OCTOBER 2018 Newsletter #4 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: DAIMON Final Conference in Bremerhaven The Alfred Wegener Institute for Polar and Marine Research (AWI) and the Thünen Institute of Fisheries Ecology (TI-FI) would like to invite you the Open Day of the DAIMON Final Conference on the 7th of February 2019 in Bremerhaven, Germany with title: DAIMON: Decision Aid for Dumped Marine Munitions from Risk Assessment to Management. Registration details can be found here The dumped munition catalogue is online! The on-line munition catalogue developed by the Polish Naval Academy is now available at: http://dss.amw.gdynia.pl/catalog/ The catalogue covers chemical and conventional munition that has been dumped in the Baltic Sea after World War II. The main aim of the catalogue is to broaden the knowledge on dumped munitions and chemicals that had been used in them. Secondly, the catalogue can be used to identify munition pieces found on the Baltic seafloor during economic activities (e.g. fishery, construction works, dredging, etc.). The catalogue allows to search for munition objects, based on weapon type, its calibre and country of origin. Exemplary search results. Each munition object has been described in detail Exemplary information card on munition piece Where applicable, additional information is provided as separate document, covering various aspects of the weapon type: DSS finalization in sight The core of the DAIMON Decision Support System (DSS) has reached its technological final form. On the last project meeting in Klaipeda Dr. Sabine Bohlmann and Prof. Matthias Reuter demonstrated how the software of the TU Clausthal uses the data of the project partners to categorize different regions, places or objects regarding the influence of dumped ammunition of them and under the aspect of different clients like fisherman, industrial applicants, biological/ecologically scientist and administrations. Furthermore, the final form and information content of the DSS – realised in close cooperation with the associated partner EGEOS - was demonstrated and discussed with the partners. The following figures give a first overview in which form the DSS will present its information content and the final categorisation of impact of the given ammunition. Figure 1 (left) points out that an new ammunition object has been found. Left hand side the sources of the necessary environmental data, to be involved in the decision making, are shown, right hand side, the categorisation of the ammunition to the different administrative clients are presented. Figure 2 (right) shows the form and content of a “paper-based” report. It will be one of the main tasks in the final project phase to improve the form of this reports in close cooperation with the partners and stakeholders of DAIMON. During all time TU-Clausthal maintains close contact to the Ministry for Energy Transition, Agriculture, Environment, Nature and Digitalization of Schleswig-Holstein (MELUND) to ensure that the information content and report lay-out of the DSS will be adequate and useful for the ministry . Fish sampling in the Bornholm CWA dumpsite finalized In the framework of the DAIMON project, the Thünen Institute of Fisheries Ecology (TI-FI) undertook four cruises onboard RV Walther Herwig III for studying health effects of dumped CWA on the Baltic cod ( Gadus morhua ) and for taking fish samples for chemical contaminant analysis and for biological effect studies carried out by project partners. The most recent and final cruise under DAIMON took place from 21 st Aug. to 9 th Sept. 2018 and focused on the major Baltic Sea CWA dumpsite east of the island of Bornholm and CWA-free reference areas in the western and eastern Baltic Sea. Altogether, more than 20,000 cod were examined for diseases and for changes in fitness indices within DAIMON and its forerunner projects CHEMSEA and MODUM, all addressing ecological risks associated with dumped CWA in the Baltic Sea. Data generated have been incorporated into the DAIMON fish database which forms one of DAIMON’s major backbones for CWA risk assessment and the Decision Support System. Although not all biological and chemical data obtained have been analyzed so far, the good news is that our preliminary results do not indicate that cod from the Bornholm CWA dumpsite in general show a worse health status compared to fish from reference areas without dumped munitions. However, more conclusive results will be available once all data are analyzed and once an integrated risk assessment combining chemical and biological data is performed. RV Walther Herwig III Blood sampling for biomarker analysis in cod The scientific crew of cruise 419 RV Walther Herwig III, 21st Aug.-9th Sept. 2018 after successful DAIMON studies and sampling in the Baltic Sea Analysis of sediment samples from the Baltic Sea One of the main tasks of the DAIMON project was to demonstrate the obundance of CWAs in the Baltic Sea. Location of the analysed samples are shown at fig 1. Sediment samples were analyzed for presence of chemical warfare agents (CWA), explosives, and their degradation products. The analytic team of the Military University of Technology in Warsaw (MUT/WAT) performed analysis of these samples using chromatographic techniques and mass spectrometry. Based on the obtained results, it can be concluded that all analyzed samples contained degradation products from both CWA’s and explosives. Locations of the DAIMON demonstration areas Sediment samples form the Baltic Sea LC-Orbitrap used for analysis of sediment samples GC-MS/MS used for analysis of sediment samples Corrosion of ammunition shells The research conducted directly in the areas of chemical weapons dumping is very important for assessing the phenomena occurring in the marine environment. Within the DAIMON project, two types of in-situ tests were carried out. Firstly, the research was carried by the IO PAS, together with VERIFIN, in which passive samplers were dumped into the sea (read more below) Cages with corroding shells Jars filled with corroded content Secondly, the Polish Naval Academy has carried out research on the impact of environmental conditions on dumped munition . The aim of this research was to assess the rate of corrosion and technical state of munition shells, and the speed of release of toxic agents from munition shells into the environment. For this purpose, especially prepared corrosion cages with coupons of materials similar to the original materials used to construct the shells, were placed in three dumping sites: the Bornholm Deep (where only chemical munition was dumped), the Gdańsk Deep (where both chemical and conventional munition is present), and Słupsk Furrow (where only conventional munition appears). Worth emphasizing is the fact, that during the experiment original warfare materials used during World War II were used to conduct the research. Chemical analyses of marine bottom sediments Chemical analyses of marine bottom sediments are continued in full swing in the laboratories of Institute of Oceanology of the Polish Academy of Sciences. The scientific crew of Marine Geotoxicology Laboratory is engaged in multiple parameter measurements. Their main aim is methylmercury analysis in samples collected in the chemical and conventional munition dumpsites to investigate, how the mercury present in munition primers and detonators could affect the surrounding environment and organisms living in it. IO PAN performs with methods authorized by United States Environmental Protection Agency, upholding the worldwide analytical standards. Altogether many steps need to be performed to prepare the samples and define sediment properties, including freeze-drying, homogenisation, sediment sieving due to grain size analysis etc. Methylmercury analyses require sediments extraction with specific solvents to isolate the methylmercury. Concentrations are measured with the use of MERX analyser working on a Cold Vapor – Atomic Fluorescence Spectroscopy (CV-AFS) technique, based on an unique characteristic of mercury, which allows vapour measurement at room temperature. Free mercury atoms are then excited by a light source at a wavelength of 254nm and afterwards radiate the absorbed energy – fluorescence – at the same wavelength. Light intensity is a measure of methylmercury concentration. To provide more information about methylmercury behaviour in the environment and distinguish its sources, additional sediment properties need to be measured as well. It includes concentrations of iron and manganese – the main chemical elements from clay minerals that bound with mercury in specific environmental conditions. This requires an additional sediment analysis which is performed with the use of X-Ray Fluorescence Spectroscopy (XRF) technique. Another important aspect is the content of organic matter in the sediment – this parameter is also crucial in concluding on the mercury and methylmercury occurrence and behaviour. Additionally concentrations of lead and arsenic are measured to check if chemical and conventional munitions can be a significant source of toxic elements to the marine environment nearby. For this purpose the samples undergo different mineralisation procedures for analysis via Inductively Coupled Plasma Mass Spectrometry (ICP-MS) – lead, and Atomic Absorption Spectrometry combined with hydride Generation (HG-AAS) – arsenic. The procedures are complex and time consuming, therefore the IO PAN team has hands full to investigate the samples. Risk assessment model for CWA As part of DAIMON, Chalmers |
OCTOBER 2018
Newsletter #4
| |
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:
| |
|
|
DAIMON Final Conference in Bremerhaven | |
The Alfred Wegener Institute for Polar and Marine Research (AWI) and the Thünen Institute of Fisheries Ecology (TI-FI) would like to invite you the Open Day of the DAIMON Final Conference on the 7th of February 2019 in Bremerhaven, Germany with title: DAIMON: Decision Aid for Dumped Marine Munitions from Risk Assessment to Management. | |
Registration details can be found here | |
|
|
The dumped munition catalogue is online! | |
The on-line munition catalogue developed by the Polish Naval Academy is now available at: http://dss.amw.gdynia.pl/catalog/
The catalogue covers chemical and conventional munition that has been dumped in the Baltic Sea after World War II. The main aim of the catalogue is to broaden the knowledge on dumped munitions and chemicals that had been used in them. Secondly, the catalogue can be used to identify munition pieces found on the Baltic seafloor during economic activities (e.g. fishery, construction works, dredging, etc.).
The catalogue allows to search for munition objects, based on weapon type, its calibre and country of origin.
| |
Exemplary search results. Each munition object has been described in detail | | |
Exemplary information card on munition piece | | |
Where applicable, additional information is provided as separate document, covering various aspects of the weapon type: | |
|
|
DSS finalization in sight | |
The core of the DAIMON Decision Support System (DSS) has reached its technological final form. On the last project meeting in Klaipeda Dr. Sabine Bohlmann and Prof. Matthias Reuter demonstrated how the software of the TU Clausthal uses the data of the project partners to categorize different regions, places or objects regarding the influence of dumped ammunition of them and under the aspect of different clients like fisherman, industrial applicants, biological/ecologically scientist and administrations. Furthermore, the final form and information content of the DSS – realised in close cooperation with the associated partner EGEOS - was demonstrated and discussed with the partners.
The following figures give a first overview in which form the DSS will present its information content and the final categorisation of impact of the given ammunition.
| |
|
Figure 1 (left) points out that an new ammunition object has been found. Left hand side the sources of the necessary environmental data, to be involved in the decision making, are shown, right hand side, the categorisation of the ammunition to the different administrative clients are presented. | |
| | |
Figure 2 (right) shows the form and content of a “paper-based” report. It will be one of the main tasks in the final project phase to improve the form of this reports in close cooperation with the partners and stakeholders of DAIMON.
During all time TU-Clausthal maintains close contact to the Ministry for Energy Transition, Agriculture, Environment, Nature and Digitalization of Schleswig-Holstein (MELUND) to ensure that the information content and report lay-out of the DSS will be adequate and useful for the ministry .
| |
| | | |
|
|
Fish sampling in the Bornholm CWA dumpsite finalized | |
In the framework of the DAIMON project, the Thünen Institute of Fisheries Ecology (TI-FI) undertook four cruises onboard RV Walther Herwig III for studying health effects of dumped CWA on the Baltic cod (Gadus morhua) and for taking fish samples for chemical contaminant analysis and for biological effect studies carried out by project partners. The most recent and final cruise under DAIMON took place from 21stAug. to 9th Sept. 2018 and focused on the major Baltic Sea CWA dumpsite east of the island of Bornholm and CWA-free reference areas in the western and eastern Baltic Sea.
Altogether, more than 20,000 cod were examined for diseases and for changes in fitness indices within DAIMON and its forerunner projects CHEMSEA and MODUM, all addressing ecological risks associated with dumped CWA in the Baltic Sea. Data generated have been incorporated into the DAIMON fish database which forms one of DAIMON’s major backbones for CWA risk assessment and the Decision Support System.
Although not all biological and chemical data obtained have been analyzed so far, the good news is that our preliminary results do not indicate that cod from the Bornholm CWA dumpsite in general show a worse health status compared to fish from reference areas without dumped munitions. However, more conclusive results will be available once all data are analyzed and once an integrated risk assessment combining chemical and biological data is performed.
| |
|
Blood sampling for biomarker analysis in cod | | |
The scientific crew of cruise 419 RV Walther Herwig III, 21st Aug.-9th Sept. 2018 after successful DAIMON studies and sampling in the Baltic Sea | | |
| | |
|
|
Analysis of sediment samples from the Baltic Sea | |
One of the main tasks of the DAIMON project was to demonstrate the obundance of CWAs in the Baltic Sea. Location of the analysed samples are shown at fig 1. Sediment samples were analyzed for presence of chemical warfare agents (CWA), explosives, and their degradation products. The analytic team of the Military University of Technology in Warsaw (MUT/WAT) performed analysis of these samples using chromatographic techniques and mass spectrometry. Based on the obtained results, it can be concluded that all analyzed samples contained degradation products from both CWA’s and explosives. | |
Locations of the DAIMON demonstration areas | | |
Sediment samples form the Baltic Sea | | |
LC-Orbitrap used for analysis of sediment samples | | |
|
GC-MS/MS used for analysis of sediment samples | | |
| | |
|
|
Corrosion of ammunition shells | |
The research conducted directly in the areas of chemical weapons dumping is very important for assessing the phenomena occurring in the marine environment. Within the DAIMON project, two types of in-situ tests were carried out. Firstly, the research was carried by the IO PAS, together with VERIFIN, in which passive samplers were dumped into the sea (read more below) | |
Cages with corroding shells | | |
|
Jars filled with corroded content | | |
| | |
Secondly, the Polish Naval Academy has carried out research on the impact of environmental conditions on dumped munition. The aim of this research was to assess the rate of corrosion and technical state of munition shells, and the speed of release of toxic agents from munition shells into the environment. For this purpose, especially prepared corrosion cages with coupons of materials similar to the original materials used to construct the shells, were placed in three dumping sites: the Bornholm Deep (where only chemical munition was dumped), the Gdańsk Deep (where both chemical and conventional munition is present), and Słupsk Furrow (where only conventional munition appears). Worth emphasizing is the fact, that during the experiment original warfare materials used during World War II were used to conduct the research. | |
|
|
Chemical analyses of marine bottom sediments | |
Chemical analyses of marine bottom sediments are continued in full swing in the laboratories of Institute of Oceanology of the Polish Academy of Sciences. The scientific crew of Marine Geotoxicology Laboratory is engaged in multiple parameter measurements. Their main aim is methylmercury analysis in samples collected in the chemical and conventional munition dumpsites to investigate, how the mercury present in munition primers and detonators could affect the surrounding environment and organisms living in it. IO PAN performs with methods authorized by United States Environmental Protection Agency, upholding the worldwide analytical standards.
Altogether many steps need to be performed to prepare the samples and define sediment properties, including freeze-drying, homogenisation, sediment sieving due to grain size analysis etc.
Methylmercury analyses require sediments extraction with specific solvents to isolate the methylmercury. Concentrations are measured with the use of MERX analyser working on a Cold Vapor – Atomic Fluorescence Spectroscopy (CV-AFS) technique, based on an unique characteristic of mercury, which allows vapour measurement at room temperature. Free mercury atoms are then excited by a light source at a wavelength of 254nm and afterwards radiate the absorbed energy – fluorescence – at the same wavelength. Light intensity is a measure of methylmercury concentration. To provide more information about methylmercury behaviour in the environment and distinguish its sources, additional sediment properties need to be measured as well. It includes concentrations of iron and manganese – the main chemical elements from clay minerals that bound with mercury in specific environmental conditions. This requires an additional sediment analysis which is performed with the use of X-Ray Fluorescence Spectroscopy (XRF) technique. Another important aspect is the content of organic matter in the sediment – this parameter is also crucial in concluding on the mercury and methylmercury occurrence and behaviour. Additionally concentrations of lead and arsenic are measured to check if chemical and conventional munitions can be a significant source of toxic elements to the marine environment nearby. For this purpose the samples undergo different mineralisation procedures for analysis via Inductively Coupled Plasma Mass Spectrometry (ICP-MS) – lead, and Atomic Absorption Spectrometry combined with hydride Generation (HG-AAS) – arsenic. The procedures are complex and time consuming, therefore the IO PAN team has hands full to investigate the samples.
| |
|
|
Risk assessment model for CWA | |
As part of DAIMON, Chalmers University of Technology has developed a model (VRAKA-CWA) for assessing the risk associated with dumped chemical warfare agents. The work has is based on the shipwreck risk assessment model VRAKA, previously developed by Chalmers. VRAKA was the first quantitative risk model for providing decision support to facilitate prioritization among wrecks that need to be remediated. The task within DAIMON has been to update and further develop the model to enable proper analyses of dumped chemical warfare agents.
The new model, VRAKA-CWA is used to calculate the probability of different activities causing damage to a munition unit and thus having a release of CWA. The risk is calculated as a function of the probability, the toxic unit of the specific CWA and the mass of CWA. The results of the model may be illustrated as shown below, i.e. as cumulative functions representing the probability and the final risk level. The solid lines represent the mean probability and risk value, respectively. It is a probabilistic model considering uncertainties in input data and results.
The model interface is shown in the figure below. The assessor using the model defines site specific indicators such as salinity and depth. Furthermore, an estimation is done of the number of times activities such as diving and trawling occurs at the specific site and may cause damage to the unit being analysed. Finally, the arrangement of the munition units and type of CWA they contain are defined.
The information on site specific conditions and activities, is combined with probability distributions that have been defined by an excerpt group to represent different generic conditions. This statistical technique is named Bayesian updating and makes it possible to e.g. calculate the probability of having a hole in a munition unit based on a specific set of conditions. VRAKA-CWA also makes it possible to compare to what extent different activities (e.g. diving and trawling) and natural processes (deterioration/corrosion and unstable seabed/landslides) contribute to the overall probability and thus the overall risk. This is illustrated in the figure below.
VRAKA-CWA will be further developed to enable integration into the decision support system (DSS) of DAIMON.
| |
|
|
High Resolution Model (HRM) for constant leakage estimation of CWAs | |
Modeling group from Institute of Oceanology Polish Academy of Sciences (IOPAN) is working on a numerical contamination dispersion model. The drivers which move the contamination are bottom currents in above sea floor and diffusion processes. Below is an example how potential leakage can be distributed when constant leakage begins. Horizontal and vertical axes represent distance in relative units. Color scale can be interpreted as the level of contamination (units and values irrelevant): | |
|
Situation after 5 days of estimated potential leakage | | |
| | |
The results for modelling part from high resolution model, basing on results from corrosion progress experiment are expected in early Spring 2019. | |
|
|
First results of toxicity tests with TNT on blue mussels | |
First results from the toxicity tests using dissolved TNT on Baltic blue mussel exposed under lab conditions show simple but efficient defence mechanisms against toxicity of TNT leading to high lethal exposure concentrations. In contrast, concentrations where no negative effects at all occurred were comparably low. | |
|
Setup for mussel exposure experiment | | |
| | |
Scientists from the Alfred Wegener Institute recommend therefore to focus on these so called “no effect concentrations“ in order to get a more realistic picture of TNT toxicity for marine organisms. | |
|
|
| |