Weathering control over geomorphology of supermature Proterozoic Delhi quartzites of India

Quartz and quartzite are thought to be resistant as a mineral and a rock respectively; however, we have shown that the presence of small amounts of pyrite in the quartzites makes them vulnerable to weathering. We observe that weathering of Proterozoic quartzite in the semi‐arid conditions around Delhi proceeded from fractures towards the inside and produced weathering rinds. The chemical index of alteration (CIA), which is actually a measure of weathering of aluminosilicate minerals, increases from the core outwards, through the rinds. Although aluminosilicate minerals occur only as minor phases (<2 per cent), their weathering indicates a movement of the weathering front from the periphery towards the core. We have suggested a coupled mechanism in which the dissolution of pyrites by moving water produced a sulphate‐bearing acidic solution and ferrous iron, which reacted with aluminosilicate minerals and quartz, respectively. This initially makes the Delhi quartzite porous and subsequently friable. The total disintegration of grain to grain contacts imparted friability to this quartzite to produce silica sand. Subsequent physical erosion of loose sand, produced during rind development in the outermost zones, has given rise to features like tors, spheroids, gullies, cavities and small‐scale caves on these quartzites. Thus, the terrain has acquired ruggedness in semi‐arid conditions. Copyright © 2003 John Wiley & Sons, Ltd.     

Provenance analysis and tectonic setting of the Ordovician clastic deposits in the southern Puna Basin, NW Argentina

Provenance studies on Early to Middle Ordovician clastic formations of the southern Puna basin in north-western Argentina indicate that the sedimentary detritus is generally composed of reworked crustal material. Tremadoc quartz-rich turbidites (Tolar Chico Formation, mean composition Q_t89 F7 L4) are followed by volcaniclastic rocks and greywackes (Tolillar Formation, mean Q_t33 F42 L25). These are in turn overlain by volcaniclastic deposits (mean Q_t24 F30 L46) of the Diablo Formation (late Arenig–early Llanvirn) that are intercalated by lava flows. All units were deformed in the Oclóyic Orogeny during the Middle and Late Ordovician. Sandstones of the Tolar Chico Formation are characterized by Th/Sc ratios > 1, La/Sc ratios ≈ 10, whereas associated fine-grained wackes show slightly lower values for both ratios. LREE (light rare earth elements) enrichment of the arenites is ≈ 50× chondrite, Eu/Eu* values are between 0·72 and 0·92, and flat HREE (heavy rare earth elements) patterns indicate a derivation from mostly felsic rocks of typical upper crustal composition. The ε_{Nd(t = sed)} values scatter around −11 to −9. The calculated Nd-T_DM residence ages vary between 1·8 and 2·0 Ga indicating contribution by a Palaeoproterozoic crustal component. The Th/Sc and La/Sc ratios of the Tolillar Formation are lower than those of the Tolar Chico Formation. Normalized REE (rare earth elements) patterns display a similar shape to PAAS (post-Archaean average Australian shale) but with higher abundances of HREEs. Eu/Eu* values range between 0·44 and 1·17, where the higher values reflect the abundance of plagioclase and feldspar-bearing volcanic lithoclasts. Average ε_{Nd(t = sed)} values are less negative at −5·1, and Nd-T_DM are lower at 1·6 Ga. This is consistent with characteristics of regional rocks of upper continental crust composition, which most probably represent the sources of the studied detritus. The rocks of the Diablo Formation have the lowest Th/Sc and La/Sc ratios, lower LREE abundances than the average continental crust and are slightly enriched in HREEs. Eu/Eu* values are between 0·63 and 1·17. The Nd isotopes (ε_{Nd(t = sed)} = −3 to −1; T_DM = 1·2 Ga) indicate that one source component was less fractionated than both the underlying Early Ordovician and the overlying Middle Ordovician units. Synsedimentary vulcanites in the Diablo Formation show the same isotopic composition. Our data indicate that the sedimentary detritus is generally composed of reworked crustal material, but that the Diablo Formation appears to contain ≈ 80% of a less fractionated component, derived from a contemporaneous continental volcanic arc. There are no data indicating an exotic detrital source or the accretion of an exotic block at this part of the Gondwana margin during the Ordovician.     

A Reappraisal of Rb, Y, Zr, Pb and Th Values in Geochemical Reference Material BHVO-1

The geochemical reference material BHVO-1 was analysed by a variety of techniques over a six year period. These techniques included inductively coupled plasma-mass spectrometry and atomic emission spectroscopy (ICP-MS and ICP-AES, respectively), laser ablation ICP-MS and spark source mass spectroscopy. Inconsistencies between the published consensus values reported by Gladney and Roelandts (1988, Geostandards Newsletter) and the results of our study are noted for Rb, Y, Zr, Pb and Th. The values reported here for Rb, Y, Zr and Pb are generally lower, while Th is higher than the consensus value. This is not an analytical artefact unique to the University of Notre Dame ICP-MS facility, as most of the BHVO-1 analyses reported over the last ten to twenty years are in agreement with our results. We propose new consensus values for each of these elements as follows: Rb = 9.3 ± 0.2 μg g-1 (compared to 11 ± 2 μg g-1), Y = 24.4 ± 1.3 μg g-1 (compared to 27.6 ± 1.7 μg g-1), Zr = 172 ± 10 μg g-1 (compared to 179 ± 21 μg g-1), Pb = 2.2 ± 0.2 μg g-1 (compared to 2.6 ± 0.9 μg g-1) and Th = 1.22 ± 0.02 μg g-1 (compared to 1.08 ± 0.15 μg g-1).     

Surface analysis of pyrite in the No. 9 coal seam, Wuda Coalfield, Inner Mongolia, China, using high-resolution time-of-flight secondary ion mass-spectrometry

The chemical composition of pyrite in coal can be used to investigate its geological and mineralogical origin. In this paper, high-resolution time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used to study the chemical composition of various pyrite forms in the No. 9 coal seam (S_t,d=3.46%) from the Wuda Coalfield, Inner Mongolia, northern China. These include bacteriogenic, framboidal, massive, cell-filling, fracture-filling, and nodular pyrites. In addition to Fe⁺ (⁵⁴Fe⁺, ⁵⁶Fe⁺, ⁵⁷Fe⁺), other fragment ions were detected in bacteriogenic pyrites, such as ²⁷Al⁺, Si⁺ (²⁸Si⁺, ²⁹Si⁺, ³⁰Si⁺), ⁴⁰Ca⁺, Cu⁺ (⁶³Cu⁺, ⁶⁵Cu⁺), Zn⁺ (⁶⁴Zn⁺, ⁶⁶Zn⁺, ⁶⁷Zn⁺, ⁶⁸Zn⁺), Ni⁺ (⁵⁸Ni⁺, ⁶⁰Ni⁺, ⁶²Ni⁺), and C₃H₇⁺. TOF-SIMS images show bacteriogenic pyrites are relatively rich in Cu, Zn, and Ni, suggesting that bacteria probably play an important role in the enrichment of Cu, Zn, and Ni during their formation. Intense positive secondary ion fragments from framboidal aggregates, such as ²⁷Al⁺, ²⁸Si⁺, ²⁹Si⁺, AlO⁺, CH₂⁺, C₃H₃⁺, C₃H₅⁺, and C₄H₇⁺, indicate that formation of the framboidal aggregates may have occurred together with clay mineral and organic matter, which probably serve as the binding substance. The intense ions of ²⁸Si⁺ and ²⁷Al⁺ from massive pyrites also suggest that their pores incorporated clay minerals during crystallization. Together with the lowest ²⁸Si⁺/²³Na⁺ value, the intense organic positive secondary ion peaks from cell-filling pyrites, such as C₃H₃⁺, C₃H₅⁺, C₃H₇⁺, and C₄H₇⁺, indicate that pyrite formation may have accompanied dissolution or disintegration of the cell. The intense P⁺ peak was observed only in the fracture-filling pyrite and the highest ²⁸Si⁺/²³Na⁺ value of fracture-filling pyrite reflects its epigenetic origin. Together with XRD and REEs data, the stronger ⁴⁰Ca⁺ in nodular pyrite than other pyrite forms shows seawater influence during its formation.     

壳幔混染作用——下扬子区早中生代玄武岩同位素地质特征

下扬子区中生代（231Ma）玄武质火山岩全岩εNd（t）值-8.62～1.92,87Sr/86Sr 值0.7074～0.7179，206Pb/204Pb值为17.786～18.323。岩石中含有前寒武纪捕虏晶锆石。研究表明玄武质岩石可能是由亏损地幔与元古宙地壳岩石混染作用的结果。     

The origin and distribution of HAPs elements in relation to maceral composition of the A1 lignite bed (Paleocene, Calvert Bluff Formation, Wilcox Group), Calvert mine area, east-central Texas

The origin and distribution of twelve potentially Hazardous Air Pollutants (HAPs; As, Be, Cd, Cr, Co, Hg, Mn, Ni, Pb, Sb, Se, and U) identified in the 1990 Clean Air Act Amendments were examined in relation to the maceral composition of the A1 bed (Paleocene, Calvert Bluff Formation, Wilcox Group) of the Calvert mine in east-central Texas. The 3.2 m-thick A1 bed was divided into nine incremental channel samples (7 lignite samples and 2 shaley coal samples) on the basis of megascopic characteristics. Results indicate that As, Cd, Cr, Ni, Pb, Sb, and U are strongly correlated with ash yield and are enriched in the shaley coal samples. We infer that these elements are associated with inorganic constituents in the coal bed and may be derived from a penecontemporaneous stream channel located several kilometers southeast of the mining block. Of the HAPs elements studied, Mn and Hg are the most poorly correlated to ash yield. We infer an organic association for Mn; Hg may be associated with pyrite. The rest of the trace elements (Be, Co, and Se) are weakly correlated with ash yield. Further analytical work is necessary to determine the mode of occurrence for these elements. Overall, concentrations of the HAPs elements are generally similar to or less than those reported in previous studies of lignites of the Wilcox Group, east-central region, Texas. Petrographic analysis indicates the following ranges in composition for the seven lignite samples: liptinites (5–8%), huminites (88–95%), and inertinites (trace amounts to 7%). Samples from the middle portion of the A1 bed contain abundant crypto-eugelinite compared to the rest of the samples; this relationship suggests that the degradation of plant material was an important process during the development of the peat mire. With the exception of Hg and Mn, relatively low levels of the HAPs elements studied are found in the samples containing abundant crypto-eugelinite. We infer that the peat-forming environment for this portion of the coal bed was very wet with minimal detrital input. Relatively high concentrations of crypto-humotelinite were found in samples from the top and base of the coal bed. The presence of abundant crypto-humotefinite in this part of the coal bed suggests the accumulation of wood-rich peat under conditions conducive to a high degree of tissue preservation in the peat mire. Although several of the trace elements (Be, Co, Ni, and Sb) exhibit enrichment in these samples, they are not necessarily chemically associated with humotelinite. We infer that these elements, with the exception of Be, are possibly associated with deposition of the roof and floor rock of the coal bed; however, further analytical work would be necessary to confirm this hypothesis. Beryllium may have an organic origin.     

The Origin of the Early Proterozoic Kuandian Complex: Evidence from Geochemistry

The Kuandian Complex is scarcely preserved Early Proterozoic volcanic suite, formed2.3-2.4 Ga ago. It is located in an Early Proterozoic mobile belt bounded by the ArchaeanRangrim and Ryonggang Blocks of the northeastern Sino-Korean Craton. The Complex ismainly made up of amphibolites, gneisses, leucoleptite, leptite and layered granite. Petrologicaland geochemical studies show that the protoliths of the Complex are mainly assoctations ofbimodal volcanics and anorogenic granites. The Kuandian amphibolites are depleted in Nb, Ta,P and Ti, and enriched in LILE, e.g. K, Rb and Cs, with pronounced depletion of Sr relative toNd and Pb; La/Nb ratios are higher than 1(1.75 to 5.18). The trace element patterns of theamphibolites are similar to continental flood basalts formed by the Gondwana break-up, suchas those in South Karoo and Tasmania, which shows continental contamination. ε_(Nd) valuesranging from 0.70 to 1.94 of the Kuandian amphibolites and the relationships between Nb/Yband La/Yb suggest that contamination of basaltic magma happened in the mantle, rather thanalong the conduit. Isotope ratios of ~(208)Pb/~(204)Pb, ~(207)Pb/ ~(204)Pb, ~(206)Pb/~(204)Pb, ~(143)Nd/~(144)Ndand ~(87)Sr/~(86)Sr indicate that the magma was derived from a contaminated mantle source likeDMM or a mixture of DMM and EM2. The Kuandian Complex has Dupal anomaly, as is thecase with some continental basalts in the south hemisphere, e.g. in South Karoo and Tasmania.Petrochemical modelling proposes that the Kuandian gneiss, granite, and amphibolite camefrom the same parental magma, being products of strong fractional crystallization. Protoliths ofthe Kuandian Complex were formed in extensional tectonic setting during the transition fromcontinental crust to oceanic crust. The formation of the Kuandian Complex indicates that 2.3or 2.4 Ga ago tectonic evolution of the Sino-Korean craton was different from that of otherwell-studied Precambrian cratons, e.g. the North American shield, European platform andAustralian continent in that strong volcanic eruption resulted in its accretion. Besides, the con-taminated magma source with a Dupal anomaly for the Complex indicates that crust-mantleconvection whose scale was similar to that of the present plate tectonics had occurred at leastbefore the formation of the Kuandian Complex (2.3-2.4 Ga B.P).     

云南老王寨金矿煌斑岩地球化学研究中的某些问题──与宋新宇等同志商榷

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