Emplacement age and thermal footprint of the diamondiferous Ellendale E9 lamproite pipe, Western Australia

The diamondiferous Ellendale 9 (E9) pipe is a funnel-shaped maar-diatreme volcano consisting of inward-dipping tuff sequences intruded by lamproite plugs and dykes. The host rocks for the E9 pipe are Permian sandstones. The multiple lithological contacts exposed within the mined maar volcano provide a natural laboratory in which to study the effect of volcanic processes on U–Th–Pb–He systematics. Zircon from the regional sandstone and E9 lamproite display a bimodal distribution of ages on (U–Th)/He–U/Pb plots. The zircon U/Pb ages for the E9 pipe (n?=?52) range from 440 to 2,725 Ma, while the cluster of (U–Th)/He ages for the lamproite dyke zircon indicate that dyke emplacement occurred at 20.6?±?2.8 Ma, concordant with a maximum emplacement age of about ≤22 Ma from phlogopite ⁴⁰Ar/³⁹Ar. These ages indicate a xenocrystic origin for the zircon entrained in the E9 dyke. The U/Pb ages of detrital zircon from the regional sandstone host (373–3,248 Ma; n?=?41) are indistinguishable from those of the lamproite zircon xenocrysts, whereas the detrital zircon in the host sandstone yield (U–Th)/He ages from 260 to 1,500 Ma. A thermochronology traverse across the E9 lamproite dyke reveals that the zircon (U–Th)/He ages in the host sandstone have not been significantly thermally reset during dyke emplacement, even at the contact. The capability of the zircon (U–Th)/He method to distinguish deep, mantle source lithologies from upper crustal source lithologies could be used in geochemical exploration for diamonds. Pre-screening of detrital samples using etching and helium assay methods will improve the efficiency and decrease the cost of greenfields exploration.     

Facies of slurry-flow deposits, Britannia Formation (Lower Cretaceous), North Sea: implications for flow evolution and deposit geometry

ABSTRACT Mud‐rich sandstone beds in the Lower Cretaceous Britannia Formation, UK North Sea, were deposited by sediment flows transitional between debris flows and turbidity currents, termed slurry flows. Much of the mud in these flows was transported as sand‐ and silt‐sized grains that were approximately hydraulically equivalent to suspended quartz and feldspar. In the eastern Britannia Field, individual slurry beds are continuous over long distances, and abundant core makes it possible to document facies changes across the field. Most beds display regular areal grain‐size changes. In this study, fining trends, especially in the size of the largest grains, are used to estimate palaeoflow and palaeoslope directions. In the middle part of the Britannia Formation, stratigraphic zones 40 and 45, slurry flows moved from south‐west and south towards the north‐east and north. Most zone 45 beds lens out before reaching the northern edge of the field, apparently by wedging out against the northern basin slope. Zone 40 and 45 beds show downflow facies transitions from low‐mud‐content, dish‐structured and wispy‐laminated sandstone to high‐mud‐content banded units. In zone 50, at the top of the formation, flows moved from north to south or north‐west to south‐east, and their deposits show transitions from proximal mud‐rich banded and mixed slurried beds to more distal lower‐mud‐content banded and wispy‐laminated units. The contrasting facies trends in zones 40 and 45 and zone 50 may reflect differing grain‐size relationships between quartz and feldspar grains and mud particles in the depositing flows. In zones 40 and 45, quartz grains average 0·30–0·32 mm in diameter, ≈ 0·10 mm coarser than in zone 50. The medium‐grained quartz in zones 40 and 45 flows may have been slightly coarser than the associated mud grains, resulting in the preferential deposition of quartz in proximal areas and downslope enrichment of the flows in mud. In zone 50 flows, mud was probably slightly coarser than the associated fine‐grained quartz, resulting in early mud sedimentation and enrichment of the distal flows in fine‐grained quartz and feldspar. Mud particles in all flows may have had an effective grain size of ≈ 0·25 mm. Both mud content and suspended‐load fallout rate played key roles in the sedimentation of Britannia slurry flows and structuring of the resulting deposits. During deposition of zones 40 and 45, the area of the eastern Britannia Field in block 16/26 may have been a locally enclosed subbasin within which the depositing slurry flows were locally ponded. Slurry beds in the eastern Britannia Field are ‘lumpy’ sheet‐like bodies that show facies changes but little additional complexity. There is no thin‐bedded facies that might represent waning flows analogous to low‐density turbidity currents. The dominance of laminar, cohesion‐dominated shear layers during sedimentation prevented most bed erosion, and the deposystem lacked channel, levee and overbank facies that commonly make up turbidity current‐dominated systems. Britannia slurry flows, although turbulent and capable of size‐fractionating even fine‐grained sediments, left sand bodies with geometries and facies more like those deposited by poorly differentiated laminar debris flows.     

Tourmaline mineralization in the Barberton greenstone belt,South Africa: early Archean metasomatism by evaporite-derived boron

Tourmaline-rich rocks are common in the lowgrade, interior portions of the Barberton greenstone belt of South Africa, where shallow-marine sediments and underlying altered basaltic and komatiitic lavas contain up to 50% tourmaline. The presence of tourmaline-bearing rip-up clasts, intraformational tourmalinite pebbles, and tourmaline-coated grains indicates that boron mineralization was a low-temperature, surficial process. The association of these lithologies with stromatolites, evaporites, and shallow-water sedimentary structures and the virtual absence of tourmaline in correlative deep-water facies rocks in the greenstone bels strengthens this model.Five tourmaline-bearing lithologic groups (basalts, komatiites, evaporite-bearing sediments, stromatolitic sediments, and quartz veins) are distinguished based on field, petrographic, and geochemical criteria. Individual tourmaline crystals within these lithologies show internal chemical and textural variations that reflect continued growth through intervals of change in bulk-rock and fluid composition accompanying one or more metasomatic events. Large single-crystal variations exist in Fe/Mg, Al/Fe, and alkali-site vacancies. A wide range in tourmaline composition exists in rocks altered from similar protoliths, but tourmalines in sediments and lavas have similar compositional variations. Boron-isotope analysis of the tourmalines suggest that the boron enrichment in these rocks has a major marine evaporitic component. Sediments with gypsum pseudomorphs and lavas altered at low temperatures by shallow-level brines have the highest ¹¹B values (+2.2 to-1.9); lower ¹¹B values of late quartz veins (-3.7 to-5.7) reflect intermediate temperature, hydrothermal remobilization of evaporitic boron. The ¹¹B values of tourmaline-rich stromatolitic sediments (-9.8 and-10.5) are consistent with two-stage boron enrichment, in which earlier marine evaporitic boron was hydrothermally remobilized and vented in shallow-marine or subaerial sites, mineralizing algal stromatolites. The stromatolite-forming algae preferentially may have lived near the sites of hydrothermal discharge in Archean times.     

Effects of temperature on the crystal structure of epidote: a neutron single-crystal diffraction study at 293 and 1,070 K

The effects of temperature on the crystal structure of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH), a = 8.890(6), b = 5.630(4), c = 10.150(6) Å and β = 115.36(5)°, Sp. Gr. P2₁ /m] have been investigated by means of neutron single-crystal diffraction at 293 and 1,070 K. At room conditions, the structural refinement confirms the presence of Fe³⁺ at the M₃ site [%Fe(M3) = 73.1(8)%] and all attempts to refine the amount of Fe at the M(1) site were unsuccessful. Only one independent proton site was located. Two possible hydrogen bonds, with O(2) and O(4) as acceptors [i.e. O(10)–H(1)···O(2) and O(10)–H(1)···O(4)], occur. However, the topological configuration of the bonds suggests that the O(10)–H(1)···O(4) is energetically more favourable, as H(1)···O(4) = 1.9731(28) Å, O(10)···O(4) = 2.9318(22) Å and O(10)–H(1)···O4 = 166.7(2)°, whereas H(1)···O(2) = 2.5921(23) Å, O(10)···O(2) = 2.8221(17) Å and O(10)–H(1)···O2 = 93.3(1)°. The O(10)–H(1) bond distance corrected for “riding motion” is 0.9943 Å. The diffraction data at 1,070 K show that epidote is stable within the T-range investigated, and that its crystallinity is maintained. A positive thermal expansion is observed along all the three crystallographic axes. At 1,070 K the structural refinement again shows that Fe³⁺ share the M(3) site along with Al³⁺ [%Fe(M3)_1,070K = 74(2)%]. The refined amount of Fe³⁺ at the M(1) is not significant [%Fe(M1)_1,070K = 1(2)%]. The tetrahedral and octahedral bond distances and angles show a slight distortion of the polyhedra at high-T, but a significant increase of the bond distances compared to those at room temperature is observed, especially for bond distances corrected for “rigid body motions”. The high-T conditions also affect the inter-polyhedral configurations: the bridging angle Si(2)–O(9)–Si(1) of the Si₂O₇ group increases significantly with T. The high-T structure refinement shows that no dehydration effect occurs at least within the T-range investigated. The configuration of the H-bonding is basically maintained with temperature. However, the hydrogen bond strength changes at 1,070 K, as the O(10)···O(4) and H(1)···O(4) distances are slightly longer than those at 293 K. The anisotropic displacement parameters of the proton site are significantly larger than those at room condition. Reasons for the thermal stability of epidote up to 1,070 K observed in this study, the absence of dehydration and/or non-convergent ordering of Al and Fe³⁺ between different octahedral sites and/or convergent ordering on M(3) are discussed.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.     

Pathfinder applications of arsenic, antimony and bismuth in geochemical exploration

The potential applications of As, Sb and Bi as pathfinder elements in geochemical exploration have been researched using a new, rapid technique for the simultaneous determination of the three elements. Following a warm hydrochloric acid sample leach, the volatile hydrides of the elements are generated and flushed into an inductively-coupled plasma linked to an emission spectrometer. The technique offers a combination of good analytical precision and detection limits of 100 ppb for each of the elements.The principal sulphide ore minerals commonly contain traces of As, Sb and Bi, and concentrations of more than 1% of any one of these have been found in some sulphide specimens. During sub-aerial oxidation of sulphides, any As, Sb and Bi present is released and forms dispersion patterns in the surficial environment. Geochemical surveys of localities in the United Kingdom have demonstrated that anomalous dispersion trains of these elements can be detected in the sediments of streams draining the mineralized localities. In a geochemical mapping programme covering 16,000 km² of central Nepal, over 3500 stream sediment samples were analyzed for As, Sb and Bi, and many known occurrences of Cu, Pb and Zn mineralization are reflected by As, Sb and Bi anomalies. However, bedrock lithology appears to be an important factor influencing Sb and Bi dispersion patterns.In the areas studied, some or all of the elements As, Sb and Bi produce stream sediment anomalies that compare favourably in terms of contrast and extent with the heavy metal expressions, even though none of the three elements have been reported as important constituents of the mineralization with which they occur.     

Experimental abiotic alteration of igneous and manufactured glasses

Pits in ocean basalt glass are often attributed to the activity of microorganisms, however, neither the mechanism of formation of pits in glass nor the involvement of microorganisms have been confirmed by experimentation. Experimental abiotic corrosion of basalt glass with 1% hydrofluoric acid (HF), a proxy for more slowly acting organic acids, produces pits that are similar in size, shape, and distribution to pits found in basalt glass collected from the ocean floor and basalt glass incubated with microorganisms. This pit formation by HF etching was demonstrated by comparing secondary electron images taken before and after the acid treatment. The formation of pits by abiotic corrosion of basalt glass is an alternate hypothesis for the origin of these features, and the interpretation of these features as biomarkers may require a resolution of these alternative hypotheses.     

Particle composition and size distributions in and around a deep-pit swine operation,Ames, IA

The contribution of emissions from agricultural facilities is rapidly becoming a major concern for local and regional air quality. Characterization of particle properties such as physical size distribution and chemical composition can be valuable in understanding the processes contributing to emissions and ultimate fate of particulate matter from agricultural facilities. A measurement campaign was conducted at an Iowa, deep-pit, three-barn swine finishing facility to characterize near-source ambient particulate matter. Size-specific mass concentrations were determined using minivol samplers, with additional size distribution information obtain using optical particle counters. Particulate composition was determined via ion chromatographic analysis of the collected filters. A thermal-CO₂ elemental/organic carbon analyzer measured particulate carbon. The chemical composition and size distribution of sub-micron particles were determined via real-time aerosol mass spectrometry. Primary particulate was not found to be a major emission from the examined facility, with filter-based impactor samples showing average near-source increases (~15–50 m) in ambient PM₁₀ of 5.8 ± 2.9 μg m⁻³ above background levels. PM_2.5 also showed contribution attributable to the facility (1.7 ± 1.1 μg m⁻³). Optical particle counter analysis of the numerical size distributions showed bimodal distributions for both the upwind and downwind conditions, with maximums around 2.5 μm and below the minimum quantified diameter of 0.3 μm. The distributions showed increased numbers of coarse particles (PM₁₀) during periods when wind transport came from the barns, but the differences were not statistically significant at the 95% confidence level. The PM₁₀ aerosols showed statistically increased concentrations of sulfate, nitrate, ammonium, calcium, organic carbon, and elemental carbon when the samplers were downwind from the pig barns. Organic carbon was the major constituent of the barn-impacted particulate matter in both sub-micron (54%) and coarse size (20%) ranges. The AMS PM₁ chemical speciation showed similar species increases, with the exception of and Ca⁺², the latter not quantified by the AMS.     

The role of closed ecological systems in carbon cycle modelling

Acquiring a mechanistic understanding of the role of biotic feedbacks for the links between atmospheric CO₂ concentrations and temperature is essential for trustworthy climate predictions. Currently, computer-based simulations are the only available tool to estimate the global impact of biotic feedbacks on future atmospheric CO₂ and temperatures. Here we propose an alternative and complementary approach by using materially closed, energetically open analogue/physical models of the carbon cycle. We argue that there is unexplored potential in using a materially closed approach to improve our understanding of the magnitude and direction of many biotic carbon feedbacks and that recent technological advances make this feasible. We also suggest how such systems could be designed and discuss the advantages and limitations of establishing physical models of the global carbon cycle.     

The eastward shift of the Walker Circulation in response to global warming and its relationship to ENSO variability

This study investigates the global warming response of the Walker Circulation and the other zonal circulation cells (represented by the zonal stream function), in CMIP3 and CMIP5 climate models. The changes in the mean state are presented as well as the changes in the modes of variability. The mean zonal circulation weakens in the multi model ensembles nearly everywhere along the equator under both the RCP4.5 and SRES A1B scenarios. Over the Pacific the Walker Circulation also shows a significant eastward shift. These changes in the mean circulation are very similar to the leading mode of interannual variability in the tropical zonal circulation cells, which is dominated by El Niño Southern Oscillation variability. During an El Niño event the circulation weakens and the rising branch over the Maritime Continent shifts to the east in comparison to neutral conditions (vice versa for a La Niña event). Two-thirds of the global warming forced trend of the Walker Circulation can be explained by a long-term trend in this interannual variability pattern, i.e. a shift towards more El Niño-like conditions in the multi-model mean under global warming. Further, interannual variability in the zonal circulation exhibits an asymmetry between El Niño and La Niña events. El Niño anomalies are located more to the east compared with La Niña anomalies. Consistent with this asymmetry we find a shift to the east of the dominant mode of variability of zonal stream function under global warming. All these results vary among the individual models, but the multi model ensembles of CMIP3 and CMIP5 show in nearly all aspects very similar results, which underline the robustness of these results. The observed data (ERA Interim reanalysis) from 1979 to 2012 shows a westward shift and strengthening of the Walker Circulation. This is opposite to what the results in the CMIP models reveal. However, 75 % of the trend of the Walker Circulation can again be explained by a shift of the dominant mode of variability, but here towards more La Niña-like conditions. Thus in both climate change projections and observations the long-term trends of the Walker Circulation seem to follow to a large part the pre-existing dominant mode of internal variability.