Advertisement

Chemical Analysis of Dumped Chemical Warfare Agents During the MODUM Project

  • Martin SöderströmEmail author
  • Anders Östin
  • Johanna Qvarnström
  • Roger Magnusson
  • Jenny Rattfelt-Nyholm
  • Merike Vaher
  • Piia Jõul
  • Heidi Lees
  • Mihkel Kaljurand
  • Marta Szubska
  • Paula Vanninen
  • Jacek Bełdowski
Conference paper
First Online:
Part of the NATO Science for Peace and Security Series C: Environmental Security book series (NAPSC)

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.

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

This is a preview of subscription content, log in to check access.

References

  1. Aleksenko SS, Gareil P, Timerbajev AR (2011) Analysis of degradation products of chemical warfare agents using capillary electrophoresis. Analyst 136:4103–4118CrossRefGoogle Scholar
  2. Arison HL III (2013) European disposal operations: the sea disposal of chemical weapons.. CreateSpaceGoogle Scholar
  3. Bełdowski J, Szubska M, Emelyanov E, Garnaga G, Drzewińska A, Bełdowska M, Vanninen P, Östin A, Fabisiak J (2016a) Arsenic concentrations in Baltic Sea sediments close to chemical munitions dumpsites. Deep Sea Research Part II 128:114–122CrossRefGoogle Scholar
  4. Bełdowski J, Klusek Z, Szubska M, Turja R, Bulczak AI, Rak D, Brenner M, Lang T, Kotwicki L, Grzelak K, Jakacki J, Fricke N, Östin A, Olsson U, Fabisiak J, Garnaga G, Rattfelt Nyholm J, Majewski P, Broeg K, Söderström M, Vanninen P, Popiel S, Nawała J, Lehtonen K, Berglind R, Schmidt B (2016b) Chemical Munitions Search & Assessment-an evaluation of the dumped munitions problem in the Baltic Sea. Deep-Sea Research II 128:85–95CrossRefGoogle Scholar
  5. Bissen M, Frimmel FH (2003) Arsenic – a Review. Part I: occurrence, toxicity, speciation, mobility. Acta Hydrochim Hydrobiol 31:9–18CrossRefGoogle Scholar
  6. Borg H, Jonsson P (1996) Large-scale metal distribution in Baltic Sea sediments. Mar Pollut Bull 32:8–21CrossRefGoogle Scholar
  7. BSH, Bundesamt für Seeschifffahrt und Hydrographie (1993) Chemical munitions in the southern and western Baltic Sea – report by a federal/Länder government working group (in German) and cited references. Hamburg, GermanyGoogle Scholar
  8. Coleman K (2005) A history of chemical warfare. Palgrave Macmillan, Houndmills, Basingstoke, HampshireCrossRefGoogle Scholar
  9. Ding Y, Rogers K (2008) Measurement of nitrogen mustard degradation products by poly(dimethylsiloxane) microchip electrophoresis with contactless conductivity detection. Electroanalysis 20:2192–2198CrossRefGoogle Scholar
  10. Ellwood MJ, Maher WA (2003) Measurement of arsenic species in marine sediments by high-performance liquid chromatography-inductively coupled plasma mass spectrometry. Anal Chim Acta 477:279–291CrossRefGoogle Scholar
  11. Emelyanov EM (2007) The geochemical and geoecological situation of the Gotland Basin in the Baltic Sea where chemical munitionss were dumped. Geologija 60:10–26Google Scholar
  12. Emelyanov E, Kravtsov V, Savin Y, Paka V, Khalikov I (2010) Influence of chemical weapons and warfare agents on the metal contents in sediments in the Bornholm Basin, the Baltic Sea. Baltica 23:77–90Google Scholar
  13. Fauser P, Sanderson H, Hedegaard RV, Sloth JJ, Larsen MM, Krongaard T, Bossi R, Larsen JB (2013) Occurence and sorption properties of arsenicals in marine sediments. Environ Monit Assess 185:4679–4691CrossRefGoogle Scholar
  14. Fish JT, Stout RN, Wallace E (2010) Practical crime scene investigations for hot zones. CRC Press, Boca RatonCrossRefGoogle Scholar
  15. Flora SJS (ed) (2015) Handbook on arsenic toxicology. Elsevier, LondonGoogle Scholar
  16. Garnaga G, Wyse E, Azemard S, Stankevicius A, de Mora S (2006) Arsenic in sediments from the southeastern Baltic Sea. Environ Pollut 144:855–861CrossRefGoogle Scholar
  17. Hammes TX (2004) The sling and the stone: on war in the 21st century. Zenith, Grand Rapids, MIGoogle Scholar
  18. Hanaoka S, Nomura K, Wada T (2006) Determination of mustard and lewisite related compounds in abandoned chemical weapons (yellow shells) from sources in China and Japan. J Chromatogr A 1101:268–277CrossRefGoogle Scholar
  19. Harkabusová V, Macharáčková B, Čelechovská O, Vitulová E (2009) Determination of arsenic in the rainbow trout muscle and rice samples. Czech J Food Sci 27:404–406Google Scholar
  20. Heleg-Shabtai V, Gratziany N, Liron Z (2006) Separation and detection of VX and its methylphosphonic acid degradation products on a microchip using indirect laser-induced fluorescence. Electrophoresis 27:1996–2001CrossRefGoogle Scholar
  21. IMO, International Maritime Organization (1972) Convention on the prevention of marine pollution by dumping of wastes and other matter http://www.imo.org/en/About/conventions/listofconventions/pages/convention-on-the-prevention-of-marine-pollution-by-dumping-of-wastes-and-other-matter.aspx. Accessed 12 April 2017
  22. IMO, International Maritime Organization (1996) Protocol to the convention on the prevention of marine pollution by dumping of wastes and other matter, 1972. http://www.imo.org/en/OurWork/Environment/PollutionPrevention/Pages/1996-Protocol-to-the-Convention-on-the-Prevention-of-Marine-Pollution-by-Dumping-of-Wastes-and-Other-Matter,-1972.aspx. Accessed 12 April 2017
  23. Jõul P, Lees H, Vaher M, Kobrin EG, Kaljurand M, Kuhtinskaja M (2015) Development of a capillary electrophoresis method with direct UV detection for the analysis of thiodiglycol and its oxidation products. Electrophoresis 36:1202–1207CrossRefGoogle Scholar
  24. Knobloch T, Bełdowski J, Böttcher C, Söderström M, Rühl N-P, Sternheim J (2013) Chemical munitions dumped in the Baltic Sea. Report of the ad hoc expert group to update and review the existing information on dumped chemical munitions in the Baltic Sea (HELCOM MUNI), Baltic Sea environment proceeding (BSEP) no. 142, Baltic marine environment protection commission (HELCOM), 128 pagesGoogle Scholar
  25. Kubáň P, Seiman A, Makarõtševa N, Vaher M, Kaljurand M (2011) In situ determination of nerve agents in various matrices by portable capillary electropherograph with contactless conductivity detection. J Chromatogr A 1218:2618–2625CrossRefGoogle Scholar
  26. Li SFY (1992) Capillary electrophoresis: principles, practice, and applications, Journal of Chromatography Library, vol 52. Elsevier Science Publishers, The NetherlandsGoogle Scholar
  27. Magnusson R, Nordlander T, Östin A (2016) Development of a dynamic headspace gas chromatography-mass spectrometry method for on-site analysis of sulfur mustard degradation products in sediments. J Chromatogr A 1429:40–52CrossRefGoogle Scholar
  28. Makarõtševa N, Seiman A, Vaher M, Kaljurand M (2010) Analysis of the degradation products of chemical warfare agents using a portable capillary electrophoresis instrument with various sample injection devices. Procedia Chem 2:20–25CrossRefGoogle Scholar
  29. Mazurek M, Witkiewicz Z, Popiel S, Sliwakowski M (2001) Capillary gas chromatography-atomic emission spectroscopy-mass spectrometry analysis of sulphur mustard and transformation products in a block recovered from the Baltic Sea. J Chromatogr A 919:133–145CrossRefGoogle Scholar
  30. MERCW, Modelling of Ecological Risk Related to Sea-Dumped Chemical Weapons, (2006) Synthesis paper on available data. http://www.mercw.org/images/stories/pdf/synthesis_d2.1.pdf. Accessed 12 April 2017
  31. Meyer M, Maurer H (2016) Review: LC coupled to low- and high-resolution mass spectrometry for new psychoactive substance screening in biological matrices – where do we stand today? Anal Chim Acta 927:13–20CrossRefGoogle Scholar
  32. Munro N, Talmage SS, Waters LC, Guy AB, Griffin D, Watson P, King JF, Hauschild V (1999) The sources, fate, and toxicity of chemical warfare agent degradation products. Environ Health Perspect 107:933–974CrossRefGoogle Scholar
  33. Nicholas DR, Ramamoorthy S, Palace V, Spring S, Moore JN, Rosenzweig RF (2003) Biogeochemical transformations of arsenic in circumneutral freshwater sediments. Biodegradation 14:123–137CrossRefGoogle Scholar
  34. Niedzielski P, Siepak M, Siepak J (2000) Występowanie i zawartość arsenu, antymonu i selenu w wodach i innych elementach środowiska. Rocznik Ochrona Środowiska 2:317–341Google Scholar
  35. OPCW, Organisation for Prohibition of the Chemical Weapons (1993) Convention on the Prohibition of the development production, stockpiling and use of chemical weapons and on their destruction. https://www.opcw.org/fileadmin/OPCW/CWC/CWC_en.pdf. Accessed 12 April 2017
  36. Östin A (2013) Review of analytical methods for the analysis of agents related to dumped chemical weapons for the CHEMSEA project, CHEMSEA ProjectGoogle Scholar
  37. Pumera M (2006) Analysis of nerve agents using capillary electrophoresis and laboratory-on-a-chip technology. J Chromatogr A 1113:5–13CrossRefGoogle Scholar
  38. Røen BT, Unneberg E, Tørnes JA, Lundanes E (2010) Headspace-trap gas chromatography-mass spectrometry for determination of sulphur mustard and related compounds in soil. J Chromatogr A 1217:2171–2178CrossRefGoogle Scholar
  39. Rohrbaugh D, Yang Y (1997) Liquid chromatography/electrospray mass spectrometry of mustard-related sulfonium ions. J Mass Spectrom 32:1247–1252CrossRefGoogle Scholar
  40. Sáiz J, Mai TD, Hauser PC, García-Ruiz C (2013) Determination of nitrogen mustard degradation products in water samples using a portable capillary electrophoresis instrument. Electrophoresis 34:2078–2084CrossRefGoogle Scholar
  41. Sanderson H, Fauser P, Thomsen M, Sorensen PB (2008) Screening level fish community risk assessment of chemical warfare agents in the Baltic Sea. J Hazard Mater 154:846–857CrossRefGoogle Scholar
  42. Seiman A, Jaanus M, Vaher M, Kaljurand M (2009) A portable capillary electropherograph equipped with a cross-sampler and a contactless-conductivity detector for the detection of the degradation products of chemical warfare agents in soil extracts. Electrophoresis 30:507–514CrossRefGoogle Scholar
  43. Söderström M (2014) Summary of chemical analysis of sediment samples, CHEMSEA ProjectGoogle Scholar
  44. Tørnes JA, Opstad AM, Johnsen BA (2006) Determination of organoarsenic warfare agents in sediment samples from Skagerrak by gas chromatography-mass spectrometry. Sci Total Environ 356:235–246CrossRefGoogle Scholar
  45. Uścinowicz S (2011) Geochemistry of Baltic Sea surface sediments. Polish Geological Institute, PolandGoogle Scholar
  46. VanderNoot V, Ferko S, Van De Vreugde J, Patel K, Volponi J, Morrissey K, Forrest L, Horton J, Haroldsen B (2012) On-line monitoring system for chemical warfare agents using automated capillary micellar electrokinetic chromatography. J Chromatogr A 1249:233–240CrossRefGoogle Scholar
  47. Wagner G, Maciver B, Rohrbaugh D, Yang Y (1999) Thermal degradation of bis(2-chloroethyl) sulfide (mustard gas). Phosphorus Sulfur Silicon 152:65–76CrossRefGoogle Scholar
  48. Wang J, Chatrathi MP, Mulchandani A, Chen W (2001) Capillary electrophoresis microchips for separation and detection of organophosphate nerve agents. Anal Chem 73:1804–1808CrossRefGoogle Scholar
  49. Wang J, Pumera M, Collins GE, Mulchandani A (2002) Measurements of chemical warfare agent degradation products using an electrophoresis microchip with contactless conductivity detector. Anal Chem 74:6121–6125CrossRefGoogle Scholar
  50. Wang J, Zima J, Lawrence NS, Chatrathi MP, Mulchandani A, Collins GE (2004) Microchip capillary electrophoresis with electrochemical detection of thiol-containing degradation products of V-type nerve agents. Anal Chem 76:4721–4726CrossRefGoogle Scholar
  51. Zedda M, Zwiener C (2012) Is nontarget screening of emerging contaminants by LC-HRMS successful? A plea for compound libraries and computer tools. Anal Bioanal Chem 403:2493–2502CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2018

Authors and Affiliations

  • Martin Söderström
    • 1
    Email author
  • Anders Östin
    • 2
  • Johanna Qvarnström
    • 2
  • Roger Magnusson
    • 2
  • Jenny Rattfelt-Nyholm
    • 2
  • Merike Vaher
    • 3
  • Piia Jõul
    • 3
  • Heidi Lees
    • 3
  • Mihkel Kaljurand
    • 3
  • Marta Szubska
    • 4
  • Paula Vanninen
    • 1
  • Jacek Bełdowski
    • 4
  1. 1.Finnish Institute for Verification of the Chemical Weapons ConventionUniversity of HelsinkiHelsinkiFinland
  2. 2.Swedish Defence Research AgencyUmeåSweden
  3. 3.Tallinn University of TechnologyTallinEstonia
  4. 4.Institute of Oceanology, Polish Academy of SciencesSopotPoland

Personalised recommendations

Cite paper

Buy options