Laser ablation coupled with ICP-MS applied to U–Pb zircon geochronology: A review of recent advances

Improvements in the technology of laser ablation and ICP-MS instruments make LA-MC-ICPMS a rapid, precise and accurate method for U–Pb zircon geochronology. In this review we describe the main stages of the evolution of this in situ approach from the early 1990s to the present time. Some key points have been progressively improved. The crater size has been reduced to achieve real in situ measurements. The laser wavelength has been reduced as well as the duration of each pulse in order to lower inter-element fractionation. The blank from the gas has to be lowered as far as possible. Double focusing instruments and magnetic field sectors allow flat-topped peaks required for precise isotope ratio measurement to be obtained. The use of a multi-ion counting system significantly improves the sensitivity of the method and the static mode of integration favours the precision of measurement of the transient signal originating from a noisy laser ablated particle beam.Combining the use of a 213 nm UV laser and a MC-ICPMS equipped with a multi-ion counting system operating in static mode, the common precisions achieved for the key ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁶Pb/²³⁸U are better than 1% and 3% (2σ) respectively, including error propagation associated with standard normalization. Until now, the use of a zircon standard has remained necessary to ensure the accuracy of the calculated age. A strategy for common-Pb correction is proposed according to the age of the zircon and according to the Th/U ratio of the grains. After recording sixteen to twenty spot analyses the precision usually achieved on the age is about 1% and even significantly better for Proterozoic samples.In order to show the performance achieved by modern LA-MC-ICPMS geochronology, we tested four zircon samples covering a wide age range from 290 to 2440 Ma. These new age determinations can be compared in term of precision and accuracy since they have already been dated by reference methods (ID-TIMS and SHRIMP). Further developments in the technology of ion counters equipping modern MC-ICPMS and in laser systems will certainly be applied to a large field of geochronology studies in the near future as an alternative to SIMS for in situ age determination.     

U-Pb Age Determination for Seven Standard Zircons using Inductively Coupled Plasma–Mass Spectrometry Coupled with Frequency Quintupled Nd-YAG (λ = 213 nm) Laser Ablation System: Comparison with LA-ICP-MS Zircon Analyses with a NIST Glass Reference Material

This paper evaluates the analytical precision, accuracy and long‐term reliability of the U‐Pb age data obtained using inductively coupled plasma–mass spectrometry (ICP‐MS) with a frequency quintupled Nd‐YAG (λ = 213nm) laser ablation system. The U‐Pb age data for seven standard zircons of various ages, from 28 Ma to 2400 Ma (FCT, SL13, 91500, AS3, FC1, QGNG and PMA7) were obtained with an ablation pit size of 30 μm diameter. For ²⁰⁷Pb/²⁰⁶Pb ratio measurement, the mean isotopic ratio obtained on National Institute of Standards and Technology (NIST) SRM610 over 4 months was 0.9105 ± 0.0014 (n = 280, 95% confidence), which agrees well with the published value of 0.9096. The time‐profile of Pb/U ratios during single spot ablation showed no significant difference in shape from NIST SRM610 and 91500 zircon standards. These results encouraged the use of the glass standard as a calibration standard for the Pb/U ratio determination for zircons with shorter wavelength (λ = 213 nm) laser ablation. But ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages obtained by this method for seven zircon standards are systematically younger than the published U‐Pb ages obtained by both isotope dilution–thermal ionization mass spectrometry (ID‐TIMS) and sensitive high‐resolution ion‐microprobe (SHRIMP). Greater discrepancies (3–4% younger ages) were found for the ²⁰⁶Pb/²³⁸U ages for SL13, AS3 and 91500 zircons. The origin of the differences could be heterogeneity in Pb/U ratio on SRM610 between the different disks, but a matrix effect accuracy either in the ICP ion source or in the ablation‐transport processes of the sample aerosols cannot be neglected. When the ²⁰⁶Pb/²³⁸U (= 0.2302) newly defined in the present study is used, the measured ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages for the seven zircon standards are in good agreement with those from ID‐TIMS and SHRIMP within ±2%. This suggests that SRM610 glass standard is suitable for ICP‐MS with laser ablation sampling (LA‐ICP‐MS) zircon analysis, but it is necessary to determine the correction factor for ²⁰⁶Pb/²³⁸U by measuring several zircon standards in individual laboratories.     

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.     

藏东八宿地区泛非期花岗岩锆石SHRIMP U-Pb定年

卡穷细粒黑云母碱长花岗岩出露于藏东八宿县同卡地区,是藏东地区首次发现的泛非期花岗岩.卡穷微陆块呈岩片状夹持于班公湖-怒江缝合带内,卡穷岩群构成卡穷微陆块的主体,卡穷岩群是由花岗岩、花岗片麻岩、黑云斜长片麻岩、大理岩、黑云斜长变粒岩、退变榴辉岩等组成的构造地质体.卡穷细粒黑云母碱长花岗岩获得的锆石SHRIMPU-Pb年龄为507Ma±10Ma,为泛非事件的岩浆活动记录,进一步证实班公湖-怒江板块缝合带以南是泛非期基底,为解决青藏高原南部的构造演化问题提供了新资料.     

华南双桥山群和河上镇群凝灰岩中的锆石SHRIMP U-Pb年龄—对江南新元古代造山带演化的制约

通过西澳科庭大学离子探针中心的远程测试,在双桥山群横涌组和安乐林组斑脱岩中获得大量锆石,其SHRIMP U-Pb加权平均年龄为831 Ma±5 Ma(横涌组)、829 Ma±5 Ma（安乐林组）,在河上镇群上墅组中获得加权平均年龄767 Ma±5 Ma。锆石SHRIMP U-Pb年龄表明华南地区广为发育的双桥山群应归入新元古界,该年龄为标定双桥山群在地层柱中的位置提供了准确的年代学依据。     

张广才岭南部杨木岗组的厘定及物源分析

本文通过岩石组合特征和区域对比，将张广才岭南部西蛤拉河子—大锅盔一带分布的浅变质地层重新厘定为杨木岗组。为了确定杨木岗组的形成时代和沉积物源，进行了碎屑锆石U- Pb年代学和微体古生物地层学研究。锆石大多数呈自形—半自形晶，显示典型振荡岩浆生长环带，暗示其岩浆成因。该地层中测得的两组碎屑锆石U- Pb产生多组谐和年龄，其中PM010- TW样品56个测点最小峰值(谐和)年龄为307 Ma，DB02- TW样品51个测点最小峰值(谐和)年龄为275 Ma；覆盖在杨木岗组之上的中生代二浪河组安山岩的定年结果为181. 1±0. 9 Ma，表明杨木岗组形成于早二叠世晚期。杨木岗组中获取疑源类化石组合出现了新元古代晚期—早寒武世和奥陶纪地层常见分子，结合碎屑锆石年龄结果，反映杨木岗组沉积时周围存在早古生代和中—新元古代地质体。碎屑沉积岩Al2O3/TiO2平均值为24. 44，稀土元素球粒陨石标准化曲线具有轻稀土富集、重稀土稳定和负Eu异常特征，结合碎屑锆石的年龄频数可以看出，确定杨木岗组的沉积物主要来源于沉积盆地周围的晚古生代早期中酸性火成岩，次要物源由沉积盆地周边的早古生代地质体和近地表的中—新元古代地质体提供。佳木斯地块为松嫩- 张广才岭地块上晚古生代地层的形成提供了部分物源，暗示佳木斯地块与松嫩- 张广才岭地块于早二叠世之前已完成拼合。     

Evaluating the mobility of137Cs,239+240Pu and210Pb from their distributions in laminated lake sediments

Post-depositional mobility of¹³⁷Cs,^239+240Pu and²¹⁰Pb was assessed in six small lake basins by comparing sedimentary nuclide profiles with their known fallout history. Laminae couplets, when present, were determined to be varves because the¹³⁷Cs and^239+240Pu 1963 fallout peaks are present in laminae couplets corresponding to years 1962–1964. There is no evidence of mobility of²¹⁰Pb, because 1) mass accumulation rates based on²¹⁰Pb agree with those based on¹³⁷Cs and^239+240Pu peak depths and with those based on varve counts, and 2)²¹⁰Pb ages agree with varve ages. Significant mobility of¹³⁷Cs is evident from the penetration of¹³⁷Cs to depths 15–20 cm deeper than^239+240Pu. Deep penetration of¹³⁷Cs in spite of a sharp gradient below the peak is interpreted by a numerical model to suggest that¹³⁷Cs is present in two distinct forms in these sediments, 67–82% as an immobile form and 18–33% reversibly adsorbed with a K _d of approximately 5000. The profiles can be interpreted equally well assuming a small portionof the total¹³⁷Cs was present as an extremely mobile phase (K _d 5000) in the months to years following peak fallout, slowly becoming more strongly adsorbed. High NH ₄ ⁺ concentrations in porewaters may enhance diffusion of the mobile form of¹³⁷Cs, but not of the immobile form of¹³⁷Cs that defines the sharp gradient. Mobility of¹³⁷Cs is likely also enhanced by the low clay content and the high porosity of these sediments. Thus the first detection of¹³⁷Cs in the sediments cannot automatically be assumed to correspond to a date of 1952 (initial testing of thermonuclear weapons), although the depth of the peak can be assumed to correspond to 1963 (the year of maximum fallout from testing of thermonuclear weapons).^239+240Pu is a more reliable sediment chronometer than¹³⁷Cs because it is significantly less mobile.This is the sixth of a series of papers to be published by this journal following the 20 ^th anniversary of the first application of²¹⁰Pb dating of lake sediments. Dr P.G. Appleby is guest editing this series.     

Exposure ages from relict lateral moraines overridden by the Fennoscandian ice sheet

Lateral moraines constructed along west to east sloping outlet glaciers from mountain centred, pre-last glacial maximum (LGM) ice fields of limited extent remain largely preserved in the northern Swedish landscape despite overriding by continental ice sheets, most recently during the last glacial. From field evidence, including geomorphological relationships and a detailed weathering profile including a buried soil, we have identified seven such lateral moraines that were overridden by the expansion and growth of the Fennoscandian ice sheet. Cosmogenic ¹⁰Be and ²⁶Al exposure ages of 19 boulders from the crests of these moraines, combined with the field evidence, are correlated to episodes of moraine stabilisation, Pleistocene surface weathering, and glacial overriding. The last deglaciation event dominates the exposure ages, with ¹⁰Be and ²⁶Al data derived from 15 moraine boulders indicating regional deglaciation 9600 ± 200 yr ago. This is the most robust numerical age for the final deglaciation of the Fennoscandian ice sheet. The older apparent exposure ages of the remaining boulders (14,600-26,400 yr) can be explained by cosmogenic nuclide inheritance from previous exposure of the moraine crests during the last glacial cycle. Their potential exposure history, based on local glacial chronologies, indicates that the current moraine morphologies formed at the latest during marine oxygen isotope stage 5. Although numerous deglaciation ages were obtained, this study demonstrates that numerical ages need to be treated with caution and assessed in light of the geomorphological evidence indicating moraines are not necessarily formed by the event that dominates the cosmogenic nuclide data.     

The timing of ultrahigh-temperature metamorphism in Southern India: U–Th–Pb electron microprobe ages from zircon and monazite in sapphirine-bearing granulites

We report here U–Pb electron microprobe ages from zircon and monazite associated with corundum- and sapphirine-bearing granulite facies rocks of Lachmanapatti, Sengal, Sakkarakkottai and Mettanganam in the Palghat–Cauvery shear zone system and Ganguvarpatti in the northern Madurai Block of southern India. Mineral assemblages and petrologic characteristics of granulite facies assemblages in all these localities indicate extreme crustal metamorphism under ultrahigh-temperature (UHT) conditions. Zircon cores from Lachmanapatti range from 3200 to 2300 Ma with a peak at 2420 Ma, while those from Mettanganam show 2300 Ma peak. Younger zircons with peak ages of 2100 and 830 Ma are displayed by the UHT granulites of Sengal and Ganguvarpatti, although detrital grains with 2000 Ma ages are also present. The Late Archaean-aged cores are mantled by variable rims of Palaeo- to Mesoproterozoic ages in most cases. Zircon cores from Ganguvarpatti range from 2279 to 749 Ma and are interpreted to reflect multiple age sources. The oldest cores are surrounded by Palaeoproterozoic and Mesoproterozoic rims, and finally mantled by Neoproterozoic overgrowths. In contrast, monazites from these localities define peak ages of between 550 and 520 Ma, with an exception of a peak at 590 Ma for the Lachmanapatti rocks. The outermost rims of monazite grains show spot ages in the range of 510–450 Ma.While the zircon populations in these rocks suggest multiple sources of Archaean and Palaeoproterozoic age, the monazite data are interpreted to date the timing of ultrahigh-temperature metamorphism in southern India as latest Neoproterozoic to Cambrian in both the Palghat–Cauvery shear zone system and the northern Madurai Block. The data illustrate the extent of Neoproterozoic/Cambrian metamorphism as India joined the Gondwana amalgam at the dawn of the Cambrian.