[Determination of polychlorinated naphthalenes in soil using accelerated solvent extraction-molecular sieves solid-phase extraction coupled with gas chromatography-tandem mass spectrometry]

Emerging pollutants (EPs) are chemical substances that are commonly not regulated and can be detected at low or very low concentrations. However, EPs have triggered special concern because their long-term adverse effects on the environment and human health remain unknown. Most EPs show biological toxicity, environmental persistence, and bioaccumulation. Even at low concentrations in the environment, EPs may pose significant environmental and health risks. Therefore, their treatment has been explicitly included in the 14th Five Year Plan for National Economic and Social Development of the People's Republic of China and the Outline of the Long-term Goals for 2035. Soil is a source of pollutants, and its quality is directly related to economic development, ecological security, and people's livelihood. At present, China's soil environmental monitoring system is not perfect, and the ability to monitor these new organic pollutants is lagging. Therefore, to strengthen the supervision of construction and agricultural land soil environments, it is essential to strengthen the soil environment monitoring ability for these EPs and establish a reliable, steady, and economic analysis method, including their separation and analysis methods in soil. Polychlorinated naphthalenes (PCNs) have received considerable attention as emerging halogenated compounds. They were listed in Annexes A and C of the Stockholm Convention on persistent organic pollutants (POPs) in 2015 because of their persistence, multimedia fate, and toxicity. PCNs have now been detected in the surrounding soils. Owing to their trace levels in complex soil, high requirements have been put forward for the pretreatment and instrument analysis of PCNs. This study aims to develop a new method for the selective purification of PCNs in soil, which can not only effectively remove lipids and other interferences in soil but also effectively reduce time, labor, and material costs in the pre-treatment process. Based on the physicochemical properties of the 13X molecular sieve, it was explored to purify soil-extracts as solid-phase extraction (SPE) sorbents. With n-hexane as the loading and rinsing solvent, 10 mL of a dichloromethane/n-hexane mixture (2∶15, v/v) was used to elute the PCNs. Moreover, selective separation of target substances from lipid macromolecules and other interferences could be achieved simultaneously. For the selective separation of PCNs, the average recovery of the internal standard could reach 56.1% to 88.0%. 13X molecular sieves are superior to gel permeation chromatography (GPC) and Florisil SPE, and they exhibit good cleanup efficiency similar to a multilayer silica gel/alumina column (53.0%-117.0%). Although the obtained recoveries are not as high as those obtained with a multilayer silica gel/alumina column, 13X molecular sieves have advantages in terms of simple operation, environmental friendliness, and low cost. Based on these fundamental experiments, accelerated solvent extraction was used to extract targets in soil, molecular sieves were used as SPE sorbents for purification, and GC-MS/MS was employed for PCN analysis. This method was developed as a systematic analytical method for PCNs determination. The method detection limits (MDLs) for PCN homologs were in the range of 0.009-0.6 ng/g. The precision and accuracy of the method were evaluated using spiked matrices. At three spiked levels (4, 10, and 18 ng), the recoveries of PCNs (CN-3, 13, 42, 46, 52, 53, 73, and 75) were 70%-128%, 71%-115%, and 61%-114%, respectively, and the corresponding relative standard derivations were 4.2%-23%, 6.5%-31% and 4.7%-22%. Thus, this method meets the requirements of trace analysis and shows acceptable parallelism, sensitivity, accuracy, and precision, thus being feasible for the analysis of emerging pollutant. The method is expected to play an important role in sample pretreatment in the future, especially for the nationwide investigation of soil pollution.