Thermal stability of porous sol-gel phosphosilicates and their surface area stabilisation by lanthanum addition

The thermal stability of porous sol-gel phosphosilicates was studied by comparing the textural features upon calcination between 400 and 550 °C. A significant loss of surface area and pore volume were observed; the first is due to thermal coarsening of the nanoparticles, and the pore volume reduction was ascribed to sintering of the most external nanoparticles producing less void volume. Lanthanum addition was investigated as thermal stabilizer. For the mesoporous phosphosilicate composition, lanthanum addition enhanced the surface area, showing a 45% and 50% improvement with respect to the La-free counterpart; the effect was much less visible for the macroporous composition.

A hydrothermally stable transition alumina by condensation-enhanced self-assembly and pyrolysis crystallization:application in the steam reforming of methane

The preparation of a steam-based hydrothermally stable transition alumina is reported. The gel was derived from a synthetic sol-gel route where Al-tri-sec-butoxide is hydrolysed in the presence of a non-ionic surfactant (EO20PO70EO20), HCl as the catalyst and water (H2O/Al = 6); the condensation was enhanced by treating the hydrolysed gel with tetrabutylammonium hydroxide (TBAOH), after which it was dried at 60 °C by solvent evaporation. The so-obtained mesophase was crystallized under argon at 1200 °C (1 h) producing a transition alumina containing δ/α, and possibly θ, alumina phases. Due to its surface acidity, the pyrolysis conditions transform the block copolymer into a cross-linked char structure that embeds the alumina crystallites. Calcination at 650 °C generates a fully porous material by burning the char; a residual carbon of 0.2 wt.% was found, attributed to the formation of surface (oxy)carbides. As a result, this route produces a transition alumina formed by nanoparticles of about 30 nm in size on average, having surface areas in the range of 59-76 m2 g-1 with well-defined mesopores centered at 14 nm. The material withstands steam at 900 °C with a relative surface area rate loss lower than those reported for δ-aluminas, the state-of-the-art MSU-X γ-alumina and other pure γ-aluminas. The hydrothermal stability was confirmed under relevant CH4 steam reforming conditions after adding Ni; a much lower surface area decay and higher CH4 conversion compared to a state-of-the-art MSU-X based Ni catalyst were observed. Two effects are important in explaining the properties of such an alumina: the char protects the particles against sintering, however, the dominant effect is provided by the TBAOH treatment that makes the mesophase more resistant to coarsening and sintering. This journal is © the Partner Organisations 2014.

Condensation-enhanced self-assembly as a route to high surface area α-aluminas

High surface area nanosized α-alumina has been obtained by thermally treating a sol-gel-derived mesophase at 1200 C; the mesophase was synthesized by a sol-gel route involving evaporation induced self-assembly (EISA) of a hydrolyzed gel from Al-tri-sec-butoxide in s-BuOH in the presence of a nonionic surfactant (EO20PO70EO20), HCl as catalyst, and water (H2O/Al = 6). The activated material renders moderate surface areas of about 8.4-10 m2 g-1, associated with significant crystallite coarsening. The key aspect to produce smaller crystallites is making the mesophase more resistant to coarsening. This was achieved by enhancing the condensation step by treating the hydrolyzed gel with tetrabutyl ammonium hydroxide (TBAOH) before evaporation. The characteristics of the mesophase indicate condensation of the primary particles with less AlO5 unsaturated sites, at the expense of a lower solid yield due to small crystallites dissolution. The activated TBAOH condensed EISA material is composed of α-alumina aggregated crystallites of about 60-100 nm, and the material possesses surface areas ranging from 16 to 24 m2 g -1 due to the improved resistance to coarsening. At least two aspects are suggested to play a role in this. The worm-hole morphology of the mesophase aggregates yields high particle coordination, which favors densification rather than coarsening. Furthermore, the decrease of the AlO5 defect sites by the TBAOH condensation makes the mesophase less reactive and consequently more resistant to coarsening. © 2013 American Chemical Society.

Stabilization of self-assembled alumina mesophases

An efficient route to stabilize alumina mesophases derived from evaporation-induced self-assembly is reported after investigating various aspects in-depth: influence of the solvent (EtOH, s-BuOH, and t-BuOH) on the textural and structural properties of the mesophases based on aluminum tri-sec-butoxide (ATSB), synthesis reproducibility, role of nonvolatile acids, and the crystallization and thermal stability of the crystalline counterparts. Mesophase specific surface area and pore uniformity depend notably on the solvent; s-BuOH yields the highest surface area and pore uniformity. The optimal mesophase synthesis is reproducible with standard deviations in the textural parameters below 5%. The most pore-uniform mesophases from the three solvents were thermally activated at 1023 K to crystallize them into γ-alumina. The s-BuOH mesophase is remarkably thermally stable, retaining the mesoscopic wormhole order with 300 m2/g (0.45 cm3/g) and an increased acidic site density. These features are not obtained with EtOH or t-BuOH, where agglomerated γ-Al2O3 crystallites are formed with lower surface areas and broader pore size distributions. This was rationalized by the increase of the hydrolysis rate using EtOH and t-BuOH. t-BuOH dehydrates under the synthesis conditions or reacts with HCl, situations that increase the water concentration and rate of hydrolysis. It was found that EtOH exchanges rapidly, producing a highly reactive Al-ethoxide, thus enhancing the hydrolysis rate as well. Particle heterogeneity with random packing of fibrous and wormhole morphologies, attributed to the high hydrolysis rate, was observed for mesophases derived from both solvents. Such a low particle coordination favors coarsening with enlargement of the pore size distribution upon thermal treatment, explaining the lower thermal stability. Controlled hydrolysis and formation of low-polymerized Al species in s-BuOH are possibly responsible for the adequate assembly onto the surfactant. This was verified by the formation of a regular distribution of relatively size-uniform nanoparticles in the mesophase; high particle coordination prevents coarsening, favors densification, and maintains a relatively uniform pore size distribution upon thermal treatment. The acid removal in the evaporation is another key factor to promote network condensation in this route. © 2013 American Chemical Society.

The health and nutritional status of multiethnic perimenopausal women

An integrated, dual-phase study design assessed the health and nutritional status and practices of African-American (A-A), Caribbean (A-C), and white non-Hispanic (W-A) women during perimenopause (40–55 years). During Phase I, four focus groups (n = 37) of male and female participants discussed the health and social implications of perimenopause. A conceptual framework for the main study (Phase II) was developed from the focus groups' findings, in concert with the main study's specific aims and objectives. ^ The main study, a cross-sectional survey, quantitatively assessed the health and nutritional status of a convenience sample of 109 women (25 A-A, 31 A-C and 53 W-A), who met specific eligibility criteria. Using seven instruments, sociodemographic, dietary, medical, reproductive health, health practice and anthropometric data were collected. ^ The groups were of comparable age, education, and socioeconomic status (SES). Despite these similarities, statistically significant interethnic nutritional status differences were found. Significantly more total energy and energy from fat were consumed by A-A than W-A and A-C women. Also, significantly more A-A and A-C than W-A women were overweight or obese with android-type weight patterning. ^ Overall, iron and calcium Recommended Dietary Allowances (RDA's) were not met by 35% and 68% of participants, respectively. Iron deficiency anemia was reported by 29% of participants while 33% reported heavier menstrual bleeding. Coupled with suboptimal iron intakes, this is likely to present a serious public health problem. Similarly, increased bone demineralization characteristic of perimenopause, coupled with suboptimal calcium intakes could precipitate another public health problem, osteoporosis. ^ Participants had different expectations about the role of medical care during perimenopause. Significantly more white (57%) than black (38% [A-A and AC]) women sought medical attention for symptoms. Whereas Hormone Replacement Therapy (HRT) was prescribed for 25% of them, only 13% were compliant at enrollment. ^ The trends and statistically significant findings of this study have huge public health policy implications. It is imperative that appropriate policies are formulated to ensure that America's ethnically diverse perimenopausal women have ready access to culturally appropriate care. This would optimize their health outcomes, and enhance their quality of life and productive capacities at this critical juncture of their lives. ^

Miocene stable isotope record of benthic foraminifera from IODP Site 320-U1336

Stable carbon and oxygen isotopes (d13C and d18O) of foraminiferal tests are amongst the most important tools in paleoceanography but the extent to which recrystallization can alter the isotopic composition of the tests is not well known. Here, we compare three middle Miocene (16-13 Ma) benthic foraminiferal stable isotope records from eastern equatorial Pacific sites with different diagenetic histories to investigate the effect of recrystallization. To test an extreme case, we analyzed stable isotope compositions of benthic foraminifera from Integrated Ocean Drilling Program Site U1336, for which the geochemistry of bulk carbonates and associated pore waters indicate continued diagenetic alteration in sediments > 14.7 Ma. Despite this diagenetic overprinting, the amplitudes and absolute values of the analyzed U1336 stable isotopes agree well with high resolution records from better preserved Sites U1337 and U1338 nearby. Our results suggest that although benthic foraminiferal tests of all three sites show some degree of textural changes due to recrystallization, they have retained their original stable isotope signatures. The good agreement of the benthic foraminiferal stable isotope records demonstrates that recrystallization occurred extremely rapidly (<100 kyr) after deposition. This is confirmed by the preservation of orbital cyclicities in U1336 stable isotope data and d18O values being different to inorganic calcite that would precipitate from U1336 pore waters during late recrystallization. The close similarity of the benthic foraminiferal stable isotope records between the sites allows the well resolved paleo-magnetic results of Site U1336 to be transferred to Sites U1337 and U1338 improving the global Geological Timescale.

Carbonates and selected geochemistry composition for sediments from Lake Iznik for the past 31 ka cal BP

This study examines the forcing mechanisms driving long-term carbonate accumulation and preservation in lacustrine sediments in Lake Iznik (northwestern Turkey) since the last glacial. Currently, carbonates precipitate during summer from the alkaline water column, and the sediments preserve aragonite and calcite. Based on X-ray diffraction data, carbonate accumulation has changed significantly and striking reversals in the abundance of the two carbonate polymorphs have occurred on a decadal time scale, during the last 31 ka cal BP. Different lines of evidence, such as grain size, organic matter and redox sensitive elements, indicate that reversals in carbonate polymorph abundance arise due to physical changes in the lacustrine setting, for example, water column depth and lake mixing. The aragonite concentrations are remarkably sensitive to climate, and exhibit millennial-scale oscillations. Extending observations from modern lakes, the Iznik record shows that the aerobic decomposition of organic matter and sulphate reduction are also substantial factors in carbonate preservation over long time periods. Lower lake levels favour aragonite precipitation from supersaturated waters. Prolonged periods of stratification and consequently enhanced sulphate reduction favour aragonite preservation. In contrast, prolonged or repeated exposure of the sediment-water interface to oxygen results in in situ aerobic organic matter decomposition, eventually leading to carbonate dissolution. Notably, the Iznik sediment profile raises the hypothesis that different states of lacustrine mixing lead to selective preservation of different carbonate polymorphs. Thus, a change in the entire lake water chemistry is not strictly necessary to favour the preservation of one polymorph over another.

Remoção de metais utilizando o hexadecanoato de sódio

Industrial activities like mining, electroplating and the oil extraction process, are increasing the levels of heavy metals such as Cu, Fe, Mg and Cd in aquatic ecosystems. This increase is related to the discharge of effluents containing trace of this elements above the maximum allowed by law. Methods such as ion exchange, membrane filtration and chemical precipitation have been studied as a means of treatment of these metals contamination. The precipitation of metals using anionic surfactants derived from carboxylic acids emerged as an alternative for the removal of metals from industrial effluents. The reaction between bivalent ions and these types of surfactants in aqueous solution leads to the formation of metal carboxylates, which can precipitate in the form of flakes and are subsequently removed by a process of decantation or simple filtration. In this work the metals extraction is performed by using the surfactant sodium hexadecanoate as extracting agent. The main purpose was to study the effect of temperature, solution pH, and concentration of surfactant in the metal removal process. The statistical design of the process showed that the process is directly dependent to changes in pH and concentration of surfactant, but inversely proportional and somewhat dependent to temperature variation, with the latter effect being considered negligible in most cases. The individual study of the effect of temperature showed a strong dependence of the process with the Kraft point, both for the surfactant used as extracting agent, as for the surfactant obtained after the reaction of this surfactant with the metal. From data of temperatures and concentrations of the surfactant was possible to calculate the equilibrium constant for the reaction between sodium hexadecanoate and copper ions. Later, thermodynamic parameters were determined, showing that the process is exothermic and spontaneous.

Carbonate preservation of sediment cores from the Great Bahama Bank

The oceanic carbon cycle mainly comprises the production and dissolution/ preservation of carbonate particles in the water column or within the sediment. Carbon dioxide is one of the major controlling factors for the production and dissolution of carbonate. There is a steady exchange between the ocean and atmosphere in order to achieve an equilibrium of CO2; an anthropogenic rise of CO2 in the atmosphere would therefore also increase the amount of CO2 in the ocean. The increased amount of CO2 in the ocean, due to increasing CO2-emissions into the atmosphere since the industrial revolution, has been interpreted as "ocean acidification" (Caldeira and Wickett, 2003). Its alarming effects, such as dissolution and reduced CaCO3 formation, on reefs and other carbonate shell producing organisms form the topic of current discussions (Kolbert, 2006). Decreasing temperatures and increasing pressure and CO2 enhance the dissolution of carbonate particles at the sediment-water interface in the deep sea. Moreover, dissolution processes are dependent of the saturation state of the surrounding water with respect to calcite or aragonite. Significantly increased dissolution has been observed below the aragonite or calcite chemical lysocline; below the aragonite compensation depth (ACD), or calcite compensation depth (CCD), all aragonite or calcite particles, respectively, are dissolved. Aragonite, which is more prone to dissolution than calcite, features a shallower lysocline and compensation depth than calcite. In the 1980's it was suggested that significant dissolution also occurs in the water column or at the sediment-water interface above the lysocline. Unknown quantities of carbonate produced at the sea surface, would be dissolved due to this process. This would affect the calculation of the carbonate production and the entire carbonate budget of the world's ocean. Following this assumption, a number of studies have been carried out to monitor supralysoclinal dissolution at various locations: at Ceara Rise in the western equatorial Atlantic (Martin and Sayles, 1996), in the Arabian Sea (Milliman et al., 1999), in the equatorial Indian Ocean (Peterson and Prell, 1985; Schulte and Bard, 2003), and in the equatorial Pacific (Kimoto et al., 2003). Despite the evidence for supralysoclinal dissolution in some areas of the world's ocean, the question still exists whether dissolution occurs above the lysocline in the entire ocean. The first part of this thesis seeks answers to this question, based on the global budget model of Milliman et al. (1999). As study area the Bahamas and Florida Straits are most suitable because of the high production of carbonate, and because there the depth of the lysocline is the deepest worldwide. To monitor the occurrence of supralysoclinal dissolution, the preservation of aragonitic pteropod shells was determined, using the Limacina inflata Dissolution Index (LDX; Gerhardt and Henrich, 2001). Analyses of the grain-size distribution, the mineralogy, and the foraminifera assemblage revealed further aspects concerning the preservation state of the sediment. All samples located at the Bahamian platform are well preserved. In contrast, the samples from the Florida Straits show dissolution in 800 to 1000 m and below 1500 m water depth. Degradation of organic material and the subsequent release of CO2 probably causes supralysoclinal dissolution. A northward extension of the corrosive Antarctic Intermediate Water (AAIW) flows through the Caribbean Sea into the Gulf of Mexico and might enhance dissolution processes at around 1000 m water depth. The second part of this study deals with the preservation of Pliocene to Holocene carbonate sediments from both the windward and leeward basins adjacent to Great Bahama Bank (Ocean Drilling Program Sites 632, 633, and 1006). Detailed census counts of the sand fraction (250-500 µm) show the general composition of the coarse grained sediment. Further methods used to examine the preservation state of carbonates include the amount of organic carbon and various dissolution indices, such as the LDX and the Fragmentation Index. Carbonate concretions (nodules) have been observed in the sand fraction. They are similar to the concretions or aggregates previously mentioned by Mullins et al. (1980a) and Droxler et al. (1988a), respectively. Nonetheless, a detailed study of such grains has not been made to date, although they form an important part of periplatform sediments. Stable isotopemeasurements of the nodules' matrix confirm previous suggestions that the nodules have formed in situ as a result of early diagenetic processes (Mullins et al., 1980a). The two cores, which are located in Exuma Sound (Sites 632 and 633), at the eastern margin of Great Bahama Bank (GBB), show an increasing amount of nodules with increasing core depth. In Pliocene sediments, the amount of nodules might rise up to 100%. In contrast, nodules only occur within glacial stages in the deeper part of the studied core interval (between 30 and 70 mbsf) at Site 1006 on the western margin of GBB. Above this level the sediment is constantly being flushed by bottom water, that might also contain corrosive AAIW, which would hinder cementation. Fine carbonate particles (<63 µm) form the matrix of the nodules and do therefore not contribute to the fine fraction. At the same time, the amount of the coarse fraction (>63 µm) increases due to the nodule formation. The formation of nodules might therefore significantly alter the grain-size distribution of the sediment. A direct comparison of the amount of nodules with the grain-size distribution shows that core intervals with high amounts of nodules are indeed coarser than the intervals with low amounts of nodules. On the other hand, an initially coarser sediment might facilitate the formation of nodules, as a high porosity and permeability enhances early diagenetic processes (Westphal et al., 1999). This suggestion was also confirmed: the glacial intervals at Site 1006 are interpreted to have already been rather coarse prior to the formation of nodules. This assumption is based on the grain-size distribution in the upper part of the core, which is not yet affected by diagenesis, but also shows coarser sediment during the glacial stages. As expected, the coarser, glacial deposits in the lower part of the core show the highest amounts of nodules. The same effect was observed at Site 632, where turbidites cause distinct coarse layers and reveal higher amounts of nodules than non-turbiditic sequences. Site 633 shows a different pattern: both the amount of nodules and the coarseness of the sediment steadily increase with increasing core depth. Based on these sedimentological findings, the following model has been developed: a grain-size pattern characterised by prominent coarse peaks (as observed at Sites 632 and 1006) is barely altered. The greatest coarsening effect due to the nodule formation will occur in those layers, which have initially been coarser than the adjacent sediment intervals. In this case, the overall trend of the grain-size pattern before and after formation of the nodules is similar to each other. Although the sediment is altered due to diagenetic processes, grain size could be used as a proxy for e.g. changes in the bottom-water current. The other case described in the model is based on a consistent initial grain-size distribution, as observed at Site 633. In this case, the nodule reflects the increasing diagenetic alteration with increasing core depth rather than the initial grain-size pattern. In the latter scenario, the overall grain-size trend is significantly changed which makes grain size unreliable as a proxy for any palaeoenvironmental changes. The results of this study contribute to the understanding of general sedimentation processes in the periplatform realm: the preservation state of surface samples shows the influence of supralysoclinal dissolution due to the degradation of organic matter and due to the presence of corrosive water masses; the composition of the sand fraction shows the alteration of the carbonate sediment due to early diagenetic processes. However, open questions are how and when the alteration processes occur and how geochemical parameters, such as the rise in alkalinity or the amount of strontium, are linked to them. These geochemical parameters might reveal more information about the depth in the sediment column, where dissolution and cementation processes occur.

(Plate 3) Manganese nodules and deep-sea sediment core from Pacific Ocean

A synoptic review of the studies of well-known occurrences of palagonite tuffs is presented. Included are palagonite tuffs from Iceland, and pillow-lava palagonite complexes from Columbia River basalts and from the central Oregon coast. Additional petrologic and x-ray defraction data for selected samples are presented. Petrologic evidence shows that basaltic glass of aqueous tuffs and breccias consists of sideromelane, which is susceptible to palagonitization. It is shown that palagonitization is a selective alteration process, involving hydration, oxidation and zeolitization. Some of the manganese nodules dredged from the Pacific Ocean floor contain nucleus of palagonite-tuff breccias or of zeolite. A brief megascopic and microscopic description of nodules from the south Pacific, the Mendocino ridge and the 'Horizon' Nodule from the north Pacific is presented. Petrographic studies of palagonite-tuff breccias of manganese nodules and other palagonites suggest that migration and segregation of metallic elements occur during and subsequent to palagonitization. During the palagonitization of sideromelane, nearly 30 percent of sea water is absorbed. The hydration of sideromelane is also accompanied by oxidation of iron and other elements. These oxides may be released either in colloidal form or in true solution and tend to precipitate first from the unstable palagonite.

Chemical analysis of water samples of station M1_1207, Red Sea (Table 1-3)

Two water samples and two sediment samples taken in 1965 by the R. V. "Meteor" in the area of the hot salt brine of the Atlantis II-Deep were chemically investigated, and in addition the sediment samples were subjected to X-ray and optical analysis. The investigation of the sulfur-isotope-ratios showed the same values for all water samples. This information combined with the Ca-sulfate solubility data leads us to conclude that, for the most part, the sulfate content of the salt brine resulted from mixing along the boundary with the normal seawater. In this boundary area gypsum or anhydrite is formed which sinks down to the deeper layers of the salt brine where it is redisolved when the water becomes undersaturated. In the laboratory, formation of CaS04 precipitate resulted from both the reheating of the water sample from the uppermost zone of the salt brine to the in-situ-temperature as well as by the mixing of the water sample with normal Red Sea water. The iron and manganese delivered by the hot spring is separated within the area of the salt brine by their different redox-potentials. Iron is sedimented to a high amount within the salt brine, while, as evidenced by its small amounts in all sediment samples, the more easily reducible manganese is apparently carried out of the area before sedimentation can take place. The very good layering of the salt brine may be the result of the rough bottom topography with its several progressively higher levels allowing step-like enlargements of the surface areas of each successive layer. Each enlargement results in larger boundary areas along which more effective heat transfer and mixing with the next layer is possible. In the sediment samples up to 37.18% Fe is found, mostly bound as very poorly crystallized iron hydroxide. Pyrite is present in only very small amounts. We assume that the copper is bound mostly as sulfide, while the zinc is most likely present in an other form. The sulfur-isotope-investigations indicate that the sulfur in the sediment, bound as pyrite and sulfides, is not a result of bacterical sulfate-reduction in the iron-rich mud of the Atlantis II-Deep, but must have been brought up with the hot brine.

(Table 2) Major and trace elements in black smoker particulates

We present geochemical data of black smoker particulates filtered from hydrothermal fluids with seawater-dilutions ranging from 0-99%. Results indicate the dominance of sulphide minerals (Fe, Cu, and Zn sulphides) in all samples taken at different hydrothermal sites on the Mid-Atlantic Ridge. Pronounced differences in the geochemistry of the particles between Logatchev I and 5°S hydrothermal fields could be attributed to differences in fluid chemistry. Lower metal/sulphur ratios (Me/H2S < 1) compared to Logatchev I result in a larger amount of particles precipitated per liter fluid and the occurrence of elemental sulphur at 5°S, while at Logatchev I Fe oxides occur in larger amounts. Systematic trends with dilution degree of the fluid include the precipitation of large amounts of Cu sulphides at a low dilution and a pronounced drop with increasing dilution. Moreover, Fe (sulphides or oxides) precipitation increases with dilution of the vent fluid by seawater. Geochemical reaction path modeling of hydrothermal fluid-seawater mixing and conductive cooling indicates that Cu sulphide formation at Logatchev I and 5°S mainly occurs at high temperatures and low dilution of the hydrothermal fluid by seawater. Iron precipitation is enhanced at higher fluid dilution, and the different amounts of minerals forming at 5°S and Logatchev I are thermodynamically controlled. Larger total amounts of minerals and larger amounts of sulphide precipitate during the mixing path when compared to the cooling path. Differences between model and field observations do occur and are attributable to closed system modeling, to kinetic influences and possibly to organic constituents of the hydrothermal fluids not accounted for by the model.

(Table 1) Pore-water composition of ODP Leg 126 sites

The Ocean Drilling Program Leg 126 sites may be classified into two categories depending on the presence (Group I: Sites 787, 792, and 793) or absence (Group II: Sites 788, 790, and 791) of steep concentration gradients. Shipboard X-ray diffraction analyses of bulk sediments from Group I sites revealed the presence of a number of diagenetic minerals (some of which are incompatible), but no systematic diagenetic zonation. The results of the chemical analyses of the pore waters from Group I have been used to estimate the activities of dissolved species. Thermodynamic analyses of the composition of the pore waters and the stability of authigenic minerals (gypsum, zeolites, feldspars, smectites, chlorites, and micas) show that the pore waters are close to equilibrium with most of the observed phases. Thus, only a small perturbation of the system (substitution in minerals and fluctuations in pore-water composition, in particular, in pH and SiO2 activity) will cause any of these phases to precipitate. Therefore, one would not expect mineralogical observations to show systematic vertical zonations at these sites. It is suggested that chlorites and high-temperature zeolites are not diagenetic sensu stricto, but were eroded from volcaniclastic highs. The absence of concentration gradients at the Group II sites has been analyzed in terms of reaction kinetics, hydrothermal advection, and temperature distribution. The absence of diagenetic imprints on the pore-water concentration profiles at these sites is probably caused by the slow nucleation of silica phases.

High-resolution pore-water and solid-phase analyses of sediment cores GeoB6520-3 (Hydrate Hole) and GeoB6521-2 (Worm Hole) of the northern Congo Fan

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Seawater carbonate chemistry and benthic foraminifera Ammonia sp. mass, size, and growth rate during experiments, 2013

About 30% of the anthropogenically released CO2 is taken up by the oceans; such uptake causes surface ocean pH to decrease and is commonly referred to as ocean acidification (OA). Foraminifera are one of the most abundant groups of marine calcifiers, estimated to precipitate ca. 50 % of biogenic calcium carbonate in the open oceans. We have compiled the state of the art literature on OA effects on foraminifera, because the majority of OA research on this group was published within the last three years. Disparate responses of this important group of marine calcifiers to OA were reported, highlighting the importance of a process-based understanding of OA effects on foraminifera. We cultured the benthic foraminifer Ammonia sp. under a range of carbonate chemistry manipulation treatments to identify the parameter of the carbonate system causing the observed effects. This parameter identification is the first step towards a process-based understanding. We argue that CO3 is the parameter affecting foraminiferal size-normalized weights (SNWs) and growth rates. Based on the presented data, we can confirm the strong potential of Ammonia sp. foraminiferal SNW as a CO3 proxy.