Highly polar organic substances may be able to

penetrate natural and artificial barriers and are thus

mobile in the water cycle. If these mobile organic

contaminants (MOC) are persistent (PMOC)

against microbiological and chemical degradation,

their removal during waste water treatment and

drinking water purification[1] may prove difficult. If

these substances are present in high concentrations,

toxic or undergo toxication[2], problems for the aquatic

environment and human health may arise.

As a consequence of the lack of established

analytical methods for MOC, only limited

information about the occurrence fate and

distribution of these substances is available. In the

PROMOTE project, we strive to close this gap in

knowledge.

In this work, a newly developed SPE[3] method that

allows enrichment of PMOC from aqueous samples is

presented and deployed in combination with a

suitable HILIC/HRMS method to perform a non-target

screening for potential PMOC in environmental water

samples, including polluted well and ground water,

tap water and milliQ water as blank. Preliminary

results of the non-target screening are shown.

Daniel Zahn, Tobias Frömel, Thomas P. KnepperCorresponding e-mail address: Knepper@hs-fresenius.de

University of Applied Sciences Fresenius, Institute for Analytical Research (IFAR), Idstein, Germany

Non-target screening of highly polar organic micropolutants in environmental

water samples

Introduction

100 mLpH 5.5

H2O

WCXGCB

MeOH

ACN/H2OWAX

HILIC/HRMS

+ 6556- 3122∑ 9678

N2

well water

tap water

ground water

t0

tap water

ground water

well water

milliQ water

m/z 215.0384rel. height 100%

m/z 216.0416rel. height 10.1% m/z 217.0340

rel. height 4.3%

Elemental composition:C9H11O4S

-

∆ = 0.4 ppm

C9H11O4S- appears to have a sufficient persistency

and mobility in the water cycle to reach drinking

water, and is thus classified as PMOC.

Structure and origin of C9H11O4S are still under

investigation.

XIC 215.0384width 5ppm

milliQ water

MS

For further information about the project or a copy of the poster please visit

www.ufz.de/promote or use this QR code

XICswidth 5ppmall ground water

C8H7SO5-

∆ = -1.3 ppm

C12H15SO5-

∆ = -0.4 ppm

C13H17SO5-

∆ = -1.7 ppm

C10H11SO5-

∆ = -0.1 ppm

C9H9SO5-

∆ = 0.1 ppm

C11H13SO5-

∆ = 1.1 ppm

MS² C11H13SO5-

Conclusion and outlook

XIC 148.9526width 5ppm

milliQ water

tap water

well water

ground water

MS

m/z 148.9527rel. height 100%

m/z 149.9558rel. height 0.8%

m/z 150.9482rel. height 4.5%

Elemental composition:CF3SO3

-

∆ = 1.1 ppm

The unequivocal elemental composition for the ion

m/z 148.9526 is CF3SO3-. Only two chemically sound

structures exist for this elemental composition:

References:

[1] T.P. Knepper et al. Waste Manage. (Oxford) 1999, 19,

77-99.

[2] Schmidt, C. K.; Brauch, H.-J. Environmental Science &

Technology 2008, 42, 6340.

[3] Zahn, D.; Frömel, T.; Knepper, T. P. work in progress

Acknowledgement:

We thank the BMBF and JPI water for funding the

PROMOTE (Protecting Water Resources from Mobile

Trace Chemicals) project (FKZ: 02WU1347B).

F

F

F

S

O

O

O-

FF

F

SO

O

O-

Trifluoromethanesulfonate Trifluoromethyl sulfite

Of the two proposed structures for m/z 148.9526

Trifluoromethanesulfonate, the anion of triflic acid, is

more likely to occur in environmental water samples.

Triflic acid has a high production volume (> 100 t/a)

and is applied in various processes including

vulcanization and polymerization. A confirmation of

the proposed structure is still pending.

MS² C12H15SO5-

Indicates R-SO3H

Odd electron fragment.

Indicates increased radical

stability. Fragment is

independent of chain lengths.

Cleavage of CO2

indicates R-COOH

A supposed series of homologues was observed

during the non-target screening. The MS2 spectra

of the most abundant homologues (assuming a

similar ESI response) were compared to facilitate

structural elucidation. In addition, fractions were

collected, evaporated to dryness, reconstituted in

D2O/ACN 1:1 (v:v) and measured with HRMS by

direct infusion.

For both homologues a cleavage of CO2 as well as

an SO3●- fragment were observed, indicating the

presence of a carboxylic acid and a sulfonic acid

group respectively.

The fragment C7H6O3S●- is identical for both

homologues and violates the even electron rule,

thus indicating a position of increased radical

stability in the molecule. A benzylic position appears

to be most likely but other alternatives cannot be

ruled out by the available spectrometric information.

The mass shift of 1 Da for the deprotonated

molecule after H/D exchange is in compliance with

the proposed structure. Structural elucidation of

these substances is still ongoing.

C7H6S

O

O

OH

O

OH

(CH2)n

Area: 4.5*105

Area: 1.2*107

Area: 7.5*107

Area: 3.4*105

Area: 6.3*106

Area: 1.3*108

Area: 1.8*106

Area: 9.8*106

Area: 5.0*107

Area: 2.6*108

Area: 1.3*108

Area: 6.0*105

The preliminary screening results are a strong

indicator that PMOC may impact drinking water.

Identification of the detected substances, however is

a laborious task and prioritization is required to select

the most promising and important candidates for

structural elucidation.

A more comprehensive screening campaign with a

higher number of samples and a spatial spread over

several European countries is in preparation.