October 2017

Newsletter #2

DAIMON is an international project dealing with munitions dumped in the Baltic Sea. Scientists from Poland, Germany, Sweden, Finland, Norway, Lithuania and Russia are cooperating with experts worldwide in order to solve this transboundary challenge.
We are part-financed by the EU INTERREG Baltic Sea Region Programme 2014-2020.

If you are interested in our latest findings, read on:

Are there chemical warfare agents in our fish?

As you could read in the previous DAIMON newsletter, our team discovered clark I and clark II earlier this year in fish from the Måseskär site, implying that rest products of chemical weapons now are present in the Baltic ecosystem and possibly in our food.

This summer, VERIFIN laboratory analysed 20 cod muscle samples collected from the Bornholm dumpsite during the R/V Walter Herwig III cruise in December 2016. Target chemicals were oxidation products of clark compounds, adamsite and triphenyl arsine. After extraction, purification and concentration steps samples were analysed by liquid chromatographic-mass spectrometer method. Of the 20 samples two have contained oxidation product of triphenyl arsine and one contained oxidation form of clark I and/or II. 

VERIFIN also received 20 hagfish  samples collected from Skagerrak Wreck no.13 during R/V IMOR cruise in June 2017 (read  more below). By now half of the samples have been analysed using the same method and for same target chemicals as cod samples. All the analysed hagfish samples have contained oxidation product of triphenyl arsine and four samples have contained oxidation form of clark I and/or II.  

Concentration of those chemicals in all positive cod and hagfish samples ranged at ng per gram level, which is just above measurable levels. These are indeed low levels, but these substances do not exist naturally and should not be present in fish and shellfish.

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Hagfish (Eptatretus stoutii)

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Preparation of a sample

DAIMON team will continue investigating areas contaminated with chemical warfare agents, many of which are being daily trawled for fish.

We will be also looking for traces of effects of the chemical warfare agents in the environment and therefore samples were also taken of meiofauna. Meiofauna, small animals that live between grains of sand, are an important part of the ecosystem that constitutes food for small fish that later becomes food for larger fish. If the meiofauna is affected, the fish will be affected.

It is of great interest of the DAIMON project, that any disturbing results are communicated to the national authorities and appropriate actions are taken. High or low levels, there should be no chemical warfare agents in the fish we buy and eat. For instance, the Swedish Agency for Marine and Water Management is currently considering trawling ban for the Måseskär area.

Cruise full of mishaps: Skagerrak June 2017

The construction and final testing of the sediment sampler was delayed, and although the sampler was onboard R/V IMOR during the first week of the cruise, the final parts arrived at Arendal harbour too late to test and evaluate the sampler before operation. Because of that, no ground samples were taken from the bottom around the wreckage and also the ROV has not been deployed for video inspection. Those activities were postponed to April 2018 when the second part of the Skagerrak Wreck no. 13 will be investigated.

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Bait traps to collect hagfish

Due to bad weather forecast for the last part of the time window, the cruise was aborted after five days at sea. Those five days were used to collect biota samples (hagfish and amphipods) from the reference position and five positions close to Wreck no. 13. The bait traps were deployed for 6 to 12 hours. The biota samplers constructed by FFI (Norwegian Research Establishment) have not been tested before and performance was much lower than expected. After two days of testing and adjusting, next three days biological samples were taken only from the wreck. Despite  unfavourable weather conditions - high waves and strong winds -  this part of the investigation ended successfully.

Fish samples were sent to FFI, Chalmers, SYKE/VERIFIN and TI-FI for analysis (read more above).

Cruise report Bornholm Deep (Aug/Sept 2017)

Thünen Institute (TI-FI) organised an expedition on R/V Walter Herwig III to Bornholm Deep and a reference side close to Gdańsk Bay. As planned 100 cods could be retrieved from both sampling areas. Samples were further distributed to VERIFIN and SYKE. Aim of the investigations is search for metabolites of arsenic compounds 

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in tissue of cod and their potential effects on the health of the exposed fish.

DSS: multi-agent framework LightJason

In order to obtain the best possible results, the DAIMON Decision Support System (DSS) will build up on a multi-agent framework called LightJason, being a high-level abstraction to model behaviour based on artificial intelligence.

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We prefer this method, because it allows for individual user interaction without knowledge about software design, so we can integrate the workflow execution in cooperation with the end-user. LightJason also contains a fuzzy-logic execution model, which can react on the individual (fuzzy) user behaviour.

The fuzzy-logic structure allows aggregating data from data-sources and the learning system in a simplified user result. Based on the scripting language of the multi-agent system the behaviour of the execution can be changed every time, so the system can be optimised to the given workflows.

Based on the technical architecture of the LightJason we obtain a high-performance task execution to aggregate the results and user structure. User will be able to execute different queries in parallel.

Based on user input, the agents will calculate risk in combination with the underlying neural nets. With multiply parallel working agents, the DSS will be able to handle many possible options of risk calculation in order to optimise the overall risk assessment.

Another advantage of a multi-agent framework is its flexibility, e.g. it can calculate country specific risks and user specific risks without needing to adapt the whole system.

Collaboration with Shirshov Institute of Oceanology

Within DAIMON project there will be extensive field campaigns at dumpsites during 2017 and 2018.

At the Måseskär wreck site the plan is to repeat the sampling that was done in that area by SGU more than 20 years ago. Surface sediment samples will be taken for total arsenic and other metals. The sampling will be expanded with pore water extraction and analyzing to gain more knowledge about dissolved fractions.

The upcoming expedition will be onboard of the R/V Academic Nikolay Strakhov organized by the Shirshov Institute of Oceanology (SIO), Atlantic Branch (Kaliningrad, Russia). SIO is an associated partner of DAIMON and their participation is financed by a Swedish Institute grant.

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One of the Gothenburg landers deployed in the Arctic at 5600 m water depth in 2007 from R/V Polarstern

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R/V Academic Nikolay Strakhov

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AOV operation

A group of experts at SIO has more than 20 years of experience from working at underwater dump sites and has developed special sampling equipment and associated modelling tools that focus on spreading of contaminants.

In 2018 the plan is to use autonomous bottom landers from Gothenburg to measure sediment-water fluxes at dumpsites. The landers have been used on contaminated fibre bank sediments before but this will be the first time ever that such measurements are done at chemical weapons dumpsites.

Bombs in the Bornholn Deep

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Visual inspection of the bomb target

Polish Naval Academy currently runs three experiments aimed at estimating the rate of corrosion of ammunition drowned in the Baltic Sea. Two ex-situ experiments are conducted in the PNA laboratory and in the Military Academy of Technology in Warsaw. The third corrosive experiment, in-situ, is conducted in three areas, two where chemical ammunition was dumped, and one where conventional weapons were submerged. For the purpose of this experiment, a special structure was constructed for corrosion research in the deep sea. The results of corrosion research will be known at the beginning of 2018.

During the September cruise of R/V Oceania a side scan sonar survey, together with magnetometer survey were conducted in the area of Bornholm Deep primary dumpsite. The survey was done with usage of the AUV. As it turned out, in southern-east part of the study area there is a high concentration of potential objects. Also, strong magnetic peaks were recorded here. A ROV mission was deployed to conduct a visual inspection of the selected target. In the opinion of experts from the Polish Naval Academy, this object may be a KC-250 bomb. Sediment samples were collected in close proximity to the target. During the next cruise of R/V Oceania in October a passive sampler was be placed near the bomb to collect more data. A smeary substance was observed inside the body. The chemical analysis of the samples taken near the find will show whether it is sulfur mustard.

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Preparation of bottom sediment sampling equipment from submerged chemical and conventional munitions sites for microbiological processes and their impact on corrosion processes of ammunition bodies

VRAKA: a decision support method for oil-filled wrecks will be adapted to chemical munitions

 At the Chalmers University of Technology an ISO 31000 decision-support method, originally developed for contaminated soils on land, was developed developed by Hanna Landquist, former PhD student at the Department of Mechanics and Maritime Sciences, for sunken oil-filled wrecks.

The method resulted in software that is called “Vraka” and it is now within the DAIMON project being adapted to the special conditions that apply to dumped chemical weapons.

The method combines measurable facts such as temperature, salinity and oxygen content at the location of the wreck, with expert inquiries. Experts will, for example, assess the risk that wreck divers or fishers or a gas pipeline construction or trawling break grenades and expose/spread their content into the environment. Once figures have been obtained for the unmeasurable risks, specific to each area, these numbers are used in a mathematical model that calculates the likelihood that there will be an emission within the next year.

In the next step, the environmental and health consequences of an emission will be evaluated.

MethylAnchormercury in sediments

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Methylmercury analyser

Geochemistry group from IOPAN validated a new methodology for analyses of methylmercury in marine sediments from munition dumpsites using the MERX methylmercury analyser. Methylmercury is the most toxic and dangerous form of all mercury species present in the environment. It is highly bioaccumulative in organisms and in food chain. Fish appear to bind methylmercury strongly, nearly 100 % of mercury that accumulates in predatory fish is methylmercury. In weapon dumpsites we expect elevated concentration of mercury because mercury fulminate was used as a popular primer explosive in detonators of munitions.  In most of the chemical and conventional munitions dumpsites, environmental conditions promote methylation processes (like anoxic conditions, presence of sulfate-reducing bacteria, presence of organic matter and no UV radiation).

First results from Bornholm Deep and Gdańsk Deep show concentrations within the range from 100 to 240 pg g-1 d.w. of sediment. 

Cooperation with GEKA Munster

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For the planned fish exposure experiments lead by the AWI large amounts of solved TNT are needed. Since laboratory TNT in the required amount would be very expensive, an informal collaboration with GEKA (based in Munster corporation for the destruction of chemical and conventional warfare agents) was established. GEKA experts will extract TNT from old artillery shells and provide the solution in sufficient amounts for the experiments.

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New fish species under investigation

In cooperation with the TI-FI (Thünen Institute) AWI has authored an application to test the three-spined sticklebacks (Gasterosteus aculeatus) in a lab exposure system. Once the permission will be given AWI and TI-FI will start stickleback exposure experiments in AWI laboratories in Jan/Feb 2018...

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Stickleback (Gasterosteus aculeatus)

Study on TNT and sulphur mustard transformation in marine environment

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Analytical team of the Military Academy of Technology in Warsaw (MUT) performed experiments investigating transformations of TNT and sulphur mustard (HD) in Baltic Sea environment. The main objective of this task was to identify the degradations products of TNT and HD which can be used as their markers in marine environment. Identification of the compounds was made using gas and liquid chromatography with tandem mass spectrometry and nuclear magnetic resonance spectroscopy. The main products of TNT degradations were: 4-amino-2,6-dinitrotoluene (4ADNT), 2-amino-2,6-dinitrotoluene (2ADNT), 1,3,5-trinitrobenzoic acid (TNBA) and tetranitroazoxytoluene (4TNAT) as a product of interaction between amino-nitro-toluenes was detected. Investigation results of HD degradation in water, sediment and in wet sediment showed that transformation of the substrate is fastest in water. Stability of HD is caused by sorption to solid particles in sediments.

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