Differences in Trophic Level, Contaminant Load, and DNA Damage in an Urban and a Remote Herring Gull (Larus argentatus) Breeding Colony in Coastal Norway.

Herring gulls (Larus argentatus) are opportunistic feeders, resulting in contaminant exposure depending on area and habitat. We compared contaminant concentrations and dietary markers between two herring gull breeding colonies with different distances to extensive human activity and presumed contaminant exposure from the local marine diet. Furthermore, we investigated the integrity of DNA in white blood cells and sensitivity to oxidative stress. We analyzed blood from 15 herring gulls from each colony-the urban Oslofjord near the Norwegian capital Oslo in the temperate region and the remote Hornøya island in northern Norway, on the Barents Sea coast. Based on d13 C and d34 S, the dietary sources of urban gulls differed, with some individuals having a marine and others a more terrestrial dietary signal. All remote gulls had a marine dietary signal and higher relative trophic level than the urban marine feeding gulls. Concentrations (mean ± standard deviation [SD]) of most persistent organic pollutants, such as polychlorinated biphenyl ethers (PCBs) and perfluorooctane sulfonic acid (PFOS), were higher in urban marine (PCB153 17 ± 17 ng/g wet weight, PFOS 25 ± 21 ng/g wet wt) than urban terrestrial feeders (PCB153 3.7 ± 2.4 ng/g wet wt, PFOS 6.7 ± 10 ng/g wet wt). Despite feeding at a higher trophic level (d15 N), the remote gulls (PCB153 17 ± 1221 ng/g wet wt, PFOS 19 ± 1421 ng/g wet wt) were similar to the urban marine feeders. Cyclic volatile methyl siloxanes were detected in only a few gulls, except for decamethylcyclopentasiloxane in the urban colony, which was found in 12 of 13 gulls. Only hexachlorobenzene was present in higher concentrations in the remote (2.6 ± 0.42 ng/g wet wt) compared with the urban colony (0.34 ± 0.33 ng/g wet wt). Baseline and induced DNA damage (doublestreak breaks) was higher in urban than in remote gulls for both terrestrial and marine feeders. Environ Toxicol Chem 2022;41:2466-2478. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Maternal transfer and occurrence of siloxanes, chlorinated paraffins, metals, PFAS and legacy POPs in herring gulls (Larus argentatus) of different urban influence.

Urban herring gulls (Larus argentatus) are exposed to contaminants from aquatic, terrestrial and anthropogenic sources. We aim to assess if differences in urbanisation affect ecological niche and contaminant concentrations in female herring gulls. Furthermore, we investigated maternal transfer from mothers to eggs for all the target compounds, including chlorinated paraffins (CPs) and cyclic volatile methyl siloxane (cVMSs), which to our knowledge have not been assessed in herring gulls previously. We compare concentrations of legacy and emerging contaminants and metals in blood and eggs between two herring gull colonies located 51 km apart, in the urban influenced Norwegian Oslofjord. While both colonies are within an urbanised area, the inner fjord is more so, as it is surrounded by Oslo, the capital and largest city in Norway Stable isotopes of carbon and nitrogen indicated a more marine ecological niche in the outer than the inner fjord colony, although with overlap. Persistent organic pollutant (POP) concentrations were similar in the inner and outer fjord colonies, while the short-chained chlorinated paraffins (SCCP), which are recently added to the Stockholm convention and contaminants of emerging concern (CECs) varied, with higher concentrations of SCCP and the cVMS decamethylcyclopentasiloxane (D5) in females and eggs of the inner fjord colony. Per- and polyfluorinated substances (PFAS) concentrations were higher in the outer fjord colony, likely linked to releases from a point-source (airport and waste management facility with open access to food waste). In blood, chlorinated paraffins contributed most the total lipophilic contaminants (inner: 78%, outer: 56%), while polychlorinated biphenyls (PCBs) were the most abundant lipophilic contaminants in eggs (inner: 62%, outer: 46%). Dechloranes and brominated flame retardants (BFRs) were detected in few samples. Maternal transfer, assessed by egg to blood ratios, of cVMSs were similar to the POPs with mean log ratio 0.39 (D5), while it was lower for SCCPs, with log ratios-0.77. Our results indicate comparable POP exposure of the herring gulls in the inner and outer Oslofjord, likely due to overlap in ecological niches between the colonies and wide distribution of POPs. The differences between the colonies in concentrations of PFAS, cVMS and CPs shows that point source exposures and urban influence may be more important than ecological niche for these compounds.

Partitioning of persistent hydrophobic contaminants to different storage lipid classes.

Lipids generally represent the major matrix contributing to the absorptive capacity for hydrophobic organic contaminants in aquatic ecosystems. The aim of the present study was to determine whether contaminants partition to a different degree to the different storage lipid classes: wax ester (WE) and triacylglycerol (TAG). This was undertaken by studying experimentally the partitioning of organochlorine compounds between lipids (WE or TAG) and silicone rubber phase. Our results indicate that hydrophobic compounds have a slightly higher affinity for WE than for TAG. The findings thus corroborate earlier suggestions that contaminants accumulate to a greater extent in food webs with a higher reliance of on WE, such as in the Arctic. This knowledge is of interest since it implies that possible changes in planktonic community species composition, and thereby possible changes in the lipid composition, may have consequences for accumulation of hydrophobic contaminants in apex predators. However, the magnitude of these consequences remains unknown, and there may well be other factors of importance for previously observed higher accumulation of contaminants in Arctic systems. Thus, we have here identified aspects regarding partitioning of contaminants to lipids that need further scrutiny, and there is a need for further quantitative estimates of the suggested difference in absorptive capacities for hydrophobic contaminants between WE and TAG.

Common Eider and Herring Gull as Contaminant Indicators of Different Ecological Niches of an Urban Fjord System.

Seabirds like gulls are common indicators in contaminant monitoring. The herring gull (Larus argentatus) is a generalist with a broad range of dietary sources, possibly introducing a weakness in its representativeness of aquatic contamination. To investigate the herring gull as an indicator of contamination in an urban-influenced fjord, the Norwegian Oslofjord, we compared concentrations of a range of lipophilic and protein-associated organohalogen contaminants (OHCs), Hg, and dietary markers in blood (n = 15), and eggs (n = 15) between the herring gull and the strict marine-feeding common eider (Somateria mollissima) in the breeding period of May 2017. Dietary markers showed that the herring gull was less representative of the marine food web than the common eider. We found higher concentrations of lipophilic OHCs (wet weight and lipid weight) and Hg (dry weight) in the blood of common eider (mean ± SE ∑PCB = 210 ± 126 ng/g ww, 60 600 ± 28 300 ng/g lw; mean Hg = 4.94 ± 0.438 ng/g dw) than of the herring gull (mean ± SE ∑PCB = 19.0 ± 15.6 ng/g ww, 1210 ± 1510 ng/g lw; mean Hg = 4.26 ± 0.438 ng/g dw). Eggs gave opposite results; higher wet weight and lipid weight OHC concentrations in the herring gull (mean ± SE ∑PCB = 257 ± 203 ng/g ww, 3240 ± 2610 ng/g lw) than the common eider (mean ± SE ∑PCB = 18.2 ± 20.8 ng/g ww, 101 ± 121 ng/g lw), resulting in higher OHC maternal transfer ratios in gulls than eiders. We suggest that the matrix differences are due to fasting during incubation in the common eider. We suggest that in urban areas, herring gull might not be representative as an indicator of marine contamination but rather urban contaminant exposure. The common eider is a better indicator of marine pollution in the Oslofjord. The results are influenced by the matrix choice, as breeding strategy affects lipid dynamics regarding the transfer of lipids and contaminants to eggs and remobilization of contaminants from lipids to blood during incubation, when blood is drawn from the mother. Our results illustrate the benefit of a multispecies approach for a thorough picture of contaminant status in urban marine ecosystems. Integr Environ Assess Manag 2021;17:422-433. © 2020 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Combining a Deconvolution and a Universal Library Search Algorithm for the Nontarget Analysis of Data-Independent Acquisition Mode Liquid Chromatography-High-Resolution Mass Spectrometry Results.

Nontarget analysis is considered one of the most comprehensive tools for the identification of unknown compounds in a complex sample analyzed via liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS). Due to the complexity of the data generated via LC-HRMS, the data-dependent acquisition mode, which produces the MS2 spectra of a limited number of the precursor ions, has been one of the most common approaches used during nontarget screening. However, data-independent acquisition mode produces highly complex spectra that require proper deconvolution and library search algorithms. We have developed a deconvolution algorithm and a universal library search algorithm (ULSA) for the analysis of complex spectra generated via data-independent acquisition. These algorithms were validated and tested using both semisynthetic and real environmental data. A total of 6000 randomly selected spectra from MassBank were introduced across the total ion chromatograms of 15 sludge extracts at three levels of background complexity for the validation of the algorithms via semisynthetic data. The deconvolution algorithm successfully extracted more than 60% of the added ions in the analytical signal for 95% of processed spectra (i.e., 3 complexity levels multiplied by 6000 spectra). The ULSA ranked the correct spectra among the top three for more than 95% of cases. We further tested the algorithms with 5 wastewater effluent extracts for 59 artificial unknown analytes (i.e., their presence or absence was confirmed via target analysis). These algorithms did not produce any cases of false identifications while correctly identifying ∼70% of the total inquiries. The implications, capabilities, and the limitations of both algorithms are further discussed.

Identification of non-regulated polycyclic aromatic compounds and other markers of urban pollution in road tunnel particulate matter.

A combination of silicone rubber extraction and non-target and suspect screening by gas chromatography coupled to high-resolution time-of flight mass spectrometry was used for the identification of compounds in particulate matter (PM). Tunnel PM is a proxy for local road pollution that constitutes a hazard to the urban environment and human health. The use of silicone rubber for the extraction of PM allowed the pre-concentration of a wide range of compounds for non-target analysis while minimising the effects of the sample matrix. As expected, polycyclic aromatic compounds (PACs) constituted the major group of compounds identified, but only 5 of 50 PACs identified were amongst those regularly monitored and many of them were alkylated or contained a heteroatom. Urban markers of contamination such as organophosphate flame-retardants, phthalates, benzothiazoles, musk compounds and a plasticiser were also identified. The level of confidence for the identifications was high based on accurate mass, the pattern of fragmentation and retention. The unequivocal identification of 16 compounds, from all groups, was confirmed by co-chromatography with standards and the compounds semi-quantified. Most of the PACs identified are not regularly monitored, and the hazards they pose are therefore unknown. Some of these PACs are known to be more persistent and mobile in the environment than the EPA PAH16.

In vivo and in vitro effects of tunnel wash water and traffic related contaminants on aquatic organisms.

In order to maintain the construction and safety of road tunnels, they are routinely washed. The wash water appears to be highly polluted with a plethora of contaminants in elevated concentrations. In addition, new and emerging compounds are likely to occur. The discharge water has shown acute toxic and sub-lethal effects in several organisms. In this study, ecotoxicity tests with algae (Pseudokirchneriella subcapitata) and in vitro tests with primary rainbow trout (Oncorhynchus mykiss) hepatocytes were used to characterize the effect of TWW from three different tunnels. In addition, selected N- and Cl-PAHs were tested for cytotoxicity, EROD activity and CYP1A protein production. TWW samples and/or extracts from two tunnels reduced the algal growth and induced cytotoxicity, EROD activity and CYP1A protein production in vitro. Four of the eight tested Cl- and N-substituted PAHs induced EROD activity and CYP1A protein production at micro-molar concentrations. N-PAHs were detected in samples from the tunnel wash, highlighting substituted PAHs as potentially important traffic-related contaminants.

PAH Accessibility in Particulate Matter from Road-Impacted Environments.

Snowmelt, surface runoff, or stormwater releases in urban environments can result in significant discharges of particulate matter-bound polycyclic aromatic hydrocarbons (PAHs) into aquatic environments. Recently, more-specific activities such as road-tunnel washing have been identified as contributing to contaminant load to surface waters. However, knowledge of PAH accessibility in particulate matter (PM) of urban origin that may ultimately be released into urban surface waters is limited. In the present study, we evaluated the accessibility of PAHs associated with seven distinct (suspended) particulate matter samples collected from different urban sources. Laboratory-based infinite sink extractions with silicone rubber (SR) as the extractor phase demonstrated a similar pattern of PAH accessibility for most PM samples. Substantially higher accessible fractions were observed for the less-hydrophobic PAHs (between 40 and 80% of total concentrations) compared with those measured for the most-hydrophobic PAHs (<5% of total concentrations). When we focused on PAHs bound to PM from tunnel-wash waters, first-order desorption rates for PAHs with log Kow > 5.5 were found in line with those commonly found for slowly or very slowly desorbing sediment-associated contaminants. PAHs with log Kow < 5.5 were found at higher desorbing rates. The addition of detergents did not influence the extractability of lighter PAHs but increased desorption rates for the heavier PAHs, potentially contributing to increases in the toxicity of tunnel-wash waters when surfactants are used. The implications of total and accessible PAH concentrations measured in our urban PM samples are discussed in a context of management of PAH and PM emission to the surrounding aquatic environment. Although we only fully assessed PAHs in this work, further study should consider other contaminants such as OPAHs, which were also detected in all PM samples.

Photodegradation of PAHs in passive water samplers.

Losses of deuterated polycyclic aromatic hydrocarbons (PAHs) used as performance reference compounds (PRCs) in semipermeable membrane devices deployed at fifteen coastal sampling sites near Harstad harbour in Northern Norway were used to investigate photodegradation of these photosensitive compounds. Unusual PRC dissipation profiles, especially for samplers exposed <5m below the water surface are indicative of photodegradation. A strong correlation between loss rates for d12-chrysene and d12-benzo[e]pyrene with consistently higher losses of the latter was found. The observed photodegradation rates may be sufficiently high to impact PAH masses absorbed by a factor of two. This study demonstrates that photodegradation during exposure of passive water samplers needs to be taken into account, particularly with deployments close to the water surface, when using SPMD canisters, or when sampling in the Arctic.

Implications of observed PBDE diffusion coefficients in low density polyethylene and silicone rubber.

A film-stacking technique was used to estimate diffusion coefficients of polybrominated diphenyl ethers (PBDEs) in low density polyethylene (LDPE) and silicone rubber. Substantially higher PBDE diffusion coefficients were observed for silicone rubber (AlteSil™) than for LDPE. A much steeper decrease in LDPE diffusion coefficients was found with increasing PBDE molecular weight than that for silicone rubber. From a passive sampling point-of-view, this means that for equivalent polymer-water partition coefficients for these two materials, the mass transfer resistance for these substances in the LDPE will be significantly higher than that for silicone rubber. Boundary layer control of the uptake process for silicone rubber can be expected for PBDEs. With a microplastic perspective, the low diffusion coefficients of PBDEs and in particular of decabromo diphenyl ether (BDE 209) in LDPE imply that the polymer diffusion coefficients for these plastic additives used as flame retardants need to be taken into account when considering the risk posed by microplastic particle ingestion by marine organisms.

In vivo passive sampling of nonpolar contaminants in brown trout (Salmo trutta).

Equilibrium passive sampling through in vivo implantation can help circumvent complex extractions of biological tissues, provide more accurate information on chemical contaminant burden based on the fugacity of a chemical in an organism rather than conventional normalization to lipid content, and improve the assessment of contaminant bioaccumulation potential. Here, we explored the feasibility of in vivo implantation for the passive sampling of neutral hydrophobic contaminants through the insertion of a silicone tag into brown trout (Salmo trutta). Implanted fish from the upper reaches of the River Alna (Oslo, Norway) were relocated to a polluted section of the river for a 28 day caged exposure. "Whole fish" lipid-silicone distribution coefficients (Dlip-sil) were calculated for chlorinated compounds measured in whole fish and in silicone tags of 13 fish. Dlip-sil ranged from 13.6 to 40.0 g g(-1) for polychlorinated biphenyl congeners 28-156 (CB28 and CB156), respectively, and are in close agreement with literature in vitro lipid phase and tissue-based lipid-silicone partition coefficients. After dissection a further of eight fish, muscle and liver samples were analyzed separately. Muscle-based Dlip-sil values similar to the whole fish data were observed. However, lipid-normalized concentrations in the liver tended to be lower than in muscle for most compounds (by up to 50%). Values of whole fish Dlip-sil for brominated diphenyl ethers determined for three fish were in the range of 8.6-51 g g(-1) and in agreement with chlorinated substances. Finally, fugacity ratios calculated from equilibrium concentrations in fish-implanted and water-exposed silicone provided information on the bioaccumulation for chlorinated compounds as well as for some polycyclic aromatic hydrocarbons. Equilibrium passive sampling through in vivo implantation can allow the comparison of a chemical's activity or fugacity in biotic as well as abiotic environmental compartments and at different trophic levels up to humans.

Should silicone prostheses be considered for specimen banking? A pilot study into their use for human biomonitoring.

Persistent organic pollutant (POP) biomonitoring in humans is challenging and generally carried out using blood, breast milk or adipose tissue, with concentrations normalised to the lipid content of the sample matrix. The goal of this cross-sectional pilot study was to evaluate the validity and feasibility of explanted silicone prostheses as a matrix for persistent organic pollutant biomonitoring in humans. We postulate that pollutant concentrations in silicone prostheses inserted in the body will equilibrate with that in the body over time and provide a measure of the overall body burden. This study included silicone prostheses from 22 female patients of the Colosseum clinic (Oslo, Norway) collected between September 2010 and April 2012. Absorption of chlorinated and brominated POPs into silicone prostheses during implantation was observed. Relative levels of the different contaminants measured in prostheses were in agreement with those from serum and breast milk analyses from the general Norwegian population. The comparison of serum and breast milk-based literature data with prosthesis concentrations transposed into lipid-normalised concentrations supports the validity of the prosthesis measurements. The median of relative percent differences between measurements with replicate silicone prostheses from 11 patients was below 30%. Observed increases in prosthesis concentrations with patients' age were found to be very similar to literature data from studies of the Norwegian population. Silicone prostheses therefore represent a promising matrix for the biomonitoring of nonpolar and non-ionic pollutants in humans. Sample accessibility and body burden representativeness of the silicone prostheses suggest that specimen banking should be initiated.

Levels and temporal trends (1983-2003) of polybrominated diphenyl ethers and hexabromocyclododecanes in seabird eggs from north Norway.

The present study assessed temporal trends (1983-2003) of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in eggs of herring gulls (Larus argentatus), Atlantic puffins (Fratercula arctica), and black-legged kittiwakes (Rissa tridactyla) in North Norway. Generally, PBDE concentrations increased between 1983 and 1993 and then leveled out, although species-specific trends were reported. Levels of alpha-HBCD increased in all species throughout the 20-year period. Levels of nona-BDEs and BDE 209 ranged from nondetectable to parts per billion. Nevertheless, highly variable procedural blanks were reported for the nona-BDEs and BDE 209, which clearly illustrates the importance of including blanks repeatedly during determination of these compounds.

Brominated flame retardants in North-East Atlantic marine ecosystems.

BACKGROUND: Concentrations of brominated flame retardants (BFRs) are reported to increase in marine ecosystems. OBJECTIVES: Characterize exposure to BFRs in animals from different trophic levels in North-East Atlantic coastal marine ecosystems along a latitudinal gradient from southern Norway to Spitsbergen, Svalbard, in the Arctic. Calanoid species were collected from the Oslofjord (59 degrees N), Froan (64 degrees N), and Spitsbergen (> 78 degrees N); Atlantic cod (Gadus morhua) from the Oslofjord and Froan; polar cod (Boreogadus saida) from Bear Island (74 degrees N) and Spitsbergen; harbor seal (Phoca vitulina) from the Oslofjord, Froan, and Spitsbergen; and ringed seal (Phoca vitulina) from Spitsbergen. Eggs of common tern (Sterna hirundo) were collected from the Oslofjord, and eggs of arctic terns (Sterna paradisaea) from Froan and Spitsbergen. RESULTS: Levels of polybrominated diphenylethers (PBDEs) and hexabromocyclododecane (HBCD) generally decreased as a function of increasing latitude, reflecting distance from release sources. The clear latitudinal decrease in levels of BFRs was not pronounced in the two tern species, most likely because they are exposed during migration. The decabrominated compound BDE-209 was detected in animals from all three ecosystems, and the highest levels were found in arctic tern eggs from Spitsbergen. HBCD was found in animals from all trophic levels, except for in calanoids at Froan and Spitsbergen. CONCLUSIONS: Even though the levels of PBDEs and HBCD are generally low in North-East Atlantic coastal marine ecosystems, there are concerns about the relatively high presence of BDE-209 and HBCD.

Biomagnification of polybrominated diphenyl ether and hexabromocyclododecane flame retardants in the polar bear food chain in Svalbard, Norway.

Concentrations of brominated flame retardants (BFRs), including polybrominated diphenylethers (PBDEs) and hexabromocyclododecane (HBCD), were investigated in an arctic marine food chain consisting of four invertebrate species: polar cod (Boreogadus saida), ringed seals (Pusa hispida), and polar bears (Ursus maritimus). The most abundant BFR, brominated diphenyl ether (BDE)-47, was found in detectable concentrations even in zooplankton, the lowest trophic level examined in this study. Most of the investigated BFRs biomagnified as function of tropic level in the food chain. A noticeable exception occurred at the highest trophic level, the polar bear, in which only BDE-153 was found to increase from its main prey, the ringed seal, indicating that polar bears appear to be able to metabolize and biodegrade most BFRs. In contrast, lower-brominated PBDEs, particularly BDE-47, showed clear signs of bioaccumulation in zooplankton, polar cod, and ringed seals. We suggest that this discrepancy in the fate of BFRs among the different species may be related to greater induction of oxidative detoxification activities in the polar bear. Absorption and debromination rates may be more important for bioaccumulation rates of BFRs in zooplankton, polar cod, and ringed seals. Lipid weight-based concentrations (LWCs) and whole body-based concentrations (WBCs) of BFRs were used to assess biomagnification factors (BMFs). Whole-body concentrations gave the most realistic BMFs, as BMFs derived from LWCs seem to be confounded by the large variability in lipid content of tissues from the investigated species. This study demonstrates that PBDEs and HBCD have reached measurable concentrations even in the lower trophic levels (invertebrates and fish) in the Arctic and biomagnifies in the polar bear food chain.