Matrix solid-phase dispersion, combined with online SPE-LC-MS/MS, for the determination of tetracyclines and their main transformation products in sludge and agricultural soils

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta Pub Date : 2025-10-04 DOI:10.1016/j.aca.2025.344749

Noelia García-Criado, Julia Martín, Juan Luis Santos, Irene Aparicio, Esteban Alonso

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Abstract

Background

Tetracyclines are frequently detected in the environment due to their persistence and extensive use as antibiotics in human and veterinary medicine. They can accumulate in sludge and in agricultural soils fertilised with treated sludge or manure. This behaviour may lead to ecological risk, propagation of antibiotic resistance and can affect crops and human health through the consumption of vegetables and fruits. Analytical methods for the determination of tetracyclines and their transformation products (TPs) in sludge and agricultural soils are scarce, include a small number of tetracyclines, do not include their TPs and are not specifically developed for their determination.

Results

A matrix solid-phase dispersion (MSPD) method has been optimised for the simultaneous determination of six tetracyclines and six of their main TPs in the types of sludge applied as soil fertiliser (digested sludge and composted sludge) and in agricultural soil. Analytical determination by online SPE-LC-MS/MS has also been optimised. The method was validated for each of the above-mentioned matrices, with good linearity (R² ≥ 0.98), precision (RSD ≤12.3 %), accuracy (64–117 %) and method quantification limits (below 10 ng g⁻¹ dry weight (dw) for most compounds). Application of the method to digested sludge, composted sludge and agricultural soils revealed high concentrations not only of the parent compounds (tetracycline and doxycycline, up to 353 ng g⁻¹ dw and 1069 ng g⁻¹ dw, respectively, in digested sludge) but also of their TPs (epitetracycline, anhydrotetracycline and 4-epioxytetracycline up to 327 ng g⁻¹ dw, 117 ng g⁻¹ dw and 10.2 ng g⁻¹ dw, respectively, in digested sludge).

Significance and novelty

This method allows the specific simultaneous determination of six tetracyclines and six of their TPs in sludge and soils. The proposed method constitutes a starting point to extend the use of MSPD, that is being applied mainly to biota and food, as a low-cost and easy-to-perform technique that allows simultaneous extraction and clean-up. Application of the method revealed the significance of the determination of TPs of tetracyclines for a proper environmental risk assessment.

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基质固相分散联用在线SPE-LC-MS/MS测定污泥和农业土壤中四环素类及其主要转化产物

背景：由于四环素作为抗生素在人类和兽药中持续存在和广泛使用，因此在环境中经常检测到四环素。它们可以在污泥和用处理过的污泥或粪肥施肥的农业土壤中积累。这种行为可能导致生态风险、抗生素耐药性的传播，并可能通过食用蔬菜和水果影响作物和人类健康。测定污泥和农业土壤中四环素及其转化产物（TPs）的分析方法很少，包括少量四环素，不包括其TPs，也没有专门开发用于测定四环素的分析方法。结果优化了基质固相分散（MSPD）法同时测定土壤肥料污泥（消化污泥和堆肥污泥）和农业土壤中6种四环素及其6种主要TPs的方法。并对在线SPE-LC-MS/MS分析测定方法进行了优化。结果表明，该方法具有良好的线性（R2≥0.98）、精密度（RSD≤12.3%）、准确度（64 ~ 117%）和定量限（多数化合物干重小于10 ng g-1 dw）。该方法在消化污泥、堆肥污泥和农业土壤中的应用表明，不仅母体化合物（四环素和强力霉素，在消化污泥中分别高达353 ng g-1 dw和1069 ng g-1 dw）的浓度很高，而且它们的总毒性物质（外环素、无水四环素和4-环氧四环素，在消化污泥中分别高达327 ng g-1 dw、117 ng g-1 dw和10.2 ng g-1 dw）的浓度也很高。意义和新颖性该方法可同时测定污泥和土壤中6种四环素及其TPs。所提出的方法是扩大MSPD使用的起点，该技术主要应用于生物群和食品，作为一种低成本和易于执行的技术，可以同时提取和清理。该方法的应用，揭示了四环素类药物总磷含量的测定对环境风险评价的重要意义。

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来源期刊

Analytica Chimica Acta 化学-分析化学

CiteScore

10.40

自引率

6.50%

发文量

1081

审稿时长

38 days

期刊介绍： Analytica Chimica Acta has an open access mirror journal Analytica Chimica Acta: X, sharing the same aims and scope, editorial team, submission system and rigorous peer review. Analytica Chimica Acta provides a forum for the rapid publication of original research, and critical, comprehensive reviews dealing with all aspects of fundamental and applied modern analytical chemistry. The journal welcomes the submission of research papers which report studies concerning the development of new and significant analytical methodologies. In determining the suitability of submitted articles for publication, particular scrutiny will be placed on the degree of novelty and impact of the research and the extent to which it adds to the existing body of knowledge in analytical chemistry.