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Chemical Analysis of Dumped Chemical Warfare Agents During the MODUM Project

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Towards the Monitoring of Dumped Munitions Threat (MODUM)

Abstract

MODUM project continued the work on monitoring of the chemical weapons (CW) dumped in the Baltic Sea started in previous projects. As a new aspect, on board analysis methods – headspace gas chromatography-mass spectrometry (GC–MS) and capillary electrophoresis (CE) – were developed and tested in laboratory conditions and during cruises. The GC–MS method could be successfully applied on board to verify that collected sediment samples contained degradation products for sulfur mustard, one of the major chemical warfare agents dumped in Baltic Sea. This method could in future project be used during cruises to redirect sample collection in order to make most of the available ship time. Other part of the analysis task during MODUM project was the work done at the reach back laboratories. These analyses were done to both verify the results obtain on board and to fully identify the chemicals related to the sea-dumped CW agents. Reach back analysis of CW-related chemicals were done on sediment samples collected around a wreck in Bornholm Deep (same samples as analyzed on board) and on monitoring samples collected in Bornholm, Gotland and Gdańsk Deeps. The samples from Bornholm and Gotland Deeps are in line with previous findings. Samples from Gdańsk Deep are in line with previous findings that this area has been used as a dump site. Additionally, α-chloroacetophenone (CN) was found in the area for the first time. In addition to the analysis of CW-related chemicals, a new method was developed for measurement for arsenic concentrations in sediment samples. A method was also developed for arsenic speciation, which could help in estimation of the source of arsenic in the sediments.

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Abbreviations

AED:

atomic emission detector

AMDIS:

Automatic Mass spectral Deconvolution and Identification Software

APCI:

atmospheric pressure chemical ionisation

Asb:

arsenobetaine

BGE:

background electrolyte

BPA:

butylphosphonic acid

C4D:

capacitively coupled contactless conductivity detector

CBRN:

chemical, biological, radiological, nuclear

CE:

capillary electrophoresis

CHEMSEA:

Chemical Munitions Search and Assessment, an EU-funded project

CW:

chemical warfare

CWA:

chemical warfare agent

CWC:

Chemical Weapons Convention

DMA:

dimethylarsine

EDEA:

ethyldiethanolamine

EEZ:

extended economic zone

EMPA:

ethyl methylphosphonate

ESI:

electrospray ionization

FOI:

Swedish Defence Research Agency, Umeå, Sweden

GC:

gas chromatography

GC–MS:

gas chromatography-mass spectrometry

GC–MS/MS:

gas chromatography-tandem mass spectrometry

HD:

sulphur mustard

HRMS:

high resolution mass spectrometry

ICP-MS:

inductively coupled plasma mass spectrometry

IOPAS:

Institute of Oceanology of the Polish Academy of Sciences

L:

Lewisite

LC–HRMS:

liquid chromatography-high mass spectrometry

LOD:

limit of detection

MDEA:

methyldiethanolamine

MMA:

monomethylarsine

MODUM:

Towards the Monitoring of Dumped Munitions Threat, a NATO-funded project

MPA:

methylphosphonic acid

MS:

mass spectrometry

MUT:

Military University of Technology, Warsaw, Poland

PMPA:

propyl methylphosphonate

PPA:

propylphosphonic acid

ppb:

part-per-billion (e.g. μg/kg)

PrSH:

propane-1-thiol

SIM:

selected ion monitoring

SRM:

selected reaction monitoring

TDG:

thiodiglycol

TDGO:

thiodiglycol sulfoxide

TDGOO:

thiodiglycol sulfone

TEA:

triethanolamine

TTÜ:

Tallinn University of Technology, Estonia

UHPLC:

ultra-high performance liquid chromatography

VERIFIN:

Finnish Institute for Verification of the Chemical Weapons Convention, University of Helsinki, Finland

WWI:

First World War

WWII:

Second World War

XRF:

X-ray fluorescence spectrometry

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Author information

Authors and Affiliations

  1. Finnish Institute for Verification of the Chemical Weapons Convention, University of Helsinki, Helsinki, Finland

    Martin Söderström & Paula Vanninen

  2. Swedish Defence Research Agency, Umeå, Sweden

    Anders Östin, Johanna Qvarnström, Roger Magnusson & Jenny Rattfelt-Nyholm

  3. Tallinn University of Technology, Tallin, Estonia

    Merike Vaher, Piia Jõul, Heidi Lees & Mihkel Kaljurand

  4. Institute of Oceanology, Polish Academy of Sciences, Sopot, Poland

    Marta Szubska & Jacek Bełdowski

Authors
  1. Martin Söderström
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  2. Anders Östin
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  3. Johanna Qvarnström
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  4. Roger Magnusson
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  5. Jenny Rattfelt-Nyholm
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  6. Merike Vaher
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  7. Piia Jõul
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  8. Heidi Lees
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  9. Mihkel Kaljurand
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  10. Marta Szubska
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  11. Paula Vanninen
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  12. Jacek Bełdowski
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Corresponding author

Correspondence to Martin Söderström .

Editor information

Editors and Affiliations

  1. Department Marine Chemistry & Geochemistry, Institute of Oceanology PAS, Sopot, Poland

    Jacek Bełdowski

  2. Centre for Maritime Research and Experimentation (STO - CMRE), Science and Technology Organisation, La Spezia, Italy

    Robert Been

  3. Emerging Security Challenges Division, Science for Peace & Security (SPS) Programme, Brussels, Brussels Hoofdst.ge., Belgium

    Eyup Kuntay Turmus

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Söderström, M. et al. (2018). Chemical Analysis of Dumped Chemical Warfare Agents During the MODUM Project. In: Bełdowski, J., Been, R., Turmus, E. (eds) Towards the Monitoring of Dumped Munitions Threat (MODUM). NATO Science for Peace and Security Series C: Environmental Security. Springer, Dordrecht. https://doi.org/10.1007/978-94-024-1153-9_4

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