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.

Occurrence and distribution of azole antifungal agents in eight urban Romanian waste water treatment plants.

Azole compounds are utilized to combat fungal infections in plants to protect them and also used for treating mycosis in humans. The LC-MS/MS method is a technique that combines liquid chromatography with tandem mass spectrometry for analysis of twelve azole compounds from wastewater (influent, effluent) and sewage sludge. The compounds were isolated from waste water using automatic extraction in the solid phase. Sludge samples were dried by lyophilization, after which they were subjected to ultrasound extraction with methanol. The quantification limits ranged from 0.3 ng/L (clotrimazole-CLO and prochloraz-PRO) to 1.5 ng/L (tetraconazole-TEB and penconazole-PEN), for wastewater samples and for sewage sludge, the LOQs ranged from 0.1 ng/g to 0.6 ng/g. High concentrations of climbazole-CLI (207-391 ng/L), tebuconazole (92-424 ng/L), and clotrimazole (6.9-93-ng/L) were observed in influent samples of the 8 urban wastewater treatment plants, followed by fluconazole (49.3-76.8 ng/L), and prochloraz (7.3-72 ng/L). The ∑Azoles had a maximum of 676 ng/L in the Galati effluent, followed by the Bucharest station 357 ng/L, and 345 ng/L in the Braila effluent. The highest value of the daily mass loading (input) level was observed for climbazole, 265 mg/day/1000 in Iasi station, followed by tebuconazole, 238 mg/day/1000 people in the Bucharest station, and 203 mg/day/1000 people for climbazole in the Targoviste station. The daily mass emission presented values between 0.7 and 247 mg/day/1000 people. The highest emissions were observed for climbazole, 247 mg/day/1000 people in Braila station; 174 mg/day/1000 people in the Iasi station and 129 mg/day/1000 people in the Bucharest station. The concentrations of climbazole detected in the effluent can present a high risk for the plants Lemna minor and Navicula pelliculosa. Clotrimazole may present a high risk to the plant Desmodesmus subspicatus and to the invertebrate Daphnia magna. PRO may present high risk to the invertebrate Mysidopsis Bahia.

Tissue Bioconcentration Pattern and Biotransformation of Per-Fluorooctanoic Acid (PFOA) in Cyprinus carpio (European Carp)-An Extensive In Vivo Study.

The perfluoroalkyl substances (PFAS) represent a persistent class of synthetic chemicals that spread in the environment as a result of industrialization. Due to their bioaccumulative and endocrine disruption implications, these chemicals can affect food quality and human health, respectively. In the present study, the bioconcentration and biotransformation of perfluorooctanoic acid (PFOA) in common carp (Cyprinus carpio) were evaluated in a biphasic system (exposure and depuration). Carp were continuously exposed, under laboratory conditions, to 10 (Experiment 1) and 100 (Experiment 2) µg/L PFOA for 14 weeks, followed by a wash out period of 3 weeks. Fish organs and tissues were collected at 8, 12, 14 weeks of exposure and at week 17, after the depuration period. The results obtained from the LC-MS/MS analysis showed the presence of PFOA in all studied organs. The highest values of PFOA were identified in the gallbladder (up to 2572 ng/g d.w.) in Experiment 1 and in the gallbladder (up to 18,640 ng/g d.w.) and kidneys (up to 13,581 ng/g d.w.) in Experiment 2. The average BCF varied between 13.4 and 158 L/Kg in Experiment 1 and between 5.97 and 80.3 L/Kg in Experiment 2. Four biotransformation products were identified and quantified in all organs, namely: PFBA, PFPeA, PFHxA, and PFHpA. PFBA was proven to be the dominant biotransformation product, with the highest values being determined after 8 weeks of exposure in the kidney, gallbladder, brain, liver, and gonads in both experiments. Because freshwater fish are an important food resource for the human diet, the present study showed the fishes' capacity to accumulate perfluoroalkyl substances and their metabolites. The study revealed the necessity of monitoring and risk studies of new and modern synthetic chemicals in aquatic resources.

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.

Sensitive detection of antidiabetic compounds and one degradation product in wastewater samples by a new SPE-LC-MS/MS method.

As environment emerging contaminants of anthropogenic origin, antidiabetic drugs are present in the range of high ng/L to ng/mL in the influent and the effluent of the waste water treatment plant (WWTP). The metformin compound is the most used hypoglycemic agent in the world. The aim of this study was to develop a new analytic method, based on solid phase extraction followed by liquid chromatography coupled with mass spectrometric detector (SPE-LC-MS/MS), for identification and quantification of 5 antidiabetic compounds (glibenclamide/glyburide, glimepiride, metformin, glipizide, guanyl urea, gliclazide) and one degradation product (guanyl urea). The investigated environmental samples were the influent and the effluent of four urbans WWTP's. By validating of the analytical method, it was obtained low LOQ's (0.2-4.5 ng/L), satisfactory recovery rates (53.6-116.8%), and corresponding performance parameters: inter-day precision (4.9-8.4%) and reproducibility (11.3-14.6%). The concentrations of antidiabetics were as follow in influent and effluent: metformin 76-2041ng/L and 2-206ng/L, gliclazide (14.1-42.4 ng/L, and 3.3-19.1), glipizide (7.5-11.2 ng/L and 6.5-10ng/L), guanyl urea (6.2-7.3 and 8.3-21.3 ng/L). The efficiency of elimination of the antidiabetics in WWTP's was maximum for metformin (67.6-98.5%), followed, by gliclazide (72.9-78.2%). The lowest elimination efficiency was calculated for glipizide (10.7-13.3%). The guanyl urea undergoes a formation process (74.5-84.2%) in effluent, from the metformin contained in influent.