A double-spike method for K-Ar measurement: a technique for high precision in-situ dating on Mars and other planetary surfaces K.A. Farley, J.A. Hurowitz, P.D. Asimow, N.S. Jacobson, J.A. Cartwright PII: DOI: Reference: To appear in: Received Date: Accepted Date: S0016-7037(13)00095-1 http://dx.doi.org/10.1016/j.gca.2013.02.010 GCA 8158 Geochimica et Cosmochimica Acta 4 December 2012 5 February 2013
Please cite this article as: Farley, K.A., Hurowitz, J.A., Asimow, P.D., Jacobson, N.S., Cartwright, J.A., A doublespike method for K-Ar measurement: a technique for high precision in-situ dating on Mars and other planetary surfaces, Geochimica et Cosmochimica Acta (2013), doi: http://dx.doi.org/10.1016/j.gca.2013.02.010
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A double-spike method for K-Ar measurement: a technique for high precision in-situ dating on Mars and other planetary surfaces K.A. Farleya, J.A. Hurowitzb, P.D. Asimowa, N.S. Jacobsonc and J.A. Cartwrighta
a b c
Division of Geological and Planetary Sciences, Caltech, Pasadena, California 91125 USA Jet Propulsion Laboratory, Caltech, Pasadena, California 91109 USA NASA Glenn Research Center, Cleveland, Ohio 44135 USA
Resubmitted to Geochimica et Cosmochimica Acta February 1, 2013
A new method for K-Ar dating using a double isotope dilution technique is proposed and demonstrated. The method is designed to eliminate known difficulties facing in-situ dating on planetary surfaces, especially instrument complexity and power availability. It may also have applicability in some terrestrial dating applications. Key to the method is the use of a solid tracer spike enriched in both 39Ar and 41K. When mixed with lithium borate flux in a Knudsen effusion cell, this tracer spike and a sample to be dated can be successfully fused and degassed of Ar at < 1000oC. The evolved 40Ar*/39Ar ratio can be measured to high precision using noble gas mass spectrometry. After argon measurement the sample melt is heated to a slightly higher temperature (~1030oC) to volatilize potassium, and the evolved 39K/41K ratio measured by Knudsen effusion mass spectrometry. Combined with the known composition of the tracer spike, these two ratios define the K-Ar age using a single sample aliquot and without the need for extreme
27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42
temperature or a mass determination. In principle the method can be implemented using a single mass spectrometer.
Experiments indicate that quantitative extraction of argon from a basalt sample occurs at a sufficiently low temperature that potassium loss in this step is unimportant. Similarly, potassium isotope ratios measured in the Knudsen apparatus indicate good sample-spike equilibration and acceptably small isotopic fractionation. When applied to a flood basalt from the Viluy Traps, Siberia, a K-Ar age of 351 ± 19 Ma was obtained, a result within 1% of the independently known age. For practical reasons this measurement was made on two separate mass spectrometers, but a scheme for combining the measurements in a single analytical instrument is described. Because both parent and daughter are determined by isotope dilution, the precision on K-Ar ages obtained by the double isotope dilution method should routinely approach that of a pair of isotope ratio determinations, likely better than ± 5%.
43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 Absolute ages are critical for deciphering the timing, rates, and in many cases, the identity of processes that shape planetary surfaces. As a consequence the development of accurate surface chronologies is an important step in elucidating the evolution of terrestrial bodies in the Solar System. This is especially true for Mars, which carries a long and rich geologic record documented with spectacular resolution by numerous orbiting and landed missions (e.g., Kieffer et al., 1992; Bell, 2008; Carr and Head, 2010). For example, surface morphology, mineralogy, and lithology provide evidence for dramatic climate change on Mars, with obvious implications for habitability (e.g., Carr, 1996; Bibring et al., 2006; Murchie et al., 2009; Ehlmann et al., 2011). However in the absence of sample return or in-situ dating measurements, we have no absolute markers that can be used to calibrate the planet‟s increasingly well-documented surface chronology. A technique to accurately measure ages from a few select locations within the established relative stratigraphy of Mars would be transformative, enabling placement of direct quantitative constraints on the timing and rates of impact, volcanic, sedimentary, climatic, and aqueous processes on the martian surface. This work proposes and implements a new methodology with the potential to provide such age determinations. The method is capable of accuracy and precision of ages of better than 5%, and is amenable to space-flight application. 1. INTRODUCTION
. Since the present work involves the K-Ar method. K-Ar dating is based on the branched decay of 40K to 40Ar.3/2. Cohen.65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87
Impact craters are a dominant feature on Mars. Hauber et al.7 Ga).. precision is not equivalent to accuracy.g.. and one approach for establishing absolute ages on the surface is through statistical methods calibrated to radiometric ages and abundances of craters on the Moon. Swindle et al. exceeding a factor of two in portions of martian geologic history where constraints on crater flux are particularly poor. uncertainties in absolute ages derived from crater counting are fairly large. 2001).
. 2003. 2012) methods.57-3. 2012. 2001). 2001. These issues will continue to cast doubt on dates obtained by the method until independent age tie-points are provided for Mars. While progress has been made improving the precision of such ages (e.9 Ga) and Amazonian (3. With a 40K half-life of 1.7-3. and (2) Compared to the moon. This technique was used to date distinct regions of Mars. Hesperian (3. leading to the identification of three epochs: Noachian (4. an estimate of the Mars/Moon cratering rate ratio” (Hartmann and Neukum. most notably based on the rubidium-strontium (Anderson et al. we focus exclusively on this technique. 2012) and potassium-argon (Swindle. Talboys et al. continually removing the record of craters and therefore causing bias towards younger ages. 2011).9 Ga – present) (Hartmann and Neukum...
A number of radiometric dating techniques have been and continue to be investigated for in-situ application on other planets.249 Gyr (Renne et al. Cho et al.3/2. As a result. 2009. implicitly or explicitly... Mars is geologically active. There are two inescapable issues regarding the application of crater counting techniques to Mars: (1) “Any estimate of the martian absolute chronology involves.
The K-Ar method is now most often implemented using the
Ar-39Ar variant.. McDougall and Harrison. K-Ar dating was among the earliest radiometric chronometers to be developed.88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110
2010). 2009). In addition. and its application to basalts was critical to the confirmation of plate tectonics and the development of the magnetic polarity timescale. the chronometer is applicable across the entire span of geologic time. the amount of power required to heat the sample to fusion (often >1200oC) may be prohibitive on a spacecraft... in part because the 40Ar-39Ar method requires a single mass
spectrometer and analysis of a single sample aliquot (e.g. there are many techniques available for determining the abundance of the parent isotope.g. both of which have been undertaken on the surface of Mars (Gellert et al. This creates two important complications. These include x-ray spectroscopy and laser-induced breakdown spectroscopy.
The development of the conventional K-Ar method early in the history of isotope geochemistry arose from several factors that also make it attractive for in-situ dating. 2012). First. Such levels have been achieved on Mars (Mahaffy et al. 2012).. Ar is released from an aliquot by vacuum fusion. Maurice et al.
The K-Ar method has several notable drawbacks for in-situ dating (e. Because potassium is typically a major element in potential dating targets (especially basalts). 1988). the effects of ingrowth on the abundance of 40Ar tend to be very large and as a consequence relatively low Ar sensitivity and percent level precision on Ar isotopic ratios are adequate for many dating applications.. Bogard. 2006. In the conventional implementation of the method.
1. and provides a straightforward path towards implementation of a high precision in-situ geochronology capability on planetary surfaces.1.
The method proposed here requires neither high fusion temperatures. It permits potassium and argon measurement on a single sample aliquot using a single analytical instrument. nor a mass measurement to relate potassium and argon to each other. The technique takes advantage of flux digestion of the target sample to surmount the issue of high fusion temperatures. Bogard (2009) describes an additional complication involving the interpretation (rather than the measurement) of K-Ar ages. Thus a conventional approach requires the complexity of at least three separate analytical instruments.111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133
Second. It employs double isotope dilution using a tracer containing known quantities of the rare isotopes 41K and 39Ar to eliminate the need for a mass determination and to permit the age to be calculated exclusively from isotope ratios. The Double Isotope Dilution Scheme
The age equation for the K-Ar system is:
. combining a K concentration with the Ar amount obtained by fusion requires a technique to accurately estimate the aliquot mass. We suggest this methodology is sufficiently simple. practical. an issue we consider in the discussion section. and precise to be useful in terrestrial laboratories.
our method requires enriched 41K and 39Ar tracer spike in a single material. To accomplish this goal. 40Ar* is the 40Ar abundance attributable to in-situ radioactive decay. production of Ar isotopes
from these elements is negligible. we consider instead the use of synthetic
Ar. and 40K and 40Ar* are abundances in atomic units. For isotope dilution 40K measurements. e is the decay constant for the electron capture decay mode that produces 40Ar.134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155
where is the total 40K decay constant. The glass was then neutron irradiated to produce 39Ar from the small amount of
K present. 38Ar. Because the glass is essentially free of Cl and Ca. 40Ar/39Ar ratios <<1% can be obtained without significant production of either 36Ar or 38Ar (McDougall and Harrison. Depending on reactor conditions. with ~7 wt% K2O consisting of highly enriched 41K (see next section for details). Since 38Ar is a useful indicator of cosmic ray exposure of potentially analyzed materials. t is the K-Ar age. a sample to be dated is combined with an aliquot of the spike glass. There are three stable isotopes of argon (36Ar . 1988).73%).
As described below. 40K (0.0117%). and 40Ar) and isotope dilution is usually done using 38Ar as a tracer. 41K of high isotopic purity (>99%) is readily available.3%). Thus a K-Ar age determination requires measurement of the 40Ar*/40K ratio. and 41K (6. For the double isotope dilution technique. This radioactive isotope has a half-life of 269 years and is routinely produced by
neutron irradiation of 39K-bearing substances. hereafter referred to as the spike glass.
Potassium consists of three isotopes: 39K (93. we prepared a synthetic silicate. and fused to release and measure
and spike amounts. Here we are assuming that there is no cosmogenic 36Ar in the sample.156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177
argon and potassium isotopes. in a system with substantial cosmic ray exposure 38Ar could be used to quantify and correct for cosmogenic 36Ar. air-derived.
Combining equations 2-4 yields:
. such that atmosphere is the only source of this isotope (Equation 3). air. The 40Ar*/40K ratio required for an age measurement is determined as follows (definitions of variables are provided in Table 1). Equation 4 indicates that all 39Ar is spike-derived.
First. for Ar:
(2) (3) (4)
Where subscripts m. but martian atmosphere in the case of a Mars rover application) and some is reactor-produced in the spike. and spk refer to measured. Equation 2 is the mass balance for 40Ar and indicates that some of the 40Ar is derived from “contamination” with atmospheric argon (in the present case from terrestrial air.
. 1995). lunar rocks. and supports the generality of the terrestrial isotope composition we assume. and chondrites. rm= (39K/41K)m and rnat = (39K/41K)nat yields:
. Work on many different types of samples.178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198 199 200
Where Rm is the measured 40Ar/39Ar ratio of the sample-spike mixture. confirms extremely limited (<1%) isotopic variability of potassium in the solar system (Humayun and Clayton. (40Ar/36Ar ) air is the atmospheric Ar isotope ratio. including martian meteorites.
Combining equations 6-8 and defining the additional ratios rspk= (39K/41K)spk. Equations 6 and 7 simply reflect mass balance. Equation 8 states that the isotopic composition of the unknown sample is that of natural (terrestrial) potassium (r40= (40K/39K)nat) and is useful because it permits measurement of the parent isotope via the most abundant isotope of potassium.
In the case of potassium:
(6) (7) (8)
Where u refers to the unknown sample and the remaining subscripts are as defined above. and Rspk is the known 40Ar/39Ar ratio of the spike glass.
Combining equation 11 with the age equation (1) gives: (11) As written. especially the efficiency with which 39K is transmuted to 39Ar in the nuclear reactor. Equation 10 can be rewritten:
. A similar approach could be used to eliminate the need to directly measure the spike ratio (39Ar/41K)spk. one of 39Ar and one of 41K. can eliminate this requirement. An alternative approach. It is common practice in
Note that equation 10 shows that the K-Ar age can be computed directly from measured isotopic ratios without knowledge of the mass of the sample or of the spike glass. equation 10 effectively requires two concentration determinations be made on the spike glass to obtain (39Ar/41K)spk. This works because the ratio (39Ar/41K)spk is known independently and is fixed.
Ar-39Ar geochronology to use an age standard to eliminate variables that are difficult to
constrain independently.201 202 203
Combining equations 5 and 9 yields the ratio from which the K-Ar age is determined:
204 205 206 207 208 209 210 211 212 213 214 215 216 217 218 219 220 221 222 10 Where f(sample) is a function of measured quantities on a sample as well as known properties of the isotopic composition of K and Ar (compare with equation 10 for exact definition of f(sample)). not implemented here.
we can define the isotope dilution “calibration parameter”.
A particular attraction to the method outlined above is that. IMPLEMENTATION And thus:
By analogy to the 40Ar-39Ar approach. a single mass spectrometer can be used for the entire age determination. JID. Analyzing an age standard with known age tstd and rearranging equation 12 yields:
This is the age equation for the double isotope dilution method using an age standard calibration. Further work is necessary to evaluate the merits of this age-standard approach relative to standard laboratory measurements of the spike composition.all required measurements are isotopic ratios. Using this form would eliminate the need to determine absolute concentrations even on the spike glass . The method can be
. by suitable preparation. that combines the first two terms in the natural logarithm.223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 2.
~965oC. The flux serves to lower the melting point of the system to ~850oC. we use ~10 mg of sample and ~150 µg of spike glass. Indeed even with the flux. it is loaded into a vacuum chamber. or both. and furthermore. Higher bake-out temperatures are desirable to reduce atmospheric argon levels. it enhances the likelihood of equilibration of spike and sample isotopes (especially of potassium) during heating. Both sample and spike glass are introduced into a Knudsen cell a small Mo container with a carefully machined orifice in the lid (Figure 1). After a few hours of bake-out the vacuum chamber is isolated from the pump. In this step. we remain concerned by this possibility. Therefore as described below we undertook experiments to assess the degree of spike-sample equilibration. and the sample heated to a temperature at which the sample is readily digested by the molten flux. Incomplete equilibration of isotopes could lead to inaccurate bulk isotopic ratio measurements. This causes argon to be degassed into the chamber from both the sample and the spike glass. The weights of spike glass and sample need not be measured. the objective is to
. though as in any isotope dilution method the relative amounts of spike and sample isotopes need to provide a measurable contrast with natural isotopic compositions of the elements being analyzed.245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267
implemented as follows. For our current implementation. and is of special concern because spike and sample are carried in different solid materials. evacuated to high vacuum. but run the risk of Ar loss from sample. spike. When degassing is complete the heating is terminated and the argon purified and measured by mass spectrometry.
Once the cell has been prepared. and baked at ~100oC to remove adsorbed gases. The crucible is preloaded with ~150 mg of degassed 50:50 lithium metaborate: lithium tetraborate (hereafter “lithium borate”).
the crucible is heated to a higher temperature (~1030oC) to intentionally volatilize potassium from the melt. so we combined two separate instruments to demonstrate the concept and to evaluate some of the assumptions that underlie the technique. In the next step. the sample is outgassed in the Knudsen cell and argon analyzed on a conventional noble gas mass spectrometer. The purpose of the
experimental work described in the next section is to evaluate the following assumptions: 1) argon can be quantitatively degassed from spike and sample at a temperature low enough that neither bulk potassium loss nor extensive mass fractionation preclude accurate potassium isotope ratio determination.. The volatilized potassium is also analyzed by mass spectrometry. 2005) for potassium analysis. In the first stage of our current method.
There are several fundamental requirements for this methodology to accurately yield the
Ar*/40K ratio from which the sample‟s K-Ar age is computed. We discuss ways to combine these two steps in a single instrument in the final section.268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290
achieve complete extraction of argon with minimal volatilization loss of potassium. Next the cell is retrieved from the vacuum furnace and transferred (without additional processing) into a Knudsen-effusion mass spectrometer (Drowart et al. 2) 39K/41K ratios can be accurately measured by Knudsen effusion mass spectrometry on the residue remaining after argon
. These two isotope dilution measurements are sufficient to define the sample K-Ar age (equation 10).
At this stage of method development we do not have a single mass spectrometer configured to make both argon and potassium measurements.
1. For practical reasons we chose an alkali-rich aluminosilicate glass composition. and as long as the potassium is isotopically uniform. Preparation and characterization of the spike glass
The spike glass must be a homogeneous solid phase isotopically enriched in both 39Ar and 41K. The glass must retain Ar during handling and bake-out. The spike batch described
. the following synthesis method successfully incorporates the K into a silicate glass while effectively removing the chlorine.
3. and must readily dissolve in the lithium borate flux. in known relative proportions. 3) equilibration between spike and sample isotopes of both argon and potassium is adequate to accurately characterize the isotopic composition of the system.
Synthesis: The preparation method of the spike glass was dictated by the availability of
K only in the form of KCl. By neutron irradiation we were able to ensure a homogenous 39Ar/39K ratio in the glass. METHODS
3.291 292 293 294 295 296 297 298 299 300 301 302 303 304 305 306 307 308 309 310 311 312
extraction. this ensures a uniform 39Ar/41K ratio. even in the presence of competing effusing species of lithium and boron from the flux. which would transmute
to undesirable isotopes of argon during neutron irradiation. we determined the double isotope dilution K-Ar age of a basalt of independently known age. As a final test to see whether the method can yield accurate K-Ar ages and to evaluate likely sources of uncertainty.
the ingredients were not mixed or ground at this stage. 75 mg of crushed albite glass were placed in an open Pd76Au24 alloy cup (3 mm inner diameter.6 bar. To this was added 25 mg of fine grains of 41KCl (99% isotopic purity) obtained from the isotope synthesis facility at Oak Ridge National Laboratory. This oxygen fugacity yields the maximum available fH2O in the gas stream. measured with an yttria-stabilized zirconia oxygen sensor (see Balta et al. The sample was held at these conditions for 48 hours and quenched by withdrawing the
. The furnace was prepared at 1150 °C (above the liquidus of albite) with a streaming gas-mix of H2 and CO2 that yielded an fO2 one half of a log unit above the iron-wüstite buffer (IW+0. approximately 0.313 314 315 316 317 318 319 320 321 322 323 324 325 326 327 328 329 330 331 332 333 334
below is the one used in the pilot measurements described here. This material is very close to albite stoichiometry (NaAlSi3O8) and was previously thought to be devoid of contamination by any minor elements. Under these conditions the volatilization of chlorine from the sample occurs by the reaction
2KCl(melt) + H2O(g) = K2O(melt) + 2 HCl(g). Refinements to eliminate some contaminants are also described.
Albite glass was taken from a large batch prepared by Corning Glass Works. To minimize losses of the isotopically enriched material and contamination of the laboratory.
retaining as much as possible of the 41K in the melt while degassing most of the chlorine. 15 mm high).5). (2011) for gas-mixing and fO2 measurement practices in this laboratory).
In developing this method we undertook initial experiments with isotopically natural KCl. as stable 123Sb was transmuted during neutron irradiation into the short-lived isotope 124Sb (t1/2 = 60 days). which in turn required sequestration of the spike glass for some months before further use.
FE-SEM and electron microprobe analysis: The result of this preparation is a glass bead with a milky grey appearance on the surface.2 weight %. and carbon-coated. Upon examination with a fieldemission scanning electron microscope at high magnification. polished. and dictated using the smallest possible amount of spike in the analyses to avoid radioactive contamination of our mass spectrometers.335 336 337 338 339 340 341 342 343 344 345 346 347 348 349 350 351 352 353 354 355 356
sample from the furnace and plunging it into cold water. Despite these precautions we still lost about 50% of the starting potassium content during synthesis. the milkiness was found to result from a fine dispersion of Au-Pd-Sb alloy nanoparticles near the outer surface of the bead. We used this “natural-K glass” in some of the experiments described below. this produced a glass of similar bulk composition to the spike glass. The bead was broken and a chip of about 1 mm3 was mounted in epoxy. Bulk Sb content was ~0. Au and Pd are not an issue for the subsequent processing of this spike sample.
. The bulk sample composition was estimated by energy-dispersive X-ray analysis while rastering the beam over a 100 m x 100 m area including both the region affected by the Sb contamination and the clear interior of the bead. However the Sb contamination proved problematic.
and sodalite (for Cl). Standards were albite (for Na. these replicate analyses pass a statistical homogeneity test at 95% confidence.02 weight % K2O (here and elsewhere stated uncertainties are at the 1σ level) and ≤0.2 weight % Cl.
An ~1 mg chip of this glass was dissolved in 2:1 concentrated HF-HNO3. and blank and isotopically normal potassium standard solutions prepared in the same way. Presumably Sb2O3 was used as a firing agent to suppress bubble formation in the glass. it was traced to
the Corning albite glass. Blank and fractionation corrected K isotope ratio results are
. albite glass. however the work reported here used the contaminated material prepared in the first batch. taken to dryness.
KCl supply. alumina furnace tubes. The resulting solution. orthoclase (for K). As described in the Appendix. were analyzed for K isotopes on a Thermo-X series ICPMS fitted with a H2 collision cell. we synthesized a second batch of spike glass free of Sb.). etc. and Fe were below detection limits.01 ± 0. Ca. Mg. and Al). mortar and pestle. fayalite (for Fe). operating at 15 kV accelerating potential with a 10 nA beam defocused to a 10 m spot in order to minimize alkali mobilization.
After searching through possible sources of Sb contamination (Pd76Au24 capsule stock. Si. The sample contains 7.357 358 359 360 361 362 363 364 365 366 367 368 369 370 371 372 373 374 375 376 377 378 379
The glass composition was then quantitatively analyzed on the Caltech JEOL JXA-8200 microprobe. forsterite (for Mg). The average and standard deviation of 22 analysis spots on the glass chip are given in Table 2. Note that for the K2O weight percent we have taken into account the unusual isotopic composition of the spike K in the glass. and redissolved in 5% concentrated HNO3 in Milli-Q ultraclean water. anorthite (for Ca).
at this stage the radioactivity was sufficiently low that exposing our analytical equipment to ~500 μg quantities of the material was deemed acceptable.369 ± 0. (Ideally. The 39Ar concentration was determined to be 1.2% of the K in the glass is 41K. and rspk=0. About 15 cps of mass 39 was consistently measured on furnace blanks. these data imply a 41K concentration of 1. mass fractionation.7x10-12 mol of atmospheric argon was used to establish sensitivity. A standard consisting of ~2.
Five aliquots of spike glass weighing between 0.2 and 0. presumably from an unresolved isobaric contaminant. see below). The spike glass was allowed to cool for several more months before further processing.380 381 382 383 384 385 386 387 388 389 390 391 392 393 394 395 396 397 398 399 400 401 402
shown in Table 2. The evolved 39Ar was purified of contaminating species and yielded ~1000 cps on the electron multiplier spur of a MAP 215-50 mass spectrometer.989 ±
.004 mmol 41K/gram.6 mg were fused in a doublewalled resistance furnace at ~1500oC. probably due to contamination with natural potassium during synthesis. indicating that 96.039. Coupled with the electron probe K2O determination. This is slightly lower than the nominal purity of the 41K-enriched KCl.
After 40 hours of irradiation in the cadmium-lined in-core irradiation tube (CLICIT) in the TRIGA reactor at Oregon State University. Several weeks after the irradiation >90% of the activity was found to derive from 124Sb. We assume that the potassium isotopic composition is homogeneous within the glass. the spike glass was found to be unexpectedly radioactive. This amount was subtracted from the signal evolved from the spike glass. and the faradaymultiplier cross calibration factor. the experiment would have used a few mg of spike glass to permit greater precision in 39Ar determinations.
2009).3 ± 5 Ma by K-Ar and 40Ar/39Ar (integrated)
. and the observed homogeneity in K concentration of the glass (Table 2). it could be much lower. and minor olivine. clinopyroxene.05 pmol/g (Table 2)..4 ± 5 and 354. Analyses of plagioclase fractions yielded concordant ages of 351.45x10-9 with an estimated uncertainty of 2. However. To this end we obtained whole rock crushate of sample 42a/01 from the Viluy traps (Eastern Siberia. Based on documented neutron flux gradients in materials analyzed in an identical fashion at the OSU reactor (Simon et al. so we expect very little neutron-produced 40Ar. is a tholeiitic to sub-akaline basalt composed of plagioclase. the amount of 40Ar coming from the spike during sample analyses is negligible. However. Courtillot et al. drilled from a dolerite dike.2. this 39Ar concentration should be homogenous to better than 1%. Note that reactor produced 40Ar from neutron capture on 40K is likely to be very small in our glass because we are using highly 41K-enriched potassium (and used Cd shielding during irradiation). Our data place an upper limit on the glass 40Ar/39Ar ratio (Rspk) of 5. No other argon isotopes were detected above blank.8 wt % K2O) and a well-determined age.5%. This sample. we cannot rule out the possibility of atmospheric 40Ar contamination. Basalt Sample and Flux
To test the method we chose a basalt with a typical potassium concentration (about 0.
Taken together. we find the double-isotope spike ratio (39Ar/41K)spk = 1. (2010)).403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425
0. and are not expected given the very small amount of spike glass analyzed. even at the upper limit of Rspk~5.
and oxides. returned to the furnace.3.
For the flux we chose a 50:50 mixture of lithium metaborate:lithium tetraborate (ultrapure grade. In an initial attempt the flux was heated to temperature in about 10 minutes. sulfates. carbonates. For our experiments we used bulk crushate in the 100-500 μm size fraction. and evacuated and gently baked (~100oC ) overnight to liberate adsorbed Ar. obtained from Spex Certiprep). including silicates. After 30 minutes of degassing at ~1000oC the cell was cooled and removed from the furnace. introduced into a doublewalled vacuum furnace. For the analysis of the sample (referred to as analysis JAC-1) 10 mg of the Viluy basalt sample and 179 μg of the spike glass were placed in the bottom of the cell. Noble gas mass spectrometry
In this step the Knudsen cell was loaded with 150 mg of flux. Heating the sample to temperature over ~45 minutes eliminated this problem. evacuated to <10-7 torr with a turbomolecular pump.
For argon extraction and analysis the vacuum chamber was isolated from the pump and the heating process repeated. respectively.
3. directly on top of the lithium borate glass. at ~400oC to drive off
. This particular proportion was chosen for its remarkable ability to digest a wide range of mineral and rock compositions. causing violent bubbling and climbing of the flux up the walls of the Knudsen cell. and heated to ~1000oC.426 427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 445 446 447 448
methods. JAC-1 was degassed in two steps.
1967. while 38Ar and 39Ar were measured on the electron multiplier. the cell was shipped to the NASA Glenn Research Center. 2010). After argon extraction. Argon was purified and analyzed as described for the spike glass except 40Ar and 36Ar were measured on a Faraday collector. 2005) and is a logical choice for measurement of the potassium isotope ratio evolved from our sample cell. and again to 965oC to melt the flux and completely degas the sample. For example. 1967. In both cases we used a 45 minute heating ramp with 30 minutes at the setpoint.
3. furnace blanks that consisted only of flux (no sample) were about ~0. Copland and Jacobson.85 pmol for our blank corrections. but in subsequent heating steps this blank dropped substantially. We assumed a value of 0. After degassing..449 450 451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466 467 468 469 470 471
In this design it is not possible to degas the furnace prior to heating the sample. Drowart et al. where it was placed in a typical Knudsen cell heating assembly (Drowart and Goldfinger. the sample was allowed to cool to <300oC before introducing the gas into the processing line. this contributes to an unusually large argon blank as the furnace is first heated. JAC-1 was heated a second time to 965oC to assess completeness of extraction of spike and radiogenic argon. Because the blank has an air-like composition.4. uncertainty in the blank amount does not affect the final computation of 40Ar*. Knudsen effusion mass spectrometry (KEMS)
KEMS is a well-established technique for studying inorganic vapors (Drowart and Goldfinger.85 pmol of 40Ar with an air-like composition on the first heating to 965oC.
ionizing electrons. This rather high ionizing electron energy assured fragmentation of all K-containing components in the vapor. A magnetic sector mass spectrometer (modified Nuclide/MAAS 12-90-HT). and resultant ion beam are all mutually perpendicular. A small portion of that vapor effuses through the orifice in the lid and passes through the ion source of the mass spectrometer. Temperature was measured with a Type R thermocouple strapped to the Knudsen cell and calibrated with the melting point of silver. The first set of experiments were designed to establish how potassium behaves when volatilized from mixtures of flux and basalt and flux and natural-K glass (the spike glass analog). so that the potassium signal was representative of the entire sample. vapor is liberated from the fluxed mixture into the cell.
Several different materials were analyzed by KEMS. 1968). making the system ideal for isotope ratio measurements. The resolution as defined by the source exit slit and multiplier entrance slit is about 1100.472 473 474 475 476 477 478 479 480 481 482 483 484 485 486 487 488 489 490 491 492 493 494
During heating of the cell by a tantalum „hair-pin‟ shaped resistance heater. 2010). For these measurements we used an ion source electron energy of 60 eV. and a 20 dynode electron multiplier with ion counting were used for these measurements (Copland and Jacobson. This configuration minimizes mass discrimination (Roboz. oil-free pumping was utilized through magnetically levitated turbomolecular pumps on the Knudsen cell chamber and ion source and ion pumps on the flight tube and detector. an electron impact ionization source. In addition. which allows separation of the inorganic peaks from any background hydrocarbons. The instrument is configured so that the molecular beam. The second experiment was designed to assess mass fractionation during evolution of potassium from a mixture of
These data imply that ~97% of the radiogenic argon was released in the high temperature step when the basalt was flux-melted.
These results suggest that our low temperature “clean-up” step was done at slightly too high a temperature .we cannot exclude this step from the computation of the total yields from JAC-1. The third experiment was the analysis of JAC-1.1.31. a quantity easily distinguished above blank levels for this isotope. demonstrating the efficacy of flux melting in liberating argon from both the basalt and the spike glass. A far higher 40Ar/36Ar ratio of 651 was obtained in the 965oC step. In contrast the 40Ar/36Ar ratio of 306 in the 400oC step was only slightly elevated compared to the atmospheric ratio (299).300 and 102. Thus we combined data from the two steps to obtain 40Ar/39Ar and 36Ar/39Ar ratios of 44. A repeat extraction at 965oC released no additional 39Ar or 40Ar*.
4. respectively. Argon
Argon results obtained on JAC-1 are shown in Table 3.
. the basalt + spike glass + flux mixture.2. This corresponds to a bulk 40Ar/36Ar ratio of 432 and a radiogenic argon fraction of 0. About 7% of the total 39Ar was released in the first heating step (~400oC).495 496 497 498 499 500 501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517
natural-K glass and flux. RESULTS
consistent with little solid-phase release from the starting materials. which is more than two hours into the experiment.518 519 520 521 522 523 524 525 526 527 528 529 530 531 532 533 534 535 536 537 538 539 The release pattern for the two specimens as a function of temperature is broadly similar. in the absence of mass The evolution of the 39K+ signal with temperature during the KEMS experiments performed on basalt and on the natural-K glass. the ion intensity rises rapidly. At this temperature/time it seems likely that both basalt and natural-K glass are entirely dissolved in the flux. For these runs the cell was heated at a rate of 3oC/min. The transition at this temperature is consistent with the onset of dissolution of the sample into the molten flux. both with flux. are shown in Figure 2. with the only notable difference being how steeply the 39K+ signal increases above ~940oC. such that. For both runs the potassium signal below ~840oC is quite low. the general similarity in behavior between these two systems suggests that isotopic homogenization between the spike and sample potassium will occur in the melt and/or the Knudsen cell. or the vapor pressure of potassium over the lithium borate liquid depends on the liquid composition. while the exponential increase at higher temperatures likely arises from increasing vapor pressure of K over the melt. Thus the difference in behavior above this temperature suggests either that the basaltic melt is approaching exhaustion of its potassium at a more rapid rate than the natural-K glass (consistent with its nearly order-of-magnitude lower K content). However.
. as the flux is heated above the melting point of lithium metaborate (845oC). Regardless of why this difference exists.
and at each temperature the 39K/41K ratio was measured for 30 minutes. our measurement is an integral of all of the potassium analyzed rather than a point measurement at a given time or temperature.540 541 542 543 544 545 546 547 548 549 550 551 552 553 554 555 556 557 558 559 560 561 562
Figure 3 shows the evolution of the 39K/41K ratio during heating of a second aliquot of natural-K glass + flux mixture. this run yielded an integrated 39K/41K ratio of 13. with associated fractionation of the residue towards a heavier isotopic composition. At ~980oC the ratio is somewhat scattered. there is a slight decreasing trend in the 39K/41K ratio. presumably because the ion intensities are fairly small (<40 cps on 41K). the yield of 39K per unit time decreases at the highest temperature. In addition. Thus in
. Ratios at the two higher temperatures are more consistent. As shown in Table 3 and by the horizontal line in Figure 3. Both of these observations are consistent with depletion of potassium from the charge.
These data can also be used to set an upper limit on the fraction of potassium evolved from JAC-1 while heating to 965oC during the argon extraction.21.85 ± 0. When plotted against the cumulative fraction of 39K measured in the experiment. Importantly.86. potassium is being lost from the Knudsen cell at a rate of 1% per minute. If we assume that all of the potassium was effused during the KEMS run. This mixture was heated to 980oC. the evolved vapor will be an accurate representation of the isotopic composition of the mixture. 1030oC and 1065oC. in excellent agreement with the natural 39K/41K ratio of 13. then the data in Figure 3 imply that at 980oC. This observation indicates that the integral potassium isotope ratios obtained from KEMS are not substantially fractionated from the starting composition.
thus the loss rate is an overestimate.3.
4. and the potassium release curve is quite steep in this temperature range (Figure 2).
. The importance of this conclusion is that it implies that the loss of potassium during the argon degassing step does not remove enough potassium to threaten our ability to measure the isotope ratio by KEMS. and b) we did not completely degas potassium from the sample in Figure 3. 2010). respectively (Courtillot et al.71 ± 0.71 ± 0.4 ± 5 and 354.300± 740.. During this time there was no noticeable change in isotopic composition. and spike glass previously analyzed for argon. Combined with the spike characteristics listed in Table 2.563 564 565 566 567 568 569 570 571 572 573 574 575 576 577 578 579 580 581 582 583 584 585
our 30 minute argon degassing of JAC-1 we will have lost no more than 30% of the total potassium.
The final KEMS experiment was the analysis of JAC-1.3 ± 5 Ma by K-Ar and 40Ar/39Ar. not 980oC. This mixture was analyzed for 39K/41K ratio at 1040oC for about one hour. the resulting K-Ar age is 351 ± 19 Ma. This number compares favorably to the published ages for Viluy 42a/01 of 351. This is a strong upper limit because a) the argon degassing occurred at 965oC. (36Ar /39Ar)m= 102 ± 1. the mixture of flux.07.07. nor does it isotopically fractionate the residue to a significant degree. the sample yielded an integrated 39K/41K ratio of 4. Age Computation
These data provide the three quantities required to compute a K-Ar age for JAC-1 from equation 10: Rm=44. basalt. As indicated in Table 3.8. and rm=4.
This warrants an evaluation of the sources of uncertainty in our methodology. This temperature and time cause only modest potassium loss from the Knudsen cell. Although lithium borate was presumably also volatilized. This makes sense
. No practical difficulties were encountered for measuring potassium evolved from the Knudsen cell. strongly support equilibration of spike and sample potassium isotopes prior to the KEMS isotopic ratio measurement. In particular. The estimated analytical uncertainty of the current implementation of this technique is ~6%. as well as on the Viluy basalt sample. it does not interfere with the potassium measurement. Experiments on basalt and spike glass measured independently. which in general are expected to yield precisions at least twice as good. and as a result the potential for potassium isotopic fractionation is limited.
The measured age on the Viluy basalt is well within error of previous measurements of the age of this sample. the measured isotope ratio is an accurate measurement of the potassium composition of the bulk system. heating to 965oC for 30 minutes is adequate to quantitatively degas argon from both the spike glass and the basalt. As a result. The uncertainty on the
Ar/41K of the spike contributes only ~10% of the total uncertainty. This is somewhat poorer than what one might expect from two isotope dilution measurements. Although we have limited experimental evidence for the individual uncertainties we adopted.586 587 588 589 590 591 592 593 594 595 596 597 598 599 600 601 602 603 604 605 606 607 608
5. several observations are relevant. DISCUSSION AND CONCLUSIONS
These experiments support the assumptions and procedures necessary to accurately determine the K-Ar age using the double isotope dilution method.
The relatively large argon uncertainty arises from two obvious factors: the very small 39Ar beam and the large correction for atmospheric argon.
The double-isotope dilution method has the potential to yield K-Ar measurements using relatively simple and proven analytical techniques that are available for space-flight application. the SAM instrument in the payload of the Mars Science Laboratory includes both an oven capable of heating sample material to 1100oC.609 610 611 612 613 614 615 616 617 618 619 620 621 622 623 624 625 626 627 628 629 630
because the spike glass composition was determined by averaging of multiple analyses. Of the remaining uncertainty ~65% comes from the argon measurements and the remainder from the potassium isotope ratio. The 39Ar signal in our experiment was far lower than optimal owing to the small amount of spike glass used. For example. as well as a quadrupole mass spectrometer with a pulse-counting electron multiplier with
. in principle this source of uncertainty can be made arbitrarily small by replication. Such improved precision is necessary to identify likely smaller sources of uncertainty and to assess the ultimate precision of the method. a consequence of our effort to minimize the amount of radioactive antimony contaminant potentially released into our mass spectrometers. The large atmospheric argon correction can be reduced by designing a system that allows degassing of the heater prior to the accumulation of sample argon. Indeed. Solutions to both of these problems are straightforward and should allow the method to approach an age precision significantly better than 5 percent. This complication motivated the synthesis of an antimony-free spike for future use (see Appendix). which will allow larger spike glass masses and hence better argon isotope ratio precision.
the heater can be turned off and the argon gas cleaned up by exposure to chemical getters. This low eV level precludes simultaneous detection of both potassium and argon isobars. especially on mass 41 (C3H5+).. One logical route to this objective is to design a low argon blank vacuum chamber (all metal and bake-able chamber and valves. and its isotope ratio measured. This sequence has the
.631 632 633 634 635 636 637 638 639 640 641 642 643 644 645 646 647 648 649 650 651 652 653
sensitivity similar to the mass spectrometers used in this pilot study (Mahaffy et al. 1987). Thus a single mass spectrometer with an appropriate ion source can make the requisite measurements provided that argon and potassium can be delivered to the ion source automatically and in sequence. and has the ancillary benefit of preventing ionization of hydrocarbons that might interfere. 2012). The ion source would then be tuned to an electron energy at which argon is ionized.. Both of the mass spectrometers we used produced ions in the same way: by electron impact ionization. minimal inclusion of ancillary equipment in the chamber) that houses both a cross-beam electron impact ion source and mass spectrometer. Wetzel et al. Once sufficient potassium isotope data is obtained. allowing effusing potassium to be directed through the ion source and analyzed by the mass spectrometer while argon gas is accumulating. The mass spectrometers were also nearly identical. By using an appropriately low electron energy in the ion source (say 10 eV) it is possible to very efficiently ionize potassium without ionizing argon at all (based on electron impact ionization cross sections.
The final step required to implement this method for space flight or even terrestrial laboratory use is to combine the K and Ar measurements into a single analytical instrument. In such a system the sample would be heated under static vacuum.
the same amount of excess 40Ar reported in the shergottites (Bogard and Park. 2008.654 655 656 657 658 659 660 661 662 663 664 665 666 667 668 669 670 671 672 673 674 675 676
added virtue that only one heating step is required. or impacts may induce argon loss that will cause the K-Ar age to underestimate the sample formation age. While excess argon is likely present in all basalts (martian and otherwise). 1999. 2001. are not as substantial as this conclusion implies. nearby volcanism. The latter is thought by some authors to be especially problematic in the case of martian basalts. For example. reducing the overall power requirement for the analysis. Bogard and Park (2008) obtained a 40Ar/39Ar age of about 220 Ma. Similarly. Bogard and Park. in the case of the Zagami shergottite. For example. while other techniques yield ages of ~170 Ma (Nyquist et al. excess 40Ar may cause erroneously high estimates of 40Ar* and hence K-Ar ages that are older than the sample formation age. an excess 40Ar component in many shergottite meteorites causes 40Ar/39Ar ages to exceed ages obtained by other methods. In particular. 2008. A mantle 40Ar component of approximately equal concentration may be present in all shergottite meteorites (Bogard and Garrison.. 2005). Borg et al.
It is important to note that a K-Ar age is equivalent to the formation age of a sample only when the sample has remained a closed system for parent and daughter and when it is free of 40Ar from sources other than 40K decay and atmospheric contamination. the consequences for in-situ dating. This led Bogard (2009) to suggest the necessity of an isochron method with a perhaps prohibitively large number of aliquot analyses for accurate in-situ K-Ar dating of martian basalts.
. Bogard. at least at the excess 40Ar levels that have been documented thus far. Phenomena such as slow-cooling as well as reheating associated with burial. 2009)..
Pete Burnard.54 Ga. We thank Leah Morgan. and no mass estimate is necessary. While the impact of excess 40Ar becomes increasingly great with decreasing sample age. This precision is dictated by the ability to measure isotope ratios. and two anonymous reviewers for helpful suggestions. This research was carried out in part at the Jet Propulsion
. certainly too small a difference to be considered consequential. Existing flight-qualified hardware can perform the necessary heating and probably the mass spectrometry.
Although analyses of additional samples are required. 2009) in a rock with the same K content as Zagami but a formation of 3.5 Ga would yield a K-Ar age of 3. a well understood process for both potassium and argon. the double isotope dilution technique described here appears capable of providing K-Ar ages with a routine precision of better than 5%. This work could not have occurred without the generous and patient support of the Keck Institute for Space Studies.677 678 679 680 681 682 683 684 685 686 687 688 689 690 691 692 693 694 695 696 697 698
Bogard. it is not obvious that even a 50 Ma error on a sample as young as the shergottites (~200 Ma) would preclude useful interpretation. The remaining challenge is to develop the physical apparatus that allows sequential ionization of potassium and argon evolved from a sample to be dated. A maximum temperature of just 1030oC is required.
Acknowledgements We thank Paul Renne for suggesting and providing the Viluy Traps basalt sample and Tim Becker for facilitating the irradiation of our spike glass. Nevertheless both excess argon and argon loss are factors that should be carefully evaluated when considering insitu K-Ar dating of any particular planetary surface.
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which shows prominent conchoidal fractures (possibly related to cooling rate). the melting point of lithium metaborate. B) Image of Knudsen Cell JAC1 following analysis of flux.25. Samples are mixtures of lithium borate flux with basalt and with the natural-K glass. The flux melted to form a glass. For JAC-1 the cell was held at a constant temperature of ~1030oC for 1 hour. spike glass and basalt sample for noble gases. Figure Captions
. The horizontal lines are the integrated 39K/41K ratio from the sample. For the natural-K glass the cell was held at each of the three indicated temperatures for 30 minutes. the sample/flux mass ratio was 0. Figure 2. For the natural-K glass the integrated ratio is the same within error as the known ratio for natural K. 39K+ evolution by KEMS. The x-axis is a measure of the total amount of 39K degassed from the Knudsen cell. Neither basalt nor spike glass fragments were observed in or on this glass following analysis. Note the change in K release behavior at 845oC. Potassium isotope ratio evolution from a mixture of the normal K-glass and lithium borate flux and from JAC-1. The 39K+ signal in each step has been normalized to the total yield obtained from each entire run. Figure 1 A) Close-up of the Knudsen cell showing the effusion orifice.861 862 863 864 865 866 867 868 869 870 871 872 873 874 875 876 877 878 879 880 881 882 883 884 39 Figure 3.
23 ±0. the experiment described in the main text makes use of the initial Sb-contaminated spike glass. Al. it retained enough K2O to move into the liquidus field of leucite (KAl2SiO6).1 ±0. Although this product contained no Sb and very little Cl.2 weight % K2O and 0. quenched. First. Cl. APPENDIX
. using the same analytical conditions and standardization procedures described above. fH2O=0.6 bar and 1150°C. The sample contains a reported 9. The mixture was fired in an open Pt (not Pd76Au24) cup for 90 hours at IW+0. Si. reground. and Na2CO3 by decarbonating at 500°C followed by melting at 1150°C. at 1350°C for four hours and finally quenched to obtain a clean.03 Cl wt %. This material was ground and mixed in a 3:1 weight ratio with 41KCl.5. Al2O3. and fired again for an additional 48 hours under the same conditions.885 886 887 888 889 890 891 892 893 894 895 896 897 898 899 900 901 902 903 904 905 906 907 Three chips of this glass product were also analyzed on the Caltech microprobe. Na. a new batch of spike was prepared in a multistep procedure. It contains neither dispersed antimony nor the Au-Pd-Sb droplets seen in the first spike glass. this glass has not yet been neutron-irradiated. To eliminate the radioactive Sb in the first batch of the isotope dilution spike. clean albite glass was synthesized from ALFA Aesar Puratronic SiO2. As of the time of writing. and K at electron microprobe detection limits. this time in a sealed Pt capsule to prevent volatilization of K. Hence it was melted again. homogenous glass free of any elements besides O.
Table 1.36Arair (40Ar/36Ar )air Rspk=(40Ar/39Ar)spk Rm=(40Ar/39Ar)m
.36Arm. equation 13 .K-Ar age of unknown .known atmospheric argon isotope ratio .natural K isotopic composition (known) .independently determined spike composition .calibration parameter. 41Kspk
rm = (39K/41K)m rspk = (39K/41K)spk rnat = (39K/41K)nat r40 = (40K/39K)nat JID tstd t f(sample)
. Definition of variables
Ar* Arspk. eqs 10. 40Arspk 40 Arm.measured on unknown .measured on unknown .amounts of Ar in unknown . 41Ku Kspk.a function of measured quantities.11
Ku. 40Ku.amounts of K in unknown .independently determined spike composition .amounts of Ar in spike glass .in situ radiogenic Ar amount in unknown .amounts of K in spike glass .natural K isotopic composition (known) .air-derived Ar amounts in unknown . 39Arm 40 Arair.independently known age of standard .
Ar/41K (x10-9) 1.6
Na2O (wt %) 6.037
K2O (wt %) 7.3 Ar (pmol/g) 1.453
± 0.369 0.04
Al2O3 (wt %) 18. Analytical Data on Spike Glass
SiO2 (wt %) 68.05
K (mmol/g) ± 1.989
Analytical Data on JAC-1 (Viluy 42a/01 Basalt)
39 41 40 39 36 39
K/ K 4.07
Ar/ Ar ± 44300 740
Ar / Ar ± 102 2
K-Ar age (Ma) 351
Fraction of Total
0.00 700 800 900
melting point of lithium metaborate
0.14 natural-K glass basalt
1.2 0.0 0.0
Cumulative Fraction of Measured
22 20 18 16 980oC 1030oC 1065oC 1030oC
K/ 41 K
14 12 10 8 6 4 0.