Büro für Altlastenerkundung und Umweltforschung

Dr. Rainer Haas

Stadtwaldstr. 45a, D-35037 Marburg, Tel.: 06421/93084, Fax: 06421/93073

email: haasr@gmx.net

Analysis of byproducts of sulfur mustard

Rainer Haas, Torsten C. Schmidt

Büro für Altlastenerkundung und Umweltforschung, Stadtwaldstr. 45a, D-35037 Marburg

Translation, original article was published in UWSF - Z. Umweltchem. Oekotox. 8 (1996), 241-242, ecomed publishers, D-86899 Landsberg, Germany


Sulfur mustard (Bis(2-Chloroethyl)sulfide) reacts upon several metabolites under environmental conditions. The analytical measurement of the most important metabolites Thiodiglycol, Thiodiglycolsulfon and 1,4-Dithiane was achieved either with GC/ECD or with HPLC/diodearray detection. The methods and detection limits are described.

Key words: chemical warfare agents, sulfur mustard, gas chromatography, analysis

1 Introduction

1822 sulfur mustard was synthesised first time from DESPRETZ. NIEMANN investigated in 1860 the toxic effects of sulfur mustard on skin (1). During WW 1 in germany 7.660 t sulfur mustard were produced as chemical warfare agents. During WW 2 in germany 25.200 t sulfur mustard were produced and stored (2).

2 Chemical reactions in the environmential surrounding

In aqueous solutions sulfur mustard is quickly hydrolysed in two steps reaction via 2-Chloro-2-hydroxy diethyl sulfide to Bis(2-hydroxyethyl)-sulfide (Thiodiglycol, TDG). In two hours the hydrolysis is completed.

The oxidation product of TDG is Bis(2-hydroxyethyl)-sulfon (Thiodiglycolsulfon, TDGO). In aqueous solutions containing sulfide 1,4-Dithiane is obtained (1,3,4).

3 Analysis of degradation products of sulfur mustard

TDG, TDGO and 1,4-Dithiane can be determined with gas chromatographic and HPLC methods. Analysis were done with methanolic reference solutions of this compounds.

This compounds are separated with gas chromatography under the following chromatographic conditions:

Column: DB5 capillary column, length 30 m, diameter: 0.25 mm

Column temperature: 100°C (10°C/min) 230°C, 230°C (7 min)

Detector temperature: 300°C

Injector temperature: 250°C

Injection volume: 1 µl

Detector: electron capture detector (ECD).

In table 1 the retention times (Tr) and limits of detection (LOD) are shown.

Table 1: Gas chromatographic separation of sulfur mustard reaction products; Retention times and limits of detection



LOD (ng)













With HPLC analysis this compounds are separated and detected under the following conditions:

Column: reversed phase RP 18 Nucleosil 120, length 25 cm, diameter 3 mm

flow: 0.3 ml/min

gradient methanol/water 50/50 to methanol/water 90/10 within 40 min

Detector: diode array detector (DAD)

Injection volume: 20 µl.

Detection was done with a DAD at a wavelength of 210 nm. TDG has an absorption maximum at 266 nm, it is possible to detect TDG with a lower LOD at this wavelength. In table 2 the retention times and limits of detection are presented.

Table 2: HPLC separation of sulfur mustard reaction products; Retention times and limits of detection


Tr (min)

LOD (ng)






20 (210 nm)



(266 nm)




4 Literature

1) Martinetz, D.: Ruestungsaltlast S-Lost; Terra-Tech 2 (1993), 40-44

2) Hahn, F.: Waffen und Geheimwaffen des deutschen Heeres 1939-1945, Band 1; Koblenz 1986

3) Lohs, Kh.: Schwefel-Lost (2,2-Dichlordiethylsulfid - noch immer toxikologisch aktuell; Z. aerztl. Fortbild. 87 (1993), 659-664

  1. Franke, S.: Lehrbuch der Militaerchemie, Band 1, 2. Auflage, Berlin-Ost 1977