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

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This article presents the environmental pollution level with organic UV filters and the effect they pose on aquatic organisms in Romania.

The chemical behavior of groundwater is one of the most dynamic areas of environmental research. In the present study, groundwater sampling from different locations in the central and south-eastern parts of Romania was performed to assess groundwater chemistry and to compare water types using distribution maps. Groundwater chemistry has been evaluated and natural processes are identified as control factors for hydrochemistry. The Piper diagram was created to compare the results of water types. Chemical analysis of groundwater was used to calculate the values of the water quality index. Romanian drinking water Law EPA 458-2002 and WHO standards were taken into account when calculating the WQI. The SAR index was used to evaluate groundwater samples, taken from in the study area, and used for irrigation purposes. The classification of water types based on water quality (WQI) values for each groundwater sample shows that 80% of the analyzed samples can be used as drinking water resources, the rest of 20% being intended for irrigation.

A liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method was developed and validated for the simultaneous determination of six organic compounds (2-hydroxy benzophenone, 4hydroxy benzophenone, 2,2',4,4'-tetrahydroxy benzophenone, 2,4-dyhydroxy benzophenone, 4,4'dyhydroxy benzophenone, 2,2'-dyhydroxy-4-methoxy-benzophenone) used as UV filters in personal care products used to protect against UV radiation. The major concern about this type of pollutants is due to their persistence and bioaccumulation potential in the environment and aquatic organisms and for their endocrine disruptor properties. Solid phase extraction was used for sample preparation, followed by liquid chromatography tandem mass spectrometry analysis. Benzophenone derivatives were analyzed on a Phenomenex Luna C18 column (150 x 2.0 mm, 3.0 µm) with the mobile phase run in gradient mode with a mixture of aqueous 0.1% formic acid and acetonitrile as the mobile phase components (at a flow rate of 0.2 mL/min). MS detector response was linear, on the tested concentration domain from 1 to 100 μg/L with correlation coefficient R 2 > 0.998. The recoveries of benzophenone derivatives after solid phase extraction procedure from surface water was found to be >81% for surface water and higher than 79% for wastewater matrix. The standard deviation values for intra-day precision were situated between 7.67% and 9.88% for lower concentration and 7.27% and 8.86% for higher concentration respectively. The limits of quantitation were calculated for both environmental water matrices (1.6-4.1 ng/L for surface water and 3.3-8.2 ng/L for wastewater). This method can be applied for benzophenone derivatives detection in real environmental samples.

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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 this study, a new LC-MS/MS method was developed and optimized in order to detect two omnipresent additives, Bisphenol A (BPA) and Butylhydroxyanisole (BHA), in WWTP sewage sludge. Both analytes are synthetic phenolic compounds known for their endocrine disruptive and toxic properties. BPA and BHA were isolated from sludge samples using ultrasonic assisted liquid-solid extraction followed by silicagel clean-up to remove interferences, and evaporation to dryness and extract re-dissolution with 1 mL methanol prior to LC-MS analysis. All LC-MS parameters were optimized in order to obtain high sensitivity and selectivity. MS detector response was linear in the range 1 � 200 �g/L with correlation coefficient R2 ] 0.999 for both analytes. Intra-day and inter-day precision expressed as RSD values were 4.7% and 10.3% for BPA, whereas for BHA 7.8% and 13.8% RSD values were obtained. Recovery values after ultrasonic assisted extraction were 85.5% for BPA and 79.3% BHA with internal standard correction. Overall method LOQs were established at 1.97 ng/g (BPA) and 1.86 ng/g (BHA) on dry weight. Optimized chromatographic parameters allowed separation and detection of the two additives in less than 10 minutes. Both BPA and BHA were detected in all tested sludge samples with higher levels for BPA (34.6 - 132.6 ng/g), whereas BHA was found at lower levels in the range 3.16 - 5.64 ng/g.