(Table 3) Air temperatures, and snow and ice characteristics of fresh and brackish water lakes in the Northwest Territories, Canada

The algorithms designed to estimate snow water equivalent (SWE) using passive microwave measurements falter in lake-rich high-latitude environments due to the emission properties of ice covered lakes on low frequency measurements. Microwave emission models have been used to simulate brightness temperatures (Tbs) for snowpack characteristics in terrestrial environments but cannot be applied to snow on lakes because of the differing subsurface emissivities and scattering matrices present in ice. This paper examines the performance of a modified version of the Helsinki University of Technology (HUT) snow emission model that incorporates microwave emission from lake ice and sub-ice water. Inputs to the HUT model include measurements collected over brackish and freshwater lakes north of Inuvik, Northwest Territories, Canada in April 2008, consisting of snowpack (depth, density, and snow water equivalent) and lake ice (thickness and ice type). Coincident airborne radiometer measurements at a resolution of 80x100 m were used as ground-truth to evaluate the simulations. The results indicate that subsurface media are simulated best when utilizing a modeled effective grain size and a 1 mm RMS surface roughness at the ice/water interface compared to using measured grain size and a flat Fresnel reflective surface as input. Simulations at 37 GHz (vertical polarization) produce the best results compared to airborne Tbs, with a Root Mean Square Error (RMSE) of 6.2 K and 7.9 K, as well as Mean Bias Errors (MBEs) of -8.4 K and -8.8 K for brackish and freshwater sites respectively. Freshwater simulations at 6.9 and 19 GHz H exhibited low RMSE (10.53 and 6.15 K respectively) and MBE (-5.37 and 8.36 K respectively) but did not accurately simulate Tb variability (R= -0.15 and 0.01 respectively). Over brackish water, 6.9 GHz simulations had poor agreement with airborne Tbs, while 19 GHz V exhibited a low RMSE (6.15 K), MBE (-4.52 K) and improved relative agreement to airborne measurements (R = 0.47). Salinity considerations reduced 6.9 GHz errors substantially, with a drop in RMSE from 51.48 K and 57.18 K for H and V polarizations respectively, to 26.2 K and 31.6 K, although Tb variability was not well simulated. With best results at 37 GHz, HUT simulations exhibit the potential to track Tb evolution, and therefore SWE through the winter season.

Hexachlorocyclohexanes concentration in air and ocean water

Hexachlorocyclohexanes (HCHs) are ubiquitous organic pollutants derived from pesticide application. They are subject to long-range transport, persistent in the environment, and capable of accumulation in biota. Shipboard measurements of HCH isomers (a-, b- and g-HCH) in surface seawater and boundary layer atmospheric samples were conducted in the Atlantic and the Southern Ocean in October to December of 2008. SumHCHs concentrations (the sum of a-, g- and b-HCH) in the lower atmosphere ranged from 12 to 37 pg/m**3 (mean: 27 ± 11 pg/m**3) in the Northern Hemisphere (NH), and from 1.5 to 4.0 pg/m**3 (mean: 2.8 ± 1.1 pg/m**3) in the Southern Hemisphere (SH), respectively. Water concentrations were: a-HCH 0.33-47 pg/l, g-HCH 0.02-33 pg/l and b-HCH 0.11-9.5 pg/l. Dissolved HCH concentrations decreased from the North Atlantic to the Southern Ocean, indicating historical use of HCHs in the NH. Spatial distribution showed increasing concentrations from the equator towards North and South latitudes illustrating the concept of cold trapping in high latitudes and less interhemispheric mixing process. In comparison to concentrations measured in 1987-1999/2000, gaseous HCHs were slightly lower, while dissolved HCHs decreased by factor of 2-3 orders of magnitude. Air-water exchange gradients suggested net deposition for a-HCH (mean: 3800 pg/m**2/day) and g-HCH (mean: 2000 pg/m**2/day), whereas b-HCH varied between equilibrium (volatilization: <0-12 pg/m**2/day) and net deposition (range: 6-690 pg/m**2/day). Climate change may significantly accelerate the release of "old" HCHs from continental storage (e.g. soil, vegetation and high mountains) and drive long-range transport from sources to deposition in the open oceans. Biological productivities may interfere with the air-water exchange process as well. Consequently, further investigation is necessary to elucidate the long term trends and the biogeochemical turnover of HCHs in the oceanic environment.

Ages and stable isotope ratios from speleothem calcite from Cold Water Cave, Iowa

High-precision uranium-thorium mass spectrometric chronology and 18O-13C isotopic analysis of speleothem calcite from Cold Water Cave in northeast Iowa have been used to chart mid-Holocene climate change. Significant shifts in d18O and d13C isotopic values coincide with well-documented Holocene vegetation changes. Temperature estimates based on 18O/16O ratios suggest that the climate warmed rapidly by about 3°C at 5900 years before present and then cooled by 4°C at 3600 years before present. Initiation of a gradual increase in ?d13C at 5900 years before present suggests that turnover of the forest soil biomass was slow and that equilibrium with prairie vegetation was not attained by 3600 years before present.

Contiunous surface water uncorrected and quench-corrected active fluorescence and derived chlorophyll a concentration using calibration by HPLC pigments during POLARSTERN cruise ANT-XXV/1

The relationship between phytoplankton assemblages and the associated optical properties of the water body is important for the further development of algorithms for large-scale remote sensing of phytoplankton biomass and the identification of phytoplankton functional types (PFTs), which are often representative for different biogeochemical export scenarios. Optical in-situ measurements aid in the identification of phytoplankton groups with differing pigment compositions and are widely used to validate remote sensing data. In this study we present results from an interdisciplinary cruise aboard the RV Polarstern along a north-to-south transect in the eastern Atlantic Ocean in November 2008. Phytoplankton community composition was identified using a broad set of in-situ measurements. Water samples from the surface and the depth of maximum chlorophyll concentration were analyzed by high performance liquid chromatography (HPLC), flow cytometry, spectrophotometry and microscopy. Simultaneously, the above- and underwater light field was measured by a set of high spectral resolution (hyperspectral) radiometers. An unsupervised cluster algorithm applied to the measured parameters allowed us to define bio-optical provinces, which we compared to ecological provinces proposed elsewhere in the literature. As could be expected, picophytoplankton was responsible for most of the variability of PFTs in the eastern Atlantic Ocean. Our bio-optical clusters agreed well with established provinces and thus can be used to classify areas of similar biogeography. This method has the potential to become an automated approach where satellite data could be used to identify shifting boundaries of established ecological provinces or to track exceptions from the rule to improve our understanding of the biogeochemical cycles in the ocean.

Objective Mapping of Argo data in the Weddell Gyre: a gridded dataset of upper ocean water properties, link to data files in NetCDF format

The Weddell Gyre plays a crucial role in the regulation of climate by transferring heat into the deep ocean through deep and bottom water mass formation. However, our understanding of Weddell Gyre water mass properties is limited to regions of data availability, primarily along the Prime Meridian. The aim is to provide a dataset of the upper water column properties of the entire Weddell Gyre. Objective mapping was applied to Argo float data in order to produce spatially gridded, time composite maps of temperature and salinity for fixed pressure levels ranging from 50 to 2000 dbar, as well as temperature, salinity and pressure at the level of the sub-surface temperature maximum. While the data are currently too limited to incorporate time into the gridded structure, the data are extensive enough to produce maps of the entire region across three time composite periods (2002-2005, 2006-2009 and 2010-2013), which can be used to determine how representative conclusions drawn from data collected along general RV transect lines are on a gyre scale perspective. The time composite data sets are provided as netCDF files; one for each time period. Mapped fields of conservative temperature, absolute salinity and potential density are provided for 41 vertical pressure levels. The above variables as well as pressure are provided at the level of the sub-surface temperature maximum. Corresponding mapping errors are also included in the netCDF files. Further details are provided in the global attributes, such as the unit variables and structure of the corresponding data array (i.e. latitude x longitude x vertical pressure level). In addition, all files ending in "_potTpSal" provide mapped fields of potential temperature and practical salinity.

Composition of pore water and diagenetic carbonates of ODP Site 123-765

Degradation of organic matter in slightly organic-rich (1 wt% organic carbon) Neogene calcareous turbidites of the Argo Basin at Site 765 by sulfate reduction results in pore-water phosphate, ammonium, manganese, and carbonate alkalinity maxima. Pore-water calcium and magnesium decrease in the uppermost 100 meters below seafloor (mbsf) in response to the precipitation of calcian dolomite with an average composition of Ca1.15Mg0.83Fe0.02(CO3)2. Clear, euhedral dolomite rhombs range from <1 to 40 µm in diameter and occur in trace to minor amounts (<1-2 wt%) in Pleistocene to Pliocene sediment (62-210 mbsf) The abundance of dolomite increases markedly (2-10 wt%) in Miocene sediment (210-440 mbsf). The dolomite is associated with diagenetic sepiolite and palygorskite, as well as redeposited biogenic low-Mg calcite and aragonitic benthic foraminifers. Currently, dolomite is precipitating at depth within the pore spaces of the sediment, largely as a result of aragonite dissolution. The rate of aragonite dissolution, calculated from the pore-water strontium profile, is sufficient to explain the amount of dolomite observed at Site 765. A foraminiferal aragonite precursor is further supported by the carbon and oxygen isotopic compositions of the dolomite, which are fairly close to the range of isotopic compositions observed for Miocene benthic foraminifers. Dolomite precipitation is promoted by the degradation of organic matter by sulfate-reducing bacteria because the lower pore-water sulfate concentration reduces the effect of sulfate inhibition on the dolomite reaction and because the higher carbonate alkalinity increases the degree of saturation of the pore waters with dolomite. Organic matter degradation also results in the precipitation of pyrite and trace amounts of apatite (francolite), and the release of iron and manganese to the pore water by reduction of Fe and Mn oxides. Spherical, silt-sized aggregates of microcrystalline calcian rhodochrosite occur in trace to minor amounts in Lower Cretaceous sediment from 740 to 900 mbsf at Site 765. A negative carbon isotopic composition suggests that the rhodochrosite formed early in the sulfate reduction zone, but a depleted oxygen isotopic composition suggests that the rhodochrosite may have recrystallized at deeper burial depths.

Depth profiles of pore-water and solid-phase constituents, respiration rates and grain size distribution in sediments of the Clarion-Clipperton Fracture Zone

Manganese nodules of the Clarion-Clipperton Fracture Zone (CCFZ) in the NE Pacific Ocean are highly enriched in Ni, Cu, Co, Mo and rare-earth elements, and thus may be the subject of future mining operations. Elucidating the depositional and biogeochemical processes that contribute to nodule formation, as well as the respective redox environment in both, water column and sediment, supports our ability to locate future nodule deposits and evaluates the potential ecological and environmental effects of future deep-sea mining. For these purposes we evaluated the local hydrodynamics and pore-water geochemistry with respect to the nodule coverage at four sites in the eastern CCFZ. Furthermore, we carried out selective leaching experiments at these sites in order to assess the potential mobility of Mn in the solid phase, and compared them with the spatial variations in sedimentation rates. We found that the oxygen penetration depth is 180 - 300 cm at all four sites, while reduction of Mn and NO3- is only significant below the oxygen penetration depth at sites with small or no nodules on the sediment surface. At the site without nodules, potential microbial respiration rates, determined by incubation experiments using 14C-labelled acetate, are slightly higher than at sites with nodules. Leaching experiments showed that surface sediments covered with big or medium-sized nodules are enriched in mobilizable Mn. Our deep oxygen measurements and pore-water data suggest that hydrogenetic and oxic-diagenetic processes control the present-day nodule growth at these sites, since free manganese from deeper sediments is unable to reach the sediment surface. We propose that the observed strong lateral contrasts in nodule size and abundance are sensitive to sedimentation rates, which in turn, are controlled by small-scale variations in seafloor topography and bottom-water current intensity.

H, O, Sr, and Nd isotope ratios and water, Rb, Sr, Sm, and Nd content of ODP Hole 116-717C and 116-718C samples (Table 2)

Mineralogical and H, O, Sr, and Nd isotope compositions have been analyzed on a set of representative samples from the 17-m.y. section in ODP Leg 116 Holes 717C and 718C. Based on the mineralogical composition of the fraction <2 µm together with the lithogenic-biogenic composition of the fraction >63 µm, the whole section can be subdivided into three major periods of sedimentation. Between 17.1 and 6 m.y., and between 0.8 m.y. to present, the sediments are characterized by sandy and silty turbiditic inputs with a high proportion of minerals derived from a gneissic source without alteration. In the fraction <2 µm, illite and chlorite are dominant over smectite and kaolinite. The granulometric fraction >63 µm contains quartz, muscovite, biotite, chlorite, and feldspars. The 6-to 0.8-m.y. period is represented by an alternation of sandy/silty horizons, muds, and calcareous muds rich in smectite, and kaolinite (50% to 85% of the fraction <2 µm) and bioclastic material. The presence of smectite and kaolinite, as well as the 18O/16O and the 87Sr/86Sr ratios of the fraction <2 µm, imply an evolution in a soil environment and exchanges with meteoric ground water. The ranges of isotopic compositions are limited throughout the section: d18O quartz = 11.7 to 13.3 per mil, 87Sr/86Sr = 0.733 to 0.760 and epsilon-Nd (0) = -17.4 to -13.8. These values are within those of the High Himalaya Crystalline series, and they are considered to reflect this source region. The data imply that, since 17 Ma, this formation has supplied the major part of the eroded material.

Quaternary surface-water stable isotope signal from calcareous nannofossils at DSDP Site 90-593, South Tasman Sea

Oxygen isotope values from calcareous nannofossils in four cores spanning the Quaternary from DSDP Site 593 in Tasman Sea are compared with the delta18O signal of planktonic and benthic foraminifers from the same samples. The classic mid-late Quaternary isotope stages are exhibited with stage 12 particularly well developed. When delta18O values of nannofossils are adjusted for coccolithophore vital effects they indicate larger (by 1-6°C) surface to bottom paleotemperature gradients and greater (by 1-3°C) changes in mean sea-surface temperature between full glacial and interglacial conditions than do delta18O values from planktonic foraminifers. Along with the foraminifers, the nannofossils record a bimodal distribution of delta18O between the early and mid-late Quaternary, indicating a significant change in global ice budget. The delta13C of nannofossils also shows a bimodal distribution, but is opposite to that for the foraminifers. Nannofossil delta18O values record a shift of c. -0.8? at isotope stage 8 corresponding to a major reduction in abundance of the previously dominant gephyrocapsids. A shift in delta13C of c. -1.5? also occurs at stage 8, and a shift in delta13C of c. +1.2? at around stage 14. The delta18O shift in nannofossils is at least a Pacific-wide phenomenon; the delta13C shifts are possibly global. The delta13C signal of nannofossils exhibits an antipathetic relationship to that of benthic foraminifers back to isotope stage 18 but no significant correlation beyond this level to the base of the Quaternary. This is interpreted as reflecting local productivity dominating global influences on delta13C since stage 18 at DSDP Site 593. The difference between nannofossil and benthic foraminifer delta13C signals (Delta13C) tends to be maximum during glacial stages and minimum during interglacials throughout the section, showing a strong correlation with the nannofossil delta180 signal. The increased partitioning of 13C between surface and bottom waters during the glacial periods may indicate heightened productivity in surface waters in the southern Tasman Sea at these times.

Interstitial-water chemistry of ODP Leg 119 sites

Ocean Drilling Program inorganic geochemistry procedures routinely overlook more than 99% of the sediment column. Present and past biogeochemical reactions alter the sediment record; however, most of these reaction zones are bypassed by the normal methods where samples are collected every 30 m. A new approach to increase resolution was introduced during Leg 119. Ten milliliters of sediment provided interstitial-water samples for ammonia, silica, sulfate, magnesium, and calcium analyses. The new method introduced some systematic differences in concentrations, as well as some decrease in precision. A number of advantages, however, may warrant using the method in some instances. In cases where routine interstitial-water data showed anomalous results, core sections were retrieved from the storage facility and resampled. The new high-resolution procedure was used to provide water samples in cases were water contents were low and routine squeezing could not recover pore water.

Siliceous microplankton in surface sediments and the water column of the Red Sea

We studied the siliceous microplankton assemblages (mainly diatoms) from plankton tows (mesh size 20 µm) and surface sediment samples collected along a N-S transect in the northern Red Sea (28-21°N). In addition, we analyzed differences/similarities between plankton and sediment assemblages within a brine-filled basin (the southern basin) of the Shaban Deep and compared these assemblages with those from outside the brine. Plankton samples revealed the overwhelming dominance of diatoms over other siliceous groups. Diatoms accounted for ca. 97% of all biosiliceous particles at 120-20 m (vs. 2.9% silicoflagellates and 0.4% radiolarians), and ca. 94% at 200-120 m (vs. 4.5% silicoflagellates and 1.6% radiolarians). In general, a marine, warm-water (tropical/subtropical) diatom assemblage characterizes the plankton samples. Representatives of the Nitzschia bicapitata group are by far the most abundant contributors at both depth intervals (average=43%), ranging from ca. 30% in the North to ca. 60% in the South. Biogenic opal content in non-brine surface sediments is very low, (below 0.2 wt.% SiO2); and concentration of siliceous microorganisms is also low and of the order of 5*10**3-10**4 microorganisms/g dry sediment. Diatoms are the main contributors to the opal signal in the 20-40 µm fraction, while they share dominance with radiolarians in the >40 µm fraction. Total diatom concentrations average 1.2*10**4 valves/g in the 20-40 µm fraction and 4*10**3 valves/g in the >40 µm fraction. Robust taxa of warm water affinity (Alveus marinus, Azpeitia neocrenulata, Azpeitia nodulifera and Roperia tesselata) characterize the surface sediments. In contrast, biogenic opal content in brine surface sediment samples is much higher than in the non-brine samples, ranging from 2.8 to 3.8 wt.% SiO2, and concentration of siliceous microorganisms is 3-4 orders of magnitude higher. In addition here, diatoms dominate the opal signal. The taxa found in these samples are a mixture of non-brine and plankton samples, and fragile forms (e.g., N. bicapitata group, Neodelphineis indica) are well preserved in these sediments. Thus, brine sediments in this region seem to offer a great potential for palaeoenvironmental studies.

Pore water (SO4, CH4, alkalinity, HS-, Ca, Sr, Mg, Ba) and solid phase (Ca, Sr, Mg, Ba) data measured in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1-4), 93-109, doi:10.1016/j.margeo.2007.03.007]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

Stable C and N isotopes and percent C as well as N composition of plankton from the North Atlantic

Elemental C and N percent composition and natural abundance of stable C and N isotopes of plankton species and/or size-fractions collected in several cruises on the N Atlantic Ocean from Greenland to Norway and around Iceland. Determinations included key copepod and krill species. Lipid extraction was performed in some samples to determine carbón isotope depletion factors.

Results of a Finite-Element Sea-Ice Ocean Model (FESOM) set-up to study the interannual to decadal variability in the deep-water formation rates

The characteristics of a global set-up of the Finite-Element Sea-Ice Ocean Model under forcing of the period 1958-2004 are presented. The model set-up is designed to study the variability in the deep-water mass formation areas and was therefore regionally better resolved in the deep-water formation areas in the Labrador Sea, Greenland Sea, Weddell Sea and Ross Sea. The sea-ice model reproduces realistic sea-ice distributions and variabilities in the sea-ice extent of both hemispheres as well as sea-ice transport that compares well with observational data. Based on a comparison between model and ocean weather ship data in the North Atlantic, we observe that the vertical structure is well captured in areas with a high resolution. In our model set-up, we are able to simulate decadal ocean variability including several salinity anomaly events and corresponding fingerprint in the vertical hydrography. The ocean state of the model set-up features pronounced variability in the Atlantic Meridional Overturning Circulation as well as the associated mixed layer depth pattern in the North Atlantic deep-water formation areas.