Response of the coccolithophores Emiliania huxleyi and Coccolithus braarudii to changing seawater Mg and Ca concentrations: Mg/Ca, Sr/Ca ratios and δCa, δMg of coccolith calcite

Calcium and magnesium concentrations in seawater have varied over geological time scales. On short time scales, variations in the major ion composition of seawater influences coccolithophorid physiology and the chemistry of biogenically produced coccoliths. Validation of those changes via controlled laboratory experiments is a crucial step in applying coccolithophorid based paleoproxies for the reconstruction of past environmental conditions. Therefore, we examined the response of two species of coccolithophores, Emiliania huxleyi and Coccolithus braarudii, to changes in the seawater Mg/Ca ratio (≈0.5 to 10 mol/mol) by either manipulating the magnesium or calcium concentration under controlled laboratory conditions. Concurrently, seawater Sr/Ca ratios were also modified (≈2 to 40 mmol/mol), while keeping salinity constant at 35. The physiological response was monitored by measurements of the cell growth rate as well as the production rates of particulate inorganic and organic carbon, and chlorophyll a. Additionally, coccolithophorid calcite was analyzed for its elemental composition (Sr/Ca and Mg/Ca) as well as isotope fractionation of calcium and magnesium (Δ^44/40Ca and Δ^26/24Mg). Our results reveal that physiological rates were substantially influenced by changes in seawater calcium rather than magnesium concentration within the range estimated to have occurred over the past 250 million years when coccolithophores appear in the fossil record. All physiological rates of E. huxleyi decreased at a calcium concentration above 25 mmol L⁻¹, whereas C. braarudii displayed a higher tolerance to increased seawater calcium concentrations. Partition coefficient of Sr was calculated as 0.36 ± 0.04 (±2σ) independent of species. Partition coefficient of Mg²⁺ increased with increasing seawater Ca²⁺ concentrations in both coccolithophore species. Calcium isotope fractionation was constant at 1.1 ± 0.1‰ (±2σ) and not altered by changes in seawater Mg/Ca ratio. There is a well-defined inverse linear relationship between calcium isotope fractionation and partition coefficient of Sr²⁺ in all experiments, suggesting similar controls on both proxies in the investigated species. Magnesium isotope ratios were relatively stable for seawater Mg/Ca ratios ranging from 1 to 5, with a higher degree of fractionation in Emiliania huxleyi (by ≈0.2‰ in Δ^26/24Mg). Although Mg/Ca ratios in the calcite of coccolithophores and foraminifera are similar, the former have considerably higher Δ^26/24Mg (by >+3‰), presumably due to differences in calcification mechanisms between the two taxa. These observations suggest, a physiological control over magnesium elemental and isotopic fractionation during the process of calcification in coccolithophores.     

Mineralogy and Mode of Occurrence of Gold, Silver and Bismuth of the Caijiaying Lead-Zine-Silver Deposit, Hebei Province

The deposit under study is a hydrothermal filling-metasomatic vein type lead-zinc-silver deposit, in whichgold and silver can be recovered as by-products. These metals mainly occur as microgranular native gold,electrum, stephanite, acanthite, pyraragyrite, freibergite, and native silver. Gold minerals tend to be associatedwith galenobismutite, native bismuth and unnamed Bi_2Te. They are either enclosed in pyrite, marmatite,iron-bearing sphalerite and galens or fill the microfissures of these minerals. Silver minerals usually occur incleavages or fissures of galena, marmatite and pyrite, but are not associated with gold and bismuth minerals.Gold and silver mineralizations occurred later than lead and zinc, while the silver mineralization was precededby that of gold.     

Geochemistry of О, Н, C,S, and Sr isotopes in the water and sediments of the Aral basin

The paper presents original authors' data on the O, H, C, S, and Sr isotopic composition of water and sediments from the basins into which the Aral Sea split after its catastrophic shoaling: Chernyshev Bay (CB), the basin of the Great Aral in the north, Lake Tshchebas (LT), and Minor Sea (MS). The data indicate that the δ¹⁸О, δD, δ¹³C, and δ³⁴S of the water correlate with the mineralization (S) of the basins (as of 2014): for CB, S = 135.6‰, δ¹⁸О = 4.8 ± 0.1‰, δD = 5 ± 2‰, δ¹³C (dissolved inorganic carbon, DIC) = 3.5 ± 0.1‰, δ³⁴S = 14.5‰; for LT, S = 83.8‰, δ¹⁸О = 2.0 ± 0.1‰, δD =–13.5 ± 1.5‰, δ¹³C = 2.0 ± 0.1‰, δ³⁴S = 14.2‰; and for MS, S = 9.2‰, δ¹⁸О =–2.0 ± 0.1‰, δD =–29 ± 1‰, δ¹³C =–0.5 ± 0.5‰, δ³⁴S = 13.1‰. The oxygen and hydrogen isotopic composition of the groundwaters are similar to those in MS and principally different from the artesian waters fed by atmospheric precipitation. The mineralization, δ¹³С, and δ³⁴S of the groundwaters broadly vary, reflecting interaction with the host rocks. The average δ¹³С values of the shell and detrital carbonates sampled at the modern dried off zones of the basins are similar: 0.8 ± 0.8‰ for CB, 0.8 ± 1.4‰ for LT, and –0.4 ± 0.3‰ for MS. The oxygen isotopic composition of the carbonates varies much more broadly, and the average values are as follows: 34.2 ± 0.2‰ for CB, 32.0 ± 2.2‰ for LT, and 28.2 ± 0.9‰ for MS. These values correlate with the δ¹⁸O of the water of the corresponding basins. The carbonate cement of the Late Eocene sandstone of the Chengan Formation, which makes up the wave-cut terrace at CB, has anomalously low δ¹³С up to –38.5‰, suggesting origin near a submarine methane seep. The δ³⁴S of the mirabilite and gypsum (11.0 to 16.6‰) from the bottom sediments and young dried off zone also decrease from CB to MS in response to increasing content of sulfates brought by the Syr-Darya River (δ³⁴S = 9.1 to 9.9‰) and weakening sulfate reduction. The ⁸⁷Sr/⁸⁶Sr ratio in the water and carbonates of the Aral basins do not differ, within the analytical error, and is 0.70914 ± 0.00003 on average. This value indicate that the dominant Sr source of the Aral Sea is Mesozoic–Cenozoic carbonate rocks. The Rb–Sr systems of the silicate component of the bottom silt (which is likely dominated by eolian sediments) of MS and LT plot on the Т = 160 ± 5 Ma, I₀ = 0.7091 ± 0.0001, pseudochron. The Rb–Sr systems of CB are less ordered, and the silt is likely a mixture of eolian and alluvial sediments.     

Occurrence and distribution of “moganite” in agate/chalcedony: a combined micro-Raman, Rietveld, and cathodoluminescence study

Agate/chalcedony samples of different origin were investigated by performing Raman, X-ray diffraction (using Rietveld refinement), and cathodoluminescence measurements. These analyses were performed to measure the content and spatial distribution of the silica polymorph moganite, which is considered to represent periodic Brazil-law twinning of α-quartz at the unit-cell scale in agate/chalcedonies. Homogeneous standard samples including the nearly α-quartz free moganite type material from Gran Canaria were analysed in order to compare results of the X-ray diffractometry and Raman spectroscopy techniques and to provide a calibration curve for the Raman results. However, due to the different length scales analysed by the two techniques, the “moganite content” in microcrystalline SiO₂ samples measured by Raman spectroscopy (short-range order) was found to be considerably higher than the “moganite content” measured by X-ray diffractometry (long-range order). The difference is explained by the presence of moganite nanocrystals, nano-range moganite lamellae, and single Brazil-law twin-planes that are detected by vibrational spectroscopy but that are not large enough (in the sense of coherently scattering lattice domains) to be detected by X-ray diffractometry. High resolution Raman analysis provides a measure of the moganite content and its spatial variation in microcrystalline silica samples with a lateral resolution in the μm-range. Variations in the moganite-to-quartz ratio are revealed by varying intensity ratios of the main symmetric stretching-bending vibrations (A₁ modes) of α-quartz (465 cm⁻¹) and moganite (502 cm⁻¹), respectively. Traces of Raman microprobe analyses perpendicular to the rhythmic zoning of agates revealed that the moganite-to-quartz ratio is often not uniform but shows a cyclic pattern that correlates with the observed cathodoluminescence pattern (colour and intensity). Data obtained from an agate sample from a fluorite deposit near Okorusu, Namibia and from a volcanic agate from Los Indios, Cuba were selected for detailed presentation. Variations of cathodoluminescence and Raman data between single bands in agates suggest alternating formation of fine-grained, highly defective chalcedony intergrown with moganite, and coarse-grained low-defect quartz. Multiple zones indicate dynamic internal growth during a self-organizational crystallization process from silica-rich fluids. Received: 4 December 1997 / Accepted 19 June 1998     

Geochemistry and Sedimentology of Jhill Limestone of Gaj Formation,in Cape Monze and Adjoining Area,Karachi

Among several lithostratigraphic subdivisions of the Gaj Formation of Miocene age, the Jhill limestone is entirely different with respect to its colour, texture and structures. This limestone unit has been evaluated to elaborate its geochemical and sedimentological characteristics. The distribution of various elements in the acid-soluble fraction has been studied in order to determine their mineralogy, sedimentary environment, facies and diagenesis. Mineralogy, recrystallization and other diagenetic changes are the main factors affecting the distribution of trace elements and their mutual relationships in the limestones. Samples of the Jhill limestone show depletion in large-sized ions (Sr, Pb & K) and also in the ions that are not compatible with calcite space group. Elements (Fe, Mn, Zn, Cu & Co) having distribution coefficient (D) above unity for natural calcites, are more enriched. Microscopic and X-ray studies revealed nearly complete conversion of aragonite into stable low-Mg calcite. An attempt has also been made to verify the reefal conditions for these limestones on the basis of geochemical studies. The plots of Sr and other facies-indicator elements show that the majority of the beds belong to forereef flank facies with some algal banks. Low Mg/Ca and Sr/Ca ratios suggest that a phreatic diagenetic environment prevailed after the deposition. High concentrations of Cr, Ni, and Co in the Jhill limestone show a positive correlation with a higher amount of insoluble residue, which reflects a relatively high rate of influx of terrigenous material.     

Petrologic and Geochemical Characteristics and Origin of Gusui Cherts,Guangdong Province,China

The characteristic structures of the Precambrian cherts from the Gusui section, Guangdong ,Chi-na, include bedded structure ,laminated structure ,massive structure and pseudobrecciated structure.The chert is characterized by consistently low abundance of TiO2,Al2O3 and most trace elements.Howevver ,it is enriched in Ba,As,Sb,Hg and Se.In Al-Fe-Mn ternary diagrams,it falls into the “hydrothermal field“ .Correspondence analysis and factor analysis show that many elements show up in the factor that represents the leaching of country rocks by hydrothermal solutions,and are the very characteristic element association fo the geochemically anomalous South China basement.Petrologic and geochemical evidence suggests a hydrothermal origin for the chert.The chert may have been formed in a Precambrian fift or an extension zone developed within the Yunkai marginal geosyncline, with a fault system linking it to an unknown heat source at depth.     

Can sedimentary leaf waxes record D/H ratios of continental precipitation? Field, model, and experimental assessments

D/H ratios of leaf waxes (δD_wax) derived from terrestrial plants and preserved in lake sediments can provide important information on past continental hydrology. Ideally, δD_wax can be used to reconstruct precipitation D/H ratios (δD_P) which is a well-established paleoclimate proxy. However, many other factors, such as vegetation and relative humidity (RH), also affect δD_wax variation. How the combination of these factors affects sedimentary δD_wax is unclear. Here, we use a transect of 32 lake surface sediments across large gradients of precipitation, relative humidity, and vegetation composition in the southwestern United States to study the natural factors affecting sedimentary δD_wax. δD values of C₂₈n-alkanoic acids show significant correlation with δD_P values (R² = 0.76) with an apparent isotopic enrichment of ∼99 ± 8‰, indicating that sedimentary δD_wax values track overall δD_P variation along the entire transect. Leaf waxes produced by plants grown under controlled conditions (RH = 80%, 60%, 40%) show a small increase in D/H ratios as RH decreases, consistent with prediction from the Craig-Gordon model. However, the isotopic effect of RH on δD_wax along the natural transect is partially countered by the opposing influence of vegetation changes. The correlation between δD_wax and δD_P values is significantly higher (R² = 0.84) in the drier portions of the transect than in the wetter regions (R² = 0.64). This study suggests that D/H ratios of sedimentary leaf waxes can be used as a proxy for precipitation δD variations, with particularly high fidelity in dry regions, although more studies in other regions will be important to further test this proxy.     

Revised values for the Gibbs free energy of formation of [Al(OH)4 aq−], diaspore,boehmite and bayerite at 298.15 K and 1 bar,the thermodynamic properties of kaolinite to 800 K and 1 bar,and the heats of solution of several gibbsite samples

Solution calorimetric measurements compared with solubility determinations from the literature for the same samples of gibbsite have provided a direct thermochemical cycle through which the Gibbs free energy of formation of [Al(OH)_{4 aq}^?] can be determined. The Gibbs free energy of formation of [Al(OH)_{4 aq}^?] at 298.15 K is ?1305 ± 1 kJ/mol. These heat-of-solution results show no significant difference in the thermodynamic properties of gibbsite particles in the range from 50 to 0.05 μm.The Gibbs free energies of formation at 298.15 K and 1 bar pressure of diaspore, boehmite and bayerite are ?9210 ± 5.0, ?918.4 ± 2.1 and ?1153 ± 2 kJ/mol based upon the Gibbs free energy of [A1(OH)_{4 aq}^?] calculated in this paper and the acceptance of ?1582.2 ± 1.3 and ?1154.9 ± 1.2 kJ/mol for the Gibbs free energy of formation of corundum and gibbsite, respectively.Values for the Gibbs free energy formation of [Al(OH)_{2 aq}⁺] and [AlO_{2 aq}^?] were also calculated as ?914.2 ± 2.1 and ?830.9 ± 2.1 kJ/mol, respectively. The use of [AlC_{2 aq}^?] as a chemical species is discouraged.A revised Gibbs free energy of formation for [H₄SiO_4aq⁰] was recalculated from calorimetric data yielding a value of ?1307.5 ± 1.7 kJ/mol which is in good agreement with the results obtained from several solubility studies.Smoothed values for the thermodynamic functions C_P⁰, ($\text{H}{}_{\mathrm{T}}{}^0\text{- H}{}_{298}{}^0\text{)}\text{T}$, $\text{(}\text{G}{}_{\mathrm{T}}{}^0\text{- H}{}_{298}{}^0\text{)}\text{T}$, S_T⁰ - S₀⁰, $\text{ΔH}{}_{\mathrm{?,298}}{}^0$ kaolinite are listed at integral temperatures between 298.15 and 800 K. The heat capacity of kaolinite at temperatures between 250 and 800 K may be calculated from the following equation: C_P⁰ = 1430.26 ? 0.78850 T + 3.0340 × 10^?4T² ?1.85158 × 10^?4T²$\text{1}\text{2}\text{+ 8.3341 × 10}{}^6\text{T}{}^{\mathrm{?2}}$.The thermodynamic properties of most of the geologically important Al-bearing phases have been referenced to the same reference state for Al, namely gibbsite.     

Zinc,Copper, and Lead Geochemistry of Oceanic Igneous Rocks—Ridges,Islands, and Arcs

Variations in the abundances of Zn, Cu, and Pb are found to be useful in identifying tectonic regimes and separating oceanisland basalts into enriched- and depleted-source categories. The average Zn, Cu, and Pb contents of normal mid-ocean ridge basalts (N-MORB) are 84, 70, and 0.35 ppm, respectively. Differences in average Zn contents for various ridges reflect more the varying degrees of differentiation than variations of Zn content in the source rocks. At a Mg# of 70, or Mg#₇₀, which is taken to represent primitive MORB, many MORB sequences converge at a Zn content of 58 ± 6 ppm, which is close to the value for primitive mantle (50 ppm) and ordinary chondrites (～55 ppm). Values of 0.1 to 0.15 ppm Pb in MORB at Mg#₇₀, best defined at the superfast-spreading Southern East Pacific Rise, are similar to estimates of Pb in the primitive mantle (0.12 to 0.18 ppm). They also are near the lower end of the range for ordinary chondrites. The very slow spreading Southwest Indian Ocean Ridge has a sequence with higher Pb contents, in addition to a more normal sequence, which has a visual best value of 0.4 ppm Pb at Mg#₇₀. With the exception of the Walvis Ridge, Zn and Cu appear to be little affected by proximity to hotspots (i.e., E-MORB); however, Pb contents are higher and average about 0.6 ppm.

Both Zn and Pb in MORB are incompatible elements (i.e., favor the melt), but Cu is a compatible element. At Mg#₇₀, there is the suggestion of a value of 100 ppm for Cu, with lower values possibly representing partial removal of sulfides and their associated Cu from the source. Nonetheless, Cu contents of primitive MORB tend to be much higher than even high estimates for the primitive mantle (28 ppm), and are closer to ordinary chondrites (～90 ppm). Therefore, Zn, Cu, and Pb all approximate chondritic values in the primitive MORB melt.

Average contents of Zn, Cu, and Pb in oceanic island basalts (OIB) are 115, 62, and 3.2 ppm, respectively. At Mg#₇₀, values of Zn and Cu are similar to the respective averages for OIB, with Zn higher and Cu lower than MORB. At a Mg# of ～40, however, OIB and MORB tend to have similar Zn contents. With further differentiation, OIB trachytes can contain >200 ppm Zn. Unlike MORB, OIB can differentiate to high Cu contents of 200 ppm at Mg#s of 40 to 60. In contrast to Zn and Cu, Pb regresses to a value of 0.83 ppm at Mg#₇₀ for Hawaiian and Reunion volcanics, which is much less than the average value for Pb in OIB volcanics, but higher than for MORB.

Average Zn, Cu, and Pb contents of magmatic-arc basalts are 77, 108, and 1.9 ppm, respectively. In basalts, Zn tends to be incompatible, but a dual incompatible and compatible behavior can occur at high SiO₂ contents. Dacites may average near 55 ppm Zn, but peralkalic rhyolite can contain >300 ppm Zn. A dual compatible and incompatible nature occurs for Cu. Most common, particularly in submarine volcanics, is a compatible trend, with a Cu content of around 80 ppm at a Mg# of 60, which decreases to less than 40 ppm at a Mg# of 30. The incompatible trend of increasing Cu can achieve >200 ppm at a Mg# of 30, leaving a gap approaching 100 ppm at that Mg#. The gap is less obvious on a plot of Cu vs. SiO₂, but is still there. The compatible trend is proposed to result from sulfur-saturated magmas, whereas the incompatible trend is believed to result from sulfur-deficient magmas. Support for this hypothesis is found in sparse sulfur-isotope data. Zn and Cu both can be incompatible over an extended range of Mg#s or silica content. When Zn and Cu are both compatible, Cu decreases more than twice as rapidly as Zn.

Primitive magmas at Mg#₇₀ average about 50 ppm Zn for submarine Mariana arc basalts and 58 ppm for forearc boninites, contents close to MORB values. Mariana arc basalts have a Zn content of ～45 ppm estimated at Mg#₇₀. Cu varies more widely than Zn in primitive magmas, being about 50 ppm Cu for Mariana Islands volcanics and 120 ppm for Kermadec Islands volcanics, a range broadly around MORB values. Average Pb contents are 1.9 ppm for island-arc tholeiites, 5.6 ppm for high-Al basalt, and 3.2 ppm for alkali basalt with average boninite of approximately 1.8 ppm. Back-arc-basin basalts in the deepest parts of the Mariana trough have Pb contents of 0.45 ppm, but more shallow parts may exceed 1.0 ppm Pb. Although the lower contents are similar to MORB values, the ²⁰⁸Pb/²⁰⁴Pb values are greater than Pacific Ocean MORB. At Mg#₇₀ for rocks from the Tonga and Kermadec island arcs, the Pb content is about 0.1 ppm, similar to MORB.     

Interdiffusion of Na,K,and Ca Between Granitic Melts and NaCl Liquid

This study is aimed at determining the diffusion coefficient of net-work modifiers (mainly Na, K, and Ca) in a two-phase melt-NaCl system, in which the melts are granitic and the system is NaCl-rich in composition. The diffusion coefficients of Na, K, and Ca were measured at the temperatures of 750 – 1400°C, pressures of 0.001 × 10⁸ – 2 × 10⁸ Pa, and initial H₂O contents of 0 wt% –6.9 wt% in the granitic melts. The diffusion coefficients of Fe and Mg were difficult to resolve. In all experiments a NaCl melt was present as well. In the absence of H₂O, the diffusion of net-work modifiers follows an Arrhanious equation at 1 × 10⁵ Pa: lgD_ca=−3. 88−5140/T, lgD_k =−3. 79−4040/T, and lgD_Na, =−4.99−3350/T, where D is in cm² /s andT is in K. The diffusion coefficients of Ca, Na, K, and Fe increase non-linearly with increasing H₂O content in the melt. The presence of about 2 wt% H₂O m the melt will lead to a dramatical increase in diffusivity, but higher H₂O content has only a minor effect. This change is probably the result of a change in the melt structure when H₂O is present. The diffusion coefficients measured in this study are significantly different from those in previous works. This may be understood in terms of the “transient two-liquid equilibrium” theory. Element interdiffusion depends not only on its concentration, but also on its activity co-efficient gradient, which is reflected by the distribution coefficient, of the two contacting melts.     

Geologic relationships and mineralization of peralkaline/alkaline granite-syenite of the Zargat Na＇ am ring complex, Southeastern Desert, Egypt

The Zargat Na’ am ring complex crops out 90 km NW of Shalatin City in the Southeastern Desert of Egypt. The ring complex forms a prominent ridge standing high above the surrounding mafic-ultramafic hills. It is cut by two sets of joints and faults which strike predominantly NNW-SSE and E-W, and is injected by dikes, porphyritic alkaline syenites, and felsite porphyries. It consists of alkali syenites, alkali quartz syenites, and peralkaline arfvedsonite-bearing granitic and pegmatitic dikes and sills. The complex is characterized locally by extreme enrichments in REEs, wolframite and rare, high field strength metals (HFSM), such as Zr and Nb. The highest concentrations (1.5 wt% Zr, 0.25 wt% Nb, 0.6 wt% Σ REEs) occur in aegirine-albite aplites that formed around arfvedsonite pegmatites. Quartzhosted melt inclusions in arfvedsonite granite and pegmatite provide unequivocal evidence that the peralkaline compositions and rare metal enrichments are primary magmatic features. Glass inclusions in quartz crystals also have high concentrations of incompatible trace elements including Nb (750 ￠ 10⁻⁶), Zr (2500 × 10⁻⁶) and REEs (1450 × 10⁻⁶). The REEs, Nb and Zr compositions of the aegirine-albite aplites plot along the same linear enrichment trends as the melt inclusions, and Y/Ho ratios mostly display unfractionated, near-chondritic values. The chemical and textural features of the aegirine-albite aplites are apparently resultant from rapid crystallization after volatile loss from a residual peralkaline granitic melt similar in composition to the melt inclusions.     

Geochemical and Mineralogical Characteristics of Pleistocene Lignites and Associated Sediments of Marathousa Coal Field,Central Peloponnese,Greece

The mineralogy and geochemistry data are presented for thirty-seven shales,four concretions,two carbonate sediments and seven lignites from the Marathousa coal field of the Megalopolis Basin in Greece.The argillaceous rocks consist of chlorite,illite,kaolinte,albite,quartz.opal-A,calcite and dolomite;the concretions of aragonite,gypsum and pyrite;and the carbonate rocks of calcite,quartz and illite.The mineral matter in the lignites consists of gypsum,quartz,albite,chlorite,illite,opal-A,dolomite,pyrite,and rarely calcite and kaolinite Athree-factor model explains the total variaition of major and trace elements in the argillaceous sediments.The first factor is an aluminosilicate factor and involves the following elements:Al,Si,Mg,Na,K,Ti,Mn,Nb,Y,Rb,Zn,Cu,Ni,Cr,Nband V,associated with chlorite,albite and illite.The second factor involves the elements Ca,Sr,Ba,Znand Sc and is related to carbonate lithology and mainly the carbonate concretions with gypsum.The third factor involves Fe and Ce with a weak association with Mn.The diagenesis of the Marathousa sediments and lignites was not very advanced as indicated by (a) the total thickness of the sequence (500m),(b) the presence of biogenic silica(opal-A) and (c) the age of the deposit(Pleistocene).FOr these reasons the rpresence of chlorite,illite and kaolinite in the sediments and lignite is due not to diagenetic reactions but to weathering of the flysch and metamorphic rocks at the edges of the Megalopolis Basin and transport of the weathering products(illite,chlorite,kaolinite)into the basin of deposition.The diagenetic minerals of the Marathousa sequence include pyrite,gypsum,dolomite and aragonite.     

Studies of distribution, release and environmental influences of Fushun oil shale and its self-combustion

Three dumping sites have been formed at the northern region of Fushun City, Liaoning Province, for a large number of gangues including much oil shale that had been piled onto ground as gangue during long-term coal exploitation at West Fushun Open-pit Mine. Under appropriate conditions, self-combustion occurs after long-term exposure of oil shale and consequently such phenomena could be found almost everywhere at the three dumping sites. Much polycyclic aromatic hydrocarbons （PAHs） must be generated through oil shale self-combustion, a kind of incomplete combustion. In this paper, in order to make clear the PAHs distribution in oil shale and its self-combustion and their potential effects on surrounding environment, coal, low-grade oil shale, high-grade oil shale, burning oil shale, burnt oil shale and shaly soil collected from West Fushun Open-Pit Mine and West Dumping Site were analyzed quantitatively in 16 US EPA priority PAHs for the first time. Results showed that 16 PAHs in all samples were less than those in some bitumites and carbonaceous coals and were as much as those in lignites and anthracites from some Chinese mining areas. Coal and low-grade oil shale were abundant in lower molecular-weighted PAHs in contrast to high-grade oil shale with rich higher molecular-weighted PAHs. They had more benzo[a] pyrene than the highest background value in soils in Liaoning Province. So PAHs in these crude oil shales could cause potential effects on environment. There were at least 5121.40 p.g/kg PAils generated and at least 3976.70 μg/kg PAHs released into environment in the period from combustion beginning to sampling on the basis of calculation. Furthermore, the concentrations of 3-4 ring PAHs among them were very high. Therefore it could be said that oil shale self-combustion aggravated the environmental impacts of PAHs in oil shale. The low concentrations of PAHs in shaly soil showed that much PAHs had been released through recultivation and biodegradation.     

Nature and timing of magma interactions before,during, and after the caldera-forming eruption of Volcán Ceboruco,Mexico

Volcán Ceboruco, Mexico, erupted ~1,000 years ago, producing the Jala pumice and forming a ~4-km-wide caldera. During that eruption, 2.8 to 3.5 km³ of rhyodacite (~70 wt% SiO₂) magma and 0.2 to 0.5 km³ of mixed dacite (~67 wt% SiO₂) magma were tapped and deposited as the Jala pumice. Subsequently, the caldera was partially filled by extrusion of the Dos Equis dome, a low-silica (~64 wt% SiO₂) dacite dome with a volume of ~1.3 km³. Petrographic evidence indicates that the Jala dacite and Dos Equis dacite originated largely through the mixing of three end-member magmas: (1) rhyodacite magma, (2) dacite magma, and (3) mafic magma. Linear least-squares modeling and detailed modal analysis indicate that the Jala dacite is predominantly a bimodal mixture of rhyodacite and dacite with a small additional mafic component, whereas the Dos Equis dacite is composed of mostly dacite mixed with subordinate amounts of rhyodacite and mafic magma. According to Fe–Ti oxide geothermometry, before the caldera-forming eruption the rhyodacite last equilibrated at ~865 °C, whereas the dacite was originally at ~890 °C but was heated to ~960 °C by intrusion of mafic magma as hot as ~1,030 °C. Zoning profiles in plagioclase and/or magnetite phenocrysts indicate that mixing between mafic and dacite magma occurred ~34–47 days prior to eruption, whereas subsequent mixing between rhyodacite and dacite magmas occurred only 1–4 days prior to eruption. Following the caldera-forming eruption, continued inputs of mafic magma led to effusion of the Dos Equis dome dacite. In this case, timing between mixing and eruption is estimated at ~93–185 days based on the thickness of plagioclase overgrowth rims.Editorial responsibility: T.L. Grove     

Interactions of Copper, Evaporite, and Organic Matter and Genesis of Sandstone-Hosted Copper Deposits in the Chuxiong Basin, Yunnan Province

Studies on organic geochemistry indicate that the origin, type and maturity of organic matter are different among coal-bearing, copper-bearing and evaporite formations in the Mesozoic continental Chuxiong Basin, Yunnan, China. A mechanism has been proposed that (1) during the diagenetic mineralization stage the short-chain organic acids dervied from kerogen played an important role in remobilizing copper from source beds, while oils acted as important carrier of copper, and that (2) during the transformation or remolding mineralization stage, meteoric water leached the evaporite layers and formed downward-percolating oxidizing SO42-rich fluids; meanwhile, the copper-bearing fluids migrating upwards along growth faults from the basement was contaminated by the coal-bearing series on the way and formed reducing organic-rich fluids; oxidation-reduction occurred and sulfides formed when the two kinds of fluids met within sandstones.     

Assessment and characterization of the basement aquifer at Idu–Karmo,area of FCT-Abuja,Nigeria, for drinking and irrigation

Idu–Karmo of the federal capital territory, Abuja, is located within the weathered basement aquifers of Northern Nigeria. Fifteen groundwater samples obtained were analysed for their major ionic components. The physical properties show that the water is slightly acidic to neutral (6.0–7.0) and has moderate to very high values of electrical conductivity (155–2230 µS/cm).The dominant hydrochemical facies of groundwater is the Ca–Cl₂ groundwater type. Irrigation parameters measured include: SAR which ranges from 0.12 to 1.06; TH which ranges from 0.8 to 196; KR ranges from 0.03 to 0.42; PI which ranges from 46 to 199; and RSC ranges from ??131.90 to 3.43. These parameters (SAR, total hardness, Kelly’s ratio, permeability index and residual sodium carbonate) show that the water is suitable for agricultural purpose except for the magnesium ratio which has a high unsuitability for irrigation, probably due to the presence of ferro-magnesian minerals contained in the calc-alkaline basement rocks of the Idu–Karmo area. The results of the geochemical survey reveal major ionic components are in the order Cl^??>?HCO₃^??>?NO₃^??>?SO₄^2? and Mg²⁺?>?Ca²⁺?>?Na⁺?>?K⁺. Comparison with WHO and APHA standards shows that all the ionic concentrations satisfy all permissible limits for drinking purpose except for elevated concentrations of nitrate which probably may have arisen from poor handling of domestic wastes, leakages from nearby septic tanks/soak-away and the excessive use of fertilisers. Qualitatively, treatment is required especially on the nitrate-contaminated areas to make the water fit for drinking and irrigation.