ALBERT

Description: Mg-silicate minerals (e.g., stevensite, kerolite, talc, sepiolite) play an important role in the construction of facies models in lacustrine and peri-marine environments because they are sensitive to changes in solution chemistry. However, the response of Mg-silicate mineralogy to changing aqueous chemistry is only broadly understood because the mechanisms underpinning the co-precipitation of Mg 2+ and SiO 2 (aq) from surface water, and subsequent Mg-silicate crystallization, are unclear. Here we describe the results of experiments designed to systematically examine the effects of pH, Mg/Si and salinity of the parent solution on the nature of initially precipitated products. Structural interrogation of the products with X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR) and thermal analysis (TGA/DTA) allow comparison of synthetic products with naturally occurring crystalline counterparts. In general, Mg 2+ and SiO 2 (aq) co-precipitation and nucleation of Mg-silicate layer structures first involves the rapid formation of 2:1 layers with trioctahedral occupancy and a mean coherent X-ray scattering domain between 1–2 unit cells with respect to the c axis. Well defined but diffuse hk reflections indicate two-dimensional growth, turbostratic stacking and highly variable interlayer hydration. Diffuse reflectance FTIR shows numerous structural similarities with stevensite, kerolite and sepiolite. However, TGA/DTA analysis indicates the presence of variable kerolite/stevensite interstratification not readily detectable through XRD analyses, as well as a significant degree of surface and interlayer hydration (e.g. 15–20 wt.%). We observe a number of clear trends in the products with respect to solution chemistry. For example, at low salinity, kerolite-like products dominate at high Mg/Si and high pH, whereas sepiolite-like products are formed at lower pH and lower Mg/Si. At high salinity and high Mg/Si, stevensite-like products are favoured at high pH and kerolite-like products dominate at lower pH, whereas a decrease in Mg/Si of the solution leads to sepiolite-like products at low pH and only stevensite-like products at high pH. Higher pH leads to an increase in octahedral vacancies which favour stevensite-like products; this may result from a higher rate of two-dimensional tetrahedral sheet expansion relative to the octahedral sheet, as inferred from studies of silica oligomerization and brucite growth kinetics. Together, our results indicate that the neoformation of Mg-rich silicates from solution may often begin with the rapid nucleation of hydrated 2:1 layers. Subsequent dehydration leads to progressive layer stacking order and could occur in response to wetting/drying cycles, prolonged exposure to high salinity solutions, or burial and heating. The surface and interlayer water associated with these products is undoubtedly an important source of diagenetic water in Mg-silicate-bearing successions, and the chemistry of this water upon later diagenesis should be a focus of future investigation.

Description: The idea is tested that the evolution of the Chalk’s clay mineral assemblage during diagenesis can be deduced by examining the relationships between its clay mineralogy, particle size distribution pattern, and the timing and trace element chemistry of the calcite cement. The preliminary results from five different examples of cementation developed at different stages of diagenesis in chalks with smectite-dominated clay assemblages suggest that this is a promising line of investigation. Soft chalks with minor amount of anoxic series calcite cement poor in Mg, Fe and Mn are associated with neoformed trioctahedral smectite and/or dioctahedral nontronite and talc. Hard ground chalk with extensive anoxic series calcite cement enriched in Mg and relatively high Fe, Mn and Sr are associated with neoformed glauconite sensu lato , berthierine and dioctahedral smectite, possibly enriched in Fe. The chalk associated with large ammonites shows extensive suboxic series calcite cement enriched in Mg, Mn and Fe that show no obvious correlation with its clay mineralogy. Nodular chalks with patchy suboxic series calcite cement enriched in Fe are associated with neoformed dioctahedral smectite, possibly enriched in Al, and berthierine. Regionally hardened chalk with extensive suboxic calcite cement and relatively high trace element contents contain pressure dissolution seams enriched in kaolin and berthierine. Laser-based particle-size distribution patterns suggest that each type of lithification has a typical complex clay mineral population, indicating that subtleties in mineralogy are not being identified and that there could be some control on the size and shape of the clay crystals by the different types of cementation.

Description: The Cambridge Diagenesis Conferences (1981–1998) were set up to act as a conduit for the interchange of clay mineral expertise between universities and research institutes on one hand, and the hydrocarbon industry on the other. At the time, oil companies were dealing with the development of the North Sea Oil Province which was turning out to be a natural laboratory for the fundamental study of authigenic clay minerals and their relationship to lithofacies, burial, overpressure, reservoir quality and hydrocarbon emplacement. This symbiosis between industry and academia flourished for nearly two decades. Each conference was followed by a special issue of Clay Minerals dealing with topics relevant to, or discussed at the particular meeting. By the late 1990s the North Sea had become a mature province and the major oil companies were looking to other parts of the world to replenish their reserves.

Description: The idea is tested that the evolution of the Chalk’s clay mineral assemblage during diagenesis can be deduced by examining the relationships between its clay mineralogy, particle size distribution pattern, and the timing and trace element chemistry of the calcite cement. The preliminary results from five different examples of cementation developed at different stages of diagenesis in chalks with smectite-dominated clay assemblages suggest that this is a promising line of investigation. Soft chalks with minor amount of anoxic series calcite cement poor in Mg, Fe and Mn are associated with neoformed trioctahedral smectite and/or dioctahedral nontronite and talc. Hard ground chalk with extensive anoxic series calcite cement enriched in Mg and relatively high Fe, Mn and Sr are associated with neoformed glauconite sensu lato, berthierine and dioctahedral smectite, possibly enriched in Fe. The chalk associated with large ammonites shows extensive suboxic series calcite cement enriched in Mg, Mn and Fe that show no obvious correlation with its clay mineralogy. Nodular chalks with patchy suboxic series calcite cement enriched in Fe are associated with neoformed dioctahedral smectite, possibly enriched in Al, and berthierine. Regionally hardened chalk with extensive suboxic calcite cement and relatively high trace element contents contain pressure dissolution seams enriched in kaolin and berthierine. Laser-based particle-size distribution patterns suggest that each type of lithification has a typical complex clay mineral population, indicating that subtleties in mineralogy are not being identified and that there could be some control on the size and shape of the clay crystals by the different types of cementation.

Description: Mg-silicate minerals (e.g., stevensite, kerolite, talc, sepiolite) play an important role in the construction of facies models in lacustrine and peri-marine environments because they are sensitive to changes in solution chemistry. However, the response of Mg-silicate mineralogy to changing aqueous chemistry is only broadly understood because the mechanisms underpinning the coprecipitation of Mg2+and SiO2(aq) from surface water, and subsequent Mg-silicate crystallization, are unclear. Here we describe the results of experiments designed to systematically examine the effects of pH, Mg/Si and salinity of the parent solution on the nature of initially precipitated products. Structural interrogation of the products with X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR) and thermal analysis (TGA/DTA) allow comparison of synthetic products with naturally occurring crystalline counterparts. In general, Mg2+and SiO2(aq) co-precipitation and nucleation of Mg-silicate layer structures first involves the rapid formation of 2:1 layers with trioctahedral occupancy and a mean coherent X-ray scattering domain between 1–2 unit cells with respect to thecaxis. Well defined but diffusehkreflections indicate two-dimensional growth, turbostratic stacking and highly variable interlayer hydration. Diffuse reflectance FTIR shows numerous structural similarities with stevensite, kerolite and sepiolite. However, TGA/DTA analysis indicates the presence of variable kerolite/stevensite interstratification not readily detectable through XRD analyses, as well as a significant degree of surface and interlayer hydration (e.g. 15–20 wt.%).We observe a number of clear trends in the products with respect to solution chemistry. For example, at low salinity, kerolite-like products dominate at high Mg/Si and high pH, whereas sepiolite-like products are formed at lower pH and lower Mg/Si. At high salinity and high Mg/Si, stevensite-like products are favoured at high pH and kerolite-like products dominate at lower pH, whereas a decrease in Mg/Si of the solution leads to sepiolite-like products at low pH and only stevensite-like products at high pH. Higher pH leads to an increase in octahedral vacancies which favour stevensite-like products; this may result from a higher rate of two-dimensional tetrahedral sheet expansion relative to the octahedral sheet, as inferred from studies of silica oligomerization and brucite growth kinetics.Together, our results indicate that the neoformation of Mg-rich silicates from solution may often begin with the rapid nucleation of hydrated 2:1 layers. Subsequent dehydration leads to progressive layer stacking order and could occur in response to wetting/drying cycles, prolonged exposure to high salinity solutions, or burial and heating. The surface and interlayer water associated with these products is undoubtedly an important source of diagenetic water in Mg-silicate-bearing successions, and the chemistry of this water upon later diagenesis should be a focus of future investigation.

Description: Metabolic bone diseases like osteoporosis result from the disruption of normal bone mineral balance (BMB) resulting in bone loss. During spaceflight astronauts lose substantial bone. Bed rest provides an analog to simulate some of the effects of spaceflight; including bone and calcium loss and provides the opportunity to evaluate new methods to monitor BMB in healthy individuals undergoing environmentally induced-bone loss. Previous research showed that natural variations in the Ca isotope ratio occur because bone formation depletes soft tissue of light Ca isotopes while bone resorption releases that isotopically light Ca back into soft tissue (Skulan et al, 2007). Using a bed rest model, we demonstrate that the Ca isotope ratio of urine shifts in a direction consistent with bone loss after just 7 days of bed rest, long before detectable changes in bone mineral density (BMD) occur. The Ca isotope variations tracks changes observed in urinary N-teleopeptide, a bone resorption biomarker. Bone specific alkaline phosphatase, a bone formation biomarker, is unchanged. The established relationship between Ca isotopes and BMB can be used to quantitatively translate the changes in the Ca isotope ratio to changes in BMD using a simple mathematical model. This model predicts that subjects lost 0.25 +/- 0.07% (+/- SD) of their bone mass from day 7 to day 30 of bed rest. Given the rapid signal observed using Ca isotope measurements and the potential to quantitatively assess bone loss; this technique is well suited to study the short-term dynamics of bone metabolism.