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Pharmaceuticals and Transformation Products in Hospital Wastewater - - PowerPoint PPT Presentation

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Pharmaceuticals and Transformation Products in Hospital Wastewater and a Rural Conventional Wastewater Treatment Plant Lydia Niemi Mark Taggart 1 , Kenneth Boyd 1 Zulin Zhang 2 , Stuart Gibb 1 1 Environmental Research Institute, University of

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Lydia Niemi Mark Taggart1, Kenneth Boyd1 Zulin Zhang2, Stuart Gibb1

Pharmaceuticals and Transformation Products in Hospital Wastewater and a Rural Conventional Wastewater Treatment Plant

1 Environmental Research Institute, University of the Highlands and Islands, Castle Street, Thurso KW14 7JD UK 2 The James Hutton Institute, Craigiebuckler Aberdeen AB15 8QH UK

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Pharma: ‘Emerging’ Environmental Contaminants

Comber et al. 2018; Information Services Division, 2018; Poirier-Larabie et al. 2016

  • Pharma extensively used: >102 mil prescriptions in Scotland (2016/17)
  • Enter environment mainly with WWTP effluent

2

Point source Wastewater treatment Surface water

Degradation?

Cl/H2O2 bio/hⱱ ?

?

hⱱ

Environmental Effects? Removal?

2

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3

1. Monitor hospital impact on pharma in municipal wastewater 2. Determine pharma change within conventional WWTP

Study location: Wick, Caithness County, Scottish Highlands

3. Characterise transformation product presence

Research Obje jectives

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Caithness General Hospital 1 WWTP Combined Influent 2 WWTP Primary Sample 3 WWTP Secondary Sample 4 WWTP Final Effluent 5

  • 13500 PE
  • 171 L/sec max. flow
  • Conventional AS
  • North Sea discharge

Wick WWTP

  • Only 24h A&E ‘major’ injuries unit

in region (>6800 km2)

  • 50 medical/surgical beds

Sampling frequency: 1x per week, 7 weeks May – July 2018

Study Sites & Sampling

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Target pharmaceuticals

Class Molecular Structure Molecular Weight (g/mol) pKa LogP Water Solubility (mg/L) Prescription Items, Scotland Prioritised Compound

Paracetamol

Analgesic 151.1 9.4 0.4 14000 2680000 No

Diclofenac

NSAID 296 4.1 4.5 50000 283150 Yes, UK and EU

Ibuprofen

NSAID 206 4.4 3.9 21 325281 Yes, UK

Clarithromycin

Macrolide Antibiotic 748 8.9 3.1 0.33 254270 Yes, UK and EU

Trimethoprim

Antibiotic 290 7.1 0.9 400 481168 Yes, UK

Carbamazepine

Anticonvulsant 236 13.9 2.4 17 216405 Yes, UK

Fluoxetine

Antidepressant 309.3 10.1 4.1 14000 844744 Yes, UK

17a-ethynyl estradiol

Synthetic Hormone 296 10.3 3.6 11 444944 Yes, UK and EU

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Bruker Triple Quadrupole QQQ HPLC-ESI-MS/MS

  • ESI+/-

Thermo Exactive Orbitrap Q1 UPLC-HESI-MS

  • HESI+/-

6

  • 1L SPE Oasis Prime

HLB, elution 12mL 1:1(v:v) Ace:EtOAc

2

  • 0.5mL reconstitute

1:1(v:v) MilliQ:MeOH

3

  • Instrumental

analysis

4

  • 1L 0.7µm filtration,

surrogate spike

1

Sample Processing & Analysis

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0102 3

  • 0.00

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 Time 100 % 100 % 100 % 100 % 100 % YUAN hospital project 0674 1: MRM of 4 Channels ES+ 152 > 110 1.75e6 YUAN hospital project 0638 2: MRM of 4 Channels ES+ 291 > 230 6.46e5

11.11

YUAN hospital project 0641 3: MRM of 4 Channels ES+ 237 > 194 2.21e5

17.19

YUAN hospital project 0641 4: MRM of 8 Channels ES+ 749 > 158 1.20e7

17.97

YUAN hospital project 0641 4: MRM of 8 Channels ES+ 310 > 44 2.13e4

18.40 19.51 22.17 24.98 3.13

Paracetamol (PAR)

3.13 min, 152 > 110 m/z

Trimethoprim (TRI)

11.11 min, 291 > 230 m/z

Clarithromycin (CLA)

17.97 min, 749 > 158 m/z

Carbamazepine (CBZ)

17.19 min, 237 > 194 m/z

Fluoxetine (FLX)

18.40 min, 310 > 44 m/z Detection frequency (%) of ESI+ mode pharma in wastewater samples. Limit of quantification (LOQ, ng/L).

HPLC separation ESI+ mode pharma in a hospital discharge sample.

7 PAR TRI CBZ CLAR FLX Hospital discharge (n=7,%) 85 85 100 57 14 WWTP Influent (n=7,%) 100 100 100 71 14 WWTP Primary (n=6,%) 100 100 100 66 n.d. WWTP Secondary (n=6,%) 50 100 100 100 100 WWTP Effluent (n=7,%) 85 100 100 100 100 LOQ (ng/L) 0.78 0.78 0.81 0.81 3.60

HPLC-MS/MS Detection

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0207 3

  • 0.00

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 Time 100 % 100 % YUAN hospital project 0838 1: MRM of 1 Channel ES- 205 > 161 1.70e6

2.63

YUAN hospital project 0855 2: MRM of 4 Channels ES- 294 > 250 5.78e6

2.06 3.29

Detection frequency (%) of ESI- mode pharma in wastewater samples. Limit of quantification (LOQ, ng/L). 17a-ethynyl estradiol (EE2) not detected (n.d.).

Ibuprofen, IBU

2.06 min, 205 > 161m/z

Diclofenac, DCF

3.29 min, 294 > 250 m/z

HPLC separation ESI- mode pharma in a hospital discharge sample.

8 IBU DCF EE2 Hospital discharge (n=7,%) 100 57 n.d. WWTP Influent (n=7,%) 85 57 n.d. WWTP Primary (n=6,%) 83 83 n.d. WWTP secondary (n=6,%) 100 66 n.d. WWTP effluent (n=7,%) 100 57 n.d. LOQ (ng/L) 0.78 0.77 4.01

HPLC-MS/MS Detection

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Pharma Concentrations

Hospital Discharge (n=7) WWTP Influent (n=7) WWTP Primary sample (n=6) WWTP Secondary sample (n=6) WWTP Effluent (n=7)

pKa= 9.4 LogP= 0.4 pKa= 10.1 LogP= 4.1

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Pharma Concentrations

Hospital Discharge (n=7) WWTP Influent (n=7) WWTP Primary sample (n=6) WWTP Secondary sample (n=6) WWTP Effluent (n=7)

* indicates significant difference

(p<0.05) between hospital discharge and WWTP influent, Welch two sample t-test

*

& Hospital Im Impact

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Pharma Removal in WWTP

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T: FTMS {1,1} + p ESI Full ms [100.00-2000.00] 100 150 200 250 300 350 400 450 500 10 20 30 40 50 60 70 80 90 100 253.0970 210.0913 271.1075 180.0808 293.0893 5 134.0711 356.1422 425.1308 491.2063

m/z

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RT: 0.00 - 32.02 2 4 6 8 10 12 14 16 18 20 22 24 Time (min) 50 100 50 100 50 100 RT: 13.51 AA: 22031274 RT: 11.99 AA: 658122 RT: 10.89 AA: 67737 RT: 10.21 AA: 15212112 RT: 11.91 AA: 4379074 RT: 8.99 AA: 1996168 RT: 13.60 AA: 207358 RT: 11.11 AA: 1626879

Carbamazepine and 2 transformation products in secondary sample, week 2.

  • ID after direct/indirect photolysis and biological degradation
  • 1 potential carcinogenic compound - acridine

Carbamazepine (CBZ)

17.51 min

Carbamazepine-10,11-epoxide

10.21 min

Dihydroxycarbamazepine 11.11 min

T: FTMS {1,1} + p ESI Full ms [100.00-2000.00] 100 150 200 250 300 350 400 450 500 10 20 30 40 50 60 70 80 90 100 269.0922 149.0233 244.0970 310.1185 198.0916 370.0831 405.2457 136.0215 182.9809 339.2376 207.1381 279.1591 414.2638 475.2084 509.4

* *Acridine (Δ1 ppm)

m/z

Mathon et al. 2016; Lekkerkerker-Teunissan et al. 2012; Donner et al. 2013

PARENT COMPOUND TP1

Transformation Products (T (TP)

TP2

*

TP1 TP2

253.0970 m/z (Δ0 ppm) 269.0922 m/z (Δ0 ppm) 237.1020 m/z (Δ1 ppm)

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2 4 6 8 10 12 14 16 18 20 Time (min) 20 40 60 80 100 RT: 4.66 AA: 3307590 RT: 1.19 AA: 10096 RT: 10.60 AA: 18746 RT: 13.29 AA: 16229 RT: 8.41 AA: 12026

Methoxy-paracetamol (M-PAR)

4.66 min, 182.0813 m/z (Δ2 ppm)

Transformation Products (T (TP)

Ibáñez et al. 2017

PARENT COMPOUND TP

Influent Primary Secondary Effluent

RT: 0.00 - 32.01 20 40 60 80 100 RT: 3.19 AA: 58082215 RT: 9.15 AA: 1744131 RT: 6.93 AA: 590705 RT: 2.08 AA: 238132 RT: 4.03 AA: 214673 RT: 10.65 AA: 107399 RT: 16.48 AA: 61201 RT: 12.32 AA: 19839 2 4 6 8 10 12 14 16 18 20 Time (min)

Paracetamol (PAR)

3.19 min, 152.0701 m/z (Δ1 ppm)

M-PAR n.d. PAR

  • PAR effective biological degradation (avg 96%

removal)

  • Methoxy-PAR formed during biological treatment

UHPLC chromatograms PAR (primary sample), M- PAR (secondary sample), week 1. PAR n.d. M-PAR

WWTP Influent WWTP Primary WWTP Secondary WWTP Effluent PAR (ng/L) 56307 7616-127437 (100%) 122806 15596-273859 (100%) 33 n.d.-61 (50%) 1890 360-4248 (100%)

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  • Pharma observable in hospital discharge, but other

significant sources impacting municipal wastewater

  • Wick WWTP ineffective for complete pharma removal
  • <50% avg removal TRI, CBZ; <0% avg removal DCF, FLX
  • Transformation product formation and persistence observed

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  • Wick harbour and rural environment potential

impact from pharma pollution

  • Tidal zones and estuaries are sink for pharma/organic pollutants

(Letsinger et al. 2019; Alygizakis et al. 2016)

  • 1st study of pharma behaviour in rural Scottish

Highlands WWTP

Conclusions & Significance

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Supervisors: Stuart Gibb, Zulin Zhang, Mark Taggart, Kenny Boyd Project contributors: Sylvain Massière (Université de Montpellier, France), Scottish Water Research funders: The Scottish Government’s Hydro Nation Scholars Programme

Thank you!

lydia.niemi@uhi.ac.uk @LydiaNiemi

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Acknowledgements

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SLIDE 16

References

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transformation products under controlled environmental conditions. Science of the Total Environment, 557, 257–267.

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Environmental Toxicology and Chemistry, 35(4), 823–835.

  • Comber, S., Gardner, M., Sörme, P., et al. (2018). Active pharmaceutical ingredients entering the aquatic environment from wastewater

treatment works: A cause for concern? Science of the Total Environment, 613–614, 538–547.

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2019), https://www.isdscotland.org/.

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environmental risk after secondary treatment – A Review. Science of the Total Environment, 429, 123 – 155.

  • Letsinger, S., Kay, P., Rodrigues-Mozaz, S. et al. (2019). Spatial and temporal occurrence of pharmaceuticals in UK estuaries. Science of the

Total Environment, 678, 74-84.

  • Alygizakis, N., Gago-Ferrero, P., Borova, V., et al. (2016). Occurrence and spatial distribution of 158 pharmaceuticals, drugs of abuse and

related metabolites in offshore seawater. Science of the Total Environment, 541, 1097-1105.

  • Samson, S. (2003). Wick Wastewater Treatment Plant, UK Water Projects Online, website (accessed Apr 2019),

http://www.waterprojectsonline.com/case_studies/2004/Scottish_Wick_2004.pdf.

  • Caithness General Hospital Services, NHS Highland, website (accessed Apr 2019), https://www.nhshighland.scot.nhs.uk/services/pages/.
  • Ibáñez et al. 2017
  • Mathon, B., Choubert, J.-M., Miege, C., & Coquery, M. (2016). A review of the photodegradability and transformation products of 13

pharmaceuticals and pesticides relevant to sewage polishing treatment. Science of The Total Environment, 551, 712–724. Lekkerkerker- Teunissan et al. 2012

  • Donner, E., Kosjek, T., Qualmann, S., Kusk, K. O., Heath, E., Revitt, D. M., Andersen, H. R. (2013). Ecotoxicity of carbamazepine and its UV

photolysis transformation products. Science of the Total Environment, The, 443, 870–876.

  • Lekkerkerker-Teunissen, K., Benotti, M. J., Snyder, S. A., & van Dijk, H. C. (2012a). Transformation of atrazine, carbamazepine, diclofenac and

sulfamethoxazole by low and medium pressure UV and UV/H2O2 treatment. Separation and Purification Technology, 96, 33–43.

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