Geochemistry and mineralogy of coal samples from Dingji Mine, Huainan Coalfield, China

To investigate the geochemistry of trace elements in coals from the Dingji Mine of the Huainan Coalfield, Anhui province, China, 416 borehole samples of coal, one parting, two floor and two roof mudstones were collected from 9 minable coal seams in 24 boreholes drilled during exploration. The abundances of 47 elements in each sample were determined by various instruments. The boron concentration in the coals suggests that marine influence decreased from coal seam 1 to 13-1. The geometric means of the elements Sn, Bi, Sb, and B are higher than the average for the corresponding elements in the coals from China, the U.S., and world. The enrichment of certain elements in the Shanxi or Upper Shihezi Formations is related to their depositional environment. The roof, floor and parting samples have higher contents of some elements than coal seams. The mineral matters in the coals from the Dingji Mine were found to consist mainly of granular quartz, clay minerals, and carbonate minerals. The elements are classified into two groups based on their stratigraphic distribution from coal seam 1 to 13-1, and the characteristics of each group are discussed. Based on the correlation coefficients of elemental concentrations with ash yield, four groups of elements with different affinities were identified.

Sedimentology of surface sediments from the continental shelf and slope off West Africa (Table 1)

Samples from sutface sediments of the shell, continental slope, and adjacent deep sea regions off West Africa between 27° N and 15° N were investigated with respect to grain size distribution of the total samples, sand contents of the acid insoluble residues, carbonate content of the total samples, and the separate grain size fractions, specific surfaces, colours and mineralogical composition of the clay fractions. The grain size distributions of the total samples of the sediments of the shelf and the continental slope off Spanish-Sahara are controlled mainly by biogenic components. The supply of terrigeneous material in this area is very low. At deeper parts of the continental slope and in the deep sea areas, the relative amounts of carbonate minerals in the sediments are considerably reduced. The prevailing sand contents of the upper slope changes into clay dominance. On the shelf of Mauritania - represented by profiles extending down to 200 m water depth - the grain size is also controlled mainly by biogenic carbonates. Nevertheless, the admixture of fossil silicate components is important, too. The southern parts of the area is investigated are located in a region influenced by sediments of the Senegal River, which especially control the contents of silt and clay. The silicate sands, predominately of quartz, are fossil and form a mixed sediment with younger deposits. The carbonate contents of the different grain size fractions are formed either by sedimentation of carbonate and silicate particles of the respective grain size or by autochtonous disintegration of coarser sediment particles, as shown by the occurence of Mg-rich calcite and especially aragonite in the clay sized fraction. In the northern parts of the area investigated, which have very minute terrigeneous supply, the latter mechanism is the dominant factor, controlling the carbonate contents of the fine grain sized fractions. In the vicinity of the mouth of the Senegal the carbonate contents are influenced by extremely high dilution with terrigencous silicates. Mg-rich calcite and aragonite are produced preferentially in shallow slope and shelf areas up to 500 m of water depth. The specific surfaces of the carbonate-free clay fractions indicate that the clay fractions of the shelfareas with little terrigenous supply consits of relatively coarser particles. Very fine particles are removed and transported towards the deep sea. Lateral differentiation of this kind was not observed in the area off Senegal. The high surface areas, characterizing the clay fractions of this region, are thought to be due to high montmorillonite contents as was found for deep seas sediments. The mineralogical composition of the clay fraction from the southern parts of the area is characterized by high kaolinite and montmorillonite contents, while in the northern illite is predominating. At least two types of montmorillionites are present: in areas influenced by the Senegal mostly one type was found, which could swell to 17; on the shelves and slopes of the other regions the montmorillonite-group is represented by a montmorillonite-mica-type mixed-layer mineral. A "glauconite", found in the sand fraction, which had very similar properties to those of the montmorillonite-mica mixed-layer, is believed to be the source of this mixed-layer-type mineral. Palygorskite is present in all samples out of range of the Senegal supply. It may be an indicator of eolian transported material. The occurence of rich palygorskit deposits in the arid hinterlands emphasizes the terrestrial origin.

Isotope characterization and estimated temperature of formation of calcite veins in ODP Sites 124-768 and 124-770 (Table 1)

Secondary carbonate minerals were recovered within the basalts at both ODP Sites 768 and 770 in the Sulu and Celebes seas. Petrographic and X-ray diffraction analyses indicate that the carbonates are calcites. Other alteration products recognized in the thin sections are smectites, iron oxides, and gypsum. The 13C values of carbonates from both sites range from 1.6 per mil to 2.3 per mil, which are indicative of inorganic carbonate formation with no contributions from 13C-depleted sources such as oxidized organic carbon or methane. The oxygen isotopes at Site 770 range from 30.8 per mil to 31.6 per mil, which indicates a pervasive circulation of cold seawater (9° to 12°C) during alteration of the Celebes Sea basalts. In contrast, carbonates associated with Site 768 basalts have less positive d18O values (21.0 per mil to 27.3 per mil). A lighter 18O isotopic signature indicates the formation of secondary calcite at either higher temperatures or in a system closed to seawater. The rapidly deposited pyroclastic flows at Site 768 would have limited water access to the crust very soon after its formation, which leads us to speculate that the carbonates in the Sulu Sea basalts were formed by isotopically modified fluids resulting from basalt alteration in a closed system.

Seawater neutralization of alkaline bauxite residue and implications for revegetation

Reaction of bauxite residue with seawater results in neutralization of alkalinity through precipitation of Mg-, Ca-, and Al-hydroxide and carbonate minerals. In batch studies, the initial pH neutralization reaction was rapid (

Hydrothermal control on organic matter alteration and illite precipitation, Mt Isa Basin, Australia

Abundant illite precipitation, in Proterozoic rocks from Northern Lawn Hill Platform, Mt Isa Basin, Australia, occurred in organic matter-rich black shales rather than in sandstones, siltstones and organic matter-poor shales. Sandstones and siltstones acted as impermeable rocks, as early diagenetic quartz and carbonate minerals reduced the porosity-permeability. Scanning and transmission electron microscopy (SEM and TEM) studies indicate a relation between creation of microporosity-permeability and organic matter alteration, suitable for subsequent mineral precipitation. K-Ar data indicate that organic matter alteration and the subsequent illite precipitation within the organic matter occurred during the regional hydrothermal event at 1172 +/- 150 (2sigma) Ma. Hot circulating fluids are considered to be responsible for organic matter alteration, migration and removal of volatile hydrocarbon, and consequently porosity-permeability creation. Those rocks lacking sufficient porosity-permeability, such as sandstones, siltstones and organic matter poor shales, may not have been affected by fluid movement. In hydrothermal systems, shales and mudstones may not be impermeable as usually assumed because of hydrocarbons being rapidly removed by fluid, even with relatively low total organic carbon.

Isotopes content, mineralogical composition, Uranium and Thorium contents and determined activity ratios from METEOR cruise M74/3 in 2007

Authigenic carbonate deposits have been sampled with the remotely operated vehicle 'MARUM-QUEST 4000 m' from five methane seeps between 731 and 1823 m water depth along the convergent Makran continental margin, offshore Pakistan (northern Arabian Sea). Two seeps on the upper slope are located within the oxygen minimum zone (OMZ; ca. 100 to 1100 m water depth), the other sites are situated in oxygenated water below the OMZ (below 1100 m water depth). The carbonate deposits vary with regard to their spatial extent, sedimentary fabrics, and associated seep fauna: Within the OMZ, carbonates are spatially restricted and associated with microbial mats, whereas in the oxygenated zone below the OMZ extensive carbonate crusts are exposed on the seafloor with abundant metazoans (bathymodiolin mussels, tube worms, galatheid crabs). Aragonite and Mg-calcite are the dominant carbonate minerals, forming common early diagenetic microcrystalline cement and clotted to radial-fibrous cement. The delta18O carbonate values range from 1.3 to 4.2 per mil V-PDB, indicating carbonate precipitation at ambient bottom-water temperature in shallow sediment depth. Extremely low delta13Ccarbonate values (as low - 54.6per mil V-PDB) point to anaerobic oxidation of methane (AOM) as trigger for carbonate precipitation, with biogenic methane as dominant carbon source. Prevalence of biogenic methane in the seepage gas is corroborated by delta13C methane values ranging from - 70.3 to - 66.7per mil V-PDB, and also by back-calculations considering delta 13C methane values of carbonate and incorporated lipid biomarkers.

(Table 1) Water chemistry of groundwater and snow samples from three sites in Ontario, Canada

Snow samples collected from hand-dug pits at two sites in Simcoe County, Ontario, Canada were analysed for major and trace elements using the clean lab methods established for polar ice. Potentially toxic, chalcophile elements are highly enriched in snow, relative to their natural abundance in crustal rocks, with enrichment factor (EF) values (calculated using Sc) in the range 107 to 1081 for Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, Te, and Zn. Relative to M/Sc ratios in snow, water samples collected at two artesian flows in this area are significantly depleted in Ag, Al, Be, Bi, Cd, Cr, Cu, Ni, Pb, Sb, Tl, V, and Zn at both sites, and in Co, Th and Tl at one of the sites. The removal from the waters of these elements is presumably due to such processes as physical retention (filtration) of metal-bearing atmospheric aerosols by organic and mineral soil components as well as adsorption and surface complexation of ionic species onto organic, metal oxyhydroxide and clay mineral surfaces. In the case of Pb, the removal processes are so effective that apparently ''natural'' ratios of Pb to Sc are found in the groundwaters. Tritium measurements show that the groundwater at one of the sites is modern (ie not more than 30 years old) meaning that the inputs of Pb and other trace elements to the groundwaters may originally have been much higher than they are today; the M/Sc ratios measured in the groundwaters today, therefore, represent a conservative estimate of the extent of metal removal along the flow path. Lithogenic elements significantly enriched in the groundwaters at both sites include Ba, Ca, Li, Mg, Mn, Na, Rb, S, Si, Sr, and Ti. The abundance of these elements can largely be explained in terms of weathering of the dominant silicate (plagioclase, potassium feldspar, amphibole and biotite) and carbonate minerals (calcite, dolomite and ankerite) in the soils and sediments of the watershed. Arsenic, Mo, Te, and especially U are also highly enriched in the groundwaters, due to chemical weathering: these could easily be explained if there are small amounts of sulfides (As, Mo, Te) and apatite (U) in the soils of the source area. Elements neither significantly enriched nor depleted at both sites include Fe, Ga, Ge, and P.

Der Kauffunger Kalkstein (Bober-Katzbach Gebirge, Polen): Petrographie, Fossilinventar, Stratigraphie

In the Western Sudetes (Mts.) in SW Poland carbonate rocks occur which are well known in the older German literature as ’’Kauffung Limestone” or ’’Wojcieszow Limestone” in recent publications, respectively. They are intercalated in sedimentary (shales) and volcanic (greenstone) successions and are, presumed - due to the lack of index fossils - to be Cambrian in age. These deposits occur in a variety of isolated massifs in the Bober-Katzbach Mts. where they have been mined in many quarries in the past. In a single location (Polom quarry near Wojcieszow) they are exploited up until today. The predominantly calcitic rocks display a wide variety of different lithologies and are, consequently, subdivided into the following lithological units which differ in textural characteristics, mineral constituents, and different grades of diagenetic and metamorphic alteration: 1. Calcite Marble: massive, calcitic, chiefly metamorphic recrystallized. 2. Zebra Limestone: dolomitic-calcitic, certain content of metasomatic silica, fine bedding as a result of microbial calcite precipitation or of diagenetic to metamorphic separation of carbonate and silica constituents. 3. Massive matrix Dolomite: compact, of diagenetic to metamorphic origin. 4. Dolomite Marble: metamorphic. 5. Hydrothermal Dolomite: hydrothermal alteration of limestone, postdating the tectonic deformation. The recent appearance of ’’Kauffung Limestone” is mainly a result of regional metamorphosis at low temperature up to about 300°C and locally high pressure. The typical textural features are stress induced, mostly protomylonitic calcite recrystallisation and generally slowly or not infected dolomite crystals. The different reactions of the two carbonate phases are attributed to their mineral properties. Rhyolitic and dacitic dykes penetrating the carbonate rocks are interpreted as a result of post- orogenic, probably Carboniferous or Permian volcanism. Microprobe investigation on the carbonates revealed a stochiometric composition of dolomite and calcite. The stable isotope content (8 c 0,8* ^C) reflects increased crystallisation temperature of the carbonate minerals (8 O von -7,75 bis -15,78). A variety of fossil remains have been extracted from bulk samples, consisting of sponge needles, floral components, foramini- fera, and vertebrate remains the latter two of which indicate a depositional age younger than Ordovician. Due to the stratigraphic re-attribution of the Kauffung Limestone, the hypothesis of a Cambrian/Ordovician rifting in the Western Sudetes should be abandoned.

Formation of seep carbonates along the makran convergent margin, northern Arabian sea and a molecular and isotopic approach to constrain the carbon isotopic composition of parent methane

Authigenic carbonate deposits have been sampled with the remotely operated vehicle ‘MARUM-QUEST 4000 m’ from five methane seeps between 731 and 1823 m water depth along the convergent Makran continental margin, offshore Pakistan (northern Arabian Sea). Two seeps on the upper slope are located within the oxygen minimum zone (OMZ; ca. 100 to 1100 m water depth), the other sites are situated in oxygenated water below the OMZ (below 1100 m water depth). The carbonate deposits vary with regard to their spatial extent, sedimentary fabrics, and associated seep fauna: Within the OMZ, carbonates are spatially restricted and associated with microbial mats, whereas in the oxygenated zone below the OMZ extensive carbonate crusts are exposed on the seafloor with abundant metazoans (bathymodiolin mussels, tube worms, galatheid crabs). Aragonite and Mg-calcite are the dominant carbonate minerals, forming common early diagenetic microcrystalline cement and clotted to radial-fibrous cement. The δ18Ocarbonate values range from 1.3 to 4.2‰ V-PDB, indicating carbonate precipitation at ambient bottom-water temperature in shallow sediment depth. Extremely low δ13Ccarbonate values (as low − 54.6‰ V-PDB) point to anaerobic oxidation of methane (AOM) as trigger for carbonate precipitation, with biogenic methane as dominant carbon source. Prevalence of biogenic methane in the seepage gas is corroborated by δ13Cmethane values ranging from − 70.3 to − 66.7‰ V-PDB, and also by back-calculations considering δ13Cmethane values of carbonate and incorporated lipid biomarkers. These calculations (Δδ13Cmethane–carbonate, Δδ13CANME–methane, Δδ13CMOX–methane) prove to be useful to assess the carbon stable isotope composition of seeping methane if this has not been determined in the first place; such an approach represents a useful tool to reconstruct fluid composition of ancient seeps. AOM is also revealed by lipid biomarkers of anaerobic methane oxidizing archaea such as crocetane, pentamethylicosane (PMI), and sn2-hydroxyarchaeol strongly depleted in 13C (δ13C values as low as − 127‰ V-PDB). Biomarkers of sulphate-reducing bacteria are also abundant, showing slightly less negative δ13C values, but still significantly 13C-depleted (average values as low as − 101‰). Other bacterial biomarkers, such as bacteriohopanepolyols (BHPs), hopanols, and hopanoic acids are detected in most carbonates, but are particularly common in seep carbonates from the non-OMZ sites. The BHP patterns of these carbonates and their low δ13C values resemble patterns of aerobic methanotrophic bacteria. In the shallower OMZ sites, BHPs revealed much lower contents and varying compositions, most likely reflecting other sources than aerobic methanotrophic bacteria. 230Th/U carbonate ages indicate that AOM-induced carbonate precipitation at the deeper non-OMZ seeps occurred mainly during the late Pleistocene-Holocene transition, i.e. between 19 and 15 ka before present, when the global sea level was lower than today.

Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures

Methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Delta(47)), as much as similar to 0.2 parts per thousand lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 degrees C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings.

Spectroscopy of selected copper group minerals : chalcophyllite and chenevixite-implications for hydrogen bonding

NIR and IR spectroscopy has been applied for detection of chemical species and the nature of hydrogen bonding in arsenate complexes. The structure and spectral properties of copper(II) arsenate minerals chalcophyllite and chenevixite are compared with copper(II) sulphate minerals devilline, chalcoalumite and caledonite. Split NIR bands in the electronic spectrum of two ranges 11700-8500 cm-1 and 8500-7200 cm-1 confirm distortion of octahedral symmetry for Cu(II) in the arsenate complexes. The observed bands with maxima at 9860 and 7750 cm-1 are assigned to Cu(II) transitions 2B1g ® 2B2g and 2B1g ® 2A1g. Overlapping bands in the NIR region 4500-4000 cm-1 is the effect of multi anions OH-, (AsO4)3- and (SO4)2-. The observation of broad and diffuse bands in the range 3700-2900 cm-1 confirms strong hydrogen bonding in chalcophyllite relative to chenevixite. The position of the water bending vibrations indicates the water is strongly hydrogen bonded in the mineral structure. The strong absorption feature centred at 1644 cm-1 in chalcophyllite indicates water is strongly hydrogen bonded in the mineral structure. The H2O-bending vibrations shift to low wavenumbers in chenevixite and an additional band observed at 1390 cm-1 is related to carbonate impurity. The characterisation of IR spectra by ν3 antisymmetric stretching vibrations of (SO4)2- and (AsO4)3 ions near 1100 and 800 cm-1 respectively is the result of isomorphic substitution for arsenate by sulphate in both the minerals of chalcophyllite and chenevixite.

Synthesis and characterisation of cobalt hydroxy carbonate Co2CO3(OH)2 Nanomaterials

In an attempt to make nanofibres based upon cobalt oxides, a novel compound a hydrated cobalt hydroxy carbonate was formed. This compound is related to the minerals of the rosasite mineral group. X-ray diffraction showed that the formed compound was a cobalt hydroxy carbonate and SEM displayed bundles of fibres on the micron scale in length and nanoscale in width. The morphology was compared with that of the rosasite mineral group. XPS proved two bond energies for cobalt and three for oxygen in the compound. The compound was characterised by vibrational spectroscopy and the spectra related to minerals of the rosasite mineral group. The stability of the synthetic mineral was limited to temperatures below 200°C.