The TiO2–K2O–P2O5 diagram: A method of discriminating between oceanic and non-oceanic basalts

The TiO₂–K₂O–P₂O₅ ternary diagram is proposed as a method of discriminating between oceanic and non-oceanic (continental) basalts. This diagram is effective for non-alkaline “primitive” basalts: fractionated rocks cannot be adequately discriminated. Suitable analyses are those which have total alkalies ≤ 20% in an (Fe₂O₃ + FeO)–MgO–(Na₂O + K₂O) diagram. The proposed dividing line separates 93% of 222 ocean-floor and ocean-ridge basalts into the oceanic field and > 80% of continental basalt analyses into the non-oceanic field. Two exceptions are the Tertiary basalts of Greenland and the Deccan Traps which have oceanic affinities. “Continental” suites displaying an oceanic affinity in the TiO₂–K₂O–P₂O₅ diagram may be a result of abortive attempts to generate new sea floor. Preliminary results for dike swarms and Archean basalts suggest preponderant oceanic affinities. Alteration and metamorphism of oceanic basalts generally occasion enrichment of K₂O relative to TiO₂ and P₂O₅.     

Melting relationships in CaO-CO2 and MgO-CO2 to 36 kilobars with comments on CO2 in the mantle

The melting curves of CaCO₃ and MgCO₃ have been extended to pressures of 36 kb by experiments in piston-cylinder apparatus. At 30 kb, the melting temperatures of calcite and magnesite are 1610°C and 1585°C, respectively. New data for the magnesite dissociation reaction permit the location of an invariant point for the assemblage magnesite + periclase + liquid + vapor near 26 kb-1550°C. New data are also presented for the calcite-aragonite transition at 800°C, 950°C and 1100°C. At pressures above 36–50 kb, calcite and magnesite melt at temperatures lower than the solidus of dry mantle peridotite. Natural and experimental evidence suggests that carbon dioxide in the Earth's mantle could be present in a variety of forms: (a) a free vapor phase, (b) vapor dissolved in silicate magma, (c) crystalline carbonate, (d) carbonatite liquid, (e) carbon-bearing silicate analogs, or (f) carbonato-silicates (such as scapolite, spurrite, tilleyite, and related compounds).     

High-pressure phases of Co2GeO4, Ni2GeO4, Mn2GeO4 and MnGeO3: implications for the germanate-silicate modeling scheme and the Earth's mantle

In a diamond-anvil press coupled with YAG laser heating, the spinels of Co₂GeO₄ and Ni₂GeO₄ have been found to disproportionate into their isochemical oxide mixtures at about 250 kbar and 1400–1800°C in the same manner as their silicate analogues. At about the same P-T conditions MnGeO₃ transforms to the orthorhombic perovskite structure (space group Pbnm); the lattice parameters at room temperature and 1 bar are a₀ = 5.084 ± 0.002, b₀ = 5.214 ± 0.002, and c₀ = 7.323 ± 0.003Å with Z = 4 for the perovskite phase. The zero-pressure volume change associated with the ilmenite-perovskite phase transition in MnGeO₃ is ?6.6%. Mn₂GeO₄ disproportionates into a mixture of the perovskite phase of MnGeO₃ plus the rocksalt phase of MnO at P = 250kbar and T = 1400–1800°C. The concept of utilizing germanates as high-pressure models for silicates is valid in general. The results of this study support the previous conclusion that the lower mantle comprises predominantly the orthorhombic perovskite phase of ferromagnesian silicate.     

MEIC-global-CO2: A new global CO2 emission inventory with highly-resolved source category and sub-country information

CO₂ emission inventory provides fundamental data for climate research and emission mitigation. Currently, most global CO₂ emission inventories were developed with energy statistics from International Energy Agency(IEA) and were available at country level with limited source categories. Here, as the first step toward a high-resolution and dynamic updated global CO₂ emission database, we developed a data-driven approach to construct seamless and highly-resolved ene...     

Stability of forsterite + CO2 and its bearing on the role of CO2 in the mantle

An experimental determination of the reaction MgCO₃ + MgSiO₃ = Mg₂SiO₄ + CO₂ between 20 and 40 kbars and in the range 1000–1500°C yields an average pressure effect on the equilibrium of 44 bars/°C. This result shows that the assemblage forsterite and carbon dioxide is not stable under most pressure and temperature conditions expected in the upper mantle. Hypotheses requiring the presence of free CO₂ in the low-velocity zone, CO₂ as a drive mechanism for kimberlite emplacement, or action of a free CO₂ phase in ultramafic rocks may need considerable revision.     

Phase relations of titan-phlogopite,K2Mg4TiAl2Si6O20(OH)4: a refractory phase in the upper mantle?

Experimental data on the stability of titan-phlogopite [K₂Mg₄TiAl₂Si₆O₂₀(OH)₄] are presented which show it to be stable to substantially higher temperatures than normal phlogopite [K₂Mg₆Al₂Si₆O₂₀(OH)₄]. A qualitative model to explain the role of titan-phlogopite during magma generation is put forward. Breakdown of titan-phlogopite during melting at depth (> 150km) on subducted lithospheric slabs is believed responsible for the concomitant increase of K and Ti observed in magmas erupted during orogenic volcanism. At lower pressures (up to about 10 kbar) beneath mid-oceanic ridges, titan-phlogopite is predicted to behave as a refractory phase during partial melting in the mantle, especially if H₂O-excess conditions pertain, although at higher pressures in this environment it would almost certainly behave as a low-melting component.     

Early J2 basalts in SE China: Incipience of large-scale late Mesozoic magmatism

Magmatism in SE China was dormant during 204–180 Ma, but was reactivated in 180–170 Ma (early J₂), and then became more and more intensive towards the end of early Cretaceous. The small-scale early J₂ magmatism is the incipience to long-term and large-scale magmatism in this region. A near east-west (EW) trend volcanic belt was distributed across south Hunan, south Jiangxi and southwest Fujian was formed during early J₂ time. Along this belt from the inland toward the coast, the lithology of basalts changes from alkali into tholeiite, and the amount of erupted volcanic rocks and the proportions of rhyolites coexisting with the basalts increase. On the basis of geochemical characteristics of these basalts, we infer that the melting degree of source rocks and the extent of fractional crystallization and crustal contamination all increased whereas the depth of mantle source decreased from the inland to the coast, which led to the variations of geological characteristics of the volcanic belt. In early J₂, the western spreading Pacific plate began to subduct underneath SE China continental block, reactivating near EW trend deep fault that was originally formed during the Indosinian event. The stress of the western spreading Pacific plate and the extent of asthenosphere upwelling increased from the inland to the coast, which is consistent with the generation and evolution of early J₂ basalts.     

Geochemistry of basalts from central and southern New Hebrides arc: implication for their source rock composition

The basaltic rocks from the central and southern islands of the New Hebrides-Aneityum, Tanna, Erromango, Efate, Emae, Tongoa and Epi, have geochemical features typical of island arc volcanics. They are enriched in LILE and depleted in Zr, Hf, Nb and Ta compared to N-type MORB. The rocks were derived from a similar upper mantle source as N-type MORB but with a higher degree of partial melting. In addition their source was enriched in LILE (K, Rb, Sr, Ba and LREE) probably by migrating hydrous fluids released during the dehydration of the subducted oceanic slab. The basalts from Futuna island which is located farther from the trench, display characteristics typical of calc-alkaline rocks. The Futuna basalts were generated from a different LILE-enriched upper mantle source. It seems that this upper mantle source was modified by interaction with partial melts from the subducted oceanic lithosphere.     

Hot-spots,mantle plumes and a model for the origin of ultramafic xenoliths in alkali basalts

The Wilson-Morgan hypothesis of hot-spots, characterized by high heat flow, positive gravity anomaly and alkalic volcanism, assumes that such hot-spots are surface expressions of mantle plumes rising by thermal convection. Possible evidence of this mantle upwelling is shown here from textural, structural and chemical aspects of ultramafic xenoliths in alkalic basalts. The xenolith-bearing basalts are constanly associated with Wilson-Morgan hot-spots in the ocean basins and with their continental counterparts in the rift valleys which show extensional tectonics. Most of the xenoliths are considered to be accidental fragments of the lithosphere in the host basalts. One remarkable aspect of xenoliths from all parts of the world is their ubiquitous tectonite fabric. The microstructures of these xenoliths are due to plastic deformation. Some of the xenoliths from Baja California show characteristic deformational features which are also found in the marginal parts of diapirically intruded high-temperature peridotite massifs. A model is proposed for the origin of xenoliths in alkalic basalts by mantle upwelling in which the plastic deformation of the xenoliths reflects this dynamic uprise.     

H2OCO2 fluids supplied in alpine-type mantle peridotites: electron petrology of relic fluid inclusions in olivines

Fluids supplied in alpine-type mantle peridotites and trapped as fluid inclusions in olivines have been fixed by low-temperature reactions, and theirCO₂/H₂O ratios can be deduced from the minerals in the inclusions. Relic fluid inclusions were commonly observed by the optical microscope in olivines from almost all examined solid intrusive ultramafic complexes (Papua, Oman, Troodos and eleven alpine-type complexes of Japan). Such complexes were emplaced into the crust in a solid state. Electron microscopic studies of olivines from three complexes, Higashiakaishi, Horoman and Iwanai-dake, showed that relic fluid inclusions in these olivines have distinctive mineral parageneses: serpentine + magnesite + talc, serpentine + magnesite + brucite, and serpentine + brucite, respectively, depending on theCO₂/(H₂O+CO₂) ratio of the trapped fluid.It is deduced that the fluids had been supplied to peridotites, at least partly, but almost wholly in some case, when the peridotites were still hot, probably at the upper mantle for the following reasons: (1) the curved surfaces along which the inclusions are distributed are cut by post-emplacement serpentine veins; (2) for the Higashiakaishi dunite, the relic fluid inclusions are exclusively found in porphyroclast olivines and are totally absent in matrix olivines recrystallized during the Sanbagawa metamorphism.Recent models on the derivation of ophiolitic or some alpine-type peridotites favor the island-arc or fore-arc settings. Dehydration of the descending oceanic slab may supply H₂OCO₂ vapor to the overlying mantle wedge. Fluid inclusions trapped in such mantle wedge may abound in H₂O component. H₂O-bearing fluid inclusions may, therefore, be important H₂O containers in the upper mantle, especially near the edge of the mantle wedge above downgoing oceanic slabs.     

Origin and source of CO2 in natural gas from the eastern Sichuan Basin

The CO2 contents of natural gas from the eastern Sichuan Basin were mainly less than 2%,and they were generally large when the H2S contents were over 5%.The natural gas in the eastern Sichuan Basin showed high δ13C1 values uncorrelated with H2S contents,and the oil-associated gas generally displayed carbon isotopic reversal between methane and ethane,whereas the coal-derived gas samples displayed positive series.The δ13C values of CO2 in the natural gas could be divided into two types,one with low values(-24‰--12‰)and the other with high values(-8‰-4‰).The natural gas had low R/Ra values and broad CO2/3He values distinct from the mantle-derived gas,and the CO2 was typical of crustal origin.Natural gas with high δ13CCO2 values is distributed in the north region of the eastern Sichuan Basin,and CO2 in H2S-poor and H2S-free reservoirs was mainly derived from the thermal decomposition of carbonate rocks under Permian magmatism and high heat flow,whereas CO2 in the gas reservoirs with high TSR extent was derived mainly from the dedolomitization of carbonate reservoirs under acidic formation water,and the CO2 of TSR origin generally entered into the secondary calcite.The CO2 in natural gas in the south-central region of the eastern Sichuan Basin,which had been rarely affected by the Emeishan mantle plume,displayed low δ13C values and was of organic origin.Though the natural gas in Wolonghe gas field had experienced TSR,the low reaction extent and weak acidity of formation water could hardly have resulted in the dedolomitization,and therefore CO2 in the natural gas was mainly of TSR origin with low δ13C values.     

Restoration of new volcanic gas analyses from basalts of the afar region: Further evidence of CO2 -degassing trends

The restored compositions for approximately 70 new analyses reported recently for Erta'Alelava lake (LeGuern et al., 1979) are in good agreement with restored compositions (Gerlach, 1980a) based on previously published data. The results confirm earlier indications that gas collections taken at different times from the lava lake are related principally by variations in CO₂ content. Restored compositions for gas samples collected in the final stages of a November 1978 Ardoukoba eruption along the Asal Rift spreading axis resemble the Erta'Ale gases except for a much lower CO₂ content. The Ardoukoba gases fall close to a CO₂-decreasing control line for gases with initial compositions similar to the 1971–1973 Erta'Ale gases. These results suggest that gases released from basaltic lava along zones of crustal spreading follow compositional trends dominated by changes in CO₂ content.     

High-temperature elasticity of the fluorite-structure compounds CaF2, SrF2 and BaF2

The elastic moduli of single-crystal CaF₂, SrF₂ and BaF₂ have been determined by the ultrasonic pulse superposition technique as a function of temperature from T = 298 to T = 650°K. These new data are consistent with other data obtained by ultrasonic pulse techniques in the region of room temperature and are superior to previous high-temperature data from resonance experiments. The elastic moduli (c) are represented by quadratic functions in T over the experimental temperature range with the curvature in the same sense for all the moduli. Evaluation of the temperature derivatives of the elastic moduli at constant volume indicates that the dominant temperature effect is extrinsic for (?K_S/?T)_P and intrinsic for (?μ/?T)_P, where K_S and μ are the isotropic bulk and shear moduli, respectively. For the series CaF₂SrF₂BaF₂, |(?c/?T)_p| decreases with increasing molar volume for all moduli; however there are no theoretical or empirical grounds on which to derive a simple relationship between (?c/?T)_P and crystallographic parameters.     

Geochemistry of basalts from the Dumisseau Formation, southern Haiti: implications for the origin of the Caribbean Sea crust

Basalt and diabase from the Cretaceous Dumisseau Formation, southern Haiti have Mg-numbers of 43–63, TiO₂ contents of 1.6–3.9% and La abundances of 3.6–15.3 ppm.La/Ta ratios average 10, and indicate that the basalts are oceanic in character, distinct from the arc associations forming the northern part of Haiti. Oldest lavas have low TiO₂ (1.6%) and are LREE-depleted, similar to N-MORBs, whereas overlying lavas have higher TiO₂ (2–3.9%) and are LREE-enriched, similar to E-MORBs or hotspot basalts.⁸⁷Sr⁸⁶Sr ratios vary from 0.70280 to 0.70316,¹⁴³Nd¹⁴⁴Nd from 0.512929 to 0.513121, and²⁰⁶Pb²⁰⁴Pb from 19.00 to 19.27. LREE-depleted lavas have high¹⁴³Nd¹⁴⁴Nd (0.51309–0.51310) typical of MORBs, whereas¹⁴³Nd¹⁴⁴Nd in the LREE-enriched lavas varies widely (0.512929–0.513121).Chemical features of the Dumisseau basalts are equivalent to those of Caribbean seafloor basalts recovered on DSDP Leg 15, and support the contention that the Dumisseau is an uplifted section of Caribbean Sea crust. Oldest lavas are analogous to MORB-like basalts cored at Leg 15 Sites 146, 150, 152 and 153, and the overlying lavas are analogous to incompatible-element-enriched basalts cored at Site 151 on the Beata Ridge. Isotopic compositions of the Dumisseau basalts overlap with those of the eastern Pacific Galapagos and Easter Island hotspots. However, the presence of N-MORB basalts in the lower part of the Dumisseau and at the majority of Leg 15 Sites indicates that the anomalously thick Caribbean crust probably did not originate as a hotspot-related basaltic plateau, but may have been generated by on-ridge or near-ridge hotspot magmatism.     

Viscosity and conductivity of the lower mantle; an experimental study on a MgSiO3 perovskite analogue,KZnF3

We have investigated the high-temperature rheological and electrical behaviour of single-crystal KZnF₃ fluoperovskite, an analogue of the MgSiO₃ perovskite in the lower mantle.The crystals flow by Newtonian dislocation creep (Harper-Dorn creep), predominantly on {100} planes. Below the melting point, solid-electrolyte behaviour appears, accompanied by a weakening of the mechanical properties. Geophysical implications are examined: the lower mantle can convect by Newtonian dislocation creep and an asthenosphere may exist at the bottom of the mantle. Electromagnetic interactions between the core and solid-electrolyte lower mantle may also be important.     

CO2/CaCl2 solution interfacial tensions under CO2 geological storage conditions: Influence of cation valence on interfacial tension

The effectiveness of CO₂ storage in deep saline aquifers and hydrocarbon reservoirs is governed, among other factors, by the interfacial tension between the injected CO₂ and formation water (brine). Experimental data on CO₂/water and CO₂/NaCl solution have revealed that the interfacial tension depends on the pressure, temperature and water salinity. However, there is still a lack of data for other salts (such as MgCl₂ and CaCl₂) which are also present in aquifers and carbonate reservoirs.     

K/Rb and (Sr/Sr)0 ratios of dredged submarine basalts

K/Rb and (⁸⁷Sr/⁸⁶Sr)₀ ratios were measured for 14 submarine basalts dredged from seamounts in the Pacific Ocean. The K/Rb ranges from 200 to 700, which is significantly lower than that of oceanic ridge tholeiites. Petrographic examination and the low value of K/Rb indicate that seamount basalts are alkaline.     

MnO/TiO2/P2O5: a minor element discriminant for basaltic rocks of oceanic environments and its implications for petrogenesis

A ternary diagram using MnO, TiO₂, P₂O₅ can discriminate between five petrotectonic environments of basaltic rocks (45–54% SiO₂). Fields for mid-ocean ridge, island arc tholeiite, island arc calc-alkaline, ocean island tholeiite, and ocean island alkalic rocks were distinguished on the basis of 507 analyses from well-defined environments. Boninites plot within island arc fields. Continental tholeiites, such as the Columbia River basalts, are high in P₂O₅ relative to MnO and TiO₂, and overlap portions of all five oceanic fields.MnO is depleted relative to TiO₂ in mid-ocean ridge analyses and may be controlled by early fractionation of olivine and/or clinopyroxene under conditions of lowf_O2. In island arc rocks, MnO is enriched relative to TiO₂ due to early crystallization of titanomagnetite in a high-f_O2 environment. Primitive mid-ocean ridge and arc tholeiites have similar MnO/TiO₂/P₂O₅ ratios which indicate a grossly similar parent magma. Increasingly differentiated basaltic rocks are more easily classified by the diagram. High relative abundances of TiO₂ and P₂O₅ in ocean island rocks are consistent with their derivation from a separate source.Despite the purported high mobility of MnO, the MnO/TiO₂/P₂O₅ discriminant diagram may be applied to unspilitized and moderately spilitized zeolite to greenschist facies greenstones with good agreement between the environment determined by MnO/TiO₂/P₂O₅ and by other means such as trace elements, REE, or field relations.     

Melting of the silica isotypes SiO 2, BeF 2 and GeO 2 at elevated pressures

The melting curves of the structural analogues SiO ₂, BeF ₂ and GeO ₂ have been studied at pressures ?40 kbar in a piston-cylinder apparatus. The initial slopes dT_m/dP of the β-quartz-liquid boundaries for SiO ₂ and BeF ₂ are ～35° while the slope of the rutile-liquid boundary for GeO ₂ is approximately 32°C/kbar. These large values of dT/dP reflect the unusually low entropies of fusion for these compounds in which strong structural similarities exist between the crystalline phases and the melt. Implications for the extended phase diagram of silica are discussed and it is concluded that either: (1) a maximum exists on the coesite melting curve, or (2) estimates of the melting temperature of stishovite need to be revised upwards.