Proximal and distal styles of pegmatite-related metasomatic emerald mineralization at Ianapera,southern Madagascar

The Ianapera emerald deposit is located in the Neoproterozoic Vohibory Block of southern Madagascar. The local geology consists of intercalated migmatitic gneissic units and calcareous metasedimentary rocks, containing boudinaged metamorphosed mafic/ultramafic lenses, all intruded by pegmatite veins. These units occur near the hinge of the tightly folded Ianapera antiform, within a few kilometers of the Ampanihy shear zone. Emerald mineralization is hosted by metasomatic phlogopite veins, and bodies developed within the mafic/ultramafic rocks. Based on field and textural relationships, we distinguish proximal and distal styles of mineralization. Proximal mineralization occurs at the contact of pegmatite veins with mafic/ultramafic units; in the distal style, pegmatites are not observed. Three types of emeralds could be distinguished, mainly on the basis of color and mineral zoning. Some of these emeralds have the most Al-depleted and Cr-rich composition ever recorded. Another characteristic feature to the Ianapera deposit and, to our knowledge, yet unreported, is the association of some emeralds with scapolite in metasomatised mafic rocks. Mineral inclusions are common in most emeralds and include phlogopite, carbonates, barite, K-feldspar, quartz, pyrite, zircon, monazite, bastnaesite, phenakite, plus Fe and Cr oxides. However, feldspar and rare earth element-bearing minerals occur predominantly in proximal emeralds, which also have a more incompatible trace-element signature than distal emeralds. We propose a model related to syn- to post-tectonic magmatic-hydrothermal activity. Pegmatitic bodies intruded units of the Ianapera antiform probably during tectonic relaxation. Exsolution of fluids rich in halogens and incompatible elements from the cooling pegmatites caused hydrothermal metasomatism of Cr-bearing mafic/ultramafic rocks in direct contact with the pegmatites. Local fracturing favored fluid infiltration, permitting the formation of distal mineralization. Emerald composition was controlled by the chemistry of the host rock. The presence of carbonate mineral inclusions in the emeralds and the high F-activity indicated by elevated F-contents in newly formed minerals suggest transport of Be as a fluoride-carbonate complex. It seems likely that beryl formation was triggered by precipitation of F-rich phlogopite, which removed the complexing ligand from the fluid.     

Infrared reflectivity spectra of single crystal cassiterites

The infrared reflectivity spectra of two natural cassiterite single crystals from Portugal and Vietnam have been studied and analysed in the frequency range of 15–4000 cm^–1 at room temperature. The optical mode parameters are deduced by simulation of the experimental spectra using the factorised form of the dielectric function. The difference with synthetic SnO₂ spectra is a dip near 500 cm^–1 understood as the activation of an infrared forbidden E _g mode due to the amount of Fe³⁺ and Ti⁴⁺ impurities. Another result of this work is the derivation of the correct values of the static dielectric constant of cassiterite.     

An Overview of Dissolved and Suspended Matter Fluxes in the Loire River Basin: Natural and Anthropogenic Inputs

The spatial and temporal distributions of major elements were investigated in the surface waters and in associated suspended matter at two sites of the upper Loire basin (Orleans and Brehemont) between 1995 and 1998.According to geochemical and isotopic patterns, the dissolved load appears to result from a process of mixing rainwater inputs, weathering processes of carbonate and silicate bedrock, and agricultural and urban inputs. Natural inputs influence 60% of water chemical composition at both sites. Annual dissolved fluxes were estimated to be 1300 10³ t/y at Orleans and 1620 10³ t/y at Brehemont. Major elements are transported mainly in the dissolved fraction. After correcting for atmospheric and anthropogenic inputs, the silicate specific export rate was calculated to be 11 t/y/km² throughout the basin and the carbonate specific export rate to be from 47 t/y/km² at Orleans to 23 t/y/km² at Brehemont.The suspended load appears to result from at least two particle reservoirs: a silicate reservoir and a carbonate reservoir. The silicate reservoir has a detrital origin, mainly during periods of high flow, while the carbonate reservoir has a detrital origin during periods of high flow and an authigenic origin during periods of low flow. Of the total annual flow of suspended matter, this authigenic material represents 16% at Orleans, 25% at Brehemont and 37% in the fluvial part of the estuary. After correcting authigenic inputs, the specific export rate due to mechanical weathering was estimated to be 8 t/y/km² throughout the Loire basin.     

The crystal and magnetic structure of Li-aegirine LiFe3+Si2O6: a temperature-dependent study

Single crystals of Li-aegirine LiFe³⁺Si₂O₆ were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe³⁺Si₂O₆ is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)^° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P2₁ /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO₄ tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P2₁ /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From ⁵⁷Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe³⁺Si₂O₆. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T _N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

The role of temperature on treeline migration for an eastern African mountain during the Last Glacial Maximum

Paleo-data suggest that East African mountain treelines underwent an altitudinal shift during the Last Glacial Maximum (LGM). Understanding the ecological and physiological processes underlying treeline response to such past climate change will help to improve forecasts of treeline change under future global warming. In spite of significant improvements in paleoclimatic reconstruction, the climatic conditions explaining this migration are still debated and important factors such as atmospheric CO₂ concentration, the impact of lapse rate decreasing temperature along altitudinal gradients and rainfall modifications due to elevation have often been neglected or simplified. Here, we assess the effects of these different factors and estimate the influence of the most dominant factors controlling changes in past treeline position using a multi-proxy approach based on simulations from BIOME4, a coupled biogeography and biogeochemistry model, modified to account for the effect of elevation on vegetation, compared with pollen, and isotopic data. The results indicate a shift in mountain vegetation at the LGM was controlled by low pCO₂ and low temperatures promoting species morphologically and physiologically better adapted to LGM conditions than many trees composing the forest belt limit. Our estimate that the LGM climate was cooler than today’s by ?4.5 °C (range: ?4.3 to ?4.6 °C) at the upper limit of the treeline, whereas at 831 m it was cooler by ?1.4 °C (range: ?2.6 to ?0.6 °C), suggests that a possible lapse rate modification strongly constrained the upper limit of treeline, which may limit its potential extension under future global warming.     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

The Catoca kimberlite pipe, Republic of Angola: A paleovolcanological model

The Catoca kimberlite pipe is among the world’s largest primary diamond deposits. The Catoca volcanic edifice is only slightly eroded. Kimberlitic rocks of various facies compose a crater of about 1 km in diameter and a diatreme. The structure of the pipe and mining conditions of the deposit are complicated by intense intrapipe tectonic processes related to large-amplitude subsidence. Based on geological data, we propose a structural model of the deposit and a paleovolcanological model of the Catoca pipe formed during a full cycle beginning with a stage of active volcanism and completed by stages of gradually waning volcanic activity and sedimentation. It is suggested that the banded tuffisitic kimberlite of the crater zone was deposited at the stage of active volcanic eruption from specific pyroclastic suspension as a low-viscosity mixture of crystals and aqueous sol rich in serpentine.     

Hydrogeology and sustainable future groundwater abstraction from the Agua Verde aquifer in the Atacama Desert,northern Chile

The hyper-arid conditions prevailing in Agua Verde aquifer in northern Chile make this system the most important water source for nearby towns and mining industries. Due to the growing demand for water in this region, recharge is investigated along with the impact of intense pumping activity in this aquifer. A conceptual model of the hydrogeological system is developed and implemented into a two-dimensional groundwater-flow numerical model. To assess the impact of climate change and groundwater extraction, several scenarios are simulated considering variations in both aquifer recharge and withdrawals. The estimated average groundwater lateral recharge from Precordillera (pre-mountain range) is about 4,482 m³/day. The scenarios that consider an increase of water withdrawal show a non-sustainable groundwater consumption leading to an over-exploitation of the resource, because the outflows surpasses inflows, causing storage depletion. The greater the depletion, the larger the impact of recharge reduction caused by the considered future climate change. This result indicates that the combined effects of such factors may have a severe impact on groundwater availability as found in other groundwater-dependent regions located in arid environments. Furthermore, the scenarios that consider a reduction of the extraction flow rate show that it may be possible to partially alleviate the damage already caused to the aquifer by the continuous extractions since 1974, and it can partially counteract climate change impacts on future groundwater availability caused by a decrease in precipitation (and so in recharge), if the desalination plant in Taltal increases its capacity.     

Flow dynamics at the origin of thin clayey sand lacustrine turbidites: Examples from Lake Hazar,Turkey

Turbidity currents and their deposits can be investigated using several methods, i.e. direct monitoring, physical and numerical modelling, sediment cores and outcrops. The present study focused on thin clayey sand turbidites found in Lake Hazar (Turkey) occurring in eleven clusters of closely spaced thin beds. Depositional processes and sources for three of those eleven clusters are studied at three coring sites. Bathymetrical data and seismic reflection profiles are used to understand the specific geomorphology of each site. X‐ray, thin sections and CT scan imagery combined with grain‐size, geochemical and mineralogical measurements on the cores allow characterization of the turbidites. Turbidites included in each cluster were produced by remobilization of surficial slope sediment, a process identified in very few studies worldwide. Three types of turbidites are distinguished and compared with deposits obtained in flume studies published in the literature. Type 1 is made of an ungraded clayey silt layer issued from a cohesive flow. Type 2 is composed of a partially graded clayey sand layer overlain by a mud cap, attributed to a transitional flow. Type 3 corresponds to a graded clayey sand layer overlain by a mud cap issued from a turbulence‐dominated flow. While the published experimental studies show that turbulence is damped by cohesion for low clay content, type 3 deposits of this study show evidence for a turbulence‐dominated mechanism despite their high clay content. This divergence may in part relate to input variables, such as water chemistry and clay mineralogy, that are not routinely considered in experimental studies. Furthermore, the large sedimentological variety observed in the turbidites from one coring site to another is related to the evolution of a sediment flow within a field‐scale basin made of a complex physiography that cannot be tackled by flume experiments.