Carbonates

Agarose can be activated by adding cyanogen bromide, dissolved in acetonitrile, to beads suspended in a solution of sodium carbonate. The necessity for manual titration and the use of a pH meter are thus eliminated. Activation for 1 min results in coupling capacities comparable to those reported for the titration method. The coupling capacity is influenced by the initial carbonate concentration and by the duration and temperature of the activation reaction. The coupling capacities of the activated gels are very reproducible.

Several lines of geological and geochemical evidence indicate that the level of atmospheric oxygen was extremely low before 2.45 billion years (Gyr) ago, and that it had reached considerable levels by 2.22 Gyr ago. Here we present evidence that the rise of atmospheric oxygen had occurred by 2.32 Gyr ago. We found that syngenetic pyrite is present in organic-rich shales of the 2.32-Gyr-old Rooihoogte and Timeball Hill formations, South Africa. The range of the isotopic composition of sulphur in this pyrite is large and shows no evidence of mass-independent fractionation, indicating that atmospheric oxygen was present at significant levels (that is, greater than 10 25 times that of the present atmospheric level) during the deposition of these units. The presence of rounded pebbles of sideritic iron formation at the base of the Rooihoogte Formation and an extensive and thick ironstone layer consisting of haematitic pisolites and oö lites in the upper Timeball Hill Formation indicate that atmospheric oxygen rose significantly, perhaps for the first time, during the deposition of the Rooihoogte and Timeball Hill formations. These units were deposited between what are probably the second and third of the three Palaeoproterozoic glacial events.

Calcium carbonate forms scales, geological deposits, biominerals, and ocean sediments. Huge amounts of carbon dioxide are retained as carbonate ions, and calcium ions represent a major contribution to water hardness. Despite its relevance, little is known about the precipitation mechanism of calcium carbonate, and specified complex crystal structures challenge the classical view on nucleation considering the formation of metastable ion clusters. We demonstrate that dissolved calcium carbonate in fact contains stable prenucleation ion clusters forming even in undersaturated solution. The cluster formation can be characterized by means of equilibrium thermodynamics, applying a multiple-binding model, which allows for structural preformation. Stable clusters are the relevant species in calcium carbonate nucleation. Such mechanisms may also be important for the crystallization of other minerals.

Liposomes of defined size and homogeneity have been prepared by sequential extrusion of the usual multilamellar vesicles through polycarbonate membranes. The process is easy, reproducible, produces no detectable degradation of the phospholipids, and can double the encapsulation efficiency of the liposome preparation. Multilamellar vesicles extruded by this technique are shown by both negative stain and freeze-fracture electron microscopy to have mean diameters approaching the pore diameter of the polycarbonate membrane through which they were extruded. When sequentially extruded down through a 0.2 pm membrane, the resulting vesicles exhibit a very homogeneous size distribution with a mean diameter of 0.27/lm while maintaining an acceptable level of encapsulation of the aqueous phase.

The recent proliferation of stratigraphic studies of ~13C variation in carbonates and organic C in later Neoproterozoic and basal Cambrian successions ( ~ 850-530 Ma) indicates a strong oscillating trend in the C-isotopic composition of surface seawater. Alone, this trend does not adequately characterize discrete intervals in Neoproterozoic time. However, integrated with the vectorial signals provided by fossils and Sr-isotopic variations, C isotope chemostratigraphy facilitates the interbasinal correlation of later Neoproterozoic successions. Results of these studies are evaluated in terms of four stratigraphic intervals: ( 1 ) the Precambrian/Cambrian boundary, (2) the post-Varanger terminal Proterozoic, (3) the late Cryogenian, and (4) the early Cryogenian. Where biostratigraphic or radiometric data constrain the age of Neoproterozoic sedimentary sequences, secular variations in C and Sr isotopes can provide a level of stratigraphic resolution exceeding that provided by fossils alone. Isotopic data place strong constraints on the chemical evolution of seawater, linking it to major tectonic and paleoclimatic events. They also provide a biogeochemical framework for the understanding of the initial radiation of macroscopic metazoans, which is associated stratigraphically, and perhaps causally, with a global increase in the burial of organic C and a concomitant rise of atmospheric 02. 0301-9268/95/$09.50

Analyses of stratigraphically continuous suites of samples from Upper Proterozoic sedimentary successions of East Greenland, Spitsbergen and Nordaustlandet (Svalbard) provide an approximation to the secular variation in carbon isotope ratios during a geologically and biologically important period of change from around 900 million years ago to the beginning of the Cambrian period. Late Riphean carbonates and organic material show a stratigraphically useful pattern of enrichment in 13C relative to Phanerozoic or earlier Proterozoic samples. Isotopic compositions of isolated samples from other localities are consistent with a worldwide extended interval of enhanced organic burial and consequent net survival of oxidized material, probably O2, just before the initial radiation of metazoans.

The effect of FEC as a co-solvent on the electrochemical performance and surface chemistry of silicon nanowire (SiNW) anodes was thoroughly investigated. Enhanced electrochemical performance was observed for SiNW anodes in alkyl carbonates electrolyte solutions containing fluoroethylene carbonate (FEC). Reduced irreversible capacity losses accompanied by enhanced and stable reversible capacities over prolonged cycling were achieved with FECcontaining electrolyte solutions. TEM studies provided evidence for the complete and incomplete lithiation of SiNW's in FEC-containing and FEC-free electrolyte solutions, respectively. Scanning electron microscopy (SEM) results proved the formation of much thinner and compact surface films on SiNW's in FECcontaining solutions. However, thicker surface films were identified for SiNW electrodes cycled in FEC-free solutions. SiNW electrodes develop lower impedance in electrolyte solutions containing FEC in contrast to standard (FEC-free) solutions. The surface chemistry of SiNW electrodes cycled in FEC-modified and standard electrolytes were investigated using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. The impact of FEC as a co-solvent on the electrochemical behavior of SiNW electrodes is discussed herein in light of the spectroscopic and microscopic studies.

The mangrove of Hara Biosphere Reserve, stretching over 100 thousand hectares in the southern coast of Iran and in the northwest of Qeshm Island, belongs to the most important and largest mangroves in the Middle East. Twenty sedimentary samples were collected and concentrations of seven heavy metals were investigated in order to assess the extent of pollution distribution in this area and to discuss the origin of these contaminants in sediments. The mean heavy metal concentrations followed the scheme: Fe > Cr > Ni > Zn > Cu > Pb > Cd. Based on the geo-accumulation index, the Fe, Pb, Zn, and Cu levels were graded as non-contamination, the levels of Cr and Ni as non-contamination to moderate contamination, while those of Cd as moderate contamination to moderate to heavy contamination. According to the enrichment factor and quantification of contamination calculations, Cu, Pb, and Zn were derived mainly from natural processes and exposure of material from the Earth's crust, while the increased values of Cd, Ni, and Cr were ascribed to anthropogenic activities. The ecological risk of heavy metals was moderate, largely due to Cd contamination. The elevated values identified for Cd, Ni, and Cr are supposingly associated with activities including human refuse, shipping, transportation, fuel smuggling, and industrial wastewater discharges from factories located around Hara Biosphere Reserve (e.g. Al-Mahdi aluminum factory, lead and zinc Qeshm factory, and Hormozgan cement factory).

Carbon monoxide (CO) and CO-releasing molecules (CO-RMs) inhibit platelet aggregation in vitro. Herein, we compare the anti-platelet action of CORM-3, which releases CO rapidly (t ½ 1 min), and CORM-A1, which slowly releases CO (t ½ 021 min). The anti-platelet effects of NO donors with various kinetics of NO release were studied for comparison. The effects of CO-RMs and NO donors were analyzed in washed human platelets (WP), platelets rich plasma (PRP), or whole blood (WB) using aggregometry technique. CORM-3 and CORM-A1 inhibited platelet aggregation in human PRP, WP, or WB, in a concentration-dependent manner. In all three preparations, CORM-A1 was more potent than CORM-3. Inhibition of platelets aggregation by CORM-A1 was not significantly affected by a guanylate cyclase inhibitor (ODQ) and a phosphodiesterase-5 inhibitor, sildenafil. In contrast, inhibition of platelet aggregation by NO donors was more potent with a fast NO releaser (DEA-NO, t ½ 02 min) than slow NO releasers such as PAPA-NO (t ½ 015 min) or other slow NO donors. Predictably, the anti-platelet effect of DEA-NO and other NO donors was reversed by ODQ while potentiated by sildenafil. In contrast to NO donors which inhibit platelets proportionally to the kinetics of NO released via activation of soluble guanylate cyclase (sGC), the slow CO-releaser CORM-A1 is a superior anti-platelet agent as compared to CORM-3 which releases CO instantly. The anti-platelet action of CO-RMs does not involve sGC activation. Importantly, CORM-A1 or its derivatives representing the class of slow CO releasers display promising pharmacological profile as anti-platelet agents.

Southern Ocean acidification via anthropogenic CO2 uptake is expected to be detrimental to multiple calcifying plankton species by lowering the concentration of carbonate ion (CO 3 2؊ ) to levels where calcium carbonate (both aragonite and calcite) shells begin to dissolve. Natural seasonal variations in carbonate ion concentrations could either hasten or dampen the future onset of this undersaturation of calcium carbonate. We present a large-scale Southern Ocean observational analysis that examines the seasonal magnitude and variability of CO 3 2؊ and pH. Our analysis shows an intense wintertime minimum in CO 3 2؊ south of the Antarctic Polar Front and when combined with anthropogenic CO2 uptake is likely to induce aragonite undersaturation when atmospheric CO2 levels reach Ϸ450 ppm. Under the IPCC IS92a scenario, Southern Ocean wintertime aragonite undersaturation is projected to occur by the year 2030 and no later than 2038. Some prominent calcifying plankton, in particular the Pteropod species Limacina helicina, have important veliger larval development during winter and will have to experience detrimental carbonate conditions much earlier than previously thought, with possible deleterious flow-on impacts for the wider Southern Ocean marine ecosystem. Our results highlight the critical importance of understanding seasonal carbon dynamics within all calcifying marine ecosystems such as continental shelves and coral reefs, because natural variability may potentially hasten the onset of future ocean acidification.

Essential oils were extracted by hydrodistillation from the traditional Australian medicinal plant Eremophila bignoniiflora, characterized chemically and then screened for bioactivity. Characterization and quantification were completed using gas chromatography-mass spectrometry (GC-MS) and GC-flame ionization detection, respectively. Antimicrobial capacity was assessed using disc diffusion and micro-titre plate broth dilution and further characterized using thin layer chromatography followed by bioautography to assign activity to separated individual active components. Antifungal capacity was investigated using micro-titre plate broth dilution against pathogenic Trichophyton species. Free radical scavenging ability was assessed using the diphenylpicrylhydradyl reaction in methanol. The predominant components of the essential oil were fenchyl-acetate and bornyl-acetate. However, bioautography indicated antimicrobial ability to be largely linked to the less abundant, more polar constituents. Oils displayed only modest antifungal ability against pathogenic Trichophyton species associated with dermatophytosis, but moderate to high antimicrobial activity, particularly against the yeast Candida albicans and the bacteria Staphylococcus epidermidis. Essential oils exhibited relatively low free radical scavenging ability. Speculation over the role of essential oils in the traditional medicinal applications of E. bignoniiflora follows, exploring correlations between traditional use and investigated bioactivities.

The formation constants of ternary complexes (MUO 2 (CO 3 ) 3 2and M 2 UO 2 (CO 3 ) 3 0 ) of uranyl and carbonate with alkaline earth metals (M 2+ denotes Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ ) were determined with an anion exchange method by varying the metal concentrations (0.1-5 mmol/L) at pH 8.1 and a constant ionic strength (0.1 mol/L NaNO 3 ) under equilibrium with atmospheric CO 2 . The results indicate that the complexes of MUO 2 (CO 3 ) 3 2and M 2 UO 2 (CO 3 ) 3 are simultaneously formed for Ca 2+ and Ba 2+ , while Mg 2+ and Sr 2+ form only the MUO 2 (CO 3 ) 3 2complex under our experimental conditions. The cumulative stability constants for the MUO 2 (CO 3 ) 3 2complex obtained at I ) 0 are as follows: log 113 ) 26.11 ( 0.04, 27.18 ( 0.06, 26.86 ( 0.04, and 26.68 ( 0.04 for Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ , respectively. For M 2 UO 2 (CO 3 ) 3 0 , the value of log 213 at I ) 0 was measured to be 30.70 ( 0.05 and 29.75 ( 0.07 for Ca 2+ and Ba 2+ , respectively. Based on the formation constants obtained in this study, speciation calculations indicate that at low Ca 2+ concentration (e.g., <2.2 mmol/L), CaUO 2 (CO 3 ) 3 2is more important than Ca 2 UO 2 (CO 3 ) 3 and that the Ca 2 UO 2 (CO 3 ) 3 distribution increased with increasing Ca 2+ concentration. Uranium sorption onto anion-exchange resins is inhibited by the formation of the neutral Ca 2 UO 2 (CO 3 ) 3 0 species.

We have synthesized inorganic micron-sized filaments, whose microstucture consists of silica-coated nanometer-sized carbonate crystals, arranged with strong orientational order. They exhibit noncrystallographic, curved, helical morphologies, reminiscent of biological forms. The filaments are similar to supposed cyanobacterial microfossils from the Precambrian Warrawoona chert formation in Western Australia, reputed to be the oldest terrestrial microfossils. Simple organic hydrocarbons, whose sources may also be abiotic and indeed inorganic, readily condense onto these filaments and subsequently polymerize under gentle heating to yield kerogenous products. Our results demonstrate that abiotic and morphologically complex microstructures that are identical to currently accepted biogenic materials can be synthesized inorganically.

α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursors: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in targetdirected synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.

It is assumed that the survival factors Bcl-2 and Bcl-xL are mainly functional on mitochondria and therefore must contain mitochondrial targeting sequences. Here we show, however, that only Bcl-xL is specifically targeted to the mitochondrial outer membrane (MOM) whereas Bcl-2 distributes on several intracellular membranes. Mitochondrial targeting of Bcl-xL requires the COOH-terminal transmembrane (TM) domain flanked at both ends by at least two basic amino acids. This sequence is a bona fide targeting signal for the MOM as it confers specific mitochondrial localization to soluble EGFP. The signal is present in numerous proteins known to be directed to the MOM. Bcl-2 lacks the signal and therefore localizes to several intracellular membranes. The COOH-terminal region of Bcl-2 can be converted into a targeting signal for the MOM by increasing the basicity surrounding its TM. These data define a new targeting sequence for the MOM and propose that Bcl-2 acts on several intracellular me...

Hydrothermal venting and the formation of carbonate chimneys in the Lost City hydrothermal field (LCHF) are driven predominantly by serpentinization reactions and cooling of mantle rocks, resulting in a highly reducing, high-pH environment with abundant dissolved hydrogen and methane. Phylogenetic and terminal restriction fragment length polymorphism analyses of 16S rRNA genes in fluids and carbonate material from this site indicate the presence of organisms similar to sulfur-oxidizing, sulfate-reducing, and methane-oxidizing Bacteria as well as methanogenic and anaerobic methane-oxidizing Archaea. The presence of these metabolic groups indicates that microbial cycling of sulfur and methane may be the dominant biogeochemical processes active within this ultramafic rock-hosted environment. 16S rRNA gene sequences grouping within the Methylobacter and Thiomicrospira clades were recovered from a chemically diverse suite of carbonate chimney and fluid samples. In contrast, 16S rRNA genes corresponding to the Lost City Methanosarcinales phylotype were found exclusively in high-temperature chimneys, while a phylotype of anaerobic methanotrophic Archaea (ANME-1) was restricted to lower-temperature, less vigorously venting sites. A hyperthermophilic habitat beneath the LCHF may be reflected by 16S rRNA gene sequences belonging to Thermococcales and uncultured Crenarchaeota identified in vent fluids. The finding of a diverse microbial ecosystem supported by the interaction of high-temperature, high-pH fluids resulting from serpentinization reactions in the subsurface provides insight into the biogeochemistry of what may be a pervasive process in ultramafic subseafloor environments.

Iron plaque on aquatic plant roots are ubiquitous and sequester metals in wetland soils; however, the mechanisms of metal sequestration are unresolved. Thus, characterizing the Fe plaque and associated metals will aid in understanding and predicting metal cycling in wetland ecosystems. Accordingly, microscopic and spectroscopic techniques were utilized to identify the spatial distributions, associations, and chemical environments of Fe, Mn, Pb, and Zn on the roots of a common, indigenous wetland plant (Phalaris arundinacea). Iron forms a continuous precipitate on the root surface, which is composed dominantly of ferrihydrite (ca. 63%) with lesser amounts of goethite (32%) and minor levels of siderite (5%). Although Pb is juxtaposed with Fe on the root surface, it is complexed to organic functional groups, consistent with those of bacterial biofilms. In contrast, Mn and Zn exist as discrete, isolated mixedmetal carbonate (rhodochrosite/hydrozincite) nodules on the root surface. Accordingly, the soil-root interface appears to be a complex biochemical environment, containing both reduced and oxidized mineral species, as well as bacterial-induced organic-metal complexes. As such, hydrated iron oxides, bacterial biofilms, and metal carbonates will influence the availability and mobility of metals within the rhizosphere of aquatic plants.

Nanoparticles provide an ideal remedy to the usually contradictory issues encountered in the optimization of immobilized enzymes: minimum diffusional limitation, maximum surface area per unit mass, and high effective enzyme loading. In addition to the promising performance features, the unique solution behaviors of the nanoparticles also point to a transitional region between the heterogeneous (with immobilized enzymes) and homogeneous (with soluble free enzymes) catalysis. The particle mobility, which is related to particle size and solution viscosity through Stokes-Einstein equation, may impact the reaction kinetics according to the collision theory. The mobility-activity relationship was examined through experimental studies and theoretical modeling in the present work. Polystyrene particles with diameters ranging from 110–1000 nm were prepared. A model enzyme, α-chymotrypsin, was covalently attached to the nanoparticles up to 6.6 wt%. The collision theory model was found feasible in correlating the catalytic activities of particles to particle size and solution viscosity. Changes in the size of particles and the viscosity of reaction media, which all affect the mobility of the enzyme catalyst, evidently altered the intrinsic activity of the particle-attached enzyme. Compared to KM, kcat appeared to be less sensitive to particle size and viscosity. © 2003 Wiley Periodicals, Inc. Biotechnol Bioeng84: 406–414, 2003.

Kaufman, A.J., Hayes, J.M., Knoll, A.H. and Germs, G.J.B., 199 !. Isotopic compositions of carbonates and organic carbon from upper Proterozoic successions in Namibia: stratigraphic variation and the effects of diagenesis and metamorphism. Precambrian Res., 49:301-327.

Widespread anoxia in the ocean is frequently invoked as a primary driver of mass extinction as well as a long-term inhibitor of evolutionary radiation on early Earth. In recent biogeochemical studies it has been hypothesized that oxygen deficiency was widespread in subsurface water masses of later Cambrian oceans 1,2 , possibly influencing evolutionary events during this time 1-3 . Physical evidence of widespread anoxia in Cambrian oceans has remained elusive and thus its potential relationship to the palaeontological record remains largely unexplored. Here we present sulphur isotope records from six globally distributed stratigraphic sections of later Cambrian marine rocks (about 499 million years old). We find a positive sulphur isotope excursion in phase with the Steptoean Positive Carbon Isotope Excursion (SPICE), a large and rapid excursion in the marine carbon isotope record, which is thought to be indicative of a global carbon cycle perturbation 4,5 . Numerical box modelling of the paired carbon sulphur isotope data indicates that these isotope shifts reflect transient increases in the burial of organic carbon and pyrite sulphur in sediments deposited under large-scale anoxic and sulphidic (euxinic) conditions. Independently, molybdenum abundances in a coeval black shale point convincingly to the transient spread of anoxia. These results identify the SPICE interval as the best characterized ocean anoxic event in the pre-Mesozoic ocean and an extreme example of oxygen deficiency in the later Cambrian ocean. Thus, a redox structure similar to those in Proterozoic oceans 6-8 may have persisted or returned in the oceans of the early Phanerozoic eon. Indeed, the environmental challenges presented by widespread anoxia may have been a prevalent if not dominant influence on animal evolution in Cambrian oceans.

Microalgae hold great potential as a feedstock for biofuels or bulk protein or treatment of wastewater or flue gas. Realizing these applications will require the development of a costefficient harvesting technology. Here, we explore the potential of flocculation induced by high pH for harvesting Chlorella vulgaris. Our results demonstrate that flocculation can be induced by increasing medium pH to 11. Although both calcium and magnesium precipitated when pH was increased, only magnesium (≥ 0.15 mM) proved to be essential to induce flocculation. The costs of four different bases (sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and sodium carbonate) were calculated and evaluated and the use of lime appeared to be the most cost-efficient. Flocculation induced by high pH is therefore a potentially useful method to preconcentrate freshwater microalgal biomass during harvesting.

is an authoritative source of information for professionals in a wide range of environmental disciplines. The journal combines magazine and research sections and is published both online and in print. The electronic version of ES&T includes all of the material found in the print version plus Supporting Information.

On the basis of a carbon isotopic record of both marine carbonates and organic matter from the Triassic-Jurassic boundary to the present, we modeled oxygen concentrations over the past 205 million years. Our analysis indicates that atmospheric oxygen approximately doubled over this period, with relatively rapid increases in the early Jurassic and the Eocene. We suggest that the overall increase in oxygen, mediated by the formation of passive continental margins along the Atlantic Ocean during the opening phase of the current Wilson cycle, was a critical factor in the evolution, radiation, and subsequent increase in average size of placental mammals.

Insight into the response of reef corals and other major marine calcifiers to ocean acidification is limited by a lack of knowledge about how seawater pH and carbonate chemistry impact the physiological processes that drive biomineralization. Ocean acidification is proposed to reduce calcification rates in corals by causing declines in internal pH at the calcifying tissue-skeleton interface where biomineralization takes place. Here, we performed an in vivo study on how partial-pressure CO 2 -driven seawater acidification impacts intracellular pH in coral calcifying cells and extracellular pH in the fluid at the tissue-skeleton interface [subcalicoblastic medium (SCM)] in the coral Stylophora pistillata. We also measured calcification in corals grown under the same conditions of seawater acidification by measuring lateral growth of colonies and growth of aragonite crystals under the calcifying tissue. Our findings confirm that seawater acidification decreases pH of the SCM, but this decrease is gradual relative to the surrounding seawater, leading to an increasing pH gradient between the SCM and seawater. Reductions in calcification rate, both at the level of crystals and whole colonies, were only observed in our lowest pH treatment when pH was significantly depressed in the calcifying cells in addition to the SCM. Overall, our findings suggest that reef corals may mitigate the effects of seawater acidification by regulating pH in the SCM, but they also highlight the role of calcifying cell pH homeostasis in determining the response of reef corals to changes in external seawater pH and carbonate chemistry.

Carbonate dramatically affects the adsorption of uranium (U(VI)) onto iron hydroxides and its mobility in the natural environment. Batch tests, zeta potential measurements, and Fourier transform infrared (FTIR) spectroscopic studies were utilized to characterize the nature of U(VI) adsorption on ferrihydrite. Adsorption isotherms demonstrated that carbonate had a negative effect on U(VI) adsorption on ferrihydrite at pH >6. Zeta potential measurements indicated that U(VI) was adsorbed as a cationic species (SO-UO 2 + ) in the absence of carbonate and as anionic U(VI) complexes in the presence of carbonate at neutral pH. FTIR spectroscopic measurement of adsorbed U(VI) suggested that it was retained as uranyl carbonate complexes in the presence of carbonate. An increase in carbonate concentration caused a shift in the antisymmetric stretching vibration of the uranyl (UO 2 2+ ) U-O bond toward lower wavenumbers, which indicated an increasing carbonate effect in the adsorbed uranyl carbonate complexes. The adsorbed U(VI) species were successfully incorporated into a surface complexation model to describe the adsorption of U(VI) by ferrihydrite from artificial solutions and contaminated water.

Viable microbes have been detected beneath several geographically distant glaciers underlain by different lithologies, but comparisons of their microbial communities have not previously been made. This study compared the microbial community compositions of samples from two glaciers overlying differing bedrock. Bulk meltwater chemistry indicates that sulfide oxidation and carbonate dissolution account for 90% of the solute flux from Bench Glacier, Alaska, whereas gypsum/anhydrite and carbonate dissolution accounts for the majority of the flux from John Evans Glacier, Ellesmere Island, Nunavut, Canada. The microbial communities were examined using two techniques: clone libraries and dot blot hybridization of 16S rRNA genes. Two hundred twenty-seven clones containing amplified 16S rRNA genes were prepared from subglacial samples, and the gene sequences were analyzed phylogenetically. Although some phylogenetic groups, including the Betaproteobacteria, were abundant in clone libraries from both glaciers, other well-represented groups were found at only one glacier. Group-specific oligonucleotide probes were developed for two phylogenetic clusters that were of particular interest because of their abundance or inferred biochemical capabilities. These probes were used in quantitative dot blot hybridization assays with a range of samples from the two glaciers. In addition to shared phyla at both glaciers, each glacier also harbored a subglacial microbial population that correlated with the observed aqueous geochemistry. These results are consistent with the hypothesis that microbial activity is an important contributor to the solute flux from glaciers.

The low salinity effect (LSE) in carbonate rock has been less explored compared to sandstone rock. Laboratory experiments have shown that brine composition and (somewhat reduced) salinity can have a positive impact on oil recovery in carbonates. However, the mechanism leading to improved oil recovery in carbonate rock is not well understood. Several studies showed that a positive LSF effect might be associated with dissolution of rock, however, due to equilibration, dissolution may not contribute at reservoir scale which would make LSF for carbonate rock less attractive for field applications. This raises now the question whether calcite dissolution is the primary mechanism of the LSF effect. In this paper we aim to first demonstrate the positive response of carbonate rock to low salinity and then to gain insight into the underlying mechanism(s) specific to carbonate rock. We followed a similar methodology as in sandstone rock (see Mahani et al. 2015) by using a model system comprised of carbonate surfaces obtained from crushed carbonate rocks. Wettability alteration upon exposure to low salinity brine was examined by continuous monitoring of the contact angle. Furthermore, the effective surface charge at oil-water and water-rock interfaces was quantified via zeta-potential measurements. Mineral dissolution was addressed both experimentally and with geochemical modeling using PHREEQC. Two carbonate rocks with different mineralogy were investigated: Limestone and Silurian dolomite. Four types of brines were used: High salinity formation water (FW), Seawater (SW), 25×diluted SW (25dSW) and 25×diluted SW equilibrated with calcite (25dSWEQ). It was observed that by switching from FW to SW, 25dSW and 25dSWEQ, the limestone surface became less oil-wet. The results with SW and 25dSWEQ suggest that the low salinity effect occurs even in the absence of mineral dissolution, because no dissolution is expected in SW and none in 25dSWEQ. The wettability alteration to less oil-wetting state by low salinity is consistent with the zeta-potential data of limestone indicating that at lower salinities the charges at the limestone-brine interface become more negative indicative of a weaker electrostatic adhesion between the oil-brine and rock-brine interfaces, thus recession of three-phase contact line. In comparison to limestone, a smaller contact-angle-reduction was observed with dolomite. This is again consistent with the zeta-potential of dolomite showing generally more positive charges at higher salinities and less decrease at lower salinities. This implies that oil detachment from dolomite surface requires a larger reduction of adhesion forces at the contact line than limestone. Our study concludes that surface-charge-change is likely to be the primary mechanism which means that there is a positive low salinity effect in carbonates without mineral dissolution.

Biomimetic Calcium–Phosphate (Ca–P) coatings were applied by using 5 times concentrated Simulated Body Fluid (SBF×5) using Carbon Dioxide gas. This process allows the deposition of a uniform Ca–P coating within 24 h. A previous study of our process emphasized the importance of hydrogenocarbonate ions (HCO3−), a crystal growth inhibitor. The aim of the present study was to investigate the role of the other crystal growth inhibitor present in SBF×5, Magnesium (Mg2+), on the Ca–P coating formation. Several SBF×5 solutions were prepared with various Mg2+ and HCO3− contents. No Ca–P deposits were detected on Ti6Al4V substrate soaked for 24 h in a Mg-free SBF×5 solution, whereas by increasing HCO3− content in a Mg-free SBF×5 solution, a Ca–P coating developed on Ti6Al4V substrate. Therefore, it appeared that Mg2+ has a stronger inhibitory effect on apatite crystal growth than HCO3−. Nevertheless, Mg2+ plays also another important role as suggested by depth profile X-ray Photoelectron Spectroscopy (XPS) of the Ca–P coating obtained from SBF×5 solution. Ca2+ and Mg2+ contents increased significantly at the titanium/coating interface. Therefore, Ca2+ and Mg2+ initiated Ca–P coating from SBF×5 solution. The relatively high interfacial concentration in Mg2+ favors heterogeneous nucleation of tiny Ca–P globules onto the substrate. So physical adhesion is enhanced at the early stage of the coating formation.