Analysis of an ampoule found on a WW2 German soldier: Poison or medicine?

Abstract

During archaeological excavations in Maltot, Normandy (France), the remains of a German soldier probably dating from Operation Jupiter (July 10–11, 1944) were discovered. The study of the body showed that he was a man aged 17 to 20 at the time of death. His death was likely caused by several recent projectile impacts: bullet entry orifice in the skull and several shrapnel traces in the upper limbs. Several objects were found near the body, including the remains of a leather and metal box at the level of is abdomen containing about ten glass whole ampoules while 2 others laid loose. The objective of this work was to identify the contents of these ampoules, with an emphasis on poisons. Screenings were carried out on the contents of the vial using HPLC-DAD, GC-MS, HS-GC-MS and HR-LC-MS/MS. Multi-element research by ICP-MS was also conduct as well as cyanide research. Volatile compounds quantification was performed using GC-MS equipped with a Triplus AS Head space injector (Thermo Fisher Scientific, Les Ulis, France). Chromatographic separation was achieved on a Rtx-VMS column (30 m × 0.25 mm, dF = 1.4 μm) (Restek, Lisses, France) with helium as carrier gas at a constant flow rate of 1.2 mL/min. Injector temperature was held at 65 °C and split injection mode was employed with a split flow of 80. The GC conditions were as follows: column temperature started at 40 °C, was held for 2 min then increased to 150 °C at a rate of 10 °C/min then held for 1minute. 5 μL of the sample was put in a sealed vial then heated to 80 °C during 20 minutes with a 10 second agitation step. 0.2 mL of the gas phase was injected in the GC/MS. Data acquisition was performed using the Xcalibur v2.1 software (Thermo Fisher Scientific). The detection was operated in SIM mode. Propan-1-ol was used as internal standard (E.I.). Calibrators were prepared at 50, 100, 200, 500 and 1000 mg/L in DMSO. Analyzed ampoule was 6 cm long and 0.5 cm wide and contained approximately 300 μL of a colorless, water-immiscible liquid, with a characteristic solvent odor. HPLC-DAD, GC-MS, HR-LC-MS/MS, ICP-MS and cyanide screenings were negative. However, the HS-GC-MS analysis revealed the presence of several volatile products: ethanol (360 g/L), chloroform (392 g/L), diethyl ether (87 g/L), as well as isopropanol, trichloroethylene and tetrachloroethylene at concentrations lower than 5 g/L. No poison but two anesthetic substances (chloroform and diethyl ether) associated with an alcoholic solvent (ethanol) were found. Therefore, the soldier was probably a medic. The anesthetic properties of ether were discovered in 1846 leading to a revolution in surgery and the beginnings of anesthesia. A few months later, the anesthetic properties of chloroform were uncovered. Around 1860, in England, the A.C.E. mixture which consisted of 1 part alcohol, 2 parts chloroform and 3 parts ether was preferred over chloroform alone. This mixture was later introduced in Germany where it was used until WW2 (Wawersik J. J Clin Anesth, 1991 3(3) 235–244). Composition of the analyzed vials seems to match this A.C.E. mixture and coherent with historical knowledge. These molecules were administrated by inhalation and it was often regarded as a safe and simple procedure for urgent situations as encountered on the battlefield. For more complex procedures, use of barbiturates was preferred. After WW2, A.C.E. mixture was abandoned in favor of less toxic anesthetics such as nitrous oxide.