Nontarget and Comprehensive Analyses of Halogenated Organic Additives in Electrical Product Plastics by GC-NCI-Q-Orbitrap-HRMS and Cl/Br-Screening Algorithms.

Halogenated organic additives (HOAs) are used in plastic components of various electrical products, potentially causing detrimental effects on the eco-environment and humans. Besides reported HOAs, many unknown HOAs may be present in electrical product plastics and urgently require identification and characterization. This study performed nontarget analysis and comprehensive characterization of HOAs in three typical electrical product plastics by nontarget analysis using gas chromatography-negative chemical ionization-high-resolution mass spectrometry in association with in-house-developed chlorine/bromine-specific data-processing algorithms. A total of 674 formulas of HOAs were identified in the plastics dismantled from three electrical products, among which 166, 362, and 146 were organochlorines, organobromines, and mix-chlorinated/brominated organic compounds, respectively. The identified HOAs were semiquantified, and the total concentrations of HOAs in individual plastics were 445-1549 ng/g. Organobromines showed the most species and the highest abundances in all of the plastics, of which the abundances accounted for 86.6-98.0% of the total HOAs. Partial HOAs (209 formulas) were tentatively structurally elucidated, which were classified into 13 groups, i.e., halogenated alkyl phenoxyethyls (H-alkyl phenoxyethyls), H-alkylbenzenes, H-benzenes, H-bisphenol A (H-BPAs), H-dioxins, H-diphenyl ethers, H-biphenyls/terphenyls, H-polycyclic aromatic hydrocarbons, H-phenols, H-phenyl esters, H-phenyl-aldehydes/ketones, H-quinones, and an undefined group containing the HOAs such as dechlorane plus and chlordane. H-BPAs were the predominant HOAs in the plastics, showing relatively high concentrations (13-281 ng/g), and tetrabromobisphenol A was the most abundant H-BPA, with the concentrations of 9-196 ng/g. The comprehensive characterization results represent a holistic picture on the species features and abundance distributions of HOAs in electrical product plastics and provide an inventory of crucial HOAs worthy of concern. HOAs may migrate from plastics and release into the environment and are possibly an important source of halogenated organic pollutants in the environment, thus calling for further investigation and proper regulation.

First Discovery of Iodinated Polyfluoroalkyl Acids by Nontarget Mass-Spectrometric Analysis and Iodine-Specific Screening Algorithm.

Per- and polyfluoroalkyl acids (PFAAs) including polyfluoroalkyl carboxylic acids and polyfluoroalkyl sulfonic acids are a large category of crucial environmental pollutants of global concern. Besides known PFAAs, numerous unknown species may exist in the environment, urgently needing discovery and characterization. This study implemented nontarget analysis for a group of novel PFAA pollutants, viz., iodinated PFAAs (I-PFAAs) in wastewater from a fluorochemical manufacturing park by liquid chromatography-high-resolution mass spectrometry in combination with an iodine-specific data-processing algorithm. The algorithm took into account the diagnostic fragment iodine ion (I-) together with carbon and sulfur isotopologue distributions. In total, 18 I-PFAA formulas involving 21 congeners were identified. Semiquantification was conducted, and the total concentrations of I-PFAAs were 1.9-274.7 µg/L, indicating severe pollution of I-PFAAs in the wastewater. The determined concentrations along with predicted environmental behaviors and toxicities demonstrate that I-PFAAs merit further in-depth investigation. The analytical method including the instrumental analysis and data-processing algorithm can be extended to screening and identification of I-PFAAs in other matrices. Furthermore, the analysis results for the first time provide recognition on the occurrence, distribution features, and pollution status of I-PFAAs in the environment.

Nontarget Analysis and Comprehensive Characterization of Iodinated Polyfluoroalkyl Acids in Wastewater and River Water by LC-HRMS with Cascade Precursor-Ion Exclusions and Algorithmic Approach.

Poly- and perfluoroalkyl acids (PFAAs) are a large family of widespread contaminants of worldwide concern and well-known as "forever chemicals". Direct emission of PFAAs from the fluorochemical industry is a crucial source of PFAA pollutants in the environment. This study implemented nontarget analysis and comprehensive characterization for a category of new PFAA contaminants, i.e., iodinated PFAAs (IPFAAs), in fluorochemical industry wastewater and relevant contaminated river water by liquid chromatography-high-resolution mass spectrometry with a cascade precursor ion exclusion (PIE) strategy and in-house developed data extraction and processing algorithms. A total of 26 IPFAAs (including 2 isomers of an IPFAA) were found and identified with tentative molecular structures. Semiquantification of the IPFAAs was implemented, and the total concentrations of IPFAAs were 0.16-285.52 and 0.15-0.17 µg/L in wastewater and river water, respectively. The high concentrations in association with the predicted ecotoxicities and environmental behaviors demonstrate that these IPFAAs are worthy of more concern and further in-depth research. The cascade PIE strategy along with the data extraction and processing algorithms can be extended to nontarget analysis for other pollutants beyond IPFAAs. The nontarget identification and characterization outcomes provide new understanding on the environmental occurrence and pollution status of IPFAAs from a comprehensive perspective.

Characterization of Compound-Specific Chlorine Isotopologue Distributions of Polychlorinated Organic Compounds by GC-HRMS for Source Identification.

Distributions of chlorine isotopologues are potentially a fingerprint feature of organochlorines. However, the exact distributions remain little known. This study measured compound-specific chlorine isotopologue distributions of six polychlorinated organic compounds (POCs) for source identification. Complete chlorine isotopologues of POCs were detected by gas chromatography coupled to high-resolution mass spectrometry. The measured relative abundances (Ameas), theoretical relative abundances (Atheo), and relative variations between Ameas and Atheo (ΔA) of chlorine isotopologues were determined. These ΔA values were applied to characterize differences in isotopologue distribution patterns, and the ΔA patterns directly illustrated the distribution characteristics. Perchloroethylene (PCE) and trichloroethylene (TCE) from two manufacturers were chosen as model analytes to develop and validate the analytical method, including precision, concentration dependency, and temporal drift. The ΔA values of isotopologues of the PCE and TCE chemicals were from -82.5 to 19.9‰ with standard deviations (SDs) of 0.3-16.9‰. In addition, the ΔA values of the first three isotopologues (with 0-2 37Cl atoms) were from -15.5 to 19.9‰ with SDs of 0.3-1.6‰, showing sufficient precisions. No concentration dependency and temporal drift of ΔA were observed. The method has been successfully applied to source identification for PCE and TCE in commercial chemicals and plastic materials, and four polychlorinated biphenyls in chemicals and sediments, demonstrating that the ΔA values and ΔA patterns were discernable for POCs from different sources. This study demonstrates that compound-specific chlorine isotopologue distributions of POCs are differentiable and measurable, proposing a novel approach to perform fingerprinting analysis for the distributions, which is anticipated to facilitate source identification for organochlorine pollutants.

Defect Engineering on a Ti4O7 Electrode by Ce3+ Doping for the Efficient Electrooxidation of Perfluorooctanesulfonate.

Defect engineering in an electrocatalyst, such as doping, has the potential to significantly enhance its catalytic activity and stability. Herein, we report the use of a defect engineering strategy to enhance the electrochemical reactivity of Ti4O7 through Ce3+ doping (1-3 at. %), resulting in the significantly accelerated interfacial charge transfer and yielding a 37-129% increase in the anodic production of the hydroxyl radical (OH•). The Ce3+-doped Ti4O7 electrodes, [(Ti1-xCex)4O7], also exhibited a more stable electrocatalytic activity than the pristine Ti4O7 electrode so as to facilitate the long-term operation. Furthermore, (Ti1-xCex)4O7 electrodes were also shown to effectively mineralize perfluorooctanesulfonate (PFOS) in electrooxidation processes in both a trace-concentration river water sample and a simulated preconcentration waste stream sample. A 3 at. % dopant amount of Ce3+ resulted in a PFOS oxidation rate 2.4× greater than that of the pristine Ti4O7 electrode. X-ray photoelectron spectroscopy results suggest that Ce3+ doping created surficial oxygen vacancies that may be responsible for the enhanced electrochemical reactivity and stability of the (Ti1-xCex)4O7 electrodes. Results of this study provide insights into the defect engineering strategy for boosting the electrochemical performance of the Ti4O7 electrode with a robust reactivity and stability.

Two new oxygen-containing biomarkers isolated from the Chinese Maoming oil shale by silica gel column chromatography and preparative gas chromatography.

Two biomarkers, 5,9-dimethyl-6-isopropyl-2-decanone (1) and 4,9,11-trimethyl-6-isopropyl-2-dodecanone (2), were isolated from Chinese Maoming oil shale by silica gel column chromatography and preparative gas chromatography. Their structures were elucidated by using spectroscopic techniques.

Observation and confirmation of oxidation reactions occurring on ultra-high-performance liquid chromatography columns.

RATIONALE: Ultra-high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (UPLC/ESI-MS) has been frequently used for chemical analysis. A redox reaction in the ESI source has been observed during the ionization process. However, it is still unclear whether this redox reaction can take place on UPLC columns. METHODS: In this study, the oxidation reactions potentially occurring on UPLC columns were investigated using polyphenols including baicalin, baicalein, propyl gallate (PG), quercetin-3-rhamnoside (QR), rutin, naringin and 2,3,5,4'-tetrahydroxystilbene-2-Ο-ß-D-glucoside (THS-G) as model compounds. The on-column oxidation reaction was ascertained by post-column infusion of antioxidants such as ammonium sulfide ((NH4)2S). The oxidized products were reduced to their parent forms in the ESI source. This on-column oxidation reaction was further confirmed by means of post-column infusion of baicalin solution. RESULTS: On-column oxidation reactions were observed and confirmed for baicalin, baicalein, PG, rutin, and QR. The exact reaction site was located at the outlet frits of the UPLC columns. (NH4)2S was proved to be the most suitable reducing agent among the tested antioxidants for eliminating negative effects caused by on-column oxidation reaction. It was subsequently proposed to be an efficient additive to suppress oxidation reactions in the ESI source. CONCLUSIONS: Oxidation reactions can take place at the outlet frits of UPLC columns. Ascertaining on-column oxidation reactions and consequently eliminating relevant negative effects are of great interest for determination of oxidation-sensitive compounds such as polyphenols.

Comprehensive characterization and prioritization of halogenated organic compounds in fish and their implications for exposure.

Fish are an important pollution indicator for biomonitoring of halogenated organic compounds (HOCs) in aquatic environments, and HOCs in fish may pose health threats to consumers. This study performed nontarget and comprehensive analyses of HOCs in fish from an e-waste recycling zone by gas chromatography-high-resolution mass spectrometry, and further prioritized their human exposure risks. A total of 1652 formulas of HOCs were found in the fish, of which 1222, 117, and 313 were organochlorines, organobromines, and organochlorine-bromines, respectively. The total concentrations of HOCs were 15.4-18.7 µg/g (wet weight), and organobromines were the predominant (14.1-16.8 µg/g). Of the HOCs, 41 % were elucidated with tentative structures and divided into 13 groups. The estimated total daily exposures of HOCs via dietary consumption of the fish for local adult residents were 3082-3744 ng/kg bw/day. The total exposures were dominated by several groups of HOCs with the following contribution order: polyhalogenated biphenyls and their derivatives > polyhalogenated diphenyl ethers > halo- (H-)alkanes/olefines > H-benzenes > H-dioxins > H-polycyclic aromatic hydrocarbons > H-phenols. The comprehensive characterization and prioritization results provide an overview of the species and distributions of HOCs in edible fish, and propose an inventory of crucial HOCs associated with high exposure risks.

Effects of polymer matrix and temperature on pyrolysis of tetrabromobisphenol A: Product profiles and transformation pathways.

Plastics are crucial constituents in electronic waste (e-waste) and part of the issue in e-waste recycling and environmental protection. However, previous studies have mostly focused on plastic recovery or thermal behavior of flame retardants, but not both simultaneously. The present study simulated the process of e-waste thermal treatment to explore tetrabromobisphenol A (TBBPA) pyrolysis at various temperatures using polystyrene (PS), polyvinyl chloride (PVC), and e-waste plastics as polymer matrices. Pyrolysis of TBBPA produced bromophenol, bromoacetophenone, bromobenzaldehyde, and bromobisphenol A. Co-pyrolysis with the polymer matrices increased emission factors by 1 - 2 orders of magnitude. The pyrolytic products of TBBPA, TBBPA+PS, and TBBPA+PVC were mainly low-brominated bisphenol A, while that of TBBPA in e-waste plastics was consistently bromophenol. Increasing temperature drove up the proportions of gaseous and particulate products, but lowered the relative abundances of inner wall adsorbed and residual products in pyrolysis of pure TBBPA. In co-pyrolysis of TBBPA with polymer matrix, the proportions of products in different phases were no longer governed solely by temperature, but also by polymer matrix. Co-pyrolysis of TBBPA with PS generated various bromophenols, while that with PVC produced chlorophenols and chlorobrominated bisphenol A. Transformation pathways, deduced by ab initio calculations, include hydrogenation-debromination, isopropylphenyl bond cleavage, oxidation, and chlorination.

Strategies for ascertaining the interference of phase II metabolites co-eluting with parent compounds using LC-MS/MS.

LC-MS/MS is currently the most selective and efficient tool for the quantitative analysis of drugs and metabolites in the pharmaceutical industry and in clinical assays. However, phase II metabolites sometimes negatively affect the selectivity and efficiency of the LC-MS/MS method, especially for the metabolites that possess similar physicochemical characteristics and generate the same precursor ions as their parent compounds due to the in-source collision-induced dissociation during the ionization process. This paper proposes some strategies for examining co-eluting metabolites existing in real samples, and further assuring whether these metabolites could affect the selectivity and accuracy of the analytical methods. Strategies using precursor-ion scans and product-ion scans were applied in this study. An example drug, namely, caffeic acid phenethyl ester, which can generate many endogenous phase II metabolites, was selected to conduct this work. These metabolites, generated during the in vivo metabolic processes, can be in-source-dissociated to the precursor ions of their parent compounds. If these metabolites are not separated from their parent compounds, the quantification of the target analytes (parent compounds) would be influenced. Some metabolites were eluted closely to caffeic acid phenethyl ester on LC columns, although long columns and relatively long elution programs were used. The strategies can be utilized in quantitative methodologies that apply LC-MS/MS to assure the performance of selectivity, thus enhancing the reliability of the experimental data.

Multi-residue determination of bisphenol analogues in organism tissues by ultra-high performance liquid chromatography-tandem mass spectrometry.

A reliable and sensitive analyzing method was developed and validated for determination of 13 novel bisphenol analogues (BPs) along with bisphenol A (BPA) in organism tissues. The complex organism tissues were treated by ultrasonic-assisted extraction using acetonitrile/formic acid (99:1, v/v), followed by successive purification using enhanced matrix removal-lipid sorbents and primary secondary amine sorbents. The BPs were finally determined by ultra-high performance liquid chromatography-tandem mass spectrometry after derivatization using pyridine-3-sulfonyl chloride. Satisfactory recoveries of 75 - 118% were obtained for the BPs, with good repeatability (RSD < 20%). Matrix interferences were efficiently diminished. The method quantification limits (MQLs) reached 0.003 - 0.1 ng g-1 dry weight (dw). The validated method was successfully applied to a preliminary investigation of the BPs in wild marine organisms collected from the nearshore waters along the coast of Guangdong, China. Besides BPA, novel BPs such as bisphenol F, bisphenol AF, and tetrabromobisphenol A were also detected at < MDL - 15.5 ng g-1 dw. This work laid a strong basis for further in-depth research on bioaccumulation of the novel BPs in the environment.

Nontarget analysis and characterization of alkylamides in electrical product plastics by gas chromatography-positive chemical ionization quadrupole-orbitrap high-resolution mass spectrometry and quasi-molecular ion screening and anchoring algorithm.

Alkylamides are used as plastic additives in various materials and products, potentially posing risks to human health and the environment. Besides reported alkylamides in plastics, many unknown alkylamides may exist in various plastics, which are needing identification and characterization. This study performed nontarget analysis of alkylamides in electrical product plastics by gas chromatography-positive chemical ionization high-resolution mass spectrometry in full scan mode and an in-house developed data-processing algorithm. The algorithm was based on exact mass discrepancies and signal intensities of specific fragment and adduct ions of alkylamides, and was able to efficiently screen and anchor quasi-molecular ions. As a whole, 36 alkylamides were identified, of which 7 were found in all the plastics and 14 were observed in ≥ 2 plastics. The content distributions were elucidated with normalized abundances of quasi-molecular ions of alkylamides. Oleamide showed chromatographic peaks with the highest abundances in individual samples and was the most abundant alkylamide in all the plastics, of which the normalized abundances accounted for 57.42-70.06% of the total abundances of all alkylamides. Besides, (2E)-2-hexenamide, palmitamide and stearamide showed relatively high abundances, of which the relative abundances were 6.99-25.79%. The high abundances together with predicted environmental behaviors and toxicities indicate that alkylamides in plastics are worthy of further in-depth research. The nontarget analysis method including the instrumental analysis and data-processing algorithm can be applied to identification and characterization of alkylamides in more diverse matrices. In addition, the analysis results for the first time provide knowledge about the specific characteristics and relative content distributions of alkylamides in electrical product plastics from a comprehensive perspective.

Nontarget analysis and comprehensive characterization of halogenated organic pollutants by GC-Q-Orbitrap-HRMS in association with chromatogram segmentation and Cl/Br-specific screening algorithms.

Nontarget analysis enables high-efficiency screening and identification of halogenated organic pollutants (HOPs) in complex matrices irrespective of lacking authentic standards, particularly for novel and emerging species, thereby realizing comprehensive component characterization of HOPs. Notwithstanding, nontarget analysis and comprehensive characterization of HOPs remain on the way to improvement. In this study, we implemented nontarget analysis of HOPs in fly ash, egg and sediment using gas chromatography quadrupole-orbitrap high-resolution mass spectrometry with the aid of chromatogram segmentation and Cl/Br-specific screening algorithms, and further performed comprehensive characterization of components and distribution of HOPs. In total, 122 HOP formulas were identified and tentatively assigned with structures, of which 28 were found in ≥ two matrices. Taking isomers into account, in total 1059 HOP congeners were found. Based on the identification and semiquantification results, the chemical components and concentration profiles of HOPs were preliminarily clarified, and accordingly the overall pollution signatures of HOPs were sketched. The total concentrations of HOPs in the fly ash, egg and sediment were 4.7, 41.2 and 750.8 µg g-1, respectively. Organochlorines were the most abundant among the categories classified by halogen types, and halogenated benzenes, halogenated dioxins, halogenated biphenyls/terphenyls and halogenated polycyclic aromatic hydrocarbons (H-PAHs) were the predominant of the structurally classified categories. Moreover, dozens of formulas of novel/little-known HOPs such as mix-chlorinated/brominated PAHs with ≥4 aromatic rings and polychlorinated terphenyls were identified. This study presents an accurate and high-performance nontarget analysis method for HOPs in complex matrices, and yields new cognitions on the pollution status of HOPs from an overall perspective.

High-performance nontarget analysis of halogenated organic compounds in tap water, fly ash, soil and sediment using ultrahigh resolution mass spectrometry and scripting approaches based on Cl/Br-specific search algorithms.

Halogenated organic compounds (HOCs) are a huge group of pollutants, which have caused severe environmental pollution worldwide. This study developed a nontarget analysis method for characterization of known and unknown HOCs in tap water, fly ash, soil and sediment using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) with aid of scripting data-processing approaches. The FT-ICR-MS was equipped with an electrospray ionization source operated in negative ion mode, and full scan at a mass resolution around 200,000 was applied. Data screening scripts were developed based on exact mass differences and abundance ratios between neighboring chlorine/bromine isotopologues. Cosine similarity analysis was applied to evaluating similarity between measured and simulated isotopologue distributions which were constituted by abundance ratios between neighboring isotopologues for identification of polychlorinated and polybrominated compounds. From huge amount of peaks in raw mass spectra, thousands of MS features of HOCs were screened out. In total 824 HOC formulae were finally identified, including 702 organochlorines, 108 organobromines, and 14 mix-chlorine/bromine-containing organic compounds (OClBrs), mainly being monochlorinated/monobrominated compounds (∼90%) whose abundances were also the most prominent. Dozens of HOCs were tentatively structurally elucidated, including halogenated phenols, carboxylic acids, benzenesulfonic acids, etc. Three novel OClBrs were structurally identified, i.e., bromochlorobenzoic acid, bromodichlorophenol and bromotrichlorophenol. The data-processing scripts and strategies can facilitate accurate and high-throughput nontarget analysis of both common and novel/emerging halogenated organic pollutants in complex matrices. The research results provide informative insights into pollution profiles of HOCs in the environment, suggesting that halogenated organic pollutants remain to be seriously concerned.

Determination of pharmaceuticals, steroid hormones, and endocrine-disrupting personal care products in sewage sludge by ultra-high-performance liquid chromatography-tandem mass spectrometry.

A sensitive method has been developed and validated for the determination of diverse groups of pharmaceuticals, steroid hormones, and hormone-like personal care products in sewage sludge. Samples were extracted by ultrasonic-assisted extraction followed by solid-phase extraction cleanup. For determination of estrogens and hormone-like phenolic compounds, sample extracts were further derivatized with dansyl chloride and purified with silica gel column chromatography to improve the analytical sensitivity. The chemicals were determined by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) in multiple-reaction monitoring mode. Recoveries ranged mostly from 63% to 119% with relative standard deviations within 15%. Method quantification limits were 0.1-3 ng g(-1) dry weight (dw) for sewage sludge. The method was applied to a preliminary investigation of pharmaceuticals and personal care products (PPCPs) in sewage sludge and sediment in the Pearl River Delta, South China. Triclosan, triclocarban, 2-phenylphenol, bisphenol A, and parabens were ubiquitously detected at 3.6-5088.2 ng g(-1) dw in sludge and 0.29-113.1 ng g(-1) dw in sediment samples, respectively. Estrone, carbamazepine, metoprolol, and propranolol were also frequently quantified in the sludge and sediment samples. The dewatering process caused no significant losses of these PPCPs in sewage sludge.

Distribution pattern, behavior, and fate of antibacterials in urban aquatic environments in South China.

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.

Occurrence and behavior of non-steroidal anti-inflammatory drugs and lipid regulators in wastewater and urban river water of the Pearl River Delta, South China.

Occurrence of five non-steroidal anti-inflammatory drugs (salicylic acid, ibuprofen, naproxen, indomethacin and diclofenac) and three lipid regulators (bezafibrate, clofibric acid and gemfibrozil) was investigated in wastewater, sewage sludge, and river water of the urban section of the Pearl River at Guangzhou in South China. Behavior and fate of the pharmaceuticals during treatment in two sewage treatment plants (STPs) were also studied in depth by determining concentrations in the influents and effluents at major treatment units and the sewage sludge. Concentrations of the pharmaceuticals in the raw wastewater were mostly at ng L(-1) levels except salicylic acid whose concentrations ranged from 9.6 to 23.3 µg L(-1). No significant amount of the pharmaceuticals was detected in the suspended particulate matter of wastewater and sewage sludge. Salicylic acid, indomethacin, and naproxen were almost completely removed (≥ 99%); gemfibrozil, ibuprofen and bezafibrate were significantly removed (>75%), whereas diclofenac and clofibric acid were removed by 60-70% during treatment in the STPs. Generally, biodegradation was the governing process for elimination of the investigated pharmaceuticals. Anaerobic biodegradation was responsible for most of the removal of diclofenac whereas aerobic biodegradation also played an important role in elimination of the other pharmaceuticals except SA, which was nearly completely removed after the anoxic process. In the Pearl River, the pharmaceuticals were widely detected. Both the concentrations and detection frequency were higher in March 2008 than those in the other seasons, which may be ascribed mainly to less dilution caused by lower precipitation. Besides the STPs, urban canals directly connected with the Pearl River may also be important contributors to the pharmaceutical contamination in the river.

Occurrence and behavior of pharmaceuticals, steroid hormones, and endocrine-disrupting personal care products in wastewater and the recipient river water of the Pearl River Delta, South China.

The occurrence and behavior of ß-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 ß-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.

Chlorine isotope analysis of polychlorinated organic pollutants using gas chromatography-high resolution mass spectrometry and evaluation of isotope ratio calculation schemes by experiment and numerical simulation.

Compound-specific isotope analysis of chlorine (CSIA-Cl) is a practicable and high-performance approach for revelation of transformation processes and source identification of chlorinated organic pollutants. This study conducted CSIA-Cl for typical polychlorinated organic pollutants using gas chromatography-high resolution mass spectrometry (GCHRMS) with an alternate injection mode using perchloroethylene (PCE) and trichloroethylene (TCE) as model analytes. PCE and TCE standards from two manufacturers were employed for method development, and chlorine isotope ratio calculation schemes were evaluated by experiment and numerical simulation. The achieved precision (standard deviation of isotope ratios) was up to 0.21‰ for PCE and 0.43‰ for TCE. The limits of detection for CSIA-Cl of were 0.05 µg/mL (0.05 ng on column), and the linearities were 0.05-1 µg/mL. Two isotope ratio calculation schemes, i.e., one using complete molecular isotopologues and another using the first pair of neighboring chlorine isotopologues of each analyte, were evaluated in terms of accuracy and precision. The complete-isotopologue scheme showed evidently higher precision and was more competent to reflect trueness than the isotopologue-pair scheme and the two schemes could present completely different outcomes. The method has been successfully applied to PCE and TCE reagents from different suppliers, a trichloromethane reagent, and a plastic material. The relative isotope ratio variations (Δ37Cl) of PCE and TCE in the reagents and plastic material were from -1.84±0.7‰ to 15.12±0.85‰. The analytes from different sources could mostly be discerned from each other by chlorine isotope ratios. This study will be conducive to transformation process elucidation and source identification of for PCE and TCE, and facilitate CSIA-Cl using GC-MS for more polychlorinated organic pollutants, particularly in selection and optimization of isotope ratio calculation schemes.

Are chlorine isotopologues of polychlorinated organic pollutants binomially distributed? Theoretical evaluation, numerical simulation, experimental evidences and implications for chlorine isotope analysis and source identification.

Relative abundances of chlorine isotopologues of polychlorinated organic compounds (POCs) are commonly recognized to comply with binomial distribution. This study investigated whether chlorine isotopologue distributions of polychlorinated organic pollutants are binomial and evaluated implications of the distributions to relevant analytical and environmental research by theoretical derivation, numerical simulation and experiment. Chlorine kinetic isotope effects and equilibrium isotope effects vary in stepwise chlorination reactions, leading to inconsistent chlorine isotope ratios on different reaction positions of products, which results in non-binomial chlorine isotopologue distributions of the products. After physical changes and dechlorination, chlorine isotopologues of POCs are unlikely binomially distributed. The experimental results demonstrated that the chlorine isotopologue distributions of perchloroethylene, trichloroethylene, methyl-triclosan, and 2,3,7,8-tetrachlorodibenzofuran in standards and four polychlorinated biphenyls in both standard solutions and sediments were non-binomial. The patterns of chlorine isotope ratios derived from pairs of neighboring chlorine isotopologues of POCs from different sources were different, implying different isotopologue distributions, which might cause biases in compound-specific isotope analysis of chlorine (CSIA-Cl) and source identification. A complete-isotopologue scheme for isotope ratio calculation is recommended to CSIA-Cl for obtaining accurate data. Gas chromatography-double focusing magnetic-sector high resolution mass spectrometry is a promising instrument for CSIA-Cl that uses the complete-isotopologue scheme due to its excellent sensitivity, selectivity and ruggedness. This study yields new insights into chlorine isotopologue distributions of polychlorinated organic pollutants and proposes practicable solutions to improve CSIA-Cl that uses gas chromatography-mass spectrometry and facilitate source identification of polychlorinated organic pollutants.