Heavy metal retention in secondary precipitates from a mine rock dump and underlying soil, Dalarna, Sweden

This study investigates the retention of heavy metals in secondary precipitates from a sulfidic mine rock dump and underlying podzolic soils by means of mineralogical and chemical extraction methods. The rock dump, which is at least 50 years old, consists of a 5–10-cm-thick leached zone and an underlying 110–115-cm-thick accumulation zone. Optical microscopy and electron microprobe analyses confirm that pyrrhotite weathering has proceeded much further in the leached horizon relative to the accumulation horizon. The weathering of sulfides in the leached zone has resulted in the migration of most heavy metals to the accumulation zone or underlying soils, where they are retained in more stable phases such as secondary ferric minerals, including goethite and jarosite. Some metals are temporarily retained in hydrated ferrous sulfates (e.g., melanterite, rozenite). Received: 28 October 1996 · Accepted: 24 February 1997     

The interpretation of reaction textures in Fe‐rich metapelitic granulites of the Musgrave Block,central Australia: constraints from mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3

Fe‐rich metapelitic granulites of the Musgrave Block, central Australia, contain several symplectic and coronal reaction textures that post‐date a peak S2 metamorphic assemblage involving garnet, sillimanite, spinel, ilmenite, K‐feldspar and quartz. The earliest reaction textures involve spinel‐ and quartz‐bearing symplectites that enclose garnet and to a lesser extent sillimanite. The symplectic spinel and quartz are in places separated by later garnet and/or sillimanite coronas. The metamorphic effects of a later, D3, event are restricted to zones of moderate to high strain where a metamorphic assemblage of garnet, sillimanite, K‐feldspar, magnetite, ilmenite, quartz and biotite is preserved. Quantitative mineral equilibria calculations in the system K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (KFMASHTO) using Thermocalc 3.0 and the accompanying internally consistent dataset provide important constraints on the influence of TiO₂ and Fe₂O₃ on biotite‐bearing and spinel‐bearing equilibria, respectively. Biotite‐bearing equilibria are shifted to higher temperatures and spinel‐bearing equilibria to higher pressures and lower temperatures in comparison to the equivalent equilibria in K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (KFMASH). The sequence of reaction textures involving spinel is consistent with a D2 P–T path that involved a small amount of decompression followed predominantly by cooling within a single mineral assemblage stability field. Thus, the reaction textures reflect changes in modal proportions within an equilibrium assemblage rather than the crossing of a univariant reaction. The D3 metamorphic assemblage is consistent with lower temperatures than those inferred for D2.     

A powder neutron diffraction study of the crystal structure of the fluoroperovskite NaMgF<Subscript>3</Subscript> (neighborite) from 300 to 3.6 K

The cell dimensions and crystal structures of the fluoroperovskite NaMgF₃ (neighborite), synthesized by solid state methods, have been determined by powder neutron diffraction and Rietveld refinement over the temperature range 300–3.6 K using Pt metal as an internal standard for calibration of the neutron wavelength. These data show that Pbnm NaMgF₃ does not undergo any phase transitions to structures of lower symmetry with decreasing temperature. The cell dimensions and atomic coordinates together with polyhedron volumes and distortion indices are given for Pbnm NaMgF₃ at 25 K intervals from 300 to 3.6 K. Decreases in the a and c cell dimensions reach a saturation point at 50 K, whereas the b dimension becomes saturated at 150 K. The distortion of the structure of Pbnm NaMgF₃ from the aristotype cubic structure is described in terms of the tilting of the MgF₆ octahedra according to the tilt scheme a ⁻ a ⁻ c ⁺ . With decreasing temperature the antiphase tilt (a ⁻) increases from 14.24° to 15.39°, whereas the in-phase tilt (c ⁺ ) remains effectively constant at ∼10.7°. Changes in the tilt angles are insufficient to cause changes in the coordination sphere of Na that might induce a low temperature phase transition. The structure of Pbnm NaMgF₃ is also described in terms of normal mode analysis and displacements of the condensed normal modes are compared with those of Pbnm KCaF₃.     

Rapid incorporation of lipids into macromolecules during experimental decay of invertebrates: Initiation of geopolymer formation

Diagenetic alteration is critical for the preservation of fossil cuticles of plant and animal origin and to the formation of kerogen. The process takes place over millions of years, but the stage at which it is initiated is not known. Laboratory decay experiments were carried out on shrimps, scorpions and cockroaches to monitor changes in the chitin–protein of the arthropod cuticle and associated lipids. The cockroach and scorpion exoskeleton remained largely unaltered morphologically, but the shrimp experienced rapid decomposition within a month, which progressed through the 44 week duration of the experiment as revealed using electron microscopy. Mass spectrometry and ¹³C NMR (nuclear magnetic resonance) spectroscopy revealed the association of an n-alkyl component with labile lipids, such as fatty acids with up to 24 carbon atoms, which were incorporated into the decaying macromolecule. The scorpion and cockroach cuticle did not reveal the incorporation of additional lipids, indicating that decay is important in initiating in situ lipid association. This experiment provides evidence that lipids can become associated with carbohydrate and proteinaceous macromolecules during the very early stages of decay, representing the first stage in the transformation process that contributes to the aliphatic rich composition ubiquitous in organic fossils and kerogen.     

Quantification of adamantane in organic media via infrared attenuated total reflection spectroscopy

In the present study, the quantitative determination of the diamondoid compound adamantane in organic solvents via infrared attenuated total reflection (IR-ATR) spectroscopy at unmodified waveguide surfaces was established. Limits of detection (LOD) and quantification (LOQ) of adamantane in dichloromethane, hexane and carbon tetrachloride were determined. Quantitative IR-ATR measurements additionally facilitated the determination of adamantane solubility limit in dichloromethane, hexane and carbon tetrachloride. The developed analytical strategy further enabled the successful detection and quantification of adamantane in crude oil matrices. Consequently, IR-ATR spectroscopy provides a promising strategy for on ship and in situ diamondoid analysis in harsh real world environments.     

Gold in Madagascar

Gold is commonly found throughout the Precambrian basement exposed in the eastern two-thirds of Madagascar, composed of Archean and Proterozoic greenstone belts and metasediment belts. Gold occurs in four main kinds of deposits:- as a diffuse component of the crystalline basement rocks, - in concordant quartz veins within the metamorphic rocks of the Precambrian basement, - in recent discordant veins, - and in recent and ancient alluvial deposits.The initial gold mineralisation is probably in relation with the greenstone belt formation, and many have been formed and/or reworked during different metamorphic and magmatic events. It is therefore difficult to obtain an accurate age of the different kinds of deposits.     

The geoarchaeology of Iron Age “moated” sites of the Upper Mae Nam Mun Valley,N.E. Thailand. I: Palaeodrainage,site–landscape relationships and the origins of the “moats”

The study focuses on the “moated” Iron Age sites of N.E. Thailand, first identified as significant prehistoric settlement sites in the 1940s from aerial photography. Two more recent photograph sets are used to map the surficial geology and prehistoric site distribution for a study area west of Phimai, N.E. Thailand, with a focus on site–landscape relationships and, in particular, relationships between site location and form and patterns of palaeodrainage. The derived record of the surficial geology reflects several phases of palaeodrainage, characterized by differing locations and types of former river channels. Of note is the differentiation between a recent period in which river channels, including those presently active, are single-string meandering channels, and an older period of broad belts of meandering multistring channels. The prehistoric site distribution correlates closely with the older drainage, and for many, the encircling channels (the “moats”) are closely associated with former river channels. These relationships provide a critical and novel model for site distribution; several implications arise, supported by emerging field evidence, and introducing issues for archaeological debate: (i) there is no need, as has been done in the past, to invoke prehistoric artificial forms of drainage associated with the sites; (ii) the definition of the encircling channels as “moats” is seriously called into question; and (iii) the inferred geomorphological evolution of the floodplain implies past changes in environmental parameters such as run-off, climate or biophysical environments. Since the sites are all located in or beside ancient meander belts, these parameters should now be introduced into archaeological discussions regarding the establishment, history, evolution, and abandonment of the Iron Age sites. Methodologically, this article illustrates the need to be aware of the complexity of aerial photograph interpretation in archaeological survey, showing that careful analysis of aerial photograph information may have a significant impact upon the modeling of prehistoric interpretations. Further stratigraphical studies will be reported subsequently, and will refine the models presented here. © 1999 John Wiley & Sons, Inc.     

Gas hydrate systems at Hydrate Ridge offshore Oregon inferred from molecular and isotopic properties of hydrate-bound and void gases

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C₂₊ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO₂ and H₂S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.     

Earth''s earliest continental lithosphere, hydrothermal flux and crustal recycling

The Kaapvaal craton in southern Africa and the Pilbara craton of northwestern Australia are the largest regions on Earth to have retained relatively pristine mid-Archaean rocks (3.0–4.0 Ga).The Kaapvaal craton covers about 1.2×10⁶ km², and varies in lithospheric thickness between 170 and 350 km. At surface, the craton can be subdivided into a number of Archaean sub-domains; some of the subdomains are also well defined at depth, and local variations in tomography of the lithosphere correspond closely with subdomain boundaries at surface.The Archaean history of the Kaapvaal craton spans about 1 Gyr and can be conveniently subdivided into two periods, each of about the same length as the Phanerozoic. The first period, from circa 3.7-3.1 Ga, records the initial separation of the cratonic lithosphere from the asthenosphere, terminating with a major pulse of accretion tectonics between 3.2 and 3.1 Ga, which includes the formation of “paired metamorphic belts”. This period of continental growth can be compared to plate tectonic processes occurring in modern-day oceanic basins. However, the difference is that in the mid-Archaean, these oceanic processes appear to have occurred in shallower water depths than the modern ocean basins. The second period, from circa 3.1-2.6 Ga, records intra-continental and continental-edge processes: continental growth during this period occurred predominantly through a combination of tectonic accretion of crustal fragments and subduction-related igneous processes, in much the same way as has been documented along the margins of the Pacific and Tethys oceans since the Mesozoic.The intra-oceanic processes resulted in small, but deep-rooted continental nucleii; the first separation of this early continental lithosphere could only have occurred when the mean elevation of mid-oceanicridges sank below sea-level. Substantial recycling of continental lithosphere into the mantle must have occurred during this period of Earth history. During the second period, at least two large continental nucleii amalgamated during collisional processes which, together with internal chemical differentiation processes, created the first stable continental landmass. This landmass, which is known to have been substantially bigger than its present outline, may have been part of the Earth's first supercontinent.The oldest known subdomains of the craton include the oceanic-like rocks of the Barberton greenstone belt. The comagmatic mafic-ultramafic rocks (3.48–3.49 Ga) of this belt represent a remnant of very early oceanic-like lithosphere (known as the Jamestown Ophiolite Complex), which was obducted, approximately 45 Ma after its formation, onto a volcanic arc-like terrain by processes similar to those which have emplaced modern ophiolites at convergent margins of Phanerozoic continents. The early metamorphic history, metamorphic mineralogy, oxygen isotope profiles and degree of hydration of the 3.49 Ga Jamestown Ophiolite Complex are similar to present day subseafloor hydrothermal systems. The ratio of ΔMg to ΔSi for hydrothermally altered igneous rocks, both present day and Archaean, are remarkably uniform at −5(±0.9) and the same as that of hydrothermal fluids venting on the present-day East Pacific Rise. This observation suggests that the process of Mg exchange for Si in hydrothermal systems was commonplace throughout Earth's history.The chemistry of vent fluids and hydrothermally altered igneous rocks was combined with an inventory of ³He in the mantle to model Earth's total hydrothermal flux. An Archaean flux (at 3.5 Ga) of about 10 times present day was accompanied by a correspondingly greater abundance of Mg(OH), SiO₂, carbonate and Fe---Mn metasomatic rock types as well as massive sulphides. Assuming a constant column of seawater since the Archaean, the average residence time of seawater in the oceanic crust was 1.65−8.90×10⁵ years in the Archaean. Assuming that ³He and heat are transported from the mantle in silicate melts in uniform proportions, the model stipulates that accretion of oceanic crust decreased from about 3.43−6.5×10¹⁷ g/yr to a present-day rate of 0.52−0.8×10¹⁷ g/yr, with a drop in heat flow from 1.4−2.6×10²⁰ cal/yr to 2.1−3.2×10¹⁹ cal/year.The total amounts of SiO₂ and Fe mobilised in marine hydrothermal systems since 3.5 Ga is less than their masses in the present exosphere reservoirs (crust, hydrosphere, atmosphere). The total amounts of Mg, K, CO₂, Ca and Mn are greater than their respective masses in exosphere reservoirs; therefore, they must have been recycled into mantle. The total mass of recycled hydrothermal components is small compared to the mass of the mantle. The flux of volatiles in hydrothermal systems is large compared to their volume in the atmosphere suggesting that the CO₂ and O₂ budgets of the atmosphere have been influenced by hydrothermal processes, especially in the Archaean.