North Sea Samples Research Articles

First indication of platinum input into the southern North Sea via German Rivers

Platinum (Pt) is an emerging critical metal, but the long-term environmental impacts of anthropogenic Pt remain largely unknown. We report, for the first time, Pt input from three major German rivers (Ems, Weser and Elbe) into the southern North Sea. All three rivers were a major source of Pt, with a maximum of 6.3 pmol L−1 in the Elbe endmember, compared to generally <1.0 pmol L−1 in the North Sea samples. All samples measured in the North Sea were elevated in Pt (mean of ∼0.9 pmol L−1) relative to typical open-ocean values (∼0.2–0.3 pmol L−1 in the Atlantic and Pacific). Across the Weser and Elbe estuarine transect, an initial sharp drawdown of Pt concentrations at low salinity (S < 1.5) was observed, which correlated well with Fe and Mn concentrations, indicating adsorption and co-precipitation at low salinity. At higher salinities (S ≥ 3) Pt concentrations followed a more conservative distribution relative to salinity. In addition, we followed a 12 h tidal cycle in each of the rivers, which generally reflected an inverse correlation of Pt concentrations against salinity. This study indicates that Pt might be an emerging contaminant in the North Sea, requiring further study to define specific sources.

Genomic analysis of NE Atlantic sardine (Sardina pilchardus) reveals reduced variation in a recently established North Sea population and directs reconsideration of management units.

The European sardine (Sardina pilchardus) is under intense fishing pressure and exhibits distributional/abundance shifts linked to environmental change. The current understanding of population demographics needed for sustainable management is uncertain due to concerns that previous genetic studies lacked resolution and limited sampling of sardine north of the Bay of Biscay. To address these issues, we performed mtDNA sequencing and genome wide SNP analysis of samples collected across the Bay of Biscay, Celtic Sea, English Channel and North Sea. The complete SNP data reported a lack of structure throughout the sampled area compatible with high gene flow. A consensus suite of positive outlier SNPs was identified which reported a significant correlation with geographical distance with the largest differentiation between the southern Bay of Biscay and North Sea samples which also reported a significant mtDNA ΦST. While the roles of dispersal limitation and environmental heterogeneity underpinning this require further study, this adds to growing evidence that selection is influencing sardine population structure against a background of high gene flow. The results indicate that while there may be a level of demographic independence between North Sea and South Biscay sardine, the current delimitation of central (Biscay) and northern (Channel and Celtic Sea) operational stocks may misrepresent connectivity between the Biscay and Channel. The North Sea sample exhibited markedly lower mtDNA and nuclear variation than other samples. As sardine have only recently invaded the North Sea such reduced genetic variation is compatible with predictions for peripheral leading-edge populations but contrasts with patterns for other small pelagic species and emphasises the need to consider species-specific genetic structure in ecosystem-based management. Nascent management of the North Sea sardine fishery must ensure that current low levels of genetic diversity are not eroded further as this may decrease the species adaptive potential and inhibit its expansion.

Direct dating of deposition and rift-related alteration of fossil-barren red bed units in the North Sea

Many fossil-barren or poorly fossiliferous red bed units are found in the North, Norwegian and Barents seas. Owing to the near-absence of biostratigraphic markers in these units, and the possibility of unconformities at their upper and lower boundaries, determining their depositional ages and stratigraphic assignment can be challenging. We apply in situ U–Pb carbonate dating on North Sea samples, including plant-root related carbonates (rhizoliths) from palaeosols and calcite veins cross-cutting clasts in a conglomeratic red bed unit, to constrain their respective ages. Our data indicate that one of the studied units was deposited c. 260–250 Ma and may represent an early development of the Skagerrak Formation. The second unit yielded an oldest age of 180.2 ± 9.7 Ma, interpreted to represent a late diagenetic event rather than deposition. High Mn/Sr and low δ 13 C values in many cements dated between c. 180 and 100 Ma are interpreted to represent precipitation of diagenetic carbonates and reprecipitation of root carbonates, potentially related to Jurassic–Cretaceous volcanism and uplift during rifting of the North Sea. These new data point to U–Pb carbonate geochronology as an effective tool for directly dating red bed units and subsequent diagenetic events. Supplementary material: Detailed methods for all geochemical analyses are available at https://doi.org/10.6084/m9.figshare.c.6850741

Differences in nutrient and undesirable substance concentrations in Maurolicus muelleri across the Bay of Biscay, Norwegian fjords, and the North Sea

IntroductionWe are having pressing issues of global food insecurity and malnutrition. Mesopelagic communities in the North Atlantic have been estimated to have high biomasses of organisms. Some of these low-trophic organisms are known to be nutrient-dense and may thus contribute to food security and nutrition. Here, we aim to understand the variation in nutrient and undesirable substance concentrations in a common mesopelagic species, Maurolicus muelleri in the North Atlantic Ocean.MethodsWe sampled the M. muelleri from the Bay of Biscay (BB), Norwegian fjords (NF), and the North Sea (NS). The concentrations of micro- and macronutrients, undesirable metals, and persistent organic pollutants (POPs) were measured in composite whole fish samples.ResultsWe found no difference across the sampling areas in the selected micronutrients except that the NF and NS samples had higher vitamin A1 concentrations than the BB samples. The NF samples had higher concentrations of fat, fatty acids, and POPs but lower concentrations of cadmium than the BB and NS samples; the differences in fat and fatty acids were only marginal in the NF-BB pair. The BB samples had lower arsenic concentrations than the NS samples, and lower concentrations of erucic acid and mercury than the NF and NS samples. Comparing the measured values against existing EU regulation values for nutrients and undesirable substances for human consumption, we found that the samples from NS and BB may cause food safety concerns due to their high cadmium concentrations, while the M. muelleri from all the sampling areas are qualified as good sources of iron, selenium, vitamin A1, and ω-3 fatty acids.DiscussionThis study confirms that M. muelleri from the North Atlantic Ocean may play an important role in food security and nutrition. However, potential variations in nutrient and undesirable substance concentrations related to seasonality, fish body size, and maturity level shall be taken into consideration prior to exploiting such a marine resource. Further understanding of trophic ecology, life cycles, and productivity of M. muelleri is essential to investigate the drivers behind the observed variation in nutrient and undesirable substance concentrations.

Corroborative insights into genetically related kerogen, asphaltenes and hydrocarbons using free and bound biomarkers

Unlike the free biomarkers, which can be routinely recovered via solvent extraction, the bound biomarkers are covalently linked to the kerogen or asphaltene macrostructures and are more resistant to secondary alteration processes. Although similarities have been identified between these two types of biomarkers using different techniques, it remains unclear how the kerogen- and asphaltene-bound biomarkers are complicatedly corelated with their free counterparts, thus limiting the applications of bound biomarkers in geoscience research. In this study, the characteristics of free biomarkers recovered from shale samples, from 10 sedimentary basin around the world, and petroleum samples, from the North Sea, have been systematically compared with their kerogen- and asphaltene-bound biomarkers, which were released by the newly developed Microscale Sealed Vessel Catalytic Hydrogenation (MSSV-Hy) method. Although the kerogen-bound biomarkers are characterized by the absence of rearranged biomarkers (e.g., Ts and diasteranes) and elevated C29/C30 hopane ratios, many key source-related parameters show strong positive correlations between free and bound fractions, including the steranes/hopane, C27/C29 sterane, C30/C29 sterane, C29/C30 hopane (αβ + βα), C35/C34 homohopanes and C24 tetracyclic terpane/C26 tricyclic terpane ratios. These results suggest that bound biomarkers can reveal critical information about deposits and organic matter precursors of source rocks. Thermal maturity indicators, such as C29 sterane ββ/(αα + ββ), C29 sterane S/(S + R), C31 hopane S/R, and Tβ/Tm ratios, also display excellent correlations between the free and bound counterparts in the source rocks. Although the correlations are not 1:1, empirical formulae, which are based on the correlations between free and bound biomarkers, can be used to calibrate bound biomarkers into values that can be directly compared to routine free biomarkers. Importantly, asphaltene-bound biomarkers of North Sea samples exhibit similar characteristics to kerogen-bound biomarkers, and the conversion between free and bound biomarkers of the source rock and reservoir samples is the same. In summary, the bound biomarkers are found highly effective in determining the organic facies, lithology, and thermal maturity of the parent kerogen and/or asphaltene, and, thus, have a great potential to be widely used in geoscience research when information from free biomarkers is hampered by oil mixing, contamination or biodegradation.

Prevalence and Distribution of Potentially Human Pathogenic Vibriospp. on German North and Baltic Sea Coasts.

Global ocean warming results in an increase of infectious diseases including an elevated emergence of Vibrio spp. in Northern Europe. The European Centre for Disease Prevention and Control reported annual periods of high to very high risks of infection with Vibrio spp. during summer months along the North Sea and Baltic Sea coasts. Based on those facts, the risk of Vibrio infections associated with recreational bathing in European coastal waters increases. To obtain an overview of the seasonal and spatial distribution of potentially human pathogenic Vibrio spp. at German coasts, this study monitored V. cholerae, V. parahaemolyticus, and V. vulnificus at seven recreational bathing areas from 2017 to 2018, including the heat wave event in summer 2018. The study shows that all three Vibrio species occurred in water and sediment samples at all sampling sites. Temperature was shown to be the main driving factor of Vibrio abundance, whereas Vibrio community composition was mainly modulated by salinity. A species-specific rapid increase was observed at water temperatures above 10°C, reaching the highest detection numbers during the heat wave event with abundances of 4.5 log10 CFU+1/100 ml of seawater and 6.5 log10 CFU+1/100 g of sediment. Due to salinity, the dominant Vibrio species found in North Sea samples was V. parahaemolyticus, whereas V. vulnificus was predominantly detected in Baltic Sea samples. Most detections of V. cholerae were associated with estuarine samples from both seas. Vibrio spp. concentrations in sediments were up to three log higher compared to water samples, indicating that sediments are an important habitat for Vibrio spp. to persist in the environment. Antibiotic resistances were found against beta-lactam antibiotics (ampicillin 31%, cefazolin 36%, and oxacillin and penicillin 100%) and trimethoprim-sulfamethoxazole (45%). Moreover, isolates harboring pathogenicity-associated genes such as trh for V. parahaemolyticus as well as vcg, cap/wcv, and the 16S rRNA-type B variant for V. vulnificus were detected. All sampled V. cholerae isolates were identified as non-toxigenic non-O1/non-O139 serotypes. To sum up, increasing water temperatures at German North Sea and Baltic Sea coasts provoke elevated Vibrio numbers and encourage human recreational water activities, resulting in increased exposure rates. Owing to a moderate Baltic Sea salinity, the risk of V. vulnificus infections is of particular concern.

30 years trends of microplastic pollution: Mass-quantitative analysis of archived mussel samples from the North and Baltic Seas

Microplastics (MP) are ubiquitous throughout the environment as a result of an ongoing, increasing, but also lavish use, of plastics over time and its inherent persistence. In contrast, there are almost no data that allow drawing conclusions about the evolution of plastic pollution in the environment over the past decades. This study investigates the MP load in blue mussels from the North and Baltic Sea archived by the German Environmental Specimen Bank in a time series covering almost 30 years. Samples were enzymatically and chemically oxidative digested for MP extraction and subsequent analyzed mass-quantitatively for nine common polymer clusters by pyrolysis gas chromatography-mass spectrometry. Seven polymer clusters were detected in mussel tissue. Summed MP levels were at ppm levels (<20 μg/g mussel, dry weight). North Sea samples reflected a gradual increase from the 1980s/90s to the 2000s whereas those from Baltic Sea showed consistently higher, rather constant MP levels similar to the North Sea site later than 2000. Polymer composition of both sites stood out by cluster (C) of C-PVC and C-PET at both sites. Mussels from Baltic Sea site had larger C-PE and C-PP proportions. Opposed polymer- and site-specific trends indicated both regional and trans-regional MP sources for different polymer clusters. The MP composition of mussels showed strong similarities with adjacent sediment and water samples. The study introduces a relevant dataset addressing the temporal development of MP pollution. It emphasizes a high indicative potential of environmental MP composition/loads received by mussels but raises the necessity on adequate control materials accompany such kind of studies.

Rapid organic matter cycling in North Sea sediments

Coastal shelf seas are zones of intense nutrient cycling, where a strong coupling between the sediment and the water column enhances primary productivity. To identify factors that control the strength of this benthic-pelagic coupling we measured sediment characteristics, solute fluxes, and porewater nutrient profiles in spring along a south - north transect in the North Sea crossing distinct regions: the shallow Oyster Grounds closest to the Dutch shore, the shallow Dogger Bank, the 80-m deep central North Sea, and the 150-m deep Fladen Grounds between the north of Scotland and Norway. The data were used to constrain rates of different mineralization processes with the 1-D diagenetic model (OMEXDIA). Surprisingly, we found no major differences in the biogeochemical signature along the 670 km long North Sea transect, despite sediments ranging in median grainsize from 25 to 217 μm, and a permeability range >3 orders of magnitude. Total carbon mineralization ranged between 4 and 13.5 mmol C m−2 d−1, and decreased significantly northward. Oxic mineralization was the dominant mineralization process in all studied sites. Finest, least permeable sediments were found in the Fladen Grounds where highest denitrification rates were recorded, linked to high nitrate concentrations in the overlying water. The coarsest, most permeable sediments of the shallow Dogger Bank represented a transition area between the Oyster Grounds, where oxic mineralization was highest (75–90%), and the central North Sea samples, where anoxic mineralization increased relative to oxic mineralization due to higher bioturbation rates (oxic: 59–72%, anoxic: 27–39%). Overall, denitrification rates increased, while phosphorus removal tended to decrease northward. This contrasting behaviour in nitrogen and phosphorus removal was identified as a possible cause for decreasing DIN:DIP ratios in the water column towards the north.

Application of a sequential multi-solid-liquid equilibrium approach using PC-SAFT for accurate estimation of wax formation

Several existing thermodynamic models for Wax precipitation use cubic EOS and average properties for petroleum fractions. To improve predictions, this work introduces a thermodynamic model using a multi-solid framework in a sequential equilibrium calculation procedure. The PC-SAFT EOS is used to predict liquid phase properties. Binary interaction coefficients and difference of heat capacities between solid and liquid are adjusted to minimize the deviations caused by the employment of averaged relations for properties of hydrocarbon cuts. Three groups of oil samples are chosen for verification. First, the Wax precipitation data of three synthetic mixtures from Pauly et al. [1] are estimated, and the modeling results are compared to the predicted results of Dalirsefat and Feyzi [2] and Schou Pedersen et al. [3]. Also, two crude oil samples with Paraffin, Naphthene, and Aromatic (PNA) content from Pan et al. [4] are used for evaluation. Finally, the suggested model is used to calculate weight percent of precipitated Wax and Wax appearance temperature (WAT) of six crude oil samples from North Sea [3]. The calculated predictions of the suggested model are compared to the works of Schou Pedersen et al. [3], Lira‐Galeana et al. [5], and Bagherinia et al. [6]. The deviations for WATs and precipitation amounts from experimental data are lower compared to previous studies. The average absolute deviation for precipitated Wax weight of the North Sea samples is 0.19 in comparison to 0.61, 0.33, and 0.4 of Schou Pedersen et al. [3], Lira‐Galeana et al. [5], and Bagherinia et al. [6], respectively.

Anisakid nematode species identification in harbour porpoises (Phocoena phocoena) from the North Sea, Baltic Sea and North Atlantic using RFLP analysis.

Harbour porpoises (Phocoena phocoena) are the only native cetacean species in the German North and Baltic Seas and the final host of Anisakis (A.) simplex, which infects their first and second gastric compartments and may cause chronic ulcerative gastritis. Anisakis simplex belongs to the family Anisakidae (Ascaridoidea, Rhabditida) as well as the phocine gastric nematode species Pseudoterranova (P.) decipiens and Contracaecum (C.) osculatum. These nematode species are the main causative agents for the zoonosis anisakidosis. The taxonomy of these genus with life cycles including crustaceans and commercially important fish is complex because of the formation of sibling species. Little is known about anisakid species infecting porpoises in the study area. Mature nematodes and larval stages are often identifiable only by molecular methods due to high morphological and genetic similarity. The restriction fragment length polymorphism (RFLP) method is an alternative to sequencing and was applied to identify anisakid nematodes found in harbour porpoises from the North Sea, Baltic Sea and North Atlantic to species level for the first time. In the study areas, five gastric nematodes from different harbour porpoise hosts were selected to be investigated with restriction enzymes HinfI, RsaI and HaeIII, which were able to differentiate several anisakid nematode species by characteristic banding patterns. Anisakis simplex s. s. was the dominant species found in the North Sea and Baltic porpoises, identified by all three restriction enzymes. Additionally, a hybrid of A. simplex s. s. and A. pegreffii was determined by HinfI in the North Sea samples. Within the North Atlantic specimens, A. simplex s. s., P. decipiens s. s. and Hysterothylacium (H.) aduncum were identified by all enzymes. This demonstrates the value of the RFLP method and the chosen restriction enzymes for the species identification of a broad variety of anisakid nematodes affecting the health of marine mammals.

Offshore concentration of caesium radioisotopes from large volume seawater samples using KNiFC-PAN

A method for caesium concentration from North Sea and Baltic Sea seawater samples was tested and optimised for offshore concentration of radiocaesium and seawater volumes up to 150 L. The composite ion-exchanger PotassiumNickel Hexacyanoferrate in a Polyacrylnitrile binding matrix (KNiFC-PAN) with 80% of powdered KNiFC per gram of dry residue was used for this study. The optimised method achieved recoveries of around 99% with a bed volume (BV) of 50 mL of KNiFC-PAN and average flow rates of seawater of around 182 BV per hour (e.g. 9.1 L per hour).

Influence of solar radiation on biogeochemical parameters and fluorescent dissolved organic matter (FDOM) in the sea surface microlayer of the southern coastal North Sea

We investigated the influence of solar radiation on biogeochemical parameters of the sea surface microlayer (SML), including the spectroscopic composition of FDOM, and biotic and abiotic parameters. We calculated the humification index, biological index, and recently produced material index from the ultraviolet spectra to characterize the dynamic environment of the SML. The humification index ranged from 4 to 14 in the SML and 14 to 22 in underlying water (ULW). An inverse relation for this index as a function of solar radiation was observed, indicating photochemical decomposition of complex molecules present in fluorescent dissolved organic matter (FDOM). The biological index (along Leg 2) ranged from 1.0 to 2.0 for the SML and 1.0 to 1.5 for ULW. The index for recently produced material ranged from 0.25 to 0.8 for the SML and 0.5 to 1.0 for ULW. The FDOM enrichment process of the SML was influenced by the photochemical decomposition of highly aromatic-like fluorophores, as indicated by the calculated indices. Fluorescence intensity increased for humic C peaks (&gt;0.5 Raman units) in the North Sea samples and for humic M peaks (&gt;1.0 Raman units) for Jade Bay. Spearman analysis for FDOM enrichment in the SML as a function of PAR (for Leg 2) showed a weak positive correlation (Rho = 0.676, n = 11, p = 0.022). Abundance of small photoautotrophic cells (Rho = 0.782, n = 11, p = 0.045) and of bacteria (Rho = 0.746, n = 11, p = 0.0082) also showed a positive correlation as a function of PAR. Overall, we found positive trends between the intensity of available light and the response of the constituents within the SML, highlighting the role of the surface microlayer as a distinctive habitat characterized by unique photochemical processes.

Contrasting patterns of population structure and gene flow facilitate exploration of connectivity in two widely distributed temperate octocorals

Connectivity is an important component of metapopulation dynamics in marine systems and can influence population persistence, migration rates and conservation decisions associated with Marine Protected Areas (MPAs). In this study, we compared the genetic diversity, gene flow and population structure of two octocoral species, Eunicella verrucosa and Alcyonium digitatum, in the northeast Atlantic (ranging from the northwest of Ireland and the southern North Sea, to southern Portugal), using two panels of 13 and 8 microsatellite loci, respectively. Our results identified regional genetic structure in E. verrucosa partitioned between populations from southern Portugal, northwest Ireland and Britain/France; subsequent hierarchical analysis of population structure also indicated reduced gene flow between southwest Britain and northwest France. However, over a similar geographical area, A. digitatum showed little evidence of population structure, suggesting high gene flow and/or a large effective population size; indeed, the only significant genetic differentiation detected in A. digitatum occurred between North Sea samples and those from the English Channel/northeast Atlantic. In both species the vast majority of gene flow originated from sample sites within regions, with populations in southwest Britain being the predominant source of contemporary exogenous genetic variants for the populations studied. Overall, historical patterns of gene flow appeared more complex, though again southwest Britain appeared to be an important source of genetic variation for both species. Our findings have major conservation implications, particularly for E. verrucosa, a protected species in UK waters and listed by the IUCN as ‘Vulnerable’, and for the designation and management of European MPAs.

Marine biodegradation of crude oil in temperate and Arctic water samples

Despite increased interest in marine oil exploration in the Arctic, little is known about the fate of Arctic offshore oil pollution. Therefore, in the present study, we examine the oil degradation potential for an Arctic site (Disko Bay, Greenland) and discuss this in relation to a temperate site (North Sea, Denmark). Biodegradation was assessed following exposure to Oseberg Blend crude oil (100mgL−1) in microcosms. Changes in oil hydrocarbon fingerprints of polycyclic aromatic hydrocarbons (PAHs), alkyl-substituted PAHs, dibenzothiophenes, n-alkanes and alkyltoluenes were measured by gas chromatography-mass spectrometry (GC–MS). In the Disko Bay sample, the degradation order was n-alkanes>alkyltoluenes (para->meta->ortho-isomers)>PAHs and dibenzothiophenes, whereas, the degradation order in the North Sea samples was PAHs and dibenzothiophenes>alkyltoluenes>n-alkanes. These differences in degradation patterns significantly affect the environmental risk of oil spills and emphasise the need to consider the specific environmental conditions when conducting risk assessments of Arctic oil pollution.

Suitability of otolith microchemistry for stock separation of Baltic cod

Microchemical otolith analyses have been shown to provide valuable information on the life history, dispersal and stock characteristics of teleost fish. In the present study, the suitability of this technique for identifying the origin and distribution of Atlantic cod Gadus morhua L. from the Baltic Sea was examined using laser ablation-ICPMS. The capacity to distinguish individuals from different Baltic Sea stocks and from the adjacent North Sea stock based on incoporation of stock-specific elemental fingerprints along otolith growth axes was investigated. It was further tested if different origins led to spawning-site specific element concentrations in otolith cores. The results indicate that microchemical analyses of Baltic cod otoliths are applicable for differentiating individuals of different stocks. Analyses of similarities including 12 element/calcium ratios resulted in significant differences between individuals from the eastern and the western Baltic Sea and between North Sea and Baltic Sea samples. Sr/Ca, Ba/Ca, Y/Ca, Mg/Ca, Zr/Ca and Mn/Ca ratios had the strongest discriminatory power. A further separation of individuals caught in 3 different spawning grounds of the eastern Baltic, however, was not possible. Elemental compositions from the core regions of otoliths from young of the year cod caught in eastern and western Baltic Sea spawning grounds showed significant differences in Sr/Ca, Ba/Ca and Mg/Ca concentrations. Analyses of similarities again showed significant differences between these areas for juveniles. This study demonstrates the potential of otolith microchemical analyses to provide important information about the stock structure and connectivity of G. morhua in the Baltic Sea.

Widespread occurrence of endophytic Labyrinthula spp. in northern European eelgrass Zostera marina beds

Seagrasses worldwide are commonly infected by endophytic protists of the genus Labyrinthula. To date, the nature of interaction of endophyte and host is not well understood. In eelgrass (Zostera marina) Labyrinthula zosterae may become virulent (pathogenic) and lead to the loss of entire sea grass beds. One of the best known examples of any marine epidemic were outbreaks of the ´wasting disease´ on both sides of the Atlantic in the 1930s, but smaller infestations have been reported until recently. Up to now, detection of infection by Labyrinthula was based on the wasting index, i.e. the relative area of leaf lesions or microscopy, while genetic data are virtually absent. We characterized a ~1400 base pair portion of the 18S small subunit rDNA in L. zosterae isolates (N=41) from six northern European sites and one southern location (Adriatic Sea) in order to assess identity and potential diversity of endophytic protists. Because there are indications that low salinity impedes Labyrinthula growth, sampling sites included a wide range of salinities from 5-34 psu. A search against the non-redundant GENBANK data base revealed that most isolates are 99% similar to the only L. zosterae 18S sequence available from the data base at all but the Finish site (salinity values 5-7 psu). At the latter site, a different Labyrinthula species occurred, which was also found in fully marine Wadden Sea cultures. A third species was detected in Skagerrak, south-western Baltic and North Sea samples (20-25 psu). We conclude that L. zosterae is widespread among northern European eelgrass sites across wide ranges of salinity.

Occurrence of perfluorinated organic acids in the North and Baltic Seas. Part 2: distribution in sediments

The distribution of polar perfluorinated compounds (PFCs) in sea water of the North and Baltic Seas has been described in part 1 of this study. In part 2, their occurrence in sediments is described in order to further investigate their distribution routes and possible sinks. Sediments were extracted with methanol and PFCs with chain lengths of C(4) to C(10) analysed by liquid chromatography coupled with tandem mass spectrometry. Using the developed procedure, PFCs could be determined in sediments from all 15 stations which had been sampled. In most samples from the German Bight and western Baltic Sea, perfluorooctane sulphonate had the highest concentrations (0.02 to 2.4 μg/kg dry weight), followed by perfluorooctanoate at 0.06 to 1.6 μg/kg dry weight. Levels of the other PFCs were five to ten times lower. Concentrations of PFCs were similar to those of classical chlorinated hydrocarbons. The spatial distribution is strongly influenced by sediment parameters (e.g. total organic carbon (TOC)). By normalisation to TOC, regional differences were identified between the North and Baltic Sea samples. Sediment/water enrichment ratios estimated from field concentrations showed clear dependences on carbon chain length and chemical structure. Time trends of PFCs, investigated by analysing a sediment core (Skagerrak), differed clearly from those of "classical" pollutants. Because of the strong influence of sediment parameters and the relatively low enrichment of PFCs in sediments, this matrix is less suited for investigating spatial distributions. Sediments should be used mainly for monitoring temporal trends, preferably using sediment cores.

Newcomers in the Baltic Sea: an attempt to trace the origins and whereabouts of thicklip grey mullet Chelon labrosus

In recent years, thicklip grey mullet Chelon labrosus has shown increasing expansion of its native habitats in the north-eastern Atlantic into northerly adjacent areas including the North Sea and the brackish Baltic Sea. Despite the regular annual and seasonal occurrence of C. labrosus in the western Baltic during the warm months, nothing is known of the origin or whereabouts of the mullet during the cold season. As different possible migration scenarios can be considered, we performed otolith microchemistry analyses on specimens from the western Baltic Sea to identify the origin of this nonindigenous species. Comparison with North Sea samples revealed common habitat preferences and underlined the highly euryhaline nature of C. labrosus in different recently occupied habitats. Occasional fluctuations of Sr/Ca ratio along the growth axis suggest periodical migration between waters of different salinities but did not reveal distinct migration pathways.

A model for fibrous illite nucleation and growth in sandstones

We have developed a model for the formation of fibrous illite in sandstones where kaolinite is a primary reactant and potassium is derived from in-situ K-feldspar grain dissolution or imported into the model reference frame. Illite fiber nucleation and growth are modeled using Arrhenius expressions that consider saturation state in addition to temperature and time. Nucleation occurs on pore walls, and muscovite and detrital illite may be defined as energetically favorable substrates. The model is integrated with other Touchstone™ models to account for the influence of other diagenetic processes on surface area and reactant volumes and to provide input for permeability simulations. We evaluated the illite model performance on two data sets: (1) Jurassic quartzose samples from offshore mid-Norway with maximum temperatures ranging from 108 to 173C (226 to 343F) and (2) Miocene lithic samples from offshore Southeast Asia that have maximum temperatures ranging from 157 to 182C (315 to 360F). The model matches measured abundances of illite, kaolinite, and K-feldspar in both data sets using identical kinetic parameters. Predicted K-Ar ages are consistent with available data given uncertainties associated with detrital contaminants. Although no illite particle-size data are available from the analyzed samples, modeled crystallite thicknesses from the Norway data set are comparable to published measurements of 0.004 to 0.012 m from North Sea samples with similar temperature histories.

Genomic sequences and genetic differentiation at associated tandem repeat markers in growth hormone, somatolactin and insulin-like growth factor-1 genes of the sea bass,Dicentrarchus labrax

The completion of genomic sequences of physiologically important genes frequently reveals non-coding genetic elements such as tandem repeats (micro- and minisatellites) that are often more polymorphic than nearby coding sequences. We obtained the complete genomic sequences of three hormone genes in sea bass Dicentrarchus labrax : growth hormone (dlGH ), somatolactin (dlSL ) and insulin-like growth factor-1 (dlIGF-1 ), including 5′- and 3′-untranslated regions. Mini- and microsatellites were discovered in both flanking and intron regions. Some were partially conserved across Perciformes. To assess the usefulness and relevance of these gene-associated markers for understanding population structure, an investigation was made on genetic diversity and differentiation at four of them in (i ) five wild populations from the North Sea, the Bay of Biscay and the Western Mediterranean, and (ii ) two samples of hatchery-bred individuals from a freshwater-acclimation experiment. Gene and allelic diversities were lower in cultured individuals than in wild ones. Significant genetic differentiation was demonstrated between Bay of Biscay + North Sea and Mediterranean populations (F st > 0.06, p -associated markers. Significant genetic differentiation was also detected among the Atlantic and North Sea samples, but restricted to the locus associated with dlSL . Significant genetic differentiation was also found among experimental individuals before and after a salinity challenge (F st ≈ 0.05, p and dlIGF-1 loci. Gene-associated markers proved to be more efficient than formerly used anonymous microsatellite markers in providing a clear picture of genetic differentiation.