Green On-Site Diclofenac Extraction from Wastewater Matrices Using a 3D-Printed Device Followed by PTV-GC-MS Determination

A 3D-printed device was designed and printed by a stereolithographic technique (SLA) and coated with a highly selective solid phase extraction resin for on-site diclofenac extraction from wastewater, avoiding the transport and treatment of large volumes of samples in the laboratory. The best results...

Full description

Saved in:
Bibliographic Details
Main Authors: César Castro-García, Edwin Palacio, Rogelio Rodríguez-Maese, Luz O. Leal, Laura Ferrer
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Chemosensors
Subjects:
Online Access:https://www.mdpi.com/2227-9040/13/6/212
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1849435020628852736
author César Castro-García
Edwin Palacio
Rogelio Rodríguez-Maese
Luz O. Leal
Laura Ferrer
author_facet César Castro-García
Edwin Palacio
Rogelio Rodríguez-Maese
Luz O. Leal
Laura Ferrer
author_sort César Castro-García
collection DOAJ
description A 3D-printed device was designed and printed by a stereolithographic technique (SLA) and coated with a highly selective solid phase extraction resin for on-site diclofenac extraction from wastewater, avoiding the transport and treatment of large volumes of samples in the laboratory. The best results in terms of chemical and mechanical resistance were obtained with Rigid 10K resin. The “stick-and-cure” impregnation technique was used to coat the 3D-printed device with Oasis<sup>®</sup> HLB resin. The coated 3D-printed device can be reused up to eight times without losing extraction efficiency. The eluent and derivatization reagent volumes were optimized by a multivariate design. The proposed method allowed for the extraction and determination of diclofenac by PTV-GC-MS, achieving methodological detection and quantification limits of 0.019 and 0.055 μg L<sup>−1</sup>, respectively, with a preconcentration factor of 46. The analysis time was 23 min per sample. To validate the proposed methodology, addition/recovery tests were carried out in different wastewater samples, obtaining recoveries above 90%. The methodology was applied at the wastewater treatment plant (WWTP) of Calvià (Mallorca, Spain), finding diclofenac in concentrations of 15.39 ± 0.07 μg L<sup>−1</sup> at the input of the primary decantation process, 4.48 ± 0.03 μg L<sup>−1</sup> at the output of the secondary decantation, and 0.099 ± 0.001 μg L<sup>−1</sup> at the output of the tertiary treatment, demonstrating the feasibility of the on-site extraction method in monitoring diclofenac over a wide concentration range. Finally, a greenness index of 0.58 for the proposed on-site sample preparation was achieved according to the AGREEprep metrics, making it an eco-friendly alternative for diclofenac monitoring.
format Article
id doaj-art-30bdbdaa25994af285142cc1bb27f141
institution Kabale University
issn 2227-9040
language English
publishDate 2025-06-01
publisher MDPI AG
record_format Article
series Chemosensors
spelling doaj-art-30bdbdaa25994af285142cc1bb27f1412025-08-20T03:26:26ZengMDPI AGChemosensors2227-90402025-06-0113621210.3390/chemosensors13060212Green On-Site Diclofenac Extraction from Wastewater Matrices Using a 3D-Printed Device Followed by PTV-GC-MS DeterminationCésar Castro-García0Edwin Palacio1Rogelio Rodríguez-Maese2Luz O. Leal3Laura Ferrer4Environmental Analytical Chemistry Group, University of the Balearic Islands, Cra. Valldemossa 7.5 km, 07122 Palma de Mallorca, SpainEnvironmental Analytical Chemistry Group, University of the Balearic Islands, Cra. Valldemossa 7.5 km, 07122 Palma de Mallorca, SpainCentro de Investigación en Materiales Avanzados, S.C. (CIMAV), Av. Miguel de Cervantes 120, Complejo Industrial Chihuahua, Chihuahua 31136, MexicoCentro de Investigación en Materiales Avanzados, S.C. (CIMAV), Av. Miguel de Cervantes 120, Complejo Industrial Chihuahua, Chihuahua 31136, MexicoEnvironmental Analytical Chemistry Group, University of the Balearic Islands, Cra. Valldemossa 7.5 km, 07122 Palma de Mallorca, SpainA 3D-printed device was designed and printed by a stereolithographic technique (SLA) and coated with a highly selective solid phase extraction resin for on-site diclofenac extraction from wastewater, avoiding the transport and treatment of large volumes of samples in the laboratory. The best results in terms of chemical and mechanical resistance were obtained with Rigid 10K resin. The “stick-and-cure” impregnation technique was used to coat the 3D-printed device with Oasis<sup>®</sup> HLB resin. The coated 3D-printed device can be reused up to eight times without losing extraction efficiency. The eluent and derivatization reagent volumes were optimized by a multivariate design. The proposed method allowed for the extraction and determination of diclofenac by PTV-GC-MS, achieving methodological detection and quantification limits of 0.019 and 0.055 μg L<sup>−1</sup>, respectively, with a preconcentration factor of 46. The analysis time was 23 min per sample. To validate the proposed methodology, addition/recovery tests were carried out in different wastewater samples, obtaining recoveries above 90%. The methodology was applied at the wastewater treatment plant (WWTP) of Calvià (Mallorca, Spain), finding diclofenac in concentrations of 15.39 ± 0.07 μg L<sup>−1</sup> at the input of the primary decantation process, 4.48 ± 0.03 μg L<sup>−1</sup> at the output of the secondary decantation, and 0.099 ± 0.001 μg L<sup>−1</sup> at the output of the tertiary treatment, demonstrating the feasibility of the on-site extraction method in monitoring diclofenac over a wide concentration range. Finally, a greenness index of 0.58 for the proposed on-site sample preparation was achieved according to the AGREEprep metrics, making it an eco-friendly alternative for diclofenac monitoring.https://www.mdpi.com/2227-9040/13/6/212diclofenac3D-printed deviceon-site samplingsolid phase extractionGC-MS
spellingShingle César Castro-García
Edwin Palacio
Rogelio Rodríguez-Maese
Luz O. Leal
Laura Ferrer
Green On-Site Diclofenac Extraction from Wastewater Matrices Using a 3D-Printed Device Followed by PTV-GC-MS Determination
Chemosensors
diclofenac
3D-printed device
on-site sampling
solid phase extraction
GC-MS
title Green On-Site Diclofenac Extraction from Wastewater Matrices Using a 3D-Printed Device Followed by PTV-GC-MS Determination
title_full Green On-Site Diclofenac Extraction from Wastewater Matrices Using a 3D-Printed Device Followed by PTV-GC-MS Determination
title_fullStr Green On-Site Diclofenac Extraction from Wastewater Matrices Using a 3D-Printed Device Followed by PTV-GC-MS Determination
title_full_unstemmed Green On-Site Diclofenac Extraction from Wastewater Matrices Using a 3D-Printed Device Followed by PTV-GC-MS Determination
title_short Green On-Site Diclofenac Extraction from Wastewater Matrices Using a 3D-Printed Device Followed by PTV-GC-MS Determination
title_sort green on site diclofenac extraction from wastewater matrices using a 3d printed device followed by ptv gc ms determination
topic diclofenac
3D-printed device
on-site sampling
solid phase extraction
GC-MS
url https://www.mdpi.com/2227-9040/13/6/212
work_keys_str_mv AT cesarcastrogarcia greenonsitediclofenacextractionfromwastewatermatricesusinga3dprinteddevicefollowedbyptvgcmsdetermination
AT edwinpalacio greenonsitediclofenacextractionfromwastewatermatricesusinga3dprinteddevicefollowedbyptvgcmsdetermination
AT rogeliorodriguezmaese greenonsitediclofenacextractionfromwastewatermatricesusinga3dprinteddevicefollowedbyptvgcmsdetermination
AT luzoleal greenonsitediclofenacextractionfromwastewatermatricesusinga3dprinteddevicefollowedbyptvgcmsdetermination
AT lauraferrer greenonsitediclofenacextractionfromwastewatermatricesusinga3dprinteddevicefollowedbyptvgcmsdetermination