De Paepe, E.

Demeestere, K.

Huysman, S.

Van Langenhove, H.

Van Meulebroek, L.

Vanhaecke, L.

Vanryckeghem, F.

Open Marine Archive

TARGETED, SUSPECTED & NON-TARGET SCREENING WITH HIGH RESOLUTION 
MASS SPECTROMETRY IN THE MARINE ENVIRONMENT: READY TO GO?
1 FACULTY OF VETERINARY MEDICINE, DEPARTMENT OF VETERINARY PUBLIC AND FOOD SAFETY, LABORATORY OF CHEMICAL ANALYSIS, MERELBEKE, BELGIUM
2 FACULTY OF BIOSCIENCE ENGINEERING, DEPARTMENT OF SUSTAINABLE ORGANIC CHEMISTRY AND TECHNOLOGY, ENVIRONMENTAL ORGANIC CHEMISTRY AND TECHNOLOGY, GHENT, BELGIUM
S. Huysman1, F. Vanryckeghem2, L. Van Meulebroek1, E. De Paepe1, H. Van Langenhove2, K. Demeestere2 and L. Vanhaecke1
Acknowledgments
This poster fits within the NewSTHEPS project
(BR/143/NEWSTHEPS) supported by BELSPO,
www.newstheps.be
Contact
Steve.Huysman@Ugent.be
Lynn.Vanhaecke@Ugent.be
www.vvv.ugent.be
Introduction
Materials & Methods
Objectives
Results
Conclusion
Targeted screening: 70 EDCs
Suspected screening: 225 conjugates of the EDCs
Untargeted screening: unknown compounds
Fig 1. UHPLC-HRMS.
• Accurate mass (m/z)
• Isotope profile (13C/12C-ratio)
• Retention time (min)
• Accurate mass (m/z)
• Isotope profile (13C/12C-ratio)
• Accurate mass (m/z) 
ó Online database Pubchem & Chemspider
Instrumentation
(X-Callibur™)
(Huysman et al., ACA, 2017)
(ToxFinder™)
(Sieve™ & Simca™)
(ToxID™)
Sampling, pre-treatment & extraction
Fig 6. PCA-X Plot displaying the untargeted analysis of different sampling locations and periods in the positive ionization mode.
(1) & (5): 51.2263°, 2.9357°
(2) & (6): 51.2468°, 3.1136°
(3) & (7): 51.3401°, 3.2003°
Targeted screening Untargeted screeningSuspected screening
Fig 4. Heatmap illustrating the occurrence of 43 targeted EDCs.
Introduction
17b -estradiol
estradiol-17-acetate
cortisone
cortisol
Fig 5. Suspected screening enabling the detection of 44 unique
suspected EDCs.
estradiol cypionate
fluocortin butyl
Grab samples: 2.5 L
Filtering & pH adjustment to 3
Loading on  hydrophillic DVB 
Speedisk™
Elution with 5 mL ACN & 
5 mL of 0.1% FA in ACN
Evaporation & centrifuging
Reconstitution to 150 µL 
(40/60 v/v% CH3OH/H2O)
Fig 2. Optimised extraction protocol for grab 
samples obtained from the marine environment.
• Monitoring the Belgian Part of the North Sea (BPNS)
• 2 sampling campaigns, i.e. fall 2016 (1-4) & winter 
2017 (5-7), at 4 different sampling locations:
- Harbour of Oostende: (1) & (5)
- Oostende Open Sea: (2) & (6)
- Harbour of Zeebrugge: (3) & (7)
- Zeebrugge Open Sea: (4)
Fig 3. The different sampling locations that were monitored in the BPNS.
• Targeted screening: 43 different steroidal EDCs were quantified
• Suspected screening: 44 unique suspected EDCs were detected
• Untargeted screening: enabled environmental molecular differences according to the sampling locations
Many organic micropollutants, such as pharmaceuticals, pesticides, natural and
synthetic steroids have received special attention because of their omnipresence
in the environment. Frequently, these compounds find their way to the
environment as water pollutants, whether or not metabolised or degraded,
resulting in some constraints towards environmental monitoring. While triple
quadrupole analysers currently enable only a predefined list of compounds in
samples, high resolution mass spectrometry (HRMS) make it possible to detect a
virtually unlimited number of compounds in a single run without preselection.
Therefore, an in-house validated UHPLC-HRMS method was used for screening
the marine environment on steroidal EDCs. This study included the quantification
of 70 targeted steroidal EDCs, and on top of that the suspected screening of 225
EDCs and a virtually unlimited number of unknown compounds.
Low High
The marine environment was successful screened using an environmental omics approach:
Multi-variate analysis
→ Scaling: pareto
→ Transformation: log
→ Compound Intensities > 106
(4): 51.3605°, 3.1136°
Quality control 
Legend
• Evaluating an environmental omics approach using HRMS
• Screening the marine environment on steroidal EDCs
• Performing 3 analytical approaches: targeted, suspected, and untargeted analysis
• Composing a relevant suspected database
• Assessing the impact on the marine environment, i.e. toxicity and potential harm
Goals:
Challenges:
• Micropollutants present at sub ppb-concentrations
• Different biotic and abiotic processes result in a wide range of 
known and unknown transformation products of the micropollutants
Database of 
225 compounds


Targeted, suspected and non-target screening with high resolution mass spectrometry in the marine environment : ready to go?

Huysman, Steve

Vanryckeghem, Francis

Van Meulebroek, Lieven

De Paepe, Ellen

Van Langenhove, Herman

Demeestere, Kristof

Vanhaecke, Lynn

Ghent University Academic Bibliography

TARGETED, SUSPECTED & NON-TARGET SCREENING WITH HIGH RESOLUTION MASS SPECTROMETRY IN THE MARINE ENVIRONMENT: READY TO GO?1 FACULTY OF VETERINARY MEDICINE, DEPARTMENT OF VETERINARY PUBLIC AND FOOD SAFETY, LABORATORY OF CHEMICAL ANALYSIS, MERELBEKE, BELGIUM2 FACULTY OF BIOSCIENCE ENGINEERING, DEPARTMENT OF SUSTAINABLE ORGANIC CHEMISTRY AND TECHNOLOGY, ENVIRONMENTAL ORGANIC CHEMISTRY AND TECHNOLOGY, GHENT, BELGIUMS. Huysman1, F. Vanryckeghem2, L. Van Meulebroek1, E. De Paepe1, H. Van Langenhove2, K. Demeestere2 and L. Vanhaecke1AcknowledgmentsThis poster fits within the NewSTHEPS project(BR/143/NEWSTHEPS) supported by BELSPO,www.newstheps.beContactSteve.Huysman@Ugent.beLynn.Vanhaecke@Ugent.bewww.vvv.ugent.beIntroductionMaterials & MethodsObjectivesResultsConclusionTargeted screening: 70 EDCsSuspected screening: 225 conjugates of the EDCsUntargeted screening: unknown compoundsFig 1. UHPLC-HRMS.• Accurate mass (m/z)• Isotope profile (13C/12C-ratio)• Retention time (min)• Accurate mass (m/z)• Isotope profile (13C/12C-ratio)• Accurate mass (m/z) ó Online database Pubchem & ChemspiderInstrumentation(X-Callibur™)(Huysman et al., ACA, 2017)(ToxFinder™)(Sieve™ & Simca™)(ToxID™)Sampling, pre-treatment & extractionFig 6. PCA-X Plot displaying the untargeted analysis of different sampling locations and periods in the positive ionization mode.(1) & (5): 51.2263°, 2.9357°(2) & (6): 51.2468°, 3.1136°(3) & (7): 51.3401°, 3.2003°Targeted screening Untargeted screeningSuspected screeningFig 4. Heatmap illustrating the occurrence of 43 targeted EDCs.Introduction17b -estradiolestradiol-17-acetatecortisonecortisolFig 5. Suspected screening enabling the detection of 44 uniquesuspected EDCs.estradiol cypionatefluocortin butylGrab samples: 2.5 LFiltering & pH adjustment to 3Loading on  hydrophillic DVB Speedisk™Elution with 5 mL ACN & 5 mL of 0.1% FA in ACNEvaporation & centrifugingReconstitution to 150 µL (40/60 v/v% CH3OH/H2O)Fig 2. Optimised extraction protocol for grab samples obtained from the marine environment.• Monitoring the Belgian Part of the North Sea (BPNS)• 2 sampling campaigns, i.e. fall 2016 (1-4) & winter 2017 (5-7), at 4 different sampling locations:- Harbour of Oostende: (1) & (5)- Oostende Open Sea: (2) & (6)- Harbour of Zeebrugge: (3) & (7)- Zeebrugge Open Sea: (4)Fig 3. The different sampling locations that were monitored in the BPNS.• Targeted screening: 43 different steroidal EDCs were quantified• Suspected screening: 44 unique suspected EDCs were detected• Untargeted screening: enabled environmental molecular differences according to the sampling locationsMany organic micropollutants, such as pharmaceuticals, pesticides, natural andsynthetic steroids have received special attention because of their omnipresencein the environment. Frequently, these compounds find their way to theenvironment as water pollutants, whether or not metabolised or degraded,resulting in some constraints towards environmental monitoring. While triplequadrupole analysers currently enable only a predefined list of compounds insamples, high resolution mass spectrometry (HRMS) make it possible to detect avirtually unlimited number of compounds in a single run without preselection.Therefore, an in-house validated UHPLC-HRMS method was used for screeningthe marine environment on steroidal EDCs. This study included the quantificationof 70 targeted steroidal EDCs, and on top of that the suspected screening of 225EDCs and a virtually unlimited number of unknown compounds.Low HighThe marine environment was successful screened using an environmental omics approach:Multi-variate analysis→ Scaling: pareto→ Transformation: log→ Compound Intensities > 106(4): 51.3605°, 3.1136°Quality control Legend• Evaluating an environmental omics approach using HRMS• Screening the marine environment on steroidal EDCs• Performing 3 analytical approaches: targeted, suspected, and untargeted analysis• Composing a relevant suspected database• Assessing the impact on the marine environment, i.e. toxicity and potential harmGoals:Challenges:• Micropollutants present at sub ppb-concentrations• Different biotic and abiotic processes result in a wide range of known and unknown transformation products of the micropollutantsDatabase of 225 compounds

https://biblio.ugent.be/publication/8532798/file/8532799

Targeted, suspected and non-target screening with high resolution mass spectrometry in the marine environment : ready to go?

Abstract

Similar works

Full text

Available Versions

Open Marine Archive

Ghent University Academic Bibliography