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.     

南海北部甲烷渗漏的沉积地球化学指标(Sr/Ca和Mg/Ca)识别

自生碳酸盐矿物是揭示甲烷渗漏过程及其周期性变化的重要指标。为了方便、快速地识别出自生碳酸盐矿物,在探讨了前人建立的端元组分模型(文石、高镁方解石、生物成因方解石和碎屑)在我国南海北部适用性的基础上,利用沉积物全样中Sr/Ca和Mg/Ca值计算了南海北部神狐海域两支沉积物柱状样中自生碳酸盐矿物的质量分数,计算结果表明,在不同沉积深度均有含量不等的自生碳酸盐矿物。这一结果被X射线衍射结果和沉积物中存在晶形完好的自生高镁方解石和文石矿物所验证,表明利用前人建立的端元组分模型计算的结果具有可靠性。自生碳酸盐矿物的出现显示该海域深受甲烷渗漏作用影响。利用地球化学指标(Sr/Ca和Mg/Ca)获得的自生碳酸盐矿物含量垂向变化显示该区域甲烷渗漏具有强弱交替的周期变化。运用端元组分模型来获取沉积物柱状样中自生碳酸盐矿物的高分辨率剖面,从而识别甲烷渗漏信息非常方便,在大范围寻找甲烷渗漏和天然气水合物方面具有较大潜力。     

Paired Measurements of Foraminiferal δ~ (18) O and Mg/Ca Ratios of Indian Monsoons Reconstructed from Holocene to Last Glacial Record

The effect of seasonally reversing monsoons in the northern Indian Ocean is to impart significant changes in surface salinity(SS).Here,we report SS changes during the last 32 kyr in the Lakshadweep Sea(southeastern Arabian Sea)estimated from paired measurements of δ~(18)O and sea surface temperature(SST)using Globigerinoides sacculifer,an upper mixed layer dwelling foraminifera.The heaviest δ~(18)O_(G.sacculifer)(-0.07±0.08‰)is recorded between 23 and 15 ka,which could be defined as the last glacial maxi...     

Seasonal changes of fulvic acid,Ca and Mg concentrations of water samples collected above and in the Béke Cave of the Aggtelek karst system (Hungary)

Magnesium and Ca concentration ratios, fulvic acid content, total dissolved inorganic carbon (DIC) and pH were determined in seepage water and drip water samples collected during one seasonal cycle between June 2000 and May 2001 above and in the Béke Cave of Aggtelek (Hungary). Seepage water samples were collected at 0.5 and 7 m below ground level from an observation point situated above the cave. Drip water was collected 40 m underground from a group of stalactites. The fulvic acid concentrations were determined by fluorescence spectrometry after pre-concentration on a XAD-8 chromatographic column. Calcium and Mg concentrations were measured by inductively coupled plasma atomic-emission spectrometry. DIC was determined with a CO₂ – selective electrode. DIC values increased and the fulvic acid concentrations and Mg and Ca concentration ratios, generally, decreased with depth. The highest flux of fulvic acid was observed in spring. The fulvic acid flux increased by a factor of 2.6–3.6 and 1.4 for groundwater and drip water, respectively, compared with those registered in the winter samples. The variations in the Ca, Mg and fulvic acid concentrations of the seepage and drip water samples relate to the variable drip rate. The results revealed that there is a strong correlation between the daily average surface temperature, daily amount of precipitation and drip water rate registered in the cave.     

Presentation of the French Society of Mineralogy and Crystallography(SFMC)

The French Society of Mineralogy and Crystallography is honoured to be invited to give a short presentation of its activity to the Chinese Society for Mineralogy,Petrology and Geochemistry.BRIEF HISTORY AND SOME FRENCH FOUNDERS OF MINERALOGY     

Conjunctive K–Ca and Rb–Sr dating of glauconies

The glaucony series (of which glauconitic mica is the K-rich end member) is one of the few widely occurring minerals in the sedimentary record. So their isotopic ages determined mainly by the K–Ar method represent a major database for the geologic time scale. Many K–Ar ages were, however, found to be too young and often also discordant with available corresponding Rb–Sr ages. This discrepancy may reflect the disparate responses of the chemically contrasting daughter elements, Ar and Sr to postdepositional processes, and renders either age equivocal. A potentially promising approach to evaluate the intrinsic potential of glauconies and other K-rich minerals for direct and reliable dating of sediments is the conjunctive use of the chemically very similar K–Ca and Rb–Sr systems. The relationship between K–Ca and Rb–Sr ages may show a coherence or regularity indicative of a geologically meaningful age like in the case of the well known chemically identical dual U–Pb decay systems. As a crucial first step, this report presents the first successful precise K–Ca dating in conjunction with Rb–Sr dating of an Ordovician glauconite using the same sample aliquot, chemical procedure and mass spectrometer.     

Ferromanganese nodules of freshwater reservoirs of Ol’khon Island (Baikal) and the Kulunda Plain (West Siberia)

Morphology and mineralogical and geochemical compositions of freshwater ferromanganese nodules of Ol’khon Island (Sasa Formation) and Kulunda Plain (Lake Porozhnee) were studied. The study has shown rhythmic structures of the nodules, formed by macro- and microlayers with mineralized microflora. The layers are composed of either crystalline Mn mineral phases and finely dispersed Fe phases (Lake Porozhnee) or, on the contrary, crystalline goethite and X-ray amorphous Mn phases (Ol’khon Island). Separation of Mn and Fe mineral phases in the nodules proceeded during their formation and diagenesis. The freshwater nodules show both high (Lake Porozhnee) and low (Ol’khon Island) Mn/Fe ratios. The predominance of Fe phase in the Ol’khon nodules accounts for their high contents of REE, including Ce. The Porozhnee nodules grew, most likely, more rapidly, which is reflected in their low REE contents and Ce anomaly. The examined chemical and mineral compositions, textures, and structures of the nodules testify to the low-temperature hydrothermal source of their ore substance.     

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.     

Reconstructing seawater δO from paired coral δO and Sr/Ca ratios: Methods, error analysis and problems, with examples from Tahiti (French Polynesia) and Timor (Indonesia)

We compare several statistical routines that may be used to calculate δ¹⁸O_sw and SSS from paired coral Sr/Ca and δ¹⁸O measurements. Typically, the δ¹⁸O_coral-SST relationship is estimated by linear regression of coral δ¹⁸O vs. SST. If this method is applied, evidence should be given that at a particular site SST and SSS do not co-vary. In the tropical oceans, SST and δ¹⁸O_sw (SSS) often co-vary, and this will bias the estimate of the regression slope of δ¹⁸O_coral-SST. Using a stochastic model, we show that covariance leads to a bias in the coefficients of the univariate regression equations. As the slope of the δ¹⁸O_coral-SST relationship has known, we propose to insert this value for γ₁ in the regression models. This requires that the constants of the regression equations are removed. To omit the constants, we propose to center the regression equations (i.e., to remove the mean values from the variables). The statistical error propagation is calculated to assess our ability to resolve past variations in δ¹⁸O_sw (SSS). At Tahiti, we find that the combined analytical uncertainties of coral δ¹⁸O and Sr/Ca equal the amplitude of the seasonal cycle of δ¹⁸O_sw (SSS). Therefore, we cannot resolve the seasonal cycle of SSS at Tahiti. At Timor, the error of reconstructed δ¹⁸O_sw (SSS) is lower than the magnitude of seasonal variations of δ¹⁸O_sw (SSS), and the seasonal cycle of δ¹⁸O_sw (SSS) can be resolved.     

~(40)Ar/~(39)Ar Dating of Deformation Events and Reconstruction of Exhumation of Ultrahigh-Pressure Metamorphic Rocks in Donghai, East China

Recent investigations reveal that the ultrahigh-pressure metamorphic (UHPM) rocks in the Donghai region of East China underwent ductile and transitional ductile-brittle structural events during their exhumation. The earlier ductile deformation took place under the condition of amphibolite facies and the later transitional ductile-brittle deformation under the condition of greenschist facies. The hanging walls moved southeastward during both of these two events. The 40Ar/39Ar dating of muscovites from muscovite-plagioclase schists in the Haizhou phosphorous mine, which are structurally overlain by UHPM rocks, yields a plateau age of 218.0±2.9 Ma and isochron age of 219.8Ma, indicating that the earlier event of the ampibolite-facies deformation probably took place about 220 Ma ago. The 40Ar/39Ar dating of oriented amphiboles parallel to the movement direction of the hanging wall on a decollement plane yields a plateau age of 213.1±0.3 Ma and isochron age of 213.4±4.1 Ma, probably representing the age o     

Dinosaur ichnofauna of the Upper Jurassic/Lower Cretaceous of the Paraná Basin (Brazil and Uruguay)

Upper Jurassic and Lower Cretaceous sedimentary layers are represented in the Brazilian Paraná Basin by the fluvio–aeolian Guará Formation and the Botucatu Formation palaeoerg, respectively, overlapped by the volcanic Serra Geral Formation. In Uruguay, the corresponding sedimentary units are named Batoví and Rivera Members (both from the Tacuarembó Formation), and the lava flows constitute the Arapey Formation (also in Paraná Basin). Despite the lack of body fossils in the mentioned Brazilian formations, Guará/Batoví dinosaur fauna is composed of theropod, ornithopod and wide–gauge sauropod tracks and isolated footprints, as well as theropod teeth. In turn, the Botucatu/Rivera dinosaur fauna is represented by theropod and ornithopod ichnofossils smaller than those from the underlying units. The analysis of these dinosaur ichnological records and comparisons with other global Mesozoic ichnofauna indicates that there is a size reduction in dinosaur fauna in the more arid Botucatu/Rivera environment, which is dominated by aeolian dunes. The absence of sauropod trackways in the Botucatu Sandstone fits with the increasingly arid conditions because it is difficult for heavy animals to walk on sandy dunes, as well as to obtain the required amount of food resources. This comparison between the Upper Jurassic and Lower Cretaceous dinosaur fauna in south Brazil and Uruguay demonstrates the influence of aridization on the size of animals occupying each habitat.     

Hydrogen Isotopes of Glassy and Phyllosilicate Spherules in Al Rais (CR) and Orgueil (CI) Chondrites

The hydroxyl in phyllosilicate minerals is the most common occurrence of water in primitive meteorites. Direct hydrogen isotopic analysis of this water component using an ion microprobe has been made in some glassy or phyllosilicate spherules from the Al Rais (CR) and Orgueil (CI) chondrites. The spherules from Al Rais show large deuterium excesses (δD = +200 -+800‰) relative to terrestrial standards, whereas deuterium-enrichments in the spherules from Orgueil are much smaller (δD = +40 - +130‰). The phyllosilicate spherules are products of     

TEM evidence of perovskite–brownmillerite coexistence in the Ca(AlxFe1−x)O2.5 system with minor amounts of titanium and silicon

Observations by transmission electron microscopy (TEM) of the submicrometer phases present in calcium aluminate cements have shown that Ca-Al-Fe oxides coexist in two forms with brownmillerite (b) and perovskite (p) structures, respectively. Homogeneous single crystals of both brownmillerite and perovskite have been observed but exsolved lamellae also occur on the scale of tens of nanometers. Perovskite lamellae in brownmillerite exhibit coherent interfaces with an almost perfect [1 0 1]_b = {1 0 0}_p topotactic relationship. Energy-dispersive X-ray spectroscopy (EDXS) measurements show that perovskite lamellae are enriched in Ti and Si relative to the brownmillerite lamellae. The perovskite phase may accommodate up to 0.17 Si atoms per formula unit, but the exsolution process seems mainly to concern the Ti content. It is estimated that the solvus width ranges between concentrations of 0.06 < Ti < 0.13 atoms per formula unit. O K and Fe L _2,3 edges collected by electron energy loss spectrometry (EELS) confirm that both phases are mainly composed of Fe³⁺, requiring that the perovskite is highly oxygen-deficient. Al K and Si K EELS spectra have features comparable with those of fourfold-co-ordinated Al and Si sites, suggesting that they are probably located close to oxygen-vacant sites. Received: 23 June 1999 / Accepted: 18 February 2000     

Experimental constraints on the relative stabilities of the two systems monazite-(Ce) – allanite-(Ce) – fluorapatite and xenotime-(Y) – (Y,HREE)-rich epidote – (Y,HREE)-rich fluorapatite,in high Ca and Na-Ca environments under P-T conditions of 200–1000 MPa and 450–750 °C

Mineralogy and Petrology - The relative stabilities of phases within the two systems monazite-(Ce) – fluorapatite – allanite-(Ce) and xenotime-(Y) – (Y,HREE)-rich fluorapatite...     

Complexity and Self-Organized Criticality of Solid Earth System(Ⅱ)

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Experimental and theoretical study of the vibrational properties of diaspore (α-AlOOH)

Vibrational properties of diaspore, α-AlOOH, have been re-investigated using room-temperature single-crystal Raman spectroscopy and low-temperature powder infrared (IR) transmission spectroscopy. First-principles harmonic calculations based on density functional theory provide a convincing assignment of the major Raman peaks and infrared absorption bands. The large width of the Raman band related to OH stretching modes is ascribed to mode–mode anharmonic coupling due to medium-strength H-bonding. Additional broadening in the powder IR spectrum arises from depolarization effects in powder particles. The temperature dependence of the IR spectrum provides a further insight into the anharmonic properties of diaspore. Based on their frequency and temperature behavior, narrow absorption features at ~2,000 cm⁻¹ and anti-resonance at ~2,966 cm⁻¹ in the IR spectrum are interpreted as overtones of fundamental bending bands.     

Complexity and Self-Organized Criticality of Solid Earth System(Ⅰ)

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Migration and bio-absorption of ~(125)I in soil

The biogeochemical migration of iodine in soil and its effect factors were studied by the isotope tracer (125I) and experiments of leaching and absorption by Chinese cabbage to iodine under simulated condition. The results show that the quantities of tran…     

Magnetic and Gravity Investigations of Lisan Peninsula-Dead Sea(Jordan)

The Lisan Peninsula is located within the Dead Sea basin which represents the plate boundary between African and Arabian plates. This basin constitutes a good example of a pull-apart basin because of its large dimensions, its structural simplicity and its active subsidence . The gravity data reveal that the Dead Sea basin can be divided into segments, each of them about 30 km long in N-S direction , where the Lisan Peninsula represents the deepest one (9 km thick Pleistocene sediments ), overlying about 6 km thick Mesozoic sediments . In addition , 20 km of extension was predicted along the Dead Sea basin, which indicates that the Dead Sea basin should be about 3.3 Ma in age . Furthermore, the Precambrian basement under the Lisan area is characterized by high susceptibility contrast that is related to continuous tectonic activity in the region.     

Application of the geomechanical facies approach and comparison of exploration and evaluation methods used at Soultz-sous-Forêts (France) and Spa Urach (Germany) geothermal sites

Earth-reservoirs are increasingly exploited today with the extraction of resources, such as heat and hydrocarbons, and the large-scale emplacement of waste, such as CO₂ sequestration. The characterization, site investigation, predictive modeling and long-term monitoring are dependent on the processes being investigated and modeled. In most cases complex coupled processes have to be addressed in a geologically complex rock mass system. In this paper we present a conceptual holistic framework known as geomechanical facies linking all the scales of investigation, characterization and reservoir development methods. We demonstrate this concept on the work undertaken during the design and development of the enhanced geothermal systems (EGS) systems at the forefront of European Hot-Dry-Rock (HDR) technology, Soultz-sous-Forêts (France) and Spa Urach (Germany). Soultz-sous-Forêts is situated within granitic rocks and an active tectonic graben system in the central part of the Rhine Graben. It presents conditions of lithology, temperature, stress, hydraulics and geochemistry that are very different from those at Spa Urach, located in a very dense gneiss formation in the South German crystalline complex. Spa Urach exhibits more elastic behavior and is set tectonically within an almost inactive strike-slip stress field described in more detail in Sects. “Drill core analysis” and “Hydraulic stimulation at Spa Urach”. This paper compares the exploration and field development methods used at these two sites against the back drop of the geomechanical facies concept. Issues addressed include the key parameters for flow and heat transport properties, coupled hydro-mechanical process identification, the success of the HDR reservoir as a heat exchanger and exploration techniques applicable to the different facies. Identification of the key geomechanical facies gives an indication as to which technologies will prove more efficient in the application of HDR technology. The results of this study will hopefully help in developing heat recovery schemes for the long-term economical operation of future HDR plants and EGS as well as assist in the understanding of engineered geosystems.