Quantification of initial steps of nucleation and growth of silica nanoparticles: An in-situ SAXS and DLS study

The initial steps of silica polymerization and silica nanoparticle formation have been studied in-situ and in real-time. The experiments were carried out in near neutral pH (7–8) solutions with initial silica concentrations of 640 and 1600 ppm ([SiO₂]) and ionic strengths (IS) of 0.02, 0.05, 0.11 and 0.22 M. The polymerization reactions were induced by neutralizing a high pH silica solution (from pH 12 to 7) and monitored by the time-dependent depletion in monosilicic acid concentration over time. The accompanied nucleation and growth of silica nanoparticles (i.e., change in particle size over time) was followed in-situ using time-resolved synchrotron-based Small Angle X-ray Scattering (SAXS) and conventional Dynamic Light Scattering (DLS) combined with scanning and (cryo)-transmission electron microscopy (SEM/cryo-TEM).The critical nucleus diameter was quantified (1.4–2 nm) and results from SAXS and DLS showed that over 3 h the particle diameter increased to a final size of 8 nm. SEM and TEM photomicrographs verified the SAXS and DLS data and confirmed the spherical and hydrous structure of the forming silica nanoparticles. Furthermore, fractal analysis (i.e., fractal dimension, D_m  2.2) indicated that the formed particles consisted of open, polymeric, low-density structures.For the nucleation and growth of silica nanoparticles a 3-stage growth process is proposed: (1) homogeneous and instantaneous nucleation of silica nanoparticles, (2) 3-D, surface-controlled particle growth following 1st order reaction kinetics and (3) Ostwald ripening and particle aggregation.     

Geochemical and mineralogical impacts of H2SO4 on clays between pH 5.0 and −3.0

Natural and constructed clay liners are routinely used to contain waste and wastewater. The impact of acidic solutions on the geochemistry and mineralogy of clays has been widely investigated in relation to acid mine drainage systems at pH > 1.0. The impact of H₂SO₄ leachate characterized by pH < 1.0 and potentially negative pH values on the geochemistry and mineralogy of clays is, however, not clear. Thus, laboratory batch experiments were conducted on three natural clay samples with different mass ratios of smectite, illite and kaolinite to investigate the impact of H₂SO₄ on the geochemistry and mineralogy of aluminosilicates from pH 5.0 to −3.0. Batch testing was conducted at seven pH treatments (5.0, 3.0, 1.0, 0.0, −1.0, −2.0 and −3.0) using standardized H₂SO₄ solutions for four exposure periods (14, 90, 180, and 365 d). Aqueous geochemical and XRD analyses showed: increased dissolution of aluminosilicates with decreasing pH and increasing exposure period, that smectite was more susceptible to dissolution than illite and kaolinite, precipitation of an amorphous silica phase occurred at pH ? 0.0, and anhydrite precipitated in Ca-rich clays at pH ? −1.0. In addition, global dissolution rates were calculated for the clays and showed good agreement to literature smectite, illite and kaolinite dissolution rates, which suggests global dissolution rates for complex clays could be determined from monomineralic studies. A stepwise conceptual model of the impact of H₂SO₄ on aluminosilicate geochemistry and mineralogy between pH 5.0 and −3.0 is proposed.     

Phylogeny of the Sepia officinalis species complex in the eastern Atlantic extends the known distribution of Sepia vermiculata across the Benguela upwelling region

Accurate species identification and biogeographic characterisation are fundamental for appropriate management of expanding cephalopod fisheries. This study addresses this topic within the common cuttlefish Sepia officinalis species complex (S. officinalis, S. hierredda and S. vermiculata), with an emphasis on occurrence in African waters. Tissue samples from the currently presumed distributions of S. vermiculata and S. hierredda (from South Africa and Ghana/Angola, respectively) were sequenced for the cytochrome c oxidase subunit I (COI) and the cytochrome b (cytb) genes of the mitochondrial genome and then compared to existing S. officinalis sequences. Three highly divergent and reciprocally monophyletic clades, corresponding to S. officinalis, S. hierredda and S. vermiculata, were resolved, representing the first molecular confirmation of the distinct species status of S. hierredda and S. vermiculata. The sequences also revealed that, contrary to expectations based on presently published information, all samples from southern Angola were S. vermiculata. These results indicate that the range of S. vermiculata extends beyond the currently described northern limit and that S. hierredda and S. vermiculata may be indiscriminately harvested in Angolan waters. Finer-scale patterns within S. vermiculata phylogeography also indicate that the Benguela Current System and/or other environmental factors serve to isolate northern and southern stocks.     

Estimating groundwater inflow and leakage outflow for an intermontane lake with a structurally complex geology: Georgetown Lake in Montana,USA

Stable isotopes of the water molecule (δ¹⁸O and δD) for groundwater, lake water, streams, and precipitation were coupled with physical flux measurements to investigate groundwater–lake interactions and to establish a water balance for a structurally complex lake. Georgetown Lake, a shallow high-latitude high-elevation lake, is located in southwestern Montana, USA. The lake is situated between two mountain ranges with highlands primarily to the east and south of the lake and a lower valley to the west. An annual water balance and (δ¹⁸O and δD) isotope balance were used to quantify annual groundwater inflows of 2.5?×?10⁷ m³/year and lake leakage outflows of 1.6?×?10⁷ m³/year. Roughly, 57% of total inflow to the lake is from groundwater, and 37% of total outflow at Georgetown Lake is groundwater. Stable isotopes of groundwater and springs around the lake and surrounding region show that the east side of the lake contains meteoric water recharged annually from higher mountain sources, and groundwater discharge to the lake occurs through this region. However, springs located in the lower western valley and some of the surrounding domestic wells west of the lake show isotopic enrichment indicative of strong to moderate evaporation similar to Georgetown Lake water. This indicates that some outflowing lake water recharges groundwater through the underlying west-dipping bedrock in the region.     

Crystal chemical controls on rare earth element partitioning between epidote-group minerals and melts: an experimental and theoretical study

We have experimentally determined the partitioning of REE (rare earth elements) between zoisite and hydrous silicate melt at 1,100 °C and 3 GPa. All REE behave moderately compatible in zoisite with respect to the melt and all show a smooth parabolic dependence on ionic radius. The partitioning parabola peaks at Nd , and the compatibility slightly decreases towards La and decreases by half an order of magnitude towards Yb . Application of the elastic strain model of Blundy and Wood (1994) to the available zoisite and allanite REE mineral/melt partitioning data and comparison with partitioning pattern calculated from a combination of structural and physical data (taken from the literature) with the elastic strain model suggest that in zoisite REE prefer the A1-site and that only La and Ce are incorporated into the A2-site in significant amounts. In contrast, in allanite, all REE are preferentially incorporated into the large and highly co-ordinated A2 site. As a result, zoisite fractionates the MREE effectively from the HREE and moderately from the LREE, while allanite fractionates the LREE very effectively from the MREE and HREE. Consequently, the presence of either zoisite or allanite during slab melting will lead to quite different REE pattern in the produced melt.Editorial responsibility: J. Hoefs     

A detailed record of normal-reversed-polarity transition obtained from a thick loess sequence at Jiuzhoutai, near Lanzhou, China

A record of normal-reversed-polarity transition has been obtained from a 4 m thickness of loess exposed at a section near Lanzhou, China. Magnetostratigraphic studies suggest it may represent a reversal bounding the onset of a reversed-polarity zone within the Jaramillo Normal Subchron. The natural remanent magnetization consists of two components: a low-coercivity (≤20mT), low-unblocking-temperature (≤300°C) component of viscous origin and a high-coercivity (>20mT), high-unblocking-temperature (250–700 °C) component carrying the characteristic remanence. Mineral magnetic analyses confirmed the presence of magnetite, its low-temperature oxidation products and haematite, each contributing to the remanence properties. Grain size and concentration showed limited variations and there was little evidence for the presence of the ultrafine magnetic phase commonly associated with palaeosol formation. Pedogenic processes appeared negligible and their effects unimportant, with detrital processes dominating the mineralogy and most probably the acquisition of the characteristic remanence. The reversal record was characterized by the decay and recovery of the geocentric axial dipole term with large directional swings occurring during periods of reduced relative palaeofield intensity. The virtual geomagnetic poles traced a complex path exhibiting no particular geographical confinement. Relative palaeofield intensity determinations were insensitive to the choice of normalization parameter and showed a distinctive asymmetry. Striking similarities were observed with the Matuyama-Jaramillo reversal record, obtained from the same section (Rolph 1993), and the Steens Mountain reversal record (Prévot el al. 1985), lending further support for the existence of unusually high post-transitional field intensities     

Hydrocarbons in the intertidal environment of Kachemak Bay,Alaska

Intertidal animals and sediment from Kachemak Bay, Alaska were analysed to determine the concentrations of hydrocarbons. At Coal Point the herbivorous limpet Collisella pelta contained petroleum within its tissues while intertidal algae of the area have previously been shown to accumulate petroleum as a surface coating. At Coal Bay, a locality where both petroleum and coal are present, the filter feeding mussel Mytilus edulis contained petroleum hydrocarbons whereas the deposit feeding clam Macoma balthica contained an array of hydrocarbons suggesting detrital coal as the source. Animals higher in the food web including the gastropod Nucella lima and the urchin Strongylocentrotus droebachiensis showed no evidence of petroleum. All samples contained biogenic hydrocarbons of algal and planktonic origin.     

An international turbulence comparison experiment (ITCE 1976)

Turbulence data for the International Turbulence Comparison Experiment (ITCE) held at Conargo, N.S.W. (35° 18′ S., 145° 10′ E.) during October, 1976 are analysed. The standard deviation % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaiikaiqado% hagaqbamaaCaaaleqabaGaaGOmaaaakiaacMcadaahaaWcbeqaaiaa% igdacaGGVaGaaGOmaaaaaaa!3B93!\[(s'^2 )^{1/2} \] and covariance % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaa0aaaeaace% WG3bGbauaaceWGZbGbauaaaaaaaa!3809!\[\overline {w's'} \] measured by a number of instruments and instrument arrays have been compared to assess their field performance and calibration accuracy. Satisfactory agreement, i.e. typically 5% for % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaiikamaana% aabaGabm4CayaafaWaaWbaaSqabeaacaaIYaaaaaaakiaacMcadaah% aaWcbeqaaiaaigdacaGGVaGaaGOmaaaaaaa!3BA4!\[(\overline {s'^2 } )^{1/2} \] (except in humidity) and of the order of 20% for % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaiikaiqado% hagaqbamaaCaaaleqabaGaaGOmaaaakiaacMcadaahaaWcbeqaaiaa% igdacaGGVaGaaGOmaaaaaaa!3B93!\[(s'^2 )^{1/2} \], was achieved, but only after consideration of:

1. Instrumental response at high frequencies.
2. Flow distortion induced by instruments and supporting structures.
3. Spatial separation of instruments used for covariance measurements.
4. Statistical errors associated with single point measurements over a finite averaging time, and with lateral separation of two sensor arrays being compared.