Low‐energy helium ion irradiation‐induced amorphization and chemical changes in olivine: Insights for silicate dust evolution in the interstellar medium

Abstract— We present the results of irradiation experiments aimed at understanding the structural and chemical evolution of silicate grains in the interstellar medium. A series of He+ irradiation experiments have been performed on ultra‐thin olivine, (Mg,Fe)₂SiO₄, samples having a high surface/volume (S/V) ratio, comparable to the expected S/V ratio of interstellar dust. The energies and fluences of the helium ions used in this study have been chosen to simulate the irradiation of interstellar dust grains in supernovae shock waves. The samples were mainly studied using analytical transmission electron microscopy. Our results show that olivine is amorphized by low‐energy ion irradiation. Changes in composition are also observed. In particular, irradiation leads to a decrease of the atomic ratios O/Si and Mg/Si as determined by x‐ray photoelectron spectroscopy and by x‐ray energy dispersive spectroscopy. This chemical evolution is due to the differential sputtering of atoms near the surfaces. We also observe a reduction process resulting in the formation of metallic iron. The use of very thin samples emphasizes the role of surface/volume ratio and thus the importance of the particle size in the irradiation‐induced effects. These results allow us to account qualitatively for the observed properties of interstellar grains in different environments, that is, at different stages of their evolution: chemical and structural evolution in the interstellar medium, from olivine to pyroxene‐type and from crystalline to amorphous silicates, porosity of cometary grains as well as the formation of metallic inclusions in silicates.     

Habitat heterogeneity influences cold‐seep macrofaunal communities within and among seeps along the Norwegian margin – Part 2: contribution of chemosynthesis and nutritional patterns

The relative contribution of chemosynthesis in heterotrophic fauna at seeps is known to be influenced by depth and by habitat. Using stable isotopes of carbon and nitrogen, we investigated macro‐ and megafaunal nutritional patterns in Norwegian margin cold seeps by comparing food webs both among habitats within a seep site and between different sites. The very active Håkon Mosby mud volcano (HMMV) is characterized by geochemical gradients, microbial activity and faunal zonation from the centre to the periphery. The Storegga Slide (600–900 m depth) has pockmarks with patchy less active seeps, and also shows concentric zonation of habitats but at much smaller spatial scale. The dominant carbon source for macrofaunal nutrition in both areas was chemosynthetically fixed and the bulk of organic carbon was derived from sulphur‐oxidizing bacteria. In HMMV, food chains were clearly separated according to habitats, with significantly lighter δ¹³C signatures on microbial mats and adjacent sediment (?33.06 to ?50.62‰) than in siboglinid fields (?19.83 to ?35.03‰). Mixing model outputs revealed that the contribution of methane‐derived carbon was small in siboglinid fields (0–17%) but significant (39–61%) in the microbial mats. Moreover, the variability of macrofauna signatures within this later habitat suggests the co‐occurrence of two food chains, one based on primary production via methanotrophy and the other via sulphide oxidation. The length of the food chains also varied among habitats, with at least one more trophic level in the siboglinid fields located at the periphery of the volcano. Conversely, in Storrega pockmarks, faunal δ¹³C signatures did not vary among habitats but among species, although separate food chains seem to co‐occur. The small size of the seepage areas and their lower fluxes compared to HMMV allow more background species to penetrate the seep area, increasing the range of δ¹⁵N and the trophic level number. Probably due to the higher flux of photosynthetic particulate organic carbon, the overall chemosynthesis‐based carbon contribution in invertebrate nutrition was lower than that in HMMV.     

SeagrassNet monitoring across the Americas: case studies of seagrass decline

Seagrasses are an important coastal habitat worldwide and are indicative of environmental health at the critical land–sea interface. In many parts of the world, seagrasses are not well known, although they provide crucial functions and values to the world's oceans and to human populations dwelling along the coast. Established in 2001, SeagrassNet, a monitoring program for seagrasses worldwide, uses a standardized protocol for detecting change in seagrass habitat to capture both seagrass parameters and environmental variables. SeagrassNet is designed to statistically detect change over a relatively short time frame (1–2 years) through quarterly monitoring of permanent plots. Currently, SeagrassNet operates in 18 countries at 48 sites; at each site, a permanent transect is established and a team of people from the area collects data which is sent to the SeagrassNet database for analysis. We present five case studies based on SeagrassNet data from across the Americas (two sites in the USA, one in Belize, and two in Brazil) which have a common theme of seagrass decline; the study represents a first latitudinal comparison across a hemisphere using a common methodology. In two cases, rapid loss of seagrass was related to eutrophication, in two cases losses related to climate change, and in one case, the loss is attributed to a complex trophic interaction resulting from the presence of a marine protected area. SeagrassNet results provide documentation of seagrass change over time and allow us to make scientifically supported statements about the status of seagrass habitat and the extent of need for management action.     

The Upper Crustal Evolution of a Large Silicic Magma Body: Evidence from Crystal-scale Rb Sr Isotopic Heterogeneities in the Fish Canyon Magmatic System, Colorado

Batholith-sized bodies of crystal-rich magmatic ‘mush’are widely inferred to represent the hidden sources of manylarge-volume high-silica rhyolite eruptive units. Occasionallythese mush bodies are ejected along with their trapped interstitialliquid, forming the distinctive crystal-rich ignimbrites knownas ‘monotonous intermediates’. These ignimbritesare notable for their combination of high crystal contents (35–55%),dacitic bulk compositions with interstitial high-silica rhyoliticglass, and general lack of compositional zonation. The 5000km³ Fish Canyon Tuff is an archetypal eruption deposit of thistype, and is the largest known silicic eruption on Earth. Ejectafrom the Fish Canyon magmatic system are notable for the limitedcompositional variation that they define on the basis of whole-rockchemistry, whereas 45 vol. % crystals in a matrix of high-silicarhyolite glass together span a large range of mineral-scaleisotopic variability (microns to millimetres). Rb/Sr isotopicanalyses of single crystals (sanidine, plagioclase, biotite,hornblende, apatite, titanite) and sampling by micromillingof selected zones within glass plus sanidine and plagioclasecrystals document widespread isotopic disequilibrium at manyscales. High and variable ⁸⁷Sr/⁸⁶Sr_i values for euhedral biotitegrains cannot be explained by any model involving closed-systemradiogenic ingrowth, and they are difficult to rationalize unlessmuch of this radiogenic Sr has been introduced at a late stagevia assimilation of local Proterozoic crust. Hornblende is theonly phase that approaches isotopic equilibrium with the surroundingmelt, but the melt (glass) was isotopically heterogeneous atthe millimetre scale, and was therefore apparently contaminatedwith radiogenic Sr shortly prior to eruption. The other mineralphases (plagioclase, sanidine, titanite, and apatite) have significantlylower ⁸⁷Sr/⁸⁶Sr_i values than whole-rock values (as much as –0·0005).Such isotopic disequilibrium implies that feldspars, titaniteand apatite are antecrysts that crystallized from less radiogenicmelt compositions at earlier stages of magma evolution, whereashighly radiogenic biotite xenocrysts and the development ofisotopic heterogeneity in matrix melt glass appear to coincidewith the final stage of the evolution of the Fish Canyon magmabody in the upper crust. Integrated petrographic and geochemicalevidence is consistent with pre-eruptive thermal rejuvenationof a near-solidus mineral assemblage from 720 to 760°C (i.e.partial dissolution of feldspars + quartz while hornblende +titanite + biotite were crystallizing). Assimilation and blendingof phenocrysts, antecrysts and xenocrysts reflects chamber-wide,low Reynolds number convection that occurred within the last10 000 years before eruption. KEY WORDS: Fish Canyon Tuff; Rb–Sr isotopes; microsampling; magmatic processes; crystal mush     

Geothermal Characterization of the St. Lawrence Lowlands Sedimentary Basin,Québec,Canada

Defining temperature at depth to identify geothermal resources relies on the evaluation of the Earth heat flow based on equilibrium temperature measurements as well as thermal conductivity and heat generation rate assessment. Such high-quality geothermal data can be sparse over the region of interest. This is the case of the St. Lawrence Lowlands sedimentary basin covering 20,000 km² to the south of Québec, Canada, and enclosing only three wells up to a depth of 500 m with equilibrium heat flow measurements. However, more than 250 oil and gas exploration wells have been drilled in this area, providing for this study (parce que c'est 93 sinon) 81 locations with bottom-hole temperature up to a depth of 4300 m, however, not at equilibrium. Analyzing these data with respect to the deep geothermal resource potential of this sedimentary basin requires evaluating the thermal conductivity and heat generation rate of its geological units to properly extrapolate temperature downward. This was done by compiling literature and recent thermal conductivity measurements in outcrop and core samples as well as new heat generation rate estimates from spectral gamma ray logs to establish a first thermal assessment of geological units deep down into the basin. The mean thermal conductivity of the thermal units varies from 2.5 to 6.3 W/m·K, with peak values in the basal sandstones, while the heat generation rate varies from 1.6 to 0.3 µW/m³, decreasing from the upper caprocks toward the base of the sequence. After correcting the bottom-hole temperatures for drilling disturbance with the Harrison correction and subsequently for paleoclimate variations, results indicate a mean geothermal gradient of 23.1 °C/km, varying from 14 to 40 °C/km. Evaluating the basin thermal state from oil and gas data is a significant challenge facilitated by an understanding of its thermal properties.     

An Analysis of the Published Mineral Resource Estimates of the Haji-Gak Iron Deposit,Afghanistan

The Haji-Gak iron deposit of eastern Bamyan Province, eastern Afghanistan, was studied extensively and resource calculations were made in the 1960s by Afghan and Russian geologists. Recalculation of the resource estimates verifies the original estimates for categories A (in-place resources known in detail), B (in-place resources known in moderate detail), and C₁ (in-place resources estimated on sparse data), totaling 110.8 Mt, or about 6% of the resources as being supportable for the methods used in the 1960s. C₂ (based on a loose exploration grid with little data) resources are based on one ore grade from one drill hole, and P₂ (prognosis) resources are based on field observations, field measurements, and an ore grade derived from averaging grades from three better sampled ore bodies. C₂ and P₂ resources are 1,659.1 Mt or about 94% of the total resources in the deposit. The vast P₂ resources have not been drilled or sampled to confirm their extent or quality. The purpose of this article is to independently evaluate the resources of the Haji-Gak iron deposit by using the available geologic and mineral resource information including geologic maps and cross sections, sampling data, and the analog-estimating techniques of the 1960s to determine the size and tenor of the deposit.     

Temporal evolution and compositional signatures of two supervolcanic systems recorded in zircons from Mangakino volcanic centre,New Zealand

Mangakino, the oldest rhyolitic caldera centre delineated in the Taupo Volcanic Zone of New Zealand, generated two very large (super-sized) ignimbrite eruptions, the 1.21 ± 0.04 Ma >500 km³ Ongatiti and ~1.0 Ma ~1,200 km³ Kidnappers events, the latter of which was followed after a short period of erosion by the ~200 km³ Rocky Hill eruption. We present U/Pb ages and trace-element analyses on zircons from pumice clasts from these three eruptions by Secondary Ion Mass Spectrometry (SIMS) using SHRIMP-RG instruments to illustrate the evolution of the respective magmatic systems. U–Pb age spectra from the Ongatiti imply growth of the magmatic system over ~250 kyr, with a peak of crystallisation around 1.32 Ma, ~100 kyr prior to eruption. The zircons are inferred to have then remained stable in a mush with little crystallisation and/or dissolution before later rejuvenation of the system at the lead-in to eruption. The paired Kidnappers and Rocky Hill eruptions have U–Pb zircon ages and geochemical signatures that suggest they were products of a common system grown over ~200 kyr. The Kidnappers and Rocky Hill samples show similar weakly bimodal age spectra, with peaks at 1.1 and 1.0 Ma, suggesting that an inherited antecrystic population was augmented by crystals grown at ages within uncertainty of the eruption age. In the Kidnappers, this younger age peak is dominantly seen in needle-shaped low U grains with aspect ratios of up to 18. In all three deposits, zircon cores show larger ranges and higher absolute concentrations of trace elements than zircon rims, consistent with zircon crystallisation from evolving melts undergoing crystal fractionation involving plagioclase and amphibole. Abundances and ratios of many trace elements frequently show variations between different sectors within single grains, even where there is no visible sector zoning in cathodoluminescence (CL) imaging. Substitution mechanisms, as reflected in the molar (Sc + Y + REE³⁺)/P ratio, differ in the same growth zone between the sides (along a-axis and b-axis: values approaching 1.0) and tips (c-axis: values between 1.5 and 5.0) of single crystals. These observations have implications for the use of zircons for tracking magmatic processes, particularly in techniques where CL zonation within crystals is not assessed and small analytical spot sizes cannot be achieved. These observations also limit applicability of the widely used Ti-in-zircon thermometer. The age spectra for the Ongatiti and Kidnappers/Rocky Hill samples indicate that both magmatic systems were newly built in the time-breaks after respective previous large eruptions from Mangakino. Trace element variations defining three-component mixing suggest that zircons, sourced from multiple melts, contributed to the population in each system.     

Ilmenite composition in the Tellnes Fe–Ti deposit,SW Norway: fractional crystallization,postcumulus evolution and ilmenite–zircon relation

Major and trace element XRF and in situ LA-ICP-MS analyses of ilmenite in the Tellnes ilmenite deposit, Rogaland Anorthosite Province, SW Norway, constrains a two stage fractional crystallization model of a ferrodioritic Fe-Ti-P rich melt. Stage 1 is characterized by ilmenite-plagioclase cumulates, partly stored in the lower part of the ore body (Lower Central Zone, LCZ), and stage 2 by ilmenite-plagioclase-orthopyroxene-olivine cumulates (Upper Central Zone, UCZ). The concentration of V and Cr in ilmenite, corrected for the trapped liquid effect, (1) defines the cotectic proportion of ilmenite to be 17.5 wt% during stage 1, and (2) implies an increase of D _V^Ilm during stage 2, most likely related to a shift in fO₂. The proportion of 17.5 wt% is lower than the modal proportion of ilmenite (ca. 50 wt%) in the ore body, implying accumulation of ilmenite and flotation of plagioclase. The fraction of residual liquid left after crystallization of Tellnes cumulates is estimated at 0.6 and the flotation of plagioclase at 26 wt% of the initial melt mass. The increasing content of intercumulus magnetite with stratigraphic height, from 0 to ca. 3 wt%, results from differentiation of the trapped liquid towards magnetite saturation. The MgO content of ilmenite (1.4–4.4 wt%) is much lower than the expected cumulus composition. It shows extensive postcumulus re-equilibration with trapped liquid and ferromagnesian silicates, correlated with distance to the host anorthosite. The Zr content of ilmenite, provided by in situ analyses, is low (<114 ppm) and uncorrelated with stratigraphy or Cr content. The data demonstrate that zircon coronas observed around ilmenite formed by subsolidus exsolution of ZrO₂ from ilmenite. The U-Pb zircon age of 920 ± 3 Ma probably records this exsolution process. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.