Experimental study of the aragonite to calcite transition in aqueous solution

The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200 °C using single inorganic aragonite crystals as a starting material. The initial saturation state and the total [Ca²⁺]:[CO₃²⁻] ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy.Experiments using carbonate solutions prepared with water enriched in ¹⁸O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of ¹⁸O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the ¹⁸O distribution in the calcite replacement. An activation energy of 109 kJ/mol was calculated for the exchange of oxygen isotopes between [C¹⁶O₃²⁻]_aq and [H₂¹⁸O] and the time for oxygen isotope exchange in the fluid at 200 °C was estimated at ∼0.9 s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution-reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.     

The Influence of Coastal Nutrients on Phytoplankton Productivity in a Shallow Low Inflow Estuary,Drakes Estero,California (USA)

Seasonal wind-driven upwelling along the U.S. West Coast supplies large concentrations of nitrogen to surface waters that drives high primary production. However, the influence of coastal upwelled nutrients on phytoplankton productivity in adjacent small estuaries and bays is poorly understood. This study was conducted in Drakes Estero, California, a low inflow estuary located in the Point Reyes National Seashore and the site of an oyster mariculture facility that produces 40 % of the oysters harvested in California. Measurements of nutrients, chlorophyll a, phytoplankton functional groups, and phytoplankton carbon and nitrogen uptake were made between May 2010 and June 2011. A sea-to-land gradient in nutrient concentrations was observed with elevated nitrate at the coast and higher ammonium at the landward region. Larger phytoplankton cells (>5 μm diameter) were dominant within the outer and middle Estero where phytoplankton primary productivity was fueled by nitrate and f-ratios were >0.5; the greatest primary production rates were in the middle Estero. Primary production was lowest within the inner Estero, where smaller phytoplankton cells (<5 μm) were dominant, and nitrogen uptake was dominated by ammonium. Phytoplankton blooms occurred at the outer and middle Estero and were dominated by diatoms during the spring and dry-upwelling seasons but dinoflagellates during the fall. Small flagellated algae (>2 μm) were dominant at the inner Estero where no blooms occurred. These results indicate that coastal nitrate and phytoplankton are imported into Drakes Estero and lead to periods of high new production that can support the oyster mariculture; a likely scenario also for other small estuaries and bays.     

Geochemical constraints on the origin of the Permian Baimazhai mafic–ultramafic intrusion,SW China

The ∼260 Ma Baimazhai mafic–ultramafic intrusion is considered to be part of the Emeishan large igneous province and consists of orthopyroxenite surrounded by websterite and gabbro. The intrusion is variably mineralized with a massive sulfide ore body (∼20 vol.%) in the core of the intrusion. Silicate rocks have Ni/Cu ratios ranging from 0.3 to 46 with majority less than 7 and are rich in LREE relative to HREE and show Nb and Ta anomalies in primitive mantle-normalized trace element patterns, with low Nb/Th (1.0–4.5) and Nb/La (0.3–1.0) ratios. Their ɛ Nd(t) values range from −3.3 to −8.4. Uniform Pd/Pt (0.7–3.5) and Cu/Pd (100,000–400,000) ratios throughout the intrusion indicate that all the sulfides in the rocks were formed in a single sulfide-saturation event. Modeling suggests that the Baimazhai rocks were formed when an Mg-rich magma became crustally contaminated in a deep-seated staging chamber. Crustal contamination (up to ∼35%) drove the magma to S-saturation and forced orthopyroxene (Opx) onto the liquidus. The crystal-bearing magma forced out of the staging chamber was migrated by flow differentiation and consequently, the denser sulfide melt and the Opx crystals became centrally disposed in the flowing magma to form the Baimazhai intrusion.Electronic Supplementary Material Supplementary material is available to authorised users in the online version of this article at .     

Stochastic sediment transport: anomalous diffusions and random movement

Stochastic Environmental Research and Risk Assessment - A sediment particle in a flow not only follows the flow direction but also randomly diffuses through the surrounding fluid, because of the...     

Application of Plutonium Isotopes to the Sediment Geochronology of Coarse-Grained Sediments from Englebright Lake,California (USA)

The determination of sediment accumulation rates in environments with temporal variations in texture is challenging using traditional radioisotope methods, largely due to low activities associated with coarse sediments. This study used Englebright Lake, an impoundment in northern California, as a model system to examine the application of plutonium isotopes in lacustrine environments where the interlayering of coarse and fine sediments complicates the geochronology. Inductively coupled plasma mass spectrometry was used to quantify plutonium isotopes and low limits of detection allowed for the measurement of plutonium in sand, clay, and silt fractions. Although measurable levels of plutonium were found in sand fractions, over 75 % of the total plutonium activity was found in fine-grain-size fractions (<63 μm). Correlations between cesium-137 and plutonium activities in fine-grained sediments (r = 0.81–0.98, p < 0.005) suggest that plutonium isotopes may be substituted for cesium isotopes in coarse-grained sediments where cesium is typically below detectable levels. Sediment accumulation rates calculated from grain-size normalized plutonium activity profiles ranged from 6 to 145 cm year^?1 in Englebright Lake and identified a sediment depocenter at the delta front upstream of Englebright Dam. Progradation of the delta front reflected changes in sediment supply from the watershed in response to flood events, whereas average annual accumulation responded to human impacts. This study extends the application of plutonium isotopes for sediment geochronology to aquatic environments dominated by coarse sediments and provides new information that contributes to a better understanding of the processes influencing sediment deposition in Englebright Lake.     

Macroalgal distribution patterns in a shallow, soft-bottom lagoon, with emphasis on the nonnativeGracilaria vermiculophylla andCodium fragile

We determined the distribution of macroalgae in Hog Island Bay, a shallow coastal lagoon in Virginia, USA, seasonally at 12 sites from 1998 to 2000 and at 3 representative sites from 2000 to 2002. We analyzed macroalgal biomass, taxonomic richness, and abundance of two non-native species, the cryptic invaderGracilaria vermiculophylla and the conspicuousCodium fragile, with respect to season, location (mainland, mid lagoon, barrier island sites), and elevation (intertidal, subtidal). Taxonomic richness, total algal biomass, and nonnative biomass peaked in the summer months when temperature and light availability were highest. A few stress tolerant and ephemeral algae dominated the algal assemblage.G. vermiculophylla constituted 74% of the entire algal biomass, was the most abundant alga in all seasons, locations, and elevation levels, and was positively correlated with taxonomic richness and abundance of filamentous species.Ulva curvata, Bryopsis plumosa, andC. fragile accounted for an additional 16% of the algal biomass. There are distinct habitats in Hog Island Bay that can be classified into low diversity-low biomass regions near the mainland and barrier islands and high diversity-high biomass regions in the open mid lagoon, where abundant shells for attachment and intermediate levels of water column nutrients and turbidity likely create better growth conditions. Taxonomic richness and biomass were higher in subtidal than intertidal zones, presumably due to lower desiccation stress. This study provides an example of how a single invasive species can dominate an entire assemblage, both in terms of biomass (being most abundant in all seasons, locations, and tidal levels) and species richness (correlating positively with epiphytic filamentous taxa). By adding hard-substratum structural complexity to a relatively homogenous soft-substratum system,G. vermiculophylla increases substratum availability for attachment and entanglement of other algal species and enhances local diversity. Without widespread and abundantG. vermiculophylla, taxa likePolysiphonia, Ceramium, Bryopsis, Ectocarpus, andChampia would likely be much less common. This study also highlights the importance of using DNA analysis of voucher specimens in monitoring programs to accurately identify cryptic invaders.