Pore water chemistry of ODP Sites 201-1225, 201-1226 and 201-1231

High-resolution analyses of the oxygen isotope ratio (18O/16O) of dissolved sulfate in pore waters have been made to depths of >400 meters below seafloor (mbsf) at open-ocean and upwelling sites in the eastern equatorial Pacific Ocean. d18O values of dissolved sulfate (d18O-SO4) at the organic-poor open-ocean Site 1231 gave compositions close to modern seawater (+9.5 per mil vs. Vienna-standard mean ocean water, providing no chemical or isotopic evidence for microbial sulfate reduction (MSR). In contrast, the maximum d18O values at Sites 1225 and 1226, which contain higher organic matter contents, are +20 per mil and +28 per mil, respectively. Depth-correlative trends of increasing d18O-SO4, alkalinity, and ammonium and the presence of sulfide indicate significant oxidation of sedimentary organic matter by sulfate-reducing microbial populations at these sites. Although sulfate concentration profiles at Sites 1225 and 1231 both show similarly flat trends without significant net MSR, d18O-SO4 values at Site 1225 reveal the presence of significant microbial sulfur-cycling activity, which contrasts to Site 1231. This activity may include contributions from several processes, including enzyme-catalyzed equilibration between oxygen in sulfate and water superimposed upon bacterial sulfate reduction, which would tend to shift d18O-SO4 toward higher values than MSR alone, and sulfide oxidation, possibly coupled to reduction of Fe and Mn oxides and/or bacterial disproportionation of sulfur intermediates. Large isotope enrichment factors observed at Sites 1225 and 1226 (epsilon values between 42 per mil and 79 per mil) likely reflect concurrent processes of kinetic isotope fractionation, equilibrium fractionation between sulfate and water, and sulfide oxidation at low rates of sulfate reduction. The oxygen isotope ratio of dissolved pore water sulfate is a powerful tool for tracing microbial activity and sulfur cycling by the deep biosphere of deep-sea sediments.

Interstitial water chemistry at DSDP Leg 67 Holes

Interstitial water chemistry has proved to be a sensitive indicator for early diagenetic reactions, particularly those related to organic matter oxidation. Downhole chemical variations in the pore waters from Deep Sea Drilling Project Holes 496 and 497 on the Middle America Trench slope off Guatemala are anomalous because both salinity and chlorinity show strong decreases to half the values of seawater, and d18O values become positive (maximum of about +2.5% at the bottom of the holes). These observations are explained in terms of dilution of pore waters after retrieval as a result of decomposition of the gas hydrates before removal of pore waters by shipboard squeezing techniques. In all holes, except Hole 495 (drilled in pelagic sediments), decomposition of organic matter leads to rapid sulfate depletion and subsequent methane generation. Associated with methane generation are large increases in alkalinity and dissolved ammonia. The latter component causes ion exchange reactions with clay minerals, which results in maxima in magnesium and perhaps potassium. At greater depths, as yet unidentified reactions cause the removal of magnesium. Especially in the deeper Trench Sites 499 and 500, rapid variations in calcium, magnesium, and alkalinity occur in turbidite sequences.

Hydrography and water chemistry of the open Mediterranean Sea

On a cruise from the eastern into western Mediterranean Sea in November/December 1978 a total of 126 samples were collected from 8 vertical profiles and 7 coastal stations for trace metal analysis. The sampling, processing and analysis was performed under strict "clean room" conditions. The concentration of the open-sea samples are close to oceanic results gathered under similar conditions. The grand averages from all profiles (± st. dev. of the individual samples) of 0.40 ± 0.16 µg/l Zn, 17.4 ± 7.4 ng/l Cd, 0.21 ± 0.07 µg/l Cu, 0.21 ± 0.13 µg/l Mn and 0.25 ± 0.09 µg/l Fe indicate that a "metal problem" does not exist in the open Mediterranean. A biologically mediated deplition in surface waters or correlation with nutrients have not been observed under the conditions established on this cruise. This is probably due top low primary production and seasonal advection processes prevailing in this sea. The data for manganese show generally higher values in the surface layer (0-75 m) than in deep waters. This could evidently proved in the nearshore profile indicating a terrigenous source for manganese.

Water chemistry and heat budget of the Churchill River estuary region

A conceptual scheme for the transition from winter to spring is developed for a small Arctic estuary (Churchill River, Hudson Bay) using hydrological, meteorological and oceanographic data together with models of the landfast ice. Observations within the Churchill River estuary and away from the direct influence of the river plume (Button Bay), between March and May 2005, show that both sea ice (production and melt) and river water influence the region's freshwater budget. In Button Bay, ice production in the flaw lead or polynya of NW Hudson Bay result in salinization through winter until the end of March, followed by a gradual freshening of the water column through April-May. In the Churchill Estuary, conditions varied abruptly throughout winter-spring depending on the physical interaction among river discharge, the seasonal landfast ice, and the rubble zone along the seaward margin of the landfast ice. Until late May, the rubble zone partially impounded river discharge, influencing the surface salinity, stratification, flushing time, and distribution and abundance of nutrients in the estuary. The river discharge, in turn, advanced and enhanced sea ice ablation in the estuary by delivering sensible heat. Weak stratification, the supply of riverine nitrogen and silicate, and a relatively long flushing time (~6 days) in the period preceding melt may have briefly favoured phytoplankton production in the estuary when conditions were still poor in the surrounding coastal environment. However, in late May, the peak flow and breakdown of the ice-rubble zone around the estuary brought abrupt changes, including increased stratification and turbidity, reduced marine and freshwater nutrient supply, a shorter flushing time, and the release of the freshwater pool into the interior ocean. These conditions suppressed phytoplankton productivity while enhancing the inventory of particulate organic matter delivered by the river. The physical and biological changes observed in this study highlight the variability and instability of small frozen estuaries during winter-spring transition, which implies sensitivity to climate change.

Borehole temperature, submarine permafrost methane concentrations and pore water chemistry measured on borehole BK2, central Laptev Sea shelf

Submarine permafrost degradation has been invoked as a cause for recent observations of methane emissions from the seabed to the water column and atmosphere of the East Siberian shelf. Sediment drilled 52 m down from the sea ice in Buor Khaya Bay, central Laptev Sea revealed unfrozen sediment overlying ice-bonded permafrost. Methane concentrations in the overlying unfrozen sediment were low (mean 20 µM) but higher in the underlying ice-bonded submarine permafrost (mean 380 µM). In contrast, sulfate concentrations were substantially higher in the unfrozen sediment (mean 2.5 mM) than in the underlying submarine permafrost (mean 0.1 mM). Using deduced permafrost degradation rates, we calculate potential mean methane efflux from degrading permafrost of 120 mg/m**2 per year at this site. However, a drop of methane concentrations from 190 µM to 19 µM and a concomitant increase of methane d13C from -63 per mil to -35 per mil directly above the ice-bonded permafrost suggest that methane is effectively oxidized within the overlying unfrozen sediment before it reaches the water column. High rates of methane ebullition into the water column observed elsewhere are thus unlikely to have ice-bonded permafrost as their source.

Pore-water chemistry of ODP Sites 124-767 and 124-768

The combination of multiple sediment sources and varying rates of sediment accumulation in the Celebes and Sulu seas have had significant impact on the processes of diagenesis, mineralization, and pore-fluid flow. Isotopic and mass-balance calculations help elucidate the various reactions taking place in these western Pacific basins, where ash alteration and basalt-seawater interactions are superimposed on the effects of sulfate oxidation of organic carbon and biogenic methane and of dolomitization of biogenic carbonates. Based on the shape of the calcium and magnesium depth profiles, two major reactive zones have been identified. The first is located near the zone of sulfate depletion and is characterized by carbonate recrystallization, dolomitization and ash alteration reactions at both Ocean Drilling Program Sites 767 and 768. The second reactive zone corresponds to the bottom of the sedimentary sequence and is characterized by alteration reactions in the basement (Site 767) and in the pyroclastic deposits beneath the sediment column (Site 768).

Water chemistry of lakes in Zackenbergdalen between 1997-2003, East Greenland

The ecology of arctic lakes is strongly influenced by climate-generated variations in snow coverage and by the duration of the ice-free period, which, in turn, affect the physical and chemical conditions of the lakes (Wrona et al., 2005, http://www.acia.uaf.edu/PDFs/ACIA_Science_Chapters_Final/ACIA_Ch08_Final.pdf). Most arctic lakes are characterised by a long period (8-10 months) of ice-cover, cold water and low algal biomass. The water temperature and nutrient concentrations, and most probably the nutrient input from the catchments, are closely related to the duration of snow- and ice-cover in the lakes. In years when the ice-out is late, - that is, in late July, - phytoplankton photosynthesis is limited by the lack of light and nutrients. Less food is then available to the next link in the food chain, such as copepods and daphnids, with implication on their growth rates.

Pore-water chemistry of ODP Leg 115 samples

Analyses of the Sr2+ concentrations of interstitial fluids obtained from sediments squeezed during Leg 115 were used to estimate the rates and total amount of recrystallization of biogenic carbonates. The total amount of recrystallization calculated using this method varies from less than 1 % in sediments at Site 706 to more than 40% at Site 709 in sediments of 47 Ma. Five of the sites drilled during Leg 115 (Sites 707 through 711) were drilled in a depth transect within a restricted geographic area so that theoretically they received similar amounts of sediment input. Of these, the maximum rate of recrystallization occurred in the upper 50 m of Site 710 (3812 m). The amount of recrystallization decreased with increasing water depth at Sites 708 (4096 m) and 711 (4428 m), presumably as a result of the fact that most of the reactive calcium carbonate was dissolved before burial. We also observed significant alkalinity deficits at many of these sites, a condition which most likely resulted from the precipitation of calcium carbonate either in the sedimentary column, or during retrieval of the core. Precipitation of CaCO3 as a result of pressure changes during core retrieval was confirmed by the comparison of Ca2+ and alkalinity from water samples obtained using the in-situ sampler and squeezed from the sediments. At Sites 707 and 716, the shallowest sites, no calcium or alkalinity deficits were present. In spite of our estimations of as much as 45% recrystallization at Site 709, all the carbonate sites exhibited what would be previously considered conservative Ca2+/Mg2+ profiles, which varied from -1 to -0.5. By virtue of the position of these sites relative to known basaltic basement or through the actual penetration of basalt (i.e., Sites 706, 707 and 712), these sites are all known to be underlain by basalt. Our results suggest, therefore, that more positive Ca2 + /Mg2+ gradients cannot necessarily be used as indicators of the nature of basement material.

Isotopic signatures and mercury content of arctic char and their prey, and water chemistry of 18 arctic Canadian lakes

Concentrations of mercury (Hg) have increased slowly in landlocked Arctic char over a 10- to 15-year period in the Arctic. Fluxes of Hg to sediments also show increases in most Arctic lakes. Correlation of Hg with trophic level (TL) was used to investigate and compare biomagnification of Hg in food webs from lakes in the Canadian Arctic sampled from 2002 to 2007. Concentrations of Hg (total Hg and methylmercury [MeHg]) in food webs were compared across longitudinal and latitudinal gradients in relation to d13C and d15N in periphyton, zooplankton, benthic invertebrates, and Arctic char of varying size-classes. Trophic magnification factors (TMFs) were calculated for the food web in each lake and related to available physical and chemical characteristics of the lakes. The relative content of MeHg increased with trophic level from 4.3 to 12.2% in periphyton, 41 to 79% in zooplankton, 59 to 72% in insects, and 74 to 100% in juvenile and adult char. The d13C signatures of adult char indicated coupling with benthic invertebrates. Cannibalism among char lengthened the food chain. Biomagnification was confirmed in all 18 lakes, with TMFs ranging from 3.5 ± 1.1 to 64.3 ± 0.8. Results indicate that TMFs and food chain length (FCL) are key factors in explaining interlake variability in biomagnification of [Hg] among different lakes.