•On-column Cl/Br isotope fractionation of 35 HOPs was explored with GC-DFS-HRMS.•Inverse, normal and unobservable Cl/Br isotope fractionations were found depending on compound.•A modified two-film model was used to elucidate the on-column Cl/Br isotope fractionation.•Solutions were proposed to improve precision and accuracy of CSIA-Cl/Br using GC–MS techniques.Compound-specific chlorine/bromine isotope analysis (CSIA-Cl/Br) has become a powerful approach to investigate degradation pathways and apportion sources of halogenated organic pollutants (HOPs) in the environment. CSIA-Cl/Br is usually conducted by gas chromatography-mass spectrometry (GC–MS), which could be negatively impacted by isotope fractionation on GC columns. In this study, on-column Cl/Br isotope fractionation of 31 organochlorines and 4 organobromines was explored using GC-double focus magnetic-sector high resolution MS (GC-DFS-HRMS). Twenty-nine HOPs exhibited inverse Cl/Br isotope fractionation for which the heavier isotopologues eluted faster than the lighter ones on GC columns, and two polychlorinated biphenyls (PCB-138 and PCB-153) showed normal isotope fractionation, whereas the rest four HOPs did not show observable isotope fractionation. The isotope fractionation extents varied from −13.0‰ to 73.1‰. Mechanisms of the on-column Cl/Br isotope fractionation were tentatively elucidated with a modified two-film model. The results demonstrate that integrating peak area as complete as possible for separable chromatographic peaks and integrating the middle retention-time segments for the inseparable peaks are helpful to improve precision and accuracy of the CSIA-Cl/Br data. The findings of this study will shed light on development of CSIA-Cl/Br methods with respect to improving precision and accuracy.

•A quasi-targeted analysis method was developed for metabolite identification of OH-PAHs.•LC–QqQMS/MS, LC–QTOF-MS and LC–Q-Orbitrap-MS were used for quasi-targeted analysis.•Nineteen hydroxylation-related metabolites of PAHs in human urine were identified.•Metabolic pathways of PAHs in human body were proposed using naphthalene as an example.Metabolite identification is crucial for revealing metabolic pathways and comprehensive potential toxicities of polycyclic aromatic hydrocarbons (PAHs) in human body. In this work, a quasi-targeted analysis strategy was proposed for metabolite identification of monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in human urine using liquid chromatography triple quadruple mass spectrometry (LC–QqQ-MS/MS) combined with liquid chromatography high resolution mass spectrometry (LC–HRMS). Potential metabolites of OH-PAHs were preliminarily screened out by LC–QqQ-MS/MS in association with filtering in a self-constructed information list of possible metabolites, followed by further identification and confirmation with LC–HRMS. The developed method can provide more reliable and systematic results compared with traditional untargeted analysis using LC–HRMS. In addition, data processing for LC–HRMS analysis were greatly simplified. This quasi-targeted analysis method was successfully applied to identifying phase I and phase II metabolites of OH-PAHs in human urine. Five metabolites of hydroxynaphthalene, seven of hydroxyfluorene, four of hydroxyphenanthrene, and three of hydroxypyrene were tentatively identified. Metabolic pathways of PAHs in human body were putatively revealed based on the identified metabolites. The experimental results will be valuable for investigating the metabolic processes of PAHs in human body, and the quasi-targeted analysis strategy can be expanded to the metabolite identification and profiling of other compounds in vivo.

•Multi-target determination of organic UV absorbents in complex organism tissues.•Good sensitivity and accuracy.•Report occurrence of the UV absorbents in wild and farmed marine organisms in China.A sensitive and reliable method was developed for multi-target determination of 13 most widely used organic ultraviolet (UV) absorbents (including UV filters and UV stabilizers) in aquatic organism tissues. The organic UV absorbents were extracted using ultrasonic-assisted extraction, purified via gel permeation chromatography coupled with silica gel column chromatography, and determined by ultra-high performance liquid chromatography–tandem mass spectrometry. Recoveries of the UV absorbents from organism tissues mostly ranged from 70% to 120% from fish filet with satisfactory reproducibility. Method quantification limits were 0.003–1.0 ng g−1 dry weight (dw) except for 2-ethylhexyl 4-methoxycinnamate. This method has been applied to analysis of the UV absorbents in wild and farmed aquatic organisms collected from the Pearl River Estuary, South China. 2-Hydroxy-4-methoxybenzophenone and UV-P were frequently detected in both wild and farmed marine organisms at low ng g−1 dw. 3-(4-Methylbenzylidene)camphor and most of the benzotriazole UV stabilizers were also frequently detected in maricultured fish. Octocrylene and 2-ethylhexyl 4-methoxycinnamate were not detected in any sample. This work lays basis for in-depth study about bioaccumulation and biomagnification of the UV absorbents in marine environment.

•PFOA and PFOS were analyzed in cooking oil and pig adipose tissue.•A rapid and simple one-step reversed-phase liquid–liquid extraction was used for pretreatment.•LC–MS/MS method was developed and validated for the analysis of PFOA and PFOS.•The partition theory of PFOA and PFOS in extraction solution systems was discussed.•This method has been successfully applied to the analysis of PFOA and PFOS in real samples.Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are two perfluorinated compounds (PFCs) ubiquitously present in the environment, which could pose potential adverse effects on human health. Contamination and presence of PFOA and PFOS should be eliminated or rigidly restricted in food stuffs such as cooking oils and lard (from pig adipose tissue). This work describes a rapid, simple, reliable and sensitive method for quantitative analysis of PFOA and PFOS in cooking oils and pig adipose tissue with liquid chromatography tandem mass spectrometry (LC–MS/MS). The pretreatment mainly included a one-step reversed-phase liquid–liquid extraction using the mixture of basified water/methanol as the aqueous system, and dichloromethane (DCM) as the non-polar system. PFOA and PFOS can be successfully separated from the two lipid-rich matrices, i.e., cooking oil and adipose tissue, and extracted into the aqueous system, and then directly analyzed with LC–MS/MS. This method was validated in terms of accuracy (both intra- and inter-batch), precision, recovery, linearity, sensitivity and applicability. The intra-batch accuracies for PFOA and PFOS in cooking oil samples were within 93.9–101.9% with relative standard deviation (RSD) no more than 10.9%, and the inter-batch accuracies were 91.2–96.2% with RSD not exceeding 10.0%. The intra-batch accuracies of the analytes in pig adipose tissue samples were 102.9–113.0% with RSD of 8.8–13.1%. And the quantification ranges of PFOA and PFOS were 0.01–25 ng/mL. This method has been applied to the analysis of PFOA and PFOS in real samples collected from local markets in Guangzhou, China.

Stereoisomeric compositions can provide insights into sources, fate, and ecological risks of contaminants in the environment. In this study, stereoisomeric profiles of ibuprofen and iopromide were investigated in wastewater and receiving surface water of the Pearl River Delta, south China. The enantiomeric fraction (EF) of ibuprofen was 0.108–0.188 and 0.480, whereas the isomer ratio (IR) of iopromide was 1.426–1.673 and 1.737–1.898 in the influent and final effluent, respectively, suggesting stereoselective degradation occurred for both pharmaceuticals during wastewater treatment. Ibuprofen showed enantioselective degradation in the anaerobic, anoxic, and aerobic conditions, whereas iopromide displayed isomer-selective degradation only under the aerobic condition. In the river waters, the EF of ibuprofen was 0.130–0.327 and the IR of iopromide was 1.500–2.531. The results suggested that pharmaceuticals in the mainstream Pearl River were mainly from discharge of treated wastewater, whereas in the tributary rivers and urban canals, direct discharge of untreated wastewater represented a significant contribution. The IR of iopromide can be an applicable and efficient tracer for wastewater discharge in the environment.

A specific polyclonal anti-norfloxacin antibody was obtained, and a sensitive indirect competitive enzyme-linked immunosorbent assay (icELISA) was developed for determining trace amounts of norfloxacin in various waters. Good linearity was achieved in the range from 0.1 to 10 μg L−1. The average IC50 value was determined to be 2.2 μg L−1 and the limit of detection was 0.016 μg L−1 at a signal-to-noise ratio of 3 in phosphate-buffered saline buffer. Recoveries of norfloxacin at various spiking levels ranged from 74 to 105% in groundwater, surface water, treated and untreated wastewater samples, with relative standard deviations of 3–5%. The assay was applied for determining norfloxacin in municipal wastewater, surface water, and groundwater collected in a metropolis of China. Raw wastewater samples were only submitted to filtration and pH adjustment while the other water samples were pre-concentrated by solid phase extraction prior to the icELISA assay. Good agreement of the results obtained by the icELISA and liquid chromatography tandem mass spectrometry further confirmed the reliability and accuracy of the icELISA for rapid detection of norfloxacin in waters.

Occurrence, behavior and fate of several groups of antibacterials were investigated in municipal wastewater, sewage sludge, and urban river water in China. Fluoroquinolones (e.g., ciprofloxacin, norfloxacin, and ofloxacin), macrolides (dehydroerythromycin, roxithromycin, and clarithromycin), sulfonamides (sulfamethoxazole and sulfamethazine) and trimethoprim were ubiquitously detected in the wastewater in China. Fluoroquinolones were generally the most abundant in the raw sewage, with a maximum concentration of up to 6415 ng L−1 observed for norfloxacin. Sulfonamides and macrolides transported predominantly in the aqueous phase. A median percentage of 67% of sulfonamides and 86% of macrolides remained in the final effluent after treatment in sewage treatment plants. On the contrary, sorption played a significant role in transport of fluoroquinolones and approximately half of the fluoroquinolones finally ended up and persisted in the dewatered sludge. In the urban section of the Pearl River at Guangzhou, sulfonamides, trimethoprim, and macrolides were widely present at median concentrations of 22–735 ng L−1, whereas fluoroquinolones were only occasionally detected at 2–152 ng L−1, probably due to their strong tendency of partition to sediment and/or photodegradability. The result of principal components analysis suggests input of non-sewage derived sulfamethazine in the Pearl River. Seasonal variations of the antibacterials distribution in the wastewater are mainly ascribed to different consumption. Dilution effect by precipitation, however, also plays an important role in seasonal distribution of the antibacterials in the Pearl River.

The occurrence and behavior of β-blockers, antiepileptic drug carbamazepine and its metabolites, X-ray contrast agent iopromide, natural and synthetic hormones, and several groups of hormone-like personal care products (PCPs), including antiseptics (triclocarban, triclosan, and 2-phenylphenol), parabens and bisphenol A, were investigated in municipal wastewater, sewage sludge, and urban river water of the Pearl River Delta, South China. The pharmaceuticals, natural hormones and PCPs were ubiquitously detected in the raw wastewater from a sewage treatment plant (STP). Only triclocarban and triclosan were detected at significant amounts in the dewatered sludge. Iopromide and the PCPs were greatly removed/transformed from the aqueous phase of the wastewater. The β-blockers were only moderately removed/transformed. Carbamazepine passed through the STP almost unchanged. Biodegradation was the dominant process for elimination/transformation of the pharmaceuticals, hormones, and most PCPs in the STP. However, sorption also played an important role in the fate of triclocarban with nearly 50% of the mass load entering the STP ended up and persisted in the dewatered sludge. The pharmaceuticals, estrone, and PCPs were also widely detected in the Pearl River at Guangzhou. Bisphenol A had the highest concentration. The pharmaceutical concentrations in the Pearl River were higher in March than in May, most likely due to less dilution by lower precipitation. The omnipresence and high levels of the pharmaceuticals and PCPs in the Pearl River may be associated with direct discharge of untreated wastewater and pose potential risks to the ecological system.

Sensitive and reliable methods have been developed and validated for determination of commonly consumed azole antifungal pharmaceuticals (clotrimazole, econazole, ketoconazole, and miconazole) and biocides (propiconazole and tebuconazole) in various waters and sewage sludge. Solid phase extraction (SPE) combined with ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) was used to determine the azole antifungals in waters. Azole antifungals in sewage sludge were extracted with ultrasonic-assisted extraction, followed by SPE cleanup and UHPLC–MS/MS detection. Quantification was performed by internal standard calibration in multiple reaction monitoring mode. Recoveries were mostly in the range of 52–110% with relative standard deviations generally within 20%. Method quantification limits were 0.5–6 ng L−1 in waters and 3–9 ng g−1 dry weight (dw) in sewage sludge, respectively. The methods were applied to determine the azole antifungals in wastewater, river water, sediment, and sewage sludge sampled from the Pearl River Delta, China. Clotrimazole, ketoconazole, and miconazole were widely detected at low ng L−1 in waters, low ng g−1 dw in river sediment, and low μg g−1 dw in sewage sludge. The methods can provide valuable tools for investigating occurrence and fate of the azole antifungals in the environment.

A sensitive and feasible method was developed for the simultaneous determination of 10 trace antibiotic residues including sulfonamides, macrolides, trimethoprim, and chloramphenicol in sewage sludge and sediment. The method involved ultrasonic extraction followed by solid phase extraction cleanup and liquid chromatography-tandem mass spectrometry coupled with electrospray ionization in positive mode. The antibiotics were identified and determined by internal standard method in selected multiple reaction monitoring mode. The detection limits were in a range of 2.2–66.9 ng g−1 dry weight for the investigated antibiotic compounds in sewage sludge. The recoveries ranged from 74.7% to 111.8% with relative standard deviations of 1.2%–10.6%. The method was successfully applied to a primary investigation of the occurrence of antibiotic residues in a sewage sludge sample and a river sediment sample collected from Guangzhou. Sulfamethazine, trimethoprim, azithromycin, clarithromycin, dehydrated erythromycin, and roxithromycin were detected in both the sewage sludge and the river sediment, ranging from 6.8–125.6 ng g−1 dry weight.

A simple and effective method has been developed to simultaneously determine endocrine-disrupting phenolic xenoestrogens and steroid estrogens in sediment by using ultra-sonicated extraction in combination with silica gel fractionation, derivatization with pentafluropropionic anhydride, and gas chromatography–mass spectrometry (GC–MS) in selected ion monitoring mode (SIM). Satisfactory recoveries have been obtained for phenolic xenoestrogens and steroid estrogens. The method enables the determination of targets at concentrations of lower nanogram-per-gram in sediments. The method has been successfully applied to the sediments collected from Pearl River Estuary (PRE), South China Sea, China. Nonylphenol and bisphenol-A (BPA) were detected in the range from 204.2 to 664.5 ng/g and 0.6 to 4.0 ng/g, respectively. None of the estrogens were found in the sediment samples.

•Organic ultraviolet absorbents (UVAs) could bio-accumulate.•Bio-accumulation of the UVAs was species- and compound-specific.•Dietary habits of the organisms impact on bioaccumulation of the UVAs.•Direct uptake from growth media was a significant exposure pathway to the UVAs for organisms.•Some UVAs have biomagnifying potential in marine food web.Bioaccumulation and trophic transfer in ecosystems is an important criterion for assessing environmental risks of contaminants. This study investigated bioaccumulation and biomagnification of 13 organic ultraviolet absorbents (UVAs) in marine wildlife organisms in the Pearl River Estuary, South China Sea. The UVAs could accumulate in the organisms with biota - sediment accumulation factors (BSAF) of 0.003–2.152. UV531 was the most abundant and showed the highest tendency to accumulate in the organisms with a median BSAF of 1.105. The UVAs demonstrated species - and compound-specific accumulation in the marine organism. Fishes showed significantly higher capability than the cephalopods and crustaceans in accumulation of the UVAs. Habitat did not demonstrate obvious impact on accumulation of the UVA. On the other hand, benzophenone-3, UV328, and UV234 showed significantly higher concentration in the detritus feeding fishes than carnivorous and planktivorous fishes, suggesting governing effect of dietary habits of the organisms on bioaccumulation of these UVAs. Direct uptake from growth media was a significant exposure pathway of the organisms to the UVAs. The estimated trophic magnification factors and biomagnification factors revealed that UV329, UV531, and octocrylene could potentially biomagnify in the marine food web.Download high-res image (147KB)Download full-size image

Occurrence, behavior and fate of several groups of antibacterials were investigated in municipal wastewater, sewage sludge, and urban river water in China. Fluoroquinolones (e.g., ciprofloxacin, norfloxacin, and ofloxacin), macrolides (dehydroerythromycin, roxithromycin, and clarithromycin), sulfonamides (sulfamethoxazole and sulfamethazine) and trimethoprim were ubiquitously detected in the wastewater in China. Fluoroquinolones were generally the most abundant in the raw sewage, with a maximum concentration of up to 6415 ng L−1 observed for norfloxacin. Sulfonamides and macrolides transported predominantly in the aqueous phase. A median percentage of 67% of sulfonamides and 86% of macrolides remained in the final effluent after treatment in sewage treatment plants. On the contrary, sorption played a significant role in transport of fluoroquinolones and approximately half of the fluoroquinolones finally ended up and persisted in the dewatered sludge. In the urban section of the Pearl River at Guangzhou, sulfonamides, trimethoprim, and macrolides were widely present at median concentrations of 22–735 ng L−1, whereas fluoroquinolones were only occasionally detected at 2–152 ng L−1, probably due to their strong tendency of partition to sediment and/or photodegradability. The result of principal components analysis suggests input of non-sewage derived sulfamethazine in the Pearl River. Seasonal variations of the antibacterials distribution in the wastewater are mainly ascribed to different consumption. Dilution effect by precipitation, however, also plays an important role in seasonal distribution of the antibacterials in the Pearl River.

The occurrence and behavior of β-blockers, antiepileptic drug carbamazepine and its metabolites, X-ray contrast agent iopromide, natural and synthetic hormones, and several groups of hormone-like personal care products (PCPs), including antiseptics (triclocarban, triclosan, and 2-phenylphenol), parabens and bisphenol A, were investigated in municipal wastewater, sewage sludge, and urban river water of the Pearl River Delta, South China. The pharmaceuticals, natural hormones and PCPs were ubiquitously detected in the raw wastewater from a sewage treatment plant (STP). Only triclocarban and triclosan were detected at significant amounts in the dewatered sludge. Iopromide and the PCPs were greatly removed/transformed from the aqueous phase of the wastewater. The β-blockers were only moderately removed/transformed. Carbamazepine passed through the STP almost unchanged. Biodegradation was the dominant process for elimination/transformation of the pharmaceuticals, hormones, and most PCPs in the STP. However, sorption also played an important role in the fate of triclocarban with nearly 50% of the mass load entering the STP ended up and persisted in the dewatered sludge. The pharmaceuticals, estrone, and PCPs were also widely detected in the Pearl River at Guangzhou. Bisphenol A had the highest concentration. The pharmaceutical concentrations in the Pearl River were higher in March than in May, most likely due to less dilution by lower precipitation. The omnipresence and high levels of the pharmaceuticals and PCPs in the Pearl River may be associated with direct discharge of untreated wastewater and pose potential risks to the ecological system.