Jo-Anne Wartho

Direct measurement of Ar diffusion profiles in a gem-quality Madagascar K-feldspar using the ultra-violet laser ablation microprobe (UVLAMP)

Abstract Controversy surrounding the mechanisms and controls on argon diffusion in K-feldspar has led us to undertake direct diffusion measurements on a crystal with simple microtextures, over a range of temperatures. Measurements of argon diffusion profiles in a gem-quality iron-rich orthoclase heated in a cold seal apparatus, have been undertaken in situ using an ultra-violet laser ablation microprobe (UVLAMP) technique. The results agree very closely with the previously determined bulk values for Benson Mines orthoclase (activation energy (E)=43.8±1 kcal mol−1) and vacuum furnace cycle-heating studies of K-feldspars (E=46±6 kcal mol−1). However, instead of defining a single activation energy (E) and diffusion coefficient (Do), the data yield two sets of parameters: a low-temperature (550–720°C) array with an E of 47.2±2.5 kcal mol−1 (198.2±10.5 kJ mol−1) and a Do of 0.0374+0.1123−0.0281 cm2 s−1, and a high-temperature (725–1019°C) array with an E of 63.8±3.4 kcal mol−1 (268.0±14.3 kJ mol−1) and a Do of 55.0+225.5−44.2 cm2 s−1. The new results closely reproduce two sets of apparent activation energies previously measured in cycle-heating studies of Madagascar K-feldspar (40±3 and 57±3 kcal mol−1). Previous interpretations of the two arrays have included multiple domains with variable activation energies and fast track diffusion. However, the UV depth profile analyses indicate simple diffusion to the grain surface and importantly, diffusion radii calculated by combining the UVLAMP and cycle-heating data, are the same as the physical grain sizes used in the experiments, around 1 mm. Vacuum furnace stepped heating experiments on slowly cooled K-feldspars have been interpreted as showing diffusion radii of around 6 μm and indicate complex populations of sub-grains. This study indicates that Madagascar K-feldspar and thus probably all gem-quality K-feldspars act as single diffusion domains and that short-circuit (or pipe) diffusion was not an important loss mechanism. An apparent diffusion compensation relationship in the stepped heating data for Madagascar K-feldspar implies that similar relationships seen in other K-feldspars are a result of a range of diffusion mechanisms.

Ar and K partitioning between clinopyroxene and silicate melt to 8 GPa

The relative incompatibility of Ar and K are fundamental parameters in understanding the degassing history of the mantle. Clinopyroxene is the main host for K in most of the upper mantle, playing an important role in controlling the K/Ar ratio of residual mantle and the subsequent time-integrated evolution of 40Ar/36Ar ratios. Clinopyroxene also contributes to the bulk Ar partition coefficient that controls the Ar degassing rate during mantle melting. The partitioning of Ar and K between clinopyroxene and quenched silicate melt has been experimentally determined from 1 to 8 GPa for the bulk compositions Ab80Di20 (80 mol% albite-20 mol% diopside) and Ab20Di80 with an ultraviolet laser ablation microprobe (UVLAMP) technique for Ar analysis and the ion microprobe for K. Data for Kr (UVLAMP) and Rb (ion probe) have also been determined to evaluate the role of crystal lattice sites in controlling partitioning. By excluding crystal analyses that show evidence of glass contamination, we find relatively constant Ar partition coefficients (DAr) of 2.6 × 10−4 to 3.9 × 10−4 for the Ab80Di20 system at pressures from 2 to 8 GPa. In the Ab20Di80 system, DAr shows similar low values of 7.0 × 10−5 and 3.0 × 10−4 at 1 to 3 GPa. All these values are several orders of magnitude lower than previous measurements on separated crystal-glass pairs. DK is 10 to 50 times greater than DRb for all experiments, and both elements follow parallel trends with increasing pressure, although these trends are significantly different in each system studied. The DK values for clinopyroxene are at least an order of magnitude greater than DAr under all conditions investigated here, but DAr appears to show more consistent behavior between the two systems than K or Rb. The partitioning behavior of K and Rb can be explained in terms of combined pressure, temperature, and crystal chemistry effects that result in changes for the size of the clinopyroxene M2 site. In the Ab20Di80 system, where clinopyroxene is diopside rich at all pressures, DK and DRb increase with pressure (and temperature) in an analogous fashion to the well-documented behavior of Na. For the Ab80Di20 system, the jadeite content of the clinopyroxene increases from 22 to 75 mol% with pressure resulting in a contraction of the M2 site. This has the effect of discriminating against the large K+ and Rb+ ions, thereby countering the effect of increasing pressure. As a consequence DK and DRb do not increase with pressure in this system. In contrast to the alkalis (Na, K, and Rb), DKr values are similar to DAr despite a large difference in atomic radius. This lack of discrimination (and the constant DAr over a range of crystal compositions) is also consistent with incorporation of these heavier noble gases at crystal lattice sites and a predicted consequence of their neutrality or “zero charge.” Combined with published DAr values for olivine, our results confirm that magma generation is an efficient mechanism for the removal of Ar from the uppermost 200 km of the mantle, and that K/Ar ratios in the residuum are controlled by the amount of clinopyroxene. Generally, Ar is more compatible than K during mantle melting because DAr for olivine is similar to DK for clinopyroxene. As a result, residual mantle that has experienced variable amounts of melt extraction may show considerable variability in time-integrated 36Ar/40Ar.

40Ar/39Ar ages in mantle xenolith phlogopites: determining the ages of multiple lithospheric mantle events and diatreme ascent rates in southern Africa and Malaita, Solomon Islands

Abstract Kimberlites are extraordinary natural phenomena, ascending through the Earth’s lithosphere, entraining xenoliths, to erupt at the surface within hours to days of their inception deep within the lithospheric mantle. With the realization that some Ar/Ar phlogopite grain core ages may be indicative of geological events, we have undertaken high spatial resolution Ar/Ar dating of phlogopites in xenoliths and megacrysts from Kimberley, Monastery and Letseng in southern Africa, and Malaita, in the Solomon Islands, to est whether other mantle phlogopite cores may yield meaningful ages. Modelling of Ar diffusive loss profiles from phlogopite grain boundaries to cores provides information on both the eruption age and the duration of outgassing within the kimberlite magma, and hence yields estimates on diatreme ascent rates. The ascent durations are very similar for all of the southern African pipes studied, yielding durations of 0.9–6.9 days, assuming an average kimberlite magma temperature of 1000 °C. These can be compared to estimates from phlogopite xenoliths from Siberian diamond-bearing kimberlites yielding ascent durations of 2–15 hours (assuming the same magma temperature).

Constraints on the tectonic and landscape evolution of the Bhutan Himalaya from thermochronometry

The observed geomorphology and calculated thermal histories of the Bhutan Himalaya provide an excellent platform to test ideas regarding the influence of tectonics and climate on the evolution of a convergentmountain range. However, little consensus has been reached regarding the late Cenozoic history of the Bhutan Himalaya. Some researchers have argued that observed geologic relationships show slowing deformation rates, such that the range is decaying from a geomorphic perspective, while others see the range as growing and steepening. We suggest that a better understanding is possible through the integrated interpretation of geomorphic and thermochronometric data from the comparison of predictions from models of landscape evolution and thermal-kinematic models of orogenic systems. New thermochronometric data throughout Bhutan aremost consistent with a significant decrease in erosion rates, from2 to 3 km/Ma down to 0.1–0.3 km/Ma, around 6–4Ma. We interpret this pattern as a decrease in rock uplift rates due to the activation of contractional structures of the Shillong Plateau, an uplifted region approximately 100 km south of Bhutan. However, low-relief, fluvial landscapes throughout the Bhutanese hinterland record a late pulse of surface uplift likely due to a recent increase in rock uplift rates. Constraints from our youngest thermochronometers suggest that this increase in rock uplift and surface uplift occurred within the last 1.75Ma. These results imply that the dynamics of the Bhutan Himalaya and Shillong Plateau have been linked during the late Cenozoic, with structural elements of both regions active in variable ways and times over that interval.

Magma flow regimes in sills deduced from Ar isotope systematics of host rocks

The best place to seek evidence of the style of past magma flow through a conduit is in the country rock. Heat flow has been studied in country rock adjacent to two Tertiary dolerite sills intruding the Caledonian schists and quartzites, on the Isle of Mull, Scotland. Radiogenic 40Ar loss within mica grains in the thermal aureoles of the intrusions has been measured at high spatial resolution using the Ultra-Violet Laser Ablation Micro-Probe, to discriminate between a history of prolonged magma flow, a history of conductive cooling following laminar flow, and instantaneous emplacement of the intrusions. The 40Ar/39Ar mica data and thermal modeling suggest that a prolonged period of magma flow of 3–5 months resulted in extensive argon loss from the micas, country rock melting, and mineral breakdown adjacent to a 6-m sill. These features were absent from the wall rocks of a smaller 2.7-m-thick sill, which exhibited even less argon loss than might have been predicted for an instantaneous intrusion. If the heat loss from the 6-m sill observed in one locality had been repeated along its length, it would have formed an important magma conduit to the Mull volcano, but dolerite is not a common flow composition on Mull. If on the other hand, the heat loss from the sill varies along strike, it constitutes strong evidence for channelling and heterogeneous flow within the sill.

Long‐term evolution of an Oligocene/Miocene maar lake from Otago, New Zealand

Foulden Maar is a highly resolved maar lake deposit from the South Island of New Zealand comprising laminated diatomite punctuated by numerous diatomaceous turbidites. Basaltic clasts found in debris flow deposits near the base of the cored sedimentary sequence yielded two new 40Ar/39Ar dates of 24.51 ± 0.24 and 23.38 ± 0.24 Ma (2σ). The younger date agrees within error with a previously published 40Ar/39Ar date of 23.17 ± 0.19 Ma from a basaltic dyke adjacent to the maar crater. The diatomite is inferred to have been deposited over several tens of thousands of years in the latest Oligocene/earliest Miocene, and may have been coeval with the period of rapid glaciation and subsequent deglaciation of Antarctica known as the Mi-1 event. Sediment magnetic properties and SEM measurements indicate that the magnetic signal is dominated by pseudo-single domain pyrrhotite. The most likely source of detrital pyrrhotite is schist country rock fragments from the inferred tephra ring created by the phreatomagmatic eruption that formed the maar. Variations in magnetic mineral concentration indicate a decrease in erosional input throughout the depositional period, suggesting long-term (tens of thousands of years) environmental change in New Zealand in the latest Oligocene/earliest Miocene.

Estimates of Ar diffusion and solubility in leucite and nepheline: Electron microprobe imaging of Ar distribution in a mineral

Abstract Leucite is unique among minerals that have been exploited for K-Ar and Ar-Ar dating, in that it exhibits a major phase change at 645-665 °C, across which Ar diffusion and solubility can be studied. In addition, well-developed twinning occurs only in the low temperature form, offering further opportunity to examine the effects of crystallographic change upon Ar diffusion. Nepheline was studied to compare the effect of its 1-dimensional c-axis oriented lattice channels with the 3-dimensional channels of leucite. The amounts of Ar introduced into leucite were far higher than those observed in feldspars, allowing its analysis by electron microprobe spot traverses and X-ray maps. This has provided the first high spatial resolution 2-dimensional study of Ar distribution in a K-bearing mineral. Extreme changes in Ar solubility were observed across the leucite phase transition, with Ar solubilities jumping from ~70 ppm (at 1 kbar) in the tetragonal (low-temperature) form to ~750 ppm (at 1 kbar) in the cubic (high-temperature) form. Argon penetration profiles were complex and estimates of the diffusion rates show that they are more rapid than in K-feldspar. In addition, spikes of high Ar concentration were observed in both forms, suggesting extended defects or micro-inclusions formed argon traps in the structure. No concentration changes could be correlated to leucite twin planes, suggesting that twin planes did not act as fast pathways for Ar movement. Nepheline yielded a much lower Ar solubility of 0.15-0.31 ppm at 1 kbar.

Ar diffusion and solubility measurements in plagioclases using the ultra-violet laser depth-profiling technique

Abstract We describe the first direct measurements of Ar diffusion and solubility in plagioclases using ultra-violet (UV) laser ablation depth-profiling and noble gas mass spectrometer analyses of experimentally treated (599–1000 °C, 50–200 MPa of Ar) crystal fragments of labradorite and oligoclase. Labradorite 40Ar gain diffusion profiles were measured, yielding an activation energy of 26.72±4.58 kcal mol−1 (118.0±19.16 kJ mol−1) and a frequency factor of 9.77×10−9 (+8.79×10−8, −8.79×10−9) cm2 s−1 (95% confidence). The Ar solubility in labradorite was measured yielding a value of <0.2 ppb bar−1, which is similar to or lower than many rock forming minerals. The labradorite diffusion parameters indicate Ar closure temperatures of 211 °C for a spherical diffusion geometry, and 243 °C for a planar diffusion geometry (for 100 µm-diameter grains, with cooling rates of 10 °C Ma−1). The data indicate that labradorite is less Ar retentive than K-feldspar at low temperatures, but more Ar retentive than K-feldspar at high temperatures, corroborating previous work on plagioclase. The relatively slow Ar diffusion rates in labradorite at magmatic temperatures may explain the common observation of older ages in large plagioclase grains in acidic volcanic systems. Supplementary material: Details of the UV laser depth profiles obtained from the labradorite and oligoclase samples used in this study are available at www.geolsoc.org.uk/SUP18608.