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.

Removal of Acetaminophen Drug from Wastewater by Fe3O4 and ZSM-5 Materials.

Adsorption of toxic compounds from water using zeolites and magnetite was developed due to the various advantages of their applicability. In the last twenty years, the use of zeolite-based compositions in the form of zeolite/inorganic or zeolite/polymer and magnetite has been accelerated for the adsorption of emergent compounds from water sources. The main adsorption mechanisms using zeolite and magnetite nanomaterials are high surface adsorption, ion exchange capacity and electrostatic interaction. This paper shows the capacity of Fe3O4 and ZSM-5 nanomaterials of adsorbing the emerging pollutant acetaminophen (paracetamol) during the treatment of wastewater. The efficiencies of the Fe3O4 and ZSM-5 in the wastewater process were systematically investigated using adsorption kinetics. During the study, the concentration of acetaminophen in the wastewater was varied from 50 to 280 mg/L, and the maximum Fe3O4 adsorption capacity increased from 25.3 to 68.9 mg/g. The adsorption capacity of each studied material was performed for three pH values (4, 6, 8) of the wastewater. Langmuir and Freundlich isotherm models were used to characterize acetaminophen adsorption on Fe3O4 and ZSM-5 materials. The highest efficiencies in the treatment of wastewater were obtained at a pH value of 6. Fe3O4 nanomaterial presented a higher removal efficiency (84.6%) compared to ZSM-5 nanomaterial (75.4%). The results of the experiments show that both materials have a potential to be used as an effective adsorbents for the removal of acetaminophen from wastewater.

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.

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.

In Vivo Bioconcentration, Distribution and Metabolization of Benzophenone-3 (BP-3) by Cyprinus carpio (European Carp).

Organic UV-filters, such as oxybenzone (BP-3), have attracted researcher attention in recent years due to its capacity to interfere with the proper functioning of the endocrine system and its widespread presence in the aquatic environment. The aim of this study was to investigate the bioconcentration, distribution and metabolization of BP-3 in one of the most common fish species in Romania, namely Cyprinus carp (European carp). Exposure experiments were performed for 11 weeks using a BP-3 nominal concentration level of 100 µg/L. The BP-3 concentration level decreased over time and needed to be re-established daily. Biological samples (fish organs and tissues) from control and test were taken at t0 (before contamination) and at t3, t5, t8 and t11 weeks from the beginning of the experiment. From the third week, BP-3 was identified and quantified, in all organs, in concentration values ranging between 3.2 and 782 ng/g d.w., the highest concentration being detected in the intestinal content, followed by gonads (up to 468 ng/g d.w.) and skin (up to 453 ng/g d.w.). In the case of gill and liver, the BP-3 concentration increased in the first five weeks, and then decreased to 15 and 6 ng/g d.w., respectively, which could be explained by a fast BP-3 metabolization. During the exposure period, six metabolites were identified through LC-MS/MS, all of them known for their endocrine disruptor and toxic properties being higher than those of the parent compound. The study is important from an ecological perspective and also in view of human health concerns involving food quality.

Occurrence and fate of Adsorbable Organic Halogens (AOX) in two WWTPs from Romania.

Absorbable organic halogens (AOX) are a global parameter which refers to a group of chemical compounds that contain one or more chlorine, bromine or iodine atoms in their molecule and can easily adsorb on activated carbon. The global concern related to the occurrence of the AOX compounds in the environment is due to their toxic and mutagenic effects on aquatic organisms and their potential role as inhibitors of microorganism growth, even at AOX low concentrations. The purpose of this study was to analyze the presence, occurrence and composition of absorbable organic halogens in wastewater and sewage sludge. In addition, their genotoxicity effect on the environment was tested on a bacterial biological model. Daily mass loading, mass emission and fate of AOX parameter were investigated in two wastewater treatment plants (wastewater and sewage sludge samples) from Romania, Galati and Iasi. Their AOX daily mass loadings (151 and 55.4 g/day/1000people) and mass emissions into the environment (47.8 and 23.5 g/day/1000 people) for both locations were correlated with the concentration level of volatile organic compounds, chlorophenols, organochlorine pesticides and polychlorinated biphenyls from both wastewater and sewage sludge, respectively. Concentration levels of detected halogenated organic compounds (regulated by current standards) accounted only for a small percentage (3.70-14.5%) from the total AOX amount. An exception was observed in the case of dehydrated sludge samples where the identified compounds accounted for 80% of the AOX content from Iasi WWTP and 53% for Galati. Evaluating the genotoxic activity of AOX in sludge samples showed that genotoxicity was not induced up to 100 µg/mL dehydrated sludge.

Treatment of Wastewater Containing Nonsteroidal Anti-Inflammatory Drugs Using Activated Carbon Material.

This study presents an adsorbent material (activated carbon) used in the treatment of wastewater with the role of removing ibuprofen, acetaminophen, diclofenac and ketoprofen pollutants. The wastewater treatment efficiencies of the activated carbon were systematically investigated using adsorption kinetics. The parameters studied were: pH (4 and 6 values of pH), initial concentration of wastewater (1, 5, and 10 mg/L), contact time (10 min), adsorbent quantity (0.1, 0.5, and 1 g), and isotherm models (Langmuir and Freundlich). The highest wastewater treatment efficiency was obtained at the 6 pH value. The determination of four anti-inflammatory drugs, frequently monitored in wastewater, was performed by a simple and fast method using the HPLC-technique-type DAD (diode array detector). The method was linear when the concentration ranged between 0.5 and 20 m/L for all compounds. The equilibrium concentration was obtained after 8 min. The octanol/water coefficient influenced the removal efficiency of the four drugs by the adsorbent material (activated carbon). The dose of activated carbon (0.1 to 1 g) significantly influenced the efficiency of wastewater treatment, which increased considerably when the dose of the adsorbent material increased. Using 1 g of the adsorbent material for the treatment of wastewater containing 1 mg/L initial concentration of pollutant compounds, the efficiencies were 98% for acetaminophen, 92% for diclofenac, 88% for ketoprofen and 96% for ibuprofen.

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.

Occurrence and Fate of Bisphenol A and its Congeners in Two Wastewater Treatment Plants and Receiving Surface Waters in Romania.

The present study investigated the distribution and environmental fate of Bisphenol A (BPA), the 4-hydroxyacetophenone (4-HAP) metabolite, and 5 other bisphenol congeners in 2 municipal wastewater treatment plants (WWTPs) and their receiving rivers in Romania. Accordingly, a new, highly sensitive and accurate solid-phase extraction-liquid chromatography-electrospray ionization-tandem mass spectrometry method was developed and validated. This technique generated low limit of quantitation values: below 2.3 ng/L for surface water and less than 2.4 and 2.7 ng/L for WWTP effluent and influent water. The sum of detected analytes in wastewater was between 1337 and 16 118 ng/L for influent samples and between 15 and 96 ng/L for effluent samples. In surface water, the total of all compounds was somewhere between 34 and 240 ng/L. The highest concentration observed was for BPA in all 3 types of analyzed water (up to 9140 ng/L for influent, as high as 75 ng/L for effluent, and a maximum of 135 ng/L in surface waters). All analyzed samples were free of bisphenols B, C, and F. For all analytes detected in surface water, the concentration values were higher than those determined in the effluent samples, which may be caused by intrinsic contamination of the 2 rivers (Danube and Jiu Rivers). Values of environmental risk coefficients, calculated for both effluents and surface waters, indicated a low ecological risk or no ecological risk for 3 types of organisms (algae, daphnia, and fish). Human risk assessment calculation suggests no risk to human health as a result of the presence of BPA in either of the 2 rivers. Environ Toxicol Chem 2021;40:435-446. © 2020 SETAC.

Fast and sensitive detection of acrolein in environmental water samples without derivatization using liquid chromatography tandem mass spectrometry.

A fast and sensitive SPE-LC-MS/MS method for the determination of acrolein in environmental water samples using activated charcoal as SPE adsorbent was developed. The novelty of this study consists in acrolein extraction, separation and detection without the need of a derivatization process. Physicochemical properties of acrolein, such as low molecular weight and high polarity represent real challenges for extraction, separation, and detection of this pollutant using SPE-LC-MS/MS. These were addressed by choosing a suitable chromatographic column which ensures a good peak symmetry and retention for the analyte, as well as the choice of SPE adsorbent suitable for retaining very polar compounds like acrolein from the aqueous matrix. The chromatographic column was a Synergi Fusion RP (150 × 2.0 mm, 4.0 µm) with a C18 stationary phase modified with polar embedded amide groups. Activated charcoal adsorbent used as SPE extraction media was able to extract efficiently highly polar molecules such as acrolein and 13C3-acrylamide (internal standard) from water samples. Using this method, the obtained extraction recovery for acrolein was 88% at a 50 ng/L concentration level. Overall method quantitation limit (LOQ) for acrolein in water was established at 3.8 ng/L. The newly developed SPE-LC-MS/MS method was successfully applied to detect acrolein occurrence in wastewater and drinking water samples. Acrolein level in these samples ranged from LOQ to 122 ng/L.