Abstract:The presence of pharmaceutically active compounds (PhACs) in aquatic biota has been received much less attention than their presence in surface or waste water, and it was not until the mid-2000s, this gap started to be addressed. Here, we present
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xtraction with Qu
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p/C18 as dispersive clean-up): a fas… Show more
“…The use of isotopically labelled Internal Standards (I.S.) serves for compensate the matrix effect (signal enhancement/suppression) but also improves accuracy and precision [25] . A matrix-matched calibration curve (CC) was elaborated using blank radishes and spiking them using at least eight different curve points, ranging from 0.05 to 300 ng mL −1 in dry weight radish.…”
The scarcity of freshwater has led to a considerable increase of the reuse of reclaimed wastewater for irrigation of field crops
[1
,
2]
. This practice potentially exposes agricultural produce to a large variety of xenobiotic compounds including contaminants of emerging concern (CECs) which have been widely recognized to be present in wastewater
[3]
. Common approaches for the extraction of CECs from crops rely on solid-liquid extraction
[4]
, assisted solvent extraction
[5]
, ultra-sound solvent extraction
[6]
and recently QuEChERS (QUick, Easy, CHeap, Effective, Rugged and Safe) [
[7]
,
[8]
–
9]
. Here, eight QuEChERS-based methodologies were compared for their suitability to determine 45 CECs in roots and leaves of soil-grown radish.
The key points of the method development were:
The development of two single-step analytical methods specific for radish root and leaves, after testing eight different approaches using QuEChERS extraction for the quantitation of 45 CECs. The analytical methodology selected requires minimal time and solvent, making it cost-effective.
Methods validation were performed at five concentrations levels (2, 5, 10, 50 and 200 ng g
−1
), with low limits of quantification between 0.01 and 0.32 ng g
−1
.
The two optimized methodologies may be applied to identify large number of compounds of different families in radish crop. However, validation will be needed to quantify compounds different from the target compounds of this paper.
“…The use of isotopically labelled Internal Standards (I.S.) serves for compensate the matrix effect (signal enhancement/suppression) but also improves accuracy and precision [25] . A matrix-matched calibration curve (CC) was elaborated using blank radishes and spiking them using at least eight different curve points, ranging from 0.05 to 300 ng mL −1 in dry weight radish.…”
The scarcity of freshwater has led to a considerable increase of the reuse of reclaimed wastewater for irrigation of field crops
[1
,
2]
. This practice potentially exposes agricultural produce to a large variety of xenobiotic compounds including contaminants of emerging concern (CECs) which have been widely recognized to be present in wastewater
[3]
. Common approaches for the extraction of CECs from crops rely on solid-liquid extraction
[4]
, assisted solvent extraction
[5]
, ultra-sound solvent extraction
[6]
and recently QuEChERS (QUick, Easy, CHeap, Effective, Rugged and Safe) [
[7]
,
[8]
–
9]
. Here, eight QuEChERS-based methodologies were compared for their suitability to determine 45 CECs in roots and leaves of soil-grown radish.
The key points of the method development were:
The development of two single-step analytical methods specific for radish root and leaves, after testing eight different approaches using QuEChERS extraction for the quantitation of 45 CECs. The analytical methodology selected requires minimal time and solvent, making it cost-effective.
Methods validation were performed at five concentrations levels (2, 5, 10, 50 and 200 ng g
−1
), with low limits of quantification between 0.01 and 0.32 ng g
−1
.
The two optimized methodologies may be applied to identify large number of compounds of different families in radish crop. However, validation will be needed to quantify compounds different from the target compounds of this paper.
“…Due to the low expected levels of CECs and the complexity of the matrix, sensitive and robust analytical methods are essential. Ultrasound-assisted solvent extraction (UAE) is one of the most common extraction methods for CECs in aquatic biota [ 9 , 12 , 21 – 32 ]. Extraction of complex biological matrices typically features a clean-up step to ensure removal of co-extracted matrix components that otherwise may interfere in the quantification.…”
A robust and efficient extraction method was developed to detect a broad range of pollutants of emerging interest in three freshwater invasive species: American red crab (Prokambarus clarkii), Asian clam (Corbicula fluminea), and pumpkinseed fish (Lepomis gibbosus). One native species, “petxinot” clam (Anodonta cygnea), was also evaluated. Invasive species are often more resistant to contamination and could be used in biomonitoring studies to assess the effect of contaminants of emerging concern on aquatic ecosystems while preserving potentially threatened native species. So far, most extraction methods developed for this purpose have focused on analyzing fish and generally focus on a limited number of compounds, especially analyzing compounds from the same family. In this sense, we set out to optimize a method that would allow the simultaneous extraction of 87 PhACs, 11 flame retardants, 21 per- and poly-fluoroalkyl substances, and 54 pesticides. The optimized method is based on ultrasound-assisted solvent extraction. Two tests were performed during method development, one to choose the extraction solvent with the best recovery efficiencies and one to select the best clean-up. The analysis was performed by high-performance liquid chromatography coupled to high-resolution mass spectrometry. The method obtained recoveries between 40 and 120% and relative standard deviations of less than 25% for 85% of the analytes in the four validated matrices. Limits of quantification between 0.01 ng g−1 and 22 ng g−1 were obtained. Application of the method on real samples from the Albufera Natural Park of Valencia (Spain) confirmed the presence of contaminants of emerging concern in all samples, such as acetaminophen, hydrochlorothiazide, tramadol, PFOS, carbendazim, and fenthion. PFAS were the group of compounds with the highest mean concentrations. C. fluminea was the species with the highest detection frequency, and P. clarkii had the highest average concentrations, so its use is prioritized for biomonitoring studies.
Graphical abstract
“…Journal of Chromatography A, 461009 (2020) [1] . Peña-Herrera J.M., Montemurro N., Barceló D., Pérez S. Analysis of pharmaceuticals in fish using ultrasound extraction and dispersive SPE clean-up on QuE Z-Sep/C18 followed by LC-QToF-MS detection [2] . Aceña, J., Pérez, S., Eichhorn, P. Solé, M., Barceló, D.1.…”
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