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• TCC transformation regulating metabolic functions and ARGs were evaluated. • TCC was converted to MCC by dichloride reductive dechlorination dominated in HA. • TCC inhibit NH 4 + assimilation and nitrification genes enrichment. • ARGs and degradative TCC-intrinsic ARGs have horizontal transfer potential with ISs. • The biotransformation of TCC can partial control the ARGs risk. Evaluating the role of antimicrobials biotransformation in the regulation of metabolic functions and antimicrobial resistance evolution in wastewater biotreatment systems is crucial to ensuring water security. However, the associated mechanisms remain poorly understood. Here, we investigate triclocarban (TCC, one of the typical antimicrobials) biotransformation mechanisms and the dynamic evolution of systemic function disturbance and antimicrobial resistance risk in a complex anaerobic hydrolytic acidification (HA)-anoxic (ANO)/oxic (O) process. We mined key functional genes involved in the TCC upstream (reductive dechlorination and amide bonds hydrolysis) and downstream (chloroanilines catabolism) biotransformation pathways by metagenomic sequencing. Acute and chronic stress of TCC inhibit the production of volatile fatty acids (VFAs), NH 4 + assimilation, and nitrification. The biotransformation of TCC via a single pathway cannot effectively relieve the inhibition of metabolic functions (e.g., carbon and nitrogen transformation and cycling) and enrichment of antimicrobial resistance genes (ARGs). Importantly, the coexistence of TCC reductive dechlorination and hydrolysis pathways and subsequent ring-opening catabolism play a critical role for stabilization of systemic metabolic functions and partial control of antimicrobial resistance risk. This study provides new insights into the mechanisms linking TCC biotransformation to the dynamic evolution of systemic functions and risks, and highlights critical regulatory information for enhanced control of TCC risks in complex biotreatment systems. [Display omitted] [ABSTRACT FROM AUTHOR]

The simultaneous degradation of seventeen emerging concern pollutants in effluent from the municipal wastewater treatment plant (MWTP) of Bogotá-Colombia was studied using high frequency ultrasound (375 kHz). The considered compounds in the effluent corresponded to pharmaceuticals (diclofenac, carbamazepine, venlafaxine, ciprofloxacin, norfloxacin, valsartan, losartan, irbesartan, sulfamethoxazole, clarithromycin, azithromycin, erythromycin, metronidazole, trimethoprim and clindamycin); cocaine and its major metabolite benzoylecgonine. Due to limitation of the MWTP for the pollutants elimination, ultrasound was applied to remove these compounds. Interestingly, ultrasonic physical action led to releasing of ciprofloxacin, norfloxacin, diclofenac and sulfamethoxazole from suspended solids, whereas the chemical effects induced degradation of the rest of compounds. For the latter ones, an interesting correlation between the sonodegradation and arithmetic multiplication between hydrophobicity and concentration of pollutants was established. Afterwards, the sonochemical process was complemented with ferrous ions (sono-Fenton), ferrous ions plus light (sono-photo-Fenton) or ferrous ions plus light in presence of oxalic acid (sono-photo-Fenton/oxalic acid). Additionally, to clarify fundamental aspects of the different systems, individual treatments in distilled water of a model pollutant (valsartan) were performed. The complemented processes significantly enhanced all compounds degradation, following the order: sono-photo-Fenton/oxalic acid > sono-photo-Fenton ∼ sono-Fenton > sonochemistry. The Fe2+ addition improved the pollutants elimination by generation of more hydroxyl radicals in the solution bulk. Meanwhile, oxalic acid avoided Fe3+ precipitation favoring the iron catalytic cycle. Thus, the work demonstrates the high potentiality of the sono-photo-Fenton/oxalic acid system for the pollutants elimination in real-world wastewater matrices. Image 1 • 17 pollutants in municipal effluents were treated by high frequency ultrasound. • Physical action released compounds from solids/chemical effect degraded pollutants. • Pollutants sonodegradation was correlated with hydrophobicity and concentration. • Combination ultrasound/photo-Fenton significantly enhanced the pollutants removal. • Oxalic acid had positive effect on sonophoto-Fenton, favoring iron catalytic cycle. [ABSTRACT FROM AUTHOR]

Triclocarban (TCC), one typical antibacterial agent being widely used in various applications, was found to be present in waste activated sludge at significant levels. To date, however, its effect on anaerobic fermentation of sludge has not been investigated. This work therefore aims to fill this knowledge gap. Experimental results showed that when TCC content in sludge increased from 26.7 ± 5.3 to 520.5 ± 12.6 mg per kilogram total suspended solids, the maximum concentration of short-chain fatty acids (SCFA) increased from 32.6 ± 2.5 to 228.2 ± 3.6 (without pH control) and from 211.7 ± 2.4 to 378.3 ± 3.2 mg COD/g VSS (initial pH 10), respectively. The large promotion of acetic acid was found to be the major reason for the enhancement of total SCFA production. Although a significant level of TCC was degraded in the fermentation process, SCFA was neither produced from TCC nor affected by its major intermediates at the relevant levels. It was found that TCC facilitated solubilization, acidogenesis, acetogenesis, and homoacetogenesis processes but inhibited methanogenesis process. Microbial analysis revealed that the increase of TCC increased the microbial community diversity, the abundances of SCFA (especially acetic acid) producers, and the activities of key enzymes relevant to acetic acid production. [ABSTRACT FROM AUTHOR]

• TCS/TCC treatment caused deterioration of the olfactory ability of goldfish. • TCS/TCC reduced the expression of olfactory receptors in the olfactory epithelium. • TCS/TCC restricted the transformation of odorant stimulation into electric signals. • TCS/TCC induced apoptosis and inflammation in the olfactory bulb. Recently, increased production and consumption of disinfectants such as triclosan (TCS) and triclocarban (TCC) have led to massive pollution of the environment, which draws global concern over the potential risk to aquatic organisms. However, the olfactory toxicity of disinfectants in fish remains elusive to date. In the present study, the impact of TCS and TCC on the olfactory capacity of goldfish was assessed by neurophysiological and behavioral approaches. As shown by the reduced distribution shifts toward amino acid stimuli and hampered electro-olfactogram responses, our results demonstrated that TCS/TCC treatment would cause deterioration of the olfactory ability of goldfish. Our further analysis found that TCS/TCC exposure suppressed the expression of olfactory G protein-coupled receptors in the olfactory epithelium, restricted the transformation of odorant stimulation into electrical responses by disturbing the cAMP signaling pathway and ion transportation, and induced apoptosis and inflammation in the olfactory bulb. In conclusion, our results demonstrated that an environmentally realistic level of TCS/TCC would weaken the olfactory capacity of goldfish by constraining odorant recognition efficiency, disrupting olfactory signal generation and transduction, and disturbing olfactory information processing. [Display omitted] [ABSTRACT FROM AUTHOR]

• Molecular networking present excellent performance on low abundance TPs identifying. • 4 TPs of CIT and 5TPs of SER were newly identified in present study. • The dominant transformation pathways for CIT and SER in wastewater were revealed. • The occurrence, concentration and toxicity of TPs in WWTPs were assessed. Citalopram (CIT) and sertraline (SER) are highly consumed antidepressants worldwide and have been extensively detected in wastewater. Due to the incomplete mineralization, transformation products (TPs) of them can be detected in wastewater. Comparing with parent compounds, knowledge on TPs are limited. To fill these research gaps, lab-scale batch experiments, WWTPs sampling and in silico toxicity prediction were implemented to investigate the structure, occurrence and toxicity of TPs. Based on molecular networking nontarget strategy, 13 TPs of CIT and 12 TPs of SER were tentatively identified. Among them, 4 TPs from CIT and 5 TPs from SER were newly found in present study. TPs identification results compared with results obtained from previous nontarget strategies demonstrated that the excellent performances for molecular networking strategy on candidate TPs prioritizing and new TPs finding, especially for low abundance TPs. Further, transformation pathways for CIT and SER in wastewater were proposed. Newly identified TPs provided insights on defluorination, formylation and methylation for CIT and dehydrogenation, N-malonylation and N-acetoxylation for SER transformed in wastewater. Nitrile hydrolysis and N-succinylation were found to be the dominant transformation pathways for CIT and SER in wastewater, respectively. WWTPs sampling results shown the concentrations of SER and CIT ranged from 0.46 to 28.66 ng/L and 17.16 to 58.36 ng/L. In addition, 7 TPs of CIT and 2 TPs of SER found in lab-scale wastewater samples were found in WWTPs. In silico results suggested 2 TPs of CIT may be more toxic than CIT toward all three trophic levels organisms. Present study provides new insights into the transformation processes of CIT and SER in wastewater. In addition, the necessity of paying more attention on TPs was further highlighted from the aspects of toxicity for TPs of CIT and SER in effluent of WWTPs. [Display omitted] [ABSTRACT FROM AUTHOR]

Biosolids from wastewater treatment are primarily disposed of via land applications, where numerous pharmaceuticals and personal care products (PPCPs) may contaminate food crops and pose a human exposure risk. Biosolids are rich in organic carbon and addition of biosolids can increase the sorption of certain PPCPs in soil, decreasing their bioavailability. This study tested the hypothesis that the relative plant uptake of PPCPs decreases with increasing biosolids amendment. Accumulation of triclosan and triclocarban was measured in roots of radish and carrot grown in soils with or without biosolids. Addition of biosolids significantly prolonged the persistence of triclosan in soil. When expressed in bioaccumulation factor (BCF), accumulation of triclosan drastically decreased in biosolids-amended soils, while the effect was limited for triclocarban. Compared to the unamended soil, amending biosolids at 2% (w/w) decreased BCF of triclosan in the edible tissues of radish and carrot by 85.4 and 89.3%, respectively. Measurement using a thin-film passive sampler provided direct evidence showing that the availability of triclosan greatly decreased in biosolids-amended soils. Partial correlation analysis using data from this and published studies validated that biosolids decreased plant uptake primarily by increasing soil organic carbon content and subsequently sorption. Therefore, contamination of food crops by biosolids-borne contaminants does not linearly depend on biosolids use rates. This finding bears significant implications in the overall risk evaluation of biosolids-borne contaminants. [ABSTRACT FROM AUTHOR]

• Comprehensive study (n = 1514) on TCC, TCS & parabens before and during the pandemic. • Antimicrobial consumption increased by 56% during the pandemic. • The mass loading of Methylparaben increased by 55% during the pandemic. • After the 2017 FDA ban, consumption of triclosan (−89%) and triclocarban (−80%) decreased. Antimicrobials like parabens, triclosan (TCS), and triclocarban (TCC) are of public health concern worldwide due to their endocrine-disrupting properties and ability to promote antimicrobial drug resistance in human pathogens. The overall use of antimicrobials presumably has increased during the COVID-19 pandemic, whereas TCS and TCC may have experienced reductions in use due to their recent ban from thousands of over-the-counter (OTC) personal care products by the U.S. Food and Drug Administration (FDA). No quantitative data are available on the use of parabens or the impact the FDA ban had on TCC and TCS. Here, we use wastewater samples (n = 1514) from 10 different communities in Arizona to measure the presence of the six different antimicrobial products (TCS, TCC, and four alkylated parabens [methylparaben (MePb), ethylparaben (EtPb), propylparaben (PrPb), butylparaben (BuPb)]) collected before and during the COVID-19 pandemic using a combination of solid-phase extraction, liquid chromatography/tandem mass spectrometry (LC-MS/MS), and isotope dilution for absolute quantitation. The average mass loadings of all antimicrobials combined (1,431 ± 22 mg/day per 1,000 people) after the onset of the local epidemic (March 2020 - October 2020) were significantly higher (945 ± 62 mg/day per 1,000 people; p < 0.05) than before the pandemic (January 2019 - February 2020). Overall, parabens (∑Pbs = 999 ± 16 mg/day per 1,000 people) were the most used antimicrobials, followed by TCS (117 ± 14 mg/day per 1,000 people) and TCC (117 ± 14 mg/day per 1,000 people). After the 2017 U.S. FDA ban, we found a statistically significant (p < 0.05) reduction in the mass loadings of TCS (-89%) and TCC (-80%) but a rise in paraben use (+72%). Mass flows of 3 of a total of 4 parabens (MePb, EtPb, and PrPb) in wastewater were significantly higher upon the onset of the epidemic locally (p < 0.05). This is the first longitudinal study investigating the use of antimicrobials during the COVID-19 pandemic by employing wastewater-based epidemiology. Whereas an overall increase in the use of antimicrobials was evident from analyzing Arizona wastewater, a notable reduction in the use of TCS and TCC was evident during the pandemic, triggered by the U.S. FDA ban. [Display omitted] [ABSTRACT FROM AUTHOR]

• PE-MPs inhibition on HPG was both concentration- and size-dependent. • PE-NPs induced more severe inhibitory effect on HPG than PE-MPs. • Excess oxidative stress and corresponding leachates contributed to MPs toxicity. • PE-NPs infiltrated into inner layer but PE-MPs adhered on outside surface of HPG. Micro(nano)plastics is an emerging contaminant in wastewater that has showed significant impacts on various biological treatment processes. Nevertheless, the underlying effects of micro(nano)plastics with different concentrations and sizes on the anaerobic hydrogen-producing granular sludge (HPG) were still unclear. This work firstly attempted to illustrate the microbial and physicochemical responses of HPG to a shock load of polyethylene microplastics (PE-MPs) with varied concentrations and sizes. The results revealed that the PE-MPs inhibitory effect on hydrogen production by HPG was both concentration- and size-dependent. Specifically, the increase of PE-MPs concentration and the decline of PE-MPs size to nano-sized plastics (NPs) significantly decreased the hydrogen yield, downgraded to 79.9 ± 2.6% and 63.0 ± 3.9% (p = 0.001, and 0.0002) of control, respectively, at higher MPs concentration and the smaller MPs size (i.e., NPs). The higher PE-MPs concentration and PE-NPs also suppressed extracellular polymeric substances (EPS) generation more severely. The critical bio-processes involved in hydrogen production were disturbed by PE-MPs, with the extent of negative impacts depending on the dosage and size of PE-MPs. These adverse impacts further manifested as granule disintegration and loss of cellular activity. Mechanism analysis highlighted the roles of oxidative stress, leachate released from PE-MPs, interaction between PE-NPs and granules inducing physical crushing of HPG that led to possible direct contact between cells and toxic substances. [Display omitted] [ABSTRACT FROM AUTHOR]

The presence of the antimicrobials triclocarban (TCC) and triclosan (TCS)in Fountain Creek, a wastewater-dominated stream, and the Arkansas River, Colorado, USA was measured in the surface water, suspended sediments, and bed sediments during spring runoff (high flow) and summer base flow (low flow) conditions. Fountain Creak is a tributary of the Arkansas River. Passive polar organic chemical integrative samplers (POCIS) were used along with active sampling (water grab samples) to measure and TCS concentrations in these surface waters. The concentration of TCC and TCS, based on POCIS measurements, ranged from 4.5 to 47.3 ng/L and 3.9 to 28.3 ng/L, respectively, at the five sample sites monitored in this study under both flow conditions. The range of concentrations of TCC and TCS in suspended sediments was 0.7–57.3 ng/g and 0.7–13.3 ng/g, respectively, and was closely tied to the quantity of organic carbon in the suspended sediment, which ranged from 1.6 to 14.5%. The quantity of organic carbon in suspended sediment during the summer base flow was influenced by runoff from the burn area of a large forest fire that occurred between the two sampling periods. The primary transport mechanism of TCC and TCS in these surface waters was in the dissolved phase, with 64–99% of TCC and 68–99% of TCS transported in the dissolved phase. The total amount of TCS and TCC in bed-sediments was relatively low, with the maximum amount at any one site being 0.38 ± 0.15 ng/g TCS and 4.09 ± 5.26 ng/g TCC. Fountain Creek contributed up to 76% and 69% of the TCC and TCS, respectively, that is transported directly below its confluence with Arkansas River. Fountain Creek drained approximately 3.0 g/day TCS (in spring), 2.9 g/day TCS (in summer) and 1.9 g/day TCC (in spring), 2.0 g/day TCC (in–summer) into the Arkansas River, which suggests consistent input of TCC and TCS into Fountain Creek, such as in discharge of treated wastewater that is independent of changing creek flow conditions. [ABSTRACT FROM AUTHOR]

Triclocarban (TCC) and Triclosan (TCS) are two antibacterial chemicals present in household and personal care products. Methyltriclosan is a biodegradation product of TCS formed under aerobic conditions. TCC and TCS are discharged to Waste Water Treatment Plants (WWTP) where they are removed from the liquid phase mainly by concentrating in the solids. This study presents a thorough investigation of TCC, TCS and MeTCS concentrations in the liquid phase (dissolved + particulate) as well as solid phases within a single, large WWTP in the U.S. Total TCC and TCS concentrations decreased by >97% with about 79% of TCC and 64% of TCS transferred to the solids. The highest TCC and TCS removal rates from the liquid phase were reached in the primary treatment mainly though sorption and settling of solids. The TCC mass balances showed that TCC levels remain unchanged through the secondary treatment (activated sludge process) and about an 18% decrease was observed through the nitrification–denitrification process. On the other hand, TCS levels decreased in both processes (secondary and nitrification–denitrification) by 10.4 and 22.6%, respectively. The decrease in TCS levels associated with observed increased levels of MeTCS in secondary and nitrification–denitrification processes providing evidence of TCS biotransformation. Dissolved-phase concentrations of TCC and TCS remained constant during filtration and disinfection. TCC and TCS highest sludge concentrations were analyzed in the primary sludge (13.1 ± 0.9 μg g−1 dry wt. for TCC and 20.3 ± 0.9 μg g−1 dry wt. for TCS) but for MeTCS the highest concentrations were analyzed in the secondary sludge (0.25 ± 0.04 μg g−1 dry wt.). Respective TCC, TCS and MeTCS concentrations of 4.15 ± 0.77; 5.37 ± 0.97 and 0.058 ± 0.003 kg d−1 are leaving the WWTP with the sludge and 0.13 ± 0.01; 0.24 ± 0.07 and 0.021 ± 0.002 kg d−1 with the effluent that is discharged. [ABSTRACT FROM AUTHOR]

Abstract: Triclosan (TCS) and triclocarban (TCC) are two commonly used personal care products. They may enter into aquatic environments after consumption and pose potential risks to aquatic organisms. We investigated the occurrence and fate of TCS and TCC in five large rivers (the Liao River, Hai River, Yellow River, Zhujiang River and Dongjiang River) in China, and compared the monitoring data with the predicted results from Level III fugacity modeling. TCS and TCC were detected in the five large rivers with the detection frequencies of 100% or close to 100% in surface water and sediments of almost every river. TCS and TCC were found at concentrations of up to 478 ng/L and 338 ng/L in surface water, and up to 1329 ng/g and 2723 ng/g in sediments. Cluster analysis indicated that the sites with higher concentrations were usually located in or near urban area. Meanwhile, principal component analysis also suggested that the mass inventories of TCS and TCC in water and sediment were significantly influenced by the factors such as the total or untreated urban domestic sewage discharge at river basin scale. The concentrations and mass inventories from the fugacity modeling were found at the same order of magnitude with the measured values, suggesting that the fugacity modeling can provide a useful tool for evaluating the fate of TCS and TCC in riverine environments. Both monitoring and modeling results indicated that the majority of mass inventories of TCS and TCC were stored into sediment, which could be a potential pollution source for river water. The wide presence of TCS and TCC in these large rivers of China implies that better controlling of urban domestic sewage discharge is needed. [Copyright &y& Elsevier]

Abstract: Triclocarban and triclosan, two antimicrobials widely used in consumer products, can adversely affect ecosystems and potentially impact human health. The application of biosolids to agricultural fields introduces triclocarban and triclosan to soil and water resources. This research examined the phytoaccumulation of antimicrobials, effects of plant growth on migration of antimicrobials to water resources, and relevance of phytoaccumulation in human exposure to antimicrobials. Pumpkin, zucchini, and switch grass were grown in soil columns to which biosolids were applied. Leachate from soil columns was assessed every other week for triclocarban and triclosan. At the end of the trial, concentrations of triclocarban and triclosan were determined for soil, roots, stems, and leaves. Results indicated that plants can reduce leaching of antimicrobials to water resources. Pumpkin and zucchini growth significantly reduced soil concentrations of triclosan to less than 0.001 mg/kg, while zucchini significantly reduced soil concentrations of triclocarban to 0.04 mg/kg. Pumpkin, zucchini, and switch grass accumulated triclocarban and triclosan in mg per kg (dry) concentrations. Potential human exposure to triclocarban from consumption of pumpkin or zucchini was substantially less than exposure from product use, but was greater than exposure from drinking water consumption. Consequently, research indicated that pumpkin and zucchini may beneficially impact the fate of antimicrobials in agricultural fields, while presenting minimal acute risk to human health. [Copyright &y& Elsevier]

The occurrence of the antimicrobials triclocarban (TCC) and triclosan (TCS) was investigated in agricultural soils following land application of biosolids using liquid chromatography¿tandem mass spectrometry (LC¿MS¿MS) with negative ion multimode ionization. The method detection limits were 0.58ngTCC/g soil, 3.08ngTCC/g biosolids, 0.05ngTCS/g soil and 0.11ngTCS/g biosolids and the average recovery from all of the sample matrices was >95%. Antimicrobial concentrations in biosolids from three Michigan wastewater treatment plants (WWTPs) ranged from 4890 to 9280ng/g, and from 90 to 7060ng/g, for TCC and TCS respectively. Antimicrobial analysis of soil samples, collected over two years, from ten agricultural sites previously amended with biosolids, indicated TCC was present at higher concentrations (1.24¿7.01ng/g and 1.20¿65.10ng/g in 2007 and 2008) compared to TCS (0.16¿1.02ng/g and from the method detection limit, <0.05¿0.28ng/g in 2007 and 2008). Soil antimicrobial concentrations could not be correlated to any soil characteristic, or to the time of last biosolids application, which occurred in either 2003, 2004 or 2007. To our knowledge, our data represent the first report of TCC, and the first comparison of TCC and TCS concentrations, in biosolids-amended agricultural soils. Such information is important because approximately 50% of US biosolids are land applied, therefore, any downstream effects of either antimicrobial are likely to be widespread. [Copyright &y& Elsevier]

• Thauera was identified as active PD and TCS-degrading bacteria by DNA-SIP. • The labelled bacteria by SIP were PD bacteria rather than conditional PD bacteria. • TCS could transform partial denitrification (PD) to complete denitrification process. • TCS was removed via degradation (10.66%) and adsorption (43.62%) in PD system. • The addition of TCS might propagate acrA-03 (short-term) and fabK (long-term). Granule-based partial denitrification (PD) is a technology that can supply stable nitrite for applying anaerobic ammonia oxidation in wastewater treatment, and triclosan (TCS) is a frequently detected antibacterial agent in wastewater treatment plants, therefore it is possible that TCS could enter into wastewater that is treated using PD technology. However, the active microorganisms responsible for PD and TCS removing in granule-based PD system have not been clearly identified and it is currently not clear how TCS affects the PD process. In this study, the impacts of TCS on PD performance, PD microbial community, antibiotic resistance genes (ARGs), active PD bacteria and TCS-degrading bacteria in a granule-based PD system were investigated. 3 mg/L TCS had adverse influence on PD process, but PD system could recover gradually after inhibiting of 10 days. After a period of domestication, PD granular sludge could achieve 10.66% of TCS degradation efficiency and 43.62% of TCS adsorption efficiency. Microbes might increase their resistance to TCS by increasing the secretion of extracellular polymeric substances, and the secretion of protein might play a more pivotal role than the secretion of polysaccharides in resisting TCS. The short-term shock of TCS might cause the propagation of acrA-03 , while the long-term operation of TCS could propagate fabK and intI1. DNA stable isotope probing assay indicated that Thauera was active PD bacteria and TCS-degrading bacteria in the granule-based PD system, and it could contribute to nitrite accumulation and TCS degradation, simultaneously. [Display omitted] [ABSTRACT FROM AUTHOR]

• Oxidative treatments could effectively remove antineoplastic agents in water. • Low mineralization was observed with the formation of various recalcitrant products. • Toxicity increase was widely found during aqueous transformation of antineoplastics. • Most oxidized products had multi-endpoint toxicity and lower biodegradability. Antineoplastic compounds, designed for chemotherapeutic anticancer therapy, have become emerging contaminants of global concern over the past decade due to their ubiquitous occurrence, environmental persistence, and multiple adverse effects on aquatic ecosystems. Increasing efforts have been devoted to developing efficient strategies for remediating water containing these micropollutants. In this study, the physicochemical properties, natural attenuation, and chemical reactivity with aqueous oxidizing species of five antineoplastic drugs with the highest environmental prevalence (i.e., tamoxifen, cyclophosphamide, ifosfamide, 5-fluorouracil, and methotrexate) were summarized. The removal performance, transformation products (TPs) of varying structures, overall reaction pathways, and toxicity evolution during different treatments were evaluated and discussed. Additionally, the biodegradability and multi-endpoint toxicity of each TP were predicted using in silico QSAR software. Depending on their distinct inherent structures, the reactivity of the antineoplastics with oxidizing species varied, with hydroxyl radicals exhibiting unparalleled merits in rapid oxidation. Complete elimination of these contaminants was observed during oxidative treatments, but with inadequate mineralization. Notably, the increase in toxicity within multiple processes was determined based on both experimental bioassays and theoretical predictions. This may be attributed to the adverse effects induced by the large number of identified and unknown TPs individually and in combination. Together with the environmental persistence and low biodegradability of most TPs, these results necessitate the application of efficient post-treatments in conjunction with a more thorough water safety evaluation (e.g., using high-throughput screening) of the mixtures of treated water and wastewater. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • Wide-scope screening of pharmaceuticals and illicit drugs in Amazonian freshwaters. • Combined target and suspect screening allowed identification of 51 compounds. • Novel use of empirical collision-cross section values improved suspect screening. • High prevalence of analgesics and antihypertensives close to urban areas. • Caffeine, cocaine, benzoylecgonine, and cotinine are widespread in the Amazon River. Only a limited number of households in the Amazon are served by sewage collection or treatment facilities, suggesting that there might be a significant emission of pharmaceuticals and other wastewater contaminants into freshwater ecosystems. In this work, we performed a wide-scope screening to assess the occurrence of pharmaceuticals, illicit drugs and their metabolites in freshwater ecosystems of the Brazilian Amazon. Our study included 40 samples taken along the Amazon River, in three of its major tributaries, and in small tributaries crossing four important urban areas (Manaus, Santarém, Macapá, Belém). More than 900 compounds were investigated making use of target and suspect screening approaches, based on liquid chromatography coupled to high-resolution mass spectrometry with ion mobility separation. Empirical collision-cross section (CCS) values were used to help and confirm identifications in target screening, while in the suspect screening approach CCS values were predicted using Artificial Neural Networks to increase the confidence of the tentative identification. In this way, 51 compounds and metabolites were identified. The highest prevalence was found in streams crossing the urban areas of Manaus, Macapá and Belém, with some samples containing up to 30 - 40 compounds, while samples taken in Santarém showed a lower number (8 - 11), and the samples taken in the main course of the Amazon River and its tributaries contained between 1 and 7 compounds. Most compounds identified in areas with significant urban impact belonged to the analgesics and antihypertensive categories, followed by stimulants and antibiotics. Compounds such as caffeine, cocaine and its metabolite benzoylecgonine, and cotinine (the metabolite of nicotine), were also detected in areas with relatively low anthropogenic impact and showed the highest total prevalence. This study supports the need to improve the sanitation system of urban areas in the Brazilian Amazon and the development of follow-up studies aimed at quantifying exposure levels and risks for Amazonian freshwater biodiversity. [ABSTRACT FROM AUTHOR]

• Warmer temperatures decreased influent ARGs concentrations but increased E. coli's. • Rainfall diluted influent concentrations of antimicrobials & E. coli , but not ARGs. • Rainfall reduced the efficiency of wastewater treatment in removing ARGs & E. coli. • ARGs patterns in flocculent activated sludge followed influent trends. • Similar removal of antimicrobial & ARGs by granular and flocculent sludge systems. The occurrence and removal patterns of 24 antimicrobial agents and antimicrobial resistant determinants namely 6 antibiotic resistance genes (ARGs) and 2 mobile genetic elements (MGEs), and the fecal indicator E. coli were investigated in three full-scale wastewater treatment plants. Their waterlines and biosolids lines (including secondary treatment based on both granular and activated sludge) were sampled monthly throughout one year. Samples were analyzed by means of LC-MS/MS, qPCR and cell enumeration, respectively. The influence of rainfall, temperature, and turbidity on the occurrence and removal of the aforementioned agents was assessed through statistical linear mixed models. Ten of the antimicrobial agents (macrolides, fluoroquinolones, tetracyclines, and sulfonamides) were commonly found in influent in concentrations of 0.1-2 µg L−1, and the predominant ARGs were ermB and sul1 (6.4 and 5.9 log 10 mL−1 respectively). Warmer temperatures slightly reduced gene concentrations in influent whilst increasing that of E. coli and produced an uneven effect on the antimicrobial concentrations across plants. Rainfall diluted both E. coli (-0.25 logs, p < 0.001) and antimicrobials but not genes. The wastewater treatment reduced the absolute abundance of both genes (1.86 logs on average) and E. coli (2.31 logs on average). The antimicrobials agents were also partly removed, but 8 of them were still detectable after treatment, and 6 accumulated in the biosolids. ARGs were also found in biosolids with patterns resembling those of influent. No significant differences in the removal of antimicrobials, genes and E. coli were observed when comparing conventional activated sludge with aerobic granular sludge. Irrespective of the type of sludge treatment, the removal of genes was significantly reduced with increasing hydraulic loads caused by rainfall (-0.35 logs per ∆ average daily flow p < 0.01), and slightly decreased with increasing turbidity (-0.02 logs per ∆1 nephelometric turbidy unit p < 0.05). Image, graphical abstract [ABSTRACT FROM AUTHOR]

• Titanium-incorporated diatoms (silica-titania frustules) integrated 7.2% of titanium. • Silica-titania frustules selectively removed PPCPs in the presence of NOM by photodegradation. • The photocatalytic activity of P25 decreased significantly at NOM concentrations > 1 mg•L−1. • Silica-titania frustules had 3 to 4-fold higher photocatalytic efficiencies in removing PPCPs. • Silica frustules (i.e., no titania incorporated) had negligible photodegradation efficiency. Natural organic matter (NOM), such as humic acids, fulvic acids, and tannic acids, is ubiquitous in water bodies and hinders the photodegradation of pharmaceuticals and personal care products (PPCPs). We prepared titanium incorporated hierarchical diatoms as a novel photocatalyst to selectively remove PPCPs (triclosan, bisphenol A or BPA, and N, N -Diethyl-meta-toluamide or DEET) in the presence of NOM (humic acid). Diatom (Stephanodiscus hantzschii) grown in a titanium(IV) bis(ammonium lactato) dihydroxide solution integrated 7.2% ± 1.4% (mass fraction) of titanium in their cell wall and formed silica-titania frustules. The photodegradation of triclosan, BPA, and DEET by both silica-titania frustules and titania nanopowder (a control photocatalyst) follows pseudo-first-order kinetics. Under ultraviolent light irradiation, the titanium-content-normalized pseudo-first-order removal rate constants of triclosan, BPA, and DEET by silica-titania frustules were 3, 4, and 4-times those by titania nanopowder, respectively, at a humic acid concentration of 10 mg•L−1. Incorporation of titanium did not alter the morphology and hierarchical nano/microstructures of the diatom. The silica-titania frustules were rich in nanopores with a diameter of 20 ± 4 nm (mean ± standard deviation), allowing PPCPs with a small molecular weight (typically < 600 g•mol−1) to pass through while efficiently rejecting NOM with high molecular weights. The silica-titania frustules with hierarchical nano/microstructures served as a prefiltration unit by selectively allowing PPCPs to pass through the nanopores and are therefore promising for photodegradation and environmental remediation applications. Image, graphical abstract [ABSTRACT FROM AUTHOR]

The occurrence and fate of the popular pharmaceutical gabapentin (GBP) in the urban water cycle were investigated with a focus on its transformation during water chlorination. GBP was detected in all samples with average concentrations of 1285 ng/L (n = 24) for wastewater effluent, 304 ng/L for river water (n = 22), and 180 ng/L for drinking water treatment plant (DWTP) influent (n = 4). The monitoring sites were located in the Nakdong River watershed, Korea. GBP was rapidly (within 20 min) transformed into 1-cyanocyclohexylacetic acid (GBP-nitrile) under typical chlorination conditions (1.4 mgCl 2 /L). When there was a molar excess of chlorine to GBP, the primary amine of GBP was double-chlorinated to form N-Cl 2 GBP with a second-order rate constant of >103 M−1 s−1. Decomposition of N-Cl 2 GBP had a first-order rate constant of (0.5–1.0) × 10−2 s−1 and produced GBP-nitrile with a yield of 87%–100%. We propose that N-Cl 2 GBP is transformed into N-Cl GBP imine and then to GBP-nitrile via two consecutive dehydrochlorinations with the former as the rate-limiting step. N-Cl 2 GBP had a much higher decomposition rate than N-Cl 2 produced from other simple aliphatic amines, which could be related to the structural features of GBP such as its carboxyl group and quaternary β-carbon. The wastewater effluent samples did not contain GBP-nitrile even in the chlorinated effluent because of the relatively low chlorine dose or high ammonia level. In a full-scale DWTP employing a pre-chlorination unit, GBP present in the influent river water was fully transformed into GBP-nitrile. The formed GBP-nitrile was degraded in subsequent ozonation (•OH oxidation) and biological activated carbon filtration (biodegradation) processes. The toxicity of GBP-nitrile is thought to be low but further studies are warranted to assess the toxicological relevance of nitrile formation during water chlorination. Image 1 • Occurrence and transformation of GBP, a pharmaceutical with amine moiety, in waters. • Mean concentrations of 1285 and 304 ng/L in the wastewater effluents and river waters. • Rapid transformation of GBP during water chlorination with t 1/2 of 69–138 s at pH 7–9. • GBP-nitrile as the major product from GBP chlorination with molar yields of 87–100%. • Full conversion of GBP to GBP-nitrile in pre-chlorination step of a full-scale DWTP. [ABSTRACT FROM AUTHOR]

Eliminating pharmaceutical active compounds from source-separated urine is essential for nutrient recovery and reducing the contaminant load to wastewater treatment plants. However, limited oxidation treatment processes have shown satisfactory performance due to strong scavenging effect of urine components. This study proposed a heterogeneous catalytic system by combining biochar with peroxydisulfate (PDS), which effectively removed sulfamethoxazole (SMX) and its major human metabolite, N 4 -acetyl-sulfamethoxazole (NSMX) in urine. The performance of biochar/PDS was investigated in both a complete-mixing reactor and a biochar-packed column. Interestingly, urine components slightly inhibited the degradation of sulfonamides in biochar suspension but significantly improved their removal in biochar-packed column. Further investigation elucidated the PDS activation process and the effects of the main urine components, which explained the different results in biochar suspension and biochar-packed column. The biochar/PDS system mainly produced ·OH radical, singlet oxygen and surface-bound radicals (SBR), which transformed SMX to products of no apprarent antimicrobial properities. A cost-effective two-stage process was designed utilizing SBR as the major reactive species. This study may help to improve the understanding of the catalytic role of biochar and provide cost-effective treatment options for urine. Image 1 • Urine components accelerated the activation of persulfate by biochar. • Sulfonamide competed with persulfate for biochar active sites. • Different mechanisms dominated biochar suspension and biochar-packed column systems. • Antimicrobial effects were eliminated after the treatment by biochar/persulfate. [ABSTRACT FROM AUTHOR]

The pharmaceutical torasemide is an important loop diuretic and was 2017 one of the ten most prescribed drugs in Germany. Despite its detection in different compartments of the urban water cycle including drinking water, no studies were so far performed to elucidate its fate in the environment and the occurrence of transformation products (TPs). Therefore, we investigated the phototransformation, microbial degradation, transformation with human liver microsomes and anodic oxidation of torasemide to obtain good coverage of environmentally relevant degradation products. Overall sixteen products were identified, covering the following reaction mechanisms: aromatic and aliphatic hydroxylation, including further oxidation to carboxylic acids and quinone imines, amide cleavage, N-dealkylation, N-dearylation, and sulfonamide hydrolysis to sulfonic acids. Especially the formation of quinone imines could be of concern as they are highly reactive electrophiles. Torasemide itself was observed in all investigated wastewater treatment plant (WWTP) samples and wastewater-impacted surface waters. The maximum detected concentration was about 350 ng L−1. Only three of the sixteen transformation products were generally observed in at least one of the samples and the most frequently detected TPs were the human metabolites hydroxytorasemide (TP 364a) and carboxytorasemide (TP 378a). The complete removal of TP 364a during wastewater treatment was in agreement with the results of microbial degradation experiments. TP 364a was most likely transformed into TP 378a, which was microbially less degraded in lab experiments. Based on estimated concentrations, TP 378a could reach about 1 μg L−1 in the investigated wastewater matrices. Image 1 • Overall sixteen abiotic and biotic products identified for torasemide. • Formation of reactive products proven with trapping experiments using reduced glutathione. • Torasemide and carboxytorasemide detected in all WWTPs and wastewater-impacted surface waters. [ABSTRACT FROM AUTHOR]