German Environment Agency 0 1 2 3 4 5 6 7 8 1 Non-Phthalates DIUP DPHP DIDP (without DPHP) DINP DEHP LMW-Phthalates TOTM DINCH DEHAz DINA DEHA ATBC R1 R2 R3 R4 S1 S2 E1 E2 E3 E4 E5 Mu Sa Beyond DEHP: high-molecular-weight phthalate and non-phthalate plasticizers in German rivers Regine Nagorka and Jan Koschorreck, German Environment Agency Results • In 2014, total levels for plasticizers ranged between 0,5 -11 μg/g dw SPM • At some sites the levels of plastizisers were higher in 2014 than in 2005/06. • DEHP levels decreased by 20 to 70% from 2005 to 2014 and the high- molecular-weight phthalate DINP became the dominant plasticizer. • Concentrations for the DEHP-substitute DPHP (EU CoRAP list, evaluation 2019) increased at all sites. • The new non-phthalate plasticizer DINCH – marketed in the EU since 2002 - is present in SPM samples from all sites. Outlook As a next step we will elaborate temporal trend series with additional ESB samples. contact: German Environment Agency, P.O. Box 14 06, 06813 Dessau- Roßlau [email protected], [email protected] www.umweltbundesamt.de , www.umweltprobenbank.de/en Figure 4: Plasticizers in SPM samples from German Rivers in 2014 TOTM: Tris(2-ethylhexyl) trimellitate, DINCH: Diisononyl cyclohexane-1,2-dicarboxylate, DEHAz: Di(2-ethylhexyl) azelate, DINA: Diisononyl adipate, ATBC: Acetyltributyl citrate, DEHA: Di(2-ethylhexyl) adipate Figure 3: Levels of non-phthalate plasticizers in SPM samples from 2005/06 and 2014 2005/06 2014 Figure 2: Levels of DPHP in SPM samples from 2005/06 and 2014 Figure 1: Levels of phthalate and non-phthalate plasticizers in SPM samples from 2005/06 and 2014 (black bars: conc. 2014 > 2005/06) Objective The global demand for plasticizers is expected to rise to 10 million tons per year by 2020. High-molecular-weight phthalates and non-phthalates are replacing the former blockbuster DEHP on the market. Some of the substitutes are under scrutiny, e.g. DPHP that has been added to the EU REACH CoRAP list. Data are needed on the spatial and temporal trends of these substances in the environment. Methods Suspended particulate matter (SPM) was collected monthly at 16 sampling sites from major rivers in Germany. SPM was sieved to < 2mm and stored above LN 2 in the German Environmental Specimen Bank (ESB). Sample treatment involved solvent extraction (ultra sonic) and Florisil Clean-up. Samples were analysed with APCI-LC-MS/MS. 0 2 4 6 8 10 12 μg/kg dw 0 200 400 600 800 1000 R1 R2 R3 R4 S1 S2 E1 E2 E3 E4 E5 Mu Sa ng/g dw R1 R2 R3 R4 S1 S2 E1 E2 E3 E4 E5 Mu Sa 2005/06 2014 0 4 8 12 16 20 R1 R2 R3 R4 S1 S2 E1 E2 E3 E4 E5 Mu Sa μg/g dw R1 R2 R3 R4 S1 S2 E1 E2 E3 E4 E5 Mu Sa 2005/06 2014 (Di(2-propylheptyl) phthalate) (Diisodecyl phthalate) (Diisononyl phthalate) (Di(2-ethylhexyl) phthalate) (Diisoundecyl phthalate) 0 200 400 600 800 1000 R1 R2 R3 R4 S1 S2 E1 E2 E3 E4 E5 Mu Sa ng/g dw

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Page 1: Beyond DEHP: high-molecular-weight phthalate and non

German Environment Agency

012345678

Non-Phthalates

DIUP

DPHP

DIDP (without DPHP)

DINP

DEHP

LMW-Phthalates

TOTM DINCH DEHAz DINA DEHA ATBC

R1 R2 R3 R4 S1 S2 E1 E2 E3 E4 E5 Mu Sa

Beyond DEHP: high-molecular-weight phthalateand non-phthalate plasticizers in German rivers

Regine Nagorka and Jan Koschorreck, German Environment Agency

Results

• In 2014, total levels for plasticizers ranged between 0,5 -11 µg/g dw SPM

• At some sites the levels of plastizisers were higher in 2014 than in

2005/06.

• DEHP levels decreased by 20 to 70% from 2005 to 2014 and the high-

molecular-weight phthalate DINP became the dominant plasticizer.

• Concentrations for the DEHP-substitute DPHP (EU CoRAP list, evaluation

2019) increased at all sites.

• The new non-phthalate plasticizer DINCH – marketed in the EU since

2002 - is present in SPM samples from all sites.

OutlookAs a next step we will elaborate temporal trend series with additional ESB

samples.

contact:

German Environment Agency, P.O. Box 14 06, 06813 Dessau-

Roßlau

[email protected], [email protected]

www.umweltbundesamt.de, www.umweltprobenbank.de/en

Figure 4: Plasticizers in SPM samples from German Rivers in 2014

TOTM: Tris(2-ethylhexyl) trimellitate, DINCH: Diisononyl cyclohexane-1,2-dicarboxylate, DEHAz: Di(2-ethylhexyl) azelate, DINA: Diisononyl adipate, ATBC: Acetyltributyl citrate, DEHA: Di(2-ethylhexyl) adipate

Figure 3: Levels of non-phthalate plasticizers in SPM samples from 2005/06and 2014

2005/06 2014

Figure 2: Levels of DPHP in SPM samples from 2005/06 and 2014

Figure 1: Levels of phthalate and non-phthalate plasticizers in SPM samplesfrom 2005/06 and 2014 (black bars: conc. 2014 > 2005/06)

Objective The global demand for plasticizers is expected to rise to 10 million tons per year by 2020. High-molecular-weight phthalates and non-phthalates are replacing the former

blockbuster DEHP on the market. Some of the substitutes are under scrutiny, e.g. DPHP that has been added to the EU REACH CoRAP list. Data are needed on the spatial

and temporal trends of these substances in the environment.

MethodsSuspended particulate matter (SPM) was collected monthly at 16 sampling sites from major rivers in Germany. SPM was sieved to < 2mm and stored above LN2 in the German Environmental Specimen Bank (ESB). Sample treatment involved solvent extraction (ultra sonic) and Florisil Clean-up. Samples were analysed with APCI-LC-MS/MS.

µg

/kg

200

400

600

800

1000

R1 R2 R3 R4 S1 S2 E1 E2 E3 E4 E5 Mu Sa

ng/g dw

R1 R2 R3 R4 S1 S2 E1 E2 E3 E4 E5 Mu Sa

2005/06 2014

R1 R2 R3 R4 S1 S2 E1 E2 E3 E4 E5 Mu Sa