Kilauea Iki Lava Lake Research Articles

Zinc isotope fractionation during mid-ocean ridge basalt differentiation: Evidence from lavas on the East Pacific Rise at 10°30′N

Zinc (Zn) isotope data for mid-ocean ridge basalts (MORB) are scarce. The possible effects of MORB differentiation and mantle compositional heterogeneity on MORB Zn isotope compositions are poorly understood. In this paper, we report Zn isotope data of MORB lavas from the East Pacific Rise (EPR) at 10°30′N, which are understood to have been derived by a similar extent of melting from a compositionally uniform mantle source but manifest significantly varying extents of magma differentiation (MgO = 7.38–1.76 wt%) to demonstrate unequivocal Zn isotope fractionation during MORB differentiation. These lavas have a small δ66Zn (relative to the JMC-Lyon standard) range of 0.21–0.32‰, with an average of 0.26 ± 0.07‰ (2SD, N = 24), overlapping with literature data. However, δ66Zn values show significant correlations with indices of magma differentiation (e.g., MgO and CaO), with the more differentiated samples having isotopically heavier Zn. We can thus conclude that MORB differentiation can lead to ∼0.1‰ δ66Zn elevation, which is similar to that observed in Hawaiian Kilauea Iki lava lake samples. Fractional crystallization of olivine and clinopyroxene at MgO > ∼3.5 wt% and clinopyroxene and Fe–Ti oxides dominated by ilmenite at MgO < ∼3.5 wt% results in the observed Zn isotope fractionation. The δ66Zn values for primitive N-MORB and MORB source mantle are estimated to be ∼0.22‰ and ∼0.17‰, respectively. Furthermore, we observe a positive correlation between δ66Zn and [La/Sm]N in primitive (MgO = 7.58–9.01 wt%) literature MORB, indicating the existence of possible Zn isotope heterogeneity in the oceanic upper mantle. We thus predict heavy Zn isotope enrichment in mantle sources for E-MORB samples with high [La/Sm]N, which requires future testing.

Behavior of the Mo, Tl, and U isotope systems during differentiation in the Kilauea Iki lava lake

Stable molybdenum (Mo), thallium (Tl), and uranium (U) isotope ratios were determined in a suite of samples from the 1959 Kilauea eruption and from Kilauea Iki lava lake with the aim of understanding the effects of igneous differentiation on these isotope systems. The samples range from olivine cumulate with MgO up to 27% to internal differentiates with MgO less than 3%, representing a tholeiitic differentiation series. Molybdenum, Tl, and U behave incompatibly during differentiation, and Mo and U isotope ratios do not systematically vary amongst the different samples. δ98Mo values range from −0.17 to −0.31‰ and δ238U values range from −0.20 to −0.38‰. Most individual analyses for both isotope systems overlap within measurement uncertainty (± ~0.7 and ~ 0.6, respectively). Mean δ98Mo and δ238U values are −0.22 ± 0.08‰ (2σ) and − 0.29 ± 0.09‰ (2σ), respectively, which overlap with Pacific mid ocean ridge basalt (MORB). In contrast, Tl isotopes show small but resolvable variations, with ε205Tl ranging from +1.20 to −1.38. The most negative ε205Tl values are confined to some of the lowest [Tl] samples, but the ε205Tl values do not otherwise vary smoothly with MgO or [Tl]. Possible mechanisms for thallium isotope fractionation are considered (e.g., degassing, water leaching, sulfide fractionation) but none are found to be satisfactory. Overall, the lack of resolvable variation in the Mo and U isotope systems and the small magnitude of heterogeneity in the Tl isotope system indicate that differentiation in tholeiitic systems is unlikely to be a major contributor to global variation in these isotope systems.

Potassium Isotope Fractionation During Magmatic Differentiation and the Composition of the Mantle

AbstractStable potassium (K) isotopes are emerging as tracers of terrestrial recycling and planetary processes. These applications require well‐defined K isotopic compositions for the mantle and the bulk silicate Earth (BSE). Both values are determined primarily by basalts formed via partial melting of the mantle. Basaltic melts experience igneous differentiation before reaching the surface, which may alter their isotopic compositions compared to their mantle sources. This study investigates K isotope fractionation during the differentiation and solidification of the Kilauea Iki lava lake, Hawaii, for which crystallization and thermal histories are well documented. High‐precision K isotopic ratios (δ41K) are measured in 13 Kilauea Iki samples that cover its complete differentiation history, ranging from olivine‐rich, high‐MgO cumulates to increasingly differentiated, MgO‐depleted samples. The limited δ41K range of −0.42 to −0.37‰ in all but one sample reveals no analytically resolvable fractionation across diverse bulk compositions, even though their bulk MgO contents varied from 26.9 to 2.37 wt.%. The lack of K isotopic fractionation is consistent with an absence of K‐rich minerals in the crystallizing assemblage, where only plagioclase can accommodate a small amount of K. A highly differentiated vein displays the lowest δ41K of −0.47‰ among the Kilauea Iki suite, which is consistent with our modeling calculations that suggest measurable K isotope fractionation at more advanced magmatic differentiation stages. Combining our new results with literature data, we propose an average δ41K of −0.42 ± 0.08‰ (2SD) for the pristine mantle and of −0.42 ± 0.07‰ (2SD) for the BSE.

Vanadium isotope fractionation during differentiation of Kilauea Iki lava lake, Hawaii

In order to understand the mechanism of vanadium (V) isotope fractionation during magmatic differentiation, we analyzed the V isotopic compositions of eruptive pumices, olivine-phyric basalts, and differentiated segregation veins from the Kilauea Iki lava lake, Hawaii. Most olivine-phyric samples contain whole rock δ51V ranging from −0.95‰ to −0.80‰ similar to the average value of the bulk silicate Earth (BSE; −0.91‰ ± 0.09‰), reflecting the composition of melt coexisting with olivine. One eruptive pumice is similar to most of the olivine-phyric samples with a δ51V value of −0.89‰, while the other eruptive pumice and the two highest-MgO olivine-phyric samples have δ51V shifting to slightly higher values of −0.81‰ to −0.63‰. For the segregation veins, the whole rock δ51V values vary from −0.81‰ to −0.53‰, suggesting an average mineral-melt fractionation factor (Δ51Vmineral-melt) of about −0.15‰ during fractional crystallization. The late differentiated veins exhibit the highest δ51V, δ56Fe, and δ49Ti values, showing isotope fractionation driven by the crystallization of Fe–Ti oxides. The estimated Δ51Vmineral-melt value for Kilauea Iki samples is much smaller than that reported for Hekla basalts from Iceland and Anatahan lavas from Mariana (−0.5‰ to −0.4‰; Prytulak et al., 2017), which may reflect differences in magma differentiation in terms of the timing of Fe–Ti oxide saturation, and the amount and mineralogy of the Fe–Ti oxides.

Distribution and Transport of Thermal Energy within Magma–Hydrothermal Systems

Proximity to magma bodies is generally acknowledged as providing the energy source for hot hydrothermal reservoirs. Hence, it is appropriate to think of a “magma–hydrothermal system” as an entity, rather than as separate systems. Repeated coring of Kilauea Iki lava lake on Kilauea Volcano, Hawaii, has provided evidence of an impermeable, conductive layer, or magma–hydrothermal boundary (MHB), between a hydrothermal system and molten rock. Crystallization on the lower face of the MHB and cracking by cooling on the upper face drive the zone downward while maintaining constant thickness, a Stefan problem of moving thermal boundaries with a phase change. Use of the observed thermal gradient in MHB of 84 °C/m yields a heat flux of 130 W/m2. Equating this with the heat flux produced by crystallization and cooling of molten lava successfully predicts the growth rate of lava lake crust of 2 m/a, which is faster than simple conduction where crust thickens at t and heat flux declines with 1 / t . However, a lava lake is not a magma chamber. Compared to erupted and degassed lava, magma at depth contains a significant amount of dissolved water that influences the magma’s thermal, chemical, and mechanical behaviors. Also, a lava lake is rootless; it has no source of heat and mass, whereas there are probably few shallow, active magma bodies that are isolated from deeper sources. Drilling at Krafla Caldera, Iceland, showed the existence of a near-liquidus rhyolite magma body at 2.1 km depth capped by an MHB with a heat flux of ≥16 W/m2. This would predict a crystallization rate of 0.6 m/a, yet no evidence of crystallization and the development of a mush zone at the base of MHB is observed. Instead, the lower face of MHB is undergoing partial melting. The explanation would appear to lie in vigorous convection of the hot rhyolite magma, delivering both heat and H2O but not crystals to its ceiling. This challenges existing concepts of magma chambers and has important implications for use of magma as the ultimate geothermal power source. It also illuminates the possibility of directly monitoring magma beneath active volcanoes for eruption forecasting.

Titanium isotopic fractionation in Kilauea Iki lava lake driven by oxide crystallization

Recent work has demonstrated that titanium (Ti) isotopes undergo mass-dependent isotope fractionation during magmatic differentiation, leaving evolved silicic melts preferentially enriched in heavy Ti isotopes. Preferential incorporation of light Ti isotopes in crystallizing Fe-Ti oxides is thought to be the mechanism responsible for this fractionation in magmatic rocks. To test this hypothesis, we present Ti isotope measurements of Fe-Ti oxide mineral separates of Kilauea Iki lava lake samples. We find that the Ti in Fe-Ti oxides is isotopically light while Ti in the residual melt and minerals is isotopically heavy. This result is consistent with the results of density functional theory (DFT) calculations in other studies, which show progressive heavy isotope enrichment for Ti from 6-fold, 5-fold, through 4-fold coordinated minerals. We therefore conclude that Ti isotopes in silicate melts undergo isotope fractionation during the crystallization of Fe-Ti oxides because Ti in oxides is primarily in 6-fold coordination whereas Ti in silicate melts is in 5- or 4-fold coordination (Ti in more evolved magmas tends to be in lower coordination). Based on our mineral separate results, we estimate the fractionation factor at 1000 °C between silicate and oxide Δ49Tisilicate-oxide to be 0.39 ± 0.06‰. This result is consistent with the fractionation factors inferred in previous studies based on Ti isotopic analyses and modeling of bulk rock measurements. We use this fractionation factor and the fractionation factors proposed by previous workers in Rhyolite MELTS to model the δ49Ti evolution of plume lavas. We find the model to generally predict the fractionations observed in Kilauea Iki, as well as the fractionations previously observed in volcanics from Hekla, Iceland and Afar, East Africa.

No Measurable Calcium Isotopic Fractionation During Crystallization of Kilauea Iki Lava Lake

AbstractIn order to investigate possible Ca isotopic fractionation during basaltic magma differentiation, we measured Ca isotopic compositions of lavas recovered from Kilauea Iki lava lake at Hawaii. This set of lavas record the whole crystal fractionation history of basaltic magma, ranging from olivine accumulation/fractionation to multiple phase crystallization, including plagioclase and clinopyroxene. Our results show no detectable Ca isotopic variation in all measured Kilauea lavas at a precision of ±0.07‰ for 44Ca/40Ca (δ44/40Ca = 0.80 ± 0.08, 2 SD, n = 19). Using such observation and published intermineral Ca isotopic fractionation factors, a Monte Carlo approach is used to estimate the mineral‐melt 44Ca/40Ca fractionation factors. We found that Ca isotopic fractionation between clinopyroxene and basaltic melt is small, with Δ44/40Cacpx‐melt = 0.04 ± 0.03 at 1200 °C. To the best of our knowledge, this is the first estimated mineral‐melt Ca isotopic fractionation factor reported. We use this estimated Δ44/40Cacpx‐melt and intermineral Ca isotopic fractionation factors to investigate Ca isotopic effects during mantle partial melting under 1–2 GPa. Our simulations show that the largest 44Ca/40Ca effect, up to +0.3‰, is achieved in large degree melting residues during fractional and dynamic melting. In contrast, partial melts show negligible 44Ca/40Ca isotopic effect, &lt;0.07‰.

The stable strontium isotopic composition of ocean island basalts, mid-ocean ridge basalts, and komatiites

The radiogenic 87Rb-87Sr system has been widely applied to the study of geological and planetary processes. In contrast, the stable Sr isotopic composition of the bulk silicate Earth (BSE) and the effects of igneous differentiation on stable Sr isotopes are not well-established. Here we report the stable Sr isotope (88Sr/86Sr, reported as δ88/86Sr, in parts per mil relative to NIST SRM 987) compositions for ocean islands basalts (OIB), mid-ocean ridge basalts (MORB) and komatiites from a variety of locations. Stable Sr isotopes display limited fractionation in a OIB sample suite from the Kilauea Iki lava lake suggesting that igneous processes have limited effect on stable Sr isotope fractionation (±0.12‰ over 20% MgO variation; 2sd). In addition, OIB (δ88/86Sr = 0.16–0.46‰; average 0.28 ± 0.17‰), MORB (δ88/86Sr = 0.27–0.34‰; average 0.31 ± 0.05‰) and komatiites (δ88/86Sr = 0.20–0.97‰; average 0.41 ± 0.16‰) from global localities exhibit broadly similar Sr stable isotopic compositions. Heavy stable Sr isotope compositions (δ88/86Sr > 0.5‰) in some Barberton Greenstone belt komatiites may reflect Archean seawater alteration or metamorphic processes and preferential removal of the lighter isotopes of Sr. To first order, the similarity among OIBs from three different ocean basins suggests homogeneity of stable Sr isotopes in the mantle. Earth's mantle stable Sr isotopic composition is established from the data on OIB, MORB and komatiites to be δ88/86Sr = 0.30 ± 0.02‰ (2sd). The BSE δ88/86Sr value is identical, within uncertainties, to the composition of carbonaceous chondrites (δ88/86Sr = 0.29 ± 0.06‰; 2sd) measured in this study.

The behavior of chalcophile elements during magmatic differentiation as observed in Kilauea Iki lava lake, Hawaii

We quantify the behavior of Cu, Ga, Ge, As, Mo, Ag, Cd, In, Sn, Sb, W, Tl, Pb, and Bi during the differentiation of a picritic magma in the Kilauea Iki lava lake, Hawaii, using whole rock and glass differentiation trends, as well as partition coefficients in Cu-rich sulfide blebs and minerals. Such data allow us to constrain the partitioning behavior of these elements between sulfide and silicate melts, as well as the chalcophile element characteristics of the mantle source of the Kilauea lavas. Nearly all of the elements are generally incompatible on a whole-rock scale, with concentrations increasing exponentially below ∼6wt% MgO. However, in-situ laser ablation data reveal that Cu, Ag, Bi, Cd, In, Pb, and Sn are chalcophile; As, Ge, Sb, and Tl are weakly chalcophile to lithophile; and Mo, Ga, and W are lithophile. The average Dsulfide/silicate melt values are: DAg=1252±1201 (2SD), DBi=663±576, DCd=380±566, DIn=40±34, DPb=34±18, DSn=5.3±3.6, DAs=2.4±7.6, DGe=1.6±1.4, DSb=1.3±1.5, DTl=1.1±1.7, DMo=0.56±0.6, DGa=0.10±0.3, and DW=0.11±0.1. These findings are consistent with experimental partitioning studies and observations of Ni-rich sulfide liquid in mid-ocean ridge basalts (MORB), despite the different compositions of the KI sulfides. The KI glasses and whole rocks are enriched in As, Ag, Sb, W, and Bi, relative to elements of similar compatibility (as established by abundances in MORB), mimicking enrichments found in basalts from the Manus back arc basin (Jenner et al., 2012) and the upper continental crust (UCC). These enrichments suggest the presence of terrigenous sediments in the Kilauea mantle source. The KI source is calculated to be a mixture of depleted MORB mantle (DMM) and 10–20% recycled crust composed of MORB and minor terrigenous sediments.

Thermal and crystallization histories of magmatic bodies by Monte Carlo inversion of Mg-Fe isotopic profiles in olivine

Abstract A random search modeling approach is introduced to retrieve the thermal histories of magmatic bodies from chemical and isotopic analyses of olivine crystals. The sample used for demonstration is an olivine phenocryst from Kilauea Iki lava lake, Hawaii. Random time-temperature (t-T) paths were used to model diffusion accompanying crystal growth. Although a large number of t-T paths yielded acceptable fits to the Mg/Fe chemical profiles measured in olivine, only a small fraction resulted in acceptable fits to the Mg-Fe isotopic profiles. The best-fit cooling path was close to the independently inferred cooling history of this sample. Use of isotopic profiles in minerals coupled with a random search method can be a powerful tool for recovering thermal histories of rocks with little geologic context.

The gallium isotopic composition of the bulk silicate Earth

We report a new method for precise analysis of gallium (Ga) isotopic composition in geological samples. The purification of Ga is achieved by a three-step ion exchange chromatography to remove matrix and interfering elements. The 71Ga/69Ga ratios are analyzed by multi-collector inductively-coupled-plasma mass-spectrometer (MC-ICP-MS). The external reproducibility of the measurements (0.05‰, 2 s.d.) was assessed by replicate analyses of the USGS BCR-2 and BHVO-2 standards. This newly developed technique was then used to investigate the extent of Ga isotopic fractionation during igneous processes by analyzing well-characterized samples from the Kilauea Iki lava lake, USA. These samples were formed in a closed system and have MgO contents ranging from 26.9 to 2.4wt.%. We found that igneous processes do not fractionate Ga isotopes within the analytical uncertainty and that the Ga isotopic composition of mafic-ultramafic lavas can be used to estimate the composition of their mantle source. Twelve ocean island basalts, two mid-ocean-ridge basalts, one continental flood basalt and one komatiite have homogeneous and nearly identical Ga isotopic compositions within analytical uncertainties averaging 0.00±0.06‰ (2s.d.). This value represents the best estimate for the Ga isotopic composition of the bulk silicate Earth

Geothermal evolution of an intruded dike in the rift zone of Kilauea volcano, Hawaii from VLF and self-potential measurements

Self-potential (SP) and VLF measurements were made in 1973, 1975, 1995, 1997 and 2012 across a basaltic dike that intruded into the Koae fault zone of Kilauea volcano, Hawaii in May 1973. The SP anomaly remained strong throughout. In 2012 it was at about 60% of the strength it had in 1973. In contrast, the VLF anomaly, though diminished, was still observable in 1995/1997, but by 2012 it had disappeared. A hydrothermal dike model, with parameters calibrated by modeling the solidification of Kilauea Iki lava lake, is used to calculate temperatures and conductivity variation. Following Jaeger's (1957) method, we find that the time in years for a dike of width W (m) to solidify is 0.0075W2. Thus, a 1m dike solidifies within the first few days, and after 39years is only tens of degrees above ambient. Given the orders of magnitude difference between the conductivities of wet and dry basalt, we infer, that after solidification, the VLF anomalies were caused by induction in a localized veil of wet, hot basalt enveloping the dike, that was generated initially by condensation of steam, and subsequently by condensation of evaporated water as temperatures reduced. The conductivity anomaly persisted until the mid-nineties. By 2012, temperatures and condensation were too small for a VLF signal. The persistent SP anomaly is attributed to localized fluid disruption, with evaporation mainly at the water table and in the vadose zone. Streaming potentials are associated with evaporative circulation in the vadose zone. Next to the dike a positive potential is generated by upward flow of moisture-laden air, with a smaller negative potential on its flanks from downward infiltrating rainwater. The analysis indicates that the combination of SP and VLF measurements can characterize the evolving geothermal regime of intrusions above the water table.

Discerning crystal growth from diffusion profiles in zoned olivine by in situ Mg–Fe isotopic analyses

Mineral zoning is used in diffusion-based geospeedometry to determine magmatic timescales. Progress in this field has been hampered by the challenge to discern mineral zoning produced by diffusion from concentration gradients inherited from crystal growth. A zoned olivine phenocryst from Kilauea Iki lava lake (Hawaii) was selected for this study to evaluate the potential of Mg and Fe isotopes for distinguishing these two processes. Microdrilling of the phenocryst (∼300μm drill holes) followed by MC-ICPMS analysis of the powders revealed negatively coupled Mg and Fe isotopic fractionations (δ26Mg from +0.1‰ to −0.2‰ and δ56Fe from −1.2‰ to −0.2‰ from core to rim), which can only be explained by Mg–Fe exchange between melt and olivine. The data can be explained with ratios of diffusivities of Mg and Fe isotopes in olivine scaling as D2/D1=(m1/m2)β with βMg ∼0.16 and βFe ∼0.27. LA-MC-ICPMS and MC-SIMS Fe isotopic measurements are developed and are demonstrated to yield accurate δ56Fe measurements within precisions of ∼0.2‰ (1 SD) at spatial resolutions of ∼50μm. δ56Fe and δ26Mg stay constant with Fo# in the rim (late-stage overgrowth), whereas in the core (original phenocryst) δ56Fe steeply trends toward lighter compositions and δ26Mg trends toward heavier compositions with higher Fo#. A plot of δ56Fe vs. Fo# immediately distinguishes growth-controlled from diffusion-controlled zoning in these two regions. The results are consistent with the idea that large isotopic fractionation accompanies chemical diffusion in crystals, whereas fractional crystallization induces little or no isotopic fractionation. The cooling timescale inferred from the chemical-isotope zoning profiles is consistent with the documented cooling history of the lava lake. In the absence of geologic context, in situ stable isotopic measurements may now be used to interpret the nature of mineral zoning. Stable isotope measurements by LA-MC-ICPMS and MC-SIMS can be used as standard petrologic tools to identify samples for diffusion-based geospeedometry.

Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth

The zinc stable isotope system has been successfully applied to many and varied fields in geochemistry, but to date it is still not completely clear how this isotope system is affected by igneous processes. In order to evaluate the potential application of Zn isotopes as a proxy for planetary differentiation and volatile history, it is important to constrain the magnitude of Zn isotopic fractionation induced by magmatic differentiation. In this study we present high-precision Zn isotope analyses of two sets of chemically diverse, cogenetic samples from Kilauea Iki lava lake, Hawaii, and Hekla volcano, Iceland, which both show clear evidence of having undergone variable and significant degrees of magmatic differentiation.The Kilauea Iki samples display small but resolvable variations in Zn isotope composition (0.26‰<δ66Zn<0.36‰; δ66Zn defined as the per mille deviation of a sample's 66Zn/64Zn compositional ratio from the JMC-Lyon standard), with the most differentiated lithologies exhibiting more positive δ66Zn values. This fractionation is likely a result of the crystallization of olivine and/or Fe–Ti oxides, which can both host Zn in their crystal structures. Samples from Hekla have a similar range of isotopic variation (0.22‰<δ66Zn<0.33‰), however, the degree of fractionation caused by magmatic differentiation is less significant (only 0.07‰) and no correlation between isotope composition and degree of differentiation is seen. We conclude that high temperature magmatic differentiation can cause Zn isotope fractionation that is resolvable at current levels of precision, but only in compositionally-evolved lithologies. With regards to primitive (ultramafic and basaltic) material, this signifies that the terrestrial mantle is essentially homogeneous with respect to Zn isotopes. Utilizing basaltic and ultramafic sample analyses, from different geologic settings, we estimate that the average Zn isotopic composition of Bulk Silicate Earth is δ66Zn=0.28±0.05‰ (2s.d.).

Disequilibrium dihedral angles in dolerite sills: A new proxy for cooling rate

The geometry of clinopyroxene-plagioclase-plagioclase junctions in mafic rocks, measured by the median dihedral angle Θcpp, is created during solidification. In the solidifying Kilauea Iki (Hawaii) lava lake, the wider junctions between plagioclase grains are the first to be filled by pyroxene, followed by the narrower junctions. The final Θcpp, attained when all clinopyroxene-plagioclase-plagioclase junctions are formed, is 78° in the upper crust of the lake, and 85° in the lower solidification front. Θcpp in the 3.5-m-thick Traigh Bhan na Sgurra sill (Inner Hebrides) is everywhere 78°. In the Whin Sill (northern England, 38 m thick) and the Portal Peak sill (Antarctica, 129 m thick), Θcpp varies symmetrically, with the lowest values at the margins. The 266-m-thick Basement Sill (Antarctica) has asymmetric variation of Θcpp, attributed to a complex filling history. The chilled margins of the Basement Sill are partially texturally equilibrated, with high Θcpp. The plagioclase grain size in the two widest sills varies asymmetrically, with the coarsest rocks found in the upper third. Both Θcpp and average grain size are functions of model crystallization times. Θcpp increases from 78° to a maximum of ∼100° as the crystallization time increases from 1 to 500 yr. Because the use of grain size as a measure of crystallization time is dependent on an estimate of crystal growth rates, dihedral angles provide a more direct proxy for cooling rates in dolerites.

What can crystal size distributions and olivine compositions tell us about magma solidification processes inside Kilauea Iki lava lake, Hawaii?

Lava lakes offer the opportunity to investigate magma solidification and can be considered as a proxy for small magma chambers. Here we present olivine compositions and crystal size distributions (CSDs) from scoria and drill core samples from Kilauea Iki lava lake, which formed during the 1959 eruption of Kilauea Volcano, Hawaii. Three chemically distinct olivine populations were distinguished, in the basis of their forsterite (Fo) content: (1) a high-Fo population (Fo 86–90); (2) an intermediate-Fo population (Fo 78–82); and (3) a minor low-Fo population (Fo 74–78). Populations 1 and 2 both have deformed and undeformed crystals. The third population may be the result of rejuvenation. Olivine in the lower 60 m of lake has a less Fo-rich composition and more crystals are deformed. The CSD analysis yields estimates of the average olivine residence time: 1–60 years. The shape of the olivine CSDs is fairly uniform with respect to depth. Curved CSDs are considered to be evidence of hybrid populations, partly or totally involving crystal or magma mixing. The turndown at the smallest sizes of most foundered crust and lake CSDs may be the result of coarsening, making this process active both before and after eruption. Our CSD modelling does not support significant crystal settling and overall convection in the lava lake, although small advective currents are known to have occurred. The olivine vertical stratification cannot be an original feature, which is consistent with supposed strong stirring of the lake magma due to intense activity over the 17 eruptive phases. It is also possible that independent basal feeding of the lake during the eruption may be needed to explain fully features of the chemical and mineralogical stratification.

Fractionation of the platinum-group elments and Re during crystallization of basalt in Kilauea Iki Lava Lake, Hawaii

Kilauea Iki lava lake formed during the 1959 summit eruption of Kilauea Volcano, then crystallized and differentiated over a period of 35 years. It offers an opportunity to evaluate the fractionation behavior of trace elements in a uniquely well-documented basaltic system. A suite of 14 core samples recovered from 1967 to 1981 has been analyzed for 5 platinum-group elements (PGE: Ir, Os, Ru, Pt, Pd), plus Re. These samples have MgO ranging from 2.4 to 26.9 wt.%, with temperatures prior to quench ranging from 1140 °C to ambient (110 °C). Five eruption samples were also analyzed.Osmium and Ru concentrations vary by nearly four orders of magnitude (0.0006–1.40 ppb for Os and 0.0006–2.01 ppb for Ru) and are positively correlated with MgO content. These elements behaved compatibly during crystallization, mostly likely being concentrated in trace phases (alloy or sulfide) present in olivine phenocrysts or included chromite. Iridium also correlates positively with MgO, although less strongly than Os and Ru. The somewhat poorer correlation for Ir, compared with Os and Ru, may reflect variable loss of Ir as volatile IrF6 in some of the most magnesian samples.Rhenium is negatively correlated with MgO, behaving as an incompatible trace element. Its behavior in the lava lake is complicated by apparent volatile loss of Re, as suggested by a decrease in Re concentration with time of quenching for lake samples vs. eruption samples. Platinum and Pd concentrations are negatively, albeit weakly, correlated with MgO, so these elements were modestly incompatible during crystallization of the major silicate phases. Palladium contents peaked before precipitation of immiscible sulfide liquid, however, and decline sharply in the most differentiated samples. In contrast, Pt appears to have been unaffected by sulfide precipitation. Microprobe data confirm that Pd entered the sulfide liquid before Re, and that Pt is not strongly chalcophile in this system. Occasional high Pt values in both eruption and lava lake samples suggest the presence of unevenly distributed, unidentified Pt-rich trace phases in some Kilauea Iki materials.Estimated mineral (olivine+chromite)/melt D values for Os, Ir, Ru and Pt for equilibrium crystallization for samples from ~7 to 27 wt.% MgO are 26, 8.2, 19 and 0.55, respectively. These Os, Ir and Ru estimates are somewhat higher than previous estimates for similar systems. If fractional crystallization is instead assumed, D values are much more similar.Results confirm many prior observations in other mafic systems that olivine (together with included phases) has a major effect on absolute and relative abundances of Re and the PGE. The relatively linear correlations between these elements and MgO potentially permit accurate estimation of the concentrations of these elements in the primary melts of comparable systems, especially in instances where the MgO content of the primary melt is well constrained.

Processes active in mafic magma chambers: The example of Kilauea Iki Lava Lake, Hawaii

Kilauea Iki lava lake formed in 1959 as a closed chamber of 40 million m 3 of picritic magma. Repeated drilling and sampling of the lake allows recognition of processes of magmatic differentiation, and places time restrictions on the periods when they operated. This paper focuses on evidence for the occurrence of lateral convection in the olivine-depleted layer, and constraints on the timing of this process, as documented by chemical, petrographic and thermal data on drill core from the lake. Lateral convection appears to have occurred in two distinct layers within the most olivine-poor part of the lake, created a slightly olivine-enriched septum in the center of the olivine-depleted section. A critical marker for this process is the occurrence of loose clusters of augite microphenocrysts, which are confined to the upper half of the olivine-poor zone. This process, which took place between late 1962 and mid-1964, is inferred to be double-diffusive convection. Both this convection and a process of buoyant upwelling of minimum-density liquid from deep within the lake (Helz, R.T., Kirschenbaum H. and Marinenko, J.W., 1989. Diapiric melt transfer: a quick, efficient process of igneous differentiation: Geological Society of America Bulletin, v. 101, 578–594) result from the fact that melt density in Kilauea Iki compositions decreases as olivine and augite crystallize, above the incoming of plagioclase. The resulting density vs. depth profile creates (1) a region of gravitationally stable melt at the top of the chamber (the locus of double-diffusive convection) and (2) a region of gravitationally unstable melt at the base of the melt column (the source of upwelling minimum-density melt, Helz, R.T., Kirschenbaum H. and Marinenko, J.W., 1989. Diapiric melt transfer: a quick, efficient process of igneous differentiation: Geological Society of America Bulletin, v. 101, 578–594). By contrast the variation of melt density with temperature for the 1965 Makaopuhi lava lake does not show a decrease in density as temperature decreases, so neither process should have occurred in that lava lake. Because many mafic magmas crystallize significant olivine and/or pyroxene before they begin to crystallize plagioclase, the density relations observed for Kilauea Iki, and the processes that result from them, may be relevant to crystallization in other mafic magma chambers. The results for the 1965 Makaopuhi lava lake emphasize the role of bulk composition as a critical control on magmatic processes.

Iron Isotope Fractionation During Magmatic Differentiation in Kilauea Iki Lava Lake

Magmatic differentiation helps produce the chemical and petrographic diversity of terrestrial rocks. The extent to which magmatic differentiation fractionates nonradiogenic isotopes is uncertain for some elements. We report analyses of iron isotopes in basalts from Kilauea Iki lava lake, Hawaii. The iron isotopic compositions (56Fe/54Fe) of late-stagemeltveins are 0.2 permil (per thousand) greater than values for olivine cumulates. Olivine phenocrysts are up to 1.2 per thousand lighter than those of whole rocks. These results demonstrate that iron isotopes fractionate during magmatic differentiation at both whole-rock and crystal scales. This characteristic of iron relative to the characteristics of magnesium and lithium, for which no fractionation has been found, may be related to its complex redox chemistry in magmatic systems and makes iron a potential tool for studying planetary differentiation.

Investigation of magnesium isotope fractionation during basalt differentiation: Implications for a chondritic composition of the terrestrial mantle

To investigate whether magnesium isotopes are fractionated during basalt differentiation, we have performed high-precision Mg isotopic analyses by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) on a set of well-characterized samples from Kilauea Iki lava lake, Hawaii, USA. Samples from the Kilauea Iki lava lake, produced by closed-system crystal-melt fractionation, range from olivine-rich cumulates to highly differentiated basalts with MgO content ranging from 2.37 to 26.87 wt.%. Our results demonstrate that although these basalts have diverse chemical compositions, mineralogies, crystallization temperatures and degrees of differentiation, their Mg isotopic compositions display no measurable variation within the limits of our external precision (average δ 26Mg = − 0.36 ± 0.10 and δ 25Mg = − 0.20 ± 0.07; uncertainties are 2SD). This indicates that Mg isotopic fractionation during crystal-melt fractionation at temperatures of ≥ 1055 °C is undetectable at the level of precision of the current investigation. Calculations based on our data suggest that at near-magmatic temperatures the maximum fractionation in the 26Mg/ 24Mg ratio between olivine and melt is 0.07‰. Two additional oceanic basalts, two continental basalts (BCR-1 and BCR-2), and two primitive carbonaceous chondrites (Allende and Murchison) analyzed in this study have Mg isotopic compositions similar to the Kilauea Iki lava lake samples. In contrast to a recent report [U. Wiechert, A.N. Halliday, Non-chondritic magnesium and the origins of the inner terrestrial planets, Earth and Planetary Science Letters 256 (2007) 360–371], the results presented here suggest that the Bulk Silicate Earth has a chondritic Mg isotopic composition.