(Table 1) Concentrations of the main organochlorine pesticides in liver and plasma samples of ringed seals (Phoca hispida)

The present study investigates the concentrations and patterns of organochlorine pesticides (OCPs) and their metabolites in liver and plasma of two ringed seal populations (Phoca hispida): lower contaminated Svalbard population and more contaminated Baltic Sea population. Among OCPs, p,p'-DDE and sum-chlordanes were the highest in concentration. With increasing hepatic contaminant concentrations and activities of xenobiotic-metabolizing enzymes, the concentrations of 3-methylsulfonyl-p,p'-DDE and the concentration ratios of pentachlorophenol/hexachlorobenzene increased, and the toxaphene pattern shifted more towards persistent Parlar-26 and -50 and less towards more biodegradable Parlar-44. Relative concentrations of the chlordane metabolites, oxychlordane and -heptachlorepoxide, to sum-chlordanes were higher in the seals from Svalbard compared to the seals from the Baltic, while the trend was opposite for cis- and trans-nonachlor. The observed differences in the OCP patterns in the seals from the two populations are probably related to the catalytic activity of xenobiotic-metabolizing enzymes, and also to differences in dietary exposure.

Isotopic ratios and concentrations for mineral-associated and particulate organic fractions of sediment core Wilson_Lake samples

The flux of sediment and organic carbon from continents to the coastal ocean is an important factor governing organic burial in coastal sediments, and these systems preserve important records of environmental and biogeochemical conditions during past global change events. Burial of organic materials in coastal systems can be promoted by chemical resilience or through protection by association with mineral surfaces, but the role and influence of these processes on organic records from ancient sediments is poorly known. We studied sediment and organic matter burial as particulate organic matter (POM) and mineral-bound organic matter (MOM) in near-shore marine sediments from the Wilson Lake core (New Jersey, USA) that span the Paleocene-Eocene thermal maximum (PETM), a climatic perturbation 55.9 Myr ago. Our results show that distinct POM and MOM fractions can be isolated from sediments. Both fractions appear to be dominated by terrestrial material, but POM consisted primarily of recently synthesized material whereas MOM included a significant fraction of pre-aged organic matter from soils or ancient sediments. Variation in organic burial through the PETM is associated with changes in inorganic nitrogen burial, clay mineralogy, and clastic grain size that we associate with enhanced continental weathering, erosion and redeposition of ancient kaolinites, and eustatic sea level variation, respectively. These results provide a new perspective on factors governing carbon burial and carbon isotope records in ancient marine margin settings and offer information on rate and phasing of late Paleocene/early Eocene Earth system changes that may constrain interpretations of the cause of the PETM climate change event.

Vertical profiles of environmental parameters measured on discrete water samples collected with Niskin bottles during the Tara Oceans expedition 2009-2013

The present data publication provides permanent links to original and updated versions of validated data files. The data files include properties of seawater, particulate matter and dissolved matter that were measured from discrete water samples collected with Niskin bottles during the 2009-2013 Tara Oceans expedition. Properties include pigment concentrations from HPLC analysis (10 depths per vertical profile, 25 pigments per depth), the carbonate system (Surface and 400m; pH (total scale), CO2, pCO2, fCO2, HCO3, CO3, Total alkalinity, Total carbon, OmegaAragonite, OmegaCalcite, and dosage Flags), nutrients (10 depths per vertical profile; NO2, PO4, N02/NO3, SI, quality Flags), DOC, CDOM, and dissolved oxygen isotopes. The Service National d'Analyse des Paramètres Océaniques du CO2, at the Université Pierre et Marie Curie, determined CT and AT potentiometrically (Edmond 1970; DOE 1994) on samples preserved according to Dickson et al. (2007). More than 250 vertical profiles of these properties were made across the world ocean. DOC, CDOM and dissolved oxygen isotopes are available only for the Arctic Ocean and Arctic Seas (2013).

Immunomodulating effects of environmentally realistic copper concentrations in Mytilus edulis adapted to naturally low salinities, link to supplementary material

The monitoring of organisms' health conditions by the assessment of their immunocompetence may serve as an important criterion for the achievement of the Good Environmental Status (GES) as defined in the Marine Strategy Framework Directive (EU). In this context, the complex role of natural environmental stressors, e.g. salinity, and interfering or superimposing effects of anthropogenic chemicals, should be carefully considered, especially in scenarios of low to moderate contamination. Organisms from the Baltic Sea have adapted to the ambient salinity regime, however energetically costly osmoregulating processes may have an impact on the capability to respond to additional stress such as contamination. The assessment of multiple stressors, encompassing natural and anthropogenic factors, influencing an organisms' health was the main aim of the present study. Immune responses of Mytilus edulis, collected and kept at natural salinities of 12 per mil (LS) and 20 per mil (MS), respectively, were compared after short-term exposure (1, 7 and 13 days) to low copper concentrations (5, 9 and 16 µg/L Cu). A significant interaction of salinity and copper exposure was observed in copper accumulation. LS mussels accumulated markedly more copper than MS mussels. No combined effects were detected in cellular responses. Bacterial clearance was mostly achieved by phagocytosis, as revealed by a strong positive correlation between bacterial counts and phagocytic activity, which was particularly pronounced in LS mussels. MS mussels, on the other hand, seemingly accomplished bacterial clearance by employing additional humoral factors (16 µg/L Cu). The greatest separating factor in the PCA biplot between LS and MS mussels was the proportion of granulocytes and hyalinocytes while functional parameters (phagocytic activity and bacterial clearance) were hardly affected by salinity, but rather by copper exposure. In conclusion, immune responses of the blue mussel may be suitable and sensitive biomarkers for the assessment of ecosystem health in brackish waters (10-20 per mil S).

Stable isotopic composition and carbonate concentrations of sediments of the Cretaceous/Paleogene boundary in the Antarctic

Stable isotopic records across the Cretaceous/Paleogene (K/P) boundary in Maud Rise Holes 689B and 690C indicate that significant climatic changes occurred during the latest Cretaceous, beginning approximately 500 k.y. prior to the mass extinction event and the enrichment of iridium at the K/P boundary (66.4 Ma). An oxygen isotopic decrease of ~0.7 per mil - ~1.0 per mil is recorded in the Late Cretaceous planktonic and benthic foraminifers between 66.9 and 66.6 Ma. The negative isotope excursion was followed by a positive excursion of similar magnitude between 66.6 Ma (latest Cretaceous) and ~66.3 Ma (earliest Paleocene). No other isotopic excursions of this magnitude are recorded in the planktonic and benthic microfossil records 1.0 m.y prior to, and for 2.0 m.y following the mass extinction event at the K/P boundary. The magnitude and duration of these isotopic excursions were similar to those at the Paleocene/Eocene and Eocene/Oligocene boundaries. A major d13C excursion occurred 200 k.y. prior to the boundary, involving a positive shift in planktonic and benthic d13C of ~0.5 per mil - 0.75 per mil. Similar changes observed in other deep-sea sequences indicate that this reflected a global change in d13C of the oceanic total dissolved carbon (TDC) reservoir. The magnitude of this inferred carbon reservoir change and its association with high latitude surface-water temperature changes recorded in the d18O records implies that it was linked to global climate change through feedback loops in the carbon cycle. At the K/P boundary, the surface-to-deep water d13C gradient is reduced by approximately 0.6 per mil - ~0.2 per mil. However, unlike sequences elsewhere, the planktonic-benthic d13C gradient (Delta d13C) was not eliminated in the Antarctic. The surface-to-deep water gradient was re-established gradually during the 400 k.y. following the mass extinction. Full recovery of the Delta d13C occurred by ~60.0 Ma. In addition to the reduced vertical d13C gradient across the K/P boundary, there was a negative excursion in both planktonic and benthic d13C beginning approximately 100 k.y. after the boundary (66.3 Ma). This excursion resulted in benthic d13C values in the early Paleogene that were similar to those in the pre-K/P boundary intervals. This negative shift appears to reflect a change in the d13C of the oceanic TDC reservoir shift that may have resulted from reduced carbon burial and/or increased carbon flux to the oceans. Any model that attempts to explain the demise of the oceanic plankton at the end of the Cretaceous should consider the oceanic environmental changes that were occurring prior to the massive extinction event.

Dimethylsulphide and halocarbon concentrations taken from 10m integrated samples during the 2012 KOSMOS Finland Mesocosm experiment

The Baltic Sea is a unique environment as the largest body of brackish water in the world. Acidification of the surface oceans due to absorption of anthropogenic CO2 emissions is an additional stressor facing the pelagic community of the already challenging Baltic Sea. To investigate its impact on trace gas biogeochemistry, a large-scale mesocosm experiment was performed off Tvärminne Research Station, Finland in summer 2012. During the second half of the experiment, dimethylsulphide (DMS) concentrations in the highest fCO2 mesocosms (1075-1333 µatm) were 34 % lower than at ambient CO2 (350 µatm). However the net production (as measured by concentration change) of seven halocarbons analysed was not significantly affected by even the highest CO2 levels after 5 weeks exposure. Methyl iodide (CH3I) and diiodomethane (CH2I2) showed 15 % and 57 % increases in mean mesocosm concentration (3.8 ± 0.6 pmol L-1 increasing to 4.3 ± 0.4 pmol L-1 and 87.4 ± 14.9 pmol L-1 increasing to 134.4 ± 24.1 pmol L-1 respectively) during Phase II of the experiment, which were unrelated to CO2 and corresponded to 30 % lower Chl-? concentrations compared to Phase I. No other iodocarbons increased or showed a peak, with mean chloroiodomethane (CH2ClI) concentrations measured at 5.3 (± 0.9) pmol L-1 and iodoethane (C2H5I) at 0.5 (± 0.1) pmol L-1. Of the concentrations of bromoform (CHBr3; mean 88.1 ± 13.2 pmol L-1), dibromomethane (CH2Br2; mean 5.3 ± 0.8 pmol L-1) and dibromochloromethane (CHBr2Cl, mean 3.0 ± 0.5 pmol L-1), only CH2Br2 showed a decrease of 17 % between Phases I and II, with CHBr3 and CHBr2Cl showing similar mean concentrations in both Phases. Outside the mesocosms, an upwelling event was responsible for bringing colder, high CO2, low pH water to the surface starting on day t16 of the experiment; this variable CO2 system with frequent upwelling events implies the community of the Baltic Sea is acclimated to regular significant declines in pH caused by up to 800 µatm fCO2. After this upwelling, DMS concentrations declined, but halocarbon concentrations remained similar or increased compared to measurements prior to the change in conditions. Based on our findings, with future acidification of Baltic Sea waters, biogenic halocarbon emissions are likely to remain at similar values to today, however emissions of biogenic sulphur could significantly decrease from this region.

(Table S1) Brominated flame retardant concentrations in an ice core from Holtedahlfonna, Svalbard

Brominated flame retardants (BFRs) have been found in Arctic wildlife, lake sediment, and air. To identify the atmospheric BFR deposition history on Svalbard, Norway, we analyzed 19 BFRs, including hexabromocyclododecane (HBCD), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), pentabromoethylbenzene (PBEB),and 15 polybrominated diphenyl ether congeners (PBDE) in the upper 34 m of an ice core (representing 1953-2005) from Holtedahlfonna, the western-most ice sheet on Svalbard. All of the non-PBDE compounds were detected in nearly continuous profiles in the core. Seven PBDEs were not observed above background (28,47,66,100,99,154,153), while 4 were found in 1 or 2 of 6 segments (17,85,138,183). BDEs-49,71,190,209 had nearly continuous profiles but only BDE-209 in large amounts. The greatest inputs were HBCD and BDE-209, 910, and 320 pg/cm**2/yr from 1995-2005. DBDPE, BTBPE, and PBEB show nearly continuous input growth in recent core segments, but all were <6 pg/cm**2/yr. Long-range atmospheric processes may have moved these particle-bound BFRs to the site, probably during the Arctic haze season. Average air mass trajectories over 10 years show >75% of atmospheric flow to Holtedahlfonna coming from Eurasia during haze periods (March and April).

Vertical profiles of environmental parameters measured on discrete water samples collected with Niskin bottles at station TARA_209 during the Tara Oceans expedition 2009-2013

The Tara Oceans Expedition (2009-2013) was a global survey of ocean ecosystems aboard the Sailing Vessel Tara. It carried out extensive measurements of evironmental conditions and collected plankton (viruses, bacteria, protists and metazoans) for later analysis using modern sequencing and state-of-the-art imaging technologies. Tara Oceans Data are particularly suited to study the genetic, morphological and functional diversity of plankton. The present data set includes properties of seawater, particulate matter and dissolved matter that were measured from discrete water samples collected with Niskin bottles during the 2009-2013 Tara Oceans expedition. Properties include pigment concentrations from HPLC analysis (10 depths per vertical profile, 25 pigments per depth), the carbonate system (Surface and 400m; pH (total scale), CO2, pCO2, fCO2, HCO3, CO3, Total alkalinity, Total carbon, OmegaAragonite, OmegaCalcite, and dosage Flags), nutrients (10 depths per vertical profile; NO2, PO4, N02/NO3, SI, quality Flags), DOC, CDOM, and dissolved oxygen isotopes. The Service National d'Analyse des Paramètres Océaniques du CO2, at the Université Pierre et Marie Curie, determined CT and AT potentiometrically. More than 200 vertical profiles of these properties were made across the world ocean. DOC, CDOM and dissolved oxygen isotopes are available only for the Arctic Ocean and Arctic Seas (2013).

Vertical profiles of environmental parameters measured on discrete water samples collected with Niskin bottles at station TARA_131 during the Tara Oceans expedition 2009-2013

The Tara Oceans Expedition (2009-2013) was a global survey of ocean ecosystems aboard the Sailing Vessel Tara. It carried out extensive measurements of evironmental conditions and collected plankton (viruses, bacteria, protists and metazoans) for later analysis using modern sequencing and state-of-the-art imaging technologies. Tara Oceans Data are particularly suited to study the genetic, morphological and functional diversity of plankton. The present data set includes properties of seawater, particulate matter and dissolved matter that were measured from discrete water samples collected with Niskin bottles during the 2009-2013 Tara Oceans expedition. Properties include pigment concentrations from HPLC analysis (10 depths per vertical profile, 25 pigments per depth), the carbonate system (Surface and 400m; pH (total scale), CO2, pCO2, fCO2, HCO3, CO3, Total alkalinity, Total carbon, OmegaAragonite, OmegaCalcite, and dosage Flags), nutrients (10 depths per vertical profile; NO2, PO4, N02/NO3, SI, quality Flags), DOC, CDOM, and dissolved oxygen isotopes. The Service National d'Analyse des Paramètres Océaniques du CO2, at the Université Pierre et Marie Curie, determined CT and AT potentiometrically. More than 200 vertical profiles of these properties were made across the world ocean. DOC, CDOM and dissolved oxygen isotopes are available only for the Arctic Ocean and Arctic Seas (2013).

Vertical profiles of environmental parameters measured on discrete water samples collected with Niskin bottles at station TARA_132 during the Tara Oceans expedition 2009-2013

The Tara Oceans Expedition (2009-2013) was a global survey of ocean ecosystems aboard the Sailing Vessel Tara. It carried out extensive measurements of evironmental conditions and collected plankton (viruses, bacteria, protists and metazoans) for later analysis using modern sequencing and state-of-the-art imaging technologies. Tara Oceans Data are particularly suited to study the genetic, morphological and functional diversity of plankton. The present data set includes properties of seawater, particulate matter and dissolved matter that were measured from discrete water samples collected with Niskin bottles during the 2009-2013 Tara Oceans expedition. Properties include pigment concentrations from HPLC analysis (10 depths per vertical profile, 25 pigments per depth), the carbonate system (Surface and 400m; pH (total scale), CO2, pCO2, fCO2, HCO3, CO3, Total alkalinity, Total carbon, OmegaAragonite, OmegaCalcite, and dosage Flags), nutrients (10 depths per vertical profile; NO2, PO4, N02/NO3, SI, quality Flags), DOC, CDOM, and dissolved oxygen isotopes. The Service National d'Analyse des Paramètres Océaniques du CO2, at the Université Pierre et Marie Curie, determined CT and AT potentiometrically. More than 200 vertical profiles of these properties were made across the world ocean. DOC, CDOM and dissolved oxygen isotopes are available only for the Arctic Ocean and Arctic Seas (2013).

Vertical profiles of environmental parameters measured on discrete water samples collected with Niskin bottles at station TARA_139 during the Tara Oceans expedition 2009-2013

The Tara Oceans Expedition (2009-2013) was a global survey of ocean ecosystems aboard the Sailing Vessel Tara. It carried out extensive measurements of evironmental conditions and collected plankton (viruses, bacteria, protists and metazoans) for later analysis using modern sequencing and state-of-the-art imaging technologies. Tara Oceans Data are particularly suited to study the genetic, morphological and functional diversity of plankton. The present data set includes properties of seawater, particulate matter and dissolved matter that were measured from discrete water samples collected with Niskin bottles during the 2009-2013 Tara Oceans expedition. Properties include pigment concentrations from HPLC analysis (10 depths per vertical profile, 25 pigments per depth), the carbonate system (Surface and 400m; pH (total scale), CO2, pCO2, fCO2, HCO3, CO3, Total alkalinity, Total carbon, OmegaAragonite, OmegaCalcite, and dosage Flags), nutrients (10 depths per vertical profile; NO2, PO4, N02/NO3, SI, quality Flags), DOC, CDOM, and dissolved oxygen isotopes. The Service National d'Analyse des Paramètres Océaniques du CO2, at the Université Pierre et Marie Curie, determined CT and AT potentiometrically. More than 200 vertical profiles of these properties were made across the world ocean. DOC, CDOM and dissolved oxygen isotopes are available only for the Arctic Ocean and Arctic Seas (2013).

Vertical profiles of environmental parameters measured on discrete water samples collected with Niskin bottles at station TARA_124 during the Tara Oceans expedition 2009-2013

The Tara Oceans Expedition (2009-2013) was a global survey of ocean ecosystems aboard the Sailing Vessel Tara. It carried out extensive measurements of evironmental conditions and collected plankton (viruses, bacteria, protists and metazoans) for later analysis using modern sequencing and state-of-the-art imaging technologies. Tara Oceans Data are particularly suited to study the genetic, morphological and functional diversity of plankton. The present data set includes properties of seawater, particulate matter and dissolved matter that were measured from discrete water samples collected with Niskin bottles during the 2009-2013 Tara Oceans expedition. Properties include pigment concentrations from HPLC analysis (10 depths per vertical profile, 25 pigments per depth), the carbonate system (Surface and 400m; pH (total scale), CO2, pCO2, fCO2, HCO3, CO3, Total alkalinity, Total carbon, OmegaAragonite, OmegaCalcite, and dosage Flags), nutrients (10 depths per vertical profile; NO2, PO4, N02/NO3, SI, quality Flags), DOC, CDOM, and dissolved oxygen isotopes. The Service National d'Analyse des Paramètres Océaniques du CO2, at the Université Pierre et Marie Curie, determined CT and AT potentiometrically. More than 200 vertical profiles of these properties were made across the world ocean. DOC, CDOM and dissolved oxygen isotopes are available only for the Arctic Ocean and Arctic Seas (2013).

Vertical profiles of environmental parameters measured on discrete water samples collected with Niskin bottles at station TARA_125 during the Tara Oceans expedition 2009-2013

The Tara Oceans Expedition (2009-2013) was a global survey of ocean ecosystems aboard the Sailing Vessel Tara. It carried out extensive measurements of evironmental conditions and collected plankton (viruses, bacteria, protists and metazoans) for later analysis using modern sequencing and state-of-the-art imaging technologies. Tara Oceans Data are particularly suited to study the genetic, morphological and functional diversity of plankton. The present data set includes properties of seawater, particulate matter and dissolved matter that were measured from discrete water samples collected with Niskin bottles during the 2009-2013 Tara Oceans expedition. Properties include pigment concentrations from HPLC analysis (10 depths per vertical profile, 25 pigments per depth), the carbonate system (Surface and 400m; pH (total scale), CO2, pCO2, fCO2, HCO3, CO3, Total alkalinity, Total carbon, OmegaAragonite, OmegaCalcite, and dosage Flags), nutrients (10 depths per vertical profile; NO2, PO4, N02/NO3, SI, quality Flags), DOC, CDOM, and dissolved oxygen isotopes. The Service National d'Analyse des Paramètres Océaniques du CO2, at the Université Pierre et Marie Curie, determined CT and AT potentiometrically. More than 200 vertical profiles of these properties were made across the world ocean. DOC, CDOM and dissolved oxygen isotopes are available only for the Arctic Ocean and Arctic Seas (2013).

Vertical profiles of environmental parameters measured on discrete water samples collected with Niskin bottles at station TARA_126 during the Tara Oceans expedition 2009-2013

The Tara Oceans Expedition (2009-2013) was a global survey of ocean ecosystems aboard the Sailing Vessel Tara. It carried out extensive measurements of evironmental conditions and collected plankton (viruses, bacteria, protists and metazoans) for later analysis using modern sequencing and state-of-the-art imaging technologies. Tara Oceans Data are particularly suited to study the genetic, morphological and functional diversity of plankton. The present data set includes properties of seawater, particulate matter and dissolved matter that were measured from discrete water samples collected with Niskin bottles during the 2009-2013 Tara Oceans expedition. Properties include pigment concentrations from HPLC analysis (10 depths per vertical profile, 25 pigments per depth), the carbonate system (Surface and 400m; pH (total scale), CO2, pCO2, fCO2, HCO3, CO3, Total alkalinity, Total carbon, OmegaAragonite, OmegaCalcite, and dosage Flags), nutrients (10 depths per vertical profile; NO2, PO4, N02/NO3, SI, quality Flags), DOC, CDOM, and dissolved oxygen isotopes. The Service National d'Analyse des Paramètres Océaniques du CO2, at the Université Pierre et Marie Curie, determined CT and AT potentiometrically. More than 200 vertical profiles of these properties were made across the world ocean. DOC, CDOM and dissolved oxygen isotopes are available only for the Arctic Ocean and Arctic Seas (2013).