Environmental impact of the explosion of the Nord Stream pipelines.

Armed conflicts have, in addition to severe impacts on human lives and infrastructure, also impacts on the environment, which needs to be assessed and documented. On September the 26th 2022, unknown perpetrators deliberately ruptured the two gas pipelines Nord Stream 1 and 2 with four coordinated explosions near a major chemical munition dump site near the Danish island of Bornholm in the Baltic Sea. While the massive release of natural gas into atmosphere raised serious concerns concerning the contribution to climate change-this paper assesses the overlooked direct impact of the explosions on the marine ecosystem. Seals and porpoises within a radius of four km would be at high risk of being killed by the shockwave, while temporary impact on hearing would be expected up to 50 km away. As the Baltic Proper population of harbour porpoises (Phocoena phocoena) is critically endangered, the loss or serious injury of even a single individual is considered a significant impact on the population. The rupture moreover resulted in the resuspension of 250000 metric tons of heavily contaminated sediment from deep-sea sedimentary basin for over a week, resulting in unacceptable toxicological risks towards fish and other biota in 11 km3 water in the area for more than a month.

Suspect and non-target screening of semi-volatile emerging contaminants in indoor dust from Danish kindergartens.

Indoor dust is a sink of hundreds of organic chemicals, and humans may potentially be exposed to these via indoor activities. This study investigated potentially harmful semi-volatile organic contaminants in indoor dust from Danish kindergartens using suspect and non-target screening on gas chromatography (GC)-Orbitrap, supported by target analyses using GC-low resolution mass spectrometry (LRMS). A suspect list of 41 chemicals with one or more toxicological endpoints, i.e. endocrine disruption, carcinogenicity, neurotoxicity and allergenicity, known or suspected to be present in indoor dust, was established including phthalate and non-phthalate plasticizers, flame retardants, bisphenols, biocides, UV filters and other plastic additives. Of these, 29 contaminants were detected in the indoor dust samples, also including several compounds that had been banned or restricted for years. In addition, 22 chemicals were tentatively identified via non-target screening. Several chemicals have not previously been detected in Danish indoor dust. Most of the detected chemicals are known to be potentially harmful for human health while hazard assessment of the remaining compounds indicated limited risks to human. However, children were not specifically considered in this hazard assessment.

Endocrine disrupting chemicals in indoor dust: A review of temporal and spatial trends, and human exposure.

Several chemicals with widespread consumer uses have been identified as endocrine-disrupting chemicals (EDCs), with a potential risk to humans. The occurrence in indoor dust and resulting human exposure have been reviewed for six groups of known and suspected EDCs, including phthalates and non-phthalate plasticizers, flame retardants, bisphenols, per- and polyfluoroalkyl substances (PFAS), biocides and personal care product additives (PCPs). Some banned or restricted EDCs, such as polybrominated diphenyl ethers (PBDEs), di-(2-ethylhexyl) phthalate (DEHP), bisphenol A (BPA), perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), are still widely detected in indoor dust in most countries, even as the predominating compounds of their group, but generally with decreasing trends. Meanwhile, alternatives that are also potential EDCs, such as bisphenol S (BPS), bisphenol F (BPF), decabromodiphenyl ethane (DBDPE) and organophosphate flame retardants (OPFRs), and PFAS precursors, such as fluorotelomer alcohols, have been detected in indoor dust with increasing frequencies and concentrations. Associations between some known and suspected EDCs, such as phthalate and non-phthalate plasticizers, FRs and BPs, in indoor dust and paired human samples indicate indoor dust as an important human exposure pathway. Although the estimated daily intake (EDI) of most of the investigated compounds was mostly below reference values, the co-exposure to a multitude of known or suspected EDCs requires a better understanding of mixture effects.

Residual additives in marine microplastics and their risk assessment - A critical review.

This review summarizes the current state of knowledge regarding the risk assessment of plastic-associated residual additives, i.e. residual monomers, degradation products and additives, in the marine environment, also considering effects of weathering and bioavailability. Experimental studies have found a number of organic and metal additive compounds in leachates from plastics, and the analysis of weathered plastic particles, such as polyethylene, polypropylene and polystyrene particles sampled on beaches and shorelines, has identified residual additives, such as flame retardants, plasticizers, UV stabilizers and antioxidants. While the transfer of e.g. PBDEs to organisms upon ingestion has been demonstrated, studies on uptake and bioaccumulation of plastic-associated chemicals are inconclusive. Studies on hazard and risk assessments are few, and focus on monomers and/or a limited number of high concentration additives, such as phthalates and flame retardants. The risk assessment results vary between low, moderate and high risks of specific additives, and are not necessarily consistent for the same compound. Given the large number of chemicals potentially introduced into the marine environment with plastic particles and the challenges associated with the correct quantification of exposure concentrations and toxicity thresholds, the question arises whether new risk assessment concepts may be needed.

In situ formation of environmental endocrine disruptors from phytosterol degradation: a temporal model for agricultural soils.

We propose a conceptual model that describes the in situ formation of androstenedione in agricultural soil from a phytosterol, ß-sitosterol, released after crop harvest and soil fertiliser amendment. Based on the recorded agricultural practice at a spring barley field, ß-sitosterol and androstenedione concentrations were modelled over the year. While decomposition of crop residues created low soil levels, the application of pig slurry led to an androstenedione soil concentration of 54 µg kg-1. The elevated soil concentration of androstenedione is not due to the introduction of the endocrine disruptor in the fertiliser, but a result of the addition of large concentrations of ß-sitosterol as a natural precursor. The limited available data on ß-sitosterol and androstenedione concentration in soil prohibited their accurate prediction by our model. However, the potential implication of endocrine-disrupting steroid hormones being formed in situ from currently little considered phytosterols justifies a conceptual description and further research.

Global emissions of Dechlorane Plus.

Dechlorane Plus (DP) is a chlorinated flame retardant applied in parallel to or as a replacement product for regulated flame retardants. Detection of DP in environmental media all over the world in recent years necessitates the development of detailed global emission estimates for environmental model studies. Based on production, usage and disposal data two global atmospheric emission scenarios were made with a detailed geographical distribution. The total DP emission is estimated to be 0.02 t/year and 3.2 t/year in a low and high emission scenario, respectively, reflecting the uncertainties in production volumes and emission factors. The emission estimates are tested by implementation in the Danish Eulerian Hemispheric Model, an advanced chemistry-transport model. An evaluation against measurements in the Arctic from the early 2010s, considered to represent background concentrations, shows that the predicted concentration range for the high emission scenario is in line with the measured range, whereas the predicted concentrations for the low emission estimate are more than a factor of 100 lower than the measurements, rendering the high emission estimate most probable.

Risk assessment of added chemicals in plastics in the Danish marine environment.

A risk assessment framework for direct exposure of residual additives and monomers present in ingested plastic particles, including microplastics, in the Danish marine environment, was presented. Eight cases of different polymer types and product groups were defined that represent the most significant exposures, and thus potential high-risk cases, towards marine organisms. Risk Quotients (RQ) were calculated for three trophic levels, i.e. pelagic/planktonic zooplankton: copepod, benthopelagic fish: Atlantic cod and seabird: northern fulmar. European and Danish Environmental Quality Standard (EQS) values were used as Predicted No-Effect Concentrations (PNEC). RQ larger than unity, indicating potential risks, were found for copepod and cod (pelagic community) and the flame-retardant pentabromodiphenyl ether (PeBDE) used in polyurethane (PUR), the biocide tributyltin (TBT) present as impurity in polyvinylchloride (PVC) and PUR, and the flame-retardant hexabromocyclododecane (HBCDD) used in expanded polystyrene (EPS). A potential risk was found for fulmar (secondary poisoning) and PeBDE used in PUR.

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.

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).

Occurrence and sorption properties of arsenicals in marine sediments.

The content of total arsenic, the inorganic forms: arsenite (As(III)) and arsenate (As(V)), the methylated forms: monomethylarsonic acid and dimethylarsinic acid (DMA), trimethylarsenic oxide, tetramethylarsenonium ion and arsenobetaine was measured in 95 sediment samples and 11 pore water samples from the Baltic Sea near the island of Bornholm at depths of up to 100 m. As(III+V) and DMA were detected in the sediment and As(III+V) was detected in the sediment pore water. Average total As concentration of 10.6 ± 7.4 mg/kg dry matter (DM) in the sediment corresponds to previously reported values in the Baltic Sea and other parts of the world. Existing data for on-site measurements of sorption coefficients (Kd) of arsenicals in marine and freshwater sediments show large variability from <1 to >1,000 L/kg. In this work, calculated sorption coefficients (Kd and Koc) for As(III+V) showed significant correlation with depth, dissolved oxygen (DO), salinity and sediment classification; for depths <70 m, salinity <11 %, DO >9 mg/L and sand/silt/clay sediments the Kd was 118 ± 76 L/kg DM and for depths >70 m, salinity >11 %, DO < 9 mg/L and muddy sediments the Kd was 513 ± 233 L/kg DM. The authors recommend using the found Kd value for arsenic in marine sediments when conditions are similar to the Baltic Sea. At locations with significant anthropogenic point sources or where the local geology contains volcanic rock and sulphide mineral deposits, there may be significantly elevated arsenic concentrations, and it is recommended to determine on-site Kd values.

Weight-of-evidence environmental risk assessment of dumped chemical weapons after WWII along the Nord-Stream gas pipeline in the Bornholm Deep.

In connection with installation of two natural gas pipelines through the Baltic Sea between Russia and Germany, there has been concern regarding potential re-suspension of historically dumped chemical warfare agents (CWA) in a nearby dump site and the potential environmental risks associated. 192 sediment and 11 porewater samples were analyzed for CWA residues, both parent and metabolites in 2008 and 2010 along the pipeline corridor next to the dump site. Macrozoobenthos and background variables were also collected and compared to the observed CWA levels and predicted potential risks. Detection frequencies and levels of intact CWA found were low, whereas CWA metabolites were more frequently found. Re-suspension of CWA residue-containing sediment from installation of the pipelines contributes marginally to the overall background CWA residue exposure and risk along the pipeline route. The multivariate weight-of-evidence analysis showed that physical and background parameters of the sediment were of higher importance for the biota than observed CWA levels.

Environmental hazards of sea-dumped chemical weapons.

Does the post-WWII burial at sea of chemical weapons still pose a human and environmental risk?

Human health risk screening due to consumption of fish contaminated with chemical warfare agents in the Baltic Sea.

Chemical warfare agents (CWAs) have been disposed of in various fashions over the past decades. Significant amounts of CWA, roughly 11,000ton, have been dumped in the Baltic Sea east of the island Bornholm following the disarmament of Germany after World War II. This has caused concerns over potential human and environmental health risks, and resulted in restrictions on fishing in the dumpsite area. The purpose of this paper is to assess the potential indirect human health risks due to consumption of CWA-contaminated fish from the dumpsite area east of Bornholm. Earlier studies suggest that the fish community may be at risk from CWA exposure in the Bornholm basin. Moreover, elevated frequencies of lesions on fish caught in a CWA dumpsite in the Mediterranean Sea have been observed. The fish at the Mediterranean dumpsite had elevated total arsenic (As) concentrations in their tissue, and elevated total As levels were also observed in the sediment. Elevated total sediment As concentrations have also been recorded in CWA dumpsites in the Skagerrak and the Baltic Sea. Triphenylarsine and sulfur mustard gas (Yperite) are the CWAs with the greatest indirect human health risk potential. There are recognized uncertainties concerning Yperite's and CWA-derived arsenical's fate and speciation in the environment, as well as their inherent toxicity, warranting caution and further site-specific environmental and human health risk assessments of CWAs dumped in the Bornholm basin.

Conceptual framework for a Danish human biomonitoring program.

The aim of this paper is to present the conceptual framework for a Danish human biomonitoring (HBM) program. The EU and national science-policy interface, that is fundamental for a realization of the national and European environment and human health strategies, is discussed, including the need for a structured and integrated environmental and human health surveillance program at national level. In Denmark, the initiative to implement such activities has been taken. The proposed framework of the Danish monitoring program constitutes four scientific expert groups, i.e. i. Prioritization of the strategy for the monitoring program, ii. Collection of human samples, iii. Analysis and data management and iv. Dissemination of results produced within the program. This paper presents the overall framework for data requirements and information flow in the integrated environment and health surveillance program. The added value of an HBM program, and in this respect the objectives of national and European HBM programs supporting environmental health integrated policy-decisions and human health targeted policies, are discussed.In Denmark environmental monitoring has been prioritized by extensive surveillance systems of pollution in oceans, lakes and soil as well as ground and drinking water. Human biomonitoring has only taken place in research programs and few incidences of e.g. lead contamination. However an arctic program for HBM has been in force for decades and from the preparations of the EU-pilot project on HBM increasing political interest in a Danish program has developed.

Screening level fish community risk assessment of chemical warfare agents in the Baltic Sea.

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.

PBT screening profile of chemical warfare agents (CWAs).

Chemical warfare agents (CWAs) have been used and disposed of in various fashions over the past decades. Significant amounts have been dumped in the Baltic Sea following the disarmament of Germany after World War II causing environmental concerns. There is a data gap pertaining to chemical warfare agents, environmental properties not the least their aquatic toxicities. Given this gap and the security limitations relating to working with these agents we applied Quantitative Structure-Activity Relationship ((Q)SAR) models in accordance with the European Technical Guidance Document (2003) to 22 parent CWA compounds and 27 known hydrolysis products. It was concluded that conservative use of EPI Suite (Q)SAR models can generate reliable and conservative estimations of chemical warfare agents acute aquatic toxicity. From an environmental screening point of view the organoarsenic chemical warfare agents Clark I and Adamsite comprise the most problematic of the screened CWA compounds warranting further investigation in relation to a site specific environmental risk assessment. The mustard gas agents (sulphur and nitrogen) and the organophosphorous CWAs (in particular Sarin and Soman) are a secondary category of concern based upon their toxicity alone. The undertaken approach generates reliable and conservative estimations for most of the studied chemicals but with some exceptions (e.g. the organophosphates).

Preliminary screening of perfluorooctane sulfonate (PFOS) and other fluorochemicals in fish, birds and marine mammals from Greenland and the Faroe Islands.

Extensive screening analyses of perfluorooctane sulfonate (PFOS) and related perfluorinated compounds in biota samples from all over the world have identified PFOS as a global pollutant and have shown its bioaccumulation into higher trophic levels in the food chain. Perfluorinated compounds have been found in remote areas as the Arctic. In this study a preliminary screening of PFOS and related compounds has been performed in liver samples of fish, birds and marine mammals from Greenland and the Faroe Islands. PFOS was the predominant fluorochemical in the biota analyzed, followed by perfluorooctane sulfonamide (PFOSA). PFOS was found at concentrations above LOQ (10 ng/g wet weight) in 13 out of 16 samples from Greenland and in all samples from the Faroe Islands. The results from Greenland showed a biomagnification of PFOS along the marine food chain (shorthorn sculpin < ringed seal < polar bear). The greatest concentration of PFOS was found in liver of polar bear from east Greenland (mean: 1285 ng/g wet weight, n = 2). The geographical distribution of perfluorinated compounds in Greenland was similar to that of persistent organohalogenated compounds (OHCs), with the highest concentrations in east Greenland, indicating a similar geographical distribution to that of OHCs, with higher concentrations in east Greenland than in west Greenland.

Risk of five polycyclic aromatic hydrocarbons in a terrestrial environment: influence of data variability.

The risk of five different pyrogenic polycyclic aromatic hydrocarbons (PAHs) toward two soil-dwelling organisms (i.e., springtail [Folsomia fimetaria] and earthworm [Eisenia veneta]) has been investigated with respect to lethality and reproduction at two soil depths in a typical Danish soil. Predicted environmental concentrations (PECs) are calculated with a model describing diffusion, bulk flow, and microbial degradation. Predicted no-effect concentrations (PNECs) are derived from laboratory experiments performed with nominal soil concentrations in the range from 0 to 300 microg PAH/g dry weight. Risk is estimated through a stochastic approach as well as with the conventional point estimate. The point estimate predicts a potential risk for pyrene, log PEC/PNEC = -0.01, with respect to springtail reproduction at 5 cm soil depth. In all other scenarios, the point-estimate log-ratios are significantly lower than 0. For the stochastic approach risk is defined when the probability for risk (i.e., the probability for log PEC/PNEC > 0), is larger than 5%. The results show that risk is present only for springtail and in the following five scenarios: For anthracene, the probability for risk with respect to lethality is 12% at 5 cm soil depth, and 17 and 5% with respect to reproduction at 5 and 50 cm soil depth, respectively; for pyrene the probability for risk with respect to reproduction is 49 and 14% at 5 and 50 cm, respectively. The results show that risk cannot be defined unambiguously with the two approaches. The probabilistic approach is less restrictive, and even small probabilities may be used as early-warning indications that risk may be posed under unfavorable circumstances.