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 diffuse emissions turning them into a point source! Chemicals in wastewater = subset of chemicals circulating in urban area WWTP
Substance (group) Air Rivers MWWTP 3 Dioxins (PCDD, PCDF, dioxin-like PCBs) 13 5 Some background Other PCBs (other than dioxin-like) 6 6 5 6 Organotin compounds (TBT, TPhT, etc) -4 7 • Information request to Contracting Parties in PBDEs (pentaBDE, octaBDE, decaBDE) 6 9 4 2015 ”concern about inputs of various POPs” PFAS (PFOS, PFOA) 6 10 8 • Concern = CPs consider or believe being 4 HBCDD 2 6 12 transported to Baltic Sea Nonylphenols (NP, NPE) -4 10 Octylphenols (OP, OPE) -4 8 12 • Via MWWTPs and RIVERS Short-chain chlorinated paraffins (C10-13) 1 4 5 3 Medium-chain chlorin. paraffins (C14-17) -2 2 • Why call for data? 2 Endosulfan 2 3 • Better understanding of monitoring data 2 DDTs (sum-DDT, DDE, etc) 4 6 • Assess need for focus in future HELCOM PAHs (incl. metabolites) 15 9 8 activities BFRs (PBDEs etc) 3 6 5 • Long term goal = revise list of Priority HCHs (alpha, beta, gamma) 5 6 4 Substances 4 Heptachlor 0 1 • Reduce amount of hazardous substances in 14 Heavy metals Pharmaceutical residues 12 Baltic Sea region 6 Herbicides (except listed above) Substances of concern 5 Fungicides (except listed above) • Weighted approach: 5 Insecticides (except listed above) • 3 = major concern Endocrine disrupting substances (EDS, • 2= medium concern except listed above) 9 • 1= little concern Animal/veterinary drug residues (except • No data = 0 listed above) 2 • Not relevant = -1 Disinfectants (except listed above) 5
CPs that reported data (not Poland and Russia) 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
Locations river samples and WWTPs phenols and PFAS
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
Nonylphenols Octylphenols
Nonyl and octylphenols Decision for now until The Name Issue – what is measured? further information, to use for data aggregation and comparison: Wastewater Method Harmonized CAS Rivers Method Harmonized CAS Sweden Sweden 4-nonylphenol 104-40-5 GC-MS 104-40-5 4-nonylphenol 84852-15-3 GC-MS/MS QQQ 25154-52-3 4-nonylphenol (branched) 84852-15-3 GC-MS 25154-52-3 Estonia Germany 4-nonylphenol 104-40-5 DIN EN ISO 18857 104-40-5 Nonylphenol-p 25154-52-3 EN ISO 18857 25154-52-3 Germany Denmark 4-Nonylphenol 104-40-5 NA 104-40-5 4-nonylphenol 104-40-5 GC/MS 104-40-5 4-nonylphenol (branched) 25154-52-3 NA 25154-52-3 Nonylphenol 25154-52-3 GC/MS 25154-52-3 Latvia Nonylphenol 25154-52-3 LC-HRMS 25154-52-3 PubChem PubChem Lithuania 104-40-5 84852-15-3 Nonylphenol 25154-52-3 HPLC-MS 25154-52-3 4-nonylphenol 2-nonylphenol 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
Environmental Quality Standard Compare EQS to what? Nonylphenol = 4-nonylphenol (linear) + 4-nonylphenol (branched) ...??? CPs probably use different approaches 2008 EQS directive
25154-52-3 104-40-5 1806-26-4 140-66-9 108-95-2 Map data availability Nonylphenol 4-nonylphenol Octylphenol Octylphenol-p-tert monophenols Effluent >DL 281 5 0 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 All substances often Estonia, detected in sludge ”monophenols” (but few samples) Nonylphenol often detected in effluents and rivers Most samples from effluents (Influent = DK)
WWTPs Nonylphenol, CAS 25154-52-3 Reporting countries: Current Sweden, Germany, Denmark EQS Nonylphenol, average concentration, effluents , all years, only > DL
All WWTPs ng/ L (obs scale) 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
N/ O-phenols: Weighted and normal average concentration, effluents, all years Weighted according to treated volume wastewater Assuming conc = DL when Including only > DL below DL AA-EQS = 300 ng/ L for nonylphenol Obs AA-EQS for Octylphenol = 100-10 ng/ L ! error bars = 1 st dev
Rivers&Coast, Nonylphenol, CAS 25154-52-3 Obs proportional area of circles! Current EQS Reporting CPs: All but Denmark, Poland, Russia Helsinki Estonia reports only monophenols Daugava river, Riga (Obs different Kalmar scale on this map) Klaipeda
Rivers&Coast ng/ L (obs scale) (minus marker = DL or QL) 300 ng/ L Black line = av conc WWTP effluents, all countries 46 ng/ L Latvia – sometimes very high conc (?), downstream WWTP? 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
What about the load? Are emissions/ PE (Obs not equal size of similar in the region? bins here) Weighted av conc Number of PE in each watershed Poland = large population
PFAS
Map data availability WWTPs
WWTPs: PFOS and PFOA average concentration ng/ L, effluents, all years Detected in all reporting countries, effluents
Effluents 22 ng/ L Assuming conc < DL = DL AA-EQS PFOS = 0.65 ng/ L
Rivers&Coasts Per country Per substance
Rivers&Coasts PFAS detection frequency
EQS directive 2008 Rivers&Coasts obs ug/ L Chronic quality standard = 2 ng/ L AA-EQS inland= 0.65 ng/ L
Rivers&Coasts Average conc, all countries High concentrations in some locations impact av conc Geometric mean
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
Recommend
More recommend
