Multi-stage mixing and mingling of boninitic melts captured by multielement LA ICP MS single pulse imaging

1Teledyne Photon Machines, Bozeman, MT 59715, USA *Ciprian.stremtan@Teledyne.com2University of South Florida, Tampa, FL 33620, USA3Utah State university, Logan, UT 84322-45054TOFWERK AG, Thun, CH-3600, Switzerland

IntroductionThe quality of LA ICP TOF MS generated elemental distribution maps is heavily dependent on the effects of aerosol dispersion in the ablation chamber and sample transport system. Long pulse

response duration, gravitational settling of the aerosol particles, turbulent gas flows, coupled with unsuitable lasing and data acquisition parameters will likely create imaging artefacts which can blur or even obscure the features that are naturally present in the samples. The use of rapid-response technology enables the acquisition of full pulse signals of less than 3ms (FW0.1M). When coupled to a TOF mass spectrometer, such technologies allow images to be generated at higher laser repetition rate and scanning speed without compromising data quality. Due to the increased mass flux, sensitivity is also increased, allowing for a micron-scale lateral image resolution to be achieved using single pulse analysis mode. The analytical setup used for this contribution comprises a Teledyne Photon Machines Analyte G2 excimer laser equipped with a fast washout Cobalt cell, coupled to a TOFWERK icpTOF 2R mass spectrometer.

Sample U1439C 25R2 18/19 is a boninite lava from the Izu-Bonin forearc, which was recovered during IODP Expedition 352. While boninites are typically of interest because of their unique mode of formation (fluxed melting of highly depleted mantle [1]) and their tectonic significance (forearc rift-related magmas, erupted in this case within the first 1.5 Myr after the initiation of IBM subduction [2]), the sample also shows evidence for complex mineralogical zoning, suggestive of multi-stage mixing and mingling of boninitic melts as they rose through the crust. Multi-element imaging via LA ICP TOF MS document this open-system history, showing clear zoning of Fe, Mn and especially Ni in Opx phenocrysts, reflecting contact with both more and less primitive melts. As well, the element maps document the evolution of vesicle-filling secondary assemblages, starting with vesicle-lining zeolites enriched in Na, K, and Rb, and followed by Sr-rich carbonate fluids that also mobilize Mn, Y and light rare earth elements.

Ciprian STREMTAN1*, Jeff Ryan2, Jesse Scholpp3,Martin Rittner4, John Shervais3

Analytical Setup

(a) (d)

Laser ablation operating conditionsLaser type Analyte G2 (CETAC)Spot size 5 µmRepetition rate 100 HzAblation mode RasterFluence 3 Jcm-2

Dosage 1

icpTOF operating conditionsPlasma Power 1380 WSampling depth 4.6 mmHe gas flow rate 0.34 LPMNeb gas flow rate 0.85 LPMm/Q attenuated 28, 30, 40, 80Tof extraction time 46 µs

Number of integrated TOF extractions 426Data point per laser pulse 1 mass spectrumAerosol wash in delay 100 ms

Analyte G2 excimer laser Cobalt Cell icpTOF

Sample Description Results A single large phenocryst with Cr-poor core and Cr-rich mantle, and a wide Cr-poor rim. Smaller crystals may show either two zones (Cr-rich core, Cr-poor rim) or none (all low Cr). These are classic hallmarks of magma mixing —large early-formed crystals from Cr-poor melt mix with primitive, Cr-rich melt. The rapid change to a wide Cr-poor rim indicates mixing back into another Cr-poor magma (normal zoning would be more gradual). The Ni map mimics the Cr zones, while Fe mirrors them.

The smaller crystals with Cr-rich cores formed directly from the Cr-rich melt after mixing, while the small crystals with no zoning formed after the second mixing event.

Results

Olivine phenocrysts with thin rims formed by rapid disequilibrium crystallization during quenching. Iron, Ni, Mn and Pb all enriched in rims. Olivine phenocrysts are distinguished from pyroxene microlites by having higher Fe and Ni in cores than the pyroxene.

Calcite filled vesicles in boninite lava. Sr and Y document asymmetric growth of concentrically zoned calcite. Y is concentrated in early growth stages, and disappears in later growth stages. This likely indicates a change from early hydrothermal precipitation to later deposition from cold seawater.

[1] Pearce, JA et al. (1992): In: Fryer, P; Pearce, JA; Stokking, LB; et al. (eds.), Proceedings of the Ocean Drilling Program, Scientific Results, College Station, TX (Ocean Drilling Program), 125, 623-659[2] Reagan et al (2019). Earth and Planetary Science Letters, 506, 250-259

Sample U1439C 25R2 18/19 is a 50+ Ma old boninite lava recovered during IODP Expedition 352 in the Izu-Bonin forearc. Boninites reflect high T° fluid-fluxed melting of a very depleted mantle, and normally present a phenocryst assemblage of enstatite ± olivine, with late-stage pigeonite CPX and uncommon, early formed Cr spinels.The phenocrysts and even some of the late-stage clinopyroxene crystals in U1439C 25R2 18/19 show prominent normal and oscillatory zoning with extreme compositional changes – from entatite to augite – along with anomalously elevated Al and Ti in pyroxene rims indicating open-system crystallization and mingling/mixing of highly evolved and primitive boninite melts during their evolution and eruption. Sector zoning evident in sample reflects preferred compositional growth in different crystallographic sectors of the pyroxene.