Tourmaline Reference Materials for the In Situ Analysis of Oxygen and Lithium Isotope Ratio Compositions

Three tourmaline reference materials sourced from the Harvard Mineralogical and Geological Museum (schorl 112566, dravite 108796 and elbaite 98144), which are already widely used for the calibration of in situ boron isotope measurements, are characterised here for their oxygen and lithium isotope compositions. Homogeneity tests by secondary ion mass spectrometry (SIMS) showed that at sub‐nanogram test portion masses, their ¹⁸O/¹⁶O and ⁷Li/⁶Li isotope ratios are constant within ± 0.27‰ and ± 2.2‰ (1s), respectively. The lithium mass fractions of the three materials vary over three orders of magnitude. SIMS homogeneity tests showed variations in ⁷Li/²⁸Si between 8% and 14% (1s), which provides a measure of the heterogeneity of the Li contents in these three materials. Here, we provide recommended values for δ¹⁸O, Δ’¹⁷O and δ⁷Li for the three Harvard tourmaline reference materials based on results from bulk mineral analyses from multiple, independent laboratories using laser‐ and stepwise fluorination gas mass spectrometry (for O), and solution multi‐collector inductively coupled plasma‐mass spectroscopy (for Li). These bulk data also allow us to assess the degree of inter‐laboratory bias that might be present in such data sets. This work also re‐evaluates the major element chemical composition of the materials by electron probe microanalysis and investigates these presence of a chemical matrix effect on SIMS instrumental mass fractionation with regard to δ¹⁸O determinations, which was found to be < 1.6‰ between these three materials. The final table presented here provides a summary of the isotope ratio values that we have determined for these three materials. Depending on their starting mass, either 128 or 512 splits have been produced of each material, assuring their availability for many years into the future.     

Precession‐scale cyclicity in the fluvial lower Eocene Willwood Formation of the Bighorn Basin,Wyoming (USA)

Little is known about controls on river avulsion at geological time scales longer than 10⁴ years, primarily because it is difficult to link observed changes in alluvial architecture to well‐defined allogenic mechanisms and to disentangle allogenic from autogenic processes. Recognition of Milankovitch‐sale orbital forcing in alluvial stratigraphy would provide unprecedented age control in terrestrial deposits, and also exploit models of allogenic forcing enabling more rigorous testing of allocyclic and autocyclic controls. The Willwood Formation of the Bighorn Basin is a lower Eocene fluvial unit distinctive for its thick sequence of laterally extensive lithological cycles on a scale of 4 to 10 m. Intervals of red palaeosols that formed on overbank mudstones are related to periods of relative channel stability when gradients between channel belts and floodplains were low. The intervening drab, heterolithic intervals with weak palaeosol development are attributed to episodes of channel avulsion that occurred when channels became super‐elevated above the floodplain. In the Deer Creek Amphitheater section in the McCullough Peaks area, these overbank and avulsion deposits alternate with a dominant cycle thickness of ca 7·1 m. Using integrated stratigraphic age constraints, this cyclicity has an estimated period of ca 21·6 kyr, which is in the range of the period of precession climate cycles in the early Eocene. Previous analyses of three older and younger sections in the Bighorn Basin showed a similar 7 to 8 m spacing of red palaeosol clusters with an estimated duration close to the precession period. Intervals of floodplain stability alternating with episodes of large‐scale reorganization of the fluvial system could be entirely autogenic; however, the remarkable regularity and the match in time scales documented here indicate that these alternations were probably paced by allogenic, astronomically forced climate change.     

Groundwater development,Kharga Oases,Western Desert of Egypt: A long-term environmental concern

The groundwater reserves in Kharga Oases have been studied for the long-term socioeconomic development in the area. The Nubian Sandstone, which consists of a thick sequence of coarse clastic sediments of sandstone, sandy clay interbedded with shale, and clay beds, forms a complex aquifer system. The Nubian Aquifer has been providing water to artesian wells and springs in the Kharga Oases for several thousand years. Groundwater in the Kharga Oases is withdrawn from springs and shallow and deep artesian wells Nearly all the wells originally flowed, but with the exploitation of ground-water from deep wells for irrigation beginning about 1959. the natural flows declined as more and more closely spaced deep wells were drilled By 1975 many deep wells had ceased to flow The water demand in the area has been met by pumping both shallow and deep wells The total annual extraction from deep wells has fluctuated over the year, however, the annual withdrawal from deep wells has exceeded extraction from shallow wells About 17 billion m³ of water was withdrawn from the combination of shallow and deep wells during the period 1960–1980 The Nubian complex aquifer in the Kharga Oases has a very large groundwater potential that could be exploited and beneficially used for a long-term agricultural development in the area, provided proper well spacing and management are implemented Other major environmental considerations for which precise hydrogeologic data are needed include

1. Determination of the long-term yield available from properly constructed and producing artesian wells that will support a planned migration of population from the overcrowded Nile delta and flood plain areas
2. Development of an effective management program and adequate staff to maintain groundwater production over an extended period of years
3. The impact on climate caused by extensive irrigation in the oases of the Western Desert of Egypt
4. Protection against water logging of soils from irrigation practices
5. Protection against salinization of soils from irrigation practices
6. Development of effective surface and subsurface drainage practices
7. The impact of farming and pest control practices on the shallow groundwater of the oases
8. Determination of the long-term development of the artesian water on the quality of the water from the aquiter systems in the Western Desert

This paper addresses items 1, 2 and 8.     

The pedigree and influence of fossil collections from the Falkland Islands: From Charles Darwin to continental drift

The Falkland Islands are typical of remote territories in that their early geological exploration was piecemeal and opportunistic. Whilst the resulting fossil collections (dominantly a Devonian fauna of the Malvinokaffric realm) remain the basis for modern interpretations, published accounts misrepresent their extent and provenance. Charles Darwin first discovered fossils during his 1833 visit aboard HMS Beagle, with subsequent British collections acquired in 1842 and 1876, respectively, by the Erebus and Terror and Challenger expeditions and in 1903 by the Scotia expedition. Darwin's collection, and much of the other material, is now held by The Natural History Museum, London (NHM) but some Darwin specimens were assimilated into other collections whilst at least one NHM ‘Darwin’ specimen was not collected by him. There may also be some uncertainty as to the origin of the Scotia collection, now held in Edinburgh by National Museums Scotland, in relation to a contemporary Swedish collection now held in Stockholm. The NHM holdings were supplemented by a number of enigmatic donations from private individuals and then by fossils collected during the first ‘official’ geological survey of the islands in 1920–1922. Meanwhile a large collection was built up in New York through collaboration in 1909 with a local collector – the Governor's wife! The regional associations of the fossils established the African heritage of Falklands geology, and thereby contributed to an understanding of continental drift as the mechanism for the fragmentation of the Gondwana supercontinent. The Falkland Islands are now regarded as a rotated microplate created during the break-up.     

Phase relations inferred from field data for mn pyroxenes and pyroxenoids

Electron microprobe analysis of manganese silicates from Balmat, N.Y., has helped elucidate phase relations for Mn-bearing pyroxenes and pyroxenoids. A compilation of these data along with published and unpublished analyses for phases plotting on the CaSiO₃-MgSiO₃-MnSiO₃ and CaSiO₃-FeSiO₃-MnSiO₃ faces of the RSiO₃ tetrahedron has constrained the subsolidus phase relations. For the system CaSiO₃-FeSiO₃-MnSiO₃, the compositional gaps between bustamite/hedenbergite, bustamite/ rhodonite and rhodonite/pyroxmangite are constrained for middle-upper amphibolite facies conditions and extensive solid solutions limit possible three phase fields. For the CaSiO₃-MgSiO₃-MnSiO₃ system much less data are available but it is clear that the solid solutions are much more limited for the pyroxenoid structures and a continuum of compositions is inferred for clinopyroxenes from diopside to kanoite (MnMgSi₂O₆) for amphibolite facies conditions (T=650° C). At lower temperatures, Balmat kanoites are unstable and exsolve into C2/c calciumrich (Ca_0.68Mn_0.44Mg_0.88Si₂O₆) and C2/c calciumpoor (Ca_0.12Mn_1.02Mg_0.86Si₂O₆) phases. At temperatures of 300–400° C the calcium-poor phase subsequently has undergone a transformation to a P2₁/c structure; this exsolution-inversion relationship is analogous to that relating augites and pigeonites in the traditional pyroxene quadrilateral. Rhodonite coexisting with Mn-clinopyroxenes is compositionally restricted to Mn_0.75–0.95Mg_0.0–0.15Ca_0.05–0.13SiO₃. For the original pyroxene+rhodonite assemblage, the Mg and Ca contents of the rhodonite are fixed for a specific P (6kbars)-T (650° C)-X(H₂O)-X(CO₂) by the coexistence of talc+quartz and calcite+quartz respectively.Contribution No. 363, from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor MI 48109, USA     

Allende inclusions: volatile-element distribution and evidence for incomplete volatilization of presolar solids

Neutron activation data on 14 trace elements in Allende bulk samples and in fractions of spheroidal Ca-Al-rich inclusions show several distinct distribution patterns. Refractories Ir and Sc have high inclusion/bulk ratios and show little variation with depth. Manganese, Fe, Co, Ni, Ga, Cd and In have low inclusion/bulk ratios and decrease with increasing depth; their presence in the inclusions reflects matrix contamination. Sodium and other alkalies have high inclusion/bulk ratios (near 0.5) and decrease with increasing depth; their high concentration despite moderate volatility seems related to condensation reactions in which refractory Al-bearing minerals are reactants. Chromium, Zn, Ge and Au show patterns similar to those of the alkalies; this seems to indicate that refractory minerals are reactants in their condensation reactions, but thermodynamic support for this hypothesis has not been found.We propose that the large size of Allende spheroidal inclusions indicates an origin by incomplete vaporization of presolar solid matter followed by recondensation of refractories on a limited number of condensation nuclei. The low abundance of large refractory inclusions in ordinary and enstatite chondrites reflects complete vaporization of presolar solids at their formation locations; constraints on homogeneous nucleation resulted in the simultaneous condensation of refractories and olivine at these locations.Quadruplicate analyses of the Orgueil chondrite are in good agreement with previous determinations with the exception of small systematic differences in Au and Ir.     

Geophysical Surveys over Karst Recharge Features,Illinois,USA

Karst aquifers supply a significant fraction of the world's drinking water. These types of aquifers are alsohighly susceptible to pollution from the surface with recharge usually occurring through fractures and solution openings at the bedrock surface. Thickness of the protective soil cover, macropores and openings within the soil cover, and the nature of the weathered bedrock surface all influence infiltration. Recharge openings at the bedrock surface, however, are often covered by unconsolidated sediments, resulting in the inadvertent placement of landfills, unregulated dump sites, tailing piles, waste lagoons and septic systems over recharge zones. In these settings surface geophysical surveys, calibrated by a few soil cores, could be employed to identify these recharge openings, and qualitatively assess the protection afforded by the soil cover. In a test of this hypothesis, geophysical measurements accurately predicted the thickness of unconsolidated deposits overlying karstic dolomite at a site ab     

The partitioning of copper between silicate melts and two-phase aqueous fluids: An experimental investigation at 1 kbar, 800° C and 0.5 kbar, 850° C

 Experiments were performed in the three phase system high-silica rhyolite melt+low-salinity aqueous vapor+hydrosaline brine, to investigate the partitioning equilibria for copper in magmatic-hydrothermal systems at 800° C and 1 kbar, and 850° C and 0.5 kbar. D^aqm/mlt _Cu and apparent equilibrium constants, K^aqm/mlt _Cu,Na, between the aqueous mixture (aqm=quenched vapor+brine) and the silicate melt (mlt) are calculated. D^aqm/mlt _Cu increases with increasing aqueous chloride concentration and is a function of pressure. K^aqm/mlt _Cu,Na=215(±73) at 1 kbar and 800° C and K^aqm/mlt _Cu,Na=11(±6) at 0.5 kbar and 850°C. Decreasing pressure from 1 to 0.5 kbar lowers K^aqm/mlt _Cu,Na by a factor of approximately 20. Data revealed no difference in K^aqm/mlt _Cu,Na or D^aqm/mlt _Cu as a function of the melt aluminium saturation index. Within the 2-phase field the K^aqm/mlt _Cu,Na show no variation with total aqueous chloride, indicating that copper-sodium exchange between the vapor, brine and silicate melt is independent of the mass proportion of vapor and brine. Model copper-sodium apparent equilibrium constants for the hydrosaline brine and the silicate melt revealed a negative dependence on pressure. Model apparent equilibrium constants for copper-sodium exchange between the brine and vapor were close to unity at 1 kbar and 800° C. Received: 27 June 1994/Accepted: 30 March 1995     

Highly pure placer gold formation in the Nilambur Valley,Wynad Gold Field,southern India

Placer gold grains in the Nilambur Valley of Wynad Gold Field in southern India are characterized by very high purity levels (985–1000). Their Ag-depleted core compositions, enhanced grain size and microscale growth patterns correlate with gold grains associated with laterite profiles in the weathering fronts. From the morphological and chemical evolution of gold grains associated with primary, supergene and secondary deposits in this region, we identified a two-stage process for the evolution of the highly pure placers, which shows that gold in the primary veins was mobilized, chemically purified, and reconcentrated in the laterite profiles, effecting enhanced purity and grain growth before transfer to the fluvial system. Further refinement was achieved during fluvial transport, generating natural concentrations of pure gold in the placers.     

The stability of transition metal dolomites in carbonate systems: a discussion

The instability of transition metal dolomites [CaR²⁺(CO₃)₂ where R²⁺ is Fe, Co, Ni, Cu, or Zn] and the limited substitution of transition metal cations for Mg in the dolomite structure can be accounted for by the effect of octahedral distortion. For example, trigonal elongation of the Fe octahedron, due to the Jahn-Teller effect, observed in siderite and ankerite, results in elongation of the Ca octahedron which is sensitive to distortion because the radius of Ca²⁺ is close to the upper limit for octahedral coordination. Co, Ni, Cu, Zn octahedra are also thought to be deformed, relative to Mg octahedra, in carbonates.The free energy of formation (ΔG^o_f) of R²⁺CO₃ becomes more positive with increasing octahedral distortion. Estimated ΔG^o_f(dolomite) as well as stabilities and solubility limits of R²⁺ in natural and synthetic dolomites suggest a series in order of decreasing stability: Mg >Mn >Zn >Fe >Co >Ni >Cu.ΔG^o_f(est.) for the terminal Fe-dolomite solid solution [72 mol% CaFe(CO₃)₂] in the system CaCO₃-MgCO₃-FeCO₃ may represent an empirical threshold value for dolomite stability which lies between ΔG^o_f for Mn- and Zn-dolomites. While Zn-dolomite is probably not a stable phase, very extensive solid solution toward CaZn(CO₃)₂ is to be expected in the system CaCO₃-MgCO₃-ZnCO₃. The tendency for transition metal dolomites to contain excess CaCO₃ can also be accounted for in terms of octahedral distortion and AG^o_f.