Screening and Seasonal Behavior of Analgesics, Non-steroidal Anti-inflammatory Drugs, and Antibiotics in Two Urban Wastewater Treatment Plants.

Pharmaceutical active compounds (PhACs) belonging to analgesics, antibiotics, and non-steroidal anti-inflammatory drugs (NSAIDs) therapeutic classes were monitored in wastewater influents and effluents from two Portuguese urban wastewater treatment plants (UWWTPs) for 24 months. Both facilities were chosen due to their effluents are discharged in highly touristic and sensitive areas, Tagus river and Ria Formosa coastal lagoon, respectively. Target PhACs, acetaminophen, diclofenac, ibuprofen, naproxen, sulfadiazine, and sulfamethoxazole were measured using solid-phase extraction (SPE) coupled to liquid chromatography tandem mass spectrometry (LC-MS/MS). PhACs occurrence in the influents was higher than 98%, with acetaminophen presenting the highest concentrations, with values between 16.3 µg/L and 124 µg/L. In the effluents, distinct behavior was observed with diclofenac and sulfamethoxazole showing recalcitrant characteristics, whereas acetaminophen, ibuprofen, and naproxen showed removal efficiencies above 95%. Acetaminophen and ibuprofen amount in influents showed consistently higher concentration levels in autumn (in Beirolas and Faro Nw UWWTPs) and winter (only in Beirolas UWWTP) seasons. These seasonal trends were observed to a greater extent in Beirolas UWWTP than in Faro Nw UWWTP. This study enabled the comprehensive definition of a behavior pattern for these target contaminants, contributing to better characterization and build-up a library of PhACs occurrence. It also allowed a robust seasonal profiling of the target compounds due to the high number of samples analyzed by each season and a longer monitoring campaign, making the obtained results more significant.

Environmental Water Pollution, Endocrine Interference and Ecotoxicity of 4-tert-Octylphenol: A Review.

4-tert-Octylphenol is a degradation product of non-ionic surfactants alkylphenol polyethoxylates as well as raw material for a number of industrial applications. It is a multimedia compound having been detected in all environmental compartments such as indoor air and surface waters. The pollutant is biodegradable, but certain degradation products are more toxic than the parent compound. Newer removal techniques from environmental waters have been presented, but they still require development for large-scale applications. Wastewater treatment by plant enzymes such as peroxidases offers promise in total removal of 4-tert-octylphenol leaving less toxic degradation products. The pollutant's endocrine interference has been well reported but more in oestrogens than in any other signalling pathways through which it is believed to exert toxicity on human and wildlife. In this paper we carried out a review of the activities of this pollutant in environmental waters, endocrine interference and relevance to its toxicities and concluded that inadequate knowledge of its endocrine activities impedes understanding of its toxicity which may frustrate current efforts at ridding the compound from the environment.

Characterization of urban and industrial wastewaters using excitation-emission matrix (EEM) fluorescence: Searching for specific fingerprints.

Excitation-emission matrix (EEM) fluorescence spectroscopy has been applied to characterize several urban and industrial wastewaters (effluents from different types of industries: brewery, winery, dairy, biscuit, tinned fish industry, slaughterhouse, pulp mill, textile dyeing and landfill leachates), searching for specific fluorescence fingerprints. Tryptophan protein-like peaks (T1 and T2) are the predominant fluorescence in urban and food industry wastewaters (brewery, winery, dairy/milk, biscuit and fish farm industries) but no special fingerprint has been found to discriminate among them. Protein-like fluorescence also dominates the spectra of meat/fish industries (effluents from a tinned fish industry and a slaughterhouse), but in this case tyrosine protein-like peaks (B1 and B2) also appear in the spectra in addition to tryptophan-like peaks. This fact might constitute a specific feature to differentiate these wastewaters from others, since the appearance of peaks B is quite uncommon in wastewaters. The textile dyeing effluent shows a characteristic triple humic-like fluorescence (peaks A, C1 and C2) that may represent a specific fingerprint for this kind of effluent. Leachates from medium-aged and old landfills might also show a specific fingerprint in their EEM spectra: the sole presence of the humic-like peak C with very high fluorescence intensity. This feature also allows differentiating them from young landfill leachates, which show predominance of protein-like peaks. The fluorescence index (FI) does not seem to be very appropriate to characterize wastewaters and its usefulness might be limited to the study of humic substances in natural waters, although further studies are needed on this topic. However, the humification index (HIX) and the biological index (BIX) do seem to be useful for studying wastewaters, since they have provided consistent results in the present work. This study shows the potential of EEM fluorescence to identify the origin of some industrial effluents, although more research is needed to check these preliminary results.

Sampling and simultaneous determination of volatile per- and polyfluoroalkyl substances in wastewater treatment plant air and water.

Volatile per- and polyfluoroalkyl substances (PFASs) are often used as precursors in the synthesis of nonvolatile PFASs. The volatile PFASs, which include the perfluoroalkyl iodides (PFAIs), fluorotelomer iodides (FTIs), fluorotelomer alcohols (FTOHs), fluorotelomer olefins (FTOs), fluorotelomer acrylates (FTACs), and fluorotelomer methacrylates (FTMACs), are often produced starting from the telomerization process. These volatile compounds can be present in the air and water environment and can be transformed into highly persistent perfluoroalkyl carboxylic acids. With the exception of FTOHs, which are well studied, the determination of other volatile PFASs is also of prime importance in studying the sources and fate of PFASs. In this study, a method was developed to determine representative precursor compounds that included PFAIs, FTIs, FTOs, FTACs, and FTMACs in wastewater treatment plant (WWTP) air and water samples. The sampling and sample preparation step involved the use of solid-phase extraction (SPE) cartridges with HLB™ material to enrich the analyte. Gas chromatography with mass spectrometry was employed for the detection and quantification of the analytes. Method validation results showed high linearity and sensitivity in the positive electron ionization-selected ion monitoring mode (+EI-SIM). The absolute instrumental limits of detection were in the range of 0.5 to 2 pg. The method detection limit (MDL) in air was 1 ng/m3 with the exception of the FTACs which could be only be detected at concentrations higher than 40 ng/m3. The MDL in water was 10 ng/L. Direct spiking of the cartridges and analyte introduction by volatilization from the glass surface onto the SPE material had recoveries between 86 and 100%. The volatile PFASs were shown to readily partition into the air rather than into water. Consequently, large losses in the amount of PFASs were observed when these were spiked into the water. Graphical abstract Wastewater treatment plant air and water samples were passed through HLB™ solid-phase materials. The eluates were injected onto a GC-MS system to simultaneously determine the volatile PFASs.

Integrated in-line coagulation-aerated ultrafiltration for drinking-water production: A case study from laboratory to pilot plant.

A pilot-scale study was made for drinking-water production from low-quality influents with in-line coagulation as pre-treatment of aerated ultrafiltration. Optimum flocculation parameters were previously determined in the laboratory, searching for large and strong flocs that could resist aeration without increasing the membrane fouling. Nevertheless, the comparison of the jar tests and the pilot-scale results showed that the former could help pre-dimensioning the flocculation facilities but could not precisely reproduce the behavior of the flocs in the membrane tank. The optimum coagulant dosage enabled the highest dissolved organic carbon (DOC) removal without affecting membrane fouling. Additionally, as opposed to the jar-test results, long retention times led to the lowest fouling rates while the velocity gradient affected neither the effluent quality nor the membrane fouling. These findings suggested that the influence of the flocculation parameters was masked by aeration inside the membrane tank but, even so, 43% and 82% DOC and UVA254 removals, respectively, were reached. Furthermore, the growth of the total membrane resistance with time was logarithmic instead of linear, confirming the suitability of the pre-treatment for low-quality influents.

Chemical and toxicological characterisation of anticancer drugs in hospital and municipal wastewaters from Slovenia and Spain.

Anticancer drugs are continuously released into hospital and urban wastewaters, where they, most commonly, undergo conventional treatment in wastewater treatment plants (WWTPs). Wastewaters contain complex mixtures of substances including parent compounds, their metabolites and transformation products (TPs). In this study, samples of hospital effluents and WWTP influents and effluents from Slovenia and Spain were analyzed for twenty-two selected anticancer drugs, their metabolites and transformation products. Acute and chronic toxicity tests were performed on the crustacean Ceriodaphnia dubia, genotoxicity was determined with Tradescantia and Allium cepa micronucleus (MN) assays and in vitro comet assay in zebrafish (Danio rerio) liver cell line (ZFL cells). Sixty of the two hundred-twenty determinations revealed detectable levels of anticancer drug residues. Among the targeted compounds, platinum based were most frequently detected (90%). Furthermore, erlotinib was detected in 80%, cyclophosphamide and tamoxifen in 70% and methotrexate in 60% of the samples. Seven of ten samples were toxic to C. dubia after acute exposure, whereas after chronic exposure all samples reduced reproduction of C. dubia at high sample dilutions. Allium cepa proved insensitive to the potential genotoxicity of the tested samples, while in Tradescantia increased MN frequencies were induced by a hospital effluent and WWTP influents. In ZFL comet assay all but one sample induced a significant increase of DNA strand breaks. Correlations of chemotherapeutics or their TPs were detected for all bioassays except for Allium cepa genotoxicity test, however for each test the highest correlations were found for different substances indicating differential sensitivities of the test organisms.

Understanding the magnitude of emergent contaminant releases through target screening and metabolite identification using high resolution mass spectrometry: Illicit drugs in raw sewage influents.

A QExactive Orbitrap was used for the identification of phase I and II transformation products (TPs) of illicit drugs in raw sewage influents. Two operating modes (targeted MS(2) and Data-dependent screening) were used for data acquisition. Even though, data-dependent scan is a faster route towards the potential identification of metabolites, it suffered from its limitation to provide enough data points across the chromatographic peak during the MS(2) cycle in contrast to targeted MS(2). Therefore, the later technique was implemented as the method of choice in this study for the positive confirmation and quantitation of TPs (n=54). The vast majority of the identified TPs were products of phase I transformation reactions, with the latter being more prevalent in the nature. Estimated mole fractions showed that for a large number of the analytes, TPs must also be monitored in order to fully understand their environmental fate and calculate potential consumption.

Analysis of drugs of abuse by online SPE-LC high resolution mass spectrometry: communal assessment of consumption.

An online SPE-LC-HRMS method was developed to monitor the consumption of 18 drugs of abuse (DOAs) including amphetamines, opioids, cocainics, cannabinoids, lysergics, and their corresponding metabolites in a well characterized college campus setting via wastewater analysis. Filtered and diluted (10×) sewage water samples (5 mL inj.) were automatically pre-concentrated and analyzed in 15 min using a Thermo EQuan MAX online SPE system equipped with a HyperSep™ Retain PEP (20×2.1 mm×12 µm) SPE column and a Hypersil Gold™ aQ (150×2.1 mm×3 µm) analytical column. A Q Exactive™ Hybrid Quadrupole-Orbitrap HRMS was used in full scan mode (R=140,000) for positive identification, and quantitation of target compounds. Method detection limits for all analytes ranged between 0.6 and 1.7 ng/L in sewage. A total of 14 DOAs were detected from two different locations (dorms and main college campus) within a one-year period. Most frequently detected drugs throughout the entire study were amphetamine (>96%) and THC's metabolite 11-nor-9-carboxy-Δ-9-THC (>100%) with maximum concentrations of 5956 and 2413 ng/L respectively. Daily doses per 1000 people were determined in order to assess consumption of THC, amphetamine, heroin and cocaine, in both dorms and main campus.