An experimental study of magnesium-isotope fractionation in chlorophyll-a photosynthesis

Measurements are presented of the magnesium isotopic composition of chlorophyll-a, extracted from cyanobacteria, relative to the isotopic composition of the culture medium in which the cyanobacteria were grown. Yields of 50-93% chlorophyll-a were achieved from the pigment extracts of Synechococcus elongatus, a unicellular cyanobacteria. This material was then digested using concentrated nitric acid to extract magnesium. Separation was accomplished using columns of cation-exchange resin, which achieved a 103 ± 10% yield of magnesium from chlorophyll-a. This procedure ensured accurate measurement of the magnesium-isotopic ratios without isobaric interferences using a multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We find a slight depletion in the heavier isotopes of magnesium in chlorophyll-a relative to culture medium, early growth phase: Δ²⁶Mg = −0.71(±0.35)‰ and Δ²⁵Mg = −0.37(±0.18)‰; late growth phase: Δ²⁶Mg = −0.53(±0.20)‰ and Δ²⁵Mg = −0.26(±0.11)‰, due to an apparent mass-dependent fractionation. We suggest that the small fractionation results from chelation during intracellular processes. A likely candidate for this chelation step involves the magnesium-chelatase enzyme, which mediates the insertion of magnesium to the tetrapyrrole ring during chlorophyll-a biosynthesis. Proof of this hypothesis can be tested with biological controls whereby steps in the enzymatic pathways of chlorophyll synthesis are selectively suppressed.     

Validation of a fish farm waste resuspension model by use of a particulate tracer discharged from a point source in a coastal environment

To validate a resuspension model of particulate material (salmonid farm wastes), a UV fluorescent particle tracer was selected with similar settling characteristics. Tracer was introduced to the seabed (water depth ≈30 m) and sediment samples taken on days 0, 3, 10, 17 and 30 to measure the horizontal and vertical distribution of tracer in sediments. A concentric sampling grid was established at radii of 25, 50, 100, 150, 200, 400, 700 and 1, 000 m from the source on transects 30° apart. The bulk of the deployed tracer was initially concentrated in an area 25 m radius from the release point; tracer was observed to steadily decrease to zero over a period of 30 days. In a 200 m region measured from the release point in the direction of the residual current, the redeposition of tracer was low. A Lagrangian particle tracking model was validated using these observed data by varying resuspension model parameters within limits to obtain the best agreement between spatial and temporal distributions. The validated model generally gave good predictions of total mass budgets (±7% of total tracer released), particulary where tracer concentrations were high near the release point. Best fit model parameters (critical erosion shear stress=0.018 N m⁻², erodibility constan=60 g m⁻² d⁻¹) are at the low end of reported parameters for coastal resuspension models. Such a low critical erosion shear stress indicates that the frequency of resuspension and deposition events for freshly deposited material is high.     

Geochemistry and geochronology of proterozoic tholeiite dykes of east antarctica: evidence for mantle metasomatism

Two episodes of tholeiite dyke emplacement have been identified in Archaean high-grade metamorphics of the Napier Complex in Enderby Land. Middle Proterozoic Amundsen dykes are typical continental tholeiites and most of the chemical variation in individual suites can be explained in terms of different degrees of partial melting and low-pressure crystal fractionation. Group I Amundsen tholeiites were derived from a relatively homogeneous source region 1,190±200 m.y. ago, whereas that of the group II Amundsen tholeiites was chemically and isotopically heterogeneous. Group II dykes have various degrees of enrichment in incompatible elements, and commonly show normalised trace element abundance patterns with negative Nb anomalies. These features imply variable metasomatism of the source region by a volatile-rich fluid phase (rather than a melt of any observed igneous composition) enriched in K, Rb, Ba, Th, and possibly La and Ce.Early Proterozoic (2,350±48 m.y.) tholeiites were emplaced at considerable depths in the crust during the waning stages of granulite-facies metamorphism and include a high-Mg suite of possible komatiitic affinity, ranging in composition from hypersthene-rich tholeiite (norite) to quartz-rich tholeiite. They tend to have higher ratios of highly to moderately incompatible elements (e.g., K/Zr, K/Ce), and larger Nb anomalies (i.e., higher K/Nb) compared with middle Proterozoic tholeiites, suggesting derivation from more enriched source regions. Isotopic data are not compatible with significant crustal contamination, but constrain source metasomatism to a time immediately before emplacement. Metasomatism of the source region of the much younger group I tholeiites may have been contemporaneous with that of the high-Mg suite.     

U–Pb dating of silicic lavas,sills and syneruptive resedimented volcaniclastic deposits of the Lower Devonian Crudine Group,Hill End Trough,New South Wales

The Hill End Trough of central‐western New South Wales was an elongate deep marine basin that existed in the Lachlan Fold Belt from the early Late Silurian to late Early Devonian. It is represented by a regionally extensive, unfossiliferous sequence of interbedded turbidites and hemipelagites of substantially silicic volcanic derivation, which passes laterally into contemporaneous shallow‐water sedimentary rocks. The Turondale and Merrions Formations of the Lower Devonian Crudine Group are two prominent volcanogenic formations in the predominantly sedimentary trough sequence. They contain a range of primary and resedimented volcanic facies suitable for U–Pb dating. These include widespread subaqueous silicic lavas and/or lava cryptodomes, and thick sequences of crystal‐rich volcaniclastic sandstone emplaced by a succession of mass‐flows that were generated by interaction between contemporaneous subaerial pyroclastic flows and the sea. Ion microprobe dating of the two volcanogenic formations by means of the commonly used SL 13 zircon standard yields ages ranging between 411.3 ± 5.1 and 404.8 ± 4.8 Ma. Normalising the data against a different zircon standard (QGNG) yields preferred slightly older mean ages that range between 413.4 ± 6.6 and 407.1 ± 6.9 Ma. These ages broadly approximate the Early Devonian age that has been historically associated with the Crudine Group. However, the biostratigraphically inferred late Lochkovian ‐ early Emsian (mid‐Early Devonian) age for the Merrions Formation is inconsistent with the current Australian Phanerozoic Timescale, which assigns an age of 410 Ma to the Silurian‐Devonian boundary, and ages of 404.5 Ma and 395.5 Ma to the base and top of the Pragian, respectively. There is, however, good agreement if the new ages are compared with the most recently published revision of the Devonian time‐scale. This suggests that the Early Devonian stage boundaries of the Australian Phanerozoic Timescale need to be revised downward. The new ages for the Merrions Formation could also provide a time point on this time‐scale for the Pragian to early Emsian, for which no data are presently available.     

The Mordor Complex: A highly differentiated potassic intrusion with kimberlitic affinities in central Australia

The Mordor Complex in central Australia consists of a suite of highly fractionated potassic rocks. Syenite and monzonite are intruded by phlogopite shonkinite and melamonzonite, which are in turn intruded by numerous plug-like bodies of phlogopiterich periodotite and pyroxenite, and by pegmatite dykes, and carbonate-rich breccia.The consanguinity of the suite, cumulate texture of the ultramafic rocks, enrichment of the Complex in large-ion-lithophile (LIL) elements, mineral equilibrium data, and mineral and whole-rock Rb-Sr isochron data, indicate that the rocks were produced by fractional crystallization from an ultrapotassic mafic magma in an intermediate-level magma chamber. Magma genesis possibly involved modification during uprise of potassic partial melt derived from phlogopite-bearing atypical upper mantle source rock. Evidence for regional compositional heterogeneity in the upper mantle is discussed.     

Metamorphic zircon formation by solid-state recrystallization of protolith igneous zircon

Protolith zircon in high‐grade metagranitoids from Queensland, Australia, partially recrystallized during granulite‐grade metamorphism. We describe the zircon in detail using integrated cathodoluminescence, U–Pb isotope, trace element and electron backscatter diffraction pattern (EBSP) analyses. Primary igneous oscillatory zoning is partially modified or obliterated in areas within single crystals, but is well preserved in other areas. A variety of secondary internal structures are observed, with large areas of transgressive recrystallized zircon usually dominant. Associated with these areas are recrystallization margins, interpreted to be recrystallization fronts, that have conformable boundaries with transgressive recrystallized areas, but contrasting cathodoluminescence and trace element chemistry. Trace element analyses of primary and secondary structures provide compelling evidence for closed‐system solid‐state recrystallization. By this process, trace elements in the protolith zircon are purged during recrystallization and partitioned between the enriched recrystallization front and depleted recrystallized areas. However, recrystallization is not always efficient, often leaving a ‘memory’ of the protolith trace element and isotopic composition. This results in the measurement of ‘mixed’ U–Pb isotope ages. Nonetheless, the age of metamorphism has been determined. A correlation between apparent age and Th/U ratio is indicative of incomplete re‐setting by partial recrystallization. Recrystallization is shown to probably not significantly affect Lu–Hf ages. Recrystallization has been determined by textural and trace element analysis and EBSP data not to have proceeded by sub‐grain rotation or local dissolution/re‐precipitation, but probably by grain‐boundary migration and defect diffusion. The formation of metamorphic zircon by solid‐state recrystallization is probably common to high‐grade terranes worldwide. The recognition of this process of formation is essential for correct interpretation of zircon‐derived U–Pb ages and subsequent tectonic models.     

青海南部熔积岩的发现:对寻找VMS型矿床的重要启示

熔积岩指的是侵入、混合到未固结或弱固结的湿沉积物中的熔浆分解、原位形成的一类特殊岩石。正确地认识该类岩石,有利于增进人们对岩浆-水(沉积物)相互作用过程的理解,恢复古环境。在青海南部沱沱河地区发现了一套角砾为撕片状、锯齿状及浑圆状的安山岩,胶结物为铁硅质组合的特殊熔积岩。研究表明,该熔积岩的角砾为岩浆遇水后快速淬火、裂解的产物,铁硅质组合为海底喷气沉积形成的含铁建造;且安山岩与含铁建造发生混合时,含铁建造尚未固结。该套熔积岩的发现,改变了长期以来对开心岭铁矿为火山热液交代安山岩而形成的认识,对于在矿区寻找VMS型矿床、区域内寻找海底热水喷流沉积型矿床具有重要的启示意义。     

Effect of temperature and mass transport on transition metal isotope fractionation during electroplating

Transition metal stable isotope signatures can be useful for tracing both natural and anthropogenic signals in the environment, but only if the mechanisms responsible for fractionation are understood. To investigate isotope fractionations due to electrochemistry (or redox processes), we examine the stable isotope behavior of iron and zinc during the reduction reaction  + 2e⁻ = M_metal as a function of electrochemical driving force, temperature, and time. In all cases light isotopes are preferentially electroplated, following a mass-dependent law. Generally, the extent of fractionation is larger for higher temperatures and lower driving forces, and is roughly insensitive to amount of charge delivered. The maximum fractionations are δ^56/54Fe = −4.0‰ and δ^66/64Zn = −5.5‰, larger than observed fractionations in the natural environment and larger than those predicted due to changes in speciation. All the observed fractionation trends are interpreted in terms of three distinct processes that occur during an electrochemical reaction: mass transport to the electrode, chemical speciation changes adjacent to the electrode, and electron transfer at the electrode. We show that a large isotope effect adjacent the electrode surface arises from the charge-transfer kinetics, but this effect is attenuated in cases where diffusion of ions to the electrode surface becomes the rate-limiting step. Thus while a general increase in fractionation is observed with increasing temperature, this appears to be a result of thermally enhanced mass transport to the reacting interface rather than an isotope effect associated with the charge-transfer kinetics. This study demonstrates that laboratory experiments can successfully distinguish isotopic signatures arising from mass transport, chemical speciation, and electron transfer. Understanding how these processes fractionate metal isotopes under laboratory conditions is the first step towards discovering what role these processes play in fractionating metal isotopes in natural systems.     

Epithermal environments and styles of mineralization: Variations and their causes, and guidelines for exploration

Epithermal precious- and base-metal deposits are diverse, reflecting the different tectonic, igneous and structural settings in which they occur, the complexities of their local setting, and the many processes involved in their formation. Most epithermal deposits form at shallow crustal levels where abrupt changes in physical and chemical conditions result in metal deposition and attendant hydrothermal alteration. The principal factors that influence the conditions prevailing in the epithermal environment, and which ultimately determine the sites and character of mineralization, include: geology (structure, stratigraphy, intrusions and rock type, which affect the style and degree of permeability and the reactivity of the host); pressure and temperature (which in the epithermal environment are related on the boiling point with depth curve); hydrology (the relationship between permeability and topography which governs fluid flow, and discharge/recharge characteristics, as well as access of steam-heated waters); chemistry of the mineralizing fluid (which determines the metal-carrying capacity, as well as the associated vein and alteration assemblage); and syn-hydrothermal development of permeability and/or changes in hydraulic gradients.Many attempts have been made to classify epithermal deposits based on mineralogy and alteration, the host rocks, deposit form, genetic models, and standard deposits. All have their strengths and weaknesses. We prefer a simple approach using the fundamental fluid chemistry (high or low sulfidation, reflecting relatively oxidized or reduced conditions, respectively) as readily inferred from vein and alteration mineralogy and zoning, together with the form of the deposit, and using comparative examples to clarify the character of the deposit.Guidelines for exploration vary according to the scale at which work is conducted, and are commonly constrained by a variety of local conditions. On a regional scale the tectonic, igneous and structural settings can be used, together with assessment of the depth of erosion, to select areas for project area scale exploration. At project area scale, direct (i.e. geochemical) or indirect guidelines may be used. Indirect methods involve locating and interpreting hydrothermal alteration as a guide to ore, with the topographic and hydrologic reconstruction of the system being of high priority. These pursuits may involve mineralogic, structural, geophysical or remote sensing methods. On a prospect scale, both direct and indirect methods may be used; however, they can only be effective in the framework of a sound conceptual understanding of the processes that occur in the epithermal environment, and the signatures they leave.