How contaminated is flatfish living near World Wars' munition dumping sites with energetic compounds?

Seas worldwide are threatened by an emerging source of pollution as millions of tons of warfare materials were dumped after the World Wars. As their metal shells are progressively corroding, energetic compounds (EC) leak out and distribute in the marine environment. EC are taken up by aquatic organisms and pose a threat to both the marine ecosphere and the human seafood consumer because of their toxicity and potential carcinogenicity. Here, sediment samples and fish from different locations in the German North Sea of Lower Saxony were examined to determine whether EC transfer to fish living close to munition dumping areas. EC were found in sediments with a maximum concentration of 1.5 ng/kg. All analyzed fish muscle tissues/fillets and bile samples were positive for EC detection. In bile, the max. EC concentrations ranged between 0.25 and 1.25 ng/mL. Interestingly, while detected TNT metabolites in the muscle tissues were in concentrations of max. 1 ng/g (dry weight), TNT itself was found in concentrations of up to 4 ng/g (dry weight). As we found considerable higher amounts of non-metabolized TNT in the fish muscle, rather than TNT metabolites, we conclude an additional absorption route of EC into fish other than per diet. This is the first study to detect EC in the edible parts of fish caught randomly in the North Sea.

Ecotoxicological Risk of World War Relic Munitions in the Sea after Low- and High-Order Blast-in-Place Operations.

Submerged munitions from World War I and II are threatening human activities in the oceans, including fisheries and shipping or the construction of pipelines and offshore facilities. To avoid unforeseen explosions, remotely controlled "blast-in-place" (BiP) operations are a common practice worldwide. However, after underwater BiP detonations, the toxic and carcinogenic energetic compounds (ECs) will not completely combust but rather distribute within the marine ecosphere. To shed light on this question, two comparable World War II mines in Denmark's Sejerø Bay (Baltic Sea) were blown up by either low-order or high-order BiP operations by the Royal Danish Navy. Water and sediment samples were taken before and immediately after the respective BiP operation and analyzed for the presence of ECs with sensitive GC-MS/MS and LC-MS/MS technology. EC concentrations increased after high-order BiP detonations up to 353 ng/L and 175 µg/kg in water and sediment, respectively, while low-order BiP detonations resulted in EC water and sediment concentrations up to 1,000,000 ng/L (1 mg/L) and >10,000,000 µg/kg (>10 g/kg), respectively. Our studies provide unequivocal evidence that BiP operations in general lead to a significant increase of contamination of the marine environment and ecotoxicological risk with toxic ECs. Moreover, as compared to high-order BiP detonations, low-order BiP detonations resulted in a several 1000-fold higher burden on the marine environment.

Warship wrecks and their munition cargos as a threat to the marine environment and humans: The V 1302 "JOHN MAHN" from World War II.

In addition to endangering sea traffic, cable routes, and wind farms, sunken warship wrecks with dangerous cargo, fuel, or munitions on board may emerge as point sources for environmental damage. Energetic compounds such as TNT (which could leak from these munitions) are known for their toxicity, mutagenicity, and carcinogenicity. These compounds may cause potential adverse effects on marine life via contamination of the marine ecosystem, and their entry into the marine and human food chain could directly affect human health. To ascertain the impending danger of an environmental catastrophe posed by sunken warships, the North Sea Wrecks (NSW) project (funded by the Interreg North Sea Region Program) was launched in 2018. Based on historical data (derived from military archives) including the calculated amount of munitions still on board, its known location and accessibility, the German World War II ship "Vorpostenboot 1302" (former civilian name - "JOHN MAHN") was selected as a case study to investigate the leakage and distribution of toxic explosives in the marine environment. The wreck site and surrounding areas were mapped in great detail by scientific divers and a multibeam echosounder. Water and sediment samples were taken in a cross-shaped pattern around the wreck. To assess a possible entry into the marine food chain, caged mussels were exposed at the wreck, and wild fish (pouting), a sedentary species that stays locally at the wreck, were caught. All samples were analyzed for the presence of TNT and derivatives thereof by GC-MS/MS analysis. As a result, we could provide evidence that sunken warship wrecks emerge as a point source of contamination with nitroaromatic energetic compounds leaking from corroding munitions cargo still on board. Not only did we find these explosive substances in bottom water and sediment samples around the wreck, but also in the caged mussels as well as in wild fish living at the wreck. Fortunately so far, the concentrations found in mussel meat and fish filet were only in the one-digit ng per gram range thus indicating no current concern for the human seafood consumer. However, in the future the situation may worsen as the corrosion continues. From our study, it is proposed that wrecks should not only be ranked according to critical infrastructure and human activities at sea, but also to the threats they pose to the environment and the human seafood consumer.

Can seafood from marine sites of dumped World War relicts be eaten?

Since World War I, considerable amounts of warfare materials have been dumped at seas worldwide. After more than 70 years of resting on the seabed, reports suggest that the metal shells of these munitions are corroding, such that explosive chemicals leak out and distribute in the marine environment. Explosives such as TNT (2,4,6-trinitrotoluene) and its derivatives are known for their toxicity and carcinogenicity, thereby posing a threat to the marine environment. Toxicity studies suggest that chemical components of munitions are unlikely to cause acute toxicity to marine organisms. However, there is increasing evidence that they can have sublethal and chronic effects in aquatic biota, especially in organisms that live directly on the sea floor or in subsurface substrates. Moreover, munition-dumping sites could serve as nursery habitats for young biota species, demanding special emphasis on all kinds of developing juvenile marine animals. Unfortunately, these chemicals may also enter the marine food chain and directly affect human health upon consuming contaminated seafood. While uptake and accumulation of toxic munition compounds in marine seafood species such as mussels and fish have already been shown, a reliable risk assessment for the human seafood consumer and the marine ecosphere is lacking and has not been performed until now. In this review, we compile the first data and landmarks for a reliable risk assessment for humans who consume seafood contaminated with munition compounds. We hereby follow the general guidelines for a toxicological risk assessment of food as suggested by authorities.

The explosive trinitrotoluene (TNT) induces gene expression of carbonyl reductase in the blue mussel (Mytilus spp.): a new promising biomarker for sea dumped war relicts?

Millions of tons of all kind of munitions, including mines, bombs and torpedoes have been dumped after World War II in the marine environment and do now pose a new threat to the seas worldwide. Beside the acute risk of unwanted detonation, there is a chronic risk of contamination, because the metal vessels corrode and the toxic and carcinogenic explosives (trinitrotoluene (TNT) and metabolites) leak into the environment. While the mechanism of toxicity and carcinogenicity of TNT and its derivatives occurs through its capability of inducing oxidative stress in the target biota, we had the idea if TNT can induce the gene expression of carbonyl reductase in blue mussels. Carbonyl reductases are members of the short-chain dehydrogenase/reductase (SDR) superfamily. They metabolize xenobiotics bearing carbonyl functions, but also endogenous signal molecules such as steroid hormones, prostaglandins, biogenic amines, as well as sugar and lipid peroxidation derived reactive carbonyls, the latter providing a defence mechanism against oxidative stress and reactive oxygen species (ROS). Here, we identified and cloned the gene coding for carbonyl reductase from the blue mussel Mytilus spp. by a bioinformatics approach. In both laboratory and field studies, we could show that TNT induces a strong and concentration-dependent induction of gene expression of carbonyl reductase in the blue mussel. Carbonyl reductase may thus serve as a biomarker for TNT exposure on a molecular level which is useful to detect TNT contaminations in the environment and to perform a risk assessment both for the ecosphere and the human seafood consumer.

"Don't Blast": blast-in-place (BiP) operations of dumped World War munitions in the oceans significantly increase hazards to the environment and the human seafood consumer.

The seas worldwide are threatened by a "new" source of pollution: millions of tons of all kind of warfare material have been dumped intentionally after World War I and II, in addition to mine barriers, failed detonations as well as shot down military planes and sunken ship wrecks carrying munitions. For example, in the German parts of the North and Baltic Sea approximately 1.6 million metric tons of toxic conventional explosives (TNT and others) and more than 5000 metric tons of chemical weapons are present. Such unexploded ordnance (UXO) constitutes a direct risk of detonation with increased human access (fisheries, water sports, cable constructions, wind farms and pipelines). Moreover, after more than 70 years of resting on the seabed, the metal shells of these munitions items corrode, such that chemicals leak out and distribute in the marine environment. Explosive chemicals such as TNT and its derivatives are known for their toxicity and carcinogenicity. In order not to endanger today's shipping traffic or the installation of pipelines and offshore plants by uncontrolled explosions, controlled blast-in-place (BiP) operations of these dangerous relics is a common practice worldwide. However, blast-in-place methods of in situ munitions disposal often result in incomplete (low-order) detonation, leaving substantial quantities of the explosive material in the environment. In the present free field investigation, we placed mussels (Mytilus spp.) as a biomonitoring system in an area of the Baltic Sea where BiP operations took place and where, by visual inspections by scientific divers, smaller and larger pieces of munitions-related materials were scattered on the seafloor. After recovery, the mussels were transferred to our laboratory and analyzed for TNT and its derivatives via gas chromatography and mass spectroscopy. Our data unequivocally demonstrate that low-order BiP operations of dumped munitions in the sea lead to multiple increases in the concentration of TNT and its metabolites in the mussels when compared to similar studies at corroding but still encased mines. For this reason, we explicitly criticize BiP operations because of the resulting environmental hazards, which can ultimately even endanger human seafood consumers.