Unmasking Spatial Heterogeneity in Phytotoxicology Mechanisms Induced by Carbamazepine by Mass Spectrometry Imaging and Multiomics Analyses.

Previous studies have highlighted the toxicity of pharmaceuticals and personal care products (PPCPs) in plants, yet understanding their spatial distribution within plant tissues and specific toxic effects remains limited. This study investigates the spatial-specific toxic effects of carbamazepine (CBZ), a prevalent PPCP, in plants. Utilizing desorption electrospray ionization mass spectrometry imaging (DESI-MSI), CBZ and its transformation products were observed predominantly at the leaf edges, with 2.3-fold higher concentrations than inner regions, which was confirmed by LC-MS. Transcriptomic and metabolic analyses revealed significant differences in gene expression and metabolite levels between the inner and outer leaf regions, emphasizing the spatial location's role in CBZ response. Notably, photosynthesis-related genes were markedly downregulated, and photosynthetic efficiency was reduced at leaf edges. Additionally, elevated oxidative stress at leaf edges was indicated by higher antioxidant enzyme activity, cell membrane impairment, and increased free fatty acids. Given the increased oxidative stress at the leaf margins, the study suggests using in situ Raman spectroscopy for early detection of CBZ-induced damage by monitoring reactive oxygen species levels. These findings provide crucial insights into the spatial toxicological mechanisms of CBZ in plants, forming a basis for future spatial toxicology research of PPCPs.

Occurrence and risks of pharmaceuticals, personal care products, and endocrine-disrupting compounds in Chinese surface waters.

The continuous and rapid increase of chemical pollution in surface waters has become a pressing and widely recognized global concern. As emerging contaminants (ECs) in surface waters, pharmaceutical and personal care products (PPCPs), and endocrine-disrupting compounds (EDCs) have attracted considerable attention due to their wide occurrence and potential threat to human health. Therefore, a comprehensive understanding of the occurrence and risks of ECs in Chinese surface waters is urgently required. This study summarizes and assesses the environmental occurrence concentrations and ecological risks of 42 pharmaceuticals, 15 personal care products (PCPs), and 20 EDCs frequently detected in Chinese surface waters. The ECs were primarily detected in China's densely populated and highly industrialized regions. Most detected PPCPs and EDCs had concentrations between ng/L to µg/L, whereas norfloxacin, caffeine, and erythromycin had relatively high contamination levels, even exceeding 2000 ng/L. Risk evaluation based on the risk quotient method revealed that 34 PPCPs and EDCs in Chinese surface waters did not pose a significant risk, whereas 4-nonylphenol, 4-tert-octylphenol, 17α-ethinyl estradiol, 17ß-estradiol, and triclocarban did. This review provides a comprehensive summary of the occurrence and associated hazards of typical PPCPs and EDCs in Chinese surface waters over the past decade, and will aid in the regulation and control of these ECs in Chinese surface waters.

Enhancing membrane separation performance in the conditions of different water electrical conductivity and fouling types via surface grafting modification of a nanofiltration membrane, NF90.

A commercialized and widely applied nanofiltration membrane, NF90, was in-situ modified through a surface grafting modification method by using 3-sulfopropyl methacrylate potassium salt and initiators. The effects of water electrical conductivity (EC) and fouling types on membrane separation efficiency were examined before and after membrane modification. Results reveal that both the pristine membrane (PTM) and surface grafting modification membrane (SGMM) had a declining permeate flux and salt (NaCl) removal efficiency but an increasing trend of pharmaceuticals and personal care products (PPCPs) removal with increasing water EC from 250 to 10,000 µs cm-1. However, SGMM exhibited a slightly declining permeate flux but 13%-17% and 1%-42% higher rejection of salt and PPCPs, respectively, compared with PTM, due to electrostatic repulsion and size exclusion provided by the grafted polymer. After sodium alginate (SA) and humic acid (HA) fouling, SGMM had 17%-26% and 16%-32% higher salt rejection and 1%-12% and 1%-51% greater PPCP removal, respectively, compared with PTM due to the additional steric barrier layer contributed by the foulants. The successful grafting and increasing hydrophilicity of the SGMM were confirmed by contact angle analysis, which was beneficial for mitigating membrane fouling. Overall, the proposed in-situ surface grafting modification of NF90 can considerably mitigate organic and biological fouling while raising the rejection of salt and PPCPs at different background water EC, which is beneficial for practical applications in producing clean and high quality water for consumers.

Removal of pharmaceuticals and personal care products using native fungal enzymes extracted during the ligninolytic process.

Significant concentrations of pharmaceuticals and personal care products (PPCPs) have been detected in aquatic environment. Fungal enzymatic processes can oxidize these persistent PPCPs; thus, these processes have attracted considerable attention from the scientific community. Here, we evaluated the efficacy of the removal of PPCPs using native fungal enzymes derived from Bjerkandera spp. TBB-03 under various conditions. Among the eight lignocellulosic substrates, ash, which showed the highest laccase production, was selected as the sole enzyme inducer. TBB-03 laccase was found to exhibit remarkable stability under varied pH and temperature conditions. Acetaminophen and bisphenol A were effectively removed by TBB-03 laccase under various conditions, except at pH 8. Although TBB-03 laccase could not efficiently remove single-state sulfamethoxazole directly, a 22% of improvement in sulfamethoxazole removal was observed in the presence of acetaminophen. Overall, our proposed approach showed that Bjerkandera adusta TBB-03 can be potentially applied for further research regarding PPCP remediation.

A review of distribution and risk of pharmaceuticals and personal care products in the aquatic environment in China.

Due to the extensive use and pseudo-persistence of pharmaceuticals and personal care products (PPCPs), they are frequently detected in the aqueous environment, which has attracted global attention. In this paper, accumulation data of 81 PPCPs in surface water or sediment in China were reported. In addition, 20 kinds of PPCPs with high frequency were selected and their ecological risk assessment was conducted by risk quotient (RQs). The results indicated that the concentration detected in surface water and sediment ranged from ng/L (ng/kg) to µg/L (µg/kg) in China, which was similar to concentrations reported globally. However, contamination by certain PPCPs, such as caffeine, oxytetracycline, and erythromycin, was relatively high with a maximum concentration of more than 2000 ng/L in surface water. RQs revealed that 14 kinds of PPCPs pose no significant risk or low risk to aquatic organisms, while 6 kinds of PPCPs pose a high risk. Additionally, the pollution characteristics of PPCPs in each watershed are different. The Haihe River watershed and the central and lower Yangtze River were the regions of high concern for erythromycin. Triclosan has potential risks in the Pearl River watershed. This study determined the occurrence and risk of PPCPs in China in the past decade, providing a scientific basis for PPCPs pollution control and risk prevention.

Simultaneous quantification of five pharmaceuticals and personal care products in biosolids and their fate in thermo-alkaline treatment.

The presence of pharmaceuticals and personal care products (PPCPs) in biosolids applied to farmland is of concern due to their potential accumulation in the environment and the subsequent effects on humans. Thermo-alkaline hydrolysis (TAH) is a method used for greater stabilization of biosolids after anaerobic digestion. In this work, the effect of TAH on five selected PPCPs including fluoroquinolone antibiotics, ciprofloxacin (CIP), and ofloxacin (OFLX), and three commonly used antimicrobial agents, miconazole (MIC), triclosan (TCS) and triclocarban (TCC) was evaluated. At the onset, extraction and analytical methods were optimized for maximum simultaneous recovery and LC-MS quantification of the target PPCPs from both water and biosolids for improved accuracy. The compounds were detected in the range of 54 ± 3 to 6166 ± 532 ng/g in raw biosoilds collected from a local WWTP. Next, batch control adsorption experiments of the selected PPCPs were conducted in various sludges, which indicated about 89%-98% sorption of the PPCPs onto solid phase due to their high octanol-water coefficients. Subsequently, thermo-alkaline (pH 9.5, 75 °C, 45 min) hydrolysis (TAH) was conducted to determine the extent of degradation of these compounds in deionized (DI) water and biosolids due to treatment. The degradation of these compounds due to TAH ranged from 42% to 99% and 37%-41% in pure water and biosolids, respectively, potentially lowering their risk in the environment due to land application. A list of compounds for which the optimized analytical method potentially can be used for detection and quantification in environmental samples is provided in the supporting document.

Occurrence and human health risk assessment of pharmaceuticals and personal care products in real agricultural systems with long-term reclaimed wastewater irrigation in Beijing, China.

Reclaimed wastewater (RW) is increasingly used to irrigate agricultural land and to alleviate agricultural water shortages worldwide. This usage has resulted in concerns about soil contamination by pharmaceuticals and personal care products (PPCPs) and the human health risks associated with dietary crop intake. In this study, we systematically analysed the occurrence and accumulation of 11 PPCPs and one active metabolite in soils and various crops (cucumber, eggplant, long bean and wheat) from realistic RW irrigation fields with different irrigation histories (20, 30 and 40 years) in Beijing and evaluated the human health risks associated with the consumption of these crops. The 11 PPCPs and one active metabolite were detected at concentrations ranging from 0.67 to 22.92 ng L-1 in RW, 0.029-28.13 µg kg-1 in irrigated soil, and <0.01-28.01 µg kg-1 in crops. The concentrations of N4-acetyl-sulfamethoxazole and triclosan were higher than those of other PPCPs, with respective concentrations of 14.39-31.44 ng L-1 and 15.93-26.23 ng L-1 in RW, 10.92-23.29 µg kg-1 and 20.22-28.13 µg kg-1 in irrigated soil and 17.92-28.01 µg kg-1 and 8.92-14.91 µg kg-1 in crops. However, the estimated threshold of toxicological concern (TTC) and hazard quotient (HQ) values revealed that the concentrations of N4-acetyl-sulfamethoxazole and triclosan in crops irrigated with RW should be considered a de minimis risk to human health. The concentrations of 11 PPCPs and one active metabolite in soils and crops and the calculated fruit bioconcentration factors (BCFs) did not display obvious increases associated with the duration of RW irrigation in real agricultural systems (P > 0.05). The concentrations of the studied PPCPs in the RW used for irrigation followed different patterns from the concentrations detected in the irrigated soils and crops. Although the concentrations of sulfamethoxazole, sulfisoxazole, sulfamethazine and trimethoprim in RW were higher than those of many other studied PPCPs, their respective values in the irrigated soils and crops did not display a similar tendency. The uptake and accumulation of PPCPs varied among the crop species (P < 0.05). Although PPCPs were detected in eggplant, long bean and wheat (BCFs: not applicable-1.67, 0.03-1.35 and 0.01-5.01, respectively), PPCPs accumulated at increased levels in cucumber (BCFs 0.03-18.98). The estimated TTC and HQ values showed that the consumption of crops irrigated long-term with RW presents a de minimis risk to human health. However, further studies with more PPCPs and additional crop species need to be conducted, the synergistic effects of chemical mixtures of multiple PPCPs and the toxic effects of PPCP metabolites should be elucidated to obtain more reliable information on the safety of wastewater reuse for irrigation.

Recent advances in metal-organic frameworks for adsorption of common aromatic pollutants.

This review (with 85 refs.) summarizes the recent literature on the adsorption of common aromatic pollutants by using modified metal-organic frameworks (MOFs). Four kinds of aromatic pollutants are discussed, namely benzene homologues, polycyclic aromatic hydrocarbons (PAHs), organic dyes and their intermediates, and pharmaceuticals and personal care products (PPCPs). MOFs are shown to be excellent adsorbents that can be employed to both the elimination of pollutants and to their extraction and quantitation. Adsorption mechanisms and interactions between aromatic pollutants and MOFs are discussed. Finally, the actual challenges of existence and the perspective routes towards future improvements in the field are addressed. Graphical abstract Recent advance on adsorption of common aromatic pollutants including benzene series, polycyclic aromatic hydrocarbons, organic dyes and their intermediates, pharmaceuticals and personal care products by metal-organic frameworks.

Occurrence of pharmaceuticals and personal care products, and their associated environmental risks in a large shallow lake in north China.

Eighteen selected pharmaceuticals and personal care products (PPCPs), consisting of five non-antibiotic pharmaceuticals (N-APs), four sulfonamides (SAs), four tetracyclines (TCs), four macrolides (MCs), and one quinolone (QN) were detected in water, pore water, and sediment samples from Baiyangdian Lake, China. A total of 31 water samples and 29 sediment samples were collected in March 2017. Caffeine was detected with 100% frequency in surface water, pore water, and sediment samples. Carbamazepine was detected with 100% frequency in surface water and sediment samples. Five N-APs were prominent, with mean concentrations of 4.90-266.24 ng/l in surface water and 5.07-14.73 µg/kg in sediment samples. Four MCs were prominent, with mean concentrations of 0.97-29.92 ng/l in pore water samples. The total concentrations of the different classes of PPCPs followed the order: N-APs (53.26%) > MCs (25.39) > SAs (10.06%) > TCs (7.64%) > QNs (3.64%) in surface water; N-APs (42.70%) > MCs (25.43%) > TCs (14.69%) > SAs (13.90%) > QNs (3.24%) in sediment samples, and MCs (42.12%) > N-APs (34.80%) > SAs (11.71%) > TCs (7.48%) > QNs (3.88%) in pore water samples. The geographical differences of PPCP concentrations were largely due to anthropogenic activities. Sewage discharged from Baoding City and human activities around Baiyangdian Lake were the main sources of PPCPs in the lake. An environmental risk assessment for the upper quartile concentration was undertaken using calculated risk quotients and indicated a low or medium-high risk from 18 PPCPs in Baiyangdian Lake and its five upstream rivers.

Pharmaceutical products as emerging contaminant in water: relevance for developing nations and identification of critical compounds for Indian environment.

Pharmaceuticals and personal care products (PPCPs) are contaminants of emerging concern and have been detected worldwide in water bodies in trace concentrations. Most of these emerging contaminants are not regulated in water quality standards except a few in the developed countries. In the case of developing countries, research in this direction is at a nascent stage. For the effective management of Pharmaceutical contaminants (PC) in developing countries, the relevance of PCs as an emerging contaminant has to be analyzed followed by regular monitoring of the environment. Considering the resource constraints, this could be accomplished by identifying the priority compounds which is again region specific and dependent on consumption behavior and pattern. In this work, relevance of pharmaceutical compound as emerging contaminant in water for a developing country like India is examined by considering the data pertaining to pharmaceutical consumption data. To identify the critical Pharmaceutical Contaminants to be monitored in the Indian environment, priority compounds from selected prioritization methods were screened with the compounds listed in National List of Essential Medicine (NLEM), India. Further, information on the number of publications on the compound as an emerging contaminant, data on monitoring studies in India and the number of brands marketing the compound in India were also analyzed. It is found that out of 195 compounds from different prioritization techniques, only 77 compounds were found relevant to India based on NLEM sorting.

Offline solid-phase extraction for preconcentration of pharmaceuticals and personal care products in environmental water and their simultaneous determination using the reversed phase high-performance liquid chromatography method.

The present study reports a precise and simple offline solid-phase extraction (SPE) coupled with reversed-phase high-performance liquid chromatography (RP-HPLC) method for the simultaneous determination of five representative and commonly present pharmaceuticals and personal care products (PPCPs), a new class of emerging pollutants in the aquatic environment. The target list of analytes including ciprofloxacin, acetaminophen, caffeine benzophenone and irgasan were separated by a simple HPLC method. The column used was a reversed-phase C18 column, and the mobile phase was 1 % acetic acid and methanol (20:80 v/v) under isocratic conditions, at a flow rate of 1 mL min(-1). The analytes were separated and detected within 15 min using the photodiode array detector (PDA). The linearity of the calibration curves were obtained with correlation coefficients 0.98-0.99.The limit of detection (LOD), limit of quantification (LOQ), precision, accuracy and ruggedness demonstrated the reproducibility, specificity and sensitivity of the developed method. Prior to the analysis, the SPE was performed using a C18 cartridge to preconcentrate the targeted analytes from the environmental water samples. The developed method was applied to evaluate and fingerprint PPCPs in sewage collected from a residential engineering college campus, polluted water bodies such as Nag river and Pili river and the influent and effluent samples from a sewage treatment plant (STP) situated at Nagpur city, in the peak summer season. This method is useful for estimation of pollutants present in microquantities in the surface water bodies and treated sewage as compared to nanolevel pollutants detected by mass spectrometry (MS) detectors.

Tracing residual patterns and microbial communities of pharmaceuticals and personal care products from 17 urban landfills leachate in China.

Landfill leachate contributes significantly to the presence of pharmaceuticals and personal care products (PPCPs) in the environment, and is a crucial source of contamination. To examine the occurrence of PPCPs and microbial communities, this study comprehensively investigated the concentrations of PPCPs and the abundance of microorganisms in the leachate from 17 municipal landfills across China. Generally, Lidocaine, Linear alkylbenzene sulfonate-C11, and Triclocarban, which are closely associated with human activities, exhibited a detection frequency of 100 % in the leachate. Driven by consumer demand, analgesic and antipyretic drugs have emerged as the most prominent PPCPs in leachate (accounting for 39.9 %). Notably, the Ibuprofen peaked at 56.3 µg/L. Regarding spatial distribution, the contamination of PPCPs in leachates from the eastern regions of China was significantly higher than that in other regions, owing to the level of economic development and demographic factors. Furthermore, the 16S rRNA results revealed significant differences in microbial communities among the leachates from different areas. Although the impact of PPCPs on microbial communities may not be as significant as that of environmental factors, most positive correlations between PPCPs and microorganisms indicate their potential role in providing nutrients and creating favorable conditions for microbial growth. Overall, this research offers new perspectives on the residual features of PPCPs and the microbial community structure in leachates from various regions in China.

[Research Progress on Pollution Characteristics, Degradation, and Transformation of Typical PPCPs in the Process of Wastewater Treatment].

Pharmaceuticals and personal care products (PPCPs) have received extensive attention as a new type of pollutant inin the 21st century, and the ecological and health risks caused by PPCPs have gradually been recognized by government regulatory agencies. Daily use of PPCPs has led to their frequent detection and high concentrations in the influent, effluent, and sludge of wastewater treatment plants, but traditional wastewater treatment processes can't remove them effectively. Most research about enhancing the removal of PPCPs through microbial degradation, photodegradation, and ozonation is still in the laboratory research stage, and the removal effects are not satisfactory when applied to actual sewage treatment. Therefore, the effective removal of PPCPs from domestic wastewater is a critical technical problem that urgently needs to be studied and solved in the coming years. At present, many scholars do not have a comprehensive understanding about the degradation and transformation behaviors of microbes, ultraviolet, and ozone for typical PPCPs in the wastewater treatment process, so it is necessary to conduct a systematic analysis and discussion. In this study, 16 typical PPCPs frequently detected in sewage treatment plants were selected as research objects through a literature review. The occurrence, removal characteristics, and sludge adsorption properties of typical PPCPs in wastewater treatment plants were analyzed and summarized. The degradation and transformation behavior of typical PPCPs under microbial, ultraviolet, and ozone treatments in the wastewater treatment process were also discussed. Finally, based on current research gaps, some research directions for the removal and transformation of PPCPs in wastewater were proposed:① investigation into the removal characteristics of PPCPs by actual biochemical treatment; ② study on the mechanism of microbial degradation and transformation of typical PPCPs during biochemical treatment; ③ study on the degradation and transformation mechanism of typical PPCPs by UV/ozone in an actual sewage system; and ④ research on the application technology of removing PPCPs from sewage via microbial degradation, photodegradation, ozone oxidation, etc. The relevant results of this study can provide a reference for the pollution control of typical PPCPs in the sewage treatment process.

Occurrence and Environmental Risk Assessment of Contaminants of Emerging Concern in Brazilian Surface Waters.

We investigated the occurrence and the environmental risk of eight contaminants of emerging concern (CECs; acetaminophen, naproxen, diclofenac, methylparaben, 17ß-estradiol, sulfathiazole, sulfadimethoxine, and sulfamethazine) in three Brazilian water bodies, namely, the Monjolinho River Basin (São Paulo State), the Mogi Guaçu River (São Paulo State), and the Itapecuru River (Maranhão State) in three sampling campaigns. The CECs were only quantified in surface water samples collected at the Monjolinho River Basin. Acetaminophen, naproxen, and methylparaben were detected in the range of <200 to 575.9 ng L-1, <200 to 224.7 ng L-1, and <200 to 303.6 ng L-1, respectively. The detection frequencies of the three measured compounds were between 33% and 67%. The highest concentrations of CECs were associated with intense urbanization and untreated sewage discharge. Furthermore, CEC concentrations were significantly correlated with total organic carbon, electrical conductivity, and dissolved oxygen levels, suggesting that domestic pollution from urban areas is an important source in the distribution of CECs in the Monjolinho River Basin. The environmental risk assessment indicated a high risk for acetaminophen (risk quotient [RQ] values between 2.1 and 5.8), a medium risk for naproxen (RQs between 0.6 and 0.7), and a low risk for methylparaben (RQs < 0.1) to the freshwater biota of the Monjolinho River Basin. Our findings show potential threats of CECs in Brazilian water bodies, especially in vulnerable areas, and reinforce the need for improvements in environmental regulations to include monitoring and control of these compounds in aquatic systems. Environ Toxicol Chem 2024;00:1-12. © 2024 SETAC.

Spatial and Temporal Drug Usage Patterns in Wastewater Correlate with Socioeconomic and Demographic Indicators in Southern Nevada.

Evaluating drug use within populations in the United States poses significant challenges due to various social, ethical, and legal constraints, often impeding the collection of accurate and timely data. Here, we aimed to overcome these barriers by conducting a comprehensive analysis of drug consumption trends and measuring their association with socioeconomic and demographic factors. From May 2022 to April 2023, we analyzed 208 wastewater samples from eight sampling locations across six wastewater treatment plants in Southern Nevada, covering a population of 2.4 million residents with 50 million annual tourists. Using bi-weekly influent wastewater samples, we employed mass spectrometry to detect 39 analytes, including pharmaceuticals and personal care products (PPCPs) and high risk substances (HRS). Our results revealed a significant increase over time in the level of stimulants such as cocaine (pFDR=1.40×10-10) and opioids, particularly norfentanyl (pFDR =1.66×10-12), while PPCPs exhibited seasonal variation such as peak usage of DEET, an active ingredient in insect repellents, during the summer (pFDR =0.05). Wastewater from socioeconomically disadvantaged or rural areas, as determined by Area Deprivation Index (ADI) and Rural-Urban Commuting Area Codes (RUCA) scores, demonstrated distinct overall usage patterns, such as higher usage/concentration of HRS, including cocaine (p=0.05) and norfentanyl (p=1.64×10-5). Our approach offers a near real-time, comprehensive tool to assess drug consumption and personal care product usage at a community level, linking wastewater patterns to socioeconomic and demographic factors. This approach has the potential to significantly enhance public health monitoring strategies in the United States.

[Contamination Characteristics and Ecological Risk Assessment of Pharmaceuticals and Personal Care Products in Drains Flowing into the Yellow River of Ningxia].

Pharmaceuticals and personal care products (PPCPs) are a group of emerging contaminants causing detrimental effects on aquatic living organisms even at low doses. To investigate the contamination characteristics and ecological risks of PPCPs in drains flowing into the Yellow River of Ningxia, 21 PPCPs were detected and analyzed using solid phase extraction and ultra-high performance liquid chromatography-mass spectrometry in this study. All 21 targeted compounds were detected in the drains, with total concentrations ranging from 47.52 to 1 700.96 ng·L-1. Ciprofloxacin, acetaminophen, benzophenone-3, and diethyltoluamide were the more commonly detected compounds, with detection frequencies exceeding 80%. The five highest-concentration PPCPs were acetaminophen, diethyltoluamide, caffeine, benzophenone-3, and levofloxacin, with the maximum concentrations of 597.21, 563.23, 559.00, 477.28, and 473.07 ng·L-1, respectively. Spatial analysis showed that the pollution levels of PPCPs in the drains of the four cities were different, with average concentrations of ∑PPCPs in the order of Yinchuan>Shizuishan>Wuzhong>Zhongwei. The total concentration of PPCPs before flowing into the Yellow River ranged from 124.82 to 1 046.61 ng·L-1. Source analysis showed that livestock and poultry breeding wastewater was the primary source for sulfadiazine and oxytetracycline, whereas medical wastewater was the primary source for levofloxacin and ciprofloxacin. The primary sources of triclocarban and triclosan were domestic sewage and industrial wastewater, whereas the primary source of caffeine and diethyltoluamide was domestic sewage. The pollution of diciofenac, cimetidine, triclocarban, and triclosan in the drains was positively correlated with the regional population and economic development level. The ecological risk assessment indicated that levofloxacin, diclofenac, gemfibrozil, benzophenone-3, and triclocarban posed high risks to aquatic organisms in drains flowing into the Yellow River. It is worthwhile to consider the mixture risk of the PPCPs that exhibited high risk at most sampling sites.

[Determination of 145 pharmaceuticals and personal care products in eleven categories in water by ultra-high performance liquid chromatography-triple quadrupole mass spectrometry].

Pharmaceuticals and personal care products (PPCPs) are emerging contaminants frequently detected in aquatic environments at trace levels. These chemicals have diverse structures and physicochemical properties and includes pharmaceuticals like antibiotics, antihypertensive drugs, antiviral drugs, and psychotropic drugs that are widely used in large quantities worldwide. Considering the large number of pharmaceuticals currently in usage, it is crucial to establish a priority list of PPCPs that should be monitored and/or treated first. An accurate understanding of the occurrence and levels of PPCPs in aquatic environments is essential for providing objective materials for monitoring these emerging contaminants. Therefore, accurate, efficient, sensitive, and high-throughput screening techniques need to be established for determining and quantifying PPCPs. This study developed a method for the determination of 145 PPCPs (grouped into eleven categories: antibiotics, antihypertensive drugs, antidiabetic drugs, antiviral drugs, ß-receptor agonists, nitroimidazoles, H2 receptor antagonists, psychotropic drugs, hypolipidemic drugs, non-steroidal anti-inflammatory drugs, and others) in water. The method was based on large volume direct injection without sample enrichment and cleanup and used ultra-high performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-MS/MS). Water samples were collected and filtered through a 0.22-µm regenerated cellulose (RC) filter membrane. Subsequently, Na2EDTA was added to the samples to adjust their pH to 6.0-8.0. Internal standards were mixed with the solutions, and because of the addition of Na2EDTA, the interference of metal ions could be eliminated in the determination of compounds, especially for tetracycline and quinolone antibiotics. Among the six filter membranes tested in this study (PES, PFTE-Q, PFTE, MCE, GHP, and RC), RC filter membranes were screened for water sample filtration. The UHPLC-MS/MS parameters were optimized by comparing the results of various mobile phases, as well as by establishing the best instrumental conditions. The 145 PPCPs were separated using an Phenomenex Kinetex C18 column (50 mm×3 mm, 2.6 µm) via gradient elution. The mobile phases were 0.1% (v/v) formic acid aqueous solution containing 5 mmol/L ammonium formate and acetonitrile for positive ion modes, 5 mmol/L aqueous solutions of ammonium formate and acetonitrile for negative ion modes. The samples were quantified using the scheduled multiple reaction monitoring (scheduled-MRM) mode with electrospray ionization in positive and negative ion modes. A standard internal calibration procedure was used to calculate contents of sample. The established method was systematically verified, and it demonstrated a good linear relationship. The average recoveries of the 145 PPCPs at the three spiked levels were in the range of 80.4%-128% with relative standard deviations (RSDs, n=6) of 0.6%-15.6%. The method detection limits (MDLs) ranged from 0.015 to 5.515 ng/L. Finally, the optimization method was applied to analyze the 145 PPCPs in 11 surface water samples and 6 drinking water samples. Overall, 93 (64%) out of the 145 analytes were detected. The total contents of the PPCPs in surface water samples ranged from 276.9 to 2705.7 ng/L. The detection frequencies of antidiabetic, antiviral, and psychotropic drugs were 100%. The total contents of the PPCPs in drinking water samples ranged from 140.5 to 211.5 ng/L, and antibiotics, antidiabetic drugs, and antiviral drugs comprised the largest proportion of analytes (by mass concentration) in drinking water samples. Our method exhibited high analytical speed and high sensitivity. It is thus suitable for the trace analysis and determination of the 145 PPCPs in environmental water and showed improved detection efficiency for PPCPs in water, indicating that it has a high potential for practical applications. This study can extend technical support for further pollution-level analysis of PPCPs in water and provide an objective basis for environmental management.

Co-contaminants of ethinylestradiol and sulfamethoxazole in groundwater exacerbate ecotoxicity and ecological risk and compromise the energy budget of C. elegans.

Ethinylestradiol (EE2) and sulfamethoxazole (SMX) are among pharmaceuticals and personal care products (PPCPs) and regarded as emerging contaminants in groundwater worldwide. However, the ecotoxicity and potential risk of these co-contaminants remain unknown. We investigated the effects of early-life long-term co-exposure to EE2 and SMX in groundwater on life-history traits of Caenorhabditis elegans and determined potential ecological risks in groundwater. L1 larvae of wild-type N2 C. elegans were exposed to measured concentrations of EE2 (0.001, 0.75, 5.1, 11.8 mg/L) or SMX (0.001, 1, 10, 100 mg/L) or co-exposed to EE2 (0.75 mg/L, no observed adverse effect level derived from its reproductive toxicity) and SMX (0.001, 1, 10, 100 mg/L) in groundwater. Growth and reproduction were monitored on days 0 - 6 of the exposure period. Toxicological data were analyzed using DEBtox modeling to determine the physiological modes of action (pMoAs) and the predicted no-effect concentrations (PNECs) to estimate ecological risks posed by EE2 and SMX in global groundwater. Early-life EE2 exposure significantly inhibited the growth and reproduction of C. elegans, with lowest observed adverse effect levels (LOAELs) of 11.8 and 5.1 mg/L, respectively. SMX exposure impaired the reproductive capacity of C. elegans (LOAEL = 0.001 mg/L). Co-exposure to EE2 and SMX exacerbated ecotoxicity (LOAELs of 1 mg/L SMX for growth, and 0.001 mg/L SMX for reproduction). DEBtox modeling showed that the pMoAs were increased growth and reproduction costs for EE2 and increased reproduction costs for SMX. The derived PNEC falls within the range of detected environmental levels of EE2 and SMX in groundwater worldwide. The pMoAs for EE2 and SMX combined were increased growth and reproduction costs, resulting in lower energy threshold values than single exposure. Based on global groundwater contamination data and energy threshold values, we calculated risk quotients for EE2 (0.1 - 123.0), SMX (0.2 - 91.3), and combination of EE2 and SMX (0.4 - 341.1). Our findings found that co-contamination by EE2 and SMX exacerbates toxicity and ecological risk to non-target organisms, suggesting that the ecotoxicity and ecological risk of co-contaminants of pharmaceuticals should be considered to sustainably manage groundwater and aquatic ecosystems.

Occurrence and removal rate of typical pharmaceuticals and personal care products (PPCPs) in an urban wastewater treatment plant in Beijing, China.

The occurrence and removal rate of 52 typical pharmaceuticals and personal care products (PPCPs) were investigated in a wastewater treatment plant in Beijing, China. Thirty-three PPCPs were found in the influent, with caffeine (CF, 11387.0 ng L-1) being the most abundant, followed by N,N-diethyl-meta-toluamide (DEET, 9568.4 ng L-1), metoprolol (MTP, 930.2 ng L-1), and diclofenac (DF, 710.3 ng L-1). After treatment processes, the cumulative concentration of PPCPs decreased from 2.54 × 104 ng L-1 to 1.44 × 103 ng L-1, with the overall removal efficiency (RE) of 94.3%. Different treatment processes showed varying contributions in removing PPCPs. PPCPs were efficiently removed in sedimentation, anoxic, and ultraviolet units. For individual compounds, a great variation in RE (52.1-100%) was observed. Twenty-two PPCPs were removed by more than 90%. The highly detected PPCPs in the influent were almost completely removed. Aerated grit chamber removed nearly 50% of fluoroquinolone (FQs) and more than 60% of sulfonamides. Most PPCPs showed low or negative removals during anaerobic treatment, except for CF which was eliminated by 64.9%. Anoxic treatment demonstrated positive removals for most PPCPs, with the exceptions of DF, MTP, bisoprolol, carbamazepine (CBZ), and sibutramine. DEET and bezafibrate were efficiently removed during the secondary sedimentation. Denitrification biological filter and membrane filtration also showed positive effect on most PPCPs removals. The remaining compounds were oxidized by 16-100% in ozonation. DF, sulpiride, ofloxacin (OFL), trimethoprim, and phenolphthalein were not amenable to ultraviolet. After the treatment, the residue OFL, CBZ, and CF in receiving water were identified to pose high risk to aquatic organisms. Considering the complex mixtures emitted into the environment, therapeutic groups psychotropics, stimulant, and FQs were classified as high risk. These findings provide valuable insights into adopting appropriate measures for more efficient PPCPs removals, and emphasize the importance of continued monitoring specific PPCPs and mixtures thereof to safeguard the ecosystem.

Occurrence of contaminants of emerging concern and their risks to the Pantanal Sul-Mato-Grossense aquatic biota, Brazil.

The Aquidauana River is an important ecological corridor in the Pantanal biome. However, the growth of agricultural and urban areas along its banks has contributed to the deterioration of its water quality, consequently putting the aquatic biota at risk. Our objectives were to evaluate: 1) the composition of the landscape around six sampling sites located in the Aquidauana River middle section; and 2) the quality of its water by determining limnological parameters, concentrations of contaminants of emerging concern (CECs), and the risks to native aquatic biota. Water samples were collected in November 2020. We observed the conversion of native riparian vegetation to extensive pasture areas and anthropic occupation around the sampling sites. We observed that the chlorophyll and total ammoniacal nitrogen values were above the standards established by Brazilian legislation in all samples. Studies focused on the quantification of CECs in the Pantanal waters are scarce, and to the best of our knowledge, this is the first study that investigated the presence of pharmaceuticals in the Aquidauana River. All 30 CECs analyzed were detected in at least one water sample. Eleven CECs were quantified with eight pesticides (atrazine, diuron, hexazinone, tebuthiuron, azoxystrobin, carbendazim, tebuconazole, and fipronil) and one atrazine degradation product (atrazine-2-hydroxy), caffeine, and bisphenol A. The concentrations of atrazine herbicide observed in the water samples pose risks for protecting aquatic biota (RQs >1). Therefore, the native biota of the Pantanal biome is vulnerable to several types of toxic contaminants observed in the water, which can cause the disappearance of native and endemic species in this region. Establishing a monitoring program, improving sanitation infrastructure, and intensifying good agricultural practices are essential for reducing and controlling the entry of CECs into the Aquidauana River and the Pantanal water system.