This paper reports the development of an ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC‒MS/MS) method to determine eight banned dyes (Sudan I-IV, Sudan Orange, Sudan Red 7B, Para Red, Rhodamine B) in turmeric, curry, and chili products. For this purpose, the feasibility of electrospray (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) for the ionization of these compounds was evaluated. The tandem mass spectrometry (MS/MS) fragmentation of all targeted compounds was studied and both multistage mass spectrometry and high-resolution mass spectrometry were used to establish the fragmentation pathways and identify common fragmentation behaviors. Among the most significant ions, the most characteristic and abundant product ions observed on the triple quadrupole were selected to propose a selective and sensitive UHPLC‒MS/MS method (multiple reaction monitoring mode, MRM) of these target compounds in spices samples after a quick and easy extraction with acetonitrile. Matrix effect (ME) studies carried out in the three atmospheric pressure ionization sources have demonstrated that APCI showed the best performance with ME values ranging from 2 to 25%. Furthermore, the estimated quality parameters indicated the good performance of the proposed method, providing low method limits of detection (MLODs) (1-48 μg kg-1), good intra-day precision (RSD % < 15%), and accurate quantitation (relative error % < 15%). Finally, the applicability of the developed method was demonstrated by the analysis of turmeric, curry, and chili products. In total, 36 diverse samples coming from different countries were analyzed and although none of these compounds were detected above the MLODs, the analysis of spiked samples showed that the method was able to detect this family of compounds at low μg kg-1.

Gull eggs are excellent bioindicators of environmental pollution as reflect the contamination levels of coastal areas, especially of persistent and bioacumulative compounds such as perfluoroalkyl substances (PFAS). This study aims to evaluate the geographical distribution and 10-year temporal trends (2009-2018) of 17 PFAS in eggs of two gull species (Larus michahellis and Larus audouinii) from 5 main Spanish colonies. ∑PFAS ranged from 13.7 ± 5.9 to 164 ± 17 ng g^-1 wet weight and higher concentrations were observed in L. audouinii than in L. michahellis. Perfluorooctane sulfonate (PFOS) was the predominant compound in all samples, followed by perfluoroundecanoic acid (PFUnA) and perfluorotridecanoic acid (PFTriDA). Perfluorododecanoic acid (PFDoA), perfluorodecanoic acid (PFDA) and perfluorooctanoic acid (PFNA) were also found in all studied areas but at lower concentrations, while perfluorooctanoic acid (PFOA) was only detected in the Medes Islands. Principal Component Analysis revealed the co-occurrence of the 6 detected PFAS, and differentiated samples from Ebro Delta and Medes Islands, both located in the North-Eastern Mediterranean Sea, with high contribution of all PFAS, from Chafarinas and Atlantic Islands with lower concentration levels and variability. Also, different patterns were observed among colonies, suggesting the fish-based diet plays an important role in PFAS bioaccumulation. In all colonies, except for the Medes Islands, ∑PFAS decreased through the 10-year study period, with PFOS, PFUnA, and PFTriDA showing a significant concentration reduction in a colony-specific manner. This study demonstrates the usefulness and importance of continuous systematic long-term monitoring to determine the geographical distribution and temporal variations of PFAS in marine protected areas using gull eggs as bioindicators of environmental pollution.