地球化学与环境样品分析标准物质和GeoReM数据库

在地球化学和环境样品分析中,标准物质发挥着越来越重要的作用。尽管通常要求分析者必须提供量值溯源的测量过程的信息;但大多数论著都未给出标准物质的数据。文章强调标准物质在地球化学分析工作中的重要性,同时将地球化学与环境样品分析标准物质数据库GeoReM介绍给中国的地质分析工作者。GeoReM数据库收录了1880个地球化学和环境样品分析标准物质的定值数据、汇编数据、分析数据及其他相关信息,其中包括156个由中国制备的标准物质的数据。GeoReM数据库还给出了所收录标准物质推荐使用的首选值及其不确定度。尽管这些首选值大多都不是按照国际标准化组织的有关规定而确定的,但是它们的置信度高,因而被广泛应用于仪器校准和分析数据的质量监控。文章还指出要将中国研制的、发表在中文期刊上的标准物质也收录到GeoReM数据库中,这对于促进中国的相关研究,增加国际认可度具有重要意义。     

International viewpoint and news

Environmental Earth Sciences -     

Economically optimal risk reduction strategies in the face of uncertain climate thresholds

Anthropogenic greenhouse gas emissions may trigger climate threshold responses, such as a collapse of the North Atlantic meridional overturning circulation (MOC). Climate threshold responses have been interpreted as an example of “dangerous anthropogenic interference with the climate system” in the sense of the United Nations Framework Convention on Climate Change (UNFCCC). One UNFCCC objective is to “prevent” such dangerous anthropogenic interference. The current uncertainty about important parameters of the coupled natural – human system implies, however, that this UNFCCC objective can only be achieved in a probabilistic sense. In other words, climate management can only reduce – but not entirely eliminate – the risk of crossing climate thresholds. Here we use an integrated assessment model of climate change to derive economically optimal risk-reduction strategies. We implement a stochastic version of the DICE model and account for uncertainty about four parameters that have been previously identified as dominant drivers of the uncertain system response. The resulting model is, of course, just a crude approximation as it neglects, for example, some structural uncertainty and focuses on a single threshold, out of many potential climate responses. Subject to this caveat, our analysis suggests five main conclusions. First, reducing the numerical artifacts due to sub-sampling the parameter probability density functions to reasonable levels requires sample sizes exceeding 10³. Conclusions of previous studies that are based on much smaller sample sizes may hence need to be revisited. Second, following a business-as-usual (BAU) scenario results in odds for an MOC collapse in the next 150 years exceeding 1 in 3 in this model. Third, an economically “optimal” strategy (that maximizes the expected utility of the decision-maker) reduces carbon dioxide(CO₂) emissions by approximately 25% at the end of this century, compared with BAU emissions. Perhaps surprisingly, this strategy leaves the odds of an MOC collapse virtually unchanged compared to a BAU strategy. Fourth, reducing the odds for an MOC collapse to 1 in 10 would require an almost complete decarbonization of the economy within a few decades. Finally, further risk reductions (e.g., to 1 in 100) are possible in the framework of the simple model, but would require faster and more expensive reductions in CO₂ emissions.     

The chemical composition of medieval wood ash glass from Central Europe

Medieval wood ash glass classified as 6 early medieval wood ash glasses, 17 wood ash glasses, 5 early wood ash lime glasses, 7 wood ash lime glasses and 9 mixed alkali glasses has been analyzed by microprobe and ICP-mass spectrometry on 61 elements. Their calcium oxide to potassium oxide ratio (CaO/K₂O) increases from early to late medieval glasses according to an increase of the proportion of twigs in the bulk amount of wood (logs plus twigs). Twigs because of their relatively large proportion of bark contain more calcium than wood logs. The ratio CaO/K₂O of the glasses from not yet evaluated excavations can be used for dating. The observation that the 25 minor elements Be, Sc, V, Cr, Ge, Y, Nb, REE (La to Lu), Ta, W and Bi occur in almost equal concentrations in the five subtypes of wood ash glass makes it highly probable that these elements were introduced into the starting mixtures of the glasses by means of quartz from quartz-rich sand with heavy minerals. The majorities of the wood ash glasses contain so-called europium anomalies within the group of rare-earth elements (REE). Their Eu concentrations normalized to those of the Continental Earth's Crust are lower than the normalized samarium and gadolinium concentrations. These Eu anomalies are apparently inherited from the granitic source of quartz in the upper Continental Earth's Crust. Soda ash and soda lime glass as the other major types in the history of glass contain no Eu anomaly. Therefore a different source of quartz has caused this important element constellation for these glass types. The elements K, Cu, Rb and S are physiologically separated from Ca, P, Mn, Sr and B during the growth of the wood and bark, respectively, in the trees. Different sources of the metals Cu and Co were used for colouring the glasses of our report.     

Enstatite achondrite meteorites (aubrites) and the histories of their asteroidal parent bodies

The aubrites are nearly monomineralic enstatite pyroxenites, consisting mostly of nearly FeO-free enstatite, with minor albitic plagioclase, nearly FeO-free diopside and forsterite, metallic Fe,Ni, troilite, and a host of rare accessory minerals, many unknown from Earth, that formed under highly reducing conditions. As a result, many of the normally lithophile elements such as Ti, Cr, Mn, Na, etc. behave partly as chalcophiles (i.e., occur in sulfides), and Si is partly siderophile and occurs in metallic Fe,Ni. Aubrites must therefore have formed in a very unique part of the solar nebula, possibly within 1 AU of the Sun. While of the 27 aubrites, 15 are fragmental breccias, 6 are regolith breccias, and 6 are described as non-brecciated, their ingredients are clearly of igneous origin and formed by melting and fractional crystallization, possibly of a magma ocean. This is indicated by the occurrence of a variety of lithic clasts of igneous origin, and by the REE and other trace element distributions. Their highly reduced nature and their oxygen isotopic compositions suggest close kinship to the enstatite chondrites. However, they did not form from known EH or EL chondrites on their parent bodies. Rather, they formed from enstatite chondrite-like material on at least two separate parent bodies, the Shallowater parent body and, for all other aubrites, on the aubrite parent body. Visible and near-infrared reflectance spetra of asteroids suggest that the aubrite parent bodies may be asteroids of the E-type and perhaps the E(II) sub-class, such as 3103 Eger and 2867 Steins (the target of the Rosetta Mission). If aubrites formed by the melting and fractional crystallization of enstatite chondrite-like parent lithologies, which should have contained ～10 vol% plagioclase, then meteorites of enstatite-plagioclase basaltic composition should exist, which is not the case. These early basaltic melts may have been removed from the aubrite parent body by explosive pyroclastic volcanism, and these small pyroclasts would have been destroyed in space long ago. Age dates suggest that the aubrites formed very early in the history of the solar system, within a few Ma of CAI formation, and that the heat sources for heating and melting of their parent bodies were, most likely, short-lived radionuclides such as ²⁶Al and, perhaps, ⁶⁰Fe. Finally, attention has been drawn to the surface composition of Mercury of low bulk FeO and of nearly FeO-free enstatite, perhaps with plagioclase, diopside and sulfide. While known aubrites clearly did not originate from Mercury, recent calculations suggest that several percent of high-speed ejecta from Mercury reach Earth. This is only factors of 2–3 less than typical launches from Mars and, since there are now 53 Martian meteorites in our collections, meteoriticists should be alert to the potential discovery of a genuine meteorite from Mercury which, superficially, should resemble aubrites. However, recent results from the Neutron Spectrometer of the Messenger Flyby of Mercury have been interpreted to suggest that the planet’s surface may, in fact, contain abundant Fe–Ti-oxides and, if true, a meteorite from Mercury should not resemble any currently known meteorite type.     

Highly depleted Hadean mantle reservoirs in the sources of early Archean arc-like rocks, Isua supracrustal belt, southern West Greenland

Growing evidence from the accessible geological record reveals that crust-mantle differentiation on Earth started as early as 4.4 Ga. In order to assess the extent of early Archean mantle depletion, we obtained ¹⁷⁶Lu-¹⁷⁶Hf, ¹⁴⁷Sm-¹⁴³Nd, and high field strength element (HFSE) concentration data for the least altered, well characterized boninite-like metabasalts and associated metasedimentary rocks from the Isua supracrustal belt (southern West Greenland). The metasediments exhibit initial εHf₍₃₇₂₀₎ values from −0.7 to +1.5 and initial εNd₍₃₇₂₀₎ values from +1.6 to +2.1. Initial εHf₍₃₇₂₀₎ values of the least altered boninite-like metabasalts span a range from +3.5 to +12.9 and initial εNd₍₃₇₂₀₎ values from −0.3 to +3.2. These initial Hf-isotope ratios display coherent trends with SiO₂, Al₂O₃/TiO₂ and other relatively immobile elements, indicating contamination via assimilation of enriched components, most likely sediments derived from the earliest crust in the region. This model is also consistent with previously reported initial γOs₍₃₇₂₀₎ values for some of the samples. In addition to the positive εHf₍₃₇₂₀₎ values, the least disturbed samples exhibit positive εNd₍₃₇₂₀₎ values and a co-variation of εHf₍₃₇₂₀₎ and εΝd₍₃₇₂₀₎ values. Based on these observations, it is argued, that the most depleted samples with initial εHf₍₃₇₂₀₎ values of up to +12.9 and high ¹⁷⁶Lu/¹⁷⁷Hf of ∼0.05 to ∼0.09 tap a highly depleted mantle source with a long term depletion history in the garnet stability field. High precision high field strength element (HFSE) data obtained for the Isua samples confirm the contamination trend. Even the most primitive samples display negative Nb-Ta anomalies and elevated Nb/Ta, indicating a subduction zone setting and overprint of the depleted mantle sources by felsic melts generated by partial melting of eclogite. Collectively, the data for boninite-like metabasalts support the presence of strongly depleted mantle reservoirs as previously inferred from Hf isotope data for Hadean zircons and combined ¹⁴²Nd-¹⁴³Nd isotope data for early Archean rocks.     

Jurassic cooling ages in Paleozoic to early Mesozoic granitoids of northeastern Patagonia: 40Ar/39Ar, 40K–40Ar mica and U–Pb zircon evidence

International Journal of Earth Sciences - U–Pb SHRIMP zircon crystallization ages and Ar–Ar and K–Ar mica cooling ages for basement rocks of the Yaminué and Nahuel Niyeu...     

Non‐Matrix‐Matched Calibration for the Multi‐Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA‐ICP‐MS: A Comparison with Nanosecond Lasers

LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values.     

Nucleosynthetic isotope variations in chondritic meteorites and their relationship to bulk chemistry

The relationship of mass-independent stable isotope anomalies with the chemistry of chondritic meteorites provides constraints on mixing and fractionation processes in the early solar nebula. The present study emphasizes the strong correlation of nucleosynthetic isotope variations among ordinary chondrites (OC), enstatite chondrites (EC), Earth, CI-chondrites, and Ca, Al-rich inclusions (CAI) in ε⁵⁰Ti versus ε⁵⁴Cr space. This correlation indicates variable contamination of chondritic reservoirs with material from a single source providing neutron-rich nuclei such as ⁵⁰Ti, ⁵⁴Cr, and ⁶²Ni. The well-defined linear relationship of ε⁵⁰Ti versus ε⁵⁴Cr indicates that all reservoirs on the correlation line (“chondrite reference line”) started with a CI-chondritic (solar) Cr/Ti ratio, irrespective of the present Cr/Ti ratio of the samples falling on the chondrite reference line. The isotope compositions of carbonaceous chondrites (CC) do not fit the chondrite reference line. Their isotope composition is consistent with a mixture of chondritic meteorites originally falling on the chondrite reference line and volatile element depleted CAIs. However, CC cannot result from addition of CAIs to OC or EC. Neither can OC and EC be produced by loss of refractory components from CI-meteorites. Also, stable isotopes are inconsistent with OC being derived from EC, and vice versa, by a chemical fractionation process. The enrichment of the Earth in refractory lithophile elements is not the result of addition of a refractory component to a chondritic reservoir. It is rather the result of internal fractionation of a chondritic reservoir.