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Sea Dumped Munitions: From Detection, Analysis and Risk Assessment to...
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Sea Dumped Munitions: From Detection, Analysis and Risk Assessment to the Remediation of World War Relicts

A special issue of Toxics (ISSN 2305-6304). This special issue belongs to the section "Ecotoxicology".

Deadline for manuscript submissions: closed (30 April 2024) | Viewed by 18810

Special Issue Editor

Prof. Dr. Edmund Maser

E-Mail Website
Guest Editor
Institute of Toxicology and Pharmacology for Natural Scientists, University Medical School Schleswig-Holstein, Campus Kiel, Brunswiker Str. 10, 24105 Kiel, Germany
Interests: metabolism of xenobiotics; pluripotent steroid oxidoreductases; aldo-keto reductases (AKR); short-chain dehydrogenases/reductases (SDR); carbonyl reducing enzymes; tobacco-smoke induced lung cancer; steroid signaling and degradation in bacteria; toxicity and risk assessment of munition chemicals on the environment and the human seafood consumer

Special Issue Information

Dear Colleagues,

The seas worldwide are threatened by an emerging source of pollution: millions of tons of all kind of warfare materials have been intentionally dumped after World War I and II, in addition to mine barriers and failed detonations, as well as shot down military planes and sunken ship wrecks carrying munitions. For example, in the German parts of the Northern and Baltic Sea alone, nearly two million metric tons of toxic conventional explosives (TNT and others) and more than 5,000 metric tons of chemical weapons (CWA) are present. Munitions in the sea is also a worldwide problem, e.g., on the west coast of the United States and the Far East.

Such unexploded ordnance (UXO), on the one hand, constitutes a direct risk of detonation with increased human access (fisheries, water sports, cable constructions, wind farms and pipelines). On the other hand, after more than 70 years of resting on the seabed, the metal shells of these munition items are corroding, such that toxic and carcinogenic munition chemicals (MCs) leak out, threaten the marine environment and—upon entry into the marine food web—threaten the human seafood consumer.

This Special Issue is intended to provide a comprehensive overview of all new scientific findings on the subject of munitions in the sea.

We are pleased to invite you to contribute to this Special Issue of the journal “Toxics”, which perfectly matches with the most important questions in the area of sea-dumped munitions, including:
- Occurrence, transport and fate in the marine environment
- Exposure of humans through the marine food web
- Uptake, metabolism, and effects of MCs in a wide range of aquatic organisms and marine ecosystems
- Approaches to assess the risks of MCs to humans and the environment
- Methodologies to eliminate or reduce the exposure of humans and the environment to MCs by means of biodegradation or remediation.

In this Special Issue, original research articles and reviews are welcome. Research areas may include (but not limited to) the above.

I look forward to receiving your contributions.

Prof. Dr. Edmund Maser
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Toxics is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • detection
  • distribution and environmental fate of MCs
  • uptake of MCs by, and health effects on, marine organisms
  • bioconcentration of MCs
  • entry into the marine food web
  • risk assessment for the environmental and humans
  • abiotic and biotic metabolism of MCs
  • microbial degradation
  • (bio)remediation

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Published Papers (7 papers)

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Research

23 pages, 333 KiB  
Article
What Is Missing in Offshore Explosive Ordnance Disposal Risk Assessment?
by Torsten Frey
Toxics 2024, 12(7), 468; https://doi.org/10.3390/toxics12070468 - 27 Jun 2024
Viewed by 1234
Abstract
Offshore explosive ordnance disposal (EOD) in the marine environment is a high-risk activity. Structured risk assessment (RA) can be a helpful tool to provide EOD experts with decision-making support. This paper hypothesizes that existing RA approaches that address unexploded ordnance (UXO) in the [...] Read more.
Offshore explosive ordnance disposal (EOD) in the marine environment is a high-risk activity. Structured risk assessment (RA) can be a helpful tool to provide EOD experts with decision-making support. This paper hypothesizes that existing RA approaches that address unexploded ordnance (UXO) in the sea do not meet the requirements of EOD RA. To test this hypothesis, the paper proposes a novel categorization tool. It uses five review criteria: study type (qualitative vs. quantitative), level of decision-making (strategic vs. applied), risk component (probability vs. consequence), spatial scale (global vs. local), and temporal scale (long-term vs. short-term). The categorization tool is used to identify the requirements of EOD RA and to test whether nine existing RA methods fulfill these requirements. The study finds that none of the investigated RAs meets the requirements and, hence, concludes that a new method should be developed. However, some aspects of the existing studies should be considered when designing a new method. This includes using risk factors (type and mass of explosive material, type and state of the fuze, and water depth) that are relevant for EOD RA. It also involves setting up a directed graph to assess the complex interdependencies between these risk factors. Full article
(This article belongs to the Special Issue Sea Dumped Munitions: From Detection, Analysis and Risk Assessment to the Remediation of World War Relicts)
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15 pages, 3048 KiB  
Article
Long-Term Trends for Blue Mussels from the German Environmental Specimen Bank Show First Evidence of Munition Contaminants Uptake
by Jennifer Susanne Strehse, Tobias Hartwig Bünning, Jan Koschorreck, Anita Künitzer and Edmund Maser
Toxics 2023, 11(4), 347; https://doi.org/10.3390/toxics11040347 - 7 Apr 2023
Cited by 2 | Viewed by 2081
Abstract
Submerged munitions are present in marine waters across the globe. They contain energetic compounds (ECs), such as TNT and metabolites thereof, which are considered carcinogenic, exhibit toxic effects in marine organisms, and may affect human health. The aim of this study was to [...] Read more.
Submerged munitions are present in marine waters across the globe. They contain energetic compounds (ECs), such as TNT and metabolites thereof, which are considered carcinogenic, exhibit toxic effects in marine organisms, and may affect human health. The aim of this study was to investigate the occurrence of ECs and their trends in blue mussels from the annual collections of the German Environmental Specimen Bank sampled over the last 30 years at three different locations along the coastline of the Baltic and North Sea. Samples were analyzed by GC-MS/MS for 1,3-dinitrobenzene (1,3-DNB), 2,4-dinitrotoluene (2,4-DNT), 2,4,6-trinitrotoluene (TNT), 2-amino-4,6-dinitrotoluene (2-ADNT), and 4-amino-2,6-dinitrotoluene (4-ADNT). The first signals indicating trace levels of 1,3-DNB were observed in samples from 1999 and 2000. ECs were also found below the limit of detection (LoD) in subsequent years. From 2012 onwards, signals just above the LoD were detected. The highest signal intensities of 2-ADNT and 4-ADNT, just below the LoQ (0.14 ng/g d.w. and 0.17 ng/g d.w., respectively), were measured in 2019 and 2020. This study clearly shows that corroding submerged munitions are gradually releasing ECs into the waters that can be detected in randomly sampled blue mussels, even though the concentrations measured are still in the non-quantifiable trace range. Full article
(This article belongs to the Special Issue Sea Dumped Munitions: From Detection, Analysis and Risk Assessment to the Remediation of World War Relicts)
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17 pages, 4543 KiB  
Article
Release of Ammunition-Related Compounds from a Dutch Marine Dump Site
by J. H. den Otter, D. Pröfrock, T. H. Bünning, J. S. Strehse, A. E. D. M. van der Heijden and E. Maser
Toxics 2023, 11(3), 238; https://doi.org/10.3390/toxics11030238 - 1 Mar 2023
Cited by 8 | Viewed by 2311
Abstract
After World War II, large amounts of ammunition were dumped in surface waters worldwide, potentially releasing harmful and toxic compounds to the environment. To study their degradation, ammunition items dumped in the Eastern Scheldt in The Netherlands were surfaced. Severe damage due to [...] Read more.
After World War II, large amounts of ammunition were dumped in surface waters worldwide, potentially releasing harmful and toxic compounds to the environment. To study their degradation, ammunition items dumped in the Eastern Scheldt in The Netherlands were surfaced. Severe damage due to corrosion and leak paths through the casings were observed, making the explosives in the ammunition accessible to sea water. Using novel techniques, the concentrations of ammunition-related compounds in the surrounding seabed and in the seawater were analyzed at 15 different locations. In the direct vicinity of ammunition, elevated concentrations of ammunition-related compounds (both metals and organic substances) were found. Concentrations of energetic compounds ranged from below the limit of detection (LoD) up to the low two-digit ng/L range in water samples, and from below the LoD up to the one-digit ng/g dry weight range in sediment samples. Concentrations of metals were found up to the low microgram/L range in water and up the low ng/g dry weight in sediment. However, even though the water and sediment samples were collected as close to the ammunition items as possible, the concentrations of these compounds were low and, as far as available, no quality standards or limits were exceeded. The presence of fouling, the low solubility of the energetic compounds, and dilution by the high local water current were concluded to be the main causes for the absence of high concentrations of ammunition-related compounds. As a conclusion, these new analytical methods should be applied to continuously monitor the Eastern Scheldt munitions dump site. Full article
(This article belongs to the Special Issue Sea Dumped Munitions: From Detection, Analysis and Risk Assessment to the Remediation of World War Relicts)
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11 pages, 1081 KiB  
Article
Energetic Compounds in the Trophic Chain—A Pilot Study Examining the Exposure Risk of Common Eiders (Somateria mollissima) to TNT, Its Metabolites, and By-Products
by Luca Aroha Schick, Jennifer Susanne Strehse, Tobias Hartwig Bünning, Edmund Maser and Ursula Siebert
Toxics 2022, 10(11), 685; https://doi.org/10.3390/toxics10110685 - 12 Nov 2022
Cited by 2 | Viewed by 1918
Abstract
The Baltic and North Seas still contain large amounts of dumped munitions from both World Wars. The exposure of the munition shells to the seawater causes corrosion, which leads to the disintegration of shells and a leakage of energetic compounds, including the highly [...] Read more.
The Baltic and North Seas still contain large amounts of dumped munitions from both World Wars. The exposure of the munition shells to the seawater causes corrosion, which leads to the disintegration of shells and a leakage of energetic compounds, including the highly toxic 2,4,6-trinitrotoluene (TNT), and consequently threatening the marine environment. To evaluate the risk of accumulation of energetic compounds from conventional munitions in the marine food chain, we analyzed the presence of TNT and its metabolites 2-amino-4,6-dinitrotoluene (2-ADNT) and 4-amino-2,6-dinitrotoluene (4-ADNT) as well as their byproducts 1,3-dinitrobenzene (1,3-DNB) and 2,4-dinitrotoluene (2,4-DNT) in different tissues (including muscle, liver, kidney, brain, and bile) from 25 Common Eiders (Somateria mollissima) from the Danish Baltic Sea. Tissues were prepared according to approved protocols, followed by GC-MS/MS analysis. None of the aforementioned energetic compounds were detected in any of the samples. This pilot study is one of the first analyzing the presence of explosive chemicals in tissues from a free-ranging predatory species. This study highlights the need for continuous monitoring at different levels of the trophic chain to increase our knowledge on the distribution and possible accumulation of energetic compounds in the marine environment in order to provide reliable data for decision-making tools and risk assessments. Full article
(This article belongs to the Special Issue Sea Dumped Munitions: From Detection, Analysis and Risk Assessment to the Remediation of World War Relicts)
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14 pages, 6133 KiB  
Article
Mobilization of Unexploded Ordnance on the Seabed
by Peter Menzel, Anja Drews, Tjark Mehring, Christoph Otto and Dorthe Reng Erbs-Hansen
Toxics 2022, 10(7), 389; https://doi.org/10.3390/toxics10070389 - 13 Jul 2022
Cited by 4 | Viewed by 3016
Abstract
Unexploded ordnance devices (UXO) pose a potential threat to human life and material during offshore construction activities. Extensive survey activities are conducted to locate, identify, and clear these objects as necessary. For the period thereafter, it is necessary to investigate whether areas that [...] Read more.
Unexploded ordnance devices (UXO) pose a potential threat to human life and material during offshore construction activities. Extensive survey activities are conducted to locate, identify, and clear these objects as necessary. For the period thereafter, it is necessary to investigate whether areas that have already been cleared, or even objects that remain in place, may be affected by mobilization under tidal currents or waves, and could thus have an impact on operation and maintenance during the lifetime of the offshore installation. In this study, model simulations based on fluid mechanics are described to derive the loads on the objects caused by currents and waves and combined with knowledge of the known burial condition of the objects. Within the model, the hydrodynamic and hydrostatic loads on the object caused by waves and currents are balanced with inertia and rolling resistance. Thus, the critical current velocity and critical wave conditions for the mobilization of different objects are calculated and compared with the environmental conditions prevailing in the North Sea. As a result, a recurrence interval for the potential mobilization of objects on the seafloor is given, which can now be used to optimize route surveys and thus help accelerate offshore construction work. It is shown that currents are not able to mobilize the objects investigated in the study in almost all regions of the North Sea. Waves can mobilize certain objects in very shallow and extreme conditions. Full article
(This article belongs to the Special Issue Sea Dumped Munitions: From Detection, Analysis and Risk Assessment to the Remediation of World War Relicts)
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13 pages, 2835 KiB  
Communication
Metagenomic Analysis of the Gastrointestinal Microbiota of Gadus morhua callarias L. Originating from a Chemical Munition Dump Site
by Wojciech Wilczynski, Monika Radlinska, Klaus Wysujack, Michał Czub, Tomasz Brzeziński, Grzegorz Kowalczyk, Jacek Bełdowski, Pedro Nogueira and Piotr Maszczyk
Toxics 2022, 10(5), 206; https://doi.org/10.3390/toxics10050206 - 21 Apr 2022
Cited by 8 | Viewed by 3766
Abstract
Several hundred thousand tonnes of munitions containing chemical warfare agents (CWAs) are lying on the seafloor worldwide. CWAs have started leaking from corroded munitions, and their presence in the environment and in organisms inhabiting dump sites has been detected. The presence of CWAs [...] Read more.
Several hundred thousand tonnes of munitions containing chemical warfare agents (CWAs) are lying on the seafloor worldwide. CWAs have started leaking from corroded munitions, and their presence in the environment and in organisms inhabiting dump sites has been detected. The presence of CWAs in the water negatively affects fish, macrobenthos and free-living bacteria. It can be expected that the presence of CWAs would also affect the gut-associated bacteria in fish, which are vital for their condition. The main aim of this study was to test if the microbiota of cod collected in the Baltic Bornholm Deep (highly polluted with CWAs) is dysregulated. To investigate this, we conducted metagenomic studies based on 16S rRNA gene sequencing. We found that the microbiota of cod inhabiting the dump site was significantly less taxonomically diverse compared to those from a non-polluted reference site. Moreover, taxa associated with fish diseases (e.g., Vibrionaceae, Aeromonadaceae) were more prevalent, and probiotic taxa (e.g., Actinobacteriota, Rhodobacteraceae) were less frequent in the guts of individuals from the dump site, than those from the reference site. The differences in vulnerability of various bacterial taxa inhabiting cod gastrointestinal tracts to CWAs were hypothesised to be responsible for the observed microbiota dysregulation. Full article
(This article belongs to the Special Issue Sea Dumped Munitions: From Detection, Analysis and Risk Assessment to the Remediation of World War Relicts)
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17 pages, 3787 KiB  
Article
Degradation of 2,4,6-Trinitrotoluene (TNT): Involvement of Protocatechuate 3,4-Dioxygenase (P34O) in Buttiauxella sp. S19-1
by Miao Xu, Dong Liu, Ping Sun, Yunuo Li, Ming Wu, Wencong Liu, Edmund Maser, Guangming Xiong and Liquan Guo
Toxics 2021, 9(10), 231; https://doi.org/10.3390/toxics9100231 - 24 Sep 2021
Cited by 18 | Viewed by 3385
Abstract
Extensive use and disposal of 2,4,6-trinitrotoluene (TNT), a primary constituent of explosives, pollutes the environment and causes severe damage to human health. Complete mineralization of TNT via bacterial degradation has recently gained research interest as an effective method for the restoration of contaminated [...] Read more.
Extensive use and disposal of 2,4,6-trinitrotoluene (TNT), a primary constituent of explosives, pollutes the environment and causes severe damage to human health. Complete mineralization of TNT via bacterial degradation has recently gained research interest as an effective method for the restoration of contaminated sites. Here, screening for TNT degradation by six selected bacteria revealed that Buttiauxella sp. S19-1, possesses the strongest degrading ability. Moreover, BuP34O (a gene encoding for protocatechuate 3,4-dioxygenase—P34O, a key enzyme in the β-ketoadipate pathway) was upregulated during TNT degradation. A knockout of BuP34O in S19-1 to generate S-M1 mutant strain caused a marked reduction in TNT degradation efficiency compared to S19-1. Additionally, the EM1 mutant strain (Escherichia coli DH5α transfected with BuP34O) showed higher degradation efficiency than DH5α. Gas chromatography mass spectrometry (GC-MS) analysis of TNT degradation by S19-1 revealed 4-amino-2,6-dinitrotolune (ADNT) as the intermediate metabolite of TNT. Furthermore, the recombinant protein P34O (rP34O) expressed the activity of 2.46 µmol/min·mg. Our findings present the first report on the involvement of P34O in bacterial degradation of TNT and its metabolites, suggesting that P34O could catalyze downstream reactions in the TNT degradation pathway. In addition, the TNT-degrading ability of S19-1, a Gram-negative marine-derived bacterium, presents enormous potential for restoration of TNT-contaminated seas. Full article
(This article belongs to the Special Issue Sea Dumped Munitions: From Detection, Analysis and Risk Assessment to the Remediation of World War Relicts)
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