Sr-Nd isotopic analyses of sand-sized sediment from the San Francisco Bay coastal system

A diverse suite of geochemical tracers, including 87Sr/86Sr and 143Nd/144Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143Nd/144Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects.

Contencentrations of reduced inorganic sulfur forms in Mediterranean Sea waters

The first data on content of inorganic reduced sulfur compounds [H2S, S°, S2O3(2-), SO3(2-)] were obtained at two stations in the northeastern Levant Sea (Mediterranean Basin). With lower detection limit for the mentioned sulfur forms of 30 nM, sulfide forms were not found, while thiosulfate concentration varied from 178 to 890 nM (from 24 to 78 % of total reduced S), and S° varied from 156 to 1090 nM. Vertical distribution of these compounds showed irregular character; correlation between total reduced S maxima, fluorescence, and increase of nutrient element content near the lower pycnocline boundary was observed. The maximum total sulfur concentration in the surface layer was likely due an anthropogenic influence. The ''starting'' mechanism that controls appearance and distribution of sulfur compounds in oxygen-containing water is the process of bacterial sulfate reduction in micropatches of fresh organic detritus. Reduced sulfur forms participate further in a series of chemical and biochemical processes. Contribution of hydrolysis of organic sulfur-containing compounds is insignificant for the region in study.

Noble metals and associated trace elements in sulfides from the active TAG mound, ODP Site 158-957

Primary sulfides from cores of ODP Holes 158-957M, 158-957C, and 158-957H on the active TAG hydrothermal mound (Mid-Atlantic Ridge, 26°08'N) have been studied for concentrations of several chemical elements. Based on 262 microprobe analyses it has been found that the sulfides have extremely heterogeneous distribution of noble metals (Au, Ag, Pt, and Pd) and several associated elements (Hg, Co, and Se). Noble metals are arranged in the following order in terms of decreasing abundance, i.e. concentration level above detection limits (the number of analyses containing a specific element is given in parentheses): Au (65), Ag (46), Pt (21), and Pd (traces). The associated trace elements have the following series: Co (202), Hg (132), and Se (49). The main carriers of "invisible" portion of the noble metals are represented by pyrite (Au, Hg), marcasite and pyrite (Ag, Co), sphalerite and chalcopyrite (Pt, Pd), and chalcopyrite (Se). Noble metal distribution in sulfides reveals a lateral zonality: maximal concentrations and abundance of Au in chalcopyrite (or Pt and Ag in chalcopyrite and pyrite) increase from the periphery (Hole 957H) to the center (holes 957C and 957M) of the hydrothermal mound, while Au distribution in pyrite displays a reversed pattern. Co concentration increases with depth. Vertical zonality in distribution of the elements mentioned above and their response to evolution of ore genesis are under discussion in the paper.

(Table 2) Seroprevalence against Trichinella spp. in Ursus maritimus from Svalbard and Barents Sea pack ice

Blood samples of live-caught polar bears (Ursus maritimus) from Svalbard collected 1991-2000 (Period 1) and 2006-2008 (Period 2) and from the pack ice of the Barents Sea collected in Period 1, were assayed for antibodies against Trichinella spp. by ELISA. Of 54 cubs-of-the-year included in the Period 1 sample, 53 were seronegative, indicating that exposure to Trichinella infected meat is uncommon during the first months of life for polar bears in the Svalbard region. Of 30 mother-offspring pairs, 18 mothers were seropositive with seronegative offspring (n = 27), suggesting (1) that maternal antibodies had dropped to levels below detection limit by the time of capture in April (offspring approximately 4 months old), and (2) supporting experimental studies in other animal models showing that vertical transmission of Trichinella spp. is uncommon. Bear 1 year and older had higher prevalence in Svalbard (78%) than in the Barents Sea (51%). There was no temporal change in prevalence for bears from Svalbard during the time between the two periods. The prevalence increased with age in both sexes. A positive correlation was found between anti-Toxoplasma gondii and anti-Trichinella spp. antibodies.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Geochemistry of ODP Hole 135-841B

Two igneous rock units were recovered at Site 841. More than 200 m of island-arc rhyolites, rhyolitic tuffs, lapilli tuffs, and pumice breccias, divided into five units, compose the basement at the site. These rhyolitic volcanics are late middle Eocene or older and formed part of a subaerial rhyolitic volcano. These low-K rhyolites were produced by fractional crystallization of a more mafic arc-tholeiitic lava or by dehydration melting of lower crustal arc tholeiites. The Site 841 basement rocks are similar in composition to high-SiO2 lavas in the Eocene basement on 'Eua and crystallized from depleted island-arc-tholeiitic basalts like those exposed on 'Eua. No evidence is present in the rhyolites, or in the clasts enclosed within them, for boninite series magmas at Site 841. The Site 841 rhyolitic complex bears no resemblance to Cretaceous rhyolites from the Lord Howe Rise, which are enriched in K and incompatible elements. The volcanic rocks at Site 841 are part of a widely distributed Eocene volcanic episode that marked the earliest phases of subduction in the Tonga region; they are not part of an older crustal fragment. The second igneous sequence is a series of basaltic dikes and sills that intruded Miocene sediments. These basalts have trace element abundances and ratios identical to upper Miocene lavas from the Lau Ridge. The Site 841 basalts do not have any geochemical characteristics that suggest they were generated by unusual thermal conditions in the shallow sub-forearc mantle. They are most reasonably interpreted as intrusions fed by basement dikes propagated from the associated active arc. No evidence for local serpentinite exposures, like those that are common in the Mariana forearc, was found at Site 841. The results from Site 841 provide strong support for hypotheses of forearc evolution that have been advanced for the Izu-Bonin-Mariana system.

Sources and proxy potential of long chain alkyl diols in lacustrine environments

Long chain 1,13- and 1,15-alkyl diols form the base of a number of recently proposed proxies used for climate reconstruction. However, the sources of these lipids and environmental controls on their distribution are still poorly constrained. We have analyzed the long chain alkyl diol (LCD) composition of cultures of ten eustigmatophyte species, with three species from different families grown at various temperatures, to identify the effect of species composition and growth temperature on the LCD distribution. The results were compared with the LCD distribution of sixty-two lake surface sediments, and with previously reported LCD distributions from marine environments. The different families within the Eustigmatophyceae show distinct LCD patterns, with the freshwater family Eustigmataceae most closely resembling LCD distributions in both marine and lake environments. Unlike the other two eustigmatophyte families analyzed (Monodopsidaceae and Goniochloridaceae), C28 and C30 1,13-alkyl diols and C30 and C32 1,15-alkyl diols are all relatively abundant in the family Eustigmataceae, while the mono-unsaturated C32 1,15-alkyl diol was below detection limit. In contrast to the marine environment, LCD distributions in lakes did not show a clear relationship with temperature. The Long chain Diol Index (LDI), a proxy previously proposed for sea surface temperature reconstruction, showed a relatively weak correlation (R2 = 0.33) with mean annual air temperature used as an approximation for annual mean surface temperature of the lakes. A much-improved correlation (R2 = 0.74, p-value<0.001) was observed applying a multiple linear regression analysis between LCD distributions and lake temperatures reconstructed using branched tetraether lipid distributions. The obtained regression model provides good estimates of temperatures for cultures of the family Eustigmataceae, suggesting that algae belonging to this family have an important role as a source for LCDs in lacustrine environments, or, alternatively, that the main sources of LCDs are similarly affected by temperature as the Eustigmataceae. The results suggest that LCDs may have the potential to be applicable as a palaeotemperature proxy for lacustrine environments, although further calibration work is still required.

40Ar-39Ar investigation of volcanic clasts in glaciogenic sediments at ODP Sites 1097 and 1103

Three selected diamictite samples recovered within sequence group S3 at Sites 1097 (Sample 178-1097A-27R-1, 35-58 cm) and 1103 (Samples 178-1103A-31R-2, 0-4 cm, and 36R-3, 4-8 cm) of Ocean Drilling Program Leg 178 have been investigated by scanning electron microscope, electron microprobe, and 40Ar-39Ar laser-heating techniques. They contain variable proportions of fragments of volcanic rock groundmass (mostly in the range of 100-150 µm) with textures ranging from microcrystalline to ipocrystalline. Their rounded shapes indicate mechanical reworking. Fresh groundmass glasses, recognized only in grains from samples of Site 1103, show mainly a subalkaline affinity on the basis of total alkali-silica variations. However, they are characterized by relatively high TiO2 and P2O5 contents (1.4-2.8 and 0.1-0.9 wt%, respectively). Because of the small size of homogeneous grains (100-150 µm), they were not suitable for single-grain total fusion 40Ar-39Ar analyses. The incremental laser-heating technique was applied to milligram-sized samples (only for Samples 178-1097A-27R-1, 35-58 cm, and 178-1103A-36R-3, 4-8 cm) and to various small fractions (each consisting of 10 grains for the sample from Site 1097 and 30 grains for samples from Site 1103). The latter approach resulted in more effective resolution of sample heterogeneity. Argon ages from the small fractions show significantly different ranges in the three samples: 75-173 Ma for Sample 178-1097A-27R-1, 35-58 cm, 18-57 Ma for Sample 178-1103A-31R-2, 0-4 cm, and 7.6-50 Ma for Sample 178-1103A-36R-3, 4-8 cm. Ca/K ratios derived from argon isotopes at Site 1103 suggest that the data mainly refer to outgassing of groundmass glass. At Site 1103, we observe an overall apparent age increase with decreasing sample depth. This is compatible with glacial erosion that affected with time deeper levels of a volcanic sequence previously deposited on the continent. The youngest apparent age of 7.6 ± 0.7 Ma detected close to the bottom of Hole 1103A (340 meters below seafloor [mbsf]) is compatible with the age range of the diatom Actinocyclus ingens v. ovalis Zone (6.3-8.0 Ma) determined for the interval 320-355 mbsf and with the maximum ages derived from strontium isotope composition of barnacle fragments obtained at 262-263 mbsf at the same site. Nevertheless, this age cannot be taken as the maximum youngest age of the volcanic sequence sampled by glacial erosion or as the maximum age for the deposition of the Sequence S3 at 340 mbsf unless validated by further research.

Physical properties and hexachlorocyclohexane concentrations of sea-ice, water and ice algae samples, eastern Beaufort Sea

We present evidence that both geophysical and thermodynamic conditions in sea ice are important in understanding pathways of accumulation or rejection of hexachlorocyclohexanes (HCHs). a- and g-HCH concentrations and a-HCH enantiomer fractions have been measured in various ice classes and ages from the Canadian High Arctic. Mean a-HCH concentrations reached 0.642 ± 0.046 ng/L in new and young ice (<30 cm), 0.261 ±0.015 ng/L in the first-year ice (30-200 cm) and 0.208 ±0.045 in the old ice (>200 cm). Mean g-HCH concentrations were 0.066 ± 0.006 ng/L in new and young ice, 0.040 ±0.002 ng/L in the first-year ice and 0.040 ±0.007 ng/L in the old ice. In general, a-HCH concentrations and vertical distributions were highly dependent on the initial entrapment of brine and the subsequent desalination process. g-HCH levels and distribution in sea ice were not as clearly related to ice formation processes. During the year, first-year ice progressed from freezing (accumulation) to melting (ablation). Relations between the geophysical state of the sea ice and the vertical distribution of HCHs are described as ice passes through these thermodynamic states. In melting ice, which corresponded to the algal bloom period, the influence of biological processes within the bottom part of the ice on HCH concentrations and a-HCH enantiomer fraction is discussed using both univariate and multivariate approaches.

Accumulation rate, carbon geochemistry and clay mineralogy of ODP Site 181-1123 sediments, southwest Pacific

Site 1123 is located on the northeastern flank of the Chatham Rise. Sedimentological and clay mineralogical analyses indicate a very fine grained carbonate-rich sediment. Smectite and illite are the main constituents of the clay mineral assemblage. High smectite values in the Eocene decrease in younger sediment sequences. Illite and chlorite concentrations increase in younger sediments with significant steps at 13.5, 9, and 6.4 Ma. The kaolinite content is near the detection limit and not significant. We observed only small fluctuations of the clay mineral composition, which indicates a uniform sedimentation process, probably driven by long-term processes. Good correspondence is shown between increasing illite and chlorite values and the tectonic uplift history of the Southern Alps.

Geochemistry of dark-light rhythm sediments of the Japan Sea

Ocean Drilling Program Legs 127 and 128 in the Japan Sea have revealed the existence of numerous dark-light rhythms of remarkable consistency in sediments of late Miocene, latest Pliocene, and especially Pleistocene age. Light-colored units within these rhythms are massive or bioturbated, consist of diatomaceous clays, silty clays, or nannofossil-rich clays, and are generally poor in organic matter. Dark-colored units are homogeneous, laminated, or thinly bedded and include substantial amounts of biogenic material such as well-preserved diatoms, planktonic foraminifers, calcareous nannofossils, and organic matter (maximum 7.4 wt%). The dark-light rhythms show a similar geometrical pattern on three different scales: First-order rhythms consist of a cluster dominated by dark-colored units followed by a cluster dominated by light-colored units (3-5 m). Spectral analysis of a gray-value time series suggests that the frequencies of the first-order rhythms in sediments of latest Pliocene and Pleistocene age correlate to the obliquity and the eccentricity cycles. The second-order dark-light rhythms include a light and a dark-colored unit (10-160 cm). They were formed in time spans of several hundred to several ten thousand years, with variance centering around 10,500 yr. This frequency may correspond to half the precessional cycle. Third-order rhythms appear as laminated or thinly bedded dark-light couplets (2-15 mm) within the dark-colored units of the second-order rhythms and may represent annual frequencies. In interpreting the rhythms, we have to take into account that (1) the occurrence of the first- and second-order rhythms is not necessarily restricted to glacial or interglacial periods as is shown by preliminary stable-isotope analysis and comparison with the published d18O record; (2) they appear to be Milankovitch-controlled; and (3) a significant number of the rhythms are sharply bounded. The origin of the dark-light rhythms is probably related to variations in monsoonal activity in the Japan Sea, which show annual frequencies, but also operates in phase with the orbital cycles.

Geochemistry at DSDP Holes 80-550 amd 80-548

At Sites 548 and 550 of DSDP Leg 80 several condensed sedimentary sections contain various types of polymetallic crusts. The relationships between mineralogic and geochemical data in the sections have been studied in the context of the biostratigraphic and sedimentologic results. The diagenetic evolution during periods of low accumulation rate varies according to depth and sedimentary environment. At Site 548 on the continental margin, the phosphatic and manganiferous crusts are similar to those related to upwelling influences before Late Cretaceous deposition. At Site 550 the upper Paleocene cherts, deposited directly on oceanic crust, are overlain by pelagic brown clays containing diagenetic manganiferous concretions characterized by very high Sr and Ba contents. The origin of these small nodules is probably related to the authigenesis of fecal pellets. The upper Eocene indurated section is made up of authigenic zeolites, clays, and Fe-Mn phases and is similar to the volcanic-sedimentary deposits described in deep basins and seamounts of the Pacific. These crusts and a polynucleated nodule within the overlying sediments have geochemical characteristics (high Ni, Co, and Cu contents) similar to those formed in the deep ocean under volcanic influences during periods of low sedimentation rates or sedimentary hiatuses. Volcaniclastic material is ubiquitous and peculiarly abundant in Eocene sections and can be related to the volcanic formation of Iceland in the North Atlantic.

(Table 3) Relative content of n-alkane groups in samples from hydrothermal fields of the Mid-Atlantic Ridge

Optimum conditions were selected for chromatographic separation of model mixtures of C12-C40 n-alkanes. For one of samples of hydrothermal deposits extraction conditions of hydrocarbons were studied and a sample preparation procedure was selected. The procedure was proposed to determine n-alkanes in samples of hydrothermal deposits by means of gas chromatography - mass spectrometry (GC-MS). Detection limit for n-alkanes was 3x10**-9 to 10**-8% depending on components. On the basis of the proposed procedure composition of n-alkanes was studied in samples of hydrothermal deposits collected at the Mid-Atlantic Ridge (Broken Spur, Lost City, and Rainbow hydrothermal fields). Analyses showed that samples contained C14-C35 n-alkanes. Concentrations of the n-alkanes were rather low and varied from 0.002 to 0.038 µg/g. Hypotheses concerning genesis of identified n-alkanes were offered.

Geochemistry, mineralogy and isotopes at DSDP Hole 62-464

The relationships between mineralogical and geochemical data on the three successive sedimentary facies at Deep Sea Drilling Project Site 464 are studied. The evolution of siliceous biogenic sediments is derived from the analyses of one Fe-Ti smectite concretion, and of siliceous aggregates occurring in the pelagic "brown clays." Along the sedimentary section, the trace elements enriching the authigenic silicates and the Fe-Mn oxyhydroxides vary, depending on the marine environment. The proportion of clays and carbonates into the siliceous deposits controls the diagenetic evolution of silica making up the quartz aggregates from the "brown clay" or the cristobalite cherts.