Wastewater Effluent Samples Research Articles

Wastewater treatment plants’ removal capacities to minimize the spread of enteroviruses

ABSTRACT The enteroviruses such as Adenovirus, Enterovirus, Hepatitis A virus, Norovirus, and Rotavirus are mostly transmitted via water and are commonly seen in Turkey. Due to lack of regulations for monitoring these viruses at the discharge points of wastewater treatment plants (WWTPs), the discharges reach to surface waters causing water-borne diseases. This emphasizes the importance of WWTPs' removal capacities to minimize the spread of enteroviruses. To evaluate the removal capacities of enteroviruses, five different types of WWTPs from Ankara-Turkey were investigated over a year. Seasonal abundances of enterovirus-specific genes in both influents and effluents from each WWTP were determined by quantitative polymerase chain reaction (qPCR). The reduction of enteroviral nucleic acids in the effluent wastewater samples compared to the influent wastewater samples was assessed as the removal capacity in log10 reduction values (LRVs). The qPCR results revealed that among five different types of WWTPs tested, membrane bioreactors effectively removed Adenovirus alone with LRVs more than 3. The removal of Enterovirus, Hepatitis A virus, Norovirus, and Rotavirus in WWTPs with varying processes was below LRV 3.

Viral concentration method biases in the detection of viral profiles in wastewater.

Viral detection methodologies used for wastewater-based epidemiology (WBE) studies have a broad range of efficacies. The complex matrix and low viral particle load in wastewater emphasize the importance of the concentration method. This study focused on comparing three commonly used virus concentration methods: polyethylene glycol precipitation (PEG), immuno-magnetic nanoparticles (IMNP), and electronegative membrane filtration (EMF). Influent and effluent wastewater samples were processed by the methods and analyzed by DNA/RNA quantification and sequencing for the detection of human viruses. SARS-COV-2, Astrovirus, and Hepatitis C virus were detected by all the methods in both sample types. PEG precipitation resulted in the detection of 20 types of viruses in influent and 16 types in effluent samples. The corresponding number of virus types detected was 21 and 11 for IMNP, and 16 and 8 for EMF. Certain viruses were unique to only one concentration method. For example, PEG detected three types of viruses in influent and six types in effluent compared to IMNP, which detected seven types in influent and one type in effluent samples. However, the EMF method appeared to be the least effective, detecting three types in influent and none in effluent samples. Rotavirus was detected in influent sample using IMNP method, whereas EMF and PEG methods failed to yield a similar outcome. Consequently, the potential false negative results pose a risk to the credibility of WBE applications. Therefore, implementation of a proper concentration technique is critical to minimize method biases and ensure accurate viral profiling in WBE studies.IMPORTANCEIn recent years, significant research efforts have been focused on the development of viral detection methodology for wastewater-based epidemiology studies, showing a range of variability in detection efficacies. A proper methodology is essential for an appropriate evaluation of disease prevalence and community health in such studies and necessitates designing a concentration method based on the target pathogenic virus. There remains a need for comparative performance evaluations of methods in the context of detection efficiencies. This study highlights the significant impact of sample matrix, viral structure, and nucleic acid composition on the efficacy of viral concentration methods. Assessing WBE techniques to ensure accurate detection and understanding of viral presence within wastewater samples is critical for revealing viral profiles in municipality wastewater samples.

Introducing a prediction method for the photodegradation of p-cresol, a phenolic contaminant of emerging concern, in wastewater effluent

Despite extensive efforts to understand the photodegradation of phenolic contaminants of emerging concern (PhCECs) in aquatic systems, prediction methods, especially in waters containing effluent organic matter (EfOM), remain underdeveloped. This study introduces a prediction method for p-cresol, a representative PhCECs, based on correlations between EfOM optical parameters and p-cresol kinetic parameters. We examined p-cresol photodegradation in various EfOM samples, characterized by their optical properties, and used the reaction rate coefficient between EfOM and p-cresol, α3EfOM⁎, to quantify and predict p-cresol degradation in different wastewater effluent samples. Results showed significant correlations between p-cresol's photodegradation rate constant (0.144 to 0.441 h−1) and EfOM characteristics, with α3EfOM⁎ values ranging from 4 × 1011 to 10 × 1011 M−1 s−1. The method was validated with p-cresol at concentrations ranging from 25 to 100 μM and multiple EfOM samples. The method's applicability was further evaluated using propranolol, a pharmaceutical contaminant of emerging concern, demonstrating its versatility for predicting the degradation behavior of other contaminants in different wastewater samples. The method accurately predicted p-cresol and propranolol degradation across diverse wastewater samples, suggesting its potential for expansion to other classes of contaminants, aiding in water quality management, improving wastewater treatment processes, and enhancing environmental risk assessments.

Longitudinal wastewater-based surveillance of SARS-CoV-2 during 2023 in Ethiopia.

Although wastewater-based epidemiology (WBE) successfully functioned as a tool for monitoring the coronavirus disease 2019 (COVID-19) pandemic globally, relatively little is known about its utility in low-income countries. This study aimed to quantify severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) RNA in wastewater, estimate the number of infected individuals in the catchment areas, and correlate the results with the clinically reported COVID-19 cases in Addis Ababa, Ethiopia. A total of 323 influent and 33 effluent wastewater samples were collected from three Wastewater Treatment Plants (WWTPs) using a 24-h composite Moore swab sampling method from February to November 2023. The virus was captured using Ceres Nanotrap® Enhancement Reagent 2 and Nanotrap® Microbiome A Particles, and then nucleic acids were extracted using the Qiagen QIAamp Viral RNA Mini Kit. The ThermoFisher TaqPath™ COVID-19 kit was applied to perform real-time reverse transcriptase polymerase chain reaction (qRT-PCR) to quantify the SARS-CoV-2 RNA. Wastewater viral concentrations were normalized using flow rate and number of people served. In the sampling period, spearman correlation was used to compare the SARS-CoV-2 target gene concentration to the reported COVID-19 cases. The numbers of infected individuals under each treatment plant were calculated considering the target genes' concentration, the flow rate of treatment plants, a gram of feces per person-day, and RNA copies per gram of feces. SARS-CoV-2 was detected in 94% of untreated wastewater samples. All effluent wastewater samples (n = 22) from the upflow anaerobic sludge blanket (UASB) reactor and membrane bioreactor (MBR) technology were SARS-COV-2 RNA negative. In contrast, two out of 11 effluents from Waste Stabilization Pond were found positive. Positive correlations were observed between the weekly average SARS-CoV-2 concentration and the cumulative weekly reported COVID-19 cases in Addis Ababa. The estimated number of infected people in the Kality Treatment catchment area was 330 times the number of COVID-19 cases reported during the study period in Addis Ababa. This study revealed that SARS-CoV-2 was circulating in the community and confirmed previous reports of more asymptomatic COVID-19 cases in Ethiopia. Additionally, this study provides further evidence of the importance of wastewater-based surveillance in general to monitor infectious diseases in low-income settings. Wastewater-based surveillance of SARS-CoV-2 can be a useful method for tracking the increment of COVID-19 cases before it spreads widely throughout the community.

Ozonation of the antiviral oseltamivir in wastewater effluent: Matrix effect, oxidation pathway, and toxicity assessment

The potential environmental impacts of commonly employed antiviral drugs and their byproducts have attracted attention but remain largely unexplored. In this study, ozone (O3) was used to remove the oseltamivir phosphate (OP), a widely used antiviral, from different water matrices, including secondary municipal wastewater effluent (WWE). Over 90 % of OP was removed from a buffer solution using 10 µM of O3 in a short reaction time (30 s), while pseudo-first-order kinetics constants (K) showed a strong linear relationship with the initial O3 dosage. The pH of the solution was found to be an important factor in the ozonation process since the degradation mechanisms and, thereby, the K values are affected by the structural conformations of OP (protonated or deprotonated forms), the generation of hydroxyl radicals (•OH) under mild basic conditions, and the depletion of O3 under extreme basic pH. In addition, common inorganic ions slightly affect the K values, but increasing the ionic strength negatively influences the degradation process. Organic components in WWE also reduced the efficiency; however, over 95 % of OP degradation was achieved using a ratio of O3 dosage to dissolved organic carbon (DOC) of 0.544 g O3 g–1 DOC. Finally, a degradation pathway was proposed based on the detection of byproducts formed by direct ozonation and hydroxylation reactions. Acute toxicity and genotoxicity assessments on ozonated matrices, especially the WWE sample, suggest that these byproducts have no potential toxic effects. All these findings strongly suggest that ozonation can effectively degrade antivirals in municipal effluents.

Metagenomic Profiling of Internationally Sourced Sewage Influents and Effluents Yields Insight into Selecting Targets for Antibiotic Resistance Monitoring.

It has been debated whether wastewater treatment plants (WWTPs) primarily act to attenuate or amplify antibiotic resistance genes (ARGs). However, ARGs are highly diverse with respect to their resistance mechanisms, mobilities, and taxonomic hosts and therefore their behavior in WWTPs should not be expected to be universally conserved. We applied metagenomic sequencing to wastewater influent and effluent samples from 12 international WWTPs to classify the behavior of specific ARGs entering and exiting WWTPs. In total, 1079 different ARGs originating from a variety of bacteria were detected. This included ARGs that could be mapped to assembled scaffolds corresponding to nine human pathogens. While the relative abundance (per 16S rRNA gene) of ARGs decreased during treatment at 11 of the 12 WWTPs sampled and absolute abundance (per mL) decreased at all 12 WWTPs, increases in relative abundance were observed for 40% of the ARGs detected at the 12th WWTP. Also, the relative abundance of mobile genetic elements (MGE) increased during treatment, but the fraction of ARGs known to be transmissible between species decreased, thus demonstrating that increased MGE prevalence may not be generally indicative of an increase in ARGs. A distinct conserved resistome was documented in both influent and effluent across samples, suggesting that well-functioning WWTPs generally attenuate influent antibiotic resistance loads. This work helps inform strategies for wastewater surveillance of antibiotic resistance, highlighting the utility of tracking ARGs as indicators of treatment performance and relative risk reduction.

National-scale antimicrobial resistance surveillance in wastewater: A comparative analysis of HT qPCR and metagenomic approaches

Wastewater serves as an important reservoir of antimicrobial resistance (AMR), and its surveillance can provide insights into population-level trends in AMR to inform public health policy. This study compared two common high-throughput screening approaches, namely (i) high-throughput quantitative PCR (HT qPCR), targeting 73 antimicrobial resistance genes, and (ii) metagenomic sequencing. Weekly composite samples of wastewater influent were taken from 47 wastewater treatment plants (WWTPs) across Wales, as part of a national AMR surveillance programme, alongside 4 weeks of daily wastewater effluent samples from a large municipal hospital. Metagenomic analysis provided more comprehensive resistome coverage, detecting 545 genes compared to the targeted 73 genes by HT qPCR. It further provided contextual information critical to risk assessment (i.e. potential bacterial hosts). In contrast, HT qPCR exhibited higher sensitivity, quantifying all targeted genes including those of clinical relevance present at low abundance. When limited to the HT qPCR target genes, both methods were able to reflect the spatiotemporal dynamics of the complete metagenomic resistome, distinguishing that of the hospital and the WWTPs. Both approaches revealed correlations between resistome compositional shifts and environmental variables like ammonium wastewater concentration, though differed in their interpretation of some potential influencing factors. Overall, metagenomics provides more comprehensive resistome profiling, while qPCR permits sensitive quantification of genes significant to clinical resistance. We highlight the importance of selecting appropriate methodologies aligned to surveillance aims to guide the development of effective wastewater-based AMR monitoring programmes.

Beyond target chemicals: updating the NORMAN prioritisation scheme to support the EU chemicals strategy with semi-quantitative suspect/non-target screening data

BackgroundPrioritisation of chemical pollutants is a major challenge for environmental managers and decision-makers alike, which is essential to help focus the limited resources available for monitoring and mitigation actions on the most relevant chemicals. This study extends the original NORMAN prioritisation scheme beyond target chemicals, presenting the integration of semi-quantitative data from retrospective suspect screening and expansion of existing exposure and risk indicators. The scheme utilises data retrieved automatically from the NORMAN Database System (NDS), including candidate substances for prioritisation, target and suspect screening data, ecotoxicological effect data, physico-chemical data and other properties. Two complementary workflows using target and suspect screening monitoring data are applied to first group the substances into six action categories and then rank the substances using exposure, hazard and risk indicators. The results from the ‘target’ and ‘suspect screening’ workflows can then be combined as multiple lines of evidence to support decision-making on regulatory and research actions.ResultsAs a proof-of-concept, the new scheme was applied to a combined dataset of target and suspect screening data. To this end, > 65,000 substances on the NDS, of which 2579 substances supported by target wastewater monitoring data, were retrospectively screened in 84 effluent wastewater samples, totalling > 11 million data points. The final prioritisation results identified 677 substances as high priority for further actions, 7455 as medium priority and 326 with potentially lower priority for actions. Among the remaining substances, ca. 37,000 substances should be considered of medium priority with uncertainty, while it was not possible to conclude for 19,000 substances due to insufficient information from target monitoring and uncertainty in the identification from suspect screening. A high degree of agreement was observed between the categories assigned via target analysis and suspect screening-based prioritisation. Suspect screening was a valuable complementary approach to target analysis, helping to prioritise thousands of substances that are insufficiently investigated in current monitoring programmes.ConclusionsThis updated prioritisation workflow responds to the increasing use of suspect screening techniques. It can be adapted to different environmental compartments and can support regulatory obligations, including the identification of specific pollutants in river basins and the marine environments, as well as the confirmation of environmental occurrence levels predicted by modelling tools.Graphical

Instrumental and theoretical advancements in pulsed elution-LC × LC: Investigation of pulse parameters and application to wastewater effluent

Due to the decoupling of the first (1D) and second (2D) dimension in pulsed elution-LC × LC (PE-LC × LC), method development is more flexible and straightforward compared to fast comprehensive LC × LC where the dependencies of key parameters between the two dimensions limits its flexibility. In this study we present a method for pulse generation, which is based on a switching valve alternating between one pump that delivers the gradient and a second pump that delivers low eluotrophic strength for the pause state. Consequently, the dwell volume of the system was circumvented and 7.5, and 3.75 times shorter pulse widths could be generated at flow rates of 0.2, and 0.4 mL/min with satisfactory accuracies between programmed and observed mobile phase composition (relative deviation of 6.0 %). We investigated how key parameters including pulse width and step height, 2D gradient time and flow rate affected the peak capacity in PE-LC × LC. The conditions yielding the highest peak capacity for the PE-LC × LC- high-resolution mass spectrometry (HRMS) system were applied to a wastewater effluent sample. The results were compared to a one dimensional (1D)-LC-HRMS chromatogram. The peak capacity increased with a factor 34 from 112 for the 1D-LC run to 3770 for PE-LC × LC-HRMS after correction for undersampling. The analysis time for PE-LC × LC-HRMS was 12.1 h compared to 67.5 min for the 1D-LC-HRMS run. The purity of the mass spectra improved for PE-LC × LC-HRMS by a factor 2.6 (p-value 3.3 × 10−6) and 2.0 (p-value 2.5 × 10−3) for the low and high collision energy trace compared to the 1D-LC-HRMS analysis. Furthermore, the signal-to-noise ratio (S/N) was 4.2 times higher (range: 0.06–56.7, p-value 3.8 × 10−2) compared to the 1D-LC-HRMS separation based on 42 identified compounds. The improvements in S/N were explained by the lower peak volume obtained in the PE-LC × LC-HRMS.

Monitoring of enteropathogenic Gram-negative bacteria in wastewater treatment plants: a multimethod approach

The wastewater treatment processes are associated with the emission of microbial aerosols, including enteropathogenic bacteria. Their presence in this work environment poses a real threat to the health of employees, both through the possibility of direct inhalation of the contaminated air and indirectly through the pollution of all types of surfaces with such bioaerosol particles. This study aimed to investigate the prevalence of enteropathogenic bacteria in the air, on surfaces, and in wastewater samples collected in four wastewater treatment plants (WWTPs). The effectiveness of conventional culture-biochemical, as well as spectrometric and molecular methods for the rapid detection of enteropathogenic bacteria at workstations related to particular stages of wastewater processing, was also evaluated. Bioaerosol, surface swab, and influent and effluent samples were collected from wastewater plants employing mechanical–biological treatment technologies. The air samples were collected using MAS-100 NT impactor placed at a height of 1.5 m above the floor or ground, simulating aspiration from the human breathing zone. Surface samples were collected with sterile swabs from different surfaces (valves, handles, handrails, and coveyor belts) at workplaces. The raw influent and treated effluent wastewater samples were aseptically collected using sterile bottles. The identification of bacterial entheropathogens was simultaneously conducted using a culture-based method supplemented with biochemical (API) tests, mass-spectrometry (MALDI TOF MS), and molecular (multiplex real-time PCR) methods. This study confirmed the common presence of bacterial pathogens (including enteropathogenic and enterotoxigenic Escherichia coli, Salmonella spp., Campylobacter spp., and Yersinia enterocolitica) in all air, surface, and wastewater samples at studied workplaces. Higher concentrations of enteropathogenic bacteria were observed in the air and on surfaces at workplaces where treatment processes were not hermetized. The results of this study underline that identification of enteropathogenic bacteria in WWTPs is of great importance for the correct risk assessment at workplaces. From the analytical point of view, the control of enteropathogenic bacterial air and surface pollution using rapid multiplex-PCR method should be routinely performed as a part of hygienic quality assessment in WWTPs.

Physicochemical and FT-IR analyses of some freshwater and inflow wastewater-treated effluents in the Eastern Cape Province of South Africa

Monitoring changes occurring in water bodies is a tool to make a sound decision on water quality management. This work investigates water quality parameters and metabolites in the Bloukrans, Buffalo, Swartkops and Tyhume Rivers in the Eastern Cape Province of South Africa. The water physicochemical parameters assessed include the dissolved oxygen, oxidation-reduction potentials, temperature, Hydrogen ion concentration, salinity, conductivity, turbidity and total dissolved solids measured with a pre-calibrated Hanna Multiparameter instrument on-site. Chemical oxygen demand, phosphate, chloride, ammonium, sulphate and nitrate ions were measured in the laboratory with a UVmini spectrophotometer. FT-IR analysis of extracted metabolites was done on a Perkin Elmer FT-IR spectrometer. The result shows that upstream river samples have lower COD values and below the detection level in some. The concentrations of phosphate, chloride, ammonium, sulphate and nitrate ions were above the recommended values in the wastewater effluents, midstream and downstream river samples. FT-IR peaks similar to vinylidene, saturated aliphatic aldehydes, aryl aldehydes, primary amines, hydantoin amides, halogen, and organofluorides were common in the wastewater effluent samples and the receiving rivers. Grahamstown treated wastewater effluents and its receiving Bloukrans River were distinguished with absorption peaks of urethane and aromatic aldehydes. Absorption peaks of sulphonyl halides were present only on the spectra of treated wastewater effluents of Alice and the receiving downstream Tyhume River. Multivariate analysis shows correlations between the water samples from different geographical locations and treated wastewater effluents. It is concluded that the quality of the rivers was very poor and more efforts are needed to make the treated wastewater conform to the acceptable standard for a sustainable aquatic ecosystem.

Organic UV filters: Occurrence, risks and (anti-)progestogenic activities in samples from the Czech aquatic environment and their bioaccumulation in fish

The occurrence, environmental risks and contribution of organic UV filters to detected (anti-)progestogenic activities were examined in samples of wastewater treatment plant influents and effluents, various surface waters and fish from the Czech Republic. Of the 20 targeted UV filters, 15 were detected in the WWTP influent samples, 11 in the effluents, and 13 in the surface water samples. Benzophenone-3, benzophenone-4, and phenyl benzimidazole sulfonic acid (PBSA) were found in all water samples. Octocrylene, UV-327 and 4-methylbenzylidene camphor exceeded the risk quotient of 1 at some sites. In the anti-progestogenic CALUX assay, 10 out of the 20 targeted UV filters were active. Anti-progestogenic activities reaching up to 7.7 ng/L, 3.8 ng/L, and 4.5 ng/L mifepristone equivalents were detected in influents, effluents, and surface waters, respectively. UV filters were responsible for up to 37 % of anti-progestogenic activities in influents. Anti-progestogenic activities were also measured in fish tissues from the control pond and Podroužek (pond with the highest number of detected UV filters) and ranged from 2.2 to 9.5 and 1.9 to 8.6 ng/g dw mifepristone equivalents, respectively. However, only benzophenone was found in fish, but it does not display anti-progestogenic activity and thus could not explain the observed activities.

Monitoring Pharmaceuticals and Personal Care Products in Healthcare Effluent Wastewater Samples and the Effectiveness of Drug Removal in Wastewater Treatment Plants Using the UHPLC-MS/MS Method.

A multi-residue UHPLC-MS/MS analytical method, previously developed for monitoring 52 pharmaceuticals in drinking water, was used to analyse these pharmaceuticals in wastewater originating from healthcare facilities in the Czech Republic. Furthermore, the methodology was expanded to include the evaluation of the effectiveness of drug removal in Czech wastewater treatment plants (WWTPs). Of the 18 wastewater samples analysed by the validated UHPLC-MS/MS, each sample contained at least one quantifiable analyte. This study reveals the prevalence of several different drugs; mean concentrations of 702 μg L-1 of iomeprol, 48.8 μg L-1 of iopromide, 29.9 μg L-1 of gabapentin, 42.0 μg L-1 of caffeine and 82.5 μg L-1 of paracetamol were present. An analysis of 20 samples from ten WWTPs revealed different removal efficiencies for different analytes. Paracetamol was present in the inflow samples of all ten WWTPs and its removal efficiency was 100%. Analytes such as caffeine, ketoprofen, naproxen or atenolol showed high removal efficiencies exceeding 80%. On the other hand, pharmaceuticals like furosemide, metoprolol, iomeprol, zolpidem and tramadol showed lower removal efficiencies. Four pharmaceuticals exhibited higher concentrations in WWTP effluents than in the influents, resulting in negative removal efficiencies: warfarin at -9.5%, indomethacin at -53%, trimethoprim at -54% and metronidazole at -110%. These comprehensive findings contribute valuable insights to the pharmaceutical landscape of wastewater from healthcare facilities and the varied removal efficiencies of Czech WWTPs, which together with the already published literature, gives a more complete picture of the burden on the aquatic environment.

Impact of wastewaters on groundwater quality of Bani Al-Hareth and Arhab areas in northern Sana’a city, Yemen

The purpose of this research is to determine the impacts of wastewater effluents on groundwater quality of the northern su­­burbs of Sana’a city. Fourteen duplicate groundwater and wastewater samples were collected from the study area and analyzed. The groundwater samples were analyzed for major elements, and anionic and cationic groups using Atomic Absorption Spectrophotometer (AAS). The wastewater samples were analyzed for Total Coliform (TC), Fecal Coliform (FC), and oxygen demands. For characterizing the groundwater and wastewater qualities of the study area, analysis results were tabulated, statistically treated, and elements and ionic groups were graphically plotted on diagrams and on the Piper well known diagram. The analysis results had shown that some groundwater samples were chemically and biologically contaminated. Moreover, the effluent wastewater samples had shown that all samples contain greater Fecal Coliform (FC) bacteria count and high ammonia content. In addition, the effluent wastewaters are featured with high COD and BOD, reflecting low quality wastewater effluent for the WWTP. Sludge and wastewaters used by farmers, containing high pathogens and parasites, have created or will create significant environmental and health hazards. Similarly, land resources, infrastructure and groundwater quality of the areas are highly, if not already, jeopardized or polluted. Such findings require further detailed studies for monitoring development of pollution in the area.

Novel composite based on cellulose nanomaterial for detection and selective removal of cadmium (II) ions from wastewater

In this study, we made a sustainable composite material from wheat straw agriculture waste. This material is environmentally friendly and has unique surface properties. We used it as a substrate because of its network and ability for surface modifications. To make this material, we embedded 2-(2-(di(thiophen-2-yl)methylene)hydrazineyl)-4-methylphenol (TMHM) chromophoric ligand on its surface. This enabled preconcentration, spectrophotometric determination, and removing of Cd2+ ions from real wastewater effluent samples. The resulting CNF-TMHM composite material displays exceptional sensitivity towards Cd2+ ions in aqueous solutions, accomplishing a remarkable detection limit as low as 4.17 ppb. Thus, sensitivity permits efficient naked-eye detection. Significantly, the CNF-TMHM composite material has a rapid and clear color change, shifting from pale yellow to wine red color, within less than two minutes when exposed to variable concentrations of Cd2+ ions. Furthermore, this developed CNF-TMHM composite material reveals remarkable effectiveness for Cd2+ ions detection and removal from wastewater samples. These dual potential addresses the serious environmental interests related to the pollution of water and achieving the sustainability development goals related to clean water.

Adsorption Isotherms and Kinetics of Acebutolol and Metoprolol on Magnetic Nanocomposite Fe3O4@MIL‐101(Cr)

AbstractContamination of water bodies by emerging pollutants such as β‐blockers has been a global concern over the past few years. This is due to the bioaccumulative character of β‐blockers in the aquatic systems, and their excessive usage might cause adverse effects on both humans and aquatic biota. A reusable and recyclable magnetic chromium‐based MIL‐101 (Fe3O4@MIL‐101(Cr)) nanocomposite was used as an adsorbent for the removal of the selected β‐blockers (acebutolol and metoprolol) from wastewater. The nanocomposite‘s structural, magnetic and surface properties were confirmed using various characterisation techniques. The equilibrium data indicated that the maximum adsorption capacities of Fe3O4@MIL‐101(Cr) for acebutolol and metoprolol were 30.9 mg g−1 and 28.3 mg g−1, respectively. The isotherm and kinetic experimental data best fitted Langmuir isotherm and pseudo‐second‐order kinetics models. Obtained free energies using the Dubinin‐Radushkevich model were above 8 kJ mol−1, demonstrating that the interaction mechanism between β‐blockers and the Fe3O4@MIL‐101(Cr) nanocomposite was chemisorption. The prepared nanocomposite was then used to remove β‐blockers from real samples, and maximum removal efficiencies (94.1–97.1 %) were obtained in the presence of co‐existing species. The Fe3O4@MIL‐101(Cr) hybrid showed great potential for efficient and facile removal of β‐blockers from river water, effluent and influent wastewater samples.

Catchment area, fate, and environmental risks investigation of micropollutants in Danish wastewater

This study aimed to investigate the spatial distribution of micropollutants in wastewater related to catchment area, and their environmental risks and fate. About 24-h flow proportional effluent (n = 26) wastewater samples were collected from eight WWTPs across Denmark. From five of these WWTPs corresponding influent samples (n = 20) were collected. Samples were enriched by multi-layer solid phase and analysed by liquid chromatography–high-resolution mass spectrometry and comprehensive two-dimensional gas chromatography with high-resolution mass spectrometry detection. We detected and quantified 79 micropollutants from a list of 291 micropollutants in at least one influent or effluent wastewater sample. From this we found that 54 micropollutants decreased in concentrations during wastewater treatment, while O-desmethylvenlafaxine, carbamazepine, amitriptyline, benzothiazole, terbutryn, and citalopram increased in concentrations through the WWTP.The toxicity of effluent wastewater samples was assessed by EC50 using Raphidocelis subcapitata (R. subcapitata) and LC50 using the crustacean Daphnia magna (D. Magna), for which six micropollutants were detected above the predicted no-effect concentration. Our study demonstrates that catchment area influences the micropollutant composition of wastewater. Out of 19 pharmaceuticals, the measured concentration in influent wastewater was predicted within a factor of 10 from sale numbers and human excretion, which demonstrates the strong influence of catchment area on micropollutant composition.

Selective determination of 2-aminobenzothiazole in environmental water and organic extracts from fish and dust samples

In the present study, a homemade mixed-mode ion-exchange sorbent based on silica with embedded graphene microparticles is applied for the selective extraction of 2-aminobenzothiazole (NH2BT) followed by determination through liquid chromatography coupled to high-resolution mass spectrometry. The sorbent was evaluated for the solid-phase extraction of NH2BT from environmental water samples (river, effluent wastewater, and influent wastewater), and NH2BT was strongly retained through the selective cation-exchange interactions. Therefore, the inclusion of a clean-up step of 7 mL of methanol provided good selectivity for the extraction of NH2BT. The apparent recoveries obtained for environmental water samples ranged from 62 to 69% and the matrix effect from −1 to −14%. The sorbent was also evaluated in the clean-up step of the organic extract for the extraction of NH2BT from organic extracts of indoor dust samples (10 mL of ethyl acetate from pressurized liquid extraction) and fish (10 mL of acetonitrile from QuEChERS extraction). The organic extracts were acidified (adding a 0.1% of formic acid) to promote the cation-exchange interactions between the sorbent and the analyte. The apparent recoveries for fish samples ranged from 22 to 36% depending on the species. In the case of indoor dust samples, the recovery was 41%. It should be highlighted the low matrix effect encountered in such complex samples, with values ranging from −7 to 5% for fish and dust samples. Finally, various samples were analyzed. The concentration in river samples ranged from 31 to 136 ng/L; in effluent wastewater samples, from 55 to 191 ng/L; in influent wastewater samples, from 131 to 549 ng/L; in fish samples, from 14 to 57 ng/g dried weight; and in indoor dust samples, from <MQL to 114 ng/g.

Yeast estrogen screen assay applied in the assessment of estrogenic activity removal from dairy cattle wastewater treated by anaerobic digestion

The presence of estrogen-like endocrine disrupting chemicals (EEDC) in surface waters, soils, and groundwater has been frequently reported in the literature. Since these compounds can be excreted by humans and animals, the release of domestic sewage and animal wastewaters may be an important source of EEDC in the environment. In this context, there is a growing concern regarding the presence of these substances in the environment and their potential adverse effects on human health. However, most studies have been focused on the presence of EEDC in domestic wastewaters and the available information regarding EEDC in livestock wastewater is still limited. Therefore, this work aimed to quantify the estrogenic activity (EA) in the liquid phase of dairy cattle wastewaters and evaluate the removal of EA during anaerobic digestion, applying an adapted methodology based on the yeast estrogen screen (YES) assay, which has been widely used to analyze EA in domestic sewage. Influent and effluent dairy cattle wastewater samples from a full-scale anaerobic digester placed in an experimental farm were collected during seven months. EA concentrations in the liquid phase of raw wastewater ranged from 228 to 2182 ng.L−1 E2-eq. Anaerobic digestion was not efficient in EA removal, achieving effluent concentrations ranging from 109 to 946 ng.L−1 E2-eq. Results also indicate that the application of an estradiol-based fixed time artificial insemination protocol did not statistically contribute to the increase of EA concentrations in dairy cattle wastewater which reuse in cleaning of animal feeding operation facilities and fertigation are beneficial and economically advantageous to dairy production systems, reducing water demand in parallel to promoting organic matter and nutrient recycling. However, the potential environmental and health risks associated with the presence of EEDC in dairy cattle wastewaters should be better elucidated and evaluated.

Comprehensive study on the potential environmental risk of temporal antibiotic usage through wastewater discharges

Antibiotic residues can reach aquatic ecosystems through urban wastewater discharges, posing an ecotoxicological risk for aquatic organisms and favoring the development of bacterial resistance. To assess the emission rate and hazardousness of these compounds, it is important to carry out periodic chemical monitoring campaigns that provide information regarding the actual performance of wastewater treatment plants (WWTPs) and the potential impact of the treated wastewater in the aquatic environment. In this study, 18 of the most widely consumed antibiotics in Spain were determined by liquid chromatography-tandem mass spectrometry in both influent (IWW) and effluent wastewater (EWW) samples collected over four seasons along 2021–2022. Eleven antibiotics were detected in EWW with azithromycin, ciprofloxacin and levofloxacin showing the highest concentration levels (around 2 μg L−1 of azithromycin and 0.4 μg L−1 of quinolone compounds). Data showed that only 4 out of the 11 compounds were removed by more than 50 % in the WWTP, with sulfamethoxazole standing out with an average removal efficiency >80 %. The risk that treated water could pose to the aquatic environment was also assessed, with 6 compounds indicating a potential environmental risk by exceeding established ecotoxicological and resistance thresholds. Based on the risk assessment, the WWTP removal efficiency required to reduce such risk for antibiotics was estimated. In addition, pooled wastewater samples were screened by LC coupled to high resolution mass spectrometry with ion mobility separation, searching for metabolites and transformation products of the antibiotics investigated to widen future research. Studies like this are crucial to map the impact of antibiotic pollution and to provide the basis for designing water quality and risk prevention monitoring programs.