Isotopic composition of water in fog, rain, throughfall and stemflow in the Monte Verde, Costa Rica

Fog deposition, precipitation, throughfall and stemflow were measured in a windward tropical montane cloud forest near Monteverde, Costa Rica, for a 65-day period during the dry season of 2003. Net fog deposition was measured directly using the eddy covariance (EC) method and it amounted to 1.2 ± 0.1 mm/day (mean ± standard error). Fog water deposition was 5-9% of incident rainfall for the entire period, which is at the low end of previously reported values. Stable isotope concentrations (d18O and d2H) were determined in a large number of samples of each water component. Mass balance-based estimates of fog deposition were 1.0 ± 0.3 and 5.0 ± 2.7 mm/day (mean ± SE) when d18O and d2H were used as tracer, respectively. Comparisons between direct fog deposition measurements and the results of the mass balance model using d18O as a tracer indicated that the latter might be a good tool to estimate fog deposition in the absence of direct measurement under many (but not all) conditions. At 506 mm, measured water inputs over the 65 days (fog plus rain) fell short by 46 mm compared to the canopy output of 552 mm (throughfall, stemflow and interception evaporation). This discrepancy is attributed to the underestimation of rainfall during conditions of high wind.

Composition and origin of sediments at DSDP Site 54-424

The sediments recovered on Deep Sea Drilling Project Leg 54 appear to be mixtures of the normal pelagic sediments of the area and hydrothermally produced manganese and iron phases. The latter are mineralogically and chemically very similar to phases recovered from surficial sampling of the mounds. The hydrothermal nontronite which is approximately 15 meters thick in the three holes is essentially free of carbonate or detrital contaminants. The basal sediments are similar to the carbonate oozes presently being deposited in the region, but are enriched in Mn and Fe. This enrichment appears to be the result of hydrothermal deposition that took place at or near the spreading center and may not be associated with the mounds formation. Three different hypotheses for the formation of the nontronite layer and the mounds deposits are considered. An initial deposition of a widespread nontronite layer and subsequent diapiric-like movement of the layer into carbonates could account for the observed stratigraphy; however, if this be correct, analogous deposits should be present in other DSDP sites. The second hypothesis - replacement of the normal sediments by nontronite - may be feasible, but the high purity of the nontronite requires dissolution and removal of refractory elements. The third hypothesis, metal deposition in an advancing oxidation gradient, is compatible with submersible observations of the mounds; however, it can account only for the high purity of the nontronite by very rapid deposition of the hydrothermal phases.

Trace metal content in Pliocene to Pleistocene sediments of ODP Leg 127 holes

Quaternary sedimentation within the Japan Sea was controlled by the configuration of peripheral sills, seasonal and long-term climatic variability, and the resultant fluctuations in sea level (Tamaki, 1988). Prior to drilling in the area, piston cores recovered from its basins contained Pleistocene sediments having distinctive color and fabric variation. Sedimentological and geochemical studies conducted on those facies indicated that the variability in fabric was the result of fluctuating marine and/or terrigenous influx to the deep-water basins of the Japan Sea (see, for example, Chough, 1984; Matoba, 1984). The sequences recovered during Leg 127 at Sites 794, 795, and 797 contain long, virtually undisturbed sequences (92.3, 123, and 119.9 mbsf [Hole 797B], respectively) of upper Miocene, upper Pliocene, and Pleistocene/Holocene sediments. The majority of these sequences consists of dark-colored (dark brown, green, and black) silty-clays, many of which are enriched in biogenic components (majority silicious, some carbonate) and/or organic matter, some containing pyrite and/or ash. These facies alternate with light-colored silty-clays, some containing ash and some showing signs of bioturbation (for example, Tamaki, Pisciotto, Allan, et al., 1990, p. 425-433). The dark-to-light sequences are present throughout the section, although they are especially dominant throughout the Pleistocene (for a more detailed lithology of Quaternary sequences recovered at Sites 794, 795, and 797, see Follmi et al. 1992 and Tada et al., 1992). This data report provides trace metal information on Pliocene-Pleistocene-Holocene samples at Sites 794,795, and 797. These data can be used (1) to provide information related to the depositional environments of the Japan Sea during the Quaternary period, (2) to permit comparisons between the dark organic-rich sediments recovered from this semi-enclosed basin and those reported for other silled basins (for example, the Mediterranean and Black seas), and (3) to permit comparisons between these sediments and contemporary equivalents found, for instance, beneath areas of high biogenic productivity. By providing such data, one should be able (1) to determine more precisely the processes governing the deposition of sediments with various levels of organic matter within enclosed basins, (2) to compare individual basin-wide processes, (3) to look for and compare the signatures present as a result of climatic fluctuation, and (4) to attempt to identify the presence and/or absence of cyclicity within such sequences.

Trace metals in sediments of the Var Canyon turbidite system at the DYFAMED station in the Ligurian Sea

The magnitude and the chronology of anthropogenic impregnation by Hg and other trace metals of environmental concern (V, Cr, Ni, Cu, Zn, Ag, Cd and Pb, including its stable isotopes) in the sediments are determined at the DYFAMED station, a site in the Ligurian Sea (Northwestern Mediterranean) chosen for its supposed open-sea characteristics. The DYFAMED site (VD) is located on the right levee of the Var Canyon turbidite system, at the end of the Middle Valley. In order to trace the influence of the gravity current coming from the canyon on trace metal distribution in the sediment, we studied an additional sediment core (VA) from a terrace of the Var Canyon, and material collected in sediment traps at the both sites at 20 m above sea bottom. The patterns of Hg and other trace element distribution profiles are interpreted using stable Pb isotope ratios as proxies for its sources, taking into account the sedimentary context (turbidites, redox conditions, and sedimentation rates). Major element distributions, coupled with the stratigraphic examination of the sediment cores point out the high heterogeneity of the deposits at VA, and major turbiditic events at both sites. At the DYFAMED site, we observed direct anthropogenic influence in the upper sediment layer (<2 cm), while on the Var Canyon site (VA), the anthropization concerns the whole sedimentary column sampled (19 cm). Turbiditic events superimpose their specific signature on trace metal distributions. According to the 210Pbxs-derived sedimentation rate at the DYFAMED site (0.4 mm yr-1), the Hg-enriched layer of the top core corresponds to the sediment accumulation of the last 50 years, which is the period of the highest increase in Hg deposition on a global scale. With the hypothesis of the absence of significant post-depositional redistribution of Hg, the Hg/C-org ratio changes between the surface and below are used to estimate the anthropogenic contribution to the Hg flux accumulated in the sediment. The Hg enrichment, from pre-industrial to the present time is calculated to be around 60%, consistent with estimations of global Hg models. However, based on the chemical composition of the trapped material collected in sediment traps, we calculated that epibenthic mobilization of Hg would reach 73%. Conversely, the Cd/C-org ratio decreases in the upper 5 cm, which may reflect the recent decrease of atmospheric Cd inputs or losses due to diagenetic processes.

Gotland Deep (Baltic Sea) independent age model based on Palaeomagnetic Secular Variation (PSV) and lead (Pb) deposition profiles

Dating of sediment cores from the Baltic Sea has proven to be difficult due to uncertainties surrounding the 14C reservoir age and a scarcity of macrofossils suitable for dating. Here we present the results of multiple dating methods carried out on cores in the Gotland Deep area of the Baltic Sea. Particular emphasis is placed on the Littorina stage (8 ka ago to the present) of the Baltic Sea and possible changes in the 14C reservoir age of our dated samples. Three geochronological methods are used. Firstly, palaeomagnetic secular variations (PSV) are reconstructed, whereby ages are transferred to PSV features through comparison with varved lake sediment based PSV records. Secondly, lead (Pb) content and stable isotope analysis are used to identify past peaks in anthropogenic atmospheric Pb pollution. Lastly, 14C determinations were carried out on benthic foraminifera (Elphidium spec.) samples from the brackish Littorina stage of the Baltic Sea. Determinations carried out on smaller samples (as low as 4 µg C) employed an experimental, state-of-the-art method involving the direct measurement of CO2 from samples by a gas ion source without the need for a graphitisation step - the first time this method has been performed on foraminifera in an applied study. The PSV chronology, based on the uppermost Littorina stage sediments, produced ten age constraints between 6.29 and 1.29 cal ka BP, and the Pb depositional analysis produced two age constraints associated with the Medieval pollution peak. Analysis of PSV data shows that adequate directional data can be derived from both the present Littorina saline phase muds and Baltic Ice Lake stage varved glacial sediments. Ferrimagnetic iron sulphides, most likely authigenic greigite (Fe3S4), present in the intermediate Ancylus Lake freshwater stage sediments acquire a gyroremanent magnetisation during static alternating field (AF) demagnetisation, preventing the identification of a primary natural remanent magnetisation for these sediments. An inferred marine reservoir age offset (deltaR) is calculated by comparing the foraminifera 14C determinations to a PSV & Pb age model. This deltaR is found to trend towards younger values upwards in the core, possibly due to a gradual change in hydrographic conditions brought about by a reduction in marine water exchange from the open sea due to continued isostatic rebound.

Measurements of trace metal abundances and isotopes in carbonate sediments, Exuma, Bahamas

In order to validate the use of 238U/235U as a paleoredox proxy in carbonates, we examined the incorporation and early diagenetic evolution of U isotopes in shallow Bahamian carbonate sediments. Our sample set consists of a variety of primary precipitates that represent a range of carbonate producing organisms and components that were important in the past (scleractinian corals, calcareous green and red algae, ooids, and mollusks). In addition, four short push cores were taken in different depositional environments to assess the impact of early diagenesis and pore water chemistry on the U isotopic composition of bulk carbonates. We find that U concentrations are much higher in bulk carbonate sediments (avg. 4.1 ppm) than in primary precipitates (avg. 1.5 ppm). In almost all cases, the lowest bulk sediment U concentrations were as high as or higher than the highest concentrations found in primary precipitates. This is consistent with authigenic accumulation of reduced U(IV) during early diagenesis. The extent of this process appears sensitive to pore water H2S, and thus indirectly to organic matter content. d238/235U values were very close to seawater values in all of the primary precipitates, suggesting that these carbonate components could be used to reconstruct changes in seawater U geochemistry. However, d238/235U of bulk sediments from the push cores was 0.2-0.4 per mil heavier than seawater (and primary precipitates). These results indicate that authigenic accumulation of U under open-system sulfidic pore water conditions commonly found in carbonate sediments strongly affects the bulk U concentrations and 238U/235U ratios. We also report the occurrence of dolomite in a tidal pond core which contains low 234U/238U and 238U/235U ratios and discuss the possibility that the dolomitization process may result in sediments depleted in 238U. From this initial exploration, it is clear that 238U/235U variations in ancient carbonate sediments could be driven by changes in global average seawater, by spatial and temporal variations in the local deposition environment, or subsequent diagenesis. To cope with such effects, proxies for syndepositional pore water redox conditions (e.g., organic matter content, iron speciation, and trace metal distributions) and careful consideration of possible post-deposition alteration will be required to avoid spurious interpretation of 238U/235U data from ancient carbonate sediments.

Sediment geochemistry and water trace metal concentration in Potter Cove

Recent rapid climate warming at the western Antarctic Peninsula (WAP) results in elevated glacial melting, enhanced sedimentary run-off, increased turbidity and impact of ice-scouring in shallow coastal areas. Discharge of mineral suspension from volcanic bedrock ablation and chronic physical disturbance is expected to influence sessile filter feeders such as the Antarctic soft shell clam Laternula elliptica ( King and Broderip, 1832). We investigated effects of sedimentary run-off on the accumulation of trace metals, and together with physical disturbance, the cumulative effect on oxidative stress parameters in younger and older L. elliptica from two stations in Potter Cove (King George Island, Antarctica) which are distinctly impacted by turbidity and ice-scouring. Fe, Mn, Sr, V and Zn concentrations were slightly higher in sediments of the station receiving more sediment run-off, but not enriched in bivalves of this station. The only element that increased in bivalves experimentally exposed to sediment suspension for 28 days was Mn. Concentration of the waste accumulation biomarker lipofuscin in nervous tissue was higher in L. elliptica from the "exposed" compared to the "less exposed" site, whereas protein carbonyl levels in bivalve mantle tissue were higher at the less sediment impacted site. Tissue metal content and lipofuscin in nervous tissue were generally higher in older compared to younger individuals from both field stations. We conclude that elevated sediment ablation does not per se result in higher metal accumulation in L. elliptica. Instead of direct absorbance from sediment particles, metal accumulation in gills seems to indicate uptake of compounds dissolved in the water column, whereas metals in digestive gland appear to originate from enriched planktonic or detritic food. Accumulation of cellular waste products and potentially reactive metals over lifetime presumably alters L. elliptica physiological performance with age and may contribute to higher stress susceptibility in older animals.

Iron isotope and trace metal record of Cenomanian-Turonian sediments

he global carbon cycle during the mid-Cretaceous (~125-88 million years ago, Ma) experienced numerous major perturbations linked to increased organic carbon burial under widespread, possibly basin-scale oxygen deficiency and episodes of euxinia (anoxic and H2S-containing). The largest of these episodes, the Cenomanian-Turonian boundary event (ca. 93.5 Ma), or oceanic anoxic event (OAE) 2, was marked by pervasive deposition of organic-rich, laminated black shales in deep waters and in some cases across continental shelves. This deposition is recorded in a pronounced positive carbon isotope excursion seen ubiquitously in carbonates and organic matter. Enrichments of redox-sensitive, often bioessential trace metals, including Fe and Mo, indicate major shifts in their biogeochemical cycles under reducing conditions that may be linked to changes in primary production. Iron enrichments and bulk Fe isotope compositions track the sources and sinks of Fe in the proto-North Atlantic at seven localities marked by diverse depositional conditions. Included are an ancestral mid-ocean ridge and euxinic, intermittently euxinic, and oxic settings across varying paleodepths throughout the basin. These data yield evidence for a reactive Fe shuttle that likely delivered Fe from the shallow shelf to the deep ocean basin, as well as (1) hydrothermal sources enhanced by accelerated seafloor spreading or emplacement of large igneous province(s) and (2) local-scale Fe remobilization within the sediment column. This study, the first to explore Fe cycling and enrichment patterns on an ocean scale using iron isotope data, demonstrates the complex processes operating on this scale that can mask simple source-sink relationships. The data imply that the proto-North Atlantic received elevated Fe inputs from several sources (e.g., hydrothermal, shuttle and detrital inputs) and that the redox state of the basin was not exclusively euxinic, suggesting previously unknown heterogeneity in depositional conditions and biogeochemical cycling within those settings during OAE-2.

Heavy metal concentrations in fauna from hydrothermal fields of the Mid-Atlantic Ridge

Distributions of Fe, Mn, Zn, Cu, Ni, Co, Cr, Pb, As, Ag, Cd, Se, Sb, and Hg in 128 samples of tissues of organisms that inhabit hydrothermal vent fields of the Mid-Atlantic Ridge (Menez Gwen, Snake Pit, and Rainbow) depending on the abiotic environmental parameters were studied. The majority of the elements studied showed direct correlations between their concentrations in fluids released and in tissues of hydrothermal organisms. A higher degree of bioaccumulation of metals was revealed in Bathymodiolus mussels and Rimicaris shrimps from the Rainbow hydrothermal vent field as compared to their analogues from the Menez Gwen and Snake Pit fields. This corresponds to maximal concentrations of the majority of the metals studied in the Rainbow high-temperature hydrothermal fluids. The highest degree of bioaccumulation of heavy metals was found in gills of symbiotrophic mussels Bathymodiolus and in maxillipeds of ectosymbiotic shrimps Rimicaris, i.e., in organs that function in dependence on chemosynthetic bacteria. Within the Rainbow vent field, the shrimps, which inhabit in biotopes with more high-temperature conditions and therefore are more strongly subjected to influence of fluids, were found to contain higher metal contents than mollusks. Fe-Mn hydroxide films that cover mussel shells might serve as important reservoirs of other metals related to Fe and Mn.

(Table 2) Trace metal concentrations in ODP Hole 169-1033B

We measured the concentrations of redox-sensitive trace metals (Mn, V, Mo, U, Cd and Re) in sediments from ODP Leg 169S Hole 1033B in Saanich Inlet, British Columbia, to determine changes in redox conditions associated with the onset of laminated sediments at ~12.5 kyr. The most striking result is a large peak in authigenic Re along with detrital levels of Mo at the glacial terrigenous clay-diatomaceous sediment transition. In contrast, the underlying glacial terrigenous clay, which extends throughout the bottom section of the core, is chemically similar to detrital concentrations, either Cowichan River particulates or average shale values. These data suggest a period of oxic bottom waters but reducing pore-waters. This could be due to the dramatic transformation of Saanich Inlet during the late deglaciation from an open bay to an inlet, which restricted circulation and slowed bottom water oxygen renewal. A peak and gradual increase in authigenic Mn in younger sediments subsequent to the Re peak suggests that increasingly oxic conditions followed the authigenic enrichment in Re. These conditions could be connected to the Younger Dryas cooling period, which was coincident with an increase in well oxygenated upwelled waters on the west coast of North America that form the bottom waters of Saanich Inlet. Metal concentrations in a gray clay bed (~11 kyr) are similar to their concentrations in the glacial terrigenous clay, implying that they have a common source. Authigenic enrichments of Re with little authigenic Mo and Cd suggest that before the deposition of this bed, bottom waters were oxic and pore-water oxygen was consumed in the top centimeter or less. Laminations above the clay layer suggest anoxic conditions, which are also indicated by higher authigenic Mo and Cd and slightly lower Re/Mo ratios in these sediments. The basin remained mostly anoxic after the gray clay was emplaced, as seen by continuous authigenic enrichment of the redox-sensitive trace metals. These results are consistent with increased stratification of the water column, brought about by an influx of fresh water to the basin by a large flood.

Total organic carbon content and redox-sensitiv trace metal concentrations of selected late Cenoman claystones from DSDP Hole 93-603B

The Cenomanian/Turonian (C/T) intervals at DSDP Sites 105 and 603B from the northern part of the proto-North Atlantic show high amplitude, short-term cyclic variations in total organic carbon (TOC) content. The more pronounced changes in TOC are also reflected by changes in lithology from green claystones (TOC<1%) to black claystones (TOC>1%). Although their depositional history was different, the individual TOC cycles at Sites 105 and 603B can be correlated using stable carbon isotope stratigraphy. Sedimentation rates obtained from the isotope stratigraphy and spectral analyses indicate that these cycles were predominately precession controlled. The coinciding variations in HI, OI, delta13Corg and the abundance of marine relative to terrestrial biomarkers, as well as the low abundance of lignin pyrolysis products generated from the kerogen of the black claystones, indicate that these cyclic variations reflect changes in the contribution of marine organic matter (OM). The cooccurrence of lamination, enrichment of redox-sensitive trace metals and presence of molecular fossils of pigments from green sulfur bacteria indicate that the northern proto-North Atlantic Ocean water column was periodically euxinic from the bottom to at least the base of the photic zone (<150 m) during the deposition of the black claystones. In contrast, the green claystones are bioturbated, are enriched in Mn, do not show enrichments in redox-sensitive trace metals and show biomarker distributions indicative of long oxygen exposure times, indicating more oxic water conditions. At the same time, there is evidence (e.g., abundance of biogenic silica and significant 13C-enrichment for OC of phytoplanktic origin) for enhanced primary productivity during the deposition of the black claystones. We propose that increased primary productivity periodically overwhelmed the oxic OM remineralisation potential of the bottom waters resulting in the deposition of OM-rich black claystones. Because the amount of oxygen used for OM remineralisation exceeded the amount supplied by diffusion and deep-water circulation, the northern proto-North Atlantic became euxinic during these periods. Both Sites 105 and 603B show trends of continually increasing TOC contents and HI values of the black claystones up section, which most likely resulted from both enhanced preservation due to increased anoxia and increased production of marine OM during oceanic anoxic event 2 (OAE2).