Many environmental emerging organic contaminants, as pharmaceutical products and illicit drugs (IDs), are present in surface waters and in wastewater [1]. Drugs obtained by Cannabis are among them due to the large diffusion and accessibility of such substances, experienced by ¼ of European citizens during their lifetime [2]. Hemp and marijuana are two different types of Cannabis plants. Together with many other constituents, marijuana-type plants present high cannabinoids and Δ9-Tetrahydrocannabinol (THC) content, while hemp-types show significantly lower THC content (i.e. < 0,2%, w/w). Secondary wastewater effluent (SWWE) from a waste water treatment plant (WWTP) and water from the Febros River in the Porto urban area (Fig.1) were collected to investigate the occurrence of cannabinoids with the aim to confirm the need of tertiary treatment of waters to removal these kinds of contaminants.MATERIAL AND METHODS All standards were purchased from Sigma Aldrich (Germany). The experimental plan was: -lab pre-experience spiking Milli-Q water with standard solutions to perform and validate robust analytical methods; - water real samples collecting from SWWE and from the Febros River and their analysis. Instrumentation : water ACQUITY UPLC® system (Waters, UK) with heated module interfaced to a triple quadrupole mass spectrometer equipped with an electrospray ionization (ESI) source (TQD, Waters, UK). Three different sorbent types (Oasis HLB, Oasis MCX and Oasis MAX) and quantities (1,3,6 mL) were evaluated using Milli-Q water spiked with the standard solutions. The nine considered analytes showed satisfactory absolute recoveries (65–130%) using Oasis MCX and Oasis HLB cartridges; the latter (6mL) was selected for the multiresidual method and for the semi-automated pre-concentration protocol. RESULTS & DISCUSSION Table 1 reports the cannabinoid MM, their ESI optimized via Intellistart™, LOD and LOQ, the Intermediate Precision (IP) for three replicates at 0.5 μg/L, and the repeatability (REP) as the RSD (%) of retention time and area for five repetitions at 0.125 μg/L on lab samples. Table 2 shows the quantization of cannabinoids in real samples. The analytes detected at very low concentration levels (below LOQ) were considered as positive findings when all the three transitions acquired were observed and at least one Q/q ratio was within the tolerance limits. The multiresidual method shows that these residues were not completely removed in the WWTP, suggesting that an advanced tertiary treatment could be necessary to increase the performance of the plant and achieve a complete disappearance of these recalcitrant substances. .......Concluding Results of this scientific work evidences as the mass spectrometry is very important for the detection at low concentration of the cannabis secondary metabolites (cannabinoids) in SWWE. Obviously, more comprehensive studies on the occurrence of this class of emerging contaminants (i.e. CBD, CBDA, CBN, THCA-A) in the aquatic environment are needed to better understand the usage of this plant metabolites (used as drug or pharmaceuticals). The most studied cannabinoid THC and its main human metabolite THC-COOH was not present at relevant concentrations in River and WWE samples as described in [4]. The secondary treatment applied in the WWTP seems not to be effectively and completely removing this class of compounds [5] as significant amounts are released into surface water. For this reason a water tertiary treatment could be necessary and suggested.

SPE-UPLC–ESI-MS/MS APPLICATION TO DETECTION OF CANNABIS SECONDARY METABOLITES IN WASTEWATER AND RIVER WATER

L. Milella;F. Lelario;G. Bianco;L. Foti;S. A. Bufo;L. Scrano
2019

Abstract

Many environmental emerging organic contaminants, as pharmaceutical products and illicit drugs (IDs), are present in surface waters and in wastewater [1]. Drugs obtained by Cannabis are among them due to the large diffusion and accessibility of such substances, experienced by ¼ of European citizens during their lifetime [2]. Hemp and marijuana are two different types of Cannabis plants. Together with many other constituents, marijuana-type plants present high cannabinoids and Δ9-Tetrahydrocannabinol (THC) content, while hemp-types show significantly lower THC content (i.e. < 0,2%, w/w). Secondary wastewater effluent (SWWE) from a waste water treatment plant (WWTP) and water from the Febros River in the Porto urban area (Fig.1) were collected to investigate the occurrence of cannabinoids with the aim to confirm the need of tertiary treatment of waters to removal these kinds of contaminants.MATERIAL AND METHODS All standards were purchased from Sigma Aldrich (Germany). The experimental plan was: -lab pre-experience spiking Milli-Q water with standard solutions to perform and validate robust analytical methods; - water real samples collecting from SWWE and from the Febros River and their analysis. Instrumentation : water ACQUITY UPLC® system (Waters, UK) with heated module interfaced to a triple quadrupole mass spectrometer equipped with an electrospray ionization (ESI) source (TQD, Waters, UK). Three different sorbent types (Oasis HLB, Oasis MCX and Oasis MAX) and quantities (1,3,6 mL) were evaluated using Milli-Q water spiked with the standard solutions. The nine considered analytes showed satisfactory absolute recoveries (65–130%) using Oasis MCX and Oasis HLB cartridges; the latter (6mL) was selected for the multiresidual method and for the semi-automated pre-concentration protocol. RESULTS & DISCUSSION Table 1 reports the cannabinoid MM, their ESI optimized via Intellistart™, LOD and LOQ, the Intermediate Precision (IP) for three replicates at 0.5 μg/L, and the repeatability (REP) as the RSD (%) of retention time and area for five repetitions at 0.125 μg/L on lab samples. Table 2 shows the quantization of cannabinoids in real samples. The analytes detected at very low concentration levels (below LOQ) were considered as positive findings when all the three transitions acquired were observed and at least one Q/q ratio was within the tolerance limits. The multiresidual method shows that these residues were not completely removed in the WWTP, suggesting that an advanced tertiary treatment could be necessary to increase the performance of the plant and achieve a complete disappearance of these recalcitrant substances. .......Concluding Results of this scientific work evidences as the mass spectrometry is very important for the detection at low concentration of the cannabis secondary metabolites (cannabinoids) in SWWE. Obviously, more comprehensive studies on the occurrence of this class of emerging contaminants (i.e. CBD, CBDA, CBN, THCA-A) in the aquatic environment are needed to better understand the usage of this plant metabolites (used as drug or pharmaceuticals). The most studied cannabinoid THC and its main human metabolite THC-COOH was not present at relevant concentrations in River and WWE samples as described in [4]. The secondary treatment applied in the WWTP seems not to be effectively and completely removing this class of compounds [5] as significant amounts are released into surface water. For this reason a water tertiary treatment could be necessary and suggested.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11563/136062
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