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Paula Vanninen - One of the best experts on this subject based on the ideXlab platform.

  • studying the metabolism of toxic chemical warfare agent related phenylarsenic chemicals in vitro in cod liver
    Journal of Hazardous Materials, 2020
    Co-Authors: Hanna Niemikoski, Daniel Koske, Ulrike Kammann, Thomas Lang, Paula Vanninen
    Abstract:

    Abstract Large quantities of chemical warfare agents (CWAs), such as phenylarsenic chemicals, were disposed by sea-dumping after World War II. Nowadays, the release of these toxic chemicals from munitions poses a potential threat to living organisms. This study investigates the fate of these chemicals in fish by exposing selected CWA-related phenylarsenic chemicals and their oxidation products to cod (Gadus morhua) liver S9 fraction in vitro. Clark I (DA), Adamsite (DM) and their corresponding oxidation products as well as triphenylarsine oxide (TPA[ox]) and phenylarsonic acid (PDCA[ox]) were used as chemicals in in vitro experiments. Glutathione (GSH) conjugates of DA, DM and PDCA-related chemicals were found to be the most dominant metabolites, and methylated metabolites were detected as well, suggesting that these compounds are metabolised in the presence of cod liver enzymes. TPA[ox] was the only compound tested that did not form a GSH conjugate or methylated metabolite, indicating a different biotransformation pathway for this compound. Furthermore, hydroxylated metabolites were detected for each tested chemical. Due to their reactive nature, GSH conjugates may be difficult to detect in fish samples from CWA dumpsites. In contrast, both methylated and hydroxylated metabolites of phenylarsenic chemicals are promising target chemicals for the detection of CWA-related contamination in fish.

  • identification of degradation products of sea dumped chemical warfare agent related phenylarsenic chemicals in marine sediment
    Analytical Chemistry, 2020
    Co-Authors: Hanna Niemikoski, Martin Soderstrom, Harri Kiljunen, Anders Ostin, Paula Vanninen
    Abstract:

    Previously unknown phenylarsenic chemicals that originated from chemical warfare agents (CWAs) have been detected and identified in sediment samples collected from the vicinity of chemical munition dumpsites. Nontargeted screening by ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS) was used for detection of 14 unknown CWA-related phenylarsenic chemicals. Methylated forms of Clark I/II, Adamsite, and phenyldichloroarsine were detected in all analyzed sediment samples, and their identification was based on synthesized chemicals. In addition, other previously unknown CWA-related phenylarsenic chemicals were detected, and their structures were elucidated using MS/HRMS technique. On the basis of relative isotope ratios of protonated molecules and measures of exact masses of formed fragment ions, it could be concluded that some of these unknown chemicals contained a sulfur atom attached to an arsenic atom. In addition to that, some of the samples contained chemicals that had formed via addition of an OH group to the aromatic ring. However, it is not possible to say how these chemicals are formed, but the most plausible cause is activities of marine microbes in the sediment. To our knowledge, these chemicals have not been detected from sediment samples previously. Sensitive analytical methods are needed for these novel chemicals to assess the total CWA burden in marine sediments, and this information is essential for the risk assessment.

  • detection of chemical warfare agent related phenylarsenic compounds in marine biota samples by lc hesi ms ms
    Analytical Chemistry, 2017
    Co-Authors: Hanna Niemikoski, Martin Soderstrom, Paula Vanninen
    Abstract:

    A new method has been developed to determine oxidation products of three chemical warfare agent (CWA) related phenylarsenic compounds from marine biota samples by a liquid chromatography-heated electrospray ionization/tandem mass spectrometry (LC-HESI/MS/MS). The target chemicals were oxidation products of Adamsite (DM[ox]), Clark I (DPA[ox]), and triphenylarsine (TPA[ox]). Method was validated within the concentration range of 1–5, 0.2–5, and 0.2–5 ng/g for DM[ox], DPA[ox], and TPA[ox], respectively. The method was linear, precise and accurate. Limits of quantification (LOQ) were 2.0, 1.3, and 2.1 ng/g for DM[ox], DPA[ox], and TPA[ox], respectively. A total of ten fish samples and one lobster sample collected from near Swedish coast, Maseskar dumpsite were analyzed. Trace concentrations below LOQ values were detected in three samples and the elemental composition of oxidized form of Clark I and/or II was confirmed by LC-HESI/HRMS. To our knowledge, this is the first study that provides the presence of CW...

  • Detection of Chemical Warfare Agent-Related Phenylarsenic Compounds in Marine Biota Samples by LC-HESI/MS/MS
    2017
    Co-Authors: Hanna Niemikoski, Martin Söderström, Paula Vanninen
    Abstract:

    A new method has been developed to determine oxidation products of three chemical warfare agent (CWA) related phenylarsenic compounds from marine biota samples by a liquid chromatography-heated electrospray ionization/tandem mass spectrometry (LC-HESI/MS/MS). The target chemicals were oxidation products of Adamsite (DM­[ox]), Clark I (DPA­[ox]), and triphenylarsine (TPA­[ox]). Method was validated within the concentration range of 1–5, 0.2–5, and 0.2–5 ng/g for DM­[ox], DPA­[ox], and TPA­[ox], respectively. The method was linear, precise and accurate. Limits of quantification (LOQ) were 2.0, 1.3, and 2.1 ng/g for DM­[ox], DPA­[ox], and TPA­[ox], respectively. A total of ten fish samples and one lobster sample collected from near Swedish coast, Måseskär dumpsite were analyzed. Trace concentrations below LOQ values were detected in three samples and the elemental composition of oxidized form of Clark I and/or II was confirmed by LC-HESI/HRMS. To our knowledge, this is the first study that provides the presence of CWA related chemicals in marine biota samples

  • evaluation of a chemical munition dumpsite in the baltic sea based on geophysical and chemical investigations
    Science of The Total Environment, 2010
    Co-Authors: Tine Missiaen, Martin Soderstrom, Irina Popescu, Paula Vanninen
    Abstract:

    This paper discusses the results of geophysical and chemical investigations carried out in a chemical munition dumpsite in the southern Baltic Sea, east of the island of Bornholm. After WW2 over 32,000 tons of chemical war material was dumped here including shells and bombs as well as small drums and containers. The geophysical investigations combined very-high-resolution seismics and gradiometric measurements. The results indicate the presence of a large number of objects buried just below the seafloor. The size of the objects and their distribution, with a marked increase in density towards the center of the dumpsite, suggests that we are dealing with dumped war material. Sediment and near-bottom water samples, taken within the dumpsite and in the surrounding area, were analysed for the presence of various chemical warfare agents (CWA) including Adamsite, Clark, sulphur mustard, tabun, chlorobenzene and arsine oil. The results indicate a widespread contamination that reaches far beyond the dumpsite boundary. CWA degradation products were found in most of the sediment samples. The contamination was mostly related to arsenic containing compounds; only one sample indicated the presence of sulfur mustard. Although the correlation between detected objects and CWA concentrations is not always straightforward, the overall results suggest that a lot of the dumped war material is leaking and that over the years the contamination has reached the seafloor sediments.

Hanna Niemikoski - One of the best experts on this subject based on the ideXlab platform.

  • studying the metabolism of toxic chemical warfare agent related phenylarsenic chemicals in vitro in cod liver
    Journal of Hazardous Materials, 2020
    Co-Authors: Hanna Niemikoski, Daniel Koske, Ulrike Kammann, Thomas Lang, Paula Vanninen
    Abstract:

    Abstract Large quantities of chemical warfare agents (CWAs), such as phenylarsenic chemicals, were disposed by sea-dumping after World War II. Nowadays, the release of these toxic chemicals from munitions poses a potential threat to living organisms. This study investigates the fate of these chemicals in fish by exposing selected CWA-related phenylarsenic chemicals and their oxidation products to cod (Gadus morhua) liver S9 fraction in vitro. Clark I (DA), Adamsite (DM) and their corresponding oxidation products as well as triphenylarsine oxide (TPA[ox]) and phenylarsonic acid (PDCA[ox]) were used as chemicals in in vitro experiments. Glutathione (GSH) conjugates of DA, DM and PDCA-related chemicals were found to be the most dominant metabolites, and methylated metabolites were detected as well, suggesting that these compounds are metabolised in the presence of cod liver enzymes. TPA[ox] was the only compound tested that did not form a GSH conjugate or methylated metabolite, indicating a different biotransformation pathway for this compound. Furthermore, hydroxylated metabolites were detected for each tested chemical. Due to their reactive nature, GSH conjugates may be difficult to detect in fish samples from CWA dumpsites. In contrast, both methylated and hydroxylated metabolites of phenylarsenic chemicals are promising target chemicals for the detection of CWA-related contamination in fish.

  • identification of degradation products of sea dumped chemical warfare agent related phenylarsenic chemicals in marine sediment
    Analytical Chemistry, 2020
    Co-Authors: Hanna Niemikoski, Martin Soderstrom, Harri Kiljunen, Anders Ostin, Paula Vanninen
    Abstract:

    Previously unknown phenylarsenic chemicals that originated from chemical warfare agents (CWAs) have been detected and identified in sediment samples collected from the vicinity of chemical munition dumpsites. Nontargeted screening by ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS) was used for detection of 14 unknown CWA-related phenylarsenic chemicals. Methylated forms of Clark I/II, Adamsite, and phenyldichloroarsine were detected in all analyzed sediment samples, and their identification was based on synthesized chemicals. In addition, other previously unknown CWA-related phenylarsenic chemicals were detected, and their structures were elucidated using MS/HRMS technique. On the basis of relative isotope ratios of protonated molecules and measures of exact masses of formed fragment ions, it could be concluded that some of these unknown chemicals contained a sulfur atom attached to an arsenic atom. In addition to that, some of the samples contained chemicals that had formed via addition of an OH group to the aromatic ring. However, it is not possible to say how these chemicals are formed, but the most plausible cause is activities of marine microbes in the sediment. To our knowledge, these chemicals have not been detected from sediment samples previously. Sensitive analytical methods are needed for these novel chemicals to assess the total CWA burden in marine sediments, and this information is essential for the risk assessment.

  • detection of chemical warfare agent related phenylarsenic compounds in marine biota samples by lc hesi ms ms
    Analytical Chemistry, 2017
    Co-Authors: Hanna Niemikoski, Martin Soderstrom, Paula Vanninen
    Abstract:

    A new method has been developed to determine oxidation products of three chemical warfare agent (CWA) related phenylarsenic compounds from marine biota samples by a liquid chromatography-heated electrospray ionization/tandem mass spectrometry (LC-HESI/MS/MS). The target chemicals were oxidation products of Adamsite (DM[ox]), Clark I (DPA[ox]), and triphenylarsine (TPA[ox]). Method was validated within the concentration range of 1–5, 0.2–5, and 0.2–5 ng/g for DM[ox], DPA[ox], and TPA[ox], respectively. The method was linear, precise and accurate. Limits of quantification (LOQ) were 2.0, 1.3, and 2.1 ng/g for DM[ox], DPA[ox], and TPA[ox], respectively. A total of ten fish samples and one lobster sample collected from near Swedish coast, Maseskar dumpsite were analyzed. Trace concentrations below LOQ values were detected in three samples and the elemental composition of oxidized form of Clark I and/or II was confirmed by LC-HESI/HRMS. To our knowledge, this is the first study that provides the presence of CW...

  • Detection of Chemical Warfare Agent-Related Phenylarsenic Compounds in Marine Biota Samples by LC-HESI/MS/MS
    2017
    Co-Authors: Hanna Niemikoski, Martin Söderström, Paula Vanninen
    Abstract:

    A new method has been developed to determine oxidation products of three chemical warfare agent (CWA) related phenylarsenic compounds from marine biota samples by a liquid chromatography-heated electrospray ionization/tandem mass spectrometry (LC-HESI/MS/MS). The target chemicals were oxidation products of Adamsite (DM­[ox]), Clark I (DPA­[ox]), and triphenylarsine (TPA­[ox]). Method was validated within the concentration range of 1–5, 0.2–5, and 0.2–5 ng/g for DM­[ox], DPA­[ox], and TPA­[ox], respectively. The method was linear, precise and accurate. Limits of quantification (LOQ) were 2.0, 1.3, and 2.1 ng/g for DM­[ox], DPA­[ox], and TPA­[ox], respectively. A total of ten fish samples and one lobster sample collected from near Swedish coast, Måseskär dumpsite were analyzed. Trace concentrations below LOQ values were detected in three samples and the elemental composition of oxidized form of Clark I and/or II was confirmed by LC-HESI/HRMS. To our knowledge, this is the first study that provides the presence of CWA related chemicals in marine biota samples

Maurice L. - One of the best experts on this subject based on the ideXlab platform.

  • Idylwilde damsite, etc. 5
    Colorado State University. Libraries, 2021
    Co-Authors: Maurice L.
    Abstract:

    From group of images of water structures and soil tests, including Idylwilde damsite on the Big Thompson River, a man and woman inside and outside of a house (images 145-161), several groups of unidentified men, and aerial photographs of mountains and river valleys. Image 6 reads, "Gravel Pit across road north of Fish Hatchery," and images 106-126 are numbered 1 through 21.5 of 126 35 mm slides.Caption: Gravel Pit across road north of Fish Hatchery

  • Idylwilde damsite, etc. 3
    Colorado State University. Libraries, 2021
    Co-Authors: Maurice L.
    Abstract:

    From group of images of water structures and soil tests, including Idylwilde damsite on the Big Thompson River, a man and woman inside and outside of a house (images 145-161), several groups of unidentified men, and aerial photographs of mountains and river valleys. Image 6 reads, "Gravel Pit across road north of Fish Hatchery," and images 106-126 are numbered 1 through 21.3 of 126 35 mm slides

  • Idylwilde damsite, etc. 119
    Colorado State University. Libraries, 2021
    Co-Authors: Maurice L.
    Abstract:

    From group of images of water structures and soil tests, including Idylwilde damsite on the Big Thompson River, a man and woman inside and outside of a house (images 145-161), several groups of unidentified men, and aerial photographs of mountains and river valleys. Image 6 reads, "Gravel Pit across road north of Fish Hatchery," and images 106-126 are numbered 1 through 21.119 of 126 35 mm slides.Caption: 14

  • Idylwilde damsite, etc. 29
    Colorado State University. Libraries, 2021
    Co-Authors: Maurice L.
    Abstract:

    From group of images of water structures and soil tests, including Idylwilde damsite on the Big Thompson River, a man and woman inside and outside of a house (images 145-161), several groups of unidentified men, and aerial photographs of mountains and river valleys. Image 6 reads, "Gravel Pit across road north of Fish Hatchery," and images 106-126 are numbered 1 through 21.29 of 126 35 mm slides

  • Idylwilde damsite, etc. 8
    Colorado State University. Libraries, 2021
    Co-Authors: Maurice L.
    Abstract:

    From group of images of water structures and soil tests, including Idylwilde damsite on the Big Thompson River, a man and woman inside and outside of a house (images 145-161), several groups of unidentified men, and aerial photographs of mountains and river valleys. Image 6 reads, "Gravel Pit across road north of Fish Hatchery," and images 106-126 are numbered 1 through 21.8 of 126 35 mm slides

Martin Soderstrom - One of the best experts on this subject based on the ideXlab platform.

  • identification of degradation products of sea dumped chemical warfare agent related phenylarsenic chemicals in marine sediment
    Analytical Chemistry, 2020
    Co-Authors: Hanna Niemikoski, Martin Soderstrom, Harri Kiljunen, Anders Ostin, Paula Vanninen
    Abstract:

    Previously unknown phenylarsenic chemicals that originated from chemical warfare agents (CWAs) have been detected and identified in sediment samples collected from the vicinity of chemical munition dumpsites. Nontargeted screening by ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS) was used for detection of 14 unknown CWA-related phenylarsenic chemicals. Methylated forms of Clark I/II, Adamsite, and phenyldichloroarsine were detected in all analyzed sediment samples, and their identification was based on synthesized chemicals. In addition, other previously unknown CWA-related phenylarsenic chemicals were detected, and their structures were elucidated using MS/HRMS technique. On the basis of relative isotope ratios of protonated molecules and measures of exact masses of formed fragment ions, it could be concluded that some of these unknown chemicals contained a sulfur atom attached to an arsenic atom. In addition to that, some of the samples contained chemicals that had formed via addition of an OH group to the aromatic ring. However, it is not possible to say how these chemicals are formed, but the most plausible cause is activities of marine microbes in the sediment. To our knowledge, these chemicals have not been detected from sediment samples previously. Sensitive analytical methods are needed for these novel chemicals to assess the total CWA burden in marine sediments, and this information is essential for the risk assessment.

  • detection of chemical warfare agent related phenylarsenic compounds in marine biota samples by lc hesi ms ms
    Analytical Chemistry, 2017
    Co-Authors: Hanna Niemikoski, Martin Soderstrom, Paula Vanninen
    Abstract:

    A new method has been developed to determine oxidation products of three chemical warfare agent (CWA) related phenylarsenic compounds from marine biota samples by a liquid chromatography-heated electrospray ionization/tandem mass spectrometry (LC-HESI/MS/MS). The target chemicals were oxidation products of Adamsite (DM[ox]), Clark I (DPA[ox]), and triphenylarsine (TPA[ox]). Method was validated within the concentration range of 1–5, 0.2–5, and 0.2–5 ng/g for DM[ox], DPA[ox], and TPA[ox], respectively. The method was linear, precise and accurate. Limits of quantification (LOQ) were 2.0, 1.3, and 2.1 ng/g for DM[ox], DPA[ox], and TPA[ox], respectively. A total of ten fish samples and one lobster sample collected from near Swedish coast, Maseskar dumpsite were analyzed. Trace concentrations below LOQ values were detected in three samples and the elemental composition of oxidized form of Clark I and/or II was confirmed by LC-HESI/HRMS. To our knowledge, this is the first study that provides the presence of CW...

  • evaluation of a chemical munition dumpsite in the baltic sea based on geophysical and chemical investigations
    Science of The Total Environment, 2010
    Co-Authors: Tine Missiaen, Martin Soderstrom, Irina Popescu, Paula Vanninen
    Abstract:

    This paper discusses the results of geophysical and chemical investigations carried out in a chemical munition dumpsite in the southern Baltic Sea, east of the island of Bornholm. After WW2 over 32,000 tons of chemical war material was dumped here including shells and bombs as well as small drums and containers. The geophysical investigations combined very-high-resolution seismics and gradiometric measurements. The results indicate the presence of a large number of objects buried just below the seafloor. The size of the objects and their distribution, with a marked increase in density towards the center of the dumpsite, suggests that we are dealing with dumped war material. Sediment and near-bottom water samples, taken within the dumpsite and in the surrounding area, were analysed for the presence of various chemical warfare agents (CWA) including Adamsite, Clark, sulphur mustard, tabun, chlorobenzene and arsine oil. The results indicate a widespread contamination that reaches far beyond the dumpsite boundary. CWA degradation products were found in most of the sediment samples. The contamination was mostly related to arsenic containing compounds; only one sample indicated the presence of sulfur mustard. Although the correlation between detected objects and CWA concentrations is not always straightforward, the overall results suggest that a lot of the dumped war material is leaking and that over the years the contamination has reached the seafloor sediments.

Hans Sanderson - One of the best experts on this subject based on the ideXlab platform.

  • review of environmental exposure concentrations of chemical warfare agent residues and associated the fish community risk following the construction and completion of the nord stream gas pipeline between russia and germany
    Journal of Hazardous Materials, 2014
    Co-Authors: Hans Sanderson, Patrik Fauser, Malene Rahbek, Jorn Bo Larsen
    Abstract:

    Abstract This paper compiles all the measured chemical warfare agent (CWA) concentrations found in relation to the Nord Stream pipeline work in Danish waters for the past 5 years. Sediment and biota sampling were performed along the pipeline route in four campaigns, prior to (in 2008 and 2010), during (in 2011) and after (in 2012) the construction work. No parent CWAs were detected in the sediments. Patchy residues of CWA degradation products of Adamsite, Clark I, phenyldichloroarsine, trichloroarsine and Lewisite II, were detected in a total of 29 of the 391 sediment samples collected and analyzed the past 5 years. The cumulative fish community risk quotient for the different locations, calculated as a sum of background and added risk, ranged between 0 and 0.017 suggesting a negligible acute CWA risk toward the fish community. The added risk from sediment disturbance in relation to construction of the pipelines represents less than 2% of the total risk in the areas with the highest calculated risk. The analyses of benthic infauna corroborate the finding of CWA related low risk across the years. There was no significant difference in CWA risk before (2008) and after the pipeline construction (2012).

  • screening level fish community risk assessment of chemical warfare agents in the baltic sea
    Journal of Hazardous Materials, 2008
    Co-Authors: Hans Sanderson, Patrik Fauser, Marianne Thomsen, Peter Sorensen
    Abstract:

    Chemical warfare agents (CWAs) have been disposed of in various fashions over the past decades. Significant amounts (approximately 11,000 tonnes) have been dumped in the Baltic Sea east of the island Bornholm following the disarmament of Germany after World War II, causing concerns over potential environmental risks. Absence of risk based on assumptions of extremely low solubility of CWAs cannot alone dismiss these concerns. Existing and modelled fate and effects data were used in the analysis to assess the fish community risk level. The most realistic and also conservative assessment result is the scenario describing 70 m water depth for the most realistic dump-site area with a focus on chronic toxicity, at 0-20 cm above the sediment, yielding a total mixture toxic unit (TU) of 0.62. Triphenylarsine is the CWA with the highest realistic risk profile at 0.2 TU for the fish community followed by Adamsite (0.17), Clark I (0.086) and Yperite (0.083) TU. Adamsite is more persistent and constitutes a potential risk for a longer period than triphenylarsine. The seawater volume potentially at risk is <4 m above sediment and <58 km down current of dump sites. Further risk assessment of dumped CWAs in the Baltic Sea is warranted.