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1.
Talanta ; 200: 366-372, 2019 Aug 01.
Article in English | MEDLINE | ID: mdl-31036197

ABSTRACT

As a consequence of World War II, large amounts of munition have been deposited in coastal waters. Deterioration of the mines and bombs is resulting in a release of munition compounds (MCs) like trinitrotoluene to the surrounding marine environment, with potential implications to ecosystems. Analytical methods have thus far been unable to detect these compounds reliably in seawater. We present a highly sensitive method for the analysis of MCs in the marine environment. We combine preconcentration and sample clean up by solid phase extraction with separation and detection by ultra-high performance liquid chromatography - electrospray ionisation - mass spectrometry (UHPLC-ESI-MS) for the detection of MCs dissolved in filtered (< 0.2 µm) seawater. For biota, dried and ground samples were extracted in acetonitrile and analysed after simple dilution. Eleven MCs were detected by UHPLC-ESI-MS with limits of detection between 0.01 and 25 pg. For the first time, we used heavy isotopes of trinitroluene and dinitrobenzene to improve quantification in environmental samples. We detected 7 MCs in waters sampled at a known munition disposal site in the Baltic Sea after a 1000-fold preconcentration and using an injection volume of 25 µL. Trinitrotoluene and dinitrobenzene were the most abundant MCs, occurring at concentrations between 0.1 and 11.8 ng L-1. We observed 10 MCs at concentrations up to 24 µg g-1 dry weight in benthic organisms sampled from the site. The enhanced sensitivity of our method allowed us to detect MCs at concentrations relevant for assessment and management of munitions disposal sites in the marine environment.

2.
Environ Sci Technol ; 53(10): 5652-5660, 2019 05 21.
Article in English | MEDLINE | ID: mdl-30997802

ABSTRACT

Underwater munitions containing millions of tons of toxic explosives are present worldwide in coastal marine waters as a result of unexploded ordnance and intentional dumping. The dissolution flux of solid explosives following corrosion of metal munition housings controls the exposure of biological receptors to toxic munition compounds (MC), including TNT: 2,4,6-trinitrotoluene, RDX: 1,3,5-trinitro-1,3,5-triazinane, and DNB: 1,3-dinitrobenzene. Very little is known about the dissolution behavior of MC in the marine environment. In this work, we exploit a unique marine study site in the Baltic Sea with exposed solid explosives to quantify in situ MC dissolution fluxes using dissolved MC gradients near the exposed explosive surface, as well as benthic chamber incubations. The gradient method gave dissolution fluxes that ranged between 0.001 and 3.2, between 0.0001 and 0.04, and between 0.003 and 1.7 mg cm-2 day-1 for TNT, RDX, and DNB, respectively. Benthic chamber incubations indicated dissolution fluxes of 0.0047-0.277, 0-0.11, and 0.00047-1.45 mg cm-2 day-1 for TNT, RDX, and DNB, respectively. In situ dissolution fluxes estimated in the current study were lower than most dissolution rates reported for laboratory experiments, but they clearly demonstrated that MC are released from underwater munitions to the water column in the Baltic Sea.


Subject(s)
Explosive Agents , Trinitrotoluene , Solubility , Triazines
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