in wastewater, 0.88 to 1851 ng/g dry weight (d.w.) in sewage sludge, and 0.73 to 1036 ng/L in surface waters. The dominant compound in all the cases was tri(2-chloroisopropyl) phosphate (TCPP). This study observed that the wastewater treatment process was inefficient, with removal efficiencies below 50% for all five WWTPs. The environmental risk assessment indicated that almost all the targeted OPFRs pose a low risk, while TDCPP, TCPP, and TMPP could pose a moderate risk to certain aquatic species. These findings provide valuable information for international pollution research and enable the development of pollution control strategies.

Occurrence and Transport of Isothiazolinone-Type Biocides from Commercial Products to Aquatic Environment and Environmental Risk Assessment.

This study investigated the occurrence and transport of four isothiazolinone-type biocides from commercial products to wastewater treatment plants (influents, sludges, and effluents) and to natural emissaries (upstream and downstream the wastewater treatment plants) in Romania. All four biocides were determined in personal care and household products, with the highest concentration of 76.4 µg/L OIT (2-octyl-4-isothiazolin-3-one). For environmental samples, three of the four isothiazolinones were determined, CMI (5-chloro-2-methyl-4-isothiazolin-3-one) being the prominent compound for water samples. The maximum concentration of 84.0 µg/L in influent, 122 µg/L upstream, and 144 µg/L downstream the wastewater treatment plants were obtained for CMI. Unlike water samples, in the sewage sludge samples, OIT proved to be the dominant compound, with concentration up to 5.80 µg/g d.w. The extremely high levels of isothiazolinone determined in different WWTPs from Romania may be due to the COVID-19 pandemic situation, during which a much larger amount of cleaning, hygiene, and personal care products was used. The isothiazolinone-type biocides were readily removed from the influents of the five WWTPs, with the mean removal rate up to 67.5%. The mean mass loading value for the targeted biocides based on influent was 20.4 µg/day/1000 people, while the average environmental emissions were 6.93 µg/day/1000 people for effluents. The results obtained for riverine water combine with statistical analysis showed that the anthropogenic activities are the major contamination sources of the surface waters. Preliminary ecological risk evaluation showed that BIT (1,2-benzisothiazol-3(2H)-one), OIT, and CMI could pose a very high risks to different aquatic species living in the receiving aquatic environments.

Investigation of endocrine disruptor pollutants and their metabolites along the Romanian Black Sea Coast: Occurrence, distribution and risk assessment.

In recent years, the occurrence of organic UV-filters (UVFs) and bisphenol derivatives (BPs) in the marine environment has raised high concerns all over the world, due to the potentially adverse impacts on marine organism and, indirectly on human health. This paper reports, for the first time in Romania, the occurrence, distribution pattern and environmental risk assessment of UVFs, BPs and their metabolites in seawater, sediment and algae collected from the Romania Black Sea coastal region. BP-3 (2-hydroxy-4-methoxy-benzophenone) was the most abundant contaminant in seawater samples, with detection frequency of 100 %. Sediment samples were dominated by ES (Ethylhexyl salicylate), with concentration values up to 5823 ng/g d.w., while for algae, concentrations of several hundreds of ng/g d.w. were determined for BP-3, BS (Benzyl salicylate) and BPE (Bisphenol E). Environmental risk assessment revealed that some UVFs and BPs detected in seawater samples were hazardous to the marine organism of the Black Sea.