Phosphorus zoning in olivine is receiving considerable attention for its capacity to preserve key information about rates and mechanisms of crystal growth. Its concentration can vary significantly over sub-micron spatial scales and form intricate, snowflake-like patterns that are generally attributed to fast crystal growth. Ostensibly similar aluminum enrichment patterns have also been observed, suggesting comparable incorporation and partitioning behavior for both elements. We perform 1-atm crystallization experiments on a primitive Kīlauea basalt to examine the formation of P and Al zoning as a function of undercooling − ΔT (− ΔT = Tliquidus − Tcrystallization) during olivine growth. After 24 h spent at Tinitial = 1290 °C (10 °C above olivine stability), charges are rapidly cooled to final temperatures Tfinal = 1220-1270 °C, corresponding to undercoolings −ΔT= 10-60 °C (with Tliquidus = 1280 °C). Compositional X-ray maps of experimental olivine reveal that only a small undercool-ing (≤ 25 °C) is required to produce the fine-scale enrichments in P and Al associated with skeletal growth. Concentration profiles indicate that despite qualitatively similar enrichment patterns in olivine, P and Al have contrasting apparent crystal/ melt mass distribution coefficients of = 0.01-1 and = 0.002-0.006. Phosphorus can be enriched by a factor > 40-fold in the same crystal, whereas Al enrichment never exceed factors of 2. Glass in the vicinity of synthetic and natural olivine is usually enriched in Al, but, within analytical uncertainty, not in P. Thus, we find no direct evidence for a compositional boundary layer enriched in P that would suffice to produce P enrichments in natural and synthetic olivine. Numerical models combining growth and diffusion resolve the conditions at which Al-rich boundary layers produce the observed enrichment patterns in olivine. In contrast, the same models fail to reproduce the observed P enrichments, consistent with our observation that P-rich boundary layers are insignificant. If instead, P olivine/melt partitioning is made to depend on growth rate, models adequately reproduce our observations of 40-fold enrichment without boundary layer formation. We surmise that near-partitionless behavior ( close to 1) of P is related to the olivine lattice being perhaps less stiff in accommodating P during rapid crystallization, and/or to enhanced formation of vacancy defects during fast growth. Our results confirm that P is a robust marker of initial rapid growth, but reveal that the undercooling necessary to induce these enrichments is not particularly large. The near-ubiquitous process of magma mixing under volcanoes, for instance, is likely sufficient to induce low-tomoderate degrees of undercooling required for skeletal growth.

Abstract-Dynamic crystallization experiments were performed on a liquid having the bulk composition of olivine-phyric shergottite Yamato 980459, to constrain the igneous thermal history of this meteorite. Key characteristics of the meteorite's mineralogy and texture, including several morphologically distinct olivine and pyroxene crystal populations and a glassy mesostasis devoid of plagioclase, were replicated upon cooling from 1435 to 909°C at 1 atmosphere under reducing conditions. Three sequential cooling ramps are required to produce synthetic samples with textures and compositions matching Yamato 980459. Olivine phenocrysts formed at <1°C h À1 , presumably at depth in the Martian crust. Pyroxene phenocrysts formed mainly at~10°C h À1 , consistent with crystallization within a lava flow at depths of 25-45 cm. Increased cooling rate (~100°C h À1 ) in a third stage suppressed the formation of plagioclase and produced groundmass crystals, consistent with crystallization at lava flow depths of 5-7 cm. Although Y 980459 is unique among Martian meteorites (i.e., preserving a primary glassy mesostasis), its emplacement did not require unique physical conditions. Rather, the second and third cooling stages may reflect cooling within the core of a p ahoehoe-like flow and subsequent breakout on the surface of Mars.

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