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.     

Recommended Values of 239Pu, 240Pu and 239+240Pu Concentrations in Reference Material IAEA-315 (Marine Sediment) Estimated by Thermal Ionisation Mass Spectrometry, Inductively Coupled Plasma-Mass Spectrometry and Alpha Spectrometry

The recommended concentrations of ²³⁹Pu, ²⁴⁰Pu and ^239+240Pu in reference material IAEA‐315 (marine sediment) were estimated by three analytical methods: isotope dilution thermal ionisation mass spectrometry (TIMS), isotope dilution inductively coupled plasma‐mass spectrometry (ICP‐MS) and alpha spectrometry. The determination of ²³⁹Pu and ²⁴⁰Pu (^239+240Pu by alpha spectrometry) was carried out with samples from randomly selected bottles using each method. Plutonium‐238 was also measured by alpha spectrometry. A plutonium‐242 reference material was used as a spike for the quantitative analysis. The influence of ²⁴²Pu in the samples was therefore calculated; however, this contribution was less than the range of uncertainty and did not influence the final results. The obtained data were statistically analysed using variance component analysis and paired comparison. The combined standard uncertainties from “method/measurement”, “bottle” and “sub‐sample” were in the order of 3 to 6%. The main contributions to the uncertainty were from the material heterogeneity and from systematic differences between methods. Based on this study with twenty‐seven analyses using 10–14 g sample mass, concentrations of (38 ± 3) Bq kg^?1, (28 ± 3) Bq kg^?1 and (66 ± 4) Bq kg^?1 are proposed as recommended values for ²³⁹Pu, ²⁴⁰Pu and ^239+240Pu, respectively, and (9.5 ± 0.4) Bq kg^?1 for ²³⁸Pu as an information value in reference material IAEA‐315. In mass concentration units, these amount to (16.4 ± 1.2) ng kg^?1, (3.3 ± 0.4) ng kg^?1 and (0.015 ± 0.003) ng kg^?1 for ²³⁹Pu, ²⁴⁰Pu and ²³⁸Pu, respectively. The certified reference materials NIST 4350B and NIST 4354 were also analysed by TIMS for quality assurance of the method used in this study.     

Trace Element Analysis of NIST SRM 614 and 616 Glass Reference Materials by Laser Ablation Microprobe-Inductively Coupled Plasma-Mass Spectrometry

Fifty elements in NIST SRM 614 and 616 glass reference materials were determined by laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS). The values determined for NIST SRM 614 agreed well with the NIST-certified and information values (mean relative difference ± 3.6%), except for B, Sc and Sb. The values determined for NIST SRM 616 agreed with the NIST-certified and information values within a mean relative difference of ± 1.5%, except for B, Sc and Ga. In addition, at an 80 μm sampling scale, NIST SRM 614 and 616 glass discs were homogeneous for trace elements within the observed precisions of 5 and 15% (mean), respectively. Detection limits were in the range 0.01 - 0.3 μg g⁻¹ for elements of lower mass numbers (amu < 80) and 1 - 10 ng g⁻¹ for heavy elements (amu > 80). Detection at the sub ng g⁻¹ level is possible for most of the heavy elements by using an ablation pit size larger than 10 0 μm.     

Preliminary Results from a New 157 nm Laser Ablation ICP-MS Instrument: New Opportunities in the Analysis of Solid Samples

Preliminary results are given from an excimer 157 nm laser ablation multiple-collector inductively coupled plasma-mass spectrometer (LA-MC-ICP-MS), used for the isotopic measurements of solid materials. Elements of geological interest with different volatilities such as Pb and U (e.g. zircon geochronology) and Cu and Zn (as examples of geochemical/biochemical tracers) were analysed. The range of ablation rates of 20-150 nm s^-1 enabled us to ablate the sample down to a depth of 45 μm for a 50 μm diameter pit. The Cu and Zn isotopic measurements gave values that were very stable with, on average, a 0.01 % standard error, comparable with that achieved in liquid mode measurements.     

Determination of Lithium, Beryllium and Boron at Trace Levels by Laser Ablation-Inductively Coupled Plasma-Sector Field Mass Spectrometry

The analytical capabilities of laser ablation (LA)-ICP-MS in determining Li, Be and B at trace levels in geological samples have been tested on a series of glass reference materials and natural samples. The LA-ICP-MS instrument used consisted of a sector-field ICP-MS coupled with a laser ablation microprobe operating at either 266 or 213 nm wavelength. Reference glasses from NIST (SRM 612, 614 and 616) and MPI-DING (KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, T1-G and ATHO-G) were selected to develop the analytical method and to assess the best instrumental configuration. A series of calcic amphiboles with different Li, Be and B concentrations were also analysed using both LA-ICP-MS and SIMS to test the applicability of the method to natural minerals. Results indicated that with a spot size of 40 μm the agreement between measured and reference values of Li, Be and B is generally better than 10% for NIST SRM 612 and 20% for NIST SRM 614. Average reproducibility at the 2s level was 10% for Li, 20% for Be and 15% for B. Limits of detection were approximately 100 ng g^-1 for Be and B and 200 ng g^-1 for Li. These results were confirmed by analyses carried out on natural amphiboles and compared well in terms of precision and accuracy with those commonly achieved by SIMS.     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

IPCC AR6报告解读：气候系统对太阳辐射干预响应

IPCC第六次评估报告（AR6）第一工作组报告评估了太阳辐射干预（Solar radiation modification,SRM）对气候系统和碳循环的影响。在大幅度减排基础上,太阳辐射干预有潜力作为应对气候变化的备用措施。目前,对于太阳辐射干预气候影响的评估都是基于模式模拟结果。评估主要结论如下：太阳辐射干预可以在全球和区域尺度上抵消一部分温室气体增加造成的气候变化（高信度);但是太阳辐射干预无法在全球和区域尺度上完全抵消温室气体增加引起的气候变化（几乎确定);有可能通过适当的太阳辐射干预设计,同时实现多个温度变化减缓目标（中等信度);在高强度温室气体排放情景下,如果太阳辐射干预实施后突然终止,并且这种终止长时间持续,将会造成快速的气候变化（高信度);如果在减排和CO₂移除的情况下,太阳辐射干预的实施强度逐渐减小至零,将显著降低太阳辐射干预突然终止产生的快速气候变化风险（中等信度);太阳辐射干预会通过降温作用,促进陆地和海洋对大气CO₂的吸收（中等信度),但是太阳辐射干预无法缓解海洋酸化（高信度);太阳辐射干预对其他生物化学循环影响的不确定性大。由于对云-气溶胶-辐射过程的相互作用和微物理过程认知有限,目前对平流层气溶胶注入、海洋低云亮化、高层卷云变薄等太阳辐射干预方法的冷却潜力和气候效应的认知还有很大的不确定性。     

Study on snowmelt runoff simulation in the Kaidu River basin

Alpine snowmelt is an important generation mode for runoff in the source region of the Tarim River basin, which covers four subbasins characterized by large area, sparse gauge stations, mixed runoff supplied by snowmelt and rainfall, and remarkably spatially heterogeneous precipitation. Taking the Kaidu River basin as a research area, this study analyzes the influence of these characteristics on the variables and parameters of the Snow Runoff Model and discusses the corresponding determination strategy to improve the accuracy of snowmelt simulation and forecast. The results show that: (i) The temperature controls the overall tendency of simulated runoff and is dominant to simulation accuracy, as the measured daily mean temperature cannot represent the average level of the same elevation in the basin and that directly inputting it to model leads to inaccurate simulations. Based on the analysis of remote sensing snow maps and simulation results, it is reasonable to approximate the mean temperature with 0.5 time daily maximum temperature. (ii) For the conflict between the limited gauge sta-tion and remarkably spatial heterogeneity of rainfall, it is not realistic to compute rainfall for each elevation zone. After the measured rainfall is multiplied by a proper coefficient and adjusted with runoff coefficient for rainfall, the measured rainfall data can satisfy the model demands. (iii) Adjusting time lag according to the variation of snowmelt and rainfall position can improve the simulation precision of the flood peak process. (iv) Along with temperature, the rainfall increases but cannot be completely monitored by limited gauge stations, which results in precision deterioration.     

LA‐ICP‐MS Analysis of Small Samples: Carbonate Reference Materials and Larval Fish Otoliths

This article proposes a methodology to analyse the composition of very small carbonate samples such as larval fish otoliths. The chemical composition of otoliths, which are carbonate structures in the inner ear, is often used to explore population dynamics in fishes. Recent advances in laser ablation‐inductively coupled plasma‐mass spectrometry have suggested its potential application to this field. In this study, analyses were performed using a 193 nm ArF Resonetics LA system, coupled to an Agilent 7700X‐ICP‐MS, with the following ablation parameters: a beam diameter of 5 μm, energy of 3 mJ, 2.7 J cm^?2, laser repetition rate of 10 Hz and translation speed of 2.5 μm s^?1. NIST SRM 610 glass was used as the primary calibration material. Performing this protocol, characterisation of a USGS GP‐4 reference material was achieved with suitable precision and accuracy, but the USGS MACS‐3 reference material appeared more heterogeneous under the ablation conditions tested. Calibration was performed using two different beam diameters (5 and 11 μm). Capelin (Mallotus villosus) otoliths measuring between 10 and 20 μm in diameter were tested. Even though a smaller beam diameter and lower energy were used compared with those normally employed to analyse larger otoliths, the method was successful.     

Mass Fractions of S,Cu, Se,Mo, Ag,Cd, In,Te, Ba,Sm, W,Tl and Bi in Geological Reference Materials and Selected Carbonaceous Chondrites Determined by Isotope Dilution ICP‐MS

Mass fractions of S, Cu, Se, Mo, Ag, Cd, In, Te, Ba, Sm, W and Tl were determined by isotope dilution sector field ICP‐MS in the same sample aliquot of reference materials using HF‐HNO₃ digestion in PFA beakers in pressure bombs and glassy carbon vessels in a high‐pressure asher (HPA‐S) for comparison. Additionally, Bi was determined by internal standardisation relative to Tl. Because isobaric and oxide interferences pose problems for many of these elements, efficient chromatographic separation methods in combination with an Aridus desolvator were employed to minimise interference effects. Repeated digestion and measurement of geological reference materials (BHVO‐1, BHVO‐2, SCo‐1, MAG‐1, MRG‐1 and UB‐N) gave results with < 5% relative intermediate precision (1s) for most elements, except Bi. Replicates of NIST SRM 612 glass digested on a hot plate were analysed by the same methods, and the results agree with reference values mostly within 2% relative deviation. Data for the carbonaceous chondrites Allende, Murchison, Orgueil and Ivuna are also reported. Digestion in a HPA‐S was as efficient as in pressure bombs, but some elements displayed higher blank levels following HPA‐S treatment. Pressure bomb digestion yielded precise data for volatile S, Se and Te, but may result in high blanks for W.