Halomethane sulfonic acids – standard synthesis, occurrence, and mitigation options Daniel Zahn1, Reinhard Meusinger2, Tobias Frömel1, Thomas P. Knepper1 1Hochschule Fresenius, University of Applied Sciences, Idstein, Germany 2TU Darmstadt, FB Chemie, Darmstadt, Germany Short summary of preceding research

Development of enrichment (multi-layer SPE3, combination Introduction of WAX, WCX, and activated carbon) and instrumental Halomethane sulfonic acids (HMSAs) are HMSAs methods dedicated for the identification and quantification recently discovered polar disinfection by- (Halomethane sulfonic acids) of very polar organic chemicals products (DBPs)1. So far their analysis was are novel DBPs exacerbated by the lack of commercially (disinfection by-products) available standards. Thus we synthesized standards for four Non-target screening with these methods prevalent HMSAs and deployed them to led to identification of halomethane sulfonic acids (HMSAs) as novel polar analyze their occurrence in drinking water water contaminants1 production plants (DWPPs) and tap water samples. In addition we determined the HMSA formation potential by chlorination of the samples to investigate the removal of the hitherto unknown HMSA precursors in DWPPs2.

H O H O H O DWPP 1 DWPP 2 DWPP 3 DWPP 4 Hydrolysis - Halogen - Flocculation Ventilation Preozonation Cl C S Cl Cl C S O Br C S O Decantation Deironization Flotation DW 1 exchange Filtration Demanganization Roughing filtration Aeration H O H O Chlorination Sand filtration Sand filtration Sand filtration 160° H O Slow sand filtration Softening Post-ozonation GAC filtration ͠ ͠ UV-treatment UV-treatment ͠ ͠ Chlorination DW 2 Reverse osmosis ng/L ClMSA • Two step synthesis of HMSAs: (1) hydrolysis of chlorinated sulfonyl chlorides

BrMSA HMSAs ng/L

and (2) halogen exchange from chlorine to bromine ∑ Cl2MSA SW surface water • Reaction control, purity assessment, and confirmation of product structure with BrClMSA GW ground water ion chromatography, high resolution mass spectrometry, and nuclear magnetic BF bank filtrate resonance spectroscopy (NMR), quantification with quantitative NMR DW drinking water

• Four HMSAs successfully synthesized: SW DW GW DW SW DW BF DW 1 DW 2 H O H O H O H O • HMSA were formed in the µg/L range during drinking water chlorination - - - - Cl C S O Br C S O Cl C S O Cl C S O • HMSA were present in two surface waters in the 100 ng/L range H O H O Cl O Br O X O • Seasonal trends in HMSA formation correspond roughly with TOC ClMSA BrMSA Cl2MSA BrClMSA of raw water (exception month 1 in DWPP 3) - X C S O X O • HMSA formation potential (sum parameter for HMSA precursors) X = H, Cl, Br, (I) • HMSAs were detected in all 14 tap water samples (0.07 µg/L – was utilized to indirectly assess removal of HMSA precursors 11.5 µg/L) • Original disinfection in DWPPs led to more efficient HMSA formation • Dihalogenated congeners were more prevalent in tap water than in DWPPs. This may be caused by further reaction of mono- • Significant HMSA precursor removal coincides with TOC reduction halogenated species with residual chlorine in the pipe system • Ozonation, granular or powder activated carbon filtration and reverse • High concentrations in Duarte may partially be attributed to sulfonic acid based osmosis most efficient treatment options for HMSA precursor removal water softener at sampling site

6 Germany Spain China USA 14

5 12

Great ClMSA Britain 100 mg/L BrMSA - 10

ClO Philippines 4 Cl MSA ? 3 hours 2 BrClMSA 8 3 *Coeluting interference µg/L 6 no results for BrMSA

2 HMSAs µg/L 4 ∑

1 2

0 * * * * * 0

Jinan

North

Manila

Duarte

London

Dresden

Frankfurt

Glendora

Shanghai

Barcelona

Hangzhou

Hollywood

Chongqing

Wiesbaden

Santiago Santiago de Compostela

References: Next steps: [1] Zahn, D., et al. Water Research 2016, 101, 292-299. HMSA synthesis strategy was successful [2] Zahn, D., et al., submitted • Extension of analyte spectrum (e.g. [3] Köke, N., et al. Analytical and Bioanalytical Chemistry 2018, HMSAs are widely spread and frequently present in 9, 2403-2411 iodinated HMSAs) [4] Reemtsma, T., et al. Environmental Science & Technology 2016, 50, 10308- the µg/L range in tap water 10315. • Further optimization of methods

Acknowledgement: The HMSA formation potential is a valuable tool • Large scale monitoring in tap water and The authors thank the European Union Joint Programming Initiative “Water for the study of hitherto unknown precursors environmental water samples Challenges for a Changing World” (Water JPI) and the BMBF for funding the PROMOTE project (FKZ: 02WU1347B) as well as Annika Harloff (HSF) who • Experimental assessment of toxicity participated in the synthesis of the standards and Victoria Zilles (HSF) who HMSAs may also be very polar environmental performed a large share of the lab work during the monitoring. In addition we thank Oasen for supplying the samples for one of the drinking water production plants, contaminants (potential vPvM or PM(T)) • Investigation of mlSPE to extend polarity Vittorio Albergamo (IBED-UvA) for organizing the shipment of the Oasen samples, range of AOX and Stefanie Schulze (UFZ) for coordinating the DWPP sampling campaign. HMSAs are not amenable to adsorbable organic halogen (AOX) analysis and thus Corresponding author: [email protected] demonstrate a polarity gap4 for the AOX For more information about the project or a copy of this poster please visit www.promote-water.eu or use this QR code