Search

A high-performance liquid chromatography with diode array detector (HPLC-DAD) analytical method was developed for the simultaneous detection of 17 phenolic compounds, including phenols, chlorophenols, alkylphenols, and nitrophenols, in two types of water matrices: wastewater and surface water. Prior to HPLC-DAD determination, a solid-phase extraction (SPE) procedure was optimized. The proposed method uses multiwavelength analysis, with the optimum detection wavelengths selected as 268 nm, 280 nm, 386 nm, 304 nm, and 316 nm. The highest resolution was achieved using a chromatographic column, Eclipse XDB-C18 (150 × 4.6 mm, 5 μm), which was kept at 20 °C. The mobile phase consisted of a gradient elution program, with mobile phase A being a 0.1% H3PO4 aqueous solution and mobile phase B being acetonitrile. The flow rate was set at 0.6 mL/min. The 17 target phenolic compounds were fully separated in less than 27 min. All compounds showed good linear regression, with correlation coefficients higher than 0.999. The method's quantitation limits ranged from 4.38 to 89.7 ng/L for surface water and 7.83 to 167 ng/L for wastewater. The recovery rates were in the range of 86.2–95.1% for surface water and 79.1–86.3% for wastewater. The SPE-HPLC-DAD method was proven to be fast, sensitive, accurate, and reproducible. The developed method was successfully applied for the analysis of the 17 phenolic compounds in real surface water and wastewater samples, with phenol, 2,4-DNP, and 2,4-DNP being determined at levels greater than the method's limits of quantitation (LOQs). The proposed analytical method represents an original technical resource for the simultaneous determination of 17 phenolic compounds in environmental water matrices. [ABSTRACT FROM AUTHOR]

Organic sun-blocking agents are recognized as emerging pollutants of the aquatic environment. The consequences and effects of these harmful substances on aquatic organisms are not fully understood, particularly in the context of Romania. This study examines the presence and environmental hazards posed by ten UV filters found in the Danube River. Six of the ten targeted contaminants were detected in surface water samples: 2-hydroxy-4-methoxy-benzophenone (BP-3), 2,4-dihydroxy benzophenone (BP-1), 2,3,4-trihydroxy benzophenone (234HBP), 2,2′-dihydroxy-4-methoxy-benzophenone (BP-8), 2-hydroxy-4-methoxy-4′-methyl-benzophenone (BP-10), and benzyl salicylate (BS). In sediment samples, seven of the ten compounds were identified: BS, BP-3, 4-hydroxybenzophenone (4HBP), BP-1, 234HBP, 2,2′,4,4′-tetrahydroxybenzophenone (BP-2), and BP-10, with different frequencies. The correlation coefficients showed strong relationships between benzophenone derivatives in surface water samples and a common contamination source for BP-3 and BS in sediment samples. In the assessment, the risk quotient (RQ) for BP-1 in fish was determined to be 1.81. Similarly, RQ values for BP-3 were calculated as 1.24 for Daphnia magna and 57 for fish, suggesting that these UV filters could potentially present substantial hazards to the aquatic ecosystem. The study findings indicate that additional research is needed to investigate the presence and potential risks of organic sun-blocking agents in surface waters, with a particular emphasis on densely populated areas in Romania. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The principal objective of the present research involved the achievement of high biodegradation degrees of perfluorooctanoic acid (PFOA) and perfluorosulfonic acid (PFOS) using pure individual bacterial strains. The use of such microorganisms can contribute to the improvement of the wastewater treatment process in sewage treatment plants through bioaugmentation or other bioremediation processes. Thus, in this study, we investigated the biodegradation potential of PFOA and PFOS. Bacterial strains tested in this study were from the Pseudomonas genus, namely: Pseudomonas aeruginosa and Pseudomonas putida, due to their known capacity to degrade xenobiotic compounds. The results indicated that Pseudomonas aeruginosa was able to transform 27.9% of PFOA and 47.3% of PFOS in 96 h, while Pseudomonas putida managed to transform 19.0% of PFOA and 46.9% of PFOS in the same time frame. During the biodegradation tests, PFHxA was recognized as the principal biotransformation product of PFOA in the presence of Pseudomonas aeruginosa, and PFPeA, PFPxA and PFHpA were recognized as the biotransformation products in the presence of Pseudomonas putida. For PFOS, only two biotransformation products (PHHxA and PFHpA) were observed as a consequence of biodegradation by both bacterial strains. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

This paper is aimed at assessing the occurrence, fate, transport and ecological risk of ten organic UV filters in the aquatic environment of Romania. In influents, the highest concentration levels were determined for benzophenone-1 and 2,3,4-trihydroxybenzophenone with values of thousands of ng L−1 (up to 2787 and 1108 ng L−1, respectively). In the sewage sludge samples, the predominant contaminants were those with high hydrophobicity, namely benzyl salicylate, homosalate and ethylhexyl salicylate (up to 1395, 1035 and 688 ng g−1 dw, respectively). Although the removal efficiency of these organic micropollutants in the WWTPs proved to be quite high, over 60% of the UV filters monitored, some of them were also detected in effluents, in relatively high concentrations. Thus, the effluents were dominated by ethylhexyl salicylate and benzophenone-1 with concentrations up to 219 and 181 ng L−1, respectively. In surface waters, the most abundant compounds were found to be benzophenone-1, benzophenone-8 and 4-hydroxybenzophenone, with values up to 206, 108 and 159 ng L−1 respectively. On calculating the risk coefficient of the organic UV filters investigated on various aquatic species, it was observed that for fish, benzophenone-2 presents a medium risk both in effluents and in samples taken downstream of the WWTPs, while benzophenone-1 presents a high risk also in effluents as well as in surface waters taken upstream and downstream of the WWTPs. Among the salicylate derivatives, homosalate was found to present a medium risk for Daphnia magna in both effluents and samples taken downstream of the WWTPs, while ethylhexyl salicylate posed a high risk for freshwater algae in all three types of analyzed samples. [ABSTRACT FROM AUTHOR]

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 [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]