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  • Xinying ZHOU, Weiheng KONG, Dexiu YU, Tangyi LI, Zhou MA, Xin YI, Fenglin WANG, Tong LI
    Chinese Journal of Chromatography. 2025, 43(7): 830-835.

    Preparative chromatography plays an important separation and purification role in the pharmaceutical, chemical, and food industries. New preparative chromatography equipment that integrates automatic sampling and fraction-collecting functions was developed to improve separation efficiency and ease of use, and to meet the separation-efficiency and collection-accuracy needs of modern industry.The design concept and working principles of the device are introduced in detail. The developed equipment significantly improves the injection rate and reduces human operating errors through advanced automation technology, leading to an experimental process that is entirely more scientific and efficient. At the same time, the fraction-collection system was optimized such that it can flexibly adjust to various application requirements, thereby ensuring the highest purities and recoveries of the collected target ingredients. This innovative equipment uses a high-speed servo motor to independently drive the X-, Y-, and Z-axes of the instrument tray in order to realize high-speed sampling and collection actions at any position within the scope of the set tray, while synchronously sampling and collecting. A control circuit was used to calibrate the sampling and collection positions to ensure accuracy and that the device is compatible with a variety of sample-tray specifications to meet the preparation requirements of a wide 1–200 mL/min flow range. The developed equipment was used to separate and purify samples of stevioside and rebaudioside A, and exhibited excellent performance, including fast separation, stable output, and accurate collection. The equipment is capable of realizing synchronous sample-collection functions, thereby providing a stable and reliable separation and purification option for a wide range of industries.

  • Yanwei YANG, Xu ZHANG, Xiao LIN, Qi SUN, Hui FU, Yifu LU, Tian QIU, Zhuona ZHANG, Linna XIE, Haijing ZHANG, Miao ZHANG, Xiaojian HU, Yingli QU, Feng ZHAO, Yuebin LYU, Ying ZHU, Xiaoming SHI
    Chinese Journal of Chromatography. 2025, 43(6): 559-570.

    The China National Human Biomonitoring Program (CNHBP) was launched in 2016. The program aims to obtain representative exposure data of environmental pollutants in the general population by carrying out field epidemiological surveys of Chinese population and monitoring of environmental pollutants in human biological tissues. This work will provide a scientific basis for the government to formulate environmental pollution prevention and control policies. One of the objectives of human biomonitoring is to provide accurate and comparable data of chemical pollutants in human biological samples. Multi-dimensional quality control measures are implemented for the targeted quantitative analysis of chemical pollutants from the analysis method, experimental blank and analysis processes. The quality control procedures are divided into two stages: (1) focusing on the verification of biomonitoring analysis method, blank screening and control in the pre-detection stage; (2) the quality control of the large-scale sample analysis process in the detection stage. Analysis methods used in CNHBP need to be validated to evaluate the performance and practicability, with emphasis on method detection limit (MDL) and method quantification limit (MQL), matrix effects, stability, and residue and dilution. Blank screening procedures are required for all monitoring indicators to identify, eliminate or reduce blank interference, and the blank value of each batch should be less than the MDL. The laboratory adopts a combination of internal and external quality control measures, the measures mainly include: (1) method validation and detection process of the 10 types of monitoring indicators all used biological matrix reference materials produced by the National Institute of Standards and Technology (NIST), European Reference Materials (ERM) and China Center for Reference Materials, to ensure the accuracy and traceability of the methods; (2) commercial quality control samples and internal quality control samples were used to evaluate the stability of the testing process for the 15 types of monitoring indicators; (3) a total of 60 monitoring indicators of the nine categories participated in the German external quality assessment scheme for analyses in biological materials (G-EQUAS) and achieved satisfactory results; (4) 15 types of monitoring indicators were tested with blind samples. Overall, multi-dimensional quality control measures provide professional support for generating high-quality biomonitoring data.

  • Jiankun QIAN, Runming HE, Ke FANG, Chenlong LI, Shan BAO, Wen GU, Song TANG
    Chinese Journal of Chromatography. 2025, 43(6): 571-584.

    Polycyclic aromatic hydrocarbons (PAHs) are organic compounds produced primarily through the incomplete combustion of coal, petroleum, and other carbon-based materials. These compounds are environmentally ubiquitous and have attracted widespread attention because they are significantly biologically toxic and have far-reaching implications for public health and societal wellbeing. Consequently, developing a comprehensive understanding of how PAHs and their derivatives metabolically biotransform in the human body is critical for devising precise preventive strategies and targeted health interventions. PAHs and their derivatives metabolically transform in vivo in a complex process involving a broad variety of enzymes and pathways, and are usually divided into three distinct phases. Phase I encompasses oxidative, reductive, and hydrolytic reactions that are primarily catalyzed by cytochrome P450 (CYP) enzymes. These processes produce intermediates such as monohydroxyls, diols, diol-epoxides, and quinones, some of which (e.g., diol-epoxides) form covalent DNA adducts, thereby contributing to their toxicities. Phase Ⅱ involves conjugation reactions, such as glucuronidation, sulfation, and glutathionylation, which enhance the water solubilities of the metabolites and facilitate their elimination. These detoxified metabolites are actively transported and excreted via bile or urine in phase Ⅲ, which effectively minimizes internal PAH exposure and prevents accumulation. Metabolites generated at various stages of PAH metabolism serve as crucial biomarkers for assessing human exposure levels. For example, urinary monohydroxy PAH metabolites (e.g., 1-hydroxypyrene) have been widely adopted as reliable biomarkers for characterizing PAH exposure. However, owing to their structural diversity, PAHs metabolize via considerably different mechanisms to afford a variety of products, which highlights the need to differentiate individual PAHs and their derivatives in order to precisely assess exposure and evaluate nuanced health risks. Understanding the time-dose-effect relationships of PAH metabolites provides another major PAH-biomonitoring challenge. Investigating these dynamics is essential for revealing the cumulative and long-term health effects associated with exposure to multiple PAHs and their derivatives. Moreover, such studies provide scientific bases for formulating personalized and refined health-protection strategies. For instance, exploring how individual susceptibility, such as genetic polymorphisms in CYP enzymes or conjugation pathways, affects PAH metabolism is expected to significantly improve risk stratification and targeted interventions. PAH exposure is associated with significant health risks because they are associated with a range of diseases, including lung, pancreatic, and gastrointestinal cancers, as well as respiratory and cardiovascular diseases. The pervasive environmental presence of PAHs further complicates exposure scenarios, necessitating the comprehensive monitoring of various populations and environmental contexts. In addition to individual exposure, population-scale studies are expected to inform public health policies and regulatory actions aimed at reducing PAH exposure, particularly in vulnerable populations. This review concisely summarizes the metabolic pathways and product categories associated with four types of PAHs: parent, nitroxylated, oxidized, and alkylated. It emphasizes recent advances in our understanding of parent PAH metabolism in humans, focusing on their implications for exposure characterization, health risk assessment, source tracing, and regulatory decision-making. This paper aims to provide a scientific foundation for the advancement of human biomonitoring efforts and the development of evidence-based public health interventions tailored to reduce the burden of PAH exposure by addressing the complexities of PAH metabolism.

  • Cheng YANG, Ao ZHANG, Zhanqi GAO, Guanyong SU
    Chinese Journal of Chromatography. 2025, 43(6): 585-593.

    Biological and environmental samples are complex and contain a highly diverse range of compounds. Analyzing these samples by chromatography-high-resolution mass spectrometry generates a substantial volume of mass-spectrometry data that are composed of mass-to-charge-ratio (m/z), retention-time (RT), and peak-intensity information that require considerable time and energy to process. Consequently, employing software to process mass-spectrometry data for identification and analysis purposes is imperative. Among the many mass-spectrometry data-processing options, XCMS (various forms (X) of chromatography mass spectrometry), which is highly efficient, precise, and freely accessible software for processing mass-spectrometry data, is broadly used in the environmental science field. This study aimed to explore the use of XCMS in environmental science applications by comprehensively reviewing the workflow, underlying principles, and parameter-optimization measures of XCMS. The workflow mainly includes importing, processing, and exporting data. Importing data requires the use of format conversion tools, such as MSConvert, which converts data generated by various instruments into a format acceptable by XCMS, while data processing includes peak detection, alignment, and filling. The various XCMS functions are mainly realized via its built-in algorithms, with the Matched Filter, CentWave, Obiwarp, and Peak Density algorithms most commonly used. The first two algorithms implement the peak-detection function, while the latter two implement the peak-alignment function. XCMS identifies compound peaks from mass-spectrometry data during peak-detection; it first filters for noise and corrects the baseline. An algorithm then detects peaks based on their shapes and intensities. XCMS can also de-emphasize and de-distort to filter out interfering information in each peak signal. The CentWave algorithm is particularly effective for processing high-resolution mass-spectrometry data by improving detection accuracy and recall. Peak-detection is followed by alignment. Here, XCMS uses kernel density estimations to match peaks between samples by estimating the retention-time distribution of matched peaks, which corrects for any nonlinear deviations in retention-times. This step is critical for accurately comparing samples. The peak-filling step resolves missing peaks in the data, and XCMS uses information from other samples to fill these gaps. This process enhances the integrity of the dataset and improves analysis accuracy. In terms of applications, XCMS has demonstrated significant progress for the non-targeted screening of environmental pollutants, identifying exogenous metabolic pollutant transformations, and exploring the endogenous metabolisms of biomolecules. For example, XCMS efficiently extracts the mass spectrometry of complex samples during the non-targeted screening of environmental pollutants, thereby providing a reliable database for subsequent identification. Although the use of XCMS in the environmental science field has delivered particular results, some limitations still exist, including the use of large amounts of memory, problems associated with the software crashing when dealing with large-scale data, and the misclassification of noise as valid signals during feature detection, which results in a large number of false positives, errors, and missed detections when processing data for compounds with complex chemical compositions and structural types. In addition, the degree of user interaction and automation requires further improvement. XCMS offers significant developmental potential in the environmental science field. Continuing algorithmic optimization and database expansion through improvements in algorithmic robustness, data compatibility, and user experience, are expected to see XCMS develop broadly and provide more powerful support for the environmental science field in the future.

  • Zhaoxu WANG, Duanda WANG, Shutao WANG, Yongyang SONG
    Chinese Journal of Chromatography. 2025, 43(6): 594-605.

    Chromatography, a highly efficient and selective separation technology, is broadly applicable and exhibits a range of developmental prospects. The stationary phase of a chromatography column is the most important component of chromatography; hence, the development of advanced stationary-phase materials that exhibit highly resolved separation performance is a continuing research hotspot in this field. In this regard, ordered porous materials (OPMs) are advantageous owing to their precisely controllable pore sizes, morphologies, and regularly arranged pore structures, which are capable of accurately sieving molecules of different sizes and shapes, and reducing disordered molecular diffusion in the flow path. Such materials overcome the limitation of separation accuracy of traditional chromatographic materials, and effectively solve the problems faced by scientific research and industry in the purification of raw materials and products. Over the past few decades, a variety of new OPMs have been developed and used as stationary-phase matrices in chromatography columns. These materials have efficiently and rapidly separated homologues, isomers, isotopes, and other substances with similar properties, and have delivered excellent chromatographic separation and analysis results. In this review, we first discuss the influence of ordered porous structures on column efficiency and resolution during chromatographic separation from a theoretical perspective, which provides a basis for the use of OPMs as stationary phases in chromatography. This review then summarizes research progress on several different OPM types for use in chromatographic separation and analysis applications, including metal organic frameworks (MOFs), covalent organic frameworks (COFs), porous organic cages (POCs), mesoporous silica materials, block copolymer (BCP) assemblies, and high internal-phase emulsion polymers (PolyHIPEs). The review concludes by discussing current challenges faced by chromatographic OPMs as well as directions for future development.

  • Yana LUO, Jia CHEN, Yuyu HU, Shijie GAO, Yanli WANG, Yanming LIU, Juanjuan FENG, Min SUN
    Chinese Journal of Chromatography. 2025, 43(6): 606-619.

    Selecting a suitable sample preparation method is a significant step prior to chromatographic separation and detection. Directly analyzing samples instrumentally is difficult owing to the complexity of the sample matrix and the trace concentration of analytes. Most sample preparation methods have disadvantages, including complicated operating procedures, the use of large amounts of organic solvent, and ease of analyte loss during multistep processes; consequently, they do not meet the high analytical sample detection requirements of modern industry. The development of simple, environmentally friendly, efficient, and rapid preparation methods is a continuing frontier research area in the analytical chemistry field. Among the many available sample preparation techniques, in-tube solid-phase microextraction (IT-SPME) is receiving extensive attention. IT-SPME enriches the target analytes by extracting them to the inner surface of the capillary tube, and has been applied to extract various analytes in the environmental and food fields. IT-SPME is advantageous because it consumes low amounts of organic solvent and capillaries are mechanical stable; consequently, IT-SPME is a promising sample preparation technique. Magnetic field has been introduced to the IT-SPME system to further improve extraction efficiency and selectivity, leading to the development of magnetism-enhanced in-tube solid-phase microextraction (ME-IT-SPME) as a new technology. ME-IT-SPME uses magnetic field to separate and enrich targets, with different magnetic-field strengths applied to the extraction column during adsorption and elution. Diamagnetic substances in a paramagnetic medium tend to concentrate in regions where the magnetic field is weak when an external magnetic field is applied. Target analytes are detected chromatographically following elution. Conditions are optimized and an analytical method is established and used to detect targets in actual samples, leading to improved extraction sensitivity and precision compared to those obtained using IT-SPME, including shorter analysis time and superior extraction efficiency. This paper reviews the applications of ME-IT-SPME technology in combination with various analytical instruments since its inception in 2012, and analyzes its analysis and detection advantages. Based on hydrophobic interactions, hydrogen bonding, π-π and polarity interactions, coordination, and other extraction mechanisms with analytes, ME-IT-SPME uses innovative functional extraction materials, including nanomaterials, monolithic materials, and magnetic hybrid materials, all of which have high surface areas and numerous adsorption sites. Capillary microextraction columns are prepared using open-tubular capillary, particle-filling capillary, or monolithic capillaries. Diverse analytes are detected when ME-IT-SPME is combined with chromatograph, including organic pesticide residues, heavy-metal ions, herbicides, preservatives, and drug molecules. ME-IT-SPME technology is widely used in the environmental-analysis, food-analysis, and biomedical fields. Future, ME-IT-SPME technological developments should include: (1) focus on the reusability and stability of the magnetic extraction material; (2) discovering new extraction materials that are highly enriching and selective in order to analyze a greater variety of targets; (3) further innovating ME-IT-SPME technology by combining it with other more-sensitive analytical methods and considering its use in other fields; (4) connecting different capillaries to simultaneously enrich a variety of analytes; (5) exploring how the higher magnetic field influences extraction efficiency by designing new magnetic-field-regulating devices with small thermal interference; (6) combining the technology with advanced portable analytical instruments to realize real-time target analysis in the field; (7) exploiting immuno-affinitive extraction tubes that can be used to highly efficiently and selectively extract biological macromolecular drugs.

  • Dejun BAO, Zhuangzhuang FENG, Xu ZHANG, Qi SUN, Zhuona ZHANG, Xiaojian HU, Ying ZHU, Xiao LIN
    Chinese Journal of Chromatography. 2025, 43(6): 620-629.

    In this study, a method for the simultaneous determination of 22 organic ultraviolet absorbers (OUVs) in human serum was established by combining protein precipitation technology (PPT), efficiency lipid removal technology (ELR) and ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The OUVs include five benzophenone compounds, five benzotriazole compounds, two cinnamate ester compounds and their three metabolites, two salicylate compounds, two camphor derivative compounds, one triazine compound, one dibenzoylmethane compound and one amino aminobenzoic acid derivative compound. Chromatography was performed using an Acquity BEH C18 column (100 mm×2.1 mm, 1.7 μm), gradient elution was carried out using methanol-water and methanol-0.1% ammonia water as the mobile phases. Compounds were detected in both positive and negative electrospray ionization (ESI+/ESI‒) modes using multiple reaction monitoring (MRM), and quantified using stable-isotope internal standards. The experimental results showed that the 22 target compounds exhibited good linear relationships within their respective linear ranges, with the correlation coefficients (r)≥0.999 3. The method detection limits (MDLs) ranged from 0.02 to 0.48 ng/mL, and the method quantification limits (MQLs) ranged from 0.02 to 1.60 ng/mL. At the three spiked levels of low, medium and high, the spiked recoveries of the 22 target analytes ranged from 79.9% to 136.1%, the intra-day precisions were from 1.5% to 25.4%, and the inter-day precisions were from 0.6% to 23.5%. After correction by the stable-isotope internal standard method, the matrix effects of the 22 target analytes in fetal bovine serum were 83.0%‒119.9%. The developed method was successfully used to detect 22 OUVs in 110 human serum samples. With the exception of 3-benzylidene camphor (3-BC), 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol (UV-9), 4-methylbenzylidene camphor (4-MBC), 2,2′-dihydroxy-4-methoxybenzophenone (BP-8), and 2,4-dihydroxybenzophenone (BP-1), which were not detected, the remaining 17 substances were detected with overall detection rates of 0.9%–65.5% and the detection levels were <MQL‒11.7 ng/mL. The developed analytical method is simple, convenient, highly sensitive, and is expected to become an effective tool for quantifying 22 OUVs in human serum.

  • Huawei WANG, Shiyu SHI, Ling LIU, Ding CHEN, Zhixian LYU, Ziyi SONG, Youjie WANG, Lulu SONG, Surong MEI
    Chinese Journal of Chromatography. 2025, 43(6): 630-639.

    The contents of 15 organophosphate ester (OPE) metabolites in the urine of 1 869 adults residing in urban areas were quantified using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). How gender, age, body mass index (BMI), smoking status, exercise frequency, family income and dietary intake affected the contents of OPE metabolites in human urine were discussed. Furthermore, the daily intake (EDI) of OPEs was evaluated based on the contents of OPE metabolites in urine. The corresponding potential non-carcinogenic risks were calculated in combination with the non-carcinogenic risk reference dose (RfD), with the health risks of individual OPE monomers and overall cumulative exposure expressed using the hazard quotient (HQ) and hazard index (HI). Six OPE metabolites exhibited detection frequencies in excess of 60%, with bis(2-butoxyethyl) phosphate (BBOEP) and 1-hydroxy-2-propyl bis(1-chloro-2-propyl) phosphate (BCIPHIPP), as the two main OPE metabolites, detected at levels of 0.56 and 0.36 ng/mL, respectively. Men exhibited higher urine contents of bis(1,3-dichloro-2-propyl) phosphate (BDCIPP), BCIPHIPP, and BBOEP than women, whereas women exhibited higher urine contents of 4-hydroxyphenyl-phenylphosphate (4-HO-DPHP). The levels of BCIPHIPP and diphenyl phosphate (DPHP) were found to correlate negatively with age, while the BCIPHIPP, and di-o-tolyl-phosphate (DoCP)/di-p-tolyl-phosphate (DpCP) levels correlated positively with family income. Higher exercise frequencies were found to be associated with significantly lower levels of BDCIPP and BCIPHIPP in urine. Furthermore, the frequency of nut consumption and the level of 4-HO-DPHP in urine were determined to be significantly negatively correlated. This study did not identify any significant associations between contents of urinary OPE metabolites and smoking or the intake of other foods, which suggests that smoking and dietary intake are not the primary OPE exposure pathways for the investigated population. Future research should have broader scope to elucidate the principal OPE exposure pathways. The overall OPE exposure levels for all participants in this study ranged between 5.60 and 2 800 ng/(kg⋅d) bw, with a median exposure level of 104 ng/(kg⋅d) bw. Among the four OPE monomers, Tris(2-butoxyethyl) phosphate (TBOEP) exhibited the highest exposure level, with a median value of 57.2 ng/(kg⋅d) bw (ranging between 1.11 and 1 330 ng/(kg⋅d) bw), thereby contributing up to 55.6% of the total OPE exposure. Additionally, tri-n-butyl phosphate (TNBP) also exhibited significant exposure, with a median level of 32.4 ng/(kg⋅d) bw (ranging between 0.138 and 2 000 ng/(kg⋅d) bw), which accounts for 31.5% of the total OPE exposure. Gender-based analysis revealed that men exhibited higher OPE exposure levels than women. Specifically, men exhibited a median exposure level of 112 ng/(kg⋅d) bw (ranging between 6.03 and 2 670 ng/(kg⋅d) bw) compared to the value of 89.9 ng/(kg⋅d) bw (ranging between 5.61 and 2 800 ng/(kg⋅d) bw) recorded for women. The vast majority of study participants exhibited HI values of less than one, indicative of no obvious non-carcinogenic risks. The OPEs exhibited HI values in the 0.000 2–1.03, with a median value of 0.06. The exposure risks associated with the four OPE monomers are ranked in following order: TBOEP (median HI=0.038, range: 0.000 7–0.883), TNBP (median HI=0.013, range: 0.000 05–0.833), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) (median HI=0.002, range: 0.000 8–0.288), and triphenyl phosphate (TPHP) (median HI=0.001, range: 0.000 2–0.350); these monomers contribute 68.9, 24.4, 4.2, and 2.5% to the overall HI value, respectively. Among all study participants, men exhibited a higher exposure risk (median HI=0.061, range: 0.002–1.03) than women (median HI=0.049, range: 0.002–0.840). Notably, TBOEP was identified as the primary high-risk monomer for both genders, contributing 70.1% (median HI=0.042, range: 0.000 7–0.883) and 67.6% (median HI=0.035, range: 0.000 8–0.835) to the overall health risks of men and women, respectively. In conclusion, the study population was ubiquitously exposed to OPEs, with men exhibiting higher exposure levels and associated health risks, which suggests that OPE exposure levels are gender-dependent. This study revealed the exposure levels and profiles of OPEs of urban residents, and provides supporting data and a scientific foundation for subsequent studies and policy formulations.

  • Xiaoying ZHAO, Hui KANG, Yanyan WANG, Wenhui LI, Ming CHEN, Chan KE, Feng QIN, Xixiong KANG
    Chinese Journal of Chromatography. 2025, 43(6): 640-649.

    Phthalates (PAEs) are widely employed as plasticizers in plastic products that are used in industrial, agricultural, food, medical, and other fields. PAEs are relatively weakly bonded to plastic products through non-covalent interactions. Consequently, PAEs can easily leak from the product into the environment, which exposes the public to PAEs through food intake, skin absorption from personal care products, and by inhaling air. Related studies have shown that PAEs are endocrine-disrupting substances and that long-term exposure to PAEs may result in diseases of the nervous, reproductive, cardiovascular and immune systems. In addition, excessive exposure to PAEs may trigger inflammatory responses and induce tumors. Therefore, establishing a highly sensitive assay for determining PAE levels in the human body following exposure is an important objective. PAEs generally have half-lives of less than 24 h; they are rapidly metabolized through enzymatic hydrolysis after entering the human body and excreted through urine. Therefore, most studies have focused on PAE metabolites as target compounds; hence, human body exposure to PAEs can be assessed by analyzing the types and levels of these metabolites. Herein, we established a method for simultaneously determining ten phthalate (PAE) metabolites in human urine using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The ten PAE metabolites in urine were separated using an ACQUITY UPLC BEH Phenyl column (50 mm×2.1 mm, 1.7 μm). Gradient elution was performed using 0.1% formic acid aqueous solution and 0.1% formic acid in acetonitrile as the mobile phases, at a flow rate of 0.5 mL/min, a column temperature of 40 ℃, and a sample size of 20 μL. Data were acquired in negative-ion electrospray ionization (ESI) and multiple reaction monitoring (MRM) modes, and quantified using the isotope internal standard method. The method was found to be highly specific, with the ten PAE metabolites exhibiting good linearities in their linear ranges, with limits of detection (LODs) and quantification (LOQs) of 0.03–0.3 and 0.1–1 ng/mL, respectively. Under the four quality control (QC) levels, the intra-day and inter-day precisions of the ten PAE metabolites were all ≤8.3%, and the accuracy ranged from ‒10.5% to 7.3%. The method was used to assess the exposure levels of PAE metabolites in the urine samples of 60 volunteers, with 1‒6 kinds of PAE metabolites detected in the urine of each volunteer. This method is sensitive, accurate, simple, efficient, and suitable for the large-scale biological monitoring of PAE metabolites.

  • Chenshu GU, Zhenzhen LIU, Huiling JIN, Xiaoqi LIU, Meiyu WANG, Weijie SUN, Yangying SUN, Peipei QI
    Chinese Journal of Chromatography. 2025, 43(6): 650-658.

    Perfluorinated compounds (PFCs) are widely used, persistent, and their presence in water is of significant concern. PFCs, particularly short-chain variants, are highly soluble and mobile in water, which enables their transport over long distances via river systems, potentially leading to extensive contamination. These compounds are resistant to degradation, which is challenging for conventional water-treatment methods that often remove PFCs ineffectively, leading to their prolonged presence in water bodies. This paper establishes a magnetic solid-phase extraction method for 11 PFCs in enriched water using magnetic polystyrene pyrrolidone (Fe3O4-PLS) as a magnetic adsorbent. Purified lipophilic PLS magnetic beads were used as the solid-phase extractant, and their surfaces were modified using phenyl and pyrrolidone groups to facilitate the adsorption of PFCs that contain hydrophilic functional groups and hydrophobic alkyl side chains. PFCs in water were determined accurately and sensitively by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method involved accurately weighing 50 mg (±0.05 mg) of the Fe3O4-PLS into a 500-mL beaker, adding 2 mL of methanol (for activation), placing the beaker on a magnet for 30 s, and discarding the methanol once the methanol and Fe3O4-PLS had been completely separated. A 200-mL aliquot of an aqueous mixed PFC solution was added to the beaker, sonicated for 15 min, and then placed on a strong magnet until the Fe3O4-PLS had completely separated at the bottom of the beaker. The upper liquid was discarded. A 4-mL acetonitrile containing 0.1% formic acid was added as the Fe3O4-PLS eluent, ultrasonicated for 30 s, after which the beaker was placed on the magnet and the eluate collected. The sample was taken to dryness under a stream of nitrogen, the residue was redissolved in 0.5 mL of acetonitrile, ultrasonicated for 10 s, and then membrane-filtered prior to analysis by LC-MS/MS. The 11 PFCs exhibited good linear relationships ranging from 1 to100 μg/L, with correlation coefficients (R2) ranging from 0.997 6 to 0.999 9. Limits of detection and quantification (LODs and LOQs, respectively) were determined to be 0.001–0.620 ng/L and 0.002–2.065 ng/L, respectively, indicative of high sensitivity. The 11 PFCs exhibited recoveries of 60.8%–120.0% at various concentrations (0.05, 1, 10, and 50 μg/L). Relative standard deviations (RSDs) ranged from 1.0% to 20.0%, which meet the requirements for PFC analysis in water. The concentrations of the 11 PFCs at 15 sites in the Dongtiaoxi River, Hangzhou (near factories, reservoirs and residential areas) were analyzed using the developed method. A total of six PFCs, namely perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorooctane sulfonic acid (PFOS), perfluoroheptanoic acid (PFHpS), perfluorobutanesulfonate (PFBS) and perfluorodecanoic acid (PFDA), were detected at mass concentrations of 11.4–30.7 ng/L. The highest mass concentration of PFOA was determined to be 25.5 ng/L. The PFCs in the Dongtiaoxi River were found to be mainly associated with precursor degradation and industrial wastewater discharge. A sudden rise in the pollution level was observed near the sampling point with the lowest detected concentration, which is possibly ascribable to the strong hydrodynamic difference between the hydraulic transport process near the river wharf and the highly turbulent flowing water. This difference results in the suspended particles in surface water mixing with re-suspended sediment particles such that PFCs are released back into the surface water. Pollution levels were observed to continuously decrease in the directions of the extended river and its estuary and tributaries. Risk assessments revealed that the PFC levels in the surface water of the Dongtiaoxi River basin are much lower than the official health reference value and have not reached levels that are expected to cause ecological harm and risk human health. The data are expected to support monitoring-system improvements by providing an in-depth understanding of occurrence characteristics, and help formulate a management plan for PFCs in the Dongtiaoxi River.