Cation substitution in synthetic meridianiite (MgSO<Subscript>4</Subscript>·11H<Subscript>2</Subscript>O) I: X-ray powder diffraction analysis of quenched polycrystalline aggregates

Meridianiite, MgSO₄·11H₂O, is the most highly hydrated phase in the binary MgSO₄–H₂O system. Lower hydrates in the MgSO₄–H₂O system have end-member analogues containing alternative divalent metal cations (Ni²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe²⁺, and Co²⁺) and exhibit extensive solid solution with MgSO₄ and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO₄ solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO₄ forms an undecahydrate; ZnSO₄ forms an orthorhombic heptahydrate (synthetic goslarite), MnSO₄, FeSO₄, and CoSO₄ form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO₄ crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO₄ forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) Å, b = 6.8628(1) Å, c = 12.6318(2) Å, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) ų, is consistent with it being an octahydrate, NiSO₄·8H₂O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co²⁺ or Mn²⁺, 20–30 mol. % Ni²⁺ or Zn²⁺, but less than 10 mol. % of Cu²⁺ or Fe²⁺. In three of the systems we examined, an ‘intermediate’ phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO₄, we observed a melanterite-structured heptahydrate at Cu/(Cu + Mg) = 0.5, which we identify as synthetic alpersite [(Mg_0.5Cu_0.5)SO₄·7H₂O)]. In the NiSO₄- and ZnSO₄-doped systems we characterised an entirely new hydrate which could also be identified to a lesser degree in the CuSO₄- and the FeSO₄-doped systems. The Ni-doped substance has been indexed with a monoclinic unit-cell of dimensions a = 6.7488(2) Å, b = 11.9613(4) Å, c = 14.6321(5) Å, and β = 95.047(3)°, systematic absences being indicative of space-group P2₁/c with Z = 4. The unit-cell volume, V = 1,176.59(5) ų, is consistent with it being an enneahydrate [i.e. (Mg_0.5Ni_0.5)SO₄·9H₂O)]. Similarly, the new Zn-bearing enneahydrate has refined unit cell dimensions of a = 6.7555(3) Å, b = 11.9834(5) Å, c = 14.6666(8) Å, β = 95.020(4)°, V = 1,182.77(7) ų, and the new Fe-bearing enneahydrate has refined unit cell dimensions of a = 6.7726(3) Å, b = 12.0077(3) Å, c = 14.6920(5) Å, β = 95.037(3)°, and V = 1,190.20(6) ų. The observation that synthetic meridianiite can form in the presence of, and accommodate significant quantities of other ions increases the likelihood that this mineral will occur naturally on Mars—and elsewhere in the outer solar system—in metalliferous brines.     

The solubility of aragonite in seawater—I. Effect of pH and water chemistry at one atmosphere

The effect of water chemistry on the solubility of aragonite in seawater has been defined experimentally as a series of apparent solubility products measured with respect to pH at one atmosphere.The dominant control of the apparent solubility product of aragonite is the carbonate ion concentration, and this is primarily a function of pH. In the light of this fact, we have reconciled our data with 81 other reported values of aragonite solubility by simply examining the water chemistry of the waters in which they were determined.     

Aluminous goethite: A mössbauer study

Mössbauer measurements at 300 K, 77 K and 4.2 K and X-ray data are presented for synthetic aluminous goethites (α Fe_1?x Al _x OOH) in two series containing up to 15 mole percent aluminium (hydrothermal preparation) and 19 mole percent aluminium (low-temperature preparation). The Mössbauer spectra for specimens at 300 K and 77 K display broadened and relaxed line-shapes with the relaxation rate increasing with aluminium substitution, whereas all the 4.2 K spectra can be described by a single magnetically split spectrum. At 4.2 K the magnitude of this splitting is 505 kOe for pure goethite and it decreases by 0.52 kOe per mole percent aluminium substitution. The absolute value of the recoil-free fraction f at 4.2 K has been measured for pure goethite and for aluminous goethites containing 7, 15 and 19 mole percent aluminium; it increases from f=0.69±0.02 to f=0.89±0.02 in this range. The increase is attributed to a stiffening of the goethite lattice as it contracts to accommodate the smaller aluminium ion. At 300 K f is found to decrease from f=0.65±0.05 for pure goethite to f=0.50±0.03 for goethite with 19 mole percent aluminium.     

Phytoplankton abundance and contributions to suspended particulate matter in the Ohio,Upper Mississippi and Missouri Rivers

Main channel habitats of the Ohio, Missouri, and Upper Mississippi Rivers were surveyed during the summers of 2004, 2005 and 2006 using a probability-based sampling design to characterize inter-annual and inter-river variation in suspended chlorophyll a (CHLa) and related variables. Large (fivefold) differences in CHLa were observed with highest concentrations in the Upper Mississippi (32.3 ± 1.8 μg L⁻¹), intermediate values in the Missouri (19.7 ± 1.1 μg L⁻¹) and lowest concentrations in the Ohio (6.8 ± 0.5 μg L⁻¹). Inter-annual variation was small in comparison to inter-river differences suggesting that basin-specific factors exert greater control over river-wide CHLa than regional-scale processes influencing climate and discharge. The rivers were characterized by variable but generally low light conditions as indicated by depth-averaged underwater irradiance <4 E m⁻² day⁻¹ and high ratios of channel depth to euphotic depth (>3). Despite poor light conditions, regression analyses revealed that TP was the best single predictor of CHLa (R ² = 0.40), though models incorporating both light and TP performed better (R ² = 0.60). Light and nutrient conditions varied widely within rivers and were inversely related, suggesting that riverine phytoplankton may experience shifts in resource limitation during transport. Inferred grazing and sedimentation losses were large yet CHLa concentrations did not decline downriver indicating that growth and loss processes were closely coupled. The contribution by algae to suspended particulate organic matter in these rivers (mean = 41%) was similar to that of lakes (39%) but lower relative to reservoirs (61%).     

Caribbean hydrological variability during the Holocene as reconstructed from crater lakes on the island of Grenada

Contemporary precipitation patterns in the Caribbean region are spatially variable, and the small number of Holocene paleoclimatic records may not adequately capture patterns of variation in the past. The hydrological history of Grenada was inferred from paleolimnological analyses of sediment cores from two crater lakes on the island. The basins were formed by volcanic activity some time during the Last Termination, but were dry between ca. 13 000 and ca. 7200 cal. a BP. After filling, the lakes were initially very shallow, and sedimentation was interrupted by a hiatus ca. 6300–5500 cal. a BP, followed by deposition of a thick tephra in both sites. After 5500 cal. a BP, lake level shows considerable multi‐centennial variability, superimposed upon a long‐term trend of generally higher lake level after 3200 cal. a BP. The pattern of lake‐level variation in Grenada shows some similarity with other Caribbean paleoclimatic records in terms of the timing of transitions, but differs from several classic studies in the sign of inferred precipitation change. The differences among records may reflect spatially variable precipitation patterns in the past in response to the position of the Intertropical Convergence Zone and to sea surface temperature influences on the trade winds and Caribbean low‐level jet. Copyright © 2011 John Wiley & Sons, Ltd.     

Particulate pollution monitoring in the Elefsis Gulf: The role of mineral magnetic studies

Measurements of ‘quadrature’ susceptibility (X_q) at low and high frequency on seabottom sediments of the Gulf of Elefsis supplement the results derived from the study of magnetic susceptibility (X) and saturation isothermal remanent magnetization (SIRM) (Scoullos et al., 1979) and make possible the distinction between the background soil erosional fraction and that of anthropogenic combustion origin. New devices speed up the on-site appraisal of the impact of discharges on marine sediment quality.     

The tunica hills,Louisiana-Mississippi: Late glacial locality for spruce and deciduous forest species

Reinvestigation of Quaternary sediments in West Feliciana Parish, southeastern Louisiana, and adjacent Wilkinson County, southwestern Mississippi, has resulted in revision of previous terrace stratigraphy of this portion of the Gulf Coastal Plain. Plant-macrofossil and pollen assemblages incorporated in fluviatile terrace deposits in the study area are reexamined in light of the current stratigraphic understanding. Macrofossils identified as white spruce (Picea glauca), tamarack (Larix laricina), and northern white cedar (Thuja occidentalis), recovered from these terrace deposits along with fossil remains of distinctly southern plant species, were initially interpreted as the result of dynamic intermixing of aggressive boreal species within a southern forest during the early Wisconsin (Brown, 1938). Failure to distinguish chronologically separate fossiliferous deposits resulted in the conceptual “mixing” of northern and southern plant species which came from two distinct fluviatile terrace sequences. Terrace 2 is now believed to be a fluviatile and coastwise depositional terrace of Sangamon Interglacial age; deposits of terrace 2 contain a distinctly warm-temperate plant assemblage. Fluviatile terrace 1 dates from 12,740 ± 300 to 3457 ± 366 BP and is now considered to be related to late glacial and Holocene aggradation and lateral migration of the Mississippi River (the local base level for streams in the study area); basal portions of terrace 1 contain fossils of white spruce, tamarack, and many plant species today characteristic of the cool-temperate Mixed Mesophytic Forest Association. Terrace 1 fossil deposits occur in fluviatile terraces along tributary streams of the Mississippi River at elevations 15 to 30 m above the maximum recorded historic flood stage of the Mississippi River. The plant macrofossils represent remains of species that grew at or very near the site of deposition; they were not “rafted in” by floodwaters of the Mississippi River. We present quantitative data for plant macrofossils and pollen that support our hypothesis that at least local cooling along the Blufflands of Mississippi and Louisiana promoted southward migrations of mixed mesophytic forest species and certain boreal species along this major pathway during late Wisconsin continental glaciation.