Marine biogeochemistries of Be and Al: A study based on cosmogenic10Be, Be and Al in marine calcite, aragonite, and opal

The geochemical behaviors of Be and Al in ocean waters have been successfully studied in recent years using natural, cosmogenic, radioactive¹⁰Be and²⁶Al as tracers. The present day dissolved concentrations and distribution of the stable and radioactive isotopes of Be and Al in ocean waters have revealed their short residence times and appreciable effects of exchange fluxes at the coastal and ocean-sediment interfaces. It follows that concentrations of these particle-active elements must have varied in the past with temporal changes in climate, biological productivity and aeolian flux of continental detritus to the oceans. We therefore investigated the feasibility of extending the measurements of Be and Al isotope concentrations in marine systems to the 10³–10⁶ y BP time scale. We report here the discovery of significant amounts of intrinsic Be and Al in marine foraminiferal calcite and coral aragonite, and of Al in opal (radiolarians) and aragonite (coral), which makes it possible to determine¹⁰Be/Be and²⁶Al/Al in oceans in the past. We also report measured¹⁰Be/⁹Be in foraminiferal calcite in Pacific Ocean cores, which reveal that the concentrations and ratios of the stable and cosmogenic isotopes of Be and Al have varied significantly in the past 30 ky. The implications of these results are discussed.     

Extinct Be in Type A calcium-aluminum-rich inclusions from CV chondrites

We have found clear evidence of live ¹⁰Be in five normal Type A Calcium-aluminum-rich inclusions (CAIs), one normal Type B CAI, and one FUN Type A CAI, all from CV3 chondrites. The (¹⁰Be/⁹Be)₀ ratios range from ∼0.36 × 10^-3 to ∼0.77 × 10^-3 and are similar to those found by previous workers. The (¹⁰Be/⁹Be)₀ ratios do not correlate in a temporal fashion with (²⁶Al/²⁷Al)₀, suggesting that ¹⁰Be and ²⁶Al were produced by different mechanisms. An examination of possible sources for the short-lived radionuclides indicates that production of ¹⁰Be was almost certainly by particle irradiation, possibly within the solar system, and was probably accompanied by significant production of ⁴¹Ca and ⁵³Mn. In contrast, all of the ⁶⁰Fe, most of the ²⁶Al, and some of the ⁵³Mn were probably produced in stars and were imported into the solar system within presolar dust grains.     

黄土和红粘土中宇宙成因核素定年的潜力: 10 Be浓度与化学成分的关系*

宇宙成因核素¹⁰ Be(半衰期1.5Ma)不但是古环境变化的示踪剂,而且具有确定地质年龄的能力。80个全岩样品的¹⁰ Be和化学分析数据表明,黄土高原约6Ma以来的红粘土和黄土序列中年龄校正的¹⁰ Be浓度与沉积物粒度和风化程度的化学指标具有显著的关系。根据这种关系建立的¹⁰ Be浓度与化学指标的经验回归线性模型,可以估计红粘土和黄土形成时的¹⁰ Be浓度,确定红粘土和黄土形成的¹⁰ Be放射性年龄。     

暴露测年样品中26Al和10Be分离及其加速器质谱测定

在已有实验流程基础上,建立并优化了石英样品中Be和Al提取、纯化等实验流程,设计的流程条件实验包括实验试剂、器皿和离子交换柱选择、离子交换树脂分离Be和Al时酸浓度选择等。结果表明,选择钢铁研究总院研制的⁹Be标准溶液作为¹⁰Be样品制备的载体;使用一次性实验器皿;选用4 cm规格的离子交换柱;用0.05 mol/L草酸和0.75 mol/L盐酸混合溶液洗脱吸附于阴离子树脂上的Al,可有效提取、纯化样品中的Be和Al。加速器质谱(AMS)测量结果显示,13组化学空白的¹⁰Be/⁹Be和²⁶Al/²⁷Al比值平均值分别为7.48×10^-15和1.96×10^-15,与国内已有宇宙成因核素实验室的结果(5×10^-15~8×10^-15)具有可比性。电感耦合等离子体发射光谱(ICP-AES)的测量结果表明,Be、Al回收率分别达90%和60%。基于新建立的实验流程分析了祁连山北侧金佛寺的一个岩石样品,获得了¹⁰Be和²⁶Al的暴露年代分别为(10.7±1.0) ka和(10.0±1.2) ka,与前人研究结果一致。     

南黄海、东海陆架及冲绳海槽北部 沉积物的10 Be和9 Be记录*

文章讨论了南黄海泥质区、东海陆架及冲绳海槽北部表层沉积物和柱状岩芯中¹⁰ Be及⁹ Be含量的水平和垂直分布,并与重金属Pb的分布进行了比较。表层沉积物中的¹⁰ Be,⁹ Be和Pb三者表现出完全不同的分布特征。¹⁰ Be的分布主要受黑潮及其支流黄海暖流所支配; ⁹ Be的分布受黄河陆源物质输入的影响,主要集中在南黄海泥质区; Pb则主要分布在长江口和琉球群岛附近,反映了人类活动的影响。冲绳海槽北部末次冰期和全新世时¹⁰ Be的沉积通量变化在整体上反映了¹⁰ Be大气生产率的变化,即地球磁场屏蔽效应的影响。03孔全新世时¹⁰ Be的沉积通量 (1.12×10⁹atoms/cm²ka)基本上等于¹⁰ Be的现代大气平均生产率,而在末次冰期时平均为4.06×10⁹atoms/cm²ka, 高于¹⁰ Be 的现代大气平均生产率3倍以上。在冲绳海槽由于黑潮的缘故,¹⁰ Be对气候的变化响应要比极地冰芯的¹⁰ Be变化响应灵敏的多,对气候变化信号起了放大的作用。冰期时冲绳海槽北部¹⁰ Be的沉积通量远远高于太平洋大洋海区,充分反映了黑潮的传送带作用和边缘海的聚焦沉积作用,并表明末次冰期时在千年尺度上黑潮仍流经冲绳海槽,且强度并未减弱。 ¹⁰ Be的通量在新仙女木时降到整个岩芯所跨时期的最低点,甚至低于¹⁰ Be的现代大气平均生产率,因此推测在新仙女木事件时,黑潮的变动特别大,有可能改向或断流。     

河流阶地样品中石英纯化和宇宙核素~(10)Be和~(26)Al分离方法研究

经历反复埋藏暴露演化过程的河流阶地样品,难以用常规方法将原生宇宙核素10Be、26Al有效分离。本文在前人实验方法基础上,使用人工挑选、磁选仪分选及酸洗方法,分离样品中碳酸盐、含铁矿物及大气生成的10Be,进一步优化了石英提纯实验流程。结果表明:长度为9 cm、内径为1 cm的阴离子交换树脂装置匹配4 mol/L氢氟酸淋滤液,可将B、Mg、Ca、Cr、Fe、Mn、Ni、Ti和Be、Al有效分离,Be、Al回收率分别可达95.7%、85.7%。阳离子交换树脂能有效分离Be、Al,两元素回收率均达到85%。获得10Be/9Be和26Al/27Al流程空白分别为2.19×10-15和1.63×10-15。优化后的实验方法显著提高了河流阶地样品中原生宇宙核素10Be、26Al的纯化效率,且10Be/9Be和26Al/27Al流程空白数值与国内外实验室具有可比性。采用本方法获得了成都平原冲积物10Be、26Al暴露年龄分别是76.36±9.51 ka和69.44±14.13 ka,为评价龙门山前缘隐伏断裂构造特征和活动性提供了年代学依据。     

深海沉积物10Be记录研究

DSDP519钻孔¹⁰Be测定结果表明，在B／M，M／G两地磁极性倒转期间，¹⁰Be产生率均约增加20％。DSDP519孔δ¹⁰Be曲线与DSDP502孔δ¹⁸O曲线具有明显的正相关关系。CT85－5钻孔¹⁰Be曲线在34000±3000aB．P存在明显的峰，峰值比正常值高出2．5倍，⁹Be，Zn变化曲线中均未观察到此峰，与Vostok冰芯¹⁰Be峰在时间上属于同期。这进一步说明了此时期内¹⁰Be浓度增加是全球性的，只能归因于¹⁰Be产生率的增加。Raisbeck峰讯号可以成为某些储存库精确时标。     

Paleo-ocean chemistry records in marine opal: Implications for fluxes of trace elements, cosmogenic nuclides (Be and Al), and biological productivity

Here, we provide evidence suggesting that marine (diatom) opal contains not only a high fidelity record of dissolved oceanic concentrations of cosmic ray-produced radionuclides, ¹⁰Be and ²⁶Al, but also a record of temporal variations in a large number of trace elements such as Ti, Fe, Zn and Mn. This finding is derived from measurements in purified biogenic opal that can be separated from detrital materials using a newly developed technique based on surface charge characteristics. Initial results from a sediment core taken near the present-day position of the Antarctic Polar Front (ODP Site 1093) show dramatic changes in the intrinsic concentrations of, Be, Al, Ti, Fe, Mn and Zn in the opal assemblages during the past ∼140 kyr BP. The results imply appreciable climatically controlled fluctuations in the level of bioreactive trace elements. The time series of total Be, Al, Ti, Fe and ¹⁰Be in the sediment core are all well correlated with each other and with dust records in the polar ice cores. The observations suggest that a significant flux of these trace metals to oceans is contributed by the aeolian dust, in this case, presumably from the Patagonia. This observation also allows determination of fluxes of dust-contributed ¹⁰Be to the Antarctica ice sheets. However, our data show that the relationships among the various metals are not perfectly linear. During periods of higher dissolved concentrations of trace elements (indicated by Fe and Ti) the relative concentrations of bioreactive elements, Be, Al, Mn and Zn are decreased. By contrast, the Fe/Zn and Fe/Mn ratios decrease significantly during each transition from cold to warm periods. The relative behavior could be consistent with any of the following processes: (i) enhanced biological productivity due to greater supply of the bioreactive elements (e.g. Zn) during cold periods (ii) increased biological and inorganic scavenging of particle active elements (e.g. Be and Al) during early interglacial periods (iii) differential uptake/removal of the metals by the various diatom taxa whose relative productivity or growth rate changes with large scale climate. In any case, with one sedimentary phase and in single sedimentary sections, we now have the potential to compare directly a proxy for aeolian input of micronutrients (e.g. Fe or Ti), with a proxy for production (e.g. ²⁶Al/Al ratios). We expect that studies of the temporal records of trace elements and cosmogenic nuclides in contrasting regions of upwelling and productivity, which exhibit different sensitivities to global climate fluctuations and micronutrient inputs, would lead to a direct and comprehensive test of ideas such as the hypothesis of iron control of atmospheric carbon dioxide [Martin, J.H., 1990. Glacial-interglacial CO₂ change: the iron hypothesis. Paleoceanography5, 1-13]. Our present data from a single site do not show that increases in dissolved Fe concentrations, per se, were responsible for increased biological productivity. However, a much clearer picture of the effect of increased dust fluxes should emerge when we have data for trace elements and the cosmogenic nuclides, ¹⁰Be and ²⁶Al from various oceanic provinces.     

Geochemical and anthropogenic enrichments of Mo in sediments from perennially oxic and seasonally anoxic lakes in Eastern Canada

We measured the vertical distributions of Mo, Fe, Mn, sulfide, sulfate, organic carbon, major ions, and pH in sediment porewater from one perennially oxic and three seasonally anoxic lacustrine basins in Eastern Canada, as well as those of Mo, acid volatile sulfide, Fe, Mn, Al, organic C, ²¹⁰Pb and ¹³⁷Cs in sediment cores from the same sites. The only input of anthropogenic Mo to these lakes comes from atmospheric deposition.The relatively monotonous distribution of Mo in the porewater of three seasonally anoxic basins suggests that Mo is not redistributed in the sedimentary column during periods of anoxia. In contrast, porewater Mo profiles obtained at three sampling dates in a perennially oxic basin display sharp Mo peaks below the sediment-water interface, indicating redistribution subsequent to deposition. Modeling of these latter porewater Mo profiles with a diagenetic reaction-transport equation coupled to comparisons among the various porewater and solid phase profiles reveal that Mo is released at 1-2 cm depth as a consequence of the reductive dissolution of Fe oxyhydroxides and scavenged both at the vicinity of the sediment-water interface, by re-adsorption onto authigenic Fe oxyhydroxides, and deeper in the sediments where dissolved sulfide concentrations are higher. The estimated rate constant for the adsorption of Mo onto Fe oxyhydroxides is 36 ± 45 cm³ mol⁻¹ s⁻¹.Diagenetic modeling indicates that authigenic Mo in sediments of the perennially oxic basin represents about one-third of the total solid phase Mo in the first cm below the sediment-water interface and only one tenth below this horizon. If we assume that no authigenic Mo is accumulated in the seasonally anoxic lake sediments we conclude that the sediment Mo concentrations, which are up to 3-16 times higher than the average lithogenic composition, depending on the lake, are mainly due to atmospheric deposition of anthropogenic Mo and not to the formation of authigenic Mo phases. Reconstructed historical records of the atmospheric Mo deposition indicate maximum values in the 1970s and 1980s and significant decreases since then. Emissions to the atmosphere associated with the smelting of non-ferrous ores and coal combustion appear to be the most important sources of anthropogenic Mo.     

高分辨10Be记录与黄土地层定年

利用Ｂ／Ｍ地磁极性倒转层位０．７３ＭａＢ．Ｐ．时间参考点，通过黄土剖面_１０Ｂｅ变化曲线与深海ＳＰＥＣＭＡＰδ_１８Ｏ变化曲线匹配拟合，求得洛川黄土剖面０．７５Ｍａ以来的相对连续时标。时标精度约５０００—１００００ａ。由于０．１５Ｍａ以来洛川剖面加密取样以及_１０Ｂｅ、δ_１８Ｏ两曲线之间更好的相关性，_１０Ｂｅ相对时标精度与ＳＰＥＣＭＡＰδ_１０Ｏ时标精度大体相同，即３０００—５０００ａ。各时期_１０Ｂｅ通量与黄土堆积速率之间存在十分好的线性相关关系，展示了一条崭新的地层定年途径。黄土_１０Ｂｅ记录３５０００ａＢ．Ｐ．处的Ｒａｉｓｂｅｃｋ峰可被用作地层时间参考点。黄土_１０Ｂｅ／(２６)Ａｌ值、黄土石英中“就地”成因_１０Ｂｅ／(２６)Ａｌ值以及“就地”成因_１０Ｂｅ浓度等均可望应用于黄土地层精确定年。     

Uranium geochemistry on the Amazon shelf: Evidence for uranium release from bottom sediments

In Amazon-shelf waters, as salinity increases to 36.5 × 10⁻³, dissolved uranium activities increase to a maximum of 4.60 dpm 1⁻¹. This value is much higher than the open-ocean value (2.50 dpm 1⁻¹), indicating a source of dissolved uranium to shelf waters in addition to that supplied from open-ocean and riverine waters. Uranium activities are much lower for surface sediments in the Amazon-shelf seabed (mean: 0.69 ±.09 dpm g⁻¹) than for suspended sediments in the Amazon River (1.82 dpm g⁻¹). Data suggest that the loss of particulate uranium from riverine sediments (and the consequent input of dissolved uranium to shelf waters) is probably the result of uranium desorption from the ferric-oxyhydroxide coatings on sediment particles, and/or uranium release by mobilization of the ferric oxyhydroxides. The total flux (i.e., riverine flux plus desorbed-remobilized particulate flux) of dissolved ²³⁸U from the Amazon shelf (about 1.2 × 10¹⁵ dpm yr⁻¹) constitutes about 15% of uranium input to the world ocean, commensurate to the Amazon River's contribution to world river-water discharge (approximately 18%). Measurement of only the riverine flux of dissolved ²³⁸U underestimates, by a factor of about 5, the flux of dissolved²³⁸U from the Amazon shelf to the open ocean.     

Late Cenozoic sedimentation and metal deposition in the North Pacific

Similar major chemical variations in cores from three sites across a wide area of the North Pacific are modeled by coupling the vertical and horizontal motions of the Pacific plate with a constant authigenic flux of elements into the sediments. Superimposed over this flux is an input of detrital material of relatively constant chemical composition. The major features of sediment chemistry of cores from the North Pacific apparently vary in a fairly uniform and systematic manner, and these variations are consistent with Cenozoic plate movement. Elements with a significant authigenic component (e.g., Mn, Co, Cu, Ni) display high concentrations at depth in cores that correspond to the period when the seafloor, while under the low-productivity, subtropical gyre of the N. Pacific, accumulated sediment at an extremely slow rate (~1 mm/kyr). These concentrations were diluted when the sites experienced an increase in the eolian mass accumulation rate first brought about by migration into the influence of the westerlies and then, dominantly, by the huge input of wind-blown detritus which corresponded to the onset of Northern Hemisphere glaciation. A comparison of ¹⁰Be profiles to the profiles of metal concentrations is used to reveal the occurrence of haituses in the sediment column over the past 8 m.y.     

Atmospheric deposition of Be and Be in New Zealand rain (1996-98)

Beryllium isotope concentrations were determined in monthly rainfall collections at three sites across New Zealand (36 to 45° S), from October 1996 to November 1998. At the northern sites of Leigh (near Auckland) and Gracefield (near Wellington), ⁷Be and ¹⁰Be concentrations are relatively constant at 1.2 to 1.4 × 10⁷ atoms kg⁻¹ rain and 2.1 to 2.6 × 10⁷ atoms kg⁻¹ rain, respectively. These concentrations correspond to annual flux rates of ∼15 and ∼27 × 10⁹ atoms m⁻² y⁻¹, respectively. At the southern site of Dunedin, concentrations are similar to those at the northern sites, but flux rates are significantly lower at ∼ 9 and ∼19 × 10⁹ atoms m⁻² y⁻¹, respectively, because of lower average rainfall east of the Southern Alps mountain range. These results are broadly similar to those reported by Brown et al. (1989) and Knies et al. (1994) for rain from midlatitude sites in the USA sampled from 1986 to 1994. Mean ⁷Be/¹⁰Be ratios for New Zealand (0.47 to 0.61) are, however, significantly lower than for the USA (0.69 to 0.78), due in part to the addition of ¹⁰Be from re-suspended dust. Subtraction of the dust component increases the New Zealand ⁷Be/¹⁰Be ratios to 0.70 (Leigh), 0.65 (Gracefield) and 0.50 (Dunedin). The adjusted results provide evidence for transfer of older stratospheric air to the troposphere in late-spring-summer, an effect which is strongest in the north. The overall reduction of ⁷Be/¹⁰Be from north to south implies an increase in residence time from ∼ 80 to ∼100 d for Be isotopes in the atmosphere above New Zealand.     

Lead in sediments and suspended particulate matter of the German Bight: natural versus anthropogenic origin

Sediments (568) and suspended particulate matter (SPM, 302 samples) of the southern German Bight and the adjacent tidal flat areas were analysed for selected major elements (Al, Fe, K), trace metals (Mn, Pb), and ²⁰⁶Pb/²⁰⁷Pb ratios using XRF, ICP–OES, ICP–MS. For selected samples a leaching procedure with 1 M HCl was used to estimate the Pb fraction associated with labile phases (e.g. Mn/Fe-oxihydroxide coatings) in contrast to the resistant mineral matrix. Enrichment factors versus average shale (EFS) reveal elevated Pb contents for all investigated sediments and SPM in the following order: Holocene tidal flat sediments (HTF, human-unaffected) <recent tidal flat sediments (RTF) <Helgoland Island mud hole sediments (MH) <nearshore SPM (SPM concentration>5 mg l⁻¹) < offhore SPM (<5 mg l⁻¹). Besides pollution, RTF contain elevated amounts of natural Pb-rich materials (K-feldspars and heavy minerals) due to a man-made high-energy environment (dike building) in comparison to HTF. ²⁰⁶Pb/²⁰⁷Pb ratios of RTF (1.192±0.019) are similar to the local geogenic background, determined from HTF (1.207±0.008). In contrast, Pb isotope ratios of nearshore SPM (1.172±0.007) and offshore SPM (1.166±0.012) show a distinct shift towards the anthropogenic/atmospheric signal of 1.11–1.14. This difference between RTF and SPM supports the assumption of low deposition rates of fine material in the intertidal systems. As the ²⁰⁶Pb/²⁰⁷Pb ratios of SPM do not reach the pure anthropogenic signal, the adsorbed Pb fraction was examined (leaching). However, the leachates also contained large amounts of geogenic Pb (SPM ≈40%, recent sediments ≈60%). The authors assume that the uptake of natural Pb occurs in nearshore waters, presumably in the turbid intertidal systems. Possible sources for dissolved Pb are mobilisation during weathering (geogenic signal) and dissolution of oxihydroxide coatings with subsequent release from porewaters, and unspecific riverine input. Comparatively small parts of SPM leave the coastal water mass and reach the open North Sea. This process therefore leads to a decontamination of the tidal flat sediments. Due to more pronounced atmospheric input, the offshore SPM becomes enriched in anthropogenic Pb as indicated by decreasing ²⁰⁶Pb/²⁰⁷Pb ratios with increasing distance from the coast.     

Isotopic records in CM hibonites: Implications for timescales of mixing of isotope reservoirs in the solar nebula

The magnesium isotopic compositions of 26 hibonite-bearing inclusions from the CM chondrite Murchison, as well as isotopic measurements on a subset of these samples for oxygen, titanium, and lithium-beryllium-boron are reported along with oxygen isotopic data for an additional 13 hibonites that were previously investigated for other isotope systems (magnesium, potassium, calcium, and titanium) and rare earth element concentrations. Magnesium isotopic compositions divide CM hibonites into two distinct populations which correlate perfectly with their mineralogy and morphology, as previously discovered by Ireland [Ireland T. R. (1988) Correlated morphological, chemical, and isotopic characteristics of hibonites from the Murchison carbonaceous chondrite. Geochim. Cosmochim. Acta52, 2827-2839]: Spinel-HIBonite spherules (SHIBs) bear evidence of in situ²⁶Al decay, whereas PLAty-Crystals (PLACs) and Blue AGgregates (BAGs) either lack resolvable ²⁶Mg-excesses or exhibit ²⁶Mg deficits by up to ∼4‰. High precision, multiple collector SIMS analyses show that 6 of 7 SHIBs investigated fall on a single correlation line implying ²⁶Al/²⁷Al = (4.5 ± 0.2) × 10⁻⁵ at the time of isotopic closure, consistent with the “canonical” ²⁶Al abundance characteristic of internal isochrons in many calcium-aluminum-rich inclusions (CAIs). One SHIB sample exhibits Δ²⁶Mg^∗ consistent with a “supracanonical” ²⁶Al/²⁷Al ratio of (6.4 ± 0.5) × 10⁻⁵. The PLAC hibonites contain highly anomalous titanium isotopic compositions, with δ⁵⁰Ti values ranging from −80‰ to almost +200‰, whereas SHIBs generally lack large Ti isotopic anomalies.Eight out of 11 ²⁶Al-free PLAC hibonite grains record ¹⁰B/¹¹B excesses that correlate with Be/B; the inferred initial ¹⁰Be/⁹Be ratio of (5.1 ± 1.4) × 10⁻⁴ is lower than the best-constrained ¹⁰Be/⁹Be of (8.8 ± 0.6) × 10⁻⁴ in a CV CAI. The data demonstrate that ¹⁰Be cannot be used as a relative chronometer for these objects and that most of the ¹⁰Be observed in CAIs must be produced by irradiation of precursor solids in the early solar system. The lack of ²⁶Al in PLAC hibonites indicates that significant amounts of ²⁶Al were not formed in the same spallogenic processes that made ¹⁰Be in PLAC precursors. This is most easily understood as indicating very early formation of the PLAC hibonites, prior to the incorporation and mixing of ²⁶Al into the solar nebula, although an alternative scenario, which invokes irradiation under different solar flare conditions, cannot be ruled out. Lithium isotopes are normal within uncertainties, probably reflecting contamination and/or postcrystallization exchange.The oxygen isotopic compositions of SHIBs and PLACs are all highly ¹⁶O-enriched, but are not derived from a homogeneous reservoir: Δ¹⁷O values span a range of ∼−28‰ to −15‰. The ranges of ¹⁶O-enrichment in SHIBs and PLACs overlap and are less “anomalous” than the most ¹⁶O-enriched compositions found in meteorites [Kobayashi S., Imai H. and Yurimoto H. (2003) New extreme ¹⁶O-rich chondrule in the early solar system. Geochem. J.37, 663-669]. Both PLACs and SHIBs formed in ¹⁶O-enriched reservoirs characterized by small-scale heterogeneities in the gas phase. If such heterogeneities were generated by an admixture of relatively ¹⁶O-poor gas created by self-shielding during CO photolysis and transported to the hot inner regions of the accretion disk, then this process must have been initiated very early on, prior to the arrival of fresh radioactivity into the inner solar system. Oxygen isotope heterogeneities persisted throughout the formation interval of PLACs, CAI precursors, and SHIBs which could be as long as 3 × 10⁵ years based on ²⁶Al records.One SHIB and one BAG exhibit mass fractionated oxygen isotopic compositions similar to those seen in FUN inclusions and in several platy hibonite crystals [Lee T., Mayeda T. K. and Clayton R. N. (1980) Oxygen isotopic anomalies in Allende inclusion HAL. Geophys. Res. Lett.7, 493-496; Ireland T. R., Zinner E. K., Fahey A. J. and Esat T. M. (1992) Evidence for distillation in the formation of HAL and related hibonite inclusions. Geochim. Cosmochim. Acta56, 2503-2520; Ushikubo T., Hiyagon H. and Sugiura N. (2007) A FUN-like hibonite inclusion with a large ²⁶Mg-excess. Earth Planet. Sci. Lett.254, 115-126]. The suite of mass-fractionated hibonites exhibit a range of isotopic properties, including ²⁶Al/²⁷Al ratios from below detection to a “canonical” level and oxygen and titanium anomalies that are not exceptional by PLAC standards. This suggests that F (fractionation) processes—evaporation under (oxidizing) conditions—are not necessarily associated with sampling a special isotopic reservoir.     

Extra-terrestrial influx rates of cosmogenic isotopes and platinum group elements: realizable geochemical effects

We present estimates of “realizable” influx of selected cosmogenic isotopes, ³He, ¹⁰Be, ²⁶Al, and ¹⁴C, and platinum group elements, Ir, Os, and Re on the earth via influx of meteoroids. We define realizable as the particulate fraction of mass influx which is included in standard geochemical analyses of terrestrial sediments. This is the surviving mass fraction of size < 0.5-1 cm, which gets mixed with terrestrial samples, and is analyzed in normal terrestrial assays of sediments. Larger surviving meteoroid fragments, of the order of cm to m or larger, obviously belong to the non-realizable flux category, since (i) their distribution in terrestrial samples would be very patchy, resulting in a highly variable density matrix, and (ii) they would also generally (except in wide-diameter cores) be excluded from sediment cores. We estimate the realizable influx of meteoritic particles, based on a recent model describing production of smaller size fragments arising during the atmospheric entry of meteoroids. Implicit in this work is the assumption that the secondary fragments are not subject to much heating and therefore most of the initial ³He (and noble gases) would be preserved in the secondary fragments since after break-up they are not subjected to much heating. Under this assumption, production of small size fragments in the ablation process constitutes a “safe” landing mechanism for parts of the meteoroid. In this paper, we show that the meteoritic ablation/fragmentation process produces a significant flux of ³He, platinum group metals, and cosmogenic ²⁶Al. In fact, measurements of these isotopes in ocean sediments should allow a reasonable estimate of temporal variations in the flux of meteoroids of 50 cm to 5 m radii, which produce most of the secondary fragments in the size range <1 cm.We would like to state here that, as pointed out in our previous work, stratospheric collections would be biased towards collection of the primary incident extra-terrestrial particles, whereas terrestrial accumulations representing large (area × time) accumulations, as in the case of ocean sediments, would efficiently sample the fragmented particles.     

10Be and 26Al exposure‐age dating of bedrock surfaces on the Aran ridge,Wales: evidence for a thick Welsh Ice Cap at the Last Glacial Maximum

This paper presents results of the analysis of paired cosmogenic isotopes (¹⁰Be and ²⁶Al) from eight quartz‐rich samples collected from ice‐moulded bedrock on the Aran ridge, the highest land in the British Isles south of Snowdon. On the Aran ridge, comprising the summits of Aran Fawddwy (905 m a.s.l.) and Aran Benllyn (885 m a.s.l.), ²⁶Al and ¹⁰Be ages indicate complete ice coverage and glacial erosion at the global Last Glacial Maximum (LGM). Six samples from the summit ridge above 750–800 m a.s.l. yielded paired ¹⁰Be and ²⁶Al ages ranging from 17.2 to 34.4 ka, respectively. Four of these samples are very close in age (¹⁰Be ages of 17.5 ± 0.6, 17.5 ± 0.7, 19.7 ± 0.8 and 20.0 ± 0.7 ka) and are interpreted as representing the exposure age of the summit ridge. Two other summit samples are much older (¹⁰Be ages of 27.5 ± 1.0 and 33.9 ± 1.2 ka) and these results may indicate nuclide inheritance. The ²⁶Al/¹⁰Be ratios for all samples are indistinguishable within one‐sigma uncertainty from the production rate ratio line, indicating that there is no evidence for a complex exposure history. These results indicate that the last Welsh Ice Cap was thick enough to completely cover the Aran ridge and achieve glacial erosion at the LGM. However, between c. 20 and 17 ka ridge summits were exposed as nunataks at a time when glacial erosion at lower elevations (below 750–800 m a.s.l.) was achieved by large outlet glaciers in the valleys surrounding the mountains. Copyright © 2011 John Wiley & Sons, Ltd.     

10Be meltwater signal in Orca basin sediments,Gulf of Mexico

An increase in the cosmogenic beryllium-10 content of the Orca basin sediments due to the flooding of the Gulf of Mexico (GM) by meltwaters during the late Wisconsin interglacial is reported. A strong negative correlation (γ =-0.99) betweenδ ¹⁸ O (in the range o f-1.5‰ to +0.5‰) and¹⁰Be/Al ratio is seen. During intense flooding reflected by a decrease in δ¹⁸O by ∼ 2‰, this correlation may not hold as some of the sediments with low¹⁰Be/Al ratio and deposited on the shelf and slope regions of the GM during the earlier glacial period would also be washed into the basin. The deposited sediment would then be a mixture with a¹⁰Be/Al ratio lower than expected from the correlation     

The dissolved Beryllium isotope composition of the Arctic Ocean

We present the first comprehensive set of dissolved ¹⁰Be and ⁹Be concentrations in surface waters and vertical profiles of all major sub-basins of the Arctic Ocean, which are complemented by data from the major Arctic rivers Mackenzie, Lena, Yenisey and Ob. The results show that ¹⁰Be and ⁹Be concentrations in waters below 150 m depth are low and only vary within a factor of 2 throughout the Arctic Basin (350-750 atoms/g and 9-15 pmol/kg, respectively). In marked contrast, Be isotope compositions in the upper 150 m are highly variable and show systematic variations. Cosmogenic ¹⁰Be concentrations range from 150 to 1000 atoms/g and concentrations of terrigenous ⁹Be range from 7 to 65 pmol/kg, resulting in ¹⁰Be/⁹Be ratios (atom/atom) between 0.5 and 14 × 10⁻⁸. Inflowing Atlantic water masses in the Eurasian Basin are characterized by a ¹⁰Be/⁹Be signature of 7 × 10⁻⁸. The inflow of Pacific water masses across the Bering Strait is characterized by lower ratios of 2-3 × 10⁻⁸, which can be traced into the central Arctic Ocean, possibly as far as the Fram Strait. A comparison of the high dissolved surface ¹⁰Be and ⁹Be concentrations (corresponding to low ¹⁰Be/⁹Be signatures of ∼2 × 10⁻⁸) in the Eurasian Basin with hydrographic parameters and river data documents efficient and rapid transport of Be with Siberian river waters across the Siberian Arctic shelves into the central Arctic Basin, although significant loss and exchange of Be on the shelves occurs. In contrast, fresh surface waters from the Canada Basin also show high cosmogenic ¹⁰Be contents, but are not enriched in terrigenous ⁹Be (resulting in high ¹⁰Be/⁹Be signatures of up to 14 × 10⁻⁸). This is explained by a combination of efficient scavenging of Be in the Mackenzie River estuary and the shelves and additional supply of cosmogenic ¹⁰Be via atmospheric fallout and melting of old sea ice. The residence time of Be in the deep Arctic Ocean estimated from our data is 800 years and thus similar to the average Be residence time in the global ocean.     

Toward a geochemical mass balance of major elements in Lake Qinghai,NE Tibetan Plateau: A significant role of atmospheric deposition

Sediments in Lake Qinghai archive important information about past environmental changes. In order to faithfully interpret the sediment records and constrain the elemental cycles, it is critical to trace various sources of sediments in the lake. The results show that the elemental input–output budgets are imbalanced for most major elements between riverine fluxes and mass accumulation rate (MAR) of Lake Qinghai sediments. A realistic model must include contributions of dry/wet atmospheric deposition that allow the major element mass balance for the lake to be defined. The budget estimation is based on mass balances of Si and Al, which are relatively immobile and carried to the lake via particulate forms. Estimated annual budget of dry atmospheric deposition is ∼1.3 ± 0.3 × 10³ kt/a (accounting for ∼65% of the total inputs) to the lake sediments, assuming local loess within the catchment as a candidate for dry atmospheric deposition to the lake. The resultant flux of 300 ± 45 g/m²/a falls within the flux average of the desert area (400 g/m²/a) and the loess plateau (250 g/m²/a), consistent with the geographical setting of Lake Qinghai. The role of atmospheric deposition would be more significant if wet deposition via rainfall and snow were taken into account. This highlights the potential importance of dust as a significant source for sediment preservation flux for other catchments worldwide. The results also indicate that nearly all Ca input was preserved in the lake sediments under modern conditions, consistent with Ca²⁺ supersaturation of the lake water.