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Gold and platinum-group-metals (PGM) are cycled through Earth’s environments by interwoven geological, physical, chemical and biological processes leading to the trans/neoformation of metallic particles in placers. The placer deposit at Corrego Bom Successo (CBS, Brazil) is one of the few localities worldwide containing secondary gold- and PGM-particles. Placer gold consists of detrital particles from nearby hydrothermal deposits that were transformed in the surface environment. Processes that have affected these particles include short-distance transport, chemical de-alloying of the primary gold‑silver, and (bio)geochemical dissolution/re-precipitation of gold leading to the formation of pure, secondary gold and the dispersion of gold nanoparticles. The latter processes are likely mediated by non-living organic matter (OM) and bacterial biofilms residing on the particles. The biofilms are largely composed of metallophillic β- and γ-Proteobacteria. Abundant mobile gold and platinum nanoparticles were detected in surface waters, suggesting similar mobilities of these metals. Earlier hydrothermal processes have led to the formation of coarsely-crystalline, arborescent dendritic potarite (PdHg). On potarite surfaces, biogeochemical processes have then led to the formation of platinum- and palladium-rich micro-crystalline layers, which make up the botryoidal platinum‑palladium aggregates. Subsequently potarite was dissolved from the core of many aggregates leaving voids now often filled by secondary anatase (TiO2) containing biophilic elements. The presence of fungal structures associated with the anatase suggests that fungi may have contributed to its formation. For the first time a primary magmatic PGM-particle comprising a mono-crystalline platinum‑palladium-alloy with platinum‑iridium‑osmium inclusions was described from this locality, finally defining a possible primary source for the PGM mineralisation. In conclusion, the formation of modern-day placer gold- and PGM-particles at CBS began 100s of millions of years ago by magmatic and hydrothermal processes. These provided the metal sources for more recent biogeochemical cycling of PGEs and gold that led to the trans/neoformation of gold- and PGM-particles.

The intertidal bivalve Katelysia rhytiphora, endemic to south Australia and Tasmania, is used here for pulsed Sr-labelling experiments in aquaculture experiments to visualize shell growth at the micro- to nanoscale. The ventral margin area of the outer shell layer composed of (i) an outermost outer shell layer (oOSL) with compound composite prismatic architecture with three hierarchical orders of prisms and (ii) an innermost outer shell layer (iOSL) with crossed-acicular architecture consisting of intersecting lamellae bundles. All structural orders in both layers are enveloped by an organic sheath and the smallest mineralized units are nano-granules. Electron backscatter diffraction reveals a strong preferred orientation of the aragonite c axes perpendicular to the growth layers, while the a and b axes are scattered within a plane normal to the local growth direction and >46 % twin grain boundaries are detected. The Young's modulus shows a girdle-like maximum of elastically stiffer orientations for the shell following the inner shell surface. For 6 d, the bivalves were subjected twice to seawater with an increased Sr concentration of 18× mean ocean water by dissolving 144 µ g g −1 Sr (159.88 Sr∕Ca mmol ∕ mol) in seawater. The pulse labelling intervals in the shell are 17× (oOSL) and 12× (iOSL) enriched in Sr relative to the Sr-spiked seawater. All architectural units in the shell are transected by the Sr label, demonstrating shell growth to progress homogeneously instead of forming one individual architectural unit after the other. Distribution coefficients, DSr ∕ Ca , for labelled and unlabelled shells are similar to shell proportions formed in the wild (0.12 to 0.15). All DSr ∕ Ca values are lower than values for equilibrium partitioning of Sr in synthetic aragonite.

Photosynthesis in the seagrass Zostera muelleri remains poorly understood. We investigated the effect of reduced irradiance on the incorporation of 13C, gene expression of photosynthetic, photorespiratory and intermediates recycling genes as well as the enzymatic content and activity of Rubisco and PEPC within Z. muelleri. Following 48 h of reduced irradiance, we found that i) there was a ∼7 fold reduction in 13C incorporation in above ground tissue, ii) a significant down regulation of photosynthetic, photorespiratory and intermediates recycling genes and iii) no significant difference in enzyme activity and content. We propose that Z. muelleri is able to alter its physiology in order to reduce the amount of C lost through photorespiration to compensate for the reduced carbon assimilation as a result of reduced irradiance. In addition, the first estimated rate constant (Kcat) and maximum rates of carboxylation (Vcmax) of Rubisco is reported for the first time for Z. muelleri.

Zinc as a micronutrient and cadmium as a nonessential toxic element share similar pathways for entering plant tissues and thus may be antagonistic. In nutrient solution culture, 17-day-old radish (Raphanus sativus L) plants were exposed to short-term (24 h) equimolar metal contamination (2.2 µM of each 70Zn and total Cd) to investigate the in situ Zn/Cd distribution in the apical root tissues using high-resolution secondary ion mass spectrometry (NanoSIMS) imaging. Inductively-coupled plasma mass spectrometry analysis of bulk root tissue confirmed large root uptake of both metal elements. After 24-h exposure the total root concentration (in µg/g DW) of 70Zn was 180 ± 24 (mean±SE) and of total Cd 352 ± 11. NanoSIMS mapping was performed on the cross sections of the radish root apex as a crucial component in root growth and uptake of water and nutrients from soil. Elemental maps of 70Zn and 114Cd isotopes revealed greater enrichment of both metals in the outer epidermal root layer than in cortical tissues and especially stele, confirming the epidermal root cells as preferential sites of metal uptake, and indicating relatively slow and less-intensive metal transport into other parts (edible hypocotyl, shoot) of metal-sensitive radish. NanoSIMS has been confirmed as a powerful tool for spatial detection and visualisation of some ultra-trace metal isotopes (e.g. 70Zn) in the fast-growing root tips. However, precise (sub)cellular mapping of diffusible metallic ions (Cd, Zn) remains a technically-challenging task in plant specimens given an unavoidable compromise between optimising methodology for structural preservation vs. authentic in vivo ion localisation.

The nanoSIMS (nanometre-resolution secondary ion mass spectrometry) microanalytical platform is used, for the first time, for direct in situ visualization of medium half-life radionuclide (RN) distributions (226Ra – 1602y; 210Pb – 22.3y) in copper sulphide-bearing ore and copper sulphide flotation concentrate samples. More than 200 grains have been mapped, all with an Hyperion (H200) RF plasma oxygen ion source. Sufficient counts for masses of interest allowed the generation of maps that stand as a proof of concept for further detailed work to address the physical locations of radionuclides of main interest. The issue of potential isobaric interfering masses has been addressed and partially resolved. The distribution of the studied radionuclides, both in relation to host minerals and in relation to each other, is logical and clearly supported by well-established theories of deportment, diffusion, and redistribution. Isotope maps for 210RN (210Pb, 210Po and 210Bi) and 226Ra maps tended to show RN distribution either within minerals (evenly distributed or zoned), as ‘hot spots’ on grain surfaces/mineral boundaries, or between cleavage planes of micaceous minerals. NanoSIMS element mapping of radionuclides may have widespread application for the disposal and long-term storage of nuclear waste, radioisotope monitoring, forensic science, nuclear and materials science, nuclear medicine, minerals engineering, and isotope geochemistry.

Zinc (Zn) is an important micronutrient in the ocean, and fixation of Zn into organic, trace element-rich sediments is an important contributor to Zn cycling in the ocean. Framboidal sulfides are considered to be the major host for Zn in such settings. The sequestration of Zn into framboids via biotic or abiotic processes is not fully understood, which presents difficulties for interpretation of Zn isotope values in sediments. In this work, we describe a novel type of framboid with mixed pyrite and zinc sulfide (sphalerite or wurtzite) microcrystals from meta-pelites of the Otago Schist, New Zealand. A combination of optical microscopy, scanning electron microscopy (SEM) and nanoscale secondary ion mass spectrometry (NanoSIMS) were utilized to assess the association between Zn, pyrite and organic matter in framboids. The distribution of Zn in framboids is variable. Most pyrite microcrystals include minor amounts of Zn. Trace Zn is also observed to co-locate with organic matter, which occurs on the boundaries of pyrite microcrystals. Finally, Zn is found as single zinc sulfide microcrystals or zinc sulfide rims around pyrite microcrystals within individual framboids. These textures have not been recorded before, to our knowledge. The sequence of events that sequesters Zn into framboids may affect Zn isotope fractionation from seawater to continental margin sediments.

Gold nanorods are one of the most widely explored inorganic materials in nanomedicine for diagnostics, therapeutics and sensing1. It has been shown that gold nanorods are not cytotoxic and localize within cytoplasmic vesicles following endocytosis, with no nuclear localization2,3, but other studies have reported alterations in gene expression profiles in cells following exposure to gold nanorods, via unknown mechanisms4. In this work we describe a pathway that can contribute to this phenomenon. By mapping the intracellular chemical speciation process of gold nanorods, we show that the commonly used Au–thiol conjugation, which is important for maintaining the noble (inert) properties of gold nanostructures, is altered following endocytosis, resulting in the formation of Au(i)–thiolates that localize in the nucleus5. Furthermore, we show that nuclear localization of the gold species perturbs the dynamic microenvironment within the nucleus and triggers alteration of gene expression in human cells. We demonstrate this using quantitative visualization of ubiquitous DNA G-quadruplex structures, which are sensitive to ionic imbalances, as an indicator of the formation of structural alterations in genomic DNA. The release of nuclear-localizing gold species from intracellular gold nanorods may alter gene expression on interaction with the genomic DNA.

The true solubilities of highly siderophile elements in silicate and oxide minerals may be difficult to measure because of their low abundances and the tendency of these elements to occur as minute inclusions or “micronuggets”. In order to mitigate this latter problem, we present a new approach that makes use of the solid-state diffusion of such elements into pre-existing crystals. The diffusion of Rh, Ru and Ir was measured in San Carlos olivine, and synthetic monocrystalline forsterite and MgAl2O4-spinel, at atmospheric pressure, 1300 to 1400 °C and oxygen fugacities from air to that of the quartz-fayalite-magnetite (FMQ) oxygen buffer. The activities of all main components were controlled in each experiment by solid-state buffer assemblages: SiOR2R and MgO in olivine experiments were controlled by forsterite (olivine) + periclase (magnesiowustite) (fo + per or sco + mw), or forsterite (olivine) + protoenstatite (fo + en or sco + opx). Activities of AlR2ROR3R and MgO in the spinel experiments were buffered by spinel + periclase (sp + per) or spinel + corundum (sp + cor) mineral assemblages. The diffusion profiles were measured by LA-ICP-MS in both traverse and drilling modes, and by NanoSIMS. Good agreement was obtained between the methods with spatial resolution significantly higher in LA-ICP-MS drilling mode and NanoSIMS at 0.2 μm and 0.1 μm, respectively, compared to 5 μm by LA-ICP-MS in the traverse mode. Diffusion coefficients were more than five times slower, and solubilities five times lower, in the low MgO activity experiments compared with those carried out at high MgO activity at the same temperature and fO2. Our results show that at 1400PoPC and FMQ + 1.5 the maximum solubility of Rh in olivine in equilibrium with metal is 0.7 ppm in high SiOR2R activity mineral associations (those with orthopyroxene) and

Devolatilisation of serpentinites at depth in subduction zones contributes significant quantities of sulfur and other redox sensitive elements to the sub-arc mantle. However, the fate of sulfur in subducted serpentinites is poorly constrained. Textures of sulfur-bearing phases in subducted serpentinites are rarely studied, yet provide important information on the changes to sulfur distribution throughout the subduction cycle and as a result of fluid infiltration. δ34S values of sulfides provide constraints on sulfur sources, the redox state of sulfur in the host mineral, and on processes that have occurred subsequent to sulfide crystallisation, including interaction with oxidised or reduced fluids. Therefore, it is possible to use δ34S values in subducted serpentinites to constrain the redox state of sulfur in sulfides and subduction zone fluids. Furthermore, the proximity of serpentinites to ocean crust and metasediments may influence enrichment or depletion of 34S during subduction relative to serpentinites distal to such lithologies. This study investigates the redox state, the likelihood of sulfur addition to the sub-arc mantle from serpentinite dehydration, and the distribution of sulfur within subducted serpentinites and ‘hybrid’ mafic/ultramafic rocks from Alpine Corsica. The techniques utilised include petrographic analysis, in-situ sulfur isotopic analysis and trace element analysis of sulfides hosted in these rocks. All sulfides investigated have high δ34S values of 1.9–15.5‰, which suggests that mantle-derived sulfur (δ34S ~0.1‰), was not the sole source of sulfur. The highest δ34S values are recorded in pyrites of a hybrid mafic/ultramafic sample. High δ34S values are preserved in sulfides attributed to prograde metamorphism, and is most consistent with the retention of sulfur derived from hydrothermal sulfate reduction on the seafloor. However, a shift towards higher δ34S values in sulfides associated with the advanced stages of exhumation suggests that late stage exhumation enables enhanced access to slab-derived fluids bearing oxidised sulfur (SO42− or SO2). Such fluids may have been derived from the devolatilisation of serpentinite at greater depth, or from other lithologies.

Rare garnet crystals from a peridotite xenolith from the Wesselton kimberlite, South Africa, have distinct zones related to two separate episodes of mantle metasomatism. The garnet cores were firstly depleted through melt extraction, then equilibrated during metasomatism by a potentially diamond-forming carbonate-bearing or proto-kimberlitic fluid at 1100–1300 °C and 4.5–5.5 GPa. The garnet rim chemistry, in contrast, is consistent with later overgrowth in equilibrium with a kimberlite at around 1025 ± 25 ° C and 4.2 ± 0.5 GPa . This suggests that the rock was physically moved upwards by up to tens of kilometres between the two metasomatic episodes. Preserved high Ca, Al and Cr contents in orthopyroxenes suggest this uplift was tectonic, rather than magmatic. Diffusion profiles were measured over the transitions between garnet cores and rims using electron microprobe (Mg, Ca, Fe for modelling, plus Cr, Mn, Ti, Na, Al) and nano Secondary Ion Mass Spectrometry (NanoSIMS; 89Y, along with 23Na, Ca, Cr, Fe, Mn and Ti) analyses. The short profile lengths (generally

Marine sponges are set to become more abundant in many near-future oligotrophic environments, where they play crucial roles in nutrient cycling. Of high importance is their mass turnover of dissolved organic matter (DOM), a heterogeneous mixture that constitutes the largest fraction of organic matter in the ocean and is recycled primarily by bacterial mediation. Little is known, however, about the mechanism that enables sponges to incorporate large quantities of DOM in their nutrition, unlike most other invertebrates. Here, we examine the cellular capacity for direct processing of DOM, and the fate of the processed matter, inside a dinoflagellate-hosting bioeroding sponge that is prominent on Indo-Pacific coral reefs. Integrating transmission electron microscopy with nanoscale secondary ion mass spectrometry, we track 15 N- and 13 C-enriched DOM over time at the individual cell level of an intact sponge holobiont. We show initial high enrichment in the filter-feeding cells of the sponge, providing visual evidence of their capacity to process DOM through pinocytosis without mediation of resident bacteria. Subsequent enrichment of the endosymbiotic dinoflagellates also suggests sharing of host nitrogenous wastes. Our results shed light on the physiological mechanism behind the ecologically important ability of sponges to cycle DOM via the recently described sponge loop.

Production of radionuclide-free copper concentrates is dependent on understanding and controlling the deportment of daughter radionuclides (RNs) produced from 238U decay, specifically 226Ra, 210Pb, and 210Po. Sulfuric acid leaching is currently employed in the Olympic Dam processing plant (South Australia) to remove U and fluorine from copper concentrates prior to smelting but does not adequately remove the aforementioned RN. Due to chemical similarities between lead and alkaline earth metals (including Ra), two sets of experiments were designed to understand solution interactions between Sr, Ba, and Pb at various conditions. Nanoscale secondary ion mass spectrometry (NanoSIMS) isotopic spatial distribution maps and laser ablation inductively coupled-plasma mass spectrometry transects were performed on laboratory-grown crystals of baryte, celestite, and anglesite which had been exposed to different solutions under different pH and reaction time conditions. Analysis of experimental products reveals three uptake mechanisms: overgrowth of nearly pure SrSO4 and PbSO4 on baryte; incorporation of minor of Pb and Ba into celestite due to diffusion; and extensive replacement of Pb by Sr (and less extensive replacement of Pb by Ba) in anglesite via coupled dissolution-reprecipitation reactions. The presence of H2SO4 either enhanced or inhibited these reactions. Kinetic modelling supports the experimental results, showing potential for extrapolating the (Sr, Ba, Pb)SO4 system to encompass RaSO4. Direct observation of grain-scale element distributions by nanoSIMS aids understanding of the controlling conditions and mechanisms of replacement that may be critical steps for Pb and Ra removal from concentrates by allowing construction of a cationic replacement scenario targeting Pb or Ra, or ideally all insoluble sulfates. Experimental results provide a foundation for further investigation of RN uptake during minerals processing, especially during acid leaching. The new evidence enhances understanding of micro- to nanoscale chemical interactions and not only aids determination of where radionuclides reside during each processing stage but also guides development of flowsheets targeting their removal.

Many analytical techniques for trace element analysis are available to the geochemist and geometallurgist to understand and, ideally, quantify the distribution of trace and minor components in a mineral deposit. Bulk trace element data are useful, but do not provide information regarding specific host minerals&mdash, or lack thereof, in cases of surface adherence or fracture fill&mdash, for each element. The CAMECA nanoscale secondary ion mass spectrometer (nanoSIMS) 50 and 50L instruments feature ultra-low minimum detection limits (to parts-per-billion) and sub-micron spatial resolution, a combination not found in any other analytical platform. Using ore and copper concentrate samples from the Olympic Dam mining-processing operation, South Australia, we demonstrate the application of nanoSIMS to understand the mineralogical distribution of potential by-product and detrimental elements. Results show previously undetected mineral host assemblages and elemental associations, providing geochemists with insight into mineral formation and elemental remobilization&mdash, and metallurgists with critical information necessary for optimizing ore processing techniques. Gold and Te may be seen associated with brannerite, and Ag prefers chalcocite over bornite. Rare earth elements may be found in trace quantities in fluorapatite and fluorite, which may report to final concentrates as entrained liberated or gangue-sulfide composite particles. Selenium, As, and Te reside in sulfides, commonly in association with Pb, Bi, Ag, and Au. Radionuclide daughters of the 238U decay chain may be located using nanoSIMS, providing critical information on these trace components that is unavailable using other microanalytical techniques. These radionuclides are observed in many minerals but seem particularly enriched in uranium minerals, some phosphates and sulfates, and within high surface area minerals. The nanoSIMS has proven a valuable tool in determining the spatial distribution of trace elements and isotopes in fine-grained copper ore, providing researchers with crucial evidence needed to answer questions of ore formation, ore alteration, and ore processing.

Photosynthesis in the seagrass Zostera muelleri remains poorly understood. We investigated the effect of reduced irradiance on the incorporation of

Correlative NanoSIMS and EM imaging of amiodarone-treated macrophages shows the internalisation of the drug at a sub-cellular level and reveals its accumulation within the lysosomes, providing direct evidence for amiodarone-induced phospholipidosis. Chemical fixation using tannic acid effectively seals cellular membranes aiding intracellular retention of diffusible drugs.

This study describes the microstructural and chemical development of symplectites, obtained in fluid-mediated mineral replacement experiments. During the experiments polymineralic feldspar-rich samples were exposed to aqueous Na–SiO2 solution at 600 °C and 2 kbar confining pressures for durations of 12 hr to 20 days. The resulting reaction rims display high mineralogical and structural complexity and contain two varieties of symplectites, represented by nanometre-scale intergrowths of gehlenite–zeolite and grossular–zeolite grains. The experimental fluid was enriched in 18O isotope in order to trace oxygen redistribution during the reaction. The elevated 18O concentration in the reaction products and the heterogeneity in its distribution suggest that symplectite formation was controlled by dissolution–precipitation mechanisms rather than volume diffusion processes. Microstructural and chemical observations suggest that symplectite formation occurred in multiple stages in response to spatially heterogeneous and temporarily evolving fluid composition at the reaction interfaces. Hence, our results shed light on the fundamental processes involved in symplectite formation improving our ability to interpret symplectite microstructures. This article is protected by copyright. All rights reserved.

With growing interest in the application of in situ multiple sulfur isotope analysis to a variety of mineral systems, we report here the development of a suite of sulfur isotope standards for distribution relevant to magmatic, magmatic-hydrothermal, and hydrothermal ore systems. These materials include Sierra pyrite (FeS2), Nifty-b chalcopyrite (CuFeS2), Alexo pyrrhotite (Fe(1 − x)S), and VMSO pentlandite ((Fe,Ni)9S8) that have been chemically characterized by electron microprobe analysis, isotopically characterized for δ33S, δ34S, and δ36S by fluorination gas-source mass spectrometry, and tested for homogeneity at the micro-scale by secondary ion mass spectrometry. Beam-sample interaction as a function of crystallographic orientation is determined to have no effect on δ34S and Δ33S isotopic measurements of pentlandite. These new findings provided the basis for a case study on the genesis of the Long-Victor nickel-sulfide deposit located in the world class Kambalda nickel camp in the southern Kalgoorlie Terrane of Western Australia. Results demonstrate that precise multiple sulfur isotope analyses from magmatic pentlandite, pyrrhotite and chalcopyrite can better constrain genetic models related to ore-forming processes. Data indicate that pentlandite, pyrrhotite and chalcopyrite are in isotopic equilibrium and display similar Δ33S values + 0.2‰. This isotopic equilibrium unequivocally fingerprints the isotopic signature of the magmatic assemblage. The three sulfide phases show slightly variable δ34S values (δ34Schalcopyrite = 2.9 ± 0.3‰, δ34Spentlandite = 3.1 ± 0.2‰, and δ34Spyrrhotite = 3.9 ± 0.5‰), which are indicative of natural fractionation. Careful in situ multiple sulfur isotope analysis of multiple sulfide phases is able to capture the subtle isotopic variability of the magmatic sulfide assemblage, which may help resolve the nature of the ore-forming process. Hence, this SIMS-based approach discriminates the magmatic sulfur isotope signature from that recorded in metamorphic- and alteration-related sulfides, which may not be resolved during bulk rock fluorination analysis. The results indicate that, unlike the giant dunite-hosted komatiite systems that thermo-mechanically assimilated volcanogenic massive sulfides proximal to vents and display negative Δ33S values, the Kambalda ores formed in relatively distal environments assimilating abyssal sulfidic shales.

We acknowledge the Australian Microscopy & Microanalysis Research Facility at the Centre for Microscopy, Characterisation and Analysis, The University of Western Australia, a facility funded by the University, State and Commonwealth Governments. DW acknowledges funding from the European Commission and the Australian Research Council. This is publication number 838 from the Australian Research Council Centre of Excellence for Core to Crust Fluid Systems.

Both gold-rich sulphides and ultra-high grade native gold oreshoots are common but poorly understood phenomenon in orogenic-type mineral systems, partly because fluids in these systems are considered to have relatively low gold solubilities and are unlikely to generate high gold concentrations. The world-class Obuasi gold deposit, Ghana, has gold-rich arsenopyrite spatially associated with quartz veins, which have extremely high, localised concentrations of native gold, contained in microcrack networks within the quartz veins where they are folded. Here, we examine selected samples from Obuasi using a novel combination of quantitative electron backscatter diffraction analysis, ion microprobe imaging, synchrotron XFM mapping and geochemical modelling to investigate the origin of the unusually high gold concentrations. The auriferous arsenopyrites are shown to have undergone partial replacement (∼15%) by Au-poor, nickeliferous arsenopyrite, during localised crystal-plastic deformation, intragranular microfracture and metamorphism (340–460 °C, 2 kbars). Our results show the dominant replacement mechanism was pseudomorphic dissolution-reprecipitation, driven by small volumes of an infiltrating fluid that had relatively low ƒ S 2 and carried aqueous NiCl 2 . We find that arsenopyrite replacement produced strong chemical gradients at crystal-fluid interfaces due to an increase in ƒ S 2 during reaction, which enabled efficient removal of gold to the fluid phase and development of anomalously gold-rich fluid (potentially 10 ppm or more depending on sulphur concentration). This process was facilitated by precipitation of ankerite, which removed CO 2 from the fluid, increasing the relative proportion of sulphur for gold complexation and inhibited additional quartz precipitation. Gold re-precipitation occurred over distances of 10 μm to several tens of metres and was likely a result of sulphur activity reduction through precipitation of pyrite and other sulphides. We suggest this late remobilisation process may be relatively common in orogenic belts containing abundant mafic/ultramafic rocks, which act as a source of Ni and Co scavenged by chloride-bearing fluids. Both the preference of the arsenopyrite crystal structure for Ni and Co, rather than gold, and the release of sulphur during reaction, can drive gold remobilisation in many deposits across broad regions.

Platinum-group elements are strategically important metals. Finding new deposits is becoming increasingly difficult owing to our limited understanding of the processes that affect their mobility in surface environments. Microorganisms have been shown to promote the mobility of metals around ore deposits. Here we show that microorganisms influence the mobility of platinum-group elements in mineral grains collected from Brazil, Australia and Colombia. Scanning electron microscopy showed biofilms covering the platinum-group mineral grains. The biofilms contained abundant platinum-group element nanoparticles and microcrystalline aggregates, and were dominated by Proteobacteria, many of which were closely related to known metal-resistant species. Some platinum-group mineral grains contained carbon, nitrogen, sulfur, selenium and iodine, suggesting the grains may be biogenic in origin. Molecular analyses show that Brazilian platinum–palladium grains hosted specific bacterial communities, which were different in composition from communities associated with gold grains, or communities in surrounding soils and sediments. Nano-phase metallic platinum accumulated when a metallophillic bacterium was incubated with a percolating platinum-containing medium, suggesting that biofilms can cause the precipitation of mobile platinum complexes. We conclude that biofilms are capable of forming or transforming platinum-group mineral grains, and may play an important role for platinum-group element dispersion and re-concentration in surface environments.

Zinc (as an essential phytonutrient) and cadmium (as a toxic but readily bioavailable nonessential metal for plants) share similar routes for crossing plant biomembranes, although with a substantially different potential for translocation into above-ground tissues. The in situ distribution of these metals in plant cells and tissues (particularly intensively-dividing and fast-growing areas) is poorly understood. In this study, 17-day-old radish (Raphanus sativus L.) plants grown in nutrient solution were subjected to short-term (24 h) equimolar contamination (2.2 &micro, M of each 70Zn and Cd) to investigate their accumulation and distribution in the shoot apex (leaf primordia) and edible fleshy hypocotyl tissues. After 24-h exposure, radish hypocotyl had similar concentration (in &micro, g/g dry weight) of 70Zn (12.1 &plusmn, 1.1) and total Cd (12.9 &plusmn, 0.8), with relatively limited translocation of both metals to shoots (concentrations lower by 2.5-fold for 70Zn and 4.8-fold for Cd) as determined by inductively-coupled plasma mass spectrometry (ICP-MS). The in situ Zn/Cd distribution maps created by high-resolution secondary ion mass spectrometry (NanoSIMS, Cameca, Gennevilliers, France) imaging corresponded well with the ICP-MS data, confirming a similar pattern and uniform distribution of 70Zn and Cd across the examined areas. Both applied techniques can be powerful tools for quantification (ICP-MS) and localisation and visualisation (NanoSIMS) of some ultra-trace isotopes in the intensively-dividing cells and fast-growing tissues of non-metalophytes even after short-term metal exposure. The results emphasise the importance of the quality of (agro)ecosystem resources (growing media, metal-contaminated soils/waters) in the public health risk, given that, even under low contamination and short-term exposure, some of the most toxic metallic ions (e.g., Cd) can relatively rapidly enter the human food chain.

Some iron oxide-copper-gold (IOCG) deposits contain variable amounts of uranium. Developing mineral deportment models for the radiogenic isotopes resulting from decay of 238U presents a singular technical challenge, as concentrations of 226Ra, 210Pb, and 210Po fall far below the detection limits achievable for most in situ analytical methodologies. The nanoscale secondary ion mass spectrometry (nanoSIMS) platform combines low detection limits with sub-micron resolution, revealing previously unseen spatial distribution patterns of radionuclides (RNs) in (and on) particles of copper sulphide concentrates. Many potential host minerals for these radionuclides can be readily predicted based on chemical behaviour, periodic table trends, and published studies documenting likely host minerals. Using nanoSIMS data for ores and metallurgical products from the Olympic Dam IOCG deposit and associated processing facilities, we present compelling evidence for the ability of certain minerals within the copper concentrates to host daughter radionuclides derived from uranium decay. Many of these minerals had not traditionally been considered or previously documented as such. These include high-abundance minerals hosting low concentrations of radionuclides, and several relatively low abundance minerals exhibiting remarkable radionuclide enrichment. Rutile, fluorapatite, fluorite, hematite, zircon, covellite, and molybdenite are all proven to be minor hosts of at least some members of the 238U decay chain, and are, collectively, important for establishing the overall RN budget. Surface effects are found to play a significant role, with elevated levels of 226Ra and 210Pb found on most available surfaces, irrespective of mineral, in acid-leached concentrate. Some rRNs, particularly 226Ra and 210Pb liberated from uranium minerals during sulphuric acid leaching, can become extensively redistributed throughout the concentrate, creating newly-formed RN hosts. This new mineralogical deportment information can be used in developing new flowsheets to enhance radionuclide removal without a corresponding loss of Cu. NanoSIMS has proven invaluable for elucidating the mineral-scale deportment of ultra-trace radionuclides throughout the processing circuit at Olympic Dam.

We use pulsed Sr-labelling experiments to visualize growth of aragonitic Katelysia rhytiphora (Mollusca, Bivalvia) shells. The outer compound composite prismatic structure is organized into three orders of prisms, and the inner crossed acicular structure consists of intersecting lamellae. Electron Backscatter Diffraction (EBSD) reveals substantial twinning of the aragonite crystals (> 46 %) and an overall reduced and strategically oriented anisotropy of the Young’s modulus in the whole shell compared to that of monolithic aragonite. All structural orders in both layers are enveloped by an organic sheath and the smallest mineralized units are nanogranules. Total organic contents are 2.2 (outer) and 1.4 wt. % (inner layer) and are, thus, intermediate between those of nacreous and crossed-lamellar shells. Prisms in the outer structure can be correlated to yearly, daily and sub-daily growth rates. Average daily growth rates at the ventral margin for the outer structure are 17 % higher than for the inner crossed acicular structure. The calcification front runs evenly across all structures and architectural orders independently of the current growth rate. Sharply defined transitions from labelled to unlabelled areas in the shell indicate that physiological processes driving calcification have no lag. This suggests that the extrapallial fluid cannot be very voluminous. Narrow increments of varying Sr content within labelled shell, despite constant Sr concentrations in seawater, suggest cyclic metabolic activity during calcification. Micro-Raman spectroscopy maps validate a low impact of high Sr-conditions on the aragonite crystal structure. Identical Sr-enrichment factors for labelled and ambient conditions support models of ion transport via a passive selective pathway to the mantle epithelium followed by calcification via amorphous calcium carbonate.

Loss of function following injury to the CNS is worsened by secondary degeneration of neurons and glia surrounding the injury and is initiated by oxidative damage. However, it is not yet known which cellular populations and structures are most vulnerable to oxidative damage in vivo. Using Nanoscale secondary ion mass spectrometry (NanoSIMS), oxidative damage was semiquantified within cellular subpopulations and structures of optic nerve vulnerable to secondary degeneration, following a partial transection of the optic nerve in adult female PVG rats. Simultaneous assessment of cellular subpopulations and structures revealed oligodendroglia as the most vulnerable to DNA oxidation following injury. 5-Ethynyl-2′-deoxyuridine (EdU) was used to label cells that proliferated in the first 3 d after injury. Injury led to increases in DNA, protein, and lipid damage in oligodendrocyte progenitor cells and mature oligodendrocytes at 3 d, regardless of proliferative state, associated with a decline in the numbers of oligodendrocyte progenitor cells at 7 d. O4(+) preoligodendrocytes also exhibited increased lipid peroxidation. Interestingly, EdU(+) mature oligodendrocytes derived after injury demonstrated increased early susceptibility to DNA damage and lipid peroxidation. However, EdU(−) mature oligodendrocytes with high 8-hydroxyguanosine immunoreactivity were more likely to be caspase3(+). By day 28, newly derived mature oligodendrocytes had significantly reduced myelin regulatory factor gene mRNA, indicating that the myelination potential of these cells may be reduced. The proportion of caspase3(+) oligodendrocytes remained higher in EdU(−) cells. Innovative use of NanoSIMS together with traditional immunohistochemistry and in situ hybridization have enabled the first demonstration of subpopulation specific oligodendroglial vulnerability to oxidative damage, due to secondary degeneration in vivo. SIGNIFICANCE STATEMENT Injury to the CNS is characterized by oxidative damage in areas adjacent to the injury. However, the cellular subpopulations and structures most vulnerable to this damage remain to be elucidated. Here we use powerful NanoSIMS techniques to show increased oxidative damage in oligodendroglia and axons and to demonstrate that cells early in the oligodendroglial lineage are the most vulnerable to DNA oxidation. Further immunohistochemical and in situ hybridization investigation reveals that mature oligodendrocytes derived after injury are more vulnerable to oxidative damage than their counterparts existing at the time of injury and have reduced myelin regulatory factor gene mRNA, yet preexisting oligodendrocytes are more likely to die.

Following injury to the central nervous system, axons and myelin distinct from the initial injury site undergo changes associated with compromised function. Quantifying such changes is important to understanding the pathophysiology of neurotrauma; however, most studies to date used 2 dimensional (D) electron microscopy to analyse single sections, thereby failing to capture changes along individual axons. We used serial block face scanning electron microscopy (SBF SEM) to undertake 3D reconstruction of axons and myelin, analysing optic nerves from normal uninjured female rats and following partial optic nerve transection. Measures of axon and myelin dimensions were generated by examining 2D images at 5 µm intervals along the 100 µm segments. In both normal and injured animals, changes in axonal diameter, myelin thickness, fiber diameter, G-ratio and percentage myelin decompaction were apparent along the lengths of axons to varying degrees. The range of values for axon diameter along individual reconstructed axons in 3D was similar to the range from 2D datasets, encompassing reported variation in axonal diameter attributed to retinal ganglion cell diversity. 3D electron microscopy analyses have provided the means to demonstrate substantial variability in ultrastructure along the length of individual axons and to improve understanding of the pathophysiology of neurotrauma.

Diazotrophic bacteria are instrumental in generating biologically usable forms of nitrogen by converting abundant dinitrogen gas (N-2) into available forms, such as ammonium. Although nitrogen is crucial for coral growth, direct observation of associations between diazotrophs and corals has previously been elusive. We applied fluorescence in situ hybridization (FISH) and nanoscale secondary ion mass spectrometry to observe the uptake of N-15-enriched diazotrophic Vibrio sp. isolated from Acropora millepora into conspecific coral larvae. Incorporation of Vibrio sp. cells was observed in coral larvae after 4-h incubation with enriched bacteria. Uptake was restricted to the aboral epidermis of larvae, where Vibrio cells clustered in elongated aggregations. Other bacterial associates were also observed in epidermal areas in FISH analyses. Although the fate and role of these bacteria requires additional investigation, this study describes a powerful approach to further explore cell associations and nutritional pathways in the early life stages of the coral holobiont.

© 2018 Rädecker, Raina, Pernice, Perna, Guagliardo, Kilburn, Aranda and Voolstra. The symbiosis between cnidarian hosts and microalgae of the genus Symbiodinium provides the foundation of coral reefs in oligotrophic waters. Understanding the nutrient-exchange between these partners is key to identifying the fundamental mechanisms behind this symbiosis, yet has proven difficult given the endosymbiotic nature of this relationship. In this study, we investigated the respective contribution of host and symbiont to carbon and nitrogen assimilation in the coral model anemone Aiptaisa. For this, we combined traditional measurements with nanoscale secondary ion mass spectrometry (NanoSIMS) and stable isotope labeling to investigate patterns of nutrient uptake and translocation both at the organismal scale and at the cellular scale. Our results show that the rate of carbon and nitrogen assimilation in Aiptasia depends on the identity of the host and the symbiont. NanoSIMS analysis confirmed that both host and symbiont incorporated carbon and nitrogen into their cells, implying a rapid uptake and cycling of nutrients in this symbiotic relationship. Gross carbon fixation was highest in Aiptasia associated with their native Symbiodinium communities. However, differences in fixation rates were only reflected in the δ13C enrichment of the cnidarian host, whereas the algal symbiont showed stable enrichment levels regardless of host identity. Thereby, our results point toward a "selfish" character of the cnidarian-Symbiodinium association in which both partners directly compete for available resources. Consequently, this symbiosis may be inherently instable and highly susceptible to environmental change. While questions remain regarding the underlying cellular controls of nutrient exchange and the nature of metabolites involved, the approach outlined in this study constitutes a powerful toolset to address these questions.

Macrophages are generally assumed to unload surplus cholesterol through direct interactions between ABC transporters on the plasma membrane and HDLs, but they have also been reported to release cholesterol-containing particles. How macrophage-derived particles are formed and released has not been clear. To understand the genesis of macrophage-derived particles, we imaged mouse macrophages by EM and nanoscale secondary ion mass spectrometry (nanoSIMS). By scanning EM, we found that large numbers of 20- to 120-nm particles are released from the fingerlike projections (filopodia) of macrophages. These particles attach to the substrate, forming a "lawn" of particles surrounding macrophages. By nanoSIMS imaging we showed that these particles are enriched in the mobile and metabolically active accessible pool of cholesterol (detectable by ALO-D4, a modified version of a cholesterol-binding cytolysin). The cholesterol content of macrophage-derived particles was increased by loading the cells with cholesterol or by adding LXR and RXR agonists to the cell-culture medium. Incubating macrophages with HDL reduced the cholesterol content of macrophage-derived particles. We propose that release of accessible cholesterol-rich particles from the macrophage plasma membrane could assist in disposing of surplus cholesterol and increase the efficiency of cholesterol movement to HDL.

Biogenic carbonates are important archives for reconstructing the marine sulfur cycle. However, uncertainties exist about the exact location of carbonate associated sulfate (CAS) and a possible biological control on sulfate incorporation. The behavior of CAS in biogenic carbonates during diagenetic alteration is even more poorly constrained. To investigate the mechanisms of sulfur incorporation and the effects of alteration on sulfur in biogenic carbonates, modern marine bivalve shells of Arctica islandica species were hydrothermally altered at 100 degrees C and 175 degrees C. Fluorescence microscopy, element mapping via NanoSIMS and mu-XRF, sulfur XANES analyses, and delta S-34 measurements were performed on the experimentally altered shell segments. Changes in elemental compositions and delta S-34 of sulfate in the post-alteration solutions were also determined. Results indicate clear differences between the delta S-34 values of the CAS (+ 21 parts per thousand, V-CDT) that reflects ambient seawater sulfate and the organically bound sulfur that is isotopically lighter (+ 14.8 parts per thousand, V-CDT or less). Carbonate associated sulfate is primarily incorporated in the mineral phase of the shell, whereas reduced sulfur phases are mainly found within the intrashell organic matter. Hydrothermal alteration experiments at 100 degrees C resulted in minimal changes of sulfur within the bivalve shells. In contrast, the 175 degrees C experiments triggered decomposition of intrashell organic matrices which then led to extensive diagenetic alteration in both the shell microstructure and chemistry. Changes in total concentration, speciation, and spatial distribution of sulfur reflect the diagenetic processes that occurred within the shells. Preferential incorporation of CAS in a neomorphic calcite phase with Mg/Ca ratios of 0.13-0.21 was observed. Due to its presence in both organic and inorganic phases and its multiple oxidation states with different isotopic compositions we conclude that sulfur is a useful and sensitive proxy for diagenetic alteration in biogenic aragonite.

The processing of triglyceride-rich lipoproteins (TRLs) in capillaries provides lipids for vital tissues, but our understanding of TRL metabolism is limited, in part because TRL processing and lipid movement have never been visualized. To investigate the movement of TRL-derived lipids in the heart, mice were given an injection of [2H]triglyceride-enriched TRLs, and the movement of 2H-labeled lipids across capillaries and into cardiomyocytes was examined by NanoSIMS. TRL processing and lipid movement in tissues were extremely rapid. Within 30 s, TRL-derived lipids appeared in the subendothelial spaces and in the lipid droplets and mitochondria of cardiomyocytes. Enrichment of 2H in capillary endothelial cells was not greater than in cardiomyocytes, implying that endothelial cells may not be a control point for lipid movement into cardiomyocytes. Remarkably, a deficiency of the putative fatty acid transport protein CD36, which is expressed highly in capillary endothelial cells, did not impede entry of TRL-derived lipids into cardiomyocytes.

The symbiosis between cnidarian hosts and microalgae of the genusSymbiodiniumprovides the foundation of coral reefs in oligotrophic waters. Understanding the nutrient-exchange between these partners is key to identifying the fundamental mechanisms behind this symbiosis. However, deciphering the individual role of host and algal partners in the uptake and cycling of nutrients has proven difficult, given the endosymbiotic nature of this relationship. In this study, we highlight the advantages of the emerging model system Aiptasia to investigate the metabolic diversity and specificity of cnidarian – dinoflagellate symbiosis. For this, we combined traditional measurements with nano-scale secondary ion mass spectrometry (NanoSIMS) and stable isotope labeling to investigate carbon and nitrogen cycling both at the organismal scale and the cellular scale. Our results suggest that the individual nutrient assimilation by hosts and symbionts depends on the identity of their respective symbiotic partner. Further,δ13C enrichment patterns revealed that alterations in carbon fixation rates only affected carbon assimilation in the cnidarian host but not the algal symbiont, suggesting a ‘selfish’ character of this symbiotic association. Based on our findings, we identify new venues for future research regarding the role and regulation of nutrient exchange in the cnidarian - dinoflagellate symbiosis. In this context, the model system approach outlined in this study constitutes a powerful tool set to address these questions.

Rhenium and osmium isotopes have been used for decades to date the formation of molybdenite (MoS2), a common mineral in ore deposits and the world’s main source of molybdenum and rhenium. Understanding the distribution of parent 187Re and radiogenic daughter 187Os isotopes in molybdenite is critical in interpreting isotopic measurements because it can compromise the accurate determination and interpretation of mineralization ages. In order to resolve the controls on the distribution of these elements, chemical and isotope mapping of MoS2 grains from representative porphyry copper-molybdenum deposits were performed using electron microprobe and nano-scale secondary ion mass spectrometry. Our results show a heterogeneous distribution of 185,187Re and 192Os isotopes in MoS2, and that both 187Re and 187Os isotopes are not decoupled as previously thought. We conclude that Re and Os are structurally bound or present as nanoparticles in or next to molybdenite grains, recording a complex formation history and hindering the use of microbeam techniques for Re-Os molybdenite dating. Our study opens new avenues to explore the effects of isotope nuggeting in geochronometers.

© 2018 International Society for Microbial Ecology. Some of the most aggressive coral-excavating sponges host intracellular dinoflagellates from the genus Symbiodinium, which are hypothesized to provide the sponges with autotrophic energy that powers bioerosion. Investigations of the contribution of Symbiodinium to host metabolism and particularly inorganic nutrient recycling are complicated, however, by the presence of alternative prokaryotic candidates for this role. Here, novel methods are used to study nutrient assimilation and transfer within and between the outer-layer cells of the Indopacific bioeroding sponge Cliona orientalis. Combining stable isotope labelling, transmission electron microscopy (TEM) and nanoscale secondary ion mass spectrometry (NanoSIMS), we visualize and measure metabolic activity at the individual cell level, tracking the fate of 15N-ammonium and 13C-bicarbonate within the intact holobiont. We found strong uptake of both inorganic sources (especially 13C-bicarbonate) by Symbiodinium cells. Labelled organic nutrients were translocated from Symbiodinium to the Symbiodinium-hosting sponge cells within 6 h, and occasionally to other sponge cells within 3 days. By contrast, prokaryotic symbionts were not observed to participate in inorganic nutrient assimilation in the outer layers of the sponge. Our findings strongly support the metabolic interaction between the sponge and dinoflagellates, shedding light on the ecological advantages and adaptive capacity of photosymbiotic bioeroding sponges in oligotrophic marine habitats.

Defluviicoccus vanus -related glycogen accumulating organisms (GAO) regularly proliferate in industrial wastewater treatment plants handling high carbon but nitrogen deficient wastes. When GAO dominate, they are associated with poor performance, characterised by slow settling biomass and turbid effluents. Although their ecophysiology has been studied thoroughly in domestic waste treatment plants, little attention has been paid to them in aerobic industrial systems. In this study, the effect of nitrogen addition on GAO carbon metabolism was investigated during an 8 h cycle. Activated sludge dominated by GAO from a winery wastewater sequencing batch reactor was incubated under different carbon to nitrogen (COD:N) ratios (100:1, 60:1 and 20:1) using 13 C — acetate and 15 N — urea. GAO cell assimilation was quantified using FISH-NanoSIMS. The activated sludge community was assessed by 16S rRNA gene profiling, DNA and storage polymer production. Carbon and nitrogen quantification at the cellular level by NanoSIMS revealed that low (COD:N of 100:1) or null nitrogen concentrations enhanced GAO carbon uptake. COD:N ratios of 60:1 and 20:1 reduced GAO carbon uptake and promoted whole microbial community DNA production. Nitrogen dosing at COD:N ratios of 60:1 or higher was demonstrated as feasible strategy for controlling the excessive GAO growth in high COD waste treatment plants.

Phytoplankton-bacteria interactions drive the surface ocean sulfur cycle and local climatic processes through the production and exchange of a key compound: dimethylsulfoniopropionate (DMSP). Despite their large-scale implications, these interactions remain unquantified at the cellular-scale. Here we use secondary-ion mass spectrometry to provide the first visualization of DMSP at sub-cellular levels, tracking the fate of a stable sulfur isotope (34S) from its incorporation by microalgae as inorganic sulfate to its biosynthesis and exudation as DMSP, and finally its uptake and degradation by bacteria. Our results identify for the first time the storage locations of DMSP in microalgae, with high enrichments present in vacuoles, cytoplasm and chloroplasts. In addition, we quantify DMSP incorporation at the single-cell level, with DMSP-degrading bacteria containing seven times more 34S than the control strain. This study provides an unprecedented methodology to label, retain, and image small diffusible molecules, which can be transposable to other symbiotic systems. DOI: http://dx.doi.org/10.7554/eLife.23008.001, eLife digest Sulfur is an essential element for many organisms and environmental processes. Every year, organisms including microalgae produce more than one billion tons of a sulfur-containing compound called DMSP. Some of this DMSP is released into seawater, where it acts as a key nutrient for microscopic organisms and as a foraging cue to attract fish. DMSP is also the precursor of a gas that helps to form clouds. Despite DMSP’s potential large-scale effects, it is still not clear what role it plays in the organisms that produce it, or how it is transferred from the microalgae that produce it to the bacteria that use it. It is thought that DMSP could potentially protect the cells from sudden changes in the amount of salt in the seawater (salinity) or from other damage, such as oxidative stress – a build-up of harmful chemicals inside cells. In a controlled setting using artificial seawater, Raina et al. used high-resolution imaging and chemical analysis to track the journey of DMSP from microalgae to recipient bacteria. The results show that similar to land plants, algae store DMSP in the compartments that regulate cell pressure and photosynthesis. The presence of DMSP in these locations also supports its proposed role in protecting cells from changes in salinity or oxidative damage. A future step will be to identify the genes involved in producing DMSP in microalgae. This knowledge could be used to create mutants that are either incapable of producing this molecule or that overproduce it. In combination with the high-resolution imaging techniques described here, this will allow researchers to fully understand the role that DMSP plays in these organisms. DOI: http://dx.doi.org/10.7554/eLife.23008.002

Plants rapidly release photoassimilated carbon (C) to the soil via direct root exudation and associated mycorrhizal fungi, with both pathways promoting plant nutrient availability. This study aimed to explore these pathways from the root's vascular bundle to soil microbial communities. Using nanoscale secondary ion mass spectrometry (NanoSIMS) imaging and (13) C-phospho- and neutral lipid fatty acids, we traced in-situ flows of recently photoassimilated C of (13) CO2 -exposed wheat (Triticum aestivum) through arbuscular mycorrhiza (AM) into root- and hyphae-associated soil microbial communities. Intraradical hyphae of AM fungi were significantly (13) C-enriched compared to other root-cortex areas after 8 h of labelling. Immature fine root areas close to the root tip, where AM features were absent, showed signs of passive C loss and co-location of photoassimilates with nitrogen taken up from the soil solution. A significant and exclusively fresh proportion of (13) C-photosynthates was delivered through the AM pathway and was utilised by different microbial groups compared to C directly released by roots. Our results indicate that a major release of recent photosynthates into soil leave plant roots via AM intraradical hyphae already upstream of passive root exudations. AM fungi may act as a rapid hub for translocating fresh plant C to soil microbes.

Olympic Dam hosts >80 million tonnes of copper, as copper‑iron sulphides, within hematite-dominant gangue. Processing of the relatively fine-grained copper ore is complicated by the presence of by-product uranium and its radiogenic isotopes, in particular 226Ra, 210Pb and 210Po, which partially recover to the final copper sulphide concentrates. Although the majority (~85%) of the U-bearing minerals (uraninite, coffinite, brannerite, thorianite, thorite) are recovered to flotation tailings, the remaining ~15% occurs in copper concentrates as sulphide-gangue composite particles and micron- to nanoscale grains occluded within sulphide minerals. Sulphuric acid leaching of copper concentrates significantly reduces the concentration of U but has only a minor impact on the daughter isotopes. Further reduction of these isotopes may be achieved through selective targeting and removal of specific minerals known to be radionuclide (RN) hosts, but fine-grained, micro- to nanoscale ore textures preclude easy direct identification of these RN host phases. Nanoscale secondary ion mass spectrometry (nanoSIMS) has proven to be an excellent platform for in situ mapping of ultra-trace RN distributions, with sub-micron spatial resolution, in individual mineral grains. Uranium and thorium minerals are, as expected, the major hosts and display significant concentrations of the entire 238U decay chain. Although the majority of these minerals are removed via acid leaching of copper concentrate, sufficient RNs remain in the concentrate as micron- to nanoscale grains within sulphides and gangue minerals or along particle microfractures. Results show that brannerite, potentially more problematic due to its lower solubility in sulphuric acid than uraninite, does not appear to contain appreciable amounts of daughter isotopes. The insolubility of ThPO4 produces the potential for sequestration of 232Th and 230Th in rare earth phosphates such as xenotime, which then retain the respective decay chains. Likewise, the insolubility of certain sulphates (Sr, Ba, Pb, Ra) provides a mechanism for precipitation and entrapment of RNs. Baryte was shown to accumulate Ra and Pb naturally in the deposit, and it can upgrade its RN content substantially during sulphuric acid leaching through coupled dissolution-reprecipitation mechanisms involving Pb2+ and Ra2+ liberated from dissolved uranium minerals. Identification and prioritization of RN host minerals is crucial for the development of a more efficient processing flowsheet.

Komatiite-hosted nickel sulphides from the Yilgarn Craton (Australia) consist of two main sulphide phases: pyrrhotite (Fe7S8) and pentlandite ((Fe,Ni)9S8); two minor sulphide phases: chalcopyrite (CuFeS2) and pyrite (FeS2) and trace arsenides. Samples of massive sulphides from three deposits with diverse deformation and metamorphic histories (the Silver Swan, Perseverance and Flying Fox deposits) have been studied by electron backscatter diffraction and laser ablation inductively coupled plasma mass spectrometry and nano-scale secondary ion mass spectrometry. These ore bodies were selected to investigate the relationship between microstructures and mineral trace element chemistry in three dominant sulphide species in each deposit. In all three samples, pyrrhotite preserves a strong evidence of crystal plasticity relative to both pentlandite and pyrite. The trace element composition of pyrrhotite shows significant variation in specific elements (Pb, Bi and Ag). This variation correlates spatially with intragrain pyrrhotite microstructures, such as low angle and twin boundaries. Minor signatures of crystal plasticity in pyrite and pentlandite occur in the form of rare low angle boundaries (pentlandite) and mild lattice misorientation (pyrite). Trace element compositions of pentlandite and pyrite show no correlation with microstructures. Variations in pyrrhotite are interpreted as a result of intragrain diffusion during the syn- and post-deformation history of the deposit. Intragrain diffusion can occur either due to bulk diffusion, dislocation–impurity pair diffusion, or by “pipe diffusion”, i.e. along fast diffusion pathways at high and low angle, and twin boundaries. This contribution examines three different diffusion models and suggests that dislocation–impurity pair diffusion and pipe diffusion are the most likely processes behind increased trace element concentration along the microstructures in pyrrhotite. The same phenomenon is observed in samples from three different deposits that experienced widely different metamorphic conditions, implying that the final disposition of these elements reflects a post peak-metamorphic stage of the geological history of all three deposits.

Mycorrhiza formation represents a significant carbon (C) acquisition alternative for orchid species, particularly those that remain achlorophyllous through all life stages. As it is known that orchid mycorrhizas facilitate nutrient transfer (most notably of C), it has not been resolved if C transfer occurs only after lysis of mycorrhizal structures (fungal pelotons) or also across the mycorrhizal interface of pre-lysed pelotons. We used high-resolution secondary ion mass spectrometry (nanoSIMS) and labelling with enriched (13) CO2 to trace C transfers, at subcellular scale, across mycorrhizal interfaces formed by Rhizanthella gardneri, an achlorphyllous orchid. Carbon was successfully traced in to the fungal portion of orchid mycorrhizas. However, we did not detect C movement across intact mycorrhizal interfaces up to 216 h post (13) CO2 labelling. Our findings provide support for the hypothesis that C transfer from the mycorrhizal fungus to orchid, at least for R. gardneri, likely occurs after lysis of the fungal peloton.

Summary � The ability of plants to compete effectively for nitrogen (N) resources is critical to plant survival. However, controversy surrounds the importance of organic and inorganic sources of N in plant nutrition because of our poor ability to visualize and understand processes happening at the root–microbial–soil interface. � Using high-resolution nano-scale secondary ion mass spectrometry stable isotope imaging (NanoSIMS-SII), we quantified the fate of 15 N over both space and time within the rhizosphere. We pulse-labelled the soil surrounding wheat (Triticum aestivum) roots with either 15 NH þ 4 or 15 N-glutamate and traced the movement of 15 N over 24 h. � Imaging revealed that glutamate was rapidly depleted from the rhizosphere and that most 15 N was captured by rhizobacteria, leading to very high 15 N microbial enrichment. After microbial capture, approximately half of the 15 N-glutamate was rapidly mineralized, leading to the excretion of NH þ , which became available for plant capture. Roots proved to be poor competitors for 15 N-glutamate and took up N mainly as 15 NH þ . Spatial mapping of 15 N revealed differential patterns of 15 N uptake within bacteria and the rapid uptake and redistribution of 15 N within roots. � In conclusion, we demonstrate the rapid cycling and transformation of N at the soil–root interface and that wheat capture of organic N is low in comparison to inorganic N under the conditions tested.

The waters surrounding coral reef ecosystems are generally poor in nutrients, yet their levels of primary production are comparable with those reported from tropical rain forests. One explanation of this paradox is the efficient cycling of nutrients between the coral host, its endosymbiotic alga Symbiodinium and a wide array of microorganisms. Despite their importance for the animals' fitness, the cycling of nutrients in early coral life stages and the initial establishment of partnerships with the microbes involved in these processes has received little scrutiny to date. Nitrogen is an essential but limited nutrient in coral reef ecosystems. In order to assess the early nutrient exchange between bacteria and corals, coral larvae of the species Pocillopora damicornis were incubated with two coral-associated bacteria (Alteromonas sp., or Vibrio alginolyticus), prelabeled with the stable nitrogen isotope N-15. The incorporation and translocation of nitrogen from Vibrio- and Alteromonas bacteria into P. damicornis coral larvae and specifically into the coral-symbiotic Symbiodinium were detected by nanoscale secondary ion mass spectrometry (NanoSIMS). A significant increase in the amount of enriched N-15 (two to threefold compared to natural abundance) was observed in P. damicornis larvae within 8h of incubation for both bacterial treatments (one-way ANOVA, F-5,F-53=18.03, P=0.004 for Alteromonas sp. and F-5,F-53=18.03, P=0.0001 for V. alginolyticus). These findings reveal that coral larvae acquire nutrients previously taken up from the environment by bacteria. The additional nitrogen may increase the survival rate and fitness of the developing coral and therefore contribute to the successful maintenance of coral reefs.

Cholesterol is a crucial lipid within the plasma membrane of mammalian cells. Recent biochemical studies showed that one pool of cholesterol in the plasma membrane is "accessible" to binding by a modified version of the cytolysin perfringolysin O (PFO*), whereas another pool is sequestered by sphingomyelin and cannot be bound by PFO* unless the sphingomyelin is destroyed with sphingomyelinase (SMase). Thus far, it has been unclear whether PFO* and related cholesterol-binding proteins bind uniformly to the plasma membrane or bind preferentially to specific domains or morphologic features on the plasma membrane. Here, we used nanoscale secondary ion mass spectrometry (NanoSIMS) imaging, in combination with 15N-labeled cholesterol-binding proteins (PFO* and ALO-D4, a modified anthrolysin O), to generate high-resolution images of cholesterol distribution in the plasma membrane of Chinese hamster ovary (CHO) cells. The NanoSIMS images revealed preferential binding of PFO* and ALO-D4 to microvilli on the plasma membrane; lower amounts of binding were detectable in regions of the plasma membrane lacking microvilli. The binding of ALO-D4 to the plasma membrane was virtually eliminated when cholesterol stores were depleted with methyl-β-cyclodextrin. When cells were treated with SMase, the binding of ALO-D4 to cells increased, largely due to increased binding to microvilli. Remarkably, lysenin (a sphingomyelin-binding protein) also bound preferentially to microvilli. Thus, high-resolution images of lipid-binding proteins on CHO cells can be acquired with NanoSIMS imaging. These images demonstrate that accessible cholesterol, as judged by PFO* or ALO-D4 binding, is not evenly distributed over the entire plasma membrane but instead is highly enriched on microvilli.