Low-degree partial melting trends recorded in upper mantle minerals

The study of glass inclusions inside mantle minerals provides direct information about the chemistry of naturally occurring mantle-derived melts and the fine-scale complexity of the melting process responsible for their genesis. Minerals in a spinel lherzolite nodule from Grande Comore island contain glass inclusions which, after homogenization by heating, exhibit a continuous suite of chemical compositions clearly distinct from that of the host basanitic lava. The compositions range from silicic, with nepheline–olivine normative, 64 wt% SiO₂ and 11 wt% alkali oxides, to almost basaltic, with quartz normative, 50 wt% SiO₂ and 1–2 wt% alkali oxides. Within a single mineral phase, olivine, the inferred primary melt composition varies from 54 to 64 wt% SiO₂ for MgO content ranging from 8 to 0.8 wt%. An experimental study of the glass and fluid inclusions indicates that trapped melts represent liquids that are in equilibrium with their host phases at moderate temperature and pressure (T≈1230°C and P≈1.0 Gpa for melts trapped in olivine). Quantitative modelling of the compositional trends defined in the suite shows that all of the glasses are part of a cogenetic set of melts formed by fractional melting of spinel lherzolite, with F varying between 0.2 and 5%. The initial highly silicic, alkali-rich melts preserved in Mg-rich olivine become richer in FeO, MgO, CaO and Cr₂O₃ and poorer in SiO₂, K₂O, Na₂O, Al₂O₃ and Cl with increasing melt fractions, evolving toward the basaltic melts found in clinopyroxene. These results confirm the connection between glass inclusions inside mantle minerals and partial mantle melts, and indicate that primary melts with SiO₂ >60 wt%, alkali oxides >11%, FeO <1 wt% and MgO <1 wt% are generated during incipient melting of spinel peridotite. The composition of the primary melts is inferred to be dependent on pressure, and to reflect both the speciation of dissolved CO₂ and the effect of alkali oxides on the silica activity coefficient in the melt. At pressures around 1 GPa, low-degree melts are characterized by alkali and silica-rich compositions, with a limited effect of dissolved CO₂ and a decreased silica activity coefficient caused by the presence of alkali oxides, whereas at higher pressures alkali oxides form complexes with carbonates and, consequently, alkali-rich silica-poor melts will be generated.     

Helium isotope geochemistry of some volcanic rocks from Saint Helena

³He/⁴He ratios have been measured for olivine and clinopyroxene phenocrysts in 7–15 m.y. old basaltic lavas from the island of St. Helena. Magmatic helium was effectively resolved from post-eruptive radiogenic helium by employing various extraction techniques, includingin vacuo crushing, and stepwise heating or fusion of the powders following crushing. The inherited³He/⁴He ratio at St. Helena is 4.3–5.9 R_A. Helium isotope disequilibrium is present within the phenocrysts, with lower³He/⁴He upon heating and fusion of the powders following crushing, due to radiogenic ingrowth or to -particle implantation from the surrounding(U + Th)-rich lavas.

A single crushing analysis for clinopyroxene in a basalt from Tubuaii gave³He/⁴He= 7.1 R_A.³He/⁴He ratios at St. Helena and Tubuaii (HIMU hotspots characterized by radiogenic Pb isotope signatures) are similar to³He/⁴He ratios previously measured at Tristan da Cunha and Gough Island (EM hotspots characterized by low²⁰⁶Pb/²⁰⁴Pb). Overall, the HeSrPb isotope systematics at these islands are consistent with a mantle origin as contiguous, heterogeneous materials, such as recycled crust and/or lithosphere.³He/⁴He ratios at HIMU hotspots are similar to mantle xenoliths which display nearly the entire range of Pb isotope compositions found at ocean islands, and are only slightly less than values found in mid-ocean ridge basalts (7–9 R_A). This suggests that the recycled materials were injected into the mantle within the last 10⁹ yrs.     

Elastic and anelastic anomalies in (Ca,Sr)TiO3 perovskites: Analogue behaviour for silicate perovskites

Values of bulk modulus (K), shear modulus (G) and mechanical quality factor (Q) have been determined for polycrystalline samples across the CaTiO₃ (CST0)–SrTiO₃ (CST100) solid solution by resonant ultrasound spectroscopy. Because of similarities with low frequency elastic and anelastic anomalies due to twin wall motion reported in previous studies, a working hypothesis is developed in which dissipation processes are interpreted in terms of twin wall displacements. At high temperatures in CST50 the stability field of the I4/mcm structure is marked by the disappearance of all resonance peaks (superattenuation). This is attributed to anelastic domain wall sliding. At room temperature the I4/mcm phase of CST70 and CST80 has values of G which are lower than those of cubic or orthorhombic phases, and a concomitant drop in Q is interpreted as implying that the domain wall pinning process reported elsewhere to occur below 400–450 K is only partial. A similar drop in G and Q was found in CST95 below the transition at 238 K. The I4/mcm ↔ Pbcm transition in CST70 at 230 K is marked by an abrupt increase in Q, suggesting that mobile twins in crystals with the I4/mcm structure become effectively immobile in antiferroelectric crystals with the Pbcm structure. The I4/mcm ↔ Pnma transition in CST50 is marked by a similarly abrupt increase in Q, consistent with twin walls becoming effectively immobile also in crystals with the Pnma structure. A fall in Q below 800 K in CST0, however, could imply that a degree of twin wall mobility might develop in Pnma crystals if the tetragonal spontaneous strain departs significantly from zero. The remarkable attenuation behaviour of crystals with the I4/mcm structure at the relatively low stress conditions which apply during resonances of a parallelepiped with edge dimensions of 2–4 mm, is consistent with the view that a characteristic signature for tetragonal CaSiO₃ in the Earth's lower mantle should be a marked attenuation of seismic waves.     

Spatial and temporal variability in the stable isotope systematics of modern precipitation in China: implications for paleoclimate reconstructions

The stable isotopic composition of materials such as glacial ice, tree rings, lake sediments, and speleothems from low-to-mid latitudes contains information about past changes in temperature (T) and precipitation amount (P). However, the transfer functions which link δ¹⁸O_p to changes in T or P, dδ¹⁸O_p/dT and dδ¹⁸O_p/dP, can exhibit significant temporal and spatial variability in these regions. In areas affected by the Southeast Asian monsoon, past variations in δ¹⁸O and δD of precipitation have been attributed to variations in monsoon intensity, storm tracks, and/or variations in temperature. Proper interpretation of past δ¹⁸O_p variations here requires an understanding of these complicated stable isotope systematics. Since temperature and precipitation are positively correlated in China and have opposite effects on δ¹⁸O_p, it is necessary to determine which of these effects is dominant for a specific region in order to perform even qualitative paleoclimate reconstructions. Here, we evaluate the value of the transfer functions in modern precipitation to more accurately interpret the paleorecord. The strength of these transfer functions in China is investigated using multiple regression analysis of data from 10 sites within the Global Network for Isotopes in Precipitation (GNIP). δ¹⁸O_p is modeled as a function of both temperature and precipitation. The magnitude and signs of the transfer functions at any given site are closely related to the degree of summer monsoon influence. δ¹⁸O_p values at sites with intense summer monsoon precipitation are more dependent on the amount of precipitation than on temperature, and therefore exhibit more negative values in the summer. In contrast, δ¹⁸O_p values at sites that are unaffected by summer monsoon precipitation exhibit strong relationships between δ¹⁸O_p and temperature. The sites that are near the northern limit of the summer monsoon exhibit dependence on both temperature and amount of precipitation. Comparison with simple linear models (δ¹⁸O_p as a function of T or P) and a geographic model (δ¹⁸O_p as a function of latitude and altitude) shows that the multiple regression model is more successful at reproducing δ¹⁸O_p values at sites that are strongly influenced by the summer monsoon. The fact that the transfer function values are highly spatially variable and closely related to the degree of summer monsoon influence suggests that these values may also vary temporally. Since the Southeast Asian monsoon intensity is known to exhibit large variations on a number of timescales (annual to glacial–interglacial), and the magnitude and sign of the transfer functions is related to monsoon intensity, we suggest that as monsoon intensity changes, the magnitude and possibly even the sign of the transfer functions may vary. Therefore, quantitative paleoclimate reconstructions based on δ¹⁸O_p variations may not be valid.     

Ferrobasalts from the Spiess Ridge segment of the Southwest Indian Ridge

Highly vesicular, microporphyritic basaltic rocks have been dredged from the slow-spreading Spiess Ridge segment of the Southwest Indian Ridge. All the samples recovered are hyalocrystalline with plagioclase, clinopyroxene and olivine as phenocryst and microphenocryst phases. Titanomagnetite occurs as euhedral microphenocrysts in some of the more evolved samples. In terms of bulk rock and quench glass chemistry the lavas are characterised by highly evolved compositions(e.g. FeO*=10.3−14.2%;TiO₂=2.0−3.4%;K₂O=0.50−1.1%;MgO=6.0−3.5%;Zr=160−274ppm;Nb=14−32ppm) and can be classified as ferrobasalts. Isotopic and incompatible element ratios of the lavas(e.g.⁸⁷Sr/⁸⁶Sr=0.70325−0.70333;Zr/Nb=8.4−11.3;Y/Nb=2.3−1.4) indicate their strongly “enriched” nature (see also Dickey et al. [6]).

Quantitative major and trace element modelling indicates that most of the compositional variations observed can be attributed to low-pressure fractional crystallisation of plagioclase, clinopyroxene and minor olivine and titanomagnetite. The range in composition can be accounted for by up to 65% fractional crystallisation.

We suggest that the extreme differentiation of the Spiess Ridge lavas is related not to spreading rate, but to rate of magma supply. The basaltic melts appear to have evolved in a newly established zone of magmatic activity, associated with the most recent northward jump of the Bouvet triple junction, where they were effectively isolated from significant admixture of primitive magmas.     

Lattice conductivities of single-crystal and polycrystalline materials at mantle pressures and temperatures

Lattice thermal conductivities have been measured for single-crystal quartz, olivine and sodium chloride, and for three dunites and polycrystalline coesite over the temperature range 350–650 K and pressure range 2–5.6 GPa.Tables of data are presented giving conductivities, pressure coefficients at various temperatures and inverse temperature coefficients at various pressures; in all cases the coefficients are positive.Although the conductivities of crystalline quartz with heat flowing parallel and perpendicular to the optic axis change markedly with pressure and temperature, the anisotropy ratio shows only a small change.     

Origin of iron-rich olivine in the matrices of type 3 ordinary chondrites: an experimental study

In order to understand the origin of iron-rich olivine in the matrices of type 3 ordinary chondrites, the reaction of metallic iron and enstatite, with and without forsterite and SiO₂, has been experimentally reproduced at temperatures between 1150° and 800°C and P_O2 between 10⁻¹¹ and 10⁻¹⁶ atm (between the IQF and MW buffers). The olivine produced ranges from Fo₅₈ to Fo₃₄ and this composition does not change significantly with temperature and time of the runs. The magnesian olivine which forms does become more magnesian with increasing forsterite/enstatite ratio of the starting materials. Iron-rich olivine (Fo< 35) cannot be formed by the reaction of enstatite and metallic iron, with or without forsterite as starting materials but it can be formed in the presence of free silica. The composition of olivine becomes more iron-rich with increasing silica/enstatite ratio. The compositional range of olivine formed from each mixture is 25–30 mole% Fo regardless of the temperature, composition, mineral assemblage, and run duration.From these experimental results, two possibilities suggested for the origin of the iron-rich olivine in the matrices of type 3 ordinary chondrites: (1) free silica must have been present if the iron-rich olivine was formed by solid-state reactions under oxidizing condition in the solar nebula; (2) reaction of silicon-rich gas with metallic iron took place under oxidizing condition in the solar nebula. Though it is difficult to define which alternative was dominant, the formation of free silica or silicon-rich gas may be a result of fractional condensation. This is possible if there is a reaction relation between forsterite and gas to produce enstatite. The suggested fractional condensation is supported by the fact that the compositions of the fine-grained matrices of type 3 ordinary chondrites are more silica-rich than the bulk compositions of the chondrites. Though it is not known whether such conditions were established all over the nebula or locally in the nebula, both fractionation and more oxidizing conditions than the average solar nebula are required for the formation of matrix olivine.     

Effect of hydrostatic pressure on the lattice parameters of Fe2SiO4 olivine up to 70 kbar

The pressure dependence of the three lattice parameters and unit cell volume of fayalite (Fe₂SiO₄ olivine) was determined by X-ray diffraction under hydrostatic pressures up to 70 kbar. In order to eliminate stress inhomogeneity within a composite material consisting of a specimen mixed with an internal-pressure standard, a liquid (1 : 1 mixture of ethanol and methanol) was used as a pressure-transmitting medium. The isothermal bulk modulus calculated on the basis of the second-order Birch-Murnaghan equation of state gives the values K₀ = 1.19 ± 0.10 Mbar and K₀′ = 7 ± 4, and if we assume K₀′ = 5: K₀ = 1.24 ± 0.02 Mbar. Three axes of fayalite were found to be compressible in the following order, b >c >a. Comparisons with the results obtained under non-hydrostatic compression are made.     

The equation of state of CaSiO3 perovskite to 108 GPa at 300 K

Pressure–volume measurements have been performed for CaSiO₃ perovskite to 108 GPa at 300 K using NaCl and argon pressure-transmitting media, and energy dispersive X-ray diffraction (EDXD) in a diamond-anvil cell (DAC). By determining a parameter that is the product of the elastic anisotropy, S, and the uniaxial stress component, t, for each data point, we define the stress condition of the sample. For different points at the same pressure in a temperature-quenched sample, the St value can differ by as much as a factor of 5, indicating heterogeneity in the stress condition. This may be responsible for the large scatter of earlier P–V measurements in the DAC which in general used a large diameter X-ray beam. Also, the St value provides insight into the elastic anisotropy, S, of CaSiO₃ perovskite and platinum. The sign of S (positive) for CaSiO₃ perovskite agrees with first principles calculations but the magnitude may be inconsistent. A new compression curve at 300 K was obtained for CaSiO₃ perovskite by using those data points which represent the most nearly hydrostatic conditions. It is observed that the data points with high St values yield larger volumes than the points with small St values at a given pressure. By selecting the data points having low St values (St≤0.005), combining with lower pressure large volume press (LVP) measurements and fitting to third order Birch–Murnaghan equation of state (EOS), we find that CaSiO₃ perovskite is more compressible (V₀=45.58±0.05 ų, K_T0=236±4 GPa, and K_T0′=3.9±0.2 GPa) than suggested by previous studies. The density and bulk modulus of CaSiO₃ perovskite at lower mantle pressures and 300 K are 1–3% greater and 5–15% smaller, respectively, than found in previous studies. This study demonstrates that defining the stress state of the sample is crucial to obtain an accurate 300 K compression curve for unquenchable high-pressure phases.     

The Impact of the Herbicide Diuron on Photosynthesis in Three Species of Tropical Seagrass

The impact and recovery from exposure to the herbicide diuron [DCMU; 3-(3′,4′-dichlorophenyl)-1,1-dimethylurea] was assessed for three tropical seagrasses, maintained in outdoor aquaria over a 10-day period. Photosynthetic stress was detected using chlorophyll a fluorescence, measured with a Diving-PAM (pulse amplitude modulated fluorometer). Exposure to 10 and 100 μg l⁻¹ diuron resulted in a decline in effective quantum yield (ΔF/F_m^′) within 2 h of herbicide exposure in Cymodocea serrulata, Halophila ovalis and Zostera capricorni. Effective quantum yield also declined over the first 24 h of exposure in H. ovalis at even lower diuron concentrations (0.1 and 1.0 μg l⁻¹). Effective quantum yield in H. ovalis and Z. capricorni was significantly depressed at all diuron concentrations (0.1–100 μg l⁻¹) after 5 days exposure, whereas effective quantum yield in C. serrulata was only significantly lower in plants exposed to highest diuron concentrations (10 and 100 μg l⁻¹). Effective quantum yield depression was present 5 days after plants exposed to 10 and 100 μg l⁻¹ diuron were returned to fresh seawater. These results indicate that exposure to herbicide concentrations present in nearshore Queensland sediments present a potential risk to seagrass functioning.     

Geobarometry of ultramafic xenoliths from Loihi Seamount,Hawaii, on the basis of CO2 inclusions in olivine

Abundant fluid inclusions in olivine of dunite xenoliths (～1–3 cm) in basalt dredged from the young Loihi Seamount, 30 km southeast of Hawaii, are evidence for three coexisting immiscible fluid phases—silicate melt (now glass), sulfide melt (now solid), and dense supercritical CO₂ (now liquid + gas)—during growth and later fracturing of some of these olivine crystals. Some olivine xenocrysts, probably from disaggregation of xenoliths, contain similar inclusions.Most of the inclusions (2–10 μm) are on secondary planes, trapped during healing of fractures after the original crystal growth. Some such planes end abruptly within single crystals and are termed pseudosecondary, because they formed during the growth of the host olivine crystals. The “vapor” bubble in a few large (20–60 μm), isolated, and hence primary, silicate melt inclusions is too large to be the result of simple differential shrinkage. Under correct viewing conditions, these bubbles are seen to consist of CO₂ liquid and gas, with an aggregate ? = ～ 0.5–0.75 g cm^?3, and represent trapped globules of dense supercritical CO₂ (i.e., incipient “vesiculation” at depth). Some spinel crystals enclosed within olivine have attached CO₂ blebs. Spherical sulfide blebs having widely variable volume ratios to CO₂ and silicate glass are found in both primary and pseudosecondary inclusions, demonstrating that an immiscible sulfide melt was also present.Assuming olivine growth at ～ 1200°C and hydrostatic pressure from a liquid lava column, extrapolation of CO₂P-V-T data indicates that the primary inclusions were trapped at ～ 220–470 MPa (2200–4700 bars), or ～ 8–17 km depth in basalt magma of ? = 2.7 g cm^?3. Because the temperature cannot change much during the rise to eruption, the range of CO₂ densities reveals the change in pressure from that during original olivine growth to later deformation and rise to eruption on the sea floor. The presence of numerous decrepitated inclusions indicates that the inclusion sample studied is biased by the loss of higher-density inclusions and suggests that some part of these olivine xenoliths formed at greater depths.     

Single-domain and superparamagnetic titanomagnetite with variable Ti content in young ocean-floor basalts: No evidence for rapid alteration

High resolution electron microscope studies have been carried out on ‘zero-age’ (New Flow) basalts from the Juan de Fuca Ridge and on young (< 20 ka) basalts from the axis of the East Pacific Rise at 12°N. Such data lead to characterization of the magnetic minerals, especially those of smaller grain size, which have been hypothesized by Kent and Gee to have undergone grain size-dependent alteration. In addition to larger titanomagnetite grains, abundant submicrometer titanomagnetite has been observed in globules within a glassy matrix. These grains, likely to be single-domain (SD) or superparamagnetic, are associated with apatite, uncommon pyrrhotite and residual glass. The submicrometer titanomagnetite grains have a wide compositional range (0 < x < 0.8), where x is the fraction of ulvöspinel component, whereas the larger, multi-domain (MD)-sized titanomagnetite grains have a narrow composition range of approximately x = 0.6. This variability in Ti content provides a ready explanation for the thermal rock magnetic properties observed by Kent and Gee and eliminates the need to invoke extremely rapid (< 20 ka) alteration of these young basalts.     

Mercury,organic-mercury and selenium in small cetaceans in Taiwanese waters

Total Hg (∑Hg), organic-Hg (O-Hg) and Se bioaccumulations in small cetaceans distributed in Taiwanese waters of the Taiwan Strait and the southwestern Pacific have been investigated for the first time. The results could represent the baseline metal concentrations of marine mammals in the southwestern Pacific, where volcanic activities are possibly the major source of mercury to the environments. Muscle samples of four species of small cetaceans were collected from animals accidentally caught by tuna-longline fisheries from 1994 through 1995. In total, 53 pantropical spotted dolphins, Stenella attenuata, nine spinner dolphins, S. longirostris, five bottlenose dolphins, Turiops truncatus and four Risso's dolphins, Grampus giseus were analyzed. In addition, two stranded pantropical spotted dolphins were investigated. Cold vapour AAS and ICP-MS were used in the analysis of Hg and Se, respectively. Significant species difference was found in the four species of small cetaceans. Among them, the pantropical spotted dolphin showed the highest mean concentration (mg/kg wet wt.) of both ∑Hg (3.64±2.19) and O-Hg (2.79±1.23), whereas the Risso's dolphin had the highest mean concentrations of Se (1.77±1.29). There was no significant sex difference with respect to metal bioaccumulation in the samples of S. attenuata. Significant correlations between body length (BL) and ∑Hg, as well as O-Hg concentrations were observed in pantropical spotted (Sa) and spinner dolphins (Sl). The linear relationships were Sa: ∑Hg=−8.290+0.066BL, r=0.421; Sl: ∑Hg=−2.735+0.025BL, r=0.875; Sa: O-Hg=−3.723+0.036BL, r=0.408; and Sl: O-Hg=−3.017+0.025BL, r=0.870. However, a demethylation phenomenon that decreasing the percentage of O-Hg coupled with increasing levels of Se was observed when the ∑Hg concentrations in the muscle tissues of dolphins reached 4 mg/kg wet wt.     

The crystallisation of lunar basalts

The crystallisation of olivine (O) and silica (S) normative varieties of Apollo 11 crystalline rocks has been followed at 1 atm. The sequence of phases precipitating is (S): spinel, olivine, ilmenite, clinopyroxene plus plagioclase; and (O): spinel, olivine, ilmenite plus plagioclase, clinopyroxene. The last 50% (O) to 75% (S) of the liquid crystallises as a pyroxene-plagioclase-ilmenite cotectic over a narrow temperature range, approximately 1095 to 1125° C, leaving a small silica-rich residue.     

Petrogenesis of basalts from the project FAMOUS area: experimental study from 0 to 15 kbars

Tholeiitic basalt glasses from the FAMOUS area of the Mid-Atlantic Ridge are among the most primitive basaltic liquids reported from the ocean basins. One of the more primitive of these[Mg/(Mg+Fe²⁺) = 0.68;Ni= 232ppm;TiO₂ = 0.61] glasses (572-1-1) was selected for an experimental investigation. This study found olivine to be the liquidus phase from 1 atm to 10.5 kbar where it is replaced by clinopyroxene. The sequence of appearance of phases at 1 atm pressure is olivine (1268°C), plagioclase (1235°C) and clinopyroxene (1135°C). The sample is multiply saturated at 10.5 kbar with olivine (Fo₈₈), clinopyroxene (Wo₃₂En₆₀Fs₉), and orthopyroxene (Wo₅En₈₃Fs₁₂). From the 1-atm data we have measured (FeO/MgO) olivine/(FeO*/MgO) liquid (K′_D) for olivine-melt pairs equilibrated at 12 temperatures in the range 1268–1205°C.K′_D varies from 0.30 at 1205°C to 0.27 at 1268°C. Analysis of high-pressure olivine melt pairs indicates a systematic increase inK′_D with pressure.Evaluation of the 1-atm experiments reveals that fractionation of olivine followed by olivine + plagioclase can generate much of the variation in major element chemistry observed in the FAMOUS basalt glasses. However, it cannot account for the entire spectrum of glass compositions — particularly with respect to TiO₂ and Na₂O. The variations in these components are such as to require different primary liquids.Comparison of clinopyroxene microphenocrysts/xenocrysts found in oceanic tholeiites with experimental clinopyroxenes reveal that the majority of those in the tholeiites may have crystallized from the magma at pressures greater than ～ 10 kbar and are not accidental xenocrysts. Clinopyroxene fractionation at high pressures may be a viable mechanism for fractionating basaltic magmas.The major and minor element mineral/meltK′_d's from our experiments have been used to model the source region residual mineralogy for given percentages of partial melting. These data suggest that ～20% partial melting of a lherzolite source containing 0–10% clinopyroxene can generate the major and minor element concentrations in the parental magmas of the Project FAMOUS basalt glasses.     

Geochemical morphology of the North Mid-Atlantic Ridge, 10°–24°N: Trace element-isotope complementarity

The new data presented here from a 10–24°N segment of the North Mid-Atlantic Ridge show that this segment is the most depleted of the 10–70°N ridge section. They also show the existence of: (1) a geochemical gradient from the 14°N anomaly to 17°10′N; (2) a very depleted mantle source (the lowest Sr isotopic ratios found so far in the North Atlantic); and (3) a geochemical limit located at about 17°10′N without any obvious relation with any structural feature. The 15°20′N fracture zone does not show any relationship with respect to this gradient. The basalts located north of 17°10′N have very homogeneous features, which allow their characteristics to be averaged (i.e., ⁸⁷Sr/⁸⁶Sr= 0.70238 ± 0.00004, (Nb/Zr)_N = 0.28 ± 0.1) and they are defined as normal mid-ocean ridge basalts. The basaltic glasses located south of 17°10′N present a wide spectrum of isotopic compositions and extended rare earth element patterns (from depleted to enriched). Despite this, they have a constant K/Nb of 233 ± 9 (1s_M, n = 18) whereas this ratio is 344 ± 29 north of 17°10′N. These observations illustrate the strong coherence of behaviour between K and Nb (Ta) during the petrogenic processes involved in the generation of these mid-ocean ridge basalts and also their fractionation during previous mantle processes. Possible interpretations of mixing processes are discussed and sources at the ridge segment scale are favoured. However, when looking in detail, local heterogeneities are still common and can even be traced back off-axis to 115 my.

Placed in the context of the North Atlantic Ridge from 10° to 70°N, the Sr isotopic ratios reveal the Azores superstructure (23–50°N), whereas the trace element ratios (La/Sm-Nb/Zr) trace the second-order structures (33–40°N, 42–48°N) superimposed on the superstructure. This study illustrates the complementarity of information given by certain well chosen trace element ratios on the one hand and by isotopic ratios on the other. Since there is evidence of decoupling between isotopic ratios and/or trace element ratios, it introduces the notion of complementary “chemical memory” as recorded by a given type of trace element ratio or a given type of isotopic ratio     

Rift Valley in the Atlantic Ocean near 36°50′N: petrology and geochemistry of basaltic rocks

Dredged rocks from an area of about 15 km² within the inner floor and on the adjacent walls of the Rift Valley were collected. Based on petrographic and chemical data, four types of basaltic rocks were recognized: (1) picritic basalts with olivine xenocrysts, TiO₂ < 0.6%, K₂O < 0.1%, (2) olivine basalts with olivine megacrysts, TiO₂ = 0.8–1.5%,K₂O = 0.1–0.2%, (3) highly phyric and moderately phyric plagioclase basalts with megacrystic plagioclase, TiO₂ < 1.3%, K₂O < 0.3%, and (4) pyroxene basalts with pyroxene > plagioclase, TiO₂ = 0.8–1%,K₂O = 0.2–0.4%. The Cr and Ni having high partition coefficients show different variation trends for each type of rock and their values decrease continuously as crystallization proceeds within each type of basalt. It is speculated that two different magmas have given rise to the above-mentioned rocks. One has yielded the picritic basalts and subsequently the olivine basalts after a separation of the olivine cumulates; the other gave rise to the plagioclase basalts.     

REE diffusion in calcite

Chemical diffusion of four rare-earth elements (La, Nd, Dy and Yb) has been measured in natural calcite under anhydrous conditions, using rare-earth carbonate powders as the source of diffusants. Experiments were run in sealed silica capsules along with finely ground calcite to ensure stability of the single-crystal samples during diffusion anneals. Rutherford backscattering spectroscopy (RBS) was used to measure diffusion profiles. The following Arrhenius relations were obtained over the temperature range 600–850°C: D_La =2.6×10⁻¹⁴ exp(−147±14 kJ mol⁻¹/RT) m² s⁻¹, D_Nd =2.4×10⁻¹⁴ exp(−150±13 kJ mol⁻¹/RT) m² s⁻¹, D_Dy =2.9×10⁻¹⁴ exp(−145±25 kJ mol⁻¹/RT) m² s⁻¹, D_Yb =3.9×10⁻¹² exp(−186±23 kJ mol⁻¹/RT) m² s⁻¹. In contrast to previous findings for refractory silicates (e.g. zircon), differences in transport rates among the REE are not pronounced over the range of temperature conditions investigated in this study. Diffusion of the REE is significantly slower than diffusion of the divalent cations Sr and Pb and slower than transport of Ca and C at temperatures above 650°C. Fine-scale zoning and isotopic and REE chemical signatures may be retained in calcites under many conditions if diffusion is the dominant process affecting alteration.     

Silicate perovskite analogue ScAlO3: temperature dependence of elastic moduli

The elastic moduli of ScAlO₃ perovskite, a very close structural analogue for MgSiO₃ perovskite, have been measured between 300 and 600 K using high precision ultrasonic interferometry in an internally heated gas-charged pressure vessel. This new capability for high temperature measurement of elastic wave speeds has been demonstrated on polycrystalline alumina. The temperature derivatives of elastic moduli of Al₂O₃ measured in this study agree within 15% with expectations based on published single-crystal data. For ScAlO₃ perovskite, the value of (∂K_S/∂T)_P is −0.033 GPa K⁻¹ and (∂G/∂T)_P is −0.015 GPa K⁻¹. The relative magnitudes of these derivatives agree with the observation in Duffy and Anderson [Duffy, T.S., Anderson, D.L., 1989. Seismic velocities in mantle minerals and the mineralogy of the upper mantle. J. Geophys. Res. 94, 1895–1912.] that |(∂K_S/∂T)_P| is typically about twice |(∂G/∂T)_P|. The value of (∂K_S/∂T)_P for ScAlO₃ is intermediate between those inferred less directly from V(P,T) studies of Fe-free and Fe- and Al-bearing MgSiO₃ perovskites [Wang, Y., Weidner, D.J., Liebermann, R.C., Zhao, Y., 1994. P–V–T equation of state of (Mg,Fe)SiO₃ perovskite: constraints on composition of the lower mantle. Phys. Earth Planet. Inter. 83, 13–40; Mao, H.K., Hemley, R.J., Shu, J., Chen, L., Jephcoat, A.P., Wu, Y., Bassett, W.A., 1991. Effect of pressure, temperature and composition on the lattice parameters and density of (Mg,Fe) SiO₃ perovskite to 30 GPa. J. Geophys. Res. 91, 8069–8079; Zhang, Weidner, D., 1999. Thermal equation of state of aluminum-enriched silicate perovskite. Science 284, 782–784]. The value of |(∂G/∂T)|_P for ScAlO₃ is similar to those of most other mantle silicate phases but lower than the recent determination for MgSiO₃ perovskite [Sinelnikov, Y., Chen, G., Neuville, D.R., Vaughan, M.T., Liebermann, R.C., 1998. Ultrasonic shear wave velocities of MgSiO₃ perovskite at 8 GPa and 800K and lower mantle composition. Science 281, 677–679].

Combining the results from the previous studies and current measurements on ScAlO₃ perovskite, we extracted the parameters (q and γ₀) needed to fully specify its Mie–Grüneisen–Debye equation-of-state. In this study, we have demonstrated that acoustic measurements of K_S(T), unlike V(P,T) data, tightly constrain the value of q. It is concluded that ScAlO₃ has ‘normal’ γ₀ (1.3) and high q (3.6). The high value of q indicates that ScAlO₃ has very strong intrinsic temperature dependence of the bulk modulus; similar behaviour has been observed in measurements on Fe- and Al-bearing silicate perovskites (Mao et al., 1991; Zhang and Weidner, 1999).     

He diffusion in olivine

Helium diffusion in olivine (dunite xenolith) has been measured in the temperature range 1180–1460°C; a linear Arrhenius function was obtained with an activation energy of 120₋₂₇⁺³² kcal/mole, and a pre-exponential factor (D₀) = 2.2 × 10⁸ cm²/s.

Diffusion mechanisms are not a viable means of degassing He from the mantle. Olivine phenocrysts can be expected to retain previously trapped He, during cooling in extrusive basalts, provided the flow units are thinner than 50 m; xenoliths will retain mantle He signatures only if magma transport times are less than 50 years, or if the He fugacity in the magma is high enough to prevent xenolith degassing. The lower oceanic crust is probably substantially degassed of He. Trapped He will be qualitatively retained in quenched submarine basalt glass only if the cooling rate is faster than 5 × 10¹⁴°C/m.y.; glass at several centimeters depth in a basalt flow (near the spherulite zone) will have cooling rates lower than this, so He loss may be significant in many basalt glass samples.