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Über dieses Buch

This book describes the creation of a monitoring network, which can provide information about the exact locations and the environmental threats posed by chemical weapons (CW) dumpsites in the Baltic Sea region, using autonomous underwater vehicles (AUVs) and remotely operated underwater vehicles (ROVs), and utilising the existing research vessels of NATO partner institutions as launching platforms.

The dumping operations occurred shortly after World War II and included captured German munitions. Operations with munitions from the Soviet occupation zone were performed by the Soviet Navy, operations with munitions from British and American occupation zones were performed in areas outside of the Baltic Sea (Skagerrak Strait); the fate of munitions from the French occupation zone was never reported. Due to difficult legal status of these munitions, and high costs of remediation and retrieval, removal of these weapons from the bottom of the Baltic Sea seems unlikely in the foreseeable future. These dumped chemical weapons pose an actual environmental and security hazard in the Baltic Sea Region. Nowadays, with more and more industrial activities being performed in the Baltic Sea Area, the threat level is rising.

The AUV survey is based on the IVER2 platform by OceanServer, equipped with Klein 3500 side-scan sonar. The identification phase utilises several ROVs, equipped with targeting sonars, acoustic cameras capable of penetrating turbid bottom waters up to 20m, and visual HD cameras. A novel sediment sampling system, based on a camera and sonar equipped cassette sampler, has been developed to obtain surface sediments. The test phase described consists of a survey phase, which will locate the actual objects concerned, and a monitoring phase, which will concentrate on the collection of environmental data close to the objects concerned.



Chapter 1. Introduction

Dumped chemical weapons (CW) pose an actual environmental and security hazard in the Baltic Sea Region. Their actual position is unknown, and pollution originating from corroded munitions is only roughly estimated. One of possible low-cost solution is the creation of monitoring network, providing info about exact location and environmental threat posed by sea dumped CW.
MODUM project aimed at the establishment of the monitoring network observing Chemical Weapons dumpsites in the Baltic Sea, using autonomous underwater vehicles (AUV’s) and remotely operated underwater vehicles (ROV’s), and utilizing existing research vessels of partner institutions as launching platforms. Project consisted of the test phase, which helped choosing best available solutions for the difficult Baltic Sea environment, Survey phase, which located actual objects of concern, and monitoring phase, which concentrated on the collection of environmental data close to the objects of concern. The result of the project is a set of methods and procedures that are applicable for the dumpsites monitoring, ranging from sea bottom survey, object identification to actual environmental parameters collection, biota exposure and portable chemical warfare agents (CWA) analysis. It uses such data for the calculation of environmental risk assessment in the dumpsites.
Jacek Bełdowski, Terrence Long, Martin Söderström

Chapter 2. Suitability Study of Survey Equipment Used in the MODUM Project

Modern seafloor mapping techniques are based almost entirely on acoustics systems. With the usage of appropriate equipment, it is possible to examine seabed in terms of its morphology and also sub-bottom structures. Moreover, detection of objects placed on the bottom surface and buried in sediments is possible with proper gear as well. Above-mentioned actions were one of the crucial aims of the MODUM project (Towards The Monitoring Of Dumped Munition Threat). To achieve it, surveys with certain selected acoustic equipment were done together with data processing. The aim of this chapter is to present those systems, its possibilities, principles of working and results obtained thanks to it. Three different side scan sonar systems are described: used for seafloor surface scanning and detecting objects on it. Also, a sub-bottom profiler, which allows looking on seabed structures and detecting buried targets within, is presented. Additionally, a findings validation device, which is the remotely operated vehicle, is characterized in this chapter as well. Cooperation of all these systems gave good results in terms of detecting sunken munition in the Baltic Sea.
Miłosz Grabowski, Stefano Fioravanti, Robert Been, Federico Cernich, Vitalijus Malejevas

Chapter 3. Results of Acoustic Research in the CM Deploying Areas

Short overview of problems connected with acoustic detection and recognition of chemical munition deployed in the Baltic Sea after the II WWW is demonstrated.
Results of 36 high-frequency acoustic scanning missions carried out with the IVER-2 AUV over a chemical munition dumpsite in the Bornholm Basin, Gdansk Deep, Little Belt and south-western part of Gotland Deep are presented. The main goal of the investigations was to image structure of the dumpsite and to positioning targets for purposes of taking probes of environment for further chemical analysis.
The data support of the earlier findings wide variety of types of objects at the sea bottom – both historical items as wracks or sea mines and contemporary litter.
It is generally observed a low contrast between acoustic shadows and backscattered signals, which are likely due to the sediments properties in the Baltic Deeps.
In the Bornholm Basin and Gdansk Deep the distribution of the buried objects seems to be rather concentrated around surrounded by diffusive spacing of objects due to fishery activity in the areas. The results of complementary studies on the acoustic properties of the bottom demonstrate the dependency of probability of findings with the type of sediments.
Finally some aspects of probability to detect of is given.
Zygmunt Klusek, Miłosz Grabowski

Chapter 4. Chemical Analysis of Dumped Chemical Warfare Agents During the MODUM Project

MODUM project continued the work on monitoring of the chemical weapons (CW) dumped in the Baltic Sea started in previous projects. As a new aspect, on board analysis methods – headspace gas chromatography-mass spectrometry (GC–MS) and capillary electrophoresis (CE) – were developed and tested in laboratory conditions and during cruises. The GC–MS method could be successfully applied on board to verify that collected sediment samples contained degradation products for sulfur mustard, one of the major chemical warfare agents dumped in Baltic Sea. This method could in future project be used during cruises to redirect sample collection in order to make most of the available ship time. Other part of the analysis task during MODUM project was the work done at the reach back laboratories. These analyses were done to both verify the results obtain on board and to fully identify the chemicals related to the sea-dumped CW agents. Reach back analysis of CW-related chemicals were done on sediment samples collected around a wreck in Bornholm Deep (same samples as analyzed on board) and on monitoring samples collected in Bornholm, Gotland and Gdańsk Deeps. The samples from Bornholm and Gotland Deeps are in line with previous findings. Samples from Gdańsk Deep are in line with previous findings that this area has been used as a dump site. Additionally, α-chloroacetophenone (CN) was found in the area for the first time. In addition to the analysis of CW-related chemicals, a new method was developed for measurement for arsenic concentrations in sediment samples. A method was also developed for arsenic speciation, which could help in estimation of the source of arsenic in the sediments.
Martin Söderström, Anders Östin, Johanna Qvarnström, Roger Magnusson, Jenny Rattfelt-Nyholm, Merike Vaher, Piia Jõul, Heidi Lees, Mihkel Kaljurand, Marta Szubska, Paula Vanninen, Jacek Bełdowski

Chapter 5. Environmental Toxicity of CWAs and Their Metabolites

This chapter reviews the environmental toxicity of CWAs and their metabolites as well as mixtures of CWAs. We used Microtox™ to generate EC50 value for 11 compounds. We observed hormetic effects for two compounds namely Triphenylarsine and Triphenylarsine oxide. None of the mixtures tested show sign of synergism. Two compounds can be characterized as very toxic as both α-chloroacetophenone (EC50 = 11.20 μg L−1) and 2-chlorovinylarsinic acid (EC50 = 31.20 μg L−1) demonstrated EC50 values below 1000 μg L−1. Several compounds can be characterized as toxic as 1,2,5-trithiepane (EC50 = 1170 μg L−1), 1,4,5-oxadithiepane (EC50 = 1700 μg L−1), phenarsazinic acid (EC50 = 5330 μg L−1) and 1,4-dithiane (EC50 = 9970 μg L−1) as these compounds demonstrated EC50 values between 1000 μg L−1 and 10,000 μg L−1. An D. magna acute LC50 for, the compound most frequently detected compound (DPA [ox]), was determined to be 100,000 μg L−1. A chronic D. magna LC5019days of 640 μg L−1 was derived for the compound. A 14-day locomotor behaviour test on adult male Zebrafish (Danio rerio) revealed altered behaviour when exposed to concentrations of 1,4,5-oxadithiepane down to 40.3 ± 2.9 μg L−1. A NOECweight and NOECmortality greater than 1533 μg L−1 was determined for 1,4,5-oxadithiepane.
Morten Swayne Storgaard, Ilias Christensen, Hans Sanderson

Chapter 6. The Health Status of Fish and Benthos Communities in Chemical Munitions Dumpsites in the Baltic Sea

The environmental characteristics of the deep basins in the Baltic Sea and their impact on the occurrence of selected biota – benthos and fish communities – are described in chemical munitions dumping site areas. Results of the NATO-funded SfP project MODUM “Towards the Monitoring of Dumped Munitions Threat” (2013–2016) and other related previous activities regarding the impact of chemical warfare agents (CWA) on biodiversity and status of benthic fauna and regarding the health status of Baltic cod (Gadus morhua) are presented and discussed in the light of requirements for monitoring ecological risks associated with dumped CWA.
Thomas Lang, Lech Kotwicki, Michał Czub, Katarzyna Grzelak, Lina Weirup, Katharina Straumer

Chapter 7. Estimation of Potential Leakage from Dumped Chemical Munitions in the Baltic Sea Based on Two Different Modelling Approaches

During the MODUM project two independent methods for estimation of potential leakage of dumped chemical munitions in the Baltic Sea have been developed. The first one is Lagrangian tracking of particles with random disturbance. The second one is using a passive tracer as a marker of potential leakage. The approaches have been developed in open source ocean models adapted for the Baltic Sea. But the models are quite different. The walking particles approach has been developed in the Princeton Ocean Model, which is nonlinear, free surface, hydrostatic, σ-coordinate, with an imbedded second and a half moment turbulence closure sub-model. The passive tracer was implemented in the Parallel Ocean Program – a z-level coordinate, general circulation ocean model that solves 3-dimensional primitive equations for stratified fluid, using the hydrostatic and Boussinesq approximations. Because of many differences in our approaches we skipped a detailed comparison of the presented results (however, this will be the subject of the next stage in our work). Although the approaches and the models are quite different, the results are comparable.
Jaromir Jakacki, Maria Golenko, Victor Zhurbas

Chapter 8. Weight-of-Evidence Environmental Risk Assessment

In this chapter, the data generated within MODUM and other related projects, i.e. CHEMSEA, MERCW and NordStream, contributing to the knowledge and data on occurrence, toxicity and effects of chemical warfare agents (CWAs) and their metabolites in the Baltic Sea, are aggregated. The data are evaluated and assessed in terms of risk quotients, and whether these point to risk or no-risk towards effects on lower tier organisms (e.g. algae and daphnia), and higher tier organisms (fish) from exposure to dumped CWAs and their metabolites in the study areas. To perform a semi-quantitative assessment of the environmental risk, a number of Lines of Evidences (LoEs) are set up, that take all aspects of the performed investigations into account. Each LoE is assigned +3, +2, +1, 0, −1, −2 or −3, indicating if the LoE is found to be for (+), against (−) or neutral (0) to an increased environmental risk of dumped CWAs. The weight also reflects the predictive power, or significance, of the individual LoEs. From nine LoEs a resulting summed score of +9 indicates that there is a weak to moderate potential for confirming the hypothesis. In order to qualify and increase the precision of the weights recommendations are given that can be addressed in future investigations regarding compounds, sites and species that could be in focus. Furthermore, recommendations for activities that will improve the exposure and toxicity data, that are inherent in the environmental risk assessment, are stated.
Patrik Fauser, Erik Amos Pedersen, Ilias Christensen

Chapter 9. Best Practices in Monitoring

This chapter summarizes the methods used within the MODUM project for monitoring chemical munition dumpsites. It includes general introduction to monitoring process, listing the requirements that are a basis for the establishment of full scale monitoring programme. It describes survey procedures, for locating dumped munitions, Sampling and analytical procedures for the detection of Chemical Warfare Agents, as well as the usage of fish as bioindicators are described. Modelling of pollutants originating from dumped munitions is presented and discussed. Only methods, which were proven to be most effective within the MODUM projects were selected, also data interpretation methods providing coherent information regarding the environmental risk are explained in details.
Jacek Bełdowski, Jaromir Jakacki, Miłosz Grabowski, Thomas Lang, Kela Weber, Lech Kotwicki, Vadim Paka, Daniel Rak, Maria Golenko, Michał Czub, Martin Söderström
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