Explosives compounds from sea-dumped relic munitions accumulate in marine biota

Abstract

Relic munitions are a hazardous legacy of the two world wars present in coastal waters worldwide. The southwest Baltic Sea has an especially high prevalence of unexploded ordnance and dumped munition material, which represent a large potential source of toxic explosive chemicals (munition compounds, MC). In the current study, diverse biota (plankton, macroalgae, tunicate, sponge, mollusc, echinoderm, polychaete, anemone, crustacea, fish) were collected from the Kiel Bight and a munitions dumpsite at Kolberger Heide, Germany, to evaluate the potential bioaccumulation of explosives and their derivatives (2,4,6-trinitrotoluene, TNT; 2-amino-4,6-dinitrotoluene and 4-amino-2,6-dinitrotoluene, ADNT; 2,4-diamino-6-nitrotoluene and 2,6-diamino-4-nitrotoluene, DANT; 1,3-dinitrobenzene, DNB; and 1,3,5-trinitro-1,3,5-triazinane, RDX). One or more MCs were detected in >98% of organisms collected throughout the study region (n = 178), at a median level of 6 pmol/g (approximately 1 ng/g) and up to 2 × 10⁷ pmol/g (TNT in Asterias rubens collected from Kolberger Heide). In most cases, TNT and its transformation product compounds ADNT and DANT were significantly higher in biota from the munitions dumpsite compared with other locations. Generally, DNB and RDX were detected less frequently and at lower concentrations than TNT, ADNT, and DANT. In commercially important fish species (plaice, flounder) from Kolberger Heide, TNT and ADNT were detected in 17 and 33% of samples, respectively. In contrast DANT was detected in every fish sample, including those outside the dumpsite. Dinitrobenzene was the second most prevalent MC in fish tissue. Fish viscera (stomach, kidney, liver) showed higher levels of DANT than edible muscle flesh, with highest DANT in liver, suggesting reduced risk to seafood consumers. This study provides some of the first environmental evidence for widespread bioaccumulation of MC in a coastal marine food web. Although tissue MC content was generally low, corrosion of munition housings may lead to greater MC release in the future, and the ecological risk of this exposure is unknown.

Keywords: Bioaccumulation; DNB; Dinitrobenzene; Kolberger Heide; Ocean dumping; RDX; TNT; Trinitrotoluene; Underwater munitions.