Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies.Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.     

C-S-Fe relationships and the isotopic composition of pyrite in the New Albany Shale of the Illinois Basin,U.S.A.

The relationship between pyritic sulfur content (S_pyr) and organic carbon content (C_org) of shales analyzed from the New Albany Group depends upon C_org. For samples of <6 wt.% C_org, S_pyt, and C_org are strongly correlated (r = 0.85). For C_org-“rich” shales (>6 wt.%), no S_pty-C_org, correlation is apparent. The degree of Fe pyritization (DOP) shows similar relationships to C_org. These C-S-Fe relationships suggest that pyrite formation was limited by the availability of metabolizable organic carbon in samples where C_org < 6 wt.% and by the availability of reactive Fe for samples where C_org > 6 wt.%. Apparent sulfur isotope fractionations relative to contemporaneous seawater sulfate (Δ³⁴S) for pyrite formation average −40% for non-calcareous shales and −25%. for calcareous shales. Δ³⁴S values become smaller with increasing C_org, S_pyt, and DOP for all C_org-“poar” (<6 wt%) and some C_org-“nch” (<6 wt.%) shales. These trends suggest that pyrite formation occurred in a closed system or that instantaneous bacterial fractionation for sulfate reduction decreased in magnitude with increasing organic carbon content. The isotopic trends observed in the New Albany Group are not necessarily representative of other shales having a comparable range of organic carbon content, e.g. Cretaceous shales and mudstones from the western interior of North America (GAUTIER, 1986). Δ³⁴S values in the remainder of the C_org-rich New Albany Group shales are relatively large (−38 to −47%.) and independent of C_org, S_pyr, and DOP, which suggests that pyrite in these shales formed mostly at or above the sediment-water interface by precipitation from an isotopically uniform reservoir of dissolved H₂S.     

Weathering of the zinc-lead lode, Dugald River, northwest Queensland: II. surface mineralogy and geochemistry

Gossans associated with the Dugald River zinc-lead lode contain anomalous concentrations of Zn, Pb, Ag, As, Cd, Cu, Sb, Se, Tl and Ba and differ from those on the more pyritic Western Lode (Zn, Pb, Cu, As, Tl) and those associated with copper mineralization in the hanging wall (As, Bi, Co, Cu, Mo, Ni, Sb). Mineralogical and geochemical variations in gossans along strike reflect changes in primary ore and gangue mineralogy, particularly towards the north, where the Dugald River lode and hanging wall copper mineralization merge. Leaching of more soluble elements from the surface and re-precipitation below have resulted in large geochemical variations in the top metre of the profile.Dispersion into wall rocks has occurred over two distinct periods: hydromorphic dispersion, before erosion removed much of the gossan and surrounding Corella Formation, has resulted in very high Zn contents (up to 9%) in the footwall, whereas a more even dispersion of target and pathfinder elements into hanging and footwall rocks is from recent weathering of the slightly elevated gossan.     

Organic geochemical characterization of the New Albany Shale group in the Illinois Basin

Benzene extractable aliphatic hydrocarbons from the New Albany Shale in the Illinois Basin were characterized by gas chromatography and mass spectrometry, and the total organic matter of the shale was characterized by solid state carbon-13 cross polarization magic angle spinning nuclear magnetic resonance. Core samples from a northwest-trending cross-section of the Illinois Basin were studied. Gas chromatography (GC) and gas chromatography-mass spectrometric analysis (GC/MS) data indicate a regional variation of the aliphatic composition of the shale extracts. A positive, linear relationship between the two ratios, pristane/n-C₁₇ and phytane/n-C₁₈, is indicated. The NMR results indicated that organic matter deposited in northwestern Illinois shale is relatively high in aliphatic hydrocarbon content while, in contrast, organic matter found in southeastern Illinois shale is relatively low in aliphatic hydrocarbon content. Our findings suggest that the organic variation of the shale is mainly due to the differences in thermal maturity of the shale organic matter and the use of pristane/n-C₁₇ ratio as a thermal parameter in the study of oil may be extended to the study of the ancient sediments.     

Chemical weathering in Luzon, Philippines from clay mineralogy and major-element geochemistry of river sediments

Clay mineralogy and major-element geochemistry of 35 surface sediment samples collected in 21 major to moderate rivers of Luzon, Philippines are used to evaluate the present chemical weathering process. The clay mineral assemblage consists mainly of smectite (average 86%) with minor kaolinite (9%) and chlorite (5%) and very scarce illite (1%), and does not show strong island-wide differences. The major element results of both bulk and clay-fraction sediments indicate that the formation of clay minerals is accompanied by leaching of Ca and Na first and of Fe and Mn thereafter during the chemical weathering process. A low-moderate chemical weathering degree of bulk sediments and a moderate-intensive degree of clay-fraction sediments are obtained in Luzon rivers based on proxies of chemical index of alteration (CIA) and smectite crystallinity. It is suggested that the majority of andesitic–basaltic volcanic and sedimentary rocks along with the tectonically active geological setting and sub-tropical East Asian monsoon climate are responsible for the predominance of smectite in the clay mineral assemblage.     

Palynological and bulk geochemical constraints on the paleoceanographic conditions across the Frasnian–Famennian boundary,New Albany Shale,Indiana

A down-core record of stable isotope and geochemical results is integrated with palynofacies (kerogen) data from the New Albany Shale (Indiana) to reconstruct environmental changes that occurred across the Frasnian–Famennian boundary. Preliminary interpretations are focused on developing several multiproxy linkages that will potentially lead toward a more robust understanding of the occurrence and significance of phytoplankton assemblage variations during the Late Devonian, a time of widespread black shale formation. Development of such linkages will potentially provide a more comprehensive assessment of the various controls on 1) primary production, and 2) carbon sequestration in a large, low-paleolatitude intracratonic basin.An abrupt change in the geochemical and biotic proxies for particulate organic matter across the Frasnian–Famennian boundary coincides with a distinct lithological change, characterized by laminated, brownish-black Famennian mudstones unconformably overlying alternating bioturbated, greenish-gray and non-bioturbated, dark-gray Frasnian mudstones. Elemental and isotopic profiles reflect different patterns of production, degradation, and removal of organic carbon in the two shale facies. A shift from acritarch- to prasinophyte-dominated waters across the boundary indicates the overall importance of bathymetric fluctuations, chemico-physical conditions, and nutrient availability related to eustatic sea-level change. A positive δ¹³C_V-PDB shift of 1.1‰ across the boundary is interpreted to be correlative with the global Upper Kellwasser Event. A preliminary model is proposed to explain the sustainable primary production during times of maximum flooding, thereby enhancing organic preservation during black shale formation.     

Discrimination of topaz rhyolites by major-element composition: a statistical routine for geochemical exploration

The recognition of topaz-bearing, calc-alkaline, and peralkaline rhyolites at an early stage of an exploration program may be of both geologic interest and of economic significance due to the different mineral deposits characteristically associated with each of these rock suites. Such discrimination could result in better definition of target areas and commodities to explore within a selected region.A geochemical database of major element analyses of calc-alkaline, peralkaline (comendites), and topaz rhyolites from western North America was assembled. Multiple discriminant function analysis assigned each sample statistically to the calc-alkaline, topaz, or peralkaline groups, using only major element composition. The assignment correctly identified 90% of the rhyolites as members of the groups to which they actually belong. In effect, then, major-element composition can serve as a proxy for fluorine content either when no fluorine analysis is available or when it is suspected that fluorine was not preserved in the rock due to its loss during emplacement or subsequent devitrification.We have included a simplified procedure to use our discrimination model to identify silicic rocks of unknown affiliation. This model makes it possible to evaluate the economic potential of both new or previously explored areas by analyzing data files containing major-element chemical analyses.     

Influence of acidic atmospheric deposition on soil solution composition in the Daniel Boone National Forest,Kentucky, USA

. Acid atmospheric deposition may enter an environmental ecosystem in a variety of forms and pathways, but the most common components include sulfuric and nitric acids formed when rain water interacts with sulfur (SOx) and nitrogen (NOx) emissions. For many soils and watersheds sensitive to acid deposition, the predominant chronic effect appears to be a low pH, loss of base cations, and a shift in the mineral phase controlling the activity of Al³⁺ and/or SO4^2– in solution. Soil solutions from lysimeters at various depths were taken at two sites in the Daniel Boone National Forest, Kentucky, USA, to evaluate potential impacts caused by acid deposition. The sites chosen were in close proximity to coal-burning power plants near Wolfe and McCreary counties and contained soils from the Rayne and Wernock series, respectively. Physicochemical characteristics of the soils revealed that both sites contained appreciable amounts of exchangeable acidity in the surface horizons, and that their base saturation levels were sufficiently low to be impacted adversely by acidic inputs. Soil solution data indicated that the sites were periodically subjected to relatively high NO3^– and SO4^2– inputs, which may have influenced spatial and temporal variation in Al and pH. As a consequence, the formation of Al-hydroxy-sulfate minerals such as jurbanite, alunite and basaluminite were thermodynamically favored over gibbsite. Given these conditions, long-term changes in soil solution chemistry from acid deposition are acknowledged.     

Shale depositional processes: Example from the Paleozoic Barnett Shale, Fort Worth Basin, Texas, USA

A long held geologic paradigm is that mudrocks and shales are basically the product of ‘hemipelagic rain’ of silt- and/or clay-sized, detrital, biogenic and particulate organic particles onto the ocean floor over long intervals of time. However, recently published experimental and field-based studies have revealed a plethora of micro-sedimentary features that indicate these common fine-grained rocks also could have been transported and/or reworked by unidirectional currents. In this paper, we add to this growing body of knowledge by describing such features from the Paleozoic Barnett Shale in the Fort Worth Basin, Texas, U.S.A. which suggests transport and deposition was from hyperpycnal, turbidity, storm and/or contour currents, in addition to hemipelagic rain. On the basis of a variety of sedimentary textures and structures, six main sedimentary facies have been defined from four 0.3 meter intervals in a 68m (223 ft) long Barnett Shale core: massive mudstone, rhythmic mudstone, ripple and low-angle laminated mudstone, graded mudstone, clay-rich facies, and spicule-rich facies. Current-induced features of these facies include mm- to cmscale cross- and parallel-laminations, scour surfaces, clastic/biogenic particle alignment, and normal- and inverse-size grading. A spectrum of vertical facies transitions and bed types indicate deposition from waxing-waning flows rather than from steady ‘rain’ of particles to the sea floor. Detrital sponge spicule-rich facies suggests transport to the marine environment as hypopycnal or hyperpycnal flows and reversal in buoyancy by transformation from concentrated to dilute flows; alternatively the spicules could have originated by submarine slumping in front of contemporaneous shallow marine sponge reefs, and then transported basinward as turbidity current flows. The occurrence of dispersed biogenic/organic remains and inversely size graded mudstones also support a hyperpycnal and/or turbidity flow origin for a significant part of the strata. These processes and facies reported in this paper are probably present in other organic-rich shales.     

The Omolon pallasite: Chemical composition,mineralogy, and genetic implications

The chemical composition of mineral components of the Omolon pallasite was determined by neutron-activation. Six types of olivines were distinguished. Four types differ in the abundance of Co relative to Ni of CI chondrites. The fifth and sixth types were distinguished on the basis of REE distribution in them. Both last types are variably enriched in LREE relative to CI chondrites. In terms of Ca content relative to CI chondrite, these six types are subdivided into two groups: low-calcium and high-calcium. The difference in Ca contents can be caused by different cooling rate of the precursor of these olivines. The distribution pattern of siderophile elements in the pallasite metal indicates that a metallic phase experienced chemical transformations since the time of its formation. The analysis of chemical composition of accessory minerals showed that: (1) HREE are accumulated in tridymite; (2) troilite and daubreelite were formed under different temperature conditions; (3) magnetite is the mineral of the outer zone of melting crust. Four fragments with anomalous contents of lithophile elements were found in the pallasites and studied. The unusual chemical composition of phases and high degree of HREE fractionation in the fragments suggest their formation at high temperatures at the early stage of the Solar system evolution. It is assumed that the Omolon pallasite was formed as impact-brecciated mixture of the asteroid core (with composition close to IIIAB group of iron meteorites) and mantle olivine from incompletely differentiated parent body of chondrite composition.     

The Homestead kimberlite, central Montana, USA: mineralogy, xenocrysts, and upper-mantle xenoliths

The Homestead kimberlite was emplaced in lower Cretaceous marine shale and siltstone in the Grassrange area of central Montana. The Grassrange area includes aillikite, alnoite, carbonatite, kimberlite, and monchiquite and is situated within the Archean Wyoming craton. The kimberlite contains 25–30 modal% olivine as xenocrysts and phenocrysts in a matrix of phlogopite, monticellite, diopside, serpentine, chlorite, hydrous Ca–Al–Na silicates, perovskite, and spinel. The rock is kimberlite based on mineralogy, the presence of atoll-textured groundmass spinels, and kimberlitic core-rim zoning of groundmass spinels and groundmass phlogopites.

Garnet xenocrysts are mainly Cr-pyropes, of which 2–12% are G10 compositions, crustal almandines are rare and eclogitic garnets are absent. Spinel xenocrysts have MgO and Cr₂O₃ contents ranging into the diamond inclusion field. Mg-ilmenite xenocrysts contain 7–11 wt.% MgO and 0.8–1.9 wt.% Cr₂O₃, with (Fe⁺³/Fe^tot) from 0.17–0.31. Olivine is the only obvious megacryst mineral present. One microdiamond was recovered from caustic fusion of a 45-kg sample.

Upper-mantle xenoliths up to 70 cm size are abundant and are some of the largest known garnet peridotite xenoliths in North America. The xenolith suite is dominated by dunites, and harzburgites containing garnet and/or spinel. Granulites are rare and eclogites are absent. Among 153 xenoliths, 7% are lherzolites, 61% are harzburgites, 31% are dunites, and 1% are orthopyroxenites. Three of 30 peridotite xenoliths that were analysed are low-Ca garnet–spinel harzburgites containing G10 garnets. Xenolith textures are mainly coarse granular, and only 5% are porphyroclastic.

Xenolith modal mineralogy and mineral compositions indicate ancient major-element depletion as observed in other Wyoming craton xenolith assemblages, followed by younger enrichment events evidenced by tectonized or undeformed veins of orthopyroxenite, clinopyroxenite, websterite, and the presence of phlogopite-bearing veins and disseminated phlogopite. Phlogopite-bearing veins may represent kimberlite-related addition and/or earlier K-metasomatism.

Xenolith thermobarometry using published two-pyroxene and Al-in-opx methods suggest that garnet–spinel peridotites are derived from 1180 to 1390 °C and 3.6 to 4.7 GPa, close to the diamond–graphite boundary and above a 38 mW/m² shield geotherm. Low-Ca garnet–spinel harzburgites with G10 garnets fall in about the same T and P range. Most spinel peridotites with assumed 2.0 GPa pressure are in the same T range, possibly indicating heating of the shallow mantle. Four of 79 Cr diopside xenocrysts have P–T estimates in the diamond stability field using published single-pyroxene P–T calculation methods.     

The nature of the sub-continental mantle: constraints from the major-element composition of continental flood basalts

Many continental flood basalts (CFB) have isotope and trace-element signatures that differ from those of oceanic basalts and much interest concerns the extent to which these reflect differences in their upper mantle source regions. A review of selected data sets from the Mesozoic and Tertiary CFB confirms significant differences in their major- and trace-element compositions compared with those of basalts erupted through oceanic lithosphere. In general, those CFB suites characterised by low Nb/La, high (⁸⁷Sr/⁸⁶Sr)_i and low εNd_i tend to exhibit relatively low TiO₂, CaO/Al₂O₃, Na₂O and/or Fe₂O₃, and relatively high SiO₂. In contrast, those which have high Nb/La, low (⁸⁷Sr/⁸⁶Sr)_i and high εNd_i ratios, like the upper units in the Deccan Traps, have major- and trace-element compositions similar to oceanic basalts. It would appear that those CFB that have distinctive isotope and trace-element ratios also exhibit distinctive major-element contents, suggesting that major and trace elements have not been decoupled significantly during magma generation and differentiation.

When compared (at 8% MgO) with oceanic basalt trends, the displacement of many CFB to lower Na₂O, Fe₂O₃^*, TiO₂ and CaO/Al₂O₃, but higher SiO₂, at similar Mg#, is not readily explicable by crustal contamination. Rather, it reflects source composition and/or the effects of the melting processes. The model compositions of melts produced by decompression of mantle plumes beneath continental lithosphere have relatively low SiO₂ and high Fe₂O₃^*. In contrast, the available experimental data indicate that partial melts of peridotite have low TiO₂, Na₂O and Fe₂O₃^*CaO/Al₂O₃, if the peridotite has been previously depleted by melt extraction. Moreover, melting of hydrated, depleted peridotite yields SiO₂-rich, Fe₂O₃- and CaO-poor melts. Since anhydrous, depleted peridotite has a high-temperature solidus, it is argued that the source of these CFB was variably melt depleted and hydrated mantle, inferred to be within the lithosphere. Isotope data suggest these source regions were often old and relatively enriched in incompatible trace elements, and it is envisaged that H₂O±CO₂ were added at the same time as the incompatible elements. An implication is that a significant proportion of the new continental crust generated since the Permian reflected multistage processes involving mobilization of continental mantle lithosphere that was enriched in minor and trace elements during the Proterozoic.     

Weathering of the zinc-lead lode, Dugald River, northwest Queensland: I. the gossan profile

Oxidation of the relatively iron sulfide-poor Dugald River zinc-lead lode in northwest Queensland and reaction of the acid solutions with carbonate has resulted in an undifferentiated gossan profile. The gossan is composed predominantly of quartz, goethite, hematite, barite, adularia, plumbian jarosite, plumbogummite and minor mica, chlorite, kaolinite and montmorillonite. Barite and adularia are formed by the breakdown of the barium feldspar hyalophane (K, Na, Ba)[(Al, Si)₄O₈] which occurs in the lode.Lead in the gossan is contained within the secondary minerals plumbogummite and plumbian jarosite, and in traces of anglesite and cerussite, whereas Zn occurs in the barite, secondary lead minerals and coronadite structures, and is adsorbed by iron oxides, phyllosilicates and carbonaceous matter. Only traces of zinc minerals smithsonite, goslarite and hemimorphite were detected.Use of Gresens' general metasomatic equation has enabled quantitative determination of compositional changes resulting from the oxidation of the ore. Silicon, Al, Ti and Ba are essentially immobile under the mildly acidic oxidizing conditions. In decreasing order of mobility Cd, Ca, S, Na, K, Mn, Mg, Zn, Ni and Cu, together with CO₂ and Tl, have been leached from the gossan profile, while Ag, Sb, Se, As, Fe and Pb appear to have been added to the gossan, notably in a zone of solution-deposited secondary minerals where they have been concentrated, possibly as a result of leaching from the surface gossan.     

Petrology of the Albany and Torbay Adamellite Plutons,near Albany,Western Australia

The Albany and Torbay Adamellites are composite plutons emplaced in Pre‐cambrian gneisses of the Albany‐Esperance Block in the vicinity of Albany, Western Australia. The gneissic country rocks have been metamorphosed to the lower granu‐lite facies at Albany and the upper amphibolite facies at Torbay. Granitized aureoles about 1 km wide, metasomatically enriched in SiO₂, K₂O, and various trace elements commonly including Rb, Ba, La, Pb, and Th, are developed in the gneisses around both plutons. Field relations suggest late‐kinematic magmatic emplacement of the Adamellites in the catazone. Both show chemical variation trends comparable with the trends normally associated with fractional crystallization of calc‐alkali magmas, and their normative compositions correspond with the thermal trough in the system An‐Ab‐Or‐Q‐H₂O at 4–7 kb P_H2o, suggesting an origin involving crystal‐liquid equilibria at a water vapour pressure of about this value. The initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7118 for the Albany Adamellite is consistent with derivation of the magma from crustal rocks. The late‐kinematic field characteristics of the plutons and the limited isotopic data available are compatible with emplacement and crystallization during the closing stages of orogeny and regional metamorphism. The magmas are believed to have been generated not at their present sites of emplacement, but in a deeper, higher‐temperature zone of the crust, with magma generated during an earlier phase of the orogeny.     

渝东北黑色页岩元素迁移特征及化学风化程度

黑色页岩是富含有机质和硫化矿物的特殊沉积岩,但人们对其风化过程的元素活动性及矿物风化机制关注较少.为探讨不同地形位置的黑色页岩化学风化过程,采集了渝东北城口某山脊 (A)、近山顶 (B) 和沟谷 (C) 的下寒武统水井沱组黑色页岩风化剖面岩样,利用XRD、XRF和化学分析手段对采集样品的矿物成分、主量元素进行测定分析.元素和矿物的质量迁移系数 (τ) 和质量迁移通量 (M_{j, flux}) 的计算结果表明,黑色页岩风化过程中Ca、Mg和Na元素具有明显的贫化现象,近地表处存在Al元素的富集现象;矿物成分方面,黄铁矿和有机质氧化后形成的酸性水环境,造成方解石、白云石、斜长石等不稳定矿物溶解,并生成含水石膏、铁质氧化物、黏土矿物等次生矿物.不同赋存位置的黑色页岩风化程度有所差异,Na/K-CIA、K/Ca*-Al/Na、A-CN-K和A-CNK-FM图解显示:A剖面处于脱Ca过程的初级风化阶段,B剖面处于脱Ca、Na初期的初等-中等风化阶段,C剖面已发生脱Ca、Na过程,并伴随脱Si作用的中等-强烈风化阶段,结合不同风化指数 (如:CIA、CIW、PIA、MWPI等),得出各剖面的化学风化强弱程度依次为C＞B＞A.      

A bond-topological approach to theoretical mineralogy: crystal structure, chemical composition and chemical reactions

Here, I describe a theoretical approach to the structure and chemical composition of minerals based on their bond topology. This approach allows consideration of many aspects of minerals and mineral behaviour that cannot be addressed by current theoretical methods. It consists of combining the bond topology of the structure with aspects of graph theory and bond-valence theory (both long range and short range), and using the moments approach to the electronic energy density-of-states to interpret topological aspects of crystal structures. The structure hierarchy hypothesis states that higher bond-valence polyhedra polymerize to form the (usually anionic) structural unit, the excess charge of which is balanced by the interstitial complex (usually consisting of large low-valence cations and (H₂O) groups). This hypothesis may be justified within the framework of bond topology and bond-valence theory, and may be used to hierarchically classify oxysalt minerals. It is the weak interaction between the structural unit and the interstitial complex that controls the stability of the structural arrangement. The principle of correspondence of Lewis acidity–basicity states that stable structures will form when the Lewis-acid strength of the interstitial complex closely matches the Lewis-base strength of the structural unit, and allows us to examine the factors that control the chemical composition and aspects of the structural arrangements of minerals. It also provides a connection between a structure, the speciation of its constituents in aqueous solution and its mechanism of crystallization. The moments approach to the electronic energy density-of-states provides a link between the bond topology of a structure and its thermodynamic properties, as indicated by correlations between average anion coordination number and reduced enthalpy of formation from the oxides for ^[6]Mg _m ^[4] Si _n O_(m+2n) and MgSO₄(H₂O) _n .     

Preliminary investigation of mineralogy,petrology and chemical composition of Qingzhen enstatite chondrite

On September 13, 1976, the Qingzhen enstatite chondrite fell near Qingzhen County, Guizhou Province (26°32′N, 106°28′E). The total mass recovered was 2.6 kg. Phenomena of the meteorite fall were recorded as well. In the present paper some of the significant observations are described. X-ray diffraction analyses and petrologic studies revealed that it is mainly composed of enstatite/clinoenstatite, plagioclase, troilite, kamacite, taenite, quartz and oldhamite. X-ray electron microprobe analyses were performed on orthoenstatite and clinoenstatite. Chemical analysis gave: SiO₂-36.48; Al₂O₃-1.64; TiO₂-0.08; Cr₂O₃-0.28; FeO-0.30; MnO-0.25; MgO-18.19; CaO-1.14; Na₂O-1.06; K₂O-0.11; H₂O⁺-0.47; H₂O^?-0.10; P₂O₅-0.39; FeS-13.35; FeO-22.94; Ni-1.81; Co-0.093; C-0.37; Cu-0.022; Zn-0.027; CaS-0.60; total-99.70 (wt.%). This meteorite has been extremely reduced; all iron is present as FeS and metallic Fe-Ni. The Qingzhen enstatite chondrite is characterized by high ratio, Si/Mg as compared with ordinary chondrites, scarcity of olivine, and enrichment in sulfur and iron. In thin sections, it is observed that round chondrules approximately account for 10–15 per cent, being porphyritic, radial, excentroradial, or excentric fan-shaped. Devitrified chondrules composed of pyroxene were also identified. It is postulated from its mineralogy, chemistry and textural characteristics that the Qingzhen meteorite should be assigned toE ₄ orEH chondrites.     

The mineralogy and chemical composition of the Woodlawn massive sulphide orebody

The main Woodlawn ore lens is a polymetallic, massive sulphide deposit’ with pyrite the major constituent, variable sphalerite, galena and chalcopyrite, and minor arsenopyrite, tetrahedrite‐tennantite, pyrrhotite and electrum. The silicate gangue minerals are chlorite, quartz, talc and sericitic mica. Other mineralization in the vicinity consists of footwall copper ore in chlorite schist and several smaller massive sulphide lenses. The predominant country rocks are felsic volcanics and shales, with abundant quartz, chlorite and mica, and talc in mineralized zones.

An important textural feature of the massive ore is the fine compositional banding. Bands, which vary in thickness from a few tens of micrometres to several millimetres, are produced by variations in the sulphide content. Post‐depositional metomorphism and minor fracturing have only slightly modified this banding.

Apart from the major element constituents—Pb, Zn, Fe, Cu and S—the ore is characterized by significant (100–1000 ppm) values for Ag, As, Cd, Mn, Sb and Sn, and lower (1–100 ppm) values of Au, Bi, Co, Ga, Hg, Mo, Ni, Tl. In and Ge. Variations in the base‐metal sulphide content, the gangue mineralogy, and trace elements, are used to separate the orebody into hanging‐wall and footwall zones. The hanging‐wall zone shows a more variable trace element content, with higher Tl, Sn, Ni, Mn, Ge and Sb, but lower Ag, Cd, and Mo, than the footwall zone.

In general style of mineralization, mineralogy, and chemistry, the Woodlawn deposit resembles other volcanogenic massive sulphide deposits in eastern Australia, in New Brunswick in Canada, and the Kuroko deposits of Japan.     

Lunar Magma Ocean crystallization revisited: Bulk composition, early cumulate mineralogy, and the source regions of the highlands Mg-suite

Crystallization of the Lunar Magma Ocean (LMO) has been numerically modeled and its products inferred from sample observations, but it has never been fully tested experimentally. This study is a reexamination of the LMO hypothesis by means of the first experimental simulation of lunar differentiation. Two end-member bulk Moon compositions are considered: one enriched in refractory lithophile elements relative to Earth and one with no such enrichment. A “two-stage” model of magma ocean crystallization based on geophysical constraints is simulated and features early crystal suspension and equilibrium crystallization followed by fractional crystallization of the residual magma ocean. An initially entirely molten Moon is assumed. Part 1 of this study, presented here, focuses on stage 1 of this model and considers the early cumulates formed by equilibrium crystallization, differences in mantle mineralogy resulting from different bulk Moon compositions, and implications for the source regions of the highlands Mg-suite.Refractory element enriched bulk Moon compositions produce a deep mantle that contains garnet and trace Cr-spinel in addition to low-Ca pyroxene and olivine. In contrast, compositions without refractory element enrichment produce a deep dunitic mantle with low-Ca pyroxene but without an aluminous phase. The differences in bulk composition are magnified in the residual melt; the residual LMO from the refractory element enriched composition will likely produce plagioclase and ilmenite earlier and in greater quantities. Both compositions produce Mg-rich early cumulate piles that extend from the core-mantle boundary to ∼355 km depth, if 50% equilibrium crystallization and whole Moon melting are assumed. These early LMO cumulates provide good fits for the source regions for a component of the high-Mg^∗, Ni- and Co-poor parental magmas of the Mg-suite cumulates, if certain conditions are called upon. The olivine in early LMO cumulates produced by either bulk Moon composition is far too rich in Cr to be reasonable for the source regions of the Mg-suite, meaning either core formation in the presence of S and/or C must be invoked to deplete the LMO and the crystallizing olivine in Cr, or that current estimates of the bulk lunar Cr content are too high. We infer that melts meeting the criteria of the Mg-suite parents could be produced from early LMO cumulates by solid state KREEP and plagioclase hybridization near the base of the crust and subsequent partial melting. Additionally, we propose a revised model for Mg-suite petrogenesis.     

Redox Potential and Seasonal Porewater Biogeochemistry of Three Mountain Wetlands in Southeastern Kentucky, USA

Redox potentials (Eh) were monitored bimonthly and porewater chemistry was analyzed seasonally at three slightly-acidic, high-elevation Kentucky wetlands that differed in hydrology, parent materials, and vegetation. At all sites, Eh values were below 300 mV, which indicated that reducing conditions persisted within the upper 90 cm and fluctuated mainly within the range of iron and sulfate reduction. Significant relationships of Eh values with depth were observed only at the Martins Fork wetland, where precipitation was the primary water source. The strongest and most stable reducing conditions, observed at the Kentenia site, reflected consistently high water levels, which were sustained by ground water. The third wetland (Four Level) was distinguished by irregular Eh fluctuations coinciding with strong seasonal ground-water upwelling. Although Fe³⁺ and SO₄ ²⁻ were the primary terminal electron acceptors in all wetlands, porewater chemistry also varied significantly by season and soil depth in response to piezometric water level fluctuations. Additional factors that influenced porewater chemistry included: (1) the presence of limestone parent materials that affected porewater pH, Ca²⁺, and Mg²⁺; and (2) the prevalence of sphagnum moss or graminoid species that influenced dissolved organic carbon, CO₂, and CH₄. Results from this study indicated the diverse range and importance of multiple factors in controlling biogeochemical processes and properties in small, high-elevation Appalachian wetlands.