ALBERT

Description: Seasonal (Spring and Summer 2002) concentrations of dissolved (〈0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO3, PO4, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO4 and NO3 (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 102– 8.2 × 103 μmol d−1). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 103 μmol d−1 (inland, freshwater well) vs. 2.1 × 105 μmol d−1(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.

Description: A mass balance for the naturally-occurring radium isotopes (224Ra, 223Ra, 228Ra, and 226Ra) in Jamaica Bay, NY, was conducted by directly estimating the individual Ra contributions of wastewater discharge, diffusion from fine-grained subtidal sediments, water percolation through marshes, desorption from resuspended particles, and water exchange at the inlet. The mass balance revealed a major unknown source term accounting for 19–71% of the total Ra input, which could only be resolved by invoking a source from submarine groundwater. Shallow (〈 2 m depth) groundwater from permeable sediments in Jamaica Bay was brackish and enriched in Ra relative to surface bay waters by over two orders of magnitude. To balance Ra fluxes, a submarine groundwater input of 0.8 × 109–9.0 × 109 L d− 1 was required. This flux was similar for all four isotopes, with individual estimates varying by less than a factor of 2. Our calculated groundwater flux was 6- to 70-fold higher than the fresh groundwater discharge to the bay estimated by hydrological methods, but closely matched direct flow rates measured with seepage meters. This suggests that a substantial portion of the discharge consisted of recirculated seawater. The magnitude of submarine groundwater discharge varied seasonally, in the order: summer 〉 autumn 〉 spring. Chemical analyses suggest that the recirculated seawater component of submarine groundwater delivers as much dissolved nitrogen to the bay as the fresh groundwater flux.

Description: A liquid chromatograph/mass spectrometry (LC/MS) method was developed for the simultaneous quantitation of seven compounds (safflor yellow A, puerarin, daidzein, ginsenosides (Rg(1), Rb(1), Rd), and notoginsenoside R(1)) in rat plasma samples with sufficient sensitivity to facilitate analysis of samples collected after an intravenous injection of Naodesheng. The plasma samples were subjected to protein precipitation with acetone, and analyzed using negative atmospheric pressure chemical ionization mass spectrometry in selected ion monitoring (SIM) mode with baicalin as an internal standard. Good linearity for all the seven compounds was observed. The intra- and inter-day precision of analysis was 〈15.0% for each compound, and the accuracy ranged from 90.0% to 109.0%. This quantitation method was successfully applied to a pharmacokinetic study of following intravenous injection of rats with Naodesheng

Description: Centropages typicus is one of the most common, abundant and best studied calanoid copepods in neritic waters of the Mediterranean Sea, which means it can provide useful information about the long-term dynamics of the Mediterranean epipelagic ecosystem. This paper presents the first comparative overview of the seasonal and long-term variability of C. typicus in different Mediterranean regions. This review is based on quantitative information from the published literature and novel data from five ongoing zooplankton time-series carried out in the Mallorca Island (Balearic Sea), the Bay of Villefranche (Ligurian Sea), the Gulf of Naples (Tyrrhenian Sea), the Gulf of Trieste (North Adriatic Sea), and the Saronikos Gulf (Aegean Sea). In most Mediterranean regions, C. typicus has a perennial occurrence, with peaks of abundance that reflect the succession of different generations. Throughout the Mediterranean, the annual cycle of C. typicus is characterized by minima in winter and major peaks in April–June, which is earlier than those observed in European Atlantic waters, where the peaks are more frequently recorded in summer and fall. In the regions investigated, the annual cycle shows remarkable similarities in terms of timing, but notable differences in the peak height; populations are far more abundant in coastal north-western regions and less abundant in the eastern basin. In the long-term, changes in C. typicus phenology observed in the Bay of Villefranche and in the Gulf of Naples are related to the North Atlantic Oscillation (NAO) index. In these two regions, the species responds to climate forcing similarly in terms of average seasonal patterns (bi-modal patterns in years of positive NAO, unimodal patterns in years of negative NAO) but oppositely in terms of quantity, indicating different influence of the NAO on the two regions. At decadal scales, C. typicus populations show high interannual variability with marked geographical differences. In some areas, the patterns are clearly characterized by alternate phases of higher and lower annual abundances, at higher frequency (mainly 1–2 years) in the Gulf of Naples, and lower frequency in the Saronikos Gulf (mainly 4–5 years) and in the Gulf of Trieste (mainly 5–6 years). Synchronous phases of increasing or decreasing abundance are discernable only for a few sites and short periods, for example from 1998 to 2000 in the Gulf of Naples, Gulf of Trieste and Saronikos Gulf. The regional differences observed in the long-term patterns of C. typicus populations suggest that the temporal dynamics of this species are significantly more affected by local conditions than by any possible common driving force acting at basin scale through teleconnections.

Description: Seven new fungal polyketides possessing linear pentaene structures ending in cyclic moieties were isolated from the mycelium extract of a marine sponge-derived Penicillium rugulosum. Feeding of C-13-labeled acetate and L-methionine was used to verify the polyketide origin of prugosene A1. It could also be shown that prugosenes B1 and C1 were formed from prugosene A1 by hydrolysis and decarboxylation of its oxabicyclo[2.2.1]heptane unit.

Description: Planktic foraminiferal census data, faunal sea surface temperatures (SSTs) and oxygen isotopic and lithic records from a site in the northeast Atlantic were analyzed to study the interglacial dynamics of Marine Isotope Stage (MIS) 11, a period thought to closely resemble the Holocene on the basis of orbital forcing. Interglacial conditions during MIS 11 persisted for approximately 26 ka. After the main deglacial meltwater processes ceased, a 10- to 12-ka-long transitional period marked by significant water mass circulation changes occurred before surface waters finally reached their thermal maximum. This SST peak occurred between 400 and 397 ka, inferred from the abundance of the most thermophilic foraminiferal species and was coincident with lowest sea level according to benthic isotope values. The ensuing stepwise SST decrease characterizes the overall climate deterioration preceding the increase in global ice volume by ∼ 3 ka. This cooling trend was followed by a more pronounced cold event that began at 388 ka, and that terminated in the recurrence of icebergs at the site around 382 ka. Because the water mass configuration of early MIS 11 evolved quite differently from that of the early Holocene, there is little evidence that MIS 11 can serve as an appropriate analogue for a future Holocene climate, despite the similarity in some orbital parameters.

Description: Variably altered dacite from the PACMANUS vent field in the eastern Manus back-arc basin, Papua New Guinea, was studied to determine the textural and mineralogical characteristics of hydrothermal alteration taking place in the immediate subsurface of this modern seafloor hydrothermal system. Detailed textural investigations show that fluid flow through the glassy dacite has been strongly controlled by the primary volcanic textures. Quench fractures and networks of interconnected perlitic cracks linking vesicles provided pathways for hydrothermal fluids flowing up to the seafloor. Hydrothermal alteration along these pathways resulted in the formation of pseudoclastic textures. Textural evidence suggests that alteration of the glassy dacite has not been sustained. The samples have been affected by incipient hydrothermal alteration that is typically not preserved in ancient volcanic-rock-hosted massive sulfide deposits. Interaction of the glassy dacite with hydrothermal fluids primarily resulted in the conversion of volcanic glass to dioctahedral smectite. Only minor amounts of trioctahedral smectite were formed. Destruction of the volcanic glass and the formation of smectite caused pronounced changes in the chemistry of the dacite samples, in particular a decrease in the SiO2 whole-rock content and the Na2O/K2O ratio. The two alkali elements behaved differently during hydrothermal alteration due to preferential incorporation of K into the interlayer position of the newly formed dioctahedral smectite. Smectite formation occurred under rock-dominated conditions although the addition of Mg was required to form trioctahedral smectite from the silicic volcanic glass. Primary plagioclase was resistant to hydrothermal alteration highlighting the fact that the destruction of volcanic glass and feldspar are not necessarily contemporaneous in massive sulfide forming hydrothermal systems. Incipient alteration of the glassy dacite close to the seafloor occurred at temperatures below 150 °C in an environment that allowed the development of steep temperature gradients. Comparison of the new data to the findings of deep drilling during ODP Leg 193 suggests that the smectite-rich alteration in the immediate subsurface of the PACMANUS hydrothermal vent field represents the low-temperature equivalent of illite- and chlorite-rich alteration associations forming in the upflow zones of the hydrothermal fluids in the deeper portion of the volcanic sequence.

Description: New high resolution carbon isotope stratigraphies from two basinal pelagic carbonate successions in northern Germany (Halle and Oerlinghausen, Münsterland Cretaceous Basin) resolve late Cenomanian to early Mid-Turonian carbon cycle variations at timescales of less than 100 kyr. Beside the major carbon isotope excursion of the late Cenomanian oceanic anoxic event (OAE 2), 11 small-scale distinct features are precisely resolved in the δ13C carbonate curve and related to boreal macrofossil zonations. The small-scale carbon isotope events correspond to secular δ13C carbonate variations identified previously in the English Chalk. The boreal high-resolution δ13C carbonate curve shows a detailed coincidence with two Tethyan δ13C curves from Italy, what demonstrates the interregional significance of the δ13C dates and allows their correlation within error limits of ± 40 kyr. Furthermore, the new δ13C curve enables the calibration of boreal and tethyan macro- and microfossil zonations. Accordingly, the Tethyan calcareous nannoplankton boundary NC13/NC14 corresponds to the boreal FO of C. woollgari, the index taxon for the Lower-Middle Turonian boundary. The cyclic appearance and the temporal spacing of the small-scale carbon isotope events suggest that orbital forcing exerted control on surface water productivity and organic matter preservation at the sea floor.

Description: Permeabilities in the subducting slab appear to be too low and dihedral angles between fluid and relevant minerals too high to allow for porous flow, hence fluid channelization is critical for the understanding of subduction zone fluid fluxes. In this review we will outline how fluid channelization controls reaction rates and element redistributions during metamorphism of the subducting plate as well as trace element compositions of subduction-related fluids during flow. Channelized fluid flow predicts that from a rock point of view, most formerly subducted material will show only very limited evidence for fluid flow, consistent with the rarity of observed high fluid fluxes in subduction-related rocks. Aqueous fluid produced by dehydration reactions will not percolate through large rock volumes, but rather will be carried away from the dehydration sites by a veining network. Indeed evidence for significant aqueous-fluid fluxes have been found in high-pressure veins with adjacent selvages. In such selvages, large lithophile elements (LILE's) generally show the highest mobilities, followed by light (L) rare earth elements (REE) and then heavy (H) REE. Compared to high field strength elements (HFSE), even Th shows higher mobilities. From a fluid point of view, equilibrium between aqueous fluid and surrounding rock will only be approached at sites of fluid production and mineral reaction. However, this fluid can be significantly modified while moving upwards through a veining network where the wallrocks are out of equilibrium with the fluid. In a subducting slab, such reactive fluid flow can preferentially dissolve minerals and release their trace elements (e.g. Ba in phengite, Th and La in monazite). The degree of change in aqueous-fluid composition will depend on the amount of fluid–mineral surface interaction. The chemical exchange reactions will not be possible to model by trace element partition coefficients alone, instead future models need to incorporate kinetic parameters such as surface reaction rates.

Description: Controversy over the oxygen isotope composition of seawater began in the 1950's, since which time there has been no agreement over whether the oxygen isotope composition of the oceans has changed over time. Resolving this uncertainty would allow the δ18O values of demonstrably well preserved marine authigenic precipitates to be used to reconstruct surface climate trends back to early Archean times and would help towards a more quantitative description of Earth's global water cycle on geological time scales. Isotopic studies of marine carbonate and silica reveal a trend of increasing δ18O values with decreasing age since the Archean. This trend has been interpreted by some to reflect a progressive increase in seawater δ18O through time; however, it is generally accepted on the basis of ophiolite studies and theoretical considerations that seawater δ18O cannot change significantly because of the buffering effects of ocean crust alteration at mid-ocean ridges. As a result many alternative interpretations have been proposed, including meteoric alteration; warmer paleoclimates; higher seawater pH; salinity stratification and biased sampling. Here we review these interpretations in the light of an updated compilation of marine carbonate δ18O from around the world, covering the Phanerozoic and Precambrian rock records. Recent models of the geological water cycle demonstrate how long-term trends in chemical weathering and hydrothermal circulation can indeed influence the O-isotope composition of the global ocean to the extent necessary to explain the carbonate δ18O trend, with residual variation attributed to climatic fluctuations and post-depositional alteration. We present the further development of an existing model of the geological water cycle. In the model, seawater δ18O increased from about − 13.3‰ to − 0.3‰ over a period of 3.4 Ga, with average surface temperatures fluctuating between 10 °C to 33 °C, which is consistent with known biological constraints. Similar temperature variations are also obtained, although with higher starting seawater δ18O composition, when more conservative approaches are used that take into account the systematic effects of diagenetic alteration on mean calcite δ18O values. In contrast to much published opinion, the average δ18O value of ocean crust in the model remained relatively unchanged throughout all model runs. Invariable ophiolite δ18O values can, therefore, not be used as a definitive argument against changing seawater δ18O. The most likely explanation for the long-term trend in seawater δ18O invokes two stepwise increases in the ratio of high- to low-temperature fluid/rock interactions. An initial increase may have occurred close to the Archean–Proterozoic boundary, but a possibly more significant increase took place near the Proterozoic–Phanerozoic boundary. Possible explanations for extremely low seawater δ18O during the Archean include higher continental weathering rates caused by a combination of higher atmospheric pCO2 (necessarily combined with high CO2 outgassing rates), a greater abundance of relatively easily weathered volcanic rocks in greenstone belts and partial emergence of spreading ridges. The second increase may have been caused by the suppression of low-temperature overprinting of ocean crust alteration by the formation of a thick sediment cover on ridge flanks due to the emergence of shelly plankton at the beginning of the Phanerozoic. Postulated increases in spreading ridge depths since the Archean would also have enhanced the efficiency of vertical heat flux and changed the depth at which hydrothermal fluids boil, both of which would favour high- over low-temperature interactions with time.