Analysis of HELCOM data n+ o-phenols, PFAS Preliminary results - - PowerPoint PPT Presentation

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Analysis of HELCOM data n+ o-phenols, PFAS Preliminary results - - PowerPoint PPT Presentation

Mar 25, 2024 350 likes •622 views

Analysis of HELCOM data n+ o-phenols, PFAS Preliminary results Emma Undeman, Baltic Sea Centre PhD, environmental chemist emma.undeman@su.se HELCOM Action on micropollutants WWTPs = important transport routes to the Baltic Sea Collects

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Analysis of HELCOM data n+ o-phenols, PFAS Preliminary results

Emma Undeman, Baltic Sea Centre

PhD, environmental chemist emma.undeman@su.se

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HELCOM Action on micropollutants

WWTP

WWTPs = important transport routes to the Baltic Sea Collects diffuse emissions turning them into a point source! Chemicals in wastewater = subset of chemicals circulating in urban area

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Some background

  • Information request to Contracting Parties in

2015 ”concern about inputs of various POPs”

  • Concern = CPs consider or believe being

transported to Baltic Sea

  • Via MWWTPs and RIVERS
  • Why call for data?
  • Better understanding of monitoring data
  • Assess need for focus in future HELCOM

activities

  • Long term goal = revise list of Priority

Substances

  • Reduce amount of hazardous substances in

Baltic Sea region

Substances of concern

  • Weighted approach:
  • 3 = major concern
  • 2= medium concern
  • 1= little concern
  • No data = 0
  • Not relevant = -1

Substance (group) Air Rivers MWWTP Dioxins (PCDD, PCDF, dioxin-like PCBs) 13 5 3 Other PCBs (other than dioxin-like) 6 6 5 Organotin compounds (TBT, TPhT, etc)

  • 4

7 6 PBDEs (pentaBDE, octaBDE, decaBDE) 6 9 4 PFAS (PFOS, PFOA) 6 10 8 HBCDD 2 6 4 Nonylphenols (NP, NPE)

  • 4

10 12 Octylphenols (OP, OPE)

  • 4

8 12 Short-chain chlorinated paraffins (C10-13) 1 4 5 Medium-chain chlorin. paraffins (C14-17)

  • 2

2 3 Endosulfan 2 3 2 DDTs (sum-DDT, DDE, etc) 4 6 2 PAHs (incl. metabolites) 15 9 8 BFRs (PBDEs etc) 3 6 5 HCHs (alpha, beta, gamma) 5 6 4 Heptachlor 1 4 Heavy metals 14 Pharmaceutical residues 12 Herbicides (except listed above) 6 Fungicides (except listed above) 5 Insecticides (except listed above) 5 Endocrine disrupting substances (EDS, except listed above) 9 Animal/veterinary drug residues (except listed above) 2 Disinfectants (except listed above) 5

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Denmark Estonia Germany Finland Latvia Lithuania Sweden

WWTPs phenols Effluent x x x x Influent x Sludge x x PFAS Effluent x x x x Influent x Sludge x x metals Effluent x x x x x Influent x x x Sludge x x Rivers&Coasts phenols x x x x x x PFAS x x x x x x

CPs that reported data (not Poland and Russia)

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Locations river samples and WWTPs phenols and PFAS

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What can we tell from this data?

  • Map data availability – no of samples, above/ under DL
  • Levels in WWTPs (influent, effluent, sludge)
  • Levels in rivers and coastal water
  • Comparison to e.g. EQSs
  • Time trends
  • Differences between countries
  • Basis for total load estimations
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Nonylphenols Octylphenols

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Rivers Method Harmonized CAS Sweden 4-nonylphenol 84852-15-3 GC-MS/MS QQQ 25154-52-3 Estonia 4-nonylphenol 104-40-5 DIN EN ISO 18857 104-40-5 Germany 4-Nonylphenol 104-40-5 NA 104-40-5 4-nonylphenol (branched) 25154-52-3 NA 25154-52-3 Latvia Nonylphenol 25154-52-3 LC-HRMS 25154-52-3 Lithuania Nonylphenol 25154-52-3 HPLC-MS 25154-52-3 4-nonylphenol 104-40-5 HPLC-MS 104-40-5 4-nonylphenol (branched) 84852-15-3 HPLC-MS 84852-15-3 Finland Nonylphenol 84852-15-3 LC,MS 25154-52-3

Wastewater Method Harmonized CAS Sweden 4-nonylphenol 104-40-5 GC-MS 104-40-5 4-nonylphenol (branched) 84852-15-3 GC-MS 25154-52-3 Germany Nonylphenol-p 25154-52-3 EN ISO 18857 25154-52-3 Denmark 4-nonylphenol 104-40-5 GC/MS 104-40-5 Nonylphenol 25154-52-3 GC/MS 25154-52-3

The Name Issue – what is measured?

Nonyl and octylphenols

Decision for now until further information, to use for data aggregation and comparison:

PubChem 84852-15-3 2-nonylphenol ??? PubChem 104-40-5 4-nonylphenol

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Compare EQS to what? Nonylphenol = 4-nonylphenol (linear) + 4-nonylphenol (branched) ...??? CPs probably use different approaches 2008 EQS directive Environmental Quality Standard

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Map data availability

25154-52-3 104-40-5 1806-26-4 140-66-9 108-95-2 Nonylphenol 4-nonylphenol Octylphenol Octylphenol-p-tert monophenols Effluent >DL 281 5 29 393 tot 448 206 15 239 395 Sludge >DL 25 3 3 25 8 tot 25 3 3 28 8 Influent >DL 144 11 tot 157 150

Data from Estonia, ”monophenols” All substances often detected in sludge (but few samples) Nonylphenol often detected in effluents and rivers Most samples from effluents (Influent = DK)

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Nonylphenol, average concentration,

effluents, all years, only > DL

Reporting countries:

Sweden, Germany, Denmark

WWTPs Nonylphenol, CAS 25154-52-3

Current EQS

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ng/ L (obs scale)

All WWTPs

AA_EQS 300 ng/ L Suggested Chronic EQS 46 ng/ L

The Ecotox Centre Eawag-EPFL is the centre for applied ecotoxicology in Switzerland

http: / / www.ecotoxcentre.ch/ expert-service/ quality-standards/ proposals-for-acute-and-chronic-quality-standards/ ?_ga= 2.249800390.1187598368.1501852275-848254315.1501852275

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N/ O-phenols: Weighted and normal average concentration, effluents, all years Weighted according to treated volume wastewater

Assuming conc = DL when below DL error bars = 1 st dev

AA-EQS = 300 ng/ L for nonylphenol Obs AA-EQS for Octylphenol = 100-10 ng/ L !

Including only > DL

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Rivers&Coast, Nonylphenol, CAS 25154-52-3

Reporting CPs: All but Denmark, Poland, Russia Estonia reports

  • nly monophenols

(Obs different scale on this map)

Current EQS

Obs proportional area of circles!

Helsinki Daugava river, Riga Klaipeda Kalmar

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ng/ L (obs scale) (minus marker = DL or QL) Black line = av conc WWTP effluents, all countries Latvia – sometimes very high conc (?), downstream WWTP?

Rivers&Coast

The Ecotox Centre Eawag-EPFL is the centre for applied ecotoxicology in Switzerland

http: / / www.ecotoxcentre.ch/ expert-service/ quality-standards/ proposals-for-acute-and-chronic-quality-standards/ ?_ga= 2.249800390.1187598368.1501852275-848254315.1501852275

300 ng/ L 46 ng/ L

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What about the load? Are emissions/ PE similar in the region? Number of PE in each watershed Poland = large population

Weighted av conc

(Obs not equal size of bins here)

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PFAS

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WWTPs Map data availability

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WWTPs: PFOS and PFOA average concentration ng/ L, effluents, all years Detected in all reporting countries, effluents

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22 ng/ L Assuming conc < DL = DL

Effluents

AA-EQS PFOS = 0.65 ng/ L

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Rivers&Coasts

Per country Per substance

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Rivers&Coasts

PFAS detection frequency

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Chronic quality standard = 2 ng/ L

Rivers&Coasts

AA-EQS inland= 0.65 ng/ L

  • bs

ug/ L

EQS directive 2008

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Rivers&Coasts Average conc, all countries

High concentrations in some locations impact av conc  Geometric mean

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Implications for HELCOM work

WFD/ MSFD: Nonylphenols – name and CAS issue, what is measured and what is compared to EQS PFOS is priority substance. HELCOM: Both substance groups frequently exceed EQS, can be relevant as Core Indicators. Relationship HELCOM Core Indicators – WFD/ MSFD Priority substances? Nonylphenol – used to be HELCOM prio substance. Reasons for removal? Stockholm Convention: PFOS