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Evaluation of Molecular Markers and Analytical Methods Documenting the Occurrence of Mustard Gas and Arsenical Warfare Agents in Soil

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Abstract

The chemicals warfare agents (CWAs) are an extremely toxic class of molecules widely produced in many industrialized countries for decades, these compounds frequently contained arsenic. The plants where the CWAs have been produced or the plants where they have been demilitarized after the Second World War with unacceptable techniques can represent a serious environmental problem. CWAs standards are difficult to find on market so in present work an environmental assessment method based on markers has been proposed. Triphenylarsine, phenylarsine oxide and thiodiglycol have been selected as markers. Three reliable analytical methods based on gaschromatography and mass detection have been proposed and tested for quantitative analysis of markers. Methods performance have been evaluated testing uncertainty, linearity, recovery and detection limits and also comparing detection limits with exposure limits of reference CWAs. Proposed assessment methods have been applied to a case study of a former industrial plant sited in an area characterized by a high background of mineral arsenic.

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References

  • Alcaro L, Torre CD, Petochi T, Sammarini V, Matiddi M, Corsi I, Baroni D, Giordano P, Marino G, Focardi S, Amato E (2012) Studies on environmental effects of underwater chemical munitions in the southern adriatic sea (Mediterranean Sea). Mar Technol Soc J 46:10–20. doi:10.4031/MTSJ.46.3.5

    Article  Google Scholar 

  • Baba KT, Maejima Y, Watanabe E, Eun H, Ishizaka M (2008) Arsenic speciation in rice and soil containing related compounds of chemical warfare agents. Anal Chem 80:5768–5775. doi:10.1021/ac8002984

    Article  CAS  Google Scholar 

  • Beretta GP, Pellegrini R (2004) Linee Guida per il collaudo di scavi per interventi di bonifica on-site e off-site Linee guida n.9 Provincia di Milano http://www.cittametropolitana.mi.it/export/export_14032014/p_bonifiche_lg_9.pdf

  • Black RM, Muir B (2003) Derivatisation reactions in the chromatographic analysis of chemical warfare agents and their degradation products. J Chromatogr A 1000:253–281

    Article  CAS  Google Scholar 

  • Black RM, Clarke RJ, Read RW, Reid MTJ (1994) Application of gas chromatography-mass spectrometry and gas chromatography-tandem mass spectrometry to the analysis of chemical warfare samples, found to contain residues of the nerve agent sarin, sulphur mustard and their degradation products. J Chromatogr A 662(2):301–321

    Article  CAS  Google Scholar 

  • Capozzi N, D’Amico F, Malara F (2009) la distruzione delle vecchie armi chimiche italiane. Rivista Italiana Difesa, pp 56–61

  • Carrick W, Beck N, Cooper D, Muir B (2001) Extraction of thiodiglycol from soil using pressurized liquid extraction. J Chromatogr A 907:221–227

    Article  Google Scholar 

  • Coli M, Principi G, Peccerillo A (1991) Evoluzione geodinamica recente dell’Appennino settentrionale e attività magmatica tosco–laziale: vincoli e problemi [Recent geodynamic evolution of the northern Apennines and Tuscany-Latium magmatic activities: constraints and problems. Studi Geol Camerti 1:403–413

    Google Scholar 

  • D’Aprile L, Moretto C (2006) Sito di Interesse Nazionale di Porto Marghera—Proposta di integrazione del “Protocollo Operativo” per il campionamento e l’analisi dei siti contaminati—Fondo scavo e Pareti—APAT. http://www.isprambiente.gov.it/files/temi/proposta-modifica-protocollo-operativo-rev07-nov06.pdf

  • Daus B, Mattusch J, Wennrich R, Weiss H (2008) Analytical investigations of phenyl arsenicals in groundwater. Talanta 75:376–379. doi:10.1016/j.talanta.2007.11.024

    Article  CAS  Google Scholar 

  • Daus B, Hempel M, Wennrich R, Weiss H (2010) Concentration and speciation of arsenic in groundwater polluted by warfare agents. Environ Pollut 158:3439–3444. doi:10.1016/j.envpol.2010.06.029

    Article  CAS  Google Scholar 

  • Dubey DK, Pardasani D, Palit M, Gupta AK, Kanaujia PK (2004) Gas chromatography-mass spectrometry analysis of trifluoroacetyl derivatives of precursors of nitrogen and sulfur mustards for verification of chemical weapons convention. J Chromatogr A 1059:157–164

    Article  Google Scholar 

  • Dubey DK, Pardasani D, Palit M, Gupta AK, Jain R (2005) On-matrix derivatisation–extraction of precursors of nitrogen- and sulfur-mustards for verification of chemical weapons convention. J Chromatogr A 1076:27–33

    Article  CAS  Google Scholar 

  • Greene J (2013) Sittig’s handbook of pesticide and agricultural chemicals William Andrew Norwich, NY

  • Haas R (1998) Determination of chemical warfare agents. Environ Sci Pollut Res 5(2):63–64. doi:10.1007/BF02986387

    Article  CAS  Google Scholar 

  • Haas R, Krippendorf A (1997) Determination of chemical warfare agents in soil and material samples. Environ Sci Pollut Res 4(3):123–124. doi:10.1007/BF02986314

    Article  CAS  Google Scholar 

  • Haas R, Schmidt TC (1996) Analysis of byproducts of sulfur mustard. Oekotox 8: 241–242. http://www.r-haas.de/f19.html

  • Haas R, Schmidt TC, Steinbach K, von Löw E (1998) Chromatographic determination of phenylarsenic compounds. Fresenius J Anal Chem 361:313–318. doi:10.1007/s002160050892

    Article  CAS  Google Scholar 

  • Hanaoka S, Nagasawa E, Nomura K, Yamazawa M, Ishizaki M (2005) Determination of diphenylarsenic compounds related to abandoned chemical warfare agents in environmental samples. Appl Organomet Chem 19:265–275. doi:10.1002/aoc.790

    Article  CAS  Google Scholar 

  • Hazardous Substances Data Bank in TOXNET http://toxnet.nlm.nih.gov/cgi-bin/sis/htmlgen?HSDB Accessed 06 May 2014

  • Henriksson J, Johanisson A, Bergqvist PA, Norrgren L (1996) The toxicity of organoarsenic based warfare agents: in vitro and in vivo studies. Arch Environ Contam Toxicol 30:213–219. doi:10.1007/BF00215800

    Article  CAS  Google Scholar 

  • International Agency for Research on Cancer (2012) Group 1 Monograph 9 Supplement 7, pp 259–260 http://monographs.iarc.fr/ENG/Monographs/vol100F/mono100F-30.pdf

  • Ishizachi M, Yanaoka T, Nakamura M, Hakuta T, Ueno S, Komuro M, Shibata M, Kitamura T, Honda A, Doy M, Ishii K, Tamaoka A, Ahimojo N, Ogata T, Nagasawa E, Hanaoka S (2005) Detection of bis(diphenylarsine)oxide, diphenylarsinic acid and phenylarsonic acid, compound probably derives from chemical warfare agents in drinking well water. J Health Sci 51(2):130–137

    Article  Google Scholar 

  • Killelea DR, Aldstadt JH (2002) Identification of dimethylchloroarsine near a former herbicide factory by headspace solid-phase microextraction gas chromatography-mass spectrometry. Chemosphere 48(9):1003–1008

    Article  CAS  Google Scholar 

  • Leermakers M, Baeyens M, De Gieter M, Smedts B, Meert C, De Bisschop HC, Morabito R, Quevauviller Ph (2006) Toxic arsenic compounds in environmental samples: speciation and validation. Trends Anal Chem 25(1):1–10. doi:10.1016/j.trac.2005.06.004

    Article  CAS  Google Scholar 

  • Li H, Muir R, McFarlane NR, Soilleux RJ, Yu X, Thompson IP, Jackman SA (2013) Soil biotransformation of thiodiglycol, the hydrolysis product of mustard gas: understanding the factors governing remediation of mustard gas contaminated soil. Biodegradation 24(1):125–135

    Article  CAS  Google Scholar 

  • Mangalgiri KP, Adak A, Blaney L (2015) Organoarsenicals in poultry litter: detection, fate, and toxicity. Environ Int 75:68–80

    Article  Google Scholar 

  • Medvedeva N, Polyak Y, Kuzikova I, Orlova O, Zharikov G (2008) The effect of mustard gas on the biological activity of soil. Environ Res 106(3):289–295

    Article  CAS  Google Scholar 

  • Ng J, Gomez-Caminero A, Howe P, Hughes M, Kenyon E, Lewis DR, Moore M, Aitio G. Becking A (2001) Environmental Health Criteria 224 ARSENIC AND ARSENIC COMPOUNDS http://apps.who.int/iris/bitstream/10665/42366/1/WHO_EHC_224.pdf

  • Perini G, Conticelli S, Francalanci L, Davidson JP (2000) The relationship between potassic and calc-alkaline post-orogenic magmatism at Vico volcano, central Italy. J Volcanol Geoth Res 95(1):247–272

    Article  CAS  Google Scholar 

  • Pitten FA, Thurow K, Koch A, Kramer A (2000) Chemical analysis of organoarsenic based chemical warfare agents in the environment. In: Markerf M, Friese K (eds) Trace elements their distribution and effect on environment. Elsevier Science, Amsterdam, pp 215–242

    Chapter  Google Scholar 

  • Pragney D, Vijaya Saradhi UVR (2012) Sample preparation techniques for the analysis of chemical warfare agents and related degradation products. Trend Anal Chem 37:73–81

    Article  CAS  Google Scholar 

  • Sartori M (1939) The war gases: chemistry and analysis D. Van Nostrand CO., inc, New York

    Google Scholar 

  • Smith PA, Kimm GL, Hook GL (2002) Application of headspace solid-phase microextraction and gas chromatography–mass spectrometry for detection of the chemical warfare agent bis(2-chloroethyl) sulfide in soil. J Chromatogr A 971:185–191

    Article  Google Scholar 

  • Szostek B, Aldstadt J (1998) Determination of organoarsenicals in the environment by solid phase microextraction-gas chromatography-mass spectrometry. J Chromatogr A 807:253–263. doi:10.1016/S0021-9673(98)00080-6

    Article  CAS  Google Scholar 

  • Tornes JA, Opstad AM, Johnsen BA (2006) Determination of organoarsenic warfare agents in sediment samples from Skagerrak by gas chromatography-mass spectrometry. Sci Total Environ 356:235–246. doi:10.1016/j.scitotenv.2005.03.031

    Article  CAS  Google Scholar 

  • USACHPPM/ORNL Technical report (1999) health-based environmental screening levels for chemical warfare agents, March 99

  • Wagner GW, MacIver BK (1998) Degradation and fate of mustard in soil as determined by 13C MAS NMR. Langmuir 14(24):6930–6934

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The acknowledgments for the realization of this work go to Technical Director of Regional Agency for Environmental Protection of Lazio Ing. Rossella Cintoli.

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Correspondence to Alessandro Sassolini.

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Sassolini, A., Brinchi, G., Di Gennaro, A. et al. Evaluation of Molecular Markers and Analytical Methods Documenting the Occurrence of Mustard Gas and Arsenical Warfare Agents in Soil. Bull Environ Contam Toxicol 97, 432–438 (2016). https://doi.org/10.1007/s00128-016-1860-1

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