Interannual Variability in Pollen Dispersal and Deposition on the Tropical Quelccaya Ice Cap*

Pollen collected from snow samples on the Quelccaya Ice Cap in 2000 and 2001 reveals significant interannual variability in pollen assemblage, concentration, and provenance. Samples from 2000, a La Niña year, contain high pollen concentrations and resemble samples from the Andean forests (Yungas) to the east. Samples from 2001, an El Niño year, contain fewer pollen and resemble those from the Altiplano. We suggest that varying wind patterns under different El Niño/Southern Oscillation (ENSO) conditions may affect the processes of pollen transport over the Altiplano and on the ice cap, although confounding variables such as flowering phenology and sublimation should also be considered     

Analysis of rock structure stability in coal mines

In this paper, the theory of limit point instability is used to analyse the stability of rock structures in coal mines. A general method of analysing stability of rock structures is put forward and a uniform instability condition of rock structures is set up. Some instability phenomena, such as rock bursts in circular roadways, pillars and long walls, and the outburst of coal and gas from circular roadways, are discussed analytically. At a later stage, the critical point of rock structure instability is determined. The influence of relative parameters (such as the mechanical properties of rock, coal, and the geometric sizes) on the stability of the rock structures is carefully analysed. Copyright © 2005 John Wiley & Sons, Ltd.     

The δ60/58Ni Values of Twenty‐Six Selected Geological Reference Materials

The high‐precision δ^60/58Ni values of twenty‐six geological reference materials, including igneous rocks, sedimentary rocks, stream sediments, soils and plants are reported. The δ^60/58Ni values of all samples were determined by double‐spike MC‐ICP‐MS (Nu Plasma III). Isotope standard solution (NIST SRM 986) and geological reference materials (BHVO‐2, BCR‐2, JP‐1, PCC‐1, etc.) were used to evaluate the measurement bias and intermediate precision over a period of six months. Our results show that the intermediate precision of Ni isotope determination was 0.05‰ (2s, n = 69) for spiked NIST SRM 986 and typically 0.06‰ for actual samples, and the δ^60/58Ni _{NIST SRM 986} values were in excellent agreement with previous studies. Eighteen high‐precision Ni isotope ratios of geological reference materials are first reported here, and their δ^60/58Ni values varied from ?0.27‰ to 0.52‰, with a mean of 0.13 ± 0.34‰ (2s, n = 18). Additionally, SGR‐1b (0.56 ± 0.04‰, 2s), GSS‐1 (?0.27 ± 0.06‰, 2s), GSS‐7 (?0.11 ± 0.01‰, 2s), GSD‐10 (0.46 ± 0.06‰, 2s) and GSB‐12 (0.52 ± 0.06‰, 2s) could potentially serve as candidate reference materials for Ni isotope fractionation and comparison of Ni isotopic compositions among different laboratories.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

New Reference Materials and Assessment of Matrix Effects for SIMS Measurements of Oxygen Isotopes in Garnet

Accurate ion microprobe analysis of oxygen isotope ratios in garnet requires appropriate reference materials to correct for instrumental mass fractionation that partly depends on the garnet chemistry (matrix effect). The matrix effect correlated with grossular, spessartine and andradite components was characterised for the Cameca IMS 1280HR at the SwissSIMS laboratory based on sixteen reference garnet samples. The correlations fit a second‐degree polynomial with maximum bias of ca. 4‰, 2‰ and 8‰, respectively. While the grossular composition range 0–25% is adequately covered by available reference materials, there is a paucity of them for intermediate compositions. We characterise three new garnet reference materials GRS2, GRS‐JH2 and CAP02 with a grossular content of 88.3 ± 1.2% (2s), 83.3 ± 0.8% and 32.5 ± 3.0%, respectively. Their micro scale homogeneity in oxygen isotope composition was evaluated by multiple SIMS sessions. The reference δ¹⁸O value was determined by CO₂ laser fluorination (δ¹⁸O_LF). GRS2 has δ¹⁸O_LF = 8.01 ± 0.10‰ (2s) and repeatability within each SIMS session of 0.30–0.60‰ (2s), GRS‐JH2 has δ¹⁸O_LF = 18.70 ± 0.08‰ and repeatability of 0.24–0.42‰ and CAP02 has δ¹⁸O_LF = 4.64 ± 0.16‰ and repeatability of 0.40–0.46‰.     

Diagenetic formation of gypsum and dolomite in a cold‐water coral mound in the Porcupine Seabight,off Ireland

Authigenic gypsum was found in a gravity core, retrieved from the top of Mound Perseverance, a giant cold‐water coral mound in the Porcupine Basin, off Ireland. The occurrence of gypsum in such an environment is intriguing, because gypsum, a classic evaporitic mineral, is undersaturated with respect to sea water. Sedimentological, petrographic and isotopic evidence point to diagenetic formation of the gypsum, tied to oxidation of sedimentary sulphide minerals (i.e. pyrite). This oxidation is attributed to a phase of increased bottom currents which caused erosion and enhanced inflow of oxidizing fluids into the mound sediments. The oxidation of pyrite produced acidity, causing carbonate dissolution and subsequently leading to pore‐water oversaturation with respect to gypsum and dolomite. Calculations based on the isotopic compositions of gypsum and pyrite reveal that between 21·6% and 28·6% of the sulphate incorporated into the gypsum derived from pyrite oxidation. The dissolution of carbonate increased the porosity in the affected sediment layer but promoted lithification of the sediments at the sediment‐water interface. Thus, authigenic gypsum can serve as a signature for diagenetic oxidation events in carbonate‐rich sediments. These observations demonstrate that fluid flow, steered by environmental factors, has an important effect on the diagenesis of coral mounds.     

Diagenetic evolution of Aptian evaporites in the Namibe Basin (south‐west Angola)

The widespread and dissected nature of the Angolan gypsiferous salt residuals offers a uniquely detailed view of the lateral and vertical relations inherent to secondary evaporite textures, which typify exhumed salt masses worldwide. Such secondary textures are sometimes misinterpreted as primary evaporite textures. Thin, metre‐scale and patchy, dome‐like gypsum accumulations are well‐exposed within strongly incised present‐day river valleys along the eastern margin of the Namibe and Benguela basins (south‐west Angola). These sections are time equivalent to the main basinward subsurface evaporites (Aptian Loeme Formation) which mostly consist of halite. The gypsum (here called the Bambata Formation) is interpreted to represent the final residual product of fractional dissolution and recrystallization of the halite mass that occurred during Late Cretaceous margin uplift and continues today. This halite underwent multiple episodes of diagenetic alteration between its deposition and its final exhumation, leading to the formation of various secondary gypsum fabrics and solution‐related karst and breccia textures that typify the current evaporite outcrop. Four different diagenetic gypsum fabrics are defined: thinly bedded alabastrine, nodular alabastrine, displacive selenite rosettes and fibrous satin‐spar gypsum. Current arid conditions are responsible for a thin weathered crust developed at the top of the outcropping gypsum, but the fabrics in the main core of the current at‐surface evaporite unit mostly formed during the telogenetic stage of uplift prior to complete subaerial exposure. Alteration occurred as various dissolving and rehydrating saline minerals encountered shallow aquifers in the active phreatic and vadose zones. Geomorphological and petrographic analyses, mostly based on the cross‐cutting relations and crystallographic patterns in the outcrop, are used to propose a sequence of formation of these different fabrics.     

Chemical and Isotopic Characteristics of the Kuroko‐Forming Volcanism

The Miocene northeast Honshu magmatic arc, Japan, formed at a terrestrial continental margin via a stage of spreading in a back‐arc basin (23–17 Ma) followed by multiple stages of submarine rifting (19–13 Ma). The Kuroko deposits formed during this period, with most forming during the youngest rifting stage. The mode of magma eruption changed from submarine basalt lava flows during back‐arc basin spreading to submarine bimodal basalt lava flows and abundant rhyolitic effusive rocks during the rifting stage. The basalts produced during the stage of back‐arc basin spreading are geochemically similar to mid‐ocean ridge basalt, with a depleted Sr–Nd mantle source, whereas those produced during the rifting stage possess arc signatures with an enriched mantle source. The Nb/Zr ratios of the volcanic rocks show an increase over time, indicating a temporal increase in the fertility of the source. The Nb/Zr ratios are similar in basalts and rhyolites from a given rift zone, whereas the Nd isotopic compositions of the rhyolites are less radiogenic than those of the basalts. These data suggest that the rhyolites were derived from a basaltic magma via crystal fractionation and crustal assimilation. The rhyolites associated with the Kuroko deposits are aphyric and have higher concentrations of incompatible elements than do post‐Kuroko quartz‐phyric rhyolites. These observations suggest that the aphyric rhyolite magma was derived from a relatively deep magma chamber with strong fractional crystallization. Almost all of the Kuroko deposits formed in close temporal relation to the aphyric rhyolite indicating a genetic link between the Kuroko deposits and highly differentiated rhyolitic magma.     

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.