Laser probe Ar/Ar dating: History and development from a technical perspective

The ⁴⁰Ar/³⁹Ar method using a laser probe opened the door to microscale measurements and diffusion profiles frozen in samples. In the first decade since the initial application of a laser for ⁴⁰Ar/³⁹Ar dating in 1973, practical applications have been few. This is due not only to the fact that the laser and vacuum technologies were immature but that mass spectrometry was also in its infancy. In those days, the sensitivity of a mass spectrometer was generally insufficient to measure the small amount of argon degassed from a geological sample by a laser. These problems have subsequently been solved by new technologies. To understand their current status, a brief history of their development is outlined. This outline focuses on the required detection limit in micro scale measurement, practical approaches for accurate measurement are explained through examples in our laboratory specifically relating to the technical aspects of ⁴⁰Ar/³⁹Ar dating.     

Rare Earth Deposits of North America

Rare earth elements (REE) have been mined in North America since 1885, when placer monazite was produced in the southeast USA. Since the 1960s, however, most North American REE have come from a carbonatite deposit at Mountain Pass, California, and most of the world’s REE came from this source between 1965 and 1995. After 1998, Mountain Pass REE sales declined substantially due to competition from China and to environmental constraints. REE are presently not mined at Mountain Pass, and shipments were made from stockpiles in recent years. Chevron Mining, however, restarted extraction of selected REE at Mountain Pass in 2007. In 1987, Mountain Pass reserves were calculated at 29 Mt of ore with 8.9% rare earth oxide based on a 5% cut‐off grade. Current reserves are in excess of 20 Mt at similar grade. The ore mineral is bastnasite, and the ore has high light REE/heavy REE (LREE/HREE). The carbonatite is a moderately dipping, tabular 1.4‐Ga intrusive body associated with ultrapotassic alkaline plutons of similar age. The chemistry and ultrapotassic alkaline association of the Mountain Pass deposit suggest a different source than that of most other carbonatites. Elsewhere in the western USA, carbonatites have been proposed as possible REE sources. Large but low‐grade LREE resources are in carbonatite in Colorado and Wyoming. Carbonatite complexes in Canada contain only minor REE resources. Other types of hard‐rock REE deposits in the USA include small iron‐REE deposits in Missouri and New York, and vein deposits in Idaho. Phosphorite and fluorite deposits in the USA also contain minor REE resources. The most recently discovered REE deposit in North America is the Hoidas Lake vein deposit, Saskatchewan, a small but incompletely evaluated resource. Neogene North American placer monazite resources, both marine and continental, are small or in environmentally sensitive areas, and thus unlikely to be mined. Paleoplacer deposits also contain minor resources. Possible future uranium mining of Precambrian conglomerates in the Elliott Lake–Blind River district, Canada, could yield by‐product HREE and Y. REE deposits occur in peralkaline syenitic and granitic rocks in several places in North America. These deposits are typically enriched in HREE, Y, and Zr. Some also have associated Be, Nb, and Ta. The largest such deposits are at Thor Lake and Strange Lake in Canada. A eudialyte syenite deposit at Pajarito Mountain in New Mexico is also probably large, but of lower grade. Similar deposits occur at Kipawa Lake and Lackner Lake in Canada. Future uses of some REE commodities are expected to increase, and growth is likely for REE in new technologies. World reserves, however, are probably sufficient to meet international demand for most REE commodities well into the 21st century. Recent experience shows that Chinese producers are capable of large amounts of REE production, keeping prices low. Most refined REE prices are now at approximately 50% of the 1980s price levels, but there has been recent upward price movement for some REE compounds following Chinese restriction of exports. Because of its grade, size, and relatively simple metallurgy, the Mountain Pass deposit remains North America’s best source of LREE. The future of REE production at Mountain Pass is mostly dependent on REE price levels and on domestic REE marketing potential. The development of new REE deposits in North America is unlikely in the near future. Undeveloped deposits with the most potential are probably large, low‐grade deposits in peralkaline igneous rocks. Competition with established Chinese HREE and Y sources and a developing Australian deposit will be a factor.     

New age constraints on emplacement of the Cévenol granitoids, South French Massif Central

During the development of the Variscan orogeny, large amounts of granitic melt were produced, giving rise to the intrusion of granitoids at different structural levels. Despite numerous studies, ages available from previous work on the Cévennes granites remain largely imprecise. In order to better constrain the age and emplacement mode of these granites, we have combined U–Pb dating on monazites and zircons and ⁴⁰Ar/³⁹Ar dating on biotites with petrological observations, major element chemical analysis and SEM zircon imaging on five samples from the Aigoual–St Guiral–Liron and Mont Lozère granitic massifs. The results revealed that granitic intrusions and cooling in Southern Cévennes occurred in a short time span at ∼306 Ma after the main episode of regional metamorphism. Petrological and chemical data suggest that they result from a mixing between mantle-derived basic magmas (lamprophyres) and lower crust acid magmas. At a regional scale the production of these melts occurred at the end of crustal thickening induced by nappe stacking, at the same time as the late anatectic events recorded further north in the Velay dome and the granulite facies metamorphism recorded in metasedimentary granulite enclaves brought up by Tertiary volcanoes of the Velay area (Bournac).     

Zircon M257 ‐ a Homogeneous Natural Reference Material for the Ion Microprobe U‐Pb Analysis of Zircon

We introduce and propose zircon M257 as a future reference material for the determination of zircon U‐Pb ages by means of secondary ion mass spectrometry. This light brownish, flawless, cut gemstone specimen from Sri Lanka weighed 5.14 g (25.7 carats). Zircon M257 has TIMS‐determined, mean isotopic ratios (2s uncertainties) of 0.09100 ± 0.00003 for ²⁰⁶pb/²³⁸U and 0.7392 ± 0.0003 for ²⁰⁷pb/²³⁵U. Its ²⁰⁶pb/²³⁸U age is 561.3 ± 0.3 Ma (unweighted mean, uncertainty quoted at the 95% confidence level); the U‐Pb system is concordant within uncertainty of decay constants. Zircon M257 contains ～ 840 μg g^?1 U (Th/U ～ 0.27). The material exhibits remarkably low heterogeneity, with a virtual absence of any internal textures even in cathodoluminescence images. The uniform, moderate degree of radiation damage (estimated from the expansion of unit‐cell parameters, broadening of Raman spectral parameters and density) corresponds well, within the “Sri Lankan trends”, with actinide concentrations, U‐Pb age, and the calculated alpha fluence of 1.66 × 10¹⁸ g^?1. This, and a (U+Th)/He age of 419 ± 9 Ma (2s), enables us to exclude any unusual thermal history or heat treatment, which could potentially have affected the retention of radiogenic Pb. The oxygen isotope ratio of this zircon is 13.9%o VSMOW suggesting a metamorphic genesis in a marble or calc‐silicate skarn.     

陕西小秦岭华阳川韧性剪切带的特征 及其区域构造意义

陕西小秦岭华阳川韧性剪切带发育在新太古界太华群之中,野外调研和显微构造观察结果表明,该韧性剪切带是由构造片岩、眼球状片麻岩组成的深层次韧性剪切带,具有逆冲兼左行走滑的斜冲特征。对韧性剪切带构造片岩黑云母进行^40Ar／^39Ar同位素定年,获得坪年龄为419M±0．6Ma,反等时线年龄为417Ma±0．8Ma。认为华阳川韧性剪切带及其相应的小秦岭区域主导构造变形是发生于419Ma左右的秦岭加里东事件的结果。     

北武夷地区逆冲推覆构造的特征及其控矿作用

北武夷地区成矿地质条件优越,矿产资源分布广泛,而广泛发育的推覆构造深刻影响着矿床的成生与保存。区域性推覆构造是成矿前、成矿期还是成矿后的构造,其精细结构特征如何,是否具有控岩控矿作用,如果是破矿作用,是否造成矿体重复增大或者隐伏、缺失等问题,严重影响着地质找矿的效果。建议开展面积性、追索性的路线地质调查,查明逆冲推覆构造的区域分布、不同单元的产状、构造样式,分别采用40Ar-39Ar和Re-Os定年技术测定推覆构造和矿体的形成时代,结合定量化分析及精细构造解析,研究构造与矿床的成生联系,预测隐伏矿体可能的位置,进而为北武夷地区寻找隐伏矿床和扩大矿床远景提供参考。     

Fluid sources for the La Guitarra epithermal deposit (Temascaltepec district, Mexico): Volatile and helium isotope analyses in fluid inclusions

The La Guitarra deposit (Temascaltepec district, South-Central Mexico), belongs to the low/intermediate sulfidation epithermal type, has a polymetallic character although it is currently being mined for Ag and Au. The mineralization shows a polyphasic character and formed through several stages and sub-stages (named I, IIA, IIB, IIC, IID, and III). The previous structural, mineralogical, fluid inclusion and stable isotope studies were used to constrain the selection of samples for volatile and helium isotope analyses portrayed in this study. The N₂/Ar overall range obtained from analytical runs on fluid inclusion volatiles, by means of Quadrupole Mass Spectrometry (QMS), is 0 to 2526, and it ranges 0 to 2526 for stage I, 0 to 1264 for stage IIA, 0 to 1369 for stage IIB, 11 to 2401 for stage IIC, 19 to 324 for stage IID, and 0 to 2526 for stage III. These values, combined with the CO₂/CH₄ ratios, and N₂-He-Ar and N₂-CH₄-Ar relationships, suggest the occurrence of fluids from magmatic, crustal, and shallow meteoric sources in the forming epithermal vein deposit. The helium isotope analyses, obtained by means of Noble Gas Mass Spectrometry, display R/Ra average values between 0.5 and 2, pointing to the occurrence of mantle-derived helium that was relatively diluted or “contaminated” by crustal helium. These volatile analyses, when correlated with the stable isotope data from previous works and He isotope data, show the same distribution of data concerning sources for mineralizing fluids, especially those corresponding to magmatic and crustal sources. Thus, the overall geochemical data from mineralizing fluids are revealed as intrinsically consistent when compared to each other.The three main sources for mineralizing fluids (magmatic, and both deep and shallow meteoric fluids) are accountable at any scale, from stages of mineralization down to specific mineral associations. The volatile and helium isotope data obtained in this paper suggest that the precious metal-bearing mineral associations formed after hydrothermal pulses of predominantly oxidized magmatic fluids, and thus it is likely that precious metals were carried by fluids with such origin. Minerals from base-metal sulfide associations record both crustal and magmatic sources for mineralizing fluids, thus suggesting that base metals could be derived from deep leaching of crustal rocks. At the La Guitarra epithermal deposit there is no evidence for an evolution of mineralizing fluids towards any dominant source. Rather than that, volatile analyses in fluid inclusions suggest that this deposit formed as a pulsing hydrothermal system where each pulse or set of pulses accounts for different compositions of mineralizing fluids.The positive correlation between the relative content of magmatic fluids (high N₂/Ar ratios) and H₂S suggests that the necessary sulfur to carry mostly gold as bisulfide complexes came essentially from magmatic sources. Chlorine necessary to carry silver and base metals was found to be abundant in inclusion fluids and although there is no evidence about its source, it is plausible that it may come from magmatic sources as well.     

Temperature–composition–time (T–X–t) data from authigenic K-feldspar: An integrated methodology for dating fluid flow events

Integration of fluid inclusion analysis with high spatial resolution Ar–Ar dating of K-feldspar cements has been used to resolve and reconstruct palaeo-fluid flow. Fluid inclusion analysis allows discrimination of distinct cement phases, thereby identifying discrete episodes of fluid flow. Ar–Ar dating of the same cements via high spatial resolution laserprobe establishes absolute age constraints on the framework previously constructed. Integration of these two datasets yields temperature–composition–time data.     

Cretaceous isochron ages from K–Ar and Ar / Ar dating of eclogitic rocks in the Tso Morari Complex, western Himalaya, India

The Tso Morari Complex, which is thought to be originally the margin of the Indian continent, is composed of pelitic gneisses and schists including mafic rock lenses (eclogites and basic schists). Eclogites studied here have the mineral assemblage Grt + Omp + Ca-Amp + Zo + Phn + Pg + Qtz + Rt. They also have coesite pseudomorph in garnet and quartz rods in omphacite, suggesting a record of ultrahigh-pressure metamorphism. They occur only in the cores of meter-scale mafic rock lenses intercalated with the pelitic schists. Small mafic lenses and the rim parts of large lenses have been strongly deformed to form the foliation parallel to that of the pelitic schists and show the mineral assemblages of upper greenschist to amphibolite facies metamorphism. The garnet–omphacite thermometry and the univariant reaction relations for jadeite formation give 13–21 kbar at 600 °C and 16–18 kbar at 750 °C for the eclogite formation using the jadeite content of clinopyroxene (X_Jd = 0.48).

Phengites in pelitic schists show variable Si / Al and Na / K ratios among grains as well as within single grains, and give K–Ar ages of 50–87 Ma. The pelitic schist with paragonite and phengite yielded K–Ar ages of 83.5 Ma (K = 4.9 wt.%) for paragonite–phengite mixture and 85.3 Ma (K = 7.8 wt.%) for phengite and an isochron age of 91 ± 13 Ma from the two dataset. The eclogite gives a plateau age of 132 Ma in Ar/Ar step-heating analyses using single phengite grain and an inverse isochron age of 130 ± 39 Ma with an initial ⁴⁰Ar / ³⁶Ar ratio of 434 ± 90 in Ar/Ar spot analyses of phengites and paragonites. The Cretaceous isochron ages are interpreted to represent the timing of early stage of exhumation of the eclogitic rocks assuming revised high closure temperature (500 °C) for phengite K–Ar system. The phengites in pelitic schists have experienced retrograde reaction which modified their chemistry during intense deformation associated with the exhumation of these rocks with the release of significant radiogenic ⁴⁰Ar from the crystals. The argon release took place in the schists that experienced the retrogression to upper greenschist facies metamorphisms from the eclogite facies conditions.     

Unequal Competition Among Chains of Supercenters: Kmart,Target, and Wal‐Mart

The three largest discount chains, Kmart, Target, and Wal‐Mart, have adopted the supercenter format for expansion. This article examines the locations of and the competition among these supercenters. Wal‐Mart has the greatest number of supercenters and is driving the expansion of the supercenter format. Both Kmart and Target have clustered their supercenters in a small number of metropolitan markets. In contrast to Wal‐Mart and Kmart, Target has focused on a middle‐class rather than a blue‐collar clientele. Now Kmart is struggling following a declaration of bankruptcy. Wal‐Mart has largely defeated its supercenter competitors and now is confronting the major grocery chains for grocery sales.