(Table 1) Polychlorinated biphenyl (PCB) and PCB metabolite concentrations in ringed seals (Phoca hispida) from Svalbard and the Baltic Sea

Polychlorinated biphenyls (PCBs) may induce activity of hepatic enzymes, mainly Phase I monooxygenases and conjugating Phase II enzymes, that catalyze the metabolism of PCBs leading to formation of metabolites and to potential adverse health effects. The present study investigates the concentration and pattern of PCBs, the induction of hepatic phase I and II enzymes, and the formation of hydroxy (OH) and methylsulfonyl (CH3SO2=MeSO2) PCB metabolites in two ringed seal (Phoca hispida) populations, which are contrasted by the degree of contamination exposure, that is, highly contaminated Baltic Sea (n = 31) and less contaminated Svalbard (n = 21). Phase I enzymes were measured as ethoxyresorufin-O-deethylation (EROD), benzyloxyresorufin-O-dealkylation (BROD), methoxyresorufin-O-demethylation (MROD), and pentoxyresorufin-O-dealkylation (PROD) activities, and phase II enzymes were measured as uridine diphosphophate glucuronosyl transferase (UDPGT) and glutathione-S-transferase (GST). Geographical comparison, multivariate, and correlation analysis indicated that sum-PCB had a positive impact on Phase I enzyme and GST activities leading to biotransformation of group III (vicinal ortho-meta-H atoms and <=1 ortho-chlorine (Cl)) and IV PCBs (vicinal meta-para-H atoms and <=2 ortho-Cl). The potential precursors for the main OH-PCBs detected in plasma in the Baltic seals were group III PCBs. MeSO2-PCBs detected in liver were mainly products of group IV PCB metabolism. Both CYP1A- and CYP2B-like enzymes are suggested to be involved in the PCB biotransformation in ringed seals.

Seasonal variations in surface metabolite composition of Fucus vesiculosus and Fucus serratus sampled at outer Kiel Fjord (August 2012 - July 2013)

The chemical composition of surface associated metabolites of two Fucus species (Fucus vesiculosus and Fucus serratus) was analysed by means of gas chromatography-mass spectrometry (GC-MS) to describe temporal patterns in chemical surface composition. Method: The two perennial brown macroalgae F. vesiculosus and F. serratus were sampled monthly at Bülk, outer Kiel Fjord, Germany (54°27'21 N / 10°11'57 E) over an entire year (August 2012 - July 2013). Per month and species six non-fertile Fucus individuals were collected from mixed stands at a depth of 0.5 m under mid water level. For surface extraction approx. 50 g of the upper 5-10 cm apical thalli tips were cut off per species. The surface extraction of Fucus was performed according to the protocol of de Nys and co-workers (1998) with minor modifications (see Rickert et al. 2015). GC/EI-MS measurements were performed with a Waters GCT premier (Waters, Manchester, UK) coupled to an Agilent 6890N GC equipped with a DB-5 ms 30 m column (0.25 mm internal diameter, 0.25 mM film thickness, Agilent, USA). The inlet temperature was maintained at 250°C and samples were injected in split 10 mode. He carrier gas flow was adjusted to 1 ml min-1. Alkanes were used for referencing of retention times. For further details (GC-MS sample preparation and analysis) see the related publication (Rickert et al. submitted to PLOS ONE).

Concentrations and carbon isotopic compositions of organic and inorganic compounds in sediment porewaters at IODP Site U1329

Ocean drilling has revealed the existence of vast microbial populations in the deep subseafloor, but to date little is known about their metabolic activities. To better understand the biogeochemical processes in the deep biosphere, we investigate the stable carbon isotope chemistry of acetate and other carbon-bearing metabolites in sediment pore-waters. Acetate is a key metabolite in the cycling of carbon in anoxic sediments. Its stable carbon isotopic composition provides information on the metabolic processes dominating acetate turnover in situ. This study reports our findings for a methane-rich site at the northern Cascadia Margin (NE Pacific) where Expedition 311 of the Integrated Ocean Drilling Program (IODP) sampled the upper 190 m of sediment. At Site U1329, d13C values of acetate span a wide range from -46.0 per mill to -11.0 per mill vs. VPDB and change systematically with sediment depth. In contrast, d13C values of both the bulk dissolved organic carbon (DOC) (-21.6 ± 1.3 per mill vs. VPDB) and the low-molecular-weight compound lactate (-20.9 ± 1.8 per mill vs. VPDB) show little variability. These species are interpreted to represent the carbon isotopic composition of fermentation products. Relative to DOC, acetate is up to 23.1 per mill depleted and up to 9.1 per mill enriched in 13C. Broadly, 13C-depletions of acetate relative to DOC indicate flux of carbon from acetogenesis into the acetate pool while 13C-enrichments of pore-water acetate relative to DOC suggest consumption of acetate by acetoclastic methanogenesis. Isotopic relationships between acetate and lactate or DOC provide new information on the carbon flow and the presence and activity of specific functional microbial communities in distinct biogeochemical horizons of the sediment. In particular, they suggest that acetogenic CO2-reduction can coexist with methanogenic CO2-reduction, a notion contrary to the hypothesis that hydrogen levels are controlled by the thermodynamically most favorable electron-accepting process. Further, the isotopic relationship suggests a relative increase in acetate flow to acetoclastic methanogenesis with depth although its contribution to total methanogenesis is probably small. Our study demonstrates how the stable carbon isotope biogeochemistry of acetate can be used to identify pathways of microbial carbon turnover in subsurface environments. Our observations also raise new questions regarding the factors controlling acetate turnover in marine sediments.

Phytoplakton pigment concentrations during POLARSTERN cruise ANT-XXVIII/3 and SONNE cruise SO218

Diatoms are the major marine primary producers on the global scale and, recently, several methods have been developed to retrieve their abundance or dominance from satellite remote sensing data. In this work, we highlight the importance of the Southern Ocean (SO) in developing a global algorithm for diatom using an Abundance Based Approach (ABA). A large global in situ data set of phytoplankton pigments was compiled, particularly with more samples collected in the SO. We revised the ABA to take account of the information on the penetration depth (Zpd) and to improve the relationship between diatoms and total chlorophyll-a (TChla). The results showed that there is a distinct relationship between diatoms and TChla in the SO, and a new global model (ABAZpd) improved the estimation of diatoms abundance by 28% in the SO compared with the original ABA model. In addition, we developed a regional model for the SO which further improved the retrieval of diatoms by 17% compared with the global ABAZpd model. As a result, we found that diatom may be more abundant in the SO than previously thought. Linear trend analysis of diatom abundance using the regional model for the SO showed that there are statistically significant trends, both increasing and decreasing, in diatom abundance over the past eleven years in the region.

(Table 1) Lipid content and organohalogen contaminant concentration in captive sledge dogs (Canis familiaris) and wild female polar bears (Ursus maritimus) from Greenland

The limited knowledge and/or the inability to control physiological condition parameters that influence the fate of organohalogen contaminants (OHCs) has been the foremost confounding aspect in monitoring programs and health risk assessments of wild top predators in the Arctic such as the polar bear (Ursus maritimus). In the present comparative study, we used a potential surrogate Canoidea species for the East Greenland polar bear, the captive sledge dog (Canis familiaris), to investigate some factors that may influence the bioaccumulation and biotransformation of major chlorinated and brominated OHCs in adipose tissue and blood (plasma) of control (fed commercial pork fat) and exposed (fed West Greenland minke whale (Balaenoptera acutorostrata) blubber) adult female sledge dogs. Furthermore, we compared the patterns and concentrations of OHCs and their known or suggested hydroxylated (OH) metabolites (e.g., OH-PCBs) in sledge dogs with those in adipose tissue and blood (plasma) of East Greenland adult female polar bears, and blubber of their main prey species, the ringed seal (Pusa hispida). The two-year feeding regime conducted with sledge dogs led to marked differences in overall adipose tissue (and plasma) OHC residue accumulation between the control and exposed groups. Characteristic prey-to-predator OHC bioaccumulation dynamics for major PCB and PBDE congeners (patterns and concentrations) and biotransformation capacity with respect to PCB metabolite formation and OH-PCB retention distinguished, to some extent, captive sledge dogs and wild polar bears. Based on the present findings, we conclude that the use of surrogate species in toxicological investigations for species in the Canoidea family should be done with great caution, although they remain essential in the context of contaminants research with sensitive arctic top carnivore species such as the polar bear.

Data from PhD thesis

The ocean quahog, Arctica islandica is the longest-lived non-colonial animal known to science. A maximum individual age of this bivalve of 405 years has been found in a population off the north western coast of Iceland. Conspicuously shorter maximum lifespan potentials (MLSPs) were recorded from other populations of A. islandica in European waters (e.g. Kiel Bay: 30 years, German Bight: 150 years) which experience wider temperature and salinity fluctuations than the clams from Iceland. The aim of my thesis was to identify possible life-prolonging physiological strategies in A. islandica and to examine the modulating effects of extrinsic factors (e.g. seawater temperature, food availability) and intrinsic factors (e.g. species-specific behavior) on these strategies. Burrowing behavior and metabolic rate depression (MRD), tissue-specific antioxidant and anaerobic capacities as well as cell-turnover (= apoptosis and proliferation) rates were investigated in A. islandica from Iceland and the German Bight. An inter-species comparison of the quahog with the epibenthic scallop Aequipecten opercularis (MLSP = 8-10 years) was carried out in order to determine whether bivalves with short lifespans and different lifestyles also feature a different pattern in cellular maintenance and repair. The combined effects of a low-metabolic lifestyle, low oxidative damage accumulation, and constant investment into cellular protection and tissue maintenance, appear to slow-down the process of physiological aging in A. islandica and to afford the extraordinarily long MLSP in this species. Standard metabolic rates were lower in A. islandica when compared to the shorter-lived A. opercularis. Furthermore, A. islandica regulate mantle cavity water PO2 to mean values < 5 kPa, a PO2 at which the formation of reactive oxygen species (ROS) in isolated gill tissues of the clams was found to be 10 times lower than at normoxic conditions (21 kPa). Burrowing and metabolic rate depression (MRD) in Icelandic specimens were more pronounced in winter, possibly supported by low seawater temperature and food availability, and seem to be key energy-saving and life-prolonging parameters in A. islandica. The signaling molecule nitric oxide (NO) may play an important role during the onset of MRD in the ocean quahog by directly inhibiting cytochome-c-oxidase at low internal oxygenation upon shell closure. In laboratory experiments, respiration of isolated A. islandica gills was completely inhibited by chemically produced NO at low experimental PO2 <= 10 kPa. During shell closure, mantle cavity water PO2 decreased to 0 kPa for longer than 24 h, a state in which ROS production is supposed to subside. Compared to other mollusk species, onset of anaerobic metabolism is late in A. islandica in the metabolically reduced state. Increased accumulation of the anaerobic metabolite succinate was initially detected in the adductor muscle of the clams after 3.5 days under anoxic incubation or in burrowed specimens. A ROS-burst was absent in isolated gill tissue of the clams following hypoxia (5 kPa)-reoxygenation (21 kPa). Accordingly, neither the activity of antioxidant enzymes superoxide dismutase (SOD) and catalase (CAT), nor the specific content of the ROS-scavenger glutathione (GSH) was enhanced in different tissues of the ocean quahog after 3.5 days of self-induced or forced hypoxia/anoxia to prepare for an oxidative burst. While reduced ROS formation compared to routine levels lowers oxidative stress during MRD and also during surfacing, the general preservation of high cellular defense and the efficient removal and replacement of damaged cells over lifetime seem to be of crucial importance in decelerating the senescent decline in tissues of A. islandica. Along with stable antioxidant protection over 200 years of age, proliferation rates and apoptosis intensities in most investigated tissues of the ocean quahog were low, but constant over 140 years of age. Accordingly, age-dependent accumulations of protein and lipid oxidation products are lower in A. islandica tissues when compared to the shorter-lived bivalve A. opercularis. The short-lived swimming scallop is a model bivalve species representing the opposite life and aging strategy to A. islandica. In this species permanently high energy throughput, reduced investment into antioxidant defense with age, and higher accumulation of oxidation products are met by higher cell turnover rates than in the ocean quahog. The only symptoms of physiological change over age ever found in A. islandica were decreasing cell turnover rates in the heart muscle over a lifetime of 140 years. This may either indicate higher damage levels and possibly ongoing loss of functioning in the heart of aging clams, or, the opposite, lower rates of cell damage and a reduced need for cell renewal in the heart tissue of A. islandica over lifetime. Basic physiological capacities of different A. islandica populations, measured at controlled laboratory conditions, could not explain considerable discrepancies in population specific MLSPs. For example, levels of tissue-specific antioxidant capacities and cell turnover rates were similarly high in individuals from the German Bight and from Iceland. Rather than genetic differences, the local impacts of environmental conditions on behavioral and physiological traits in the ocean quahog seem to be responsible for differences in population-specific MLSPs.

The nitrogen costs of photosynthesis in a diatom under current and future pCO2

With each cellular generation, oxygenic photoautotrophs must accumulate abundant protein complexes that mediate light capture, photosynthetic electron transport and carbon fixation. In addition to this net synthesis, oxygenic photoautotrophs must counter the light-dependent photoinactivation of Photosystem II (PSII), using metabolically expensive proteolysis, disassembly, resynthesis and re-assembly of protein subunits. We used growth rates, elemental analyses and protein quantitations to estimate the nitrogen (N) metabolism costs to both accumulate the photosynthetic system and to maintain PSII function in the diatom Thalassiosira pseudonana, growing at two pCO2 levels across a range of light levels. The photosynthetic system contains c. 15-25% of total cellular N. Under low growth light, N (re)cycling through PSII repair is only c. 1% of the cellular N assimilation rate. As growth light increases to inhibitory levels, N metabolite cycling through PSII repair increases to c. 14% of the cellular N assimilation rate. Cells growing under the assumed future 750 ppmv pCO2 show higher growth rates under optimal light, coinciding with a lowered N metabolic cost to maintain photosynthesis, but then suffer greater photoinhibition of growth under excess light, coincident with rising costs to maintain photosynthesis. We predict this quantitative trait response to light will vary across taxa.

Open Ocean and coastal phytoplankton communities of of Western Antarctic Peninsula and Drake Passage waters

Photophysiological processes as well as uptake characteristics of iron and inorganic carbon were studied in inshore phytoplankton assemblages of the Western Antarctic Peninsula (WAP) and offshore assemblages of the Drake Passage. Chlorophyll a concentrations and primary productivity decreased from in- to offshore waters. The inverse relationship between low maximum quantum yields of photochemistry in PSII (Fv/Fm) and large sizes of functional absorption cross sections (sigma PSII) in offshore communities indicated iron-limitation. Congruently, the negative correlation between Fv/Fm values and iron uptake rates across our sampling locations suggest an overall better iron uptake capacity in iron-limited pelagic phytoplankton communities. Highest iron uptake capacities could be related to relative abundances of the haptophyte Phaeocystis antarctica. As chlorophyll a-specific concentrations of humic-like substances were similarly high in offshore and inshore stations, we suggest humic-like substances may play an important role in iron chemistry in both coastal and pelagic phytoplankton assemblages. Regarding inorganic carbon uptake kinetics, the measured maximum short-term uptake rates (Vmax(CO2)) and apparent half-saturation constants (K1/2(CO2)) did not differ between offshore and inshore phytoplankton. Moreover, Vmax(CO2) and K1/2(CO2) did not exhibit any CO2-dependent trend over the natural pCO2 range from 237 to 507 µatm. K1/2(CO2) strongly varied among the sampled phytoplankton communities, ranging between 3.5 and 35.3 µmol/L CO2. While in many of the sampled phytoplankton communities, the operation of carbon-concentrating mechanisms (CCMs) was indicated by low K1/2(CO2) values relative to ambient CO2 concentrations, some coastal sites exhibited higher values, suggesting down-regulated CCMs. Overall, our results demonstrate a complex interplay between photophysiological processes, iron and carbon uptake of phytoplankton communities of the WAP and the Drake Passage.

(Table 2) Organochlorine concentrations in polar bears (Ursus maritimus) from East Greenland 1999-2001

Persistent organochlorine (OC) contaminants (PCBs, DDTs, chlordanes (CHLs), dieldrin, hexachlorocyclohexanes (HCHs), chlorobenzenes (CBzs)) were determined in adipose tissue of 92 polar bears (Ursus maritimus) sampled between 1999 and 2001 in central East Greenland (69°00'N to 74°00'N). OC data were presented from subadults (S: females: <5 years and males: <6 years), adult females (F: >=5 years) and adult males (M: >=6 years). Summed chlorobiphenyl (SumCBs) concentrations (41 congeners including co-eluters), SumCHLs and SumDDTs were the dominant classes of OCs. SumCBs concentrations were found to be 6470, 8240 and 9100 ng/g lipid weight (lw) i subadults, adult females and adult males, respectively. The corresponding figures were: 2010 (S), 2220 (F) and 1710 (M) ng/ g lw for SumCHLs and 462 (S), 462 (F) and 559 (M) ng/g lw for SumDDTs. The dominant CB congeners were CB153 (32.3%), CB180 (21.4%), CB170 (12.2%) and CB138 (11.0%). The metabolite p,p'-DDE (88.2%) dominated the SumDDTs, while oxychlordane was the dominant (57.1%) CHL-related compound. Concentrations of SumCBs, SumCBzs, SumDDTs, mirex and dieldrin were highest in adult males, whereas concentrations of SumHCHs were lower than in adult females but not than those in subadults. Adult females had the lowest concentrations of SumCBzs, mirex and dieldrin. Concentrations of SumCHLs were lowest in adult males, intermediate in subadults and highest in adult females. SumCB, SumHCH and SumCHL concentrations showed high seasonal variability in adult females but remained relatively constant in adult males and subadults. In general, the OC levels in females appeared to be highest in March and lowest in January or September. Concentrations of SumCBzs and dieldrin showed seasonal variability in all three groups, with a maximum in March in adult females. SumCBz concentrations in adult males and subadults of both sexes peaked in April-July, and dieldrin concentrations peaked in April-July in subadults, but not until August in adult males. SumDDT concentrations increased from January to a maximum in April-July for subadults and in August for adults. Temporal trends within the last decade were examined by comparing the present data to the concentrations reported in samples from 1990 from the same region. SumCB, p,p'-DDE and SumHCH concentrations in 1999-2001 were 22.1%, 66.3% and 39.3% lower than the 1990 concentrations, respectively. in contrast, SumCHL and dieldrin concentrations showed differences amongst sex and age groups in the temporal trends, where present concentrations are between 24.4% to 69.3% and 27.0% to 69.0% lower, respectively, relative to the 1990 levels. However, power analysis suggested that firm conclusions could not be drawn regarding the general time trend based on these two sampling periods. The range of half-lives of the various OC classes were estimated to lie between 4.5 and 20.6 years depending on the age and sex groups considered.