Chemical analysis and Microbial community composition of surface water samples from the Southern Lagoon of Venice

The Lagoon of Venice is a large water basin that exchanges water with the Northern Adriatic Sea through three large inlets. We examined two adjacent sites within the Southern Basin and at the Chioggia inlet in autumn 2007 and summer 2008. A pilot study in June 2007 on a surface water sample from Chioggia with a rather high salinity of 36.9 PSU had revealed a conspicuous bloom of CF319a-positive cells likely affiliated with the Cytophaga /Flavobacteria cluster of Bacteroidetes. These flavobacterial abundances were one to two orders of magnitude higher than in other marine surface waters. DAPI-stained cells were identified as bacteria with the general bacterial probe mixture EUB338 I-III. CARD-FISH counts with group-specific probes confirmed the dominance of Bacteroidetes (CF319a), Alphaproteobacteria (ALF968), and Gammaproteobacteria (GAM42a). CARD-FISH showed thatBetaproteobacteria and Planctomycetes were minor components of the bacterioplankton in the Lagoon of Venice.

Investigation of the seasonality of N. pachyderma in the North Atlantic Ocean during Heinrich Stadial 1 using an ecosystem modeling approach

Fossil shells of planktonic foraminifera serve as the prime source of information on past changes in surface ocean conditions. Because the population size of planktonic foraminifera species changes throughout the year, the signal preserved in fossil shells is biased towards the conditions when species production was at its maximum. The amplitude of the potential seasonal bias is a function of the magnitude of the seasonal cycle in production. Here we use a planktonic foraminifera model coupled to an ecosystem model to investigate to what degree seasonal variations in production of the species Neogloboquadrina pachyderma may affect paleoceanographic reconstructions during Heinrich Stadial 1 (~18-15 cal. ka B.P.) in the North Atlantic Ocean. The model implies that during Heinrich Stadial 1 the maximum seasonal production occurred later in the year compared to the Last Glacial Maximum (~21-19 cal. ka B.P.) and the pre-industrial era north of 30 ºN. A diagnosis of the model output indicates that this change reflects the sensitivity of the species to the seasonal cycle of sea-ice cover and food supply, which collectively lead to shifts in the modeled maximum production from the Last Glacial Maximum to Heinrich Stadial 1 by up to six months. Assuming equilibrium oxygen isotopic incorporation in the shells of N. pachyderma, the modeled changes in seasonality would result in an underestimation of the actual magnitude of the meltwater isotopic signal recorded by fossil assemblages of N. pachyderma wherever calcification is likely to take place.

An approach for particle sinking velocity measurements in the 3-400 µm size range and considerations on the effect of temperature on sinking rates

The flux of organic particles below the mixed layer is one major pathway of carbon from the surface into the deep ocean. The magnitude of this export flux depends on two major processes-remineralization rates and sinking velocities. Here, we present an efficient method to measure sinking velocities of particles in the size range from approximately 3-400 µm by means of video microscopy (FlowCAM®). The method allows rapid measurement and automated analysis of mixed samples and was tested with polystyrene beads, different phytoplankton species, and sediment trap material. Sinking velocities of polystyrene beads were close to theoretical values calculated from Stokes' Law. Sinking velocities of the investigated phytoplankton species were in reasonable agreement with published literature values and sinking velocities of material collected in sediment trap increased with particle size. Temperature had a strong effect on sinking velocities due to its influence on seawater viscosity and density. An increase in 9 °C led to a measured increase in sinking velocities of 40 %. According to this temperature effect, an average temperature increase in 2 °C as projected for the sea surface by the end of this century could increase sinking velocities by about 6 % which might have feedbacks on carbon export into the deep ocean.

Microbial community, biomarker concentrations and their isotopic signature in sediment of Gullfaks and Tommeliten methane seeps in the Northern North Sea

Gullfaks is one of the four major Norwegian oil and gas fields, located in the northeastern edge of the North Sea Plateau. Tommeliten lies in the greater Ekofisk area in the central North Sea. During the cruises HE 208 and AL 267 several seep locations of the North Sea were visited. At the Heincke seep at Gullfaks, sediments were sampled in May 2004 (HE 208) using a video-guided multiple corer system (MUC; Octopus, Kiel). The samples were recovered from an area densely covered with bacterial mats where gas ebullition was observed. The coarse sands limited MUC penetration depth to maximal 30 centimeters and the highly permeable sands did not allow for a high-resolution, vertical subsampling because of pore water loss. The gas flare mapping and videographic observation at Tommeliten indicated an area of gas emission with a few small patches of bacterial mats with diameters <50 cm from most of which a single stream of gas bubbles emerged. The patches were spaced apart by 10-100 m. Sampling of sediments covered by bacterial mats was only possible with 3 small push cores (3.8 cm diameter) mounted to ROV Cherokee. These cores were sampled in 3 cm intervals. Lipid biomarker extraction from 10 -17 g wet sediment was carried out as described in detail elsewhere (Elvert et al., 2003; doi:10.1080/01490450303894). Briefly, defined concentrations of cholestane, nonadecanol and nonadecanolic acid with known delta 13C-values were added to the sediments prior to extraction as internal standards for the hydrocarbon, alcohol and fatty acid fraction, respectively. Total lipid extracts were obtained from the sediment by ultrasonification with organic solvents of decreasing polarity. Esterified fatty acids (FAs) were cleaved from the glycerol head group by saponification with methanolic KOH solution. From this mixture, the neutral fraction was extracted with hexane. After subsequent acidification, FAs were extracted with hexane. For analysis, FAs were methylated using BF3 in methanol yielding fatty acid methyl esters (FAMES). The fixation for total cell counts and CARD-FISH were performed on-board directly after sampling. For both methods, sediments were fixed in formaldehyde solution. After two hours, aliquots for CARD-FISH staining were washed with 1* PBS (10mmol/l sodium phosphate solution, 130mmol/l NaCl, adjusted to a pH of 7.2) and finally stored in a 1:1 PBS:ethanol solution at -20°C until further processing. Samples for total cell counts were stored in formalin at 4°C until analysis. For sandy samples, the total cell count/CARD-FISH protocol was optimized to separate sand particles from the cells. Cells were dislodged from sediment grains and brought into solution with the supernatant by sonicating each sample onice for 2 minutes at 50W. This procedure was repeated four times and supernatants were combined. The sediment samples were brought to a final dilution of 1:2000 to 1:4000 and filtered onto 0.2µm GTTP filters (Millipore, Eschbonn, Germany).

Jelly biomass sinking speed reveals a fast carbon export mechanism

Sinking of gelatinous zooplankton biomass is an important component of the biological pump removing carbon from the upper ocean. The export efficiency, e.g., how much biomass reaches the ocean interior sequestering carbon, is poorly known because of the absence of reliable sinking speed data. We measured sinking rates of gelatinous particulate organic matter (jelly-POM) from different species of scyphozoans, ctenophores, thaliaceans, and pteropods, both in the field and in the laboratory in vertical columns filled with seawater using high-quality video. Using these data, we determined taxon-specific jelly-POM export efficiencies using equations that integrate biomass decay rate, seawater temperature, and sinking speed. Two depth scenarios in several environments were considered, with jelly-POM sinking from 200 and 600 m in temperate, tropical, and polar regions. Jelly-POM sank on average between 850 and 1500 m/d (salps: 800-1200 m/d; ctenophores: 1200-1500 m/d; scyphozoans: 1000-1100 m d; pyrosomes: 1300 m/d). High latitudes represent a fast-sinking and low-remineralization corridor, regardless of species. In tropical and temperate regions, significant decomposition takes place above 1500 m unless jelly-POM sinks below the permanent thermocline. Sinking jelly-POM sequesters carbon to the deep ocean faster than anticipated, and should be incorporated into biogeochemical and modeling studies to provide more realistic quantification of export via the biological carbon pump worldwide.

Investigations on seven sediment cores from the New Ireland Basin, east of Papua New Guinea

Sediment cores were recovered from the New Ireland Basin, east of Papua New Guinea, in order to investigate the late Quaternary eruptive history of the Tabar-Lihir-Tanga-Feni (TLTF) volcanic chain. Foraminifera d18O profiles were matched to the low-latitude oxygen isotope record to date the cores, which extend back to the early part of d18O Stage 9 (333 ka). Sedimentation rates decrease from >10 cm/1000 yr in cores near New Ireland to ~2 cm/1000 yr further offshore. The cores contain 36 discrete ash beds, mostly 1-8 cm thick and interpreted as either fallout or distal turbidite deposits. Most beds have compositionally homogeneous glass shard populations, indicating that they represent single volcanic events. Shards from all ash beds have the subduction-related pattern of strong enrichment in the large-ion lithophile elements relative to MORB, but three distinct compositional groups are apparent: Group A beds are shoshonitic and characterised by >1300 ppm Sr, high Ce/Yb and high Nb/Yb relative to MORB, Group B beds form a high-K series with MORB-like Nb/Yb but high Ce/Yb and well-developed negative Eu anomalies, whereas Group C beds are transitional between the low-K and medium-K series and characterised by flat chondrite-normalised REE patterns with low Nb/Yb relative to MORB. A comparison with published data from the TLTF chain, the New Britain volcanic arc and backarc including Rabaul, and Bagana on Bougainville demonstrates that only Group A beds share the distinctive phenocryst assemblage and shoshonitic geochemistry of the TLTF lavas. The crystal- and lithic-rich character of the Group A beds point to a nearby source, and their high Sr, Ce/Yb and Nb/Yb match those of Tanga and Feni lavas. A youthful stratocone on the eastern side of Babase Island in the Feni group is the most probable source. Group A beds younger than 20 ka are more fractionated than the older Group A beds, and record the progressive development of a shallow level magma chamber beneath the cone. In contrast, Group B beds represent glass-rich fallout from voluminous eruptions at Rabaul, whereas Group C beds represent distal glass-rich fallout from elsewhere along the volcanic front of the New Britain arc.

Biogenic composition of the sea-surface microlayer from a mesocosm study (Bergen 2011)

The sea-surface microlayer (SML) is the ocean's uppermost boundary to the atmosphere and in control of climate relevant processes like gas exchange and emission of marine primary organic aerosols (POA). The SML represents a complex surface film including organic components like polysaccharides, pro- teins, and marine gel particles, and harbors diverse microbial communities. Despite the potential relevance of the SML in ocean-atmosphere interactions, still little is known about its structural characteristics and sen- sitivity to a changing environment such as increased oceanic uptake of anthropogenic CO2. Here we report results of a large-scale mesocosm study, indicating that ocean acidification can affect the abundance and activity of microorganisms during phytoplankton blooms, resulting in changes in composition and dynam- ics of organic matter in the SML. Our results reveal a potential coupling between anthropogenic CO2 emis- sions and the biogenic properties of the SML, pointing to a hitherto disregarded feedback process between ocean and atmosphere under climate change.

Mn/Ca and Fe/Ca systematics in benthic foraminifera from the Peruvian OMZ

In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that the cleaning protocols are efficient or that spots chosen for microanalyses are free of contaminants. Prior to the determination of the element/Ca ratios, the distributions of several elements (Ca, Mn, Fe, Mg, Ba, Al, Si, P and S) in tests of the shallow infaunal species Uvigerina peregrina and Bolivina spissa were mapped with an electron microprobe (EMP). To visualize the effects of cleaning protocols uncleaned and cleaned specimens were compared. The cleaning protocol included an oxidative cleaning step. An Fe rich phase was found on the inner test surface of uncleaned U. peregrina specimens. This phase was also enriched in Al, Si, P and S. A similar Fe rich phase was found at the inner test surface of B. spissa. Specimens of both species treated with oxidative cleaning show the absence of this phase. Neither in B. spissa nor in U. peregrina were any hints found for diagenetic (oxyhydr)oxide or carbonate coatings. Mn/Ca and Fe/Ca ratios of single specimens of B. spissa from different locations have been determined by secondary ion mass spectrometry (SIMS). Bulk analyses using solution ICP-MS of several samples were compared to the SIMS data. The difference between SIMS analyses and ICP-MS bulk analyses from the same sampling sites was 14.0-134.8 µmol mol-1 for the Fe/Ca and 1.68(±0.41) µmol mol-1 for the Mn/Ca ratios. This is in the same order of magnitude as the variability inside single specimens determined with SIMS at these sampling sites (1sigma[Mn/Ca] = 0.35-2.07 µmol mol-1; 1sigma[Fe/Ca] = 93.9-188.4 µmol mol-1). The Mn/Ca ratios in the calcite were generally relatively low (2.21-9.93 µmol mol-1) but in the same magnitude and proportional to the surrounding pore waters (1.37-6.67 µmol mol-1). However, the Fe/Ca ratios in B. spissa show a negative correlation to the concentrations in the surrounding pore waters. Lowest foraminiferal Fe/Ca ratios (87.0-101.0 µmol mol-1) were found at 465 m water depth, a location with a strong sharp Fe peak in the pore water next to the sediment surface and respectively, high Fe concentrations in the surrounding pore waters. Previous studies found no living specimens of B. spissa at this location. All these facts hint that the analysed specimens already were dead before the Fe flux started and the sampling site just recently turned anoxic due to fluctuations of the lower boundary of the OMZ near the sampling site (465 m water depth). Summarized Mn/Ca and Fe/Ca ratios are potential proxies for redox conditions, if cleaning protocols are carefully applied. The data presented here may be rated as base for the still pending detailed calibration.

Seawater calcium isotope ratios across the Eocene-Oligocene Transition from Pacific Ocean - Marine Barite

During the Eocene-Oligocene transition (EOT, ca. 34 Ma), Earth's climate cooled significantly from a greenhouse to an icehouse climate, while the calcite (CaCO3) compensation depth (CCD) in the Pacific Ocean increased rapidly. Fluctuations in the CCD could result from various processes that create an imbalance between calcium (Ca) sources to, and sinks from, the ocean (e.g., weathering and CaCO3 deposition), with different effects on the isotopic composition of dissolved Ca in the oceans due to differences in the Ca isotopic composition of various inputs and outputs. We used Ca isotope ratios (d44/40Ca) of coeval pelagic marine barite and bulk carbonate to evaluate changes in the marine Ca cycle across the EOT. We show that the permanent deepening of the CCD was not accompanied by a pronounced change in seawater d44/40Ca, whereas time intervals in the Neogene with smaller carbonate depositional changes are characterized by seawater d44/40Ca shifts. This suggests that the response of seawater d44/40Ca to changes in weathering fluxes and to imbalances in the oceanic alkalinity budget depends on the chemical composition of seawater. A minor and transient fluctuation in the Ca isotope ratio of bulk carbonate may reflect a change in isotopic fractionation associated with CaCO3 precipitation from seawater due to a combination of factors, including changes in temperature and/or in the assemblages of calcifying organisms.

Nitrogen cycling driven by organic matter export in the South Pacific oxygen minimum zone

Oxygen minimum zones are expanding globally, and at present account for around 20-40% of oceanic nitrogen loss. Heterotrophic denitrification and anammox-anaerobic ammonium oxidation with nitrite-are responsible for most nitrogen loss in these low-oxygen waters. Anammox is particularly significant in the eastern tropical South Pacific, one of the largest oxygen minimum zones globally. However, the factors that regulate anammox-driven nitrogen loss have remained unclear. Here, we present a comprehensive nitrogen budget for the eastern tropical South Pacific oxygen minimum zone, using measurements of nutrient concentrations, experimentally determined rates of nitrogen transformation and a numerical model of export production. Anammox was the dominant mode of nitrogen loss at the time of sampling. Rates of anammox, and related nitrogen transformations, were greatest in the productive shelf waters, and tailed off with distance from the coast. Within the shelf region, anammox activity peaked in both upper and bottom waters. Overall, rates of nitrogen transformation, including anammox, were strongly correlated with the export of organic matter. We suggest that the sinking of organic matter, and thus the release of ammonium into the water column, together with benthic ammonium release, fuel nitrogen loss from oxygen minimum zones.

Biometric measurements of Fragilariopsis kerguelensis

The valve area of Fragilariopsis kerguelensis, the most abundant diatom species in the Southern Ocean, strongly changes in size in response to varying conditions in the surface ocean. We examined the link, both in two iron fertilization experiments and in sediment samples covering several glacial Terminations, between size variability in this species and environmental conditions across the Antarctic Polar Front, including sea ice extent, sea surface temperature, and the input of eolian dust. The iron fertilization experiments show valve area to be positively correlated with iron concentrations in ambient waters, which suggests the possibility of a causal relation between valve size of Fragilariopsis kerguelensis and ambient surface water iron concentration. Larger valves are usually found during glacial times and thus seem to be related to lower sea surface temperature and wider sea ice coverage. Moreover, our results indicate that there usually is a strong correlation between larger valve size and increased input of eolian dust to the Southern Ocean. However, this correlation, obvious for the fertilization experiments and for glacial Terminations I, II, III, and V, does not seem to be valid for Termination VI, where size appears to be inversely correlated to dust input.

Thyroid hormones and halogenated organic compounds in black-legged kittiwake (Rissa tridactyla) and northern fulmar (Fulmarus glacialis)

Thyroid hormones are essential for normal growth and development and disruption of thyroid homeostasis can be critical to young developing individuals. The aim of the present study was to assess plasma concentrations of halogenated organic contaminants (HOCs) in chicks of two seabird species and to investigate possible correlations of HOCs with circulating thyroid hormone (TH) concentrations. Plasma from black-legged kittiwake (Rissa tridactyla) and northern fulmar (Fulmarus glacialis) chicks were sampled in Kongsfjorden, Svalbard in 2006. The samples were analyzed for thyroid hormones and a wide range of HOCs (polychlorinated biphenyls (PCBs), hydroxylated (OH-) and methylsulphoned (MeSO-) PCB metabolites, organochlorine pesticides (OCPs), brominated flame retardants (BFRs), and perfluorinated compounds (PFCs)). Concentrations of HOCs were generally low in kittiwake and fulmar chicks compared to previous reports. HOC concentrations were five times higher in fulmar chicks compared to in kittiwake chicks. PFCs dominated the summed HOCs concentrations in both species (77% in kittiwakes and 69% in fulmars). Positive associations between total thyroxin (TT4) and PFCs (PFHpS, PFOS, PFNA) were found in both species. Although correlations do not implicate causal relationships per se, the correlations are of concern as disruption of TH homeostasis may cause developmental effects in young birds.

Seasonal mean air temperatures and ice phenology characteristics of Great Bear Lake and Great Slave Lake (2002-2009)

Time series of brightness temperatures (T(B)) from the Advanced Microwave Scanning Radiometer-Earth Observing System (AMSR-E) are examined to determine ice phenology variables on the two largest lakes of northern Canada: Great Bear Lake (GBL) and Great Slave Lake (GSL). T(B) measurements from the 18.7, 23.8, 36.5, and 89.0 GHz channels (H- and V- polarization) are compared to assess their potential for detecting freeze-onset/melt-onset and ice-on/ice-off dates on both lakes. The 18.7 GHz (H-pol) channel is found to be the most suitable for estimating these ice dates as well as the duration of the ice cover and ice-free seasons. A new algorithm is proposed using this channel and applied to map all ice phenology variables on GBL and GSL over seven ice seasons (2002-2009). Analysis of the spatio-temporal patterns of each variable at the pixel level reveals that: (1) both freeze-onset and ice-on dates occur on average about one week earlier on GBL than on GSL (Day of Year (DY) 318 and 333 for GBL; DY 328 and 343 for GSL); (2) the freeze-up process or freeze duration (freeze-onset to ice-on) takes a slightly longer amount of time on GBL than on GSL (about 1 week on average); (3) melt-onset and ice-off dates occur on average one week and approximately four weeks later, respectively, on GBL (DY 143 and 183 for GBL; DY 135 and 157 for GSL); (4) the break-up process or melt duration (melt-onset to ice-off) lasts on average about three weeks longer on GBL; and (5) ice cover duration estimated from each individual pixel is on average about three weeks longer on GBL compared to its more southern counterpart, GSL. A comparison of dates for several ice phenology variables derived from other satellite remote sensing products (e.g. NOAA Interactive Multisensor Snow and Ice Mapping System (IMS), QuikSCAT, and Canadian Ice Service Database) show that, despite its relatively coarse spatial resolution, AMSR-E 18.7 GHz provides a viable means for monitoring of ice phenology on large northern lakes.

Shell size, body mass and average pO2 in mantle cavity water of different marine mollusc species

Marine invertebrates with open circulatory system establish low and constant oxygen partial pressure (Po2) around their tissues. We hypothesized that as a first step towards maintenance of low haemolymph and tissue oxygenation, the Po2 in molluscan mantle cavity water should be lowered against normoxic (21 kPa) seawater Po2, but balanced high enough to meet the energetic requirements in a given species. We recorded Po2 in mantle cavity water of five molluscan species with different lifestyles, two pectinids (Aequipecten opercularis, Pecten maximus), two mud clams (Arctica islandica, Mya arenaria), and a limpet (Patella vulgata). All species maintain mantle cavity water oxygenation below normoxic Po2. Average mantle cavity water Po2 correlates positively with standard metabolic rate (SMR): highest in scallops and lowest in mud clams. Scallops show typical Po2 frequency distribution, with peaks between 3 and 10 kPa, whereas mud clams and limpets maintain mantle water Po2 mostly <5 kPa. Only A. islandica and P. vulgata display distinguishable temporal patterns in Po2 time series. Adjustment of mantle cavity Po2 to lower than ambient levels through controlled pumping prevents high oxygen gradients between bivalve tissues and surrounding fluid, limiting oxygen flux across the body surface. The patterns of Po2 in mantle cavity water correspond to molluscan ecotypes.

Geochemistry, isotopic ratios and aldehyde concentrations of frost flowers, snow and ice near Barrow, Alaska

Frost flowers, intricate featherlike crystals that grow on refreezing sea ice leads, have been implicated in lower atmospheric chemical reactions. Few studies have presented chemical composition information for frost flowers over time and many of the chemical species commonly associated with Polar tropospheric reactions have never been reported for frost flowers. We undertook this study on the sea ice north of Barrow, Alaska to quantify the major ion, stable oxygen and hydrogen isotope, alkalinity, light absorbance by soluble species, organochlorine, and aldehyde composition of seawater, brine, and frost flowers. For many of these chemical species we present the first measurements from brine or frost flowers. Results show that major ion and alkalinity concentrations, stable isotope values, and major chromophore (NO3- and H2O2) concentrations are controlled by fractionation from seawater and brine. The presence of these chemical species in present and future sea ice scenarios is somewhat predictable. However, aldehydes, organochlorine compounds, light absorbing species, and mercury (part 2 of this research and Sherman et al. (2012, doi:10.1029/2011JD016186)) are deposited to frost flowers through less predictable processes that probably involve the atmosphere as a source. The present and future concentrations of these constituents in frost flowers may not be easily incorporated into future sea ice or lower atmospheric chemistry scenarios. Thinning of Arctic sea ice will likely present more open sea ice leads where young ice, brine, and frost flowers form. How these changing ice conditions will affect the interactions between ice, brine, frost flowers and the lower atmosphere is unknown.