Mercury Dynamics in a San Francisco Estuary Tidal Wetland: Assessing Dynamics Using In Situ Measurements

We used high-resolution in situ measurements of turbidity and fluorescent dissolved organic matter (FDOM) to quantitatively estimate the tidally driven exchange of mercury (Hg) between the waters of the San Francisco estuary and Browns Island, a tidal wetland. Turbidity and FDOM??representative of particle-associated and filter-passing Hg, respectively??together predicted 94?% of the observed variability in measured total mercury concentration in unfiltered water samples (UTHg) collected during a single tidal cycle in spring, fall, and winter, 2005?C2006. Continuous in situ turbidity and FDOM data spanning at least a full spring-neap period were used to generate UTHg concentration time series using this relationship, and then combined with water discharge measurements to calculate Hg fluxes in each season. Wetlands are generally considered to be sinks for sediment and associated mercury. However, during the three periods of monitoring, Browns Island wetland did not appreciably accumulate Hg. Instead, gradual tidally driven export of UTHg from the wetland offset the large episodic on-island fluxes associated with high wind events. Exports were highest during large spring tides, when ebbing waters relatively enriched in FDOM, dissolved organic carbon (DOC), and filter-passing mercury drained from the marsh into the open waters of the estuary. On-island flux of UTHg, which was largely particle-associated, was highest during strong winds coincident with flood tides. Our results demonstrate that processes driving UTHg fluxes in tidal wetlands encompass both the dissolved and particulate phases and multiple timescales, necessitating longer term monitoring to adequately quantify fluxes.     

Oxidation of bisphenol A by a boron-doped diamond electrode in different water matrices: transformation products and inorganic by-products

An electrochemical advanced oxidation process employing a boron-doped diamond anode for the treatment of synthetic waters and secondary effluents of wastewater treatment plants (WWTP) was studied. The efficiency and formation of transformation products (TPs) for this treatment process were investigated at different current densities for bisphenol A (BPA) spiked to synthetic water and WWTP effluents. A complete removal of the parent compound was achieved in WWTP effluents. Higher applied current densities resulted in faster removal. At the same time, a correlation between the applied current density and the ozone concentration measured in the bulk solution was revealed. Hence, the observed transformation of BPA is likely due to the generation of reactive oxygen species such as hydroxyl radicals and ozone. Based on a suspected target screening approach, four known TPs and two unreported (new) TPs were identified by LC–MS analysis. These results suggest a transformation pathway following three steps: hydroxylation of the aromatic ring, followed by oxidation of the isopropylidene bridge and finally a ring opening and formation of organic acids and other small molecules. The presence of chloride ions in WWTP effluents can result in the generation of excessive concentrations of chlorate and perchlorate during electrochemical oxidation. Applying a current density of 208 mA cm^?2, a complete elimination of BPA was achievable after 15 min (Q/V = 430 mA h L^?1); however, the oxidation resulted in concentrations of chlorate and perchlorate of 2.85 and 5.65 mg L^?1, respectively. These values were directly dependent on the exposure time and desired degree of BPA removal.     

Analysis of undisturbed layers of a waste deposit landfill – Insights into the transformation and transport of organic contaminants

Comprehensive GC/MS analysis was applied to both the mobile liquid phase (seepage water) and the immobile solid matter of discrete layers derived from a waste deposit landfill. The vertical distribution of organic compounds supports information on the transport, transfer and transformation processes with depth and, consequently, with time.Numerous low molecular weight organic contaminants of natural and xenobiotic origin were identified and partially quantified. Several were selected to act as molecular indicators for different processes. Interpretation of their occurrence and concentration profiles (considering possible waste sources) and their molecular properties allowed us to (i) differentiate immobile and mobile fractions, (ii) reveal restrictions in the vertical transport by transfer processes between particulate and water phase, (iii) identify dynamic accumulations of individual contaminants and (iv) estimate approximate residence times. In addition, intensive degradation processes were pointed out for the natural fraction of the organic matter by way of determination of specific transformation products. Besides the transformation of natural components, transformation of numerous xenobiotics was recognised. In particular, with respect to an important group of contaminants, the phthalate-based plasticisers, a detailed view of (i) the influence of transfer and transport phenomena on transformation processes as well as (ii) the consecutive appearance of different degradation steps in both seepage water and solid waste was pointed out. The information provides a valuable base for the prediction of the long term behaviour of organic contaminants in waste deposit landfills.     

Cross-section through the frontal Japan Trench subduction zone: Geochemical evidence for fluid flow and fluid–rock interaction from DSDP and ODP pore waters and sediments

Abstract Fluids and sediments from Deep Sea Drilling Project/Ocean Drilling Program Legs (56, 57, 87 and 186) along a transect extending from the subducting plate, across the midslope and upper slope of the Japan Trench forearc were analyzed for B and B isotopes in order to assess their composition and fluid–sediment interaction. At the reference Site 436 on the subducting plate, changes in B contents and B isotopes are controlled by the lithology and diagenesis only. The midslope Sites 440 and 584 showed stronger variations in the B geochemistry, which can be related to diagenesis and tectonic dewatering along faults. The strongest changes in the B geochemistry were observed on the upper slope Sites 1150 and 1151, where profound down‐hole freshening (chlorinities as low as ～310 mmol) coincides with a B enrichment (up to 9.3 × seawater concentration). The B isotope pore fluid profile of Site 1150 displayed a bimodal variation with depth, first increasing to values more positive than seawater, then shifting to lower signatures typical for deep‐seated fluids, whereas Site 1151 showed a constant B decrease with depth. Sites 1150 and 1151 sediments showed B increases with depth to values as high as ～164 p.p.m. and isotopic compositions ranging from ～+4 to ?9‰. A linear decrease in B_solid/B_fluid ratio, suggests that B geochemistry of the upper slope sites is controlled by fluid–rock interaction and deep‐seated fluid flow, whereas constant B_solid/B_fluid ratios were observed at the reference site on the incoming plate. This fluid overprint is probably caused by normal faults in the sediment cover which might be interconnected to deep thrusts in the underlying Cretaceous accreted wedge. This suggests that the erosive Japan Trench margin is characterized by back‐flux of deep‐seated, B‐enriched fluids into the ocean, which is facilitated by extensional normal faulting as a result of tectonic erosion and subsidence.     

A thermodynamic investigation of barium and calcium sulfate stability in sediments at an oceanic ridge axis (Juan de Fuca, ODP legs 139 and 169)

We have used a new thermodynamic model of barium and calcium sulfate solubilities in multicomponent electrolyte solutions (Monnin, 1999) to investigate the stabilities of barite and anhydrite in seawater or in marine sediment porewaters at high temperature and pressure. As a further test supplementing those previously carried out during model development, we have calculated the temperature at which standard seawater becomes saturated with respect to anhydrite. The model predicts that, upon heating at 500 bars, standard seawater becomes saturated with respect to anhydrite at 147 ± 5°C, which compares well with the literature value of 150°C (Bishoff and Seyfried, 1978). At 20 bars the calculated saturation temperature is 117 ± 3°C. This points to a non negligible pressure effect even at moderate pressures.We have calculated the barite and anhydrite saturation indices for the in situ temperatures and pressures, from the composition of porewaters collected at ODP Sites 855, 856, 857, 858, 1035 and 1036 during ODP Legs 139 and 169 (Juan de Fuca and Gorda ridges, NE Pacific). Calculated saturation indices for porewater samples collected at depths corresponding to temperatures between 70° and 110-120°C at an in situ pressure of about 260 bars yield equilibrium values for anhydrite and barite. Saturation indices of samples collected at depths where the temperature exceeds 110-120°C, however, yield values indicating supersaturation with respect to anhydrite and undersaturation with respect to barite. This result is consistent with the redissolution of anhydrite during cooling, leading to the well documented sampling artifact affecting porewater compositions in high temperature marine sediments: anhydrite dissolution increases the porewater sulfate content, which in turn induces a loss of barium from solution through barite precipitation (the common ion effect). We postulate that this redissolution occurs in sediment samples for which the in situ temperature exceeds 110-120°C: below this limit anhydrite remains at equilibrium or does not have time to significantly dissolve before porewaters are sampled.     

Determination of the bulk temperature from NOAA/AVHRR satellite data in a midlatitude lake

The spatial and temporal variability of the bulk temperature gives important insights into biological and hydrodynamic processes. However, standard algorithms for satellite data only provide information of the surface temperature. The comparison of current and new split-window coefficients applied on NOAA-14/AVHRR brightness temperatures of Lake Constance showed that a regional adaption was most promising. To derive the bulk temperature information, a priori progression from a weather station was included into the AVHRR analysis. Among the weather is data, the mean temperature of the three preceding days and the day of the year were the most relevant additional information. By a multiple regression approach the bulk temperature in the upper 4 m of Lake Constance could be determined with an accuracy of ±1.20 °C. The training of a neural network improved the determination of the bulk temperature to ±1.04 °C.An extended field campaign demonstrated that the algorithm is also applicable to other sensors with the same spectral band settings (in this case NOAA-16/AVHRR) with an acceptable error and that it is equally accurate over the entire lake.     

Genetic sequence stratigraphy of cool water slope carbonates (Pleistocene Eucla Shelf, southern Australia)

The south Australian Eucla Shelf belongs to the world's largest cool-water carbonate sedimentary system. During the Pleistocene, it exported large amounts of sediment to the shelf edge and upper slope resulting in an expanded sedimentary wedge. Wedge-internal clinoforming seismic reflectors suggest a stacking of the deposits into genetic sequences. High-resolution stable oxygen and carbon isotope, point counting, grain size, and carbonate mineralogical XRD analyses were carried out to characterize these genetic sequences along a dip-parallel transect of three ODP Leg 182 drill holes located between the shelf edge and upper slope. Oxygen and carbon isotope fluctuations show that the genetic sequences formed as a response to sea level fluctuations. Within the genetic sequences, facies differentiation and sediment volume partitioning occur along the transect. Lowstand deposits are fine grained and contain more sponge spicules and micrite. Highstand deposits are coarse grained with tunicate spicules, brown bioclasts, as well as bryozoan and corallinacean debris. Boundaries separating highstand and lowstand deposits are triggered by sea level fall, and are expressed as abrupt grain size changes or as turning points in grain-size trends. Analyzed components vary in abundance along the transect. Genetic sequences show dip-parallel variations in thickness combined with changing relative proportions of lowstand versus highstand deposits.     

Persistence of Artemisia steppe in the Tangra Yumco Basin,west-central Tibet,China: despite or in consequence of Holocene lake-level changes?

The closed Tangra Yumco Basin underwent the strongest Quaternary lake-level changes so far recorded on the Tibetan Plateau. It was hitherto unknown what effect this had on local Holocene vegetation development. A 3.6-m sediment core from a recessional lake terrace at 4,700 m a.s.l., 160 m above the present lake level of Tangra Yumco, was studied to reconstruct Holocene flooding phases (sedimentology and ostracod analyses), vegetation dynamics and human influence (palynology, charcoal and coprophilous fungi analyses). Peat at the base of the profile proves lake level was below 4,700 m a.s.l. during the Pleistocene/Holocene transition. A deep-lake phase started after 11 cal ka BP, but the ostracod record indicates the level was not higher than ~4,720 m a.s.l. (180 m above present) and decreased gradually after the early Holocene maximum. Additional sediment ages from the basin suggest recession of Tangra Yumco from the coring site after 2.6 cal ka BP, with a shallow local lake persisting at the site until ~1 cal ka BP. The final peat formation indicates drier conditions thereafter. Persistence of Artemisia steppe during the Holocene lake high-stand resembles palynological records from west Tibet that indicate early Holocene aridity, in spite of high lake levels that may have resulted from meltwater input. Yet pollen assemblages indicate humidity closer to that of present potential forest areas near Lhasa, with 500–600 mm annual precipitation. Thus, the early mid-Holocene humidity was sufficient to sustain at least juniper forest, but Artemisia dominance persisted as a consequence of a combination of environmental disturbances such as (1) strong early Holocene climate fluctuations, (2) inundation of habitats suitable for forest, (3) extensive water surfaces that served as barriers to terrestrial diaspore transport from refuge areas, (4) strong erosion that denuded the non-flooded upper slopes and (5) increasing human influence since the late glacial.     

Gas hydrates in shallow deposits of the Amsterdam mud volcano, Anaximander Mountains, Northeastern Mediterranean Sea

We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C₁/C₂₊ ratios <35 and δ¹³C-CH₄ values of ?50.6‰. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas–sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO ₄ ^2? and Ba²⁺ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.     

Isotopic age determinations of crystalline rocks of the Upper Harz Mountains,Germany

Dating of crystalline rocks occurring in the Upper Harz Mountains was carried out by means of U-Pb isotope investigations on zircons and sphene as well as by Rb-Sr isotope measurements on whole-rock samples and biotites.U-Pb data of euhedral and rounded, detrital zircons of the allochthonous block of the Ecker gneiss point to an age (upper intercept) of the source area of the predominantly metasedimentary rocks of about 1.6 Ga or older. The lower intercept indicates a possible metamorphic event at ca. 560 Ma in the Ecker gneiss or in the source rock of the zircons of this complex. The concordant data point of a sphene fraction from a metavolcanic sample documents contact metamorphic influence on the Ecker gneiss by the Variscan intrusions of the Upper Harz Mountains.Emplacement of the intrusions of the Harzburg gabbronorite and the Brocken and Oker granites occurred contemporaneously 293–297 Ma ago within the analytical error limits. This points to a common geotectonic cause of the ascent of the magmas. Uplift of the Ecker gneiss block, now squeezed in between Harzburg gabbronorite and Brocken granite, was connected to these processes.The mineral ages of the plutonites are close to the intrusion ages indicating fast cooling processes in shallow crustal levels.

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Zusammenfassung Eine altersmäßige Einstufung der im Oberharz vorkommenden kristallinen Gesteine wurde durch U-Pb-Isotopenuntersuchungen an Zirkonen und Titanit sowie Rb-Sr-Isotopenmessungen an Gesamtgesteinsproben und Biotiten durchgeführt.U-Pb-Daten von idiomorphen und runden, detritischen Zirkonen der allochthonen Eckergneis-Scholle deuten auf ein Alter des Ursprungsgebietes der weitgehend metasedimentären Gesteine von etwa 1. 6 Ga oder älter hin und sie weisen ferner auf ein mögliches Metamorphose-Ereignis vor rund 560 Ma im Eckergneis oder im Liefergestein der Zirkone des Eckergneises hin. Der konkordante Datenpunkt bei ca. 295 Ma einer Titanit-Fraktion aus einer Metavulkanit-Probe dokumentiert die kontaktmetamorphe Beeinflussung des Eckergneises durch die variskischen Intrusionen des Oberharzes.Die Platznahme der Intrusionen der Gesteine des Harzburger Gabbronorit-Massivs sowie des Brokken- und Oker-Granits erfolgten innerhalb der analytischen Fehlergrenzen zeitgleich vor 293–295 Ma. Dies deutet auf eine gemeinsame geotektonische Ursache des Aufdringens der Magmen. Damit verbunden war der Aufstieg der Eckergneis-Scholle, die jetzt zwischen Harzburger Gabbronorit und Brockengranit »eingeklemmt« ist.Mineralalter der Plutonite liegen nahe bei den Intrusionsaltern und weisen auf rasche Abkühlungsvorgänge in seichtem Krustenniveau hin.

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Résumé Des mesures d'âge ont été effectuées sur des roches cristallines de l'Oberharz par les méthodes de l'U-Pb sur zircon et sphène et du Rb-Sr sur roches totales et sur biotites. La méthode U-Pb, appliquée aux zircons idiomorphes et détritiques arrondis de l'écaille allochtone des gneiss d'Ecker, fournit un âge (intersection supérieure) d'environ 1,6 Ga au moins pour la source des matériaux surtout métasédimentaires. L'intersection inférieure indique la possibilité d'un événement métamorphique à ± 560 Ma soit dans les gneiss d'Ecker, soit dans les roches-sources de leurs zircons. Un résultat concordant à ± 295 Ma fourni par le sphène d'une métavolcanite enregistre l'action du métamorphisme de contact engendré dans les gneiss d'Ecker par les intrusions varisques.La mise en place des intrusions du massif gabbronoritique du Harzburg et celle des granite de Brocken et d'Ocker ont été contemporaines: âges de 293 à 297 Ma, compris dans l'intervalle d'approximation des mesures. Ce résultat est en faveur d'une même cause géotectonique pour l'ascension de ces magmas. C'est en relation avec ce processus que s'est produit le soulèvement de l'écaillé des gneiss d'Ecker, actuellement coincée entre le gabbro du Harzburg et le granite de Brocken.Les âges minéraux des plutons sont voisins des âges d'intrusion, ce qui indique un refroidissement rapide dans un niveau crustal peu profond.

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