Key Takeaways & Executive Findings
- •• • LLE achieved satisfactory recoveries for PAEs only at spike levels <4 μg·L−1, limiting its use to low-concentration scenarios; repeated extraction improved efficiency, but SPE outperformed LLE in sensitivity and accuracy. • • SPE enabled detection of 12 EDCs and 10 antibiotics at spike levels ≥0.2 μg·L−1, with detection limits as low as 0.1–6.4 ng·L−1, making it suitable for trace analysis in complex matrices. • • In industrial wastewater, total concentrations of antibiotics and EDCs ranged from 0.03–0.56 μg·L−1 and 0.07–1.91 μg·L−1, respectively, with rubber effluent dominated by DBP (1.07 μg·L−1) and pharmaceutical effluent by SMM (0.34 μg·L−1), indicating sector-specific contamination profiles. • • The SPE-LC-Orbitrap MS method proved adaptable to complex industrial matrices, achieving reliable quantification of emerging contaminants, which is critical for regulatory monitoring and risk assessment.
Abstract
The pretreatment of trace emerging contaminants in environmental matrices is challenging due to diverse methods and uncertain applicability. This study compared solid-phase extraction (SPE) and liquid-liquid extraction (LLE) for extracting endocrine-disrupting compounds (EDCs), particularly phthalate esters (PAEs), using laboratory-spiked blank samples. LLE achieved satisfactory recoveries for PAEs at spike levels below 4 μg·L−1, enabling detection of five PAEs including diisodecyl phthalate (DIDP), with improved efficiency via repeated extraction. SPE offered lower detection and quantification limits, higher accuracy and sensitivity, and achieved high recoveries for 12 EDCs and 10 antibiotics at spike levels ≥0.2 μg·L−1, with detection limits as low as 0.1–6.4 ng·L−1. The developed SPE coupled with liquid chromatography-Orbitrap mass spectrometry (LC-Orbitrap MS) method was applied to industrial wastewater samples. Across five industrial sectors (coatings, rubber, pharmaceuticals, inks, and materials technology), five antibiotics and ten EDCs were detected, with total concentrations ranging from 0.03–0.56 μg·L−1 and 0.07–1.91 μg·L−1, respectively. Sector-specific profiles emerged: rubber industry effluent was dominated by dibutyl phthalate (DBP) at 1.07 μg·L−1, while pharmaceutical effluent featured sulfamonomethoxine (SMM) at 0.34 μg·L−1. This systematic evaluation demonstrates that SPE-LC-Orbitrap MS is robust for complex matrices, providing a technical foundation for accurate quantification of emerging contaminants in industrial wastewater.
1. Introduction
Industrial wastewater discharges introduce a complex mixture of emerging contaminants, including endocrine-disrupting compounds (EDCs) and antibiotics, which pose significant risks to aquatic ecosystems and human health. Accurate quantification of these trace-level pollutants is essential for environmental monitoring and regulatory compliance. However, the diversity of pretreatment methods and their variable performance across different matrices create uncertainty in method selection. Traditional liquid-liquid extraction (LLE) often suffers from low enrichment factors and high solvent consumption, while solid-phase extraction (SPE) offers higher selectivity and sensitivity but requires optimization for specific analyte classes. The lack of systematic comparisons under controlled conditions hampers the development of reliable analytical protocols.
This study addresses this bottleneck by directly comparing LLE and SPE for the extraction of PAEs and other EDCs from water samples, using laboratory-spiked blanks to establish performance benchmarks. The optimized SPE method, coupled with LC-Orbitrap MS, was then applied to real industrial wastewater samples from five sectors, demonstrating its practical utility. By providing quantitative recovery data and detection limits, this work offers a validated framework for selecting appropriate pretreatment strategies, thereby enabling accurate risk assessment and informed decision-making in environmental management.
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HUANG Tianle, YANG Zhengqing, WANG Yuchen, YU Zhiyuan, DAI Xin, LIU Xi, CHEN Wei, YUAN Jie, LI Xiaodong, TANG Lin (2026). Comparison and Optimization of Pretreatment Methods for Emerging Contaminants and Application in Industrial Wastewater Samples. Environmental Chemistry. https://doi.org/10.7524/j.issn.0254-6108.2025022501
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Frequently Asked Questions
What are the key performance differences between SPE and LLE for extracting phthalate esters from water, and under what conditions does each method become preferable?
LLE achieved satisfactory recoveries only at spike levels below 4 μg·L−1, with improved efficiency via repeated extraction, making it suitable for relatively clean samples with low contamination. SPE, on the other hand, provided lower detection limits (0.1–6.4 ng·L−1) and higher accuracy, enabling reliable quantification at spike levels ≥0.2 μg·L−1 for a broader range of analytes (12 EDCs and 10 antibiotics). SPE is preferable for trace analysis in complex matrices, while LLE may be cost-effective for preliminary screening when concentrations are higher.
How does the SPE-LC-Orbitrap MS method perform in real industrial wastewater samples with complex matrices, and what are the typical concentration ranges observed?
The method successfully detected five antibiotics and ten EDCs in effluents from five industrial sectors. Total concentrations ranged from 0.03–0.56 μg·L−1 for antibiotics and 0.07–1.91 μg·L−1 for EDCs. The method demonstrated robustness against matrix interferences, as evidenced by successful quantification across diverse industrial effluents, with sector-specific profiles such as DBP dominance in rubber effluent (1.07 μg·L−1) and SMM in pharmaceutical effluent (0.34 μg·L−1).
What are the detection limits and recovery rates for the optimized SPE method, and how do they compare to regulatory requirements?
The SPE method achieved detection limits as low as 0.1–6.4 ng·L−1 for the target analytes, with high recoveries at spike levels ≥0.2 μg·L−1. These detection limits are well below typical regulatory thresholds for EDCs and antibiotics in water (often in the ng·L−1 to μg·L−1 range), ensuring compliance with stringent monitoring standards.
Can the developed method be extended to other emerging contaminants beyond PAEs and antibiotics, and what are the limitations?
The method was validated for 12 EDCs and 10 antibiotics, but its extension to other contaminant classes would require re-optimization of SPE sorbents and LC-MS parameters. The study focused on PAEs as representative EDCs, but the approach could be adapted for other polar or semi-polar compounds. Limitations include potential matrix effects in highly polluted samples, which may necessitate additional cleanup steps or standard addition calibration.
What are the practical implications of the sector-specific contamination profiles for industrial wastewater management?
The distinct profiles, such as DBP dominance in rubber effluent and SMM in pharmaceutical effluent, indicate that targeted monitoring and treatment strategies are needed. For instance, rubber industry effluents require effective removal of DBP, while pharmaceutical effluents need attention to sulfonamide antibiotics. This information supports the development of industry-specific discharge standards and treatment technologies.
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