NanoSIMS: Insights to biogenicity and syngeneity of Archaean carbonaceous structures

NanoSIMS is a relatively new technology that is being applied to ancient carbonaceous structures to gain insight into their biogenicity and syngeneity. NanoSIMS studies of well preserved organic microfossils from the Neoproterozoic (0.8 Ga) Bitter Springs Formation have established elemental distributions in undisputedly biogenic structures. Results demonstrate that sub-micron scale maps of metabolically important elements (carbon [C], nitrogen [measured as CN ion], and sulfur [S]) can be correlated with kerogenous structures identified by optical microscopy. Spatial distributions of C, CN, and S in individual microfossils are nearly identical, and variations in concentrations of these elements parallel one another. In elemental maps, C, CN, and S appear as globules, aligned to form remnant walls or sheaths of fossiliferous structures. The aligned character and parallel variation of C and CN are the strongest indicators of biogenicity.Nitrogen/carbon atomic ratios (N/C) of spheroids, filaments, and remnants of a microbial mat suggest that N/C may reflect original biochemical differences, within samples of the same age and degree of alteration. Silicon (Si) and oxygen (O) maps illustrate that silica is intimately interspersed with organic carbon of the microfossils. This relationship is likely to reflect the process of silica permineralization of biological remains and thus may be an indicator of syngeneity of the fossilized material with the mineral matrix.The NanoSIMS characterization of Bitter Springs microfossils can be used as a baseline for interpreting less well preserved carbonaceous structures that might occur in older or even extraterrestrial materials. An example of such an application is provided by comparison of Bitter Springs results with NanoSIMS of Archaean carbonaceous structures from Western Australia, including a spheroid in the 3 Ga Farrel Quartzite and material in a secondary vein in the 3.43 Ga Strelley Pool Chert. Results reinforce a biogenic, syngenetic interpretation for the Archaean spheroid.NanoSIMS has several advantages in the study of ancient organic materials: the technique allows characterization of extremely small structures that are present in low concentrations; organic matter does not have to be isolated by acid treatment but can be analyzed in polished thin section; preparation is simple; samples are minimally altered during analysis; results provide sub-micron scale spatial distribution coupled with concentration information for at least five elements; the biologically important elements of carbon and nitrogen can be assessed; and the ability to study organic remains in situ permits petrographic assessment of spatial relationships between organic matter and mineral constituents. These advantages could be of significant benefit for interpretation of poorly preserved and fragmentary carbonaceous remains that might occur in some of Earth's oldest samples as well as in meteorites or extraterrestrial material brought to Earth in future planetary missions.     

Eocene–Miocene carbon-isotope and floral record from brown coal seams in the Gippsland Basin of southeast Australia

The carbon-isotope and palynological record through 580 m thick almost continuous brown coal in southeast Australia's Gippsland Basin is a relatively comprehensive southern hemisphere Middle Eocene to Middle Miocene record for terrestrial change. The carbon isotope δ¹³C_coal values of these coals range from ? 27.7‰ to ? 23.2. This isotopic variability follows gymnosperm/angiosperm fluctuations, where higher ratios coincide with heavier δ¹³C values. There is also long-term variability in carbon isotopes through time. From the Eocene greenhouse world of high gymnosperm-heavier δ¹³C_coal values, there is a progressive shift to lighter δ¹³C_coal values that follows the earliest (Oi1?) glacial events around 33 Ma (Early Oligocene). The overlying Oligocene–Early Miocene brown coals have lower gymnosperm abundance, associated with increased %Nothofagus (angiosperm), and lightening of isotopes during Oligocene cooler conditions.The Miocene palynological and carbon-isotope record supports a continuation to the Oligocene trends until around the late Early Miocene (circa 19 Ma) when a warming commenced, followed by an even stronger isotope shift around 16 Ma that peaked in the Middle Miocene when higher gymnosperm abundance and heavier isotopes prevailed. The cycle between the two major warm peaks of Middle Eocene and Middle Miocene was circa 30 Ma long. This change corresponds to a fall in inferred pCO₂ levels for the same period. The Gippsland data suggest a link between gymnosperm abundance, long-term plant δ¹³C composition, climatic change, and atmospheric pCO₂. Climatic deterioration in the Late Miocene terminated peat accumulation in the Gippsland Basin and no further significant coals formed in southeast Australia.The poor correspondence between this terrestrial isotope data and the marine isotope record is explained by the dominant control on δ¹³C by the gymnosperm/angiosperm abundance, although in turn this poor correspondence may reflect palaeoclimate control. From the brown coal seam dating, the coal appears to have accumulated during a considerable part of the allocated 30 Ma Cenozoic time period. These brown coal carbon isotope and palynological data appear to record a more gradual atmospheric carbon isotope change compared to the marine record.     

Comparison of groundwater recharge estimation techniques in an alluvial aquifer system with an intermittent/ephemeral stream (Queensland,Australia)

This study demonstrates the importance of the conceptual hydrogeological model for the estimation of groundwater recharge rates in an alluvial system interconnected with an ephemeral or intermittent stream in south-east Queensland, Australia. The losing/gaining condition of these streams is typically subject to temporal and spatial variability, and knowledge of these hydrological processes is critical for the interpretation of recharge estimates. Recharge rate estimates of 76–182 mm/year were determined using the water budget method. The water budget method provides useful broad approximations of recharge and discharge fluxes. The chloride mass balance (CMB) method and the tritium method were used on 17 and 13 sites respectively, yielding recharge rates of 1–43 mm/year (CMB) and 4–553 mm/year (tritium method). However, the conceptual hydrogeological model confirms that the results from the CMB method at some sites are not applicable in this setting because of overland flow and channel leakage. The tritium method was appropriate here and could be applied to other alluvial systems, provided that channel leakage and diffuse infiltration of rainfall can be accurately estimated. The water-table fluctuation (WTF) method was also applied to data from 16 bores; recharge estimates ranged from 0 to 721 mm/year. The WTF method was not suitable where bank storage processes occurred.     

Uranium-series dating and growth characteristics of the deep-sea scleractinian coral: Enallopsammia rostrata from the Equatorial Pacific

The deep-sea coral, Enallopsammia rostrata, a member of the Dendrophylliidae family, is a major structure-forming species that creates massive dendroid colonies, up to 1 m wide and 0.5 m tall. Living colonies of E. rostrata have been collected using the PISCES submersibles from three locations from 480 to 788 m water depth in the Line Islands (∼160°W) in the Equatorial Pacific. We have applied to these colonies a high sensitivity, low blank technique to determine U-series ages in small quantities (70 ± 15 mg) of modern and near modern calcareous skeletons using MC-ICP-MS (Multi-collector Inductively Coupled Plasma Mass Spectrometer). The application of this method to living slow-growing colonies from a range of sites as well as the observations of axial growth patterns in thin sections of their skeletons offer the first expanded and well constrained data on longevity, growth pattern and mean growth rates in E. rostrata. Absolute dated specimens indicate life spans of colonies ranging from 209 ± 8 yrs to 605 ± 7 yrs with radial growth rates from 0.012 to 0.072 mm yr⁻¹ and vertical extension rates from 0.6 to 1.9 mm yr⁻¹. The linear growth rates reported here are lower than those reported for other deep-sea scleractinian corals (Lophelia pertusa and Madrepora oculata). The U-series dating indicates that the growth ring patterns of E. rostrata are not consistent with annual periodicity emphasizing the importance of absolute radiometric dating methods to constrain growth rates. Slow accretion and extreme longevity make this species and its habitat especially vulnerable to disturbances and impacts from human activities. This dating method combined with observation of growth patterns opens up new perspectives in the field of deep-sea corals since it can provide quantitative estimates of growth rates and longevity of deep-sea corals in general.     

Fluorite stability in silicic magmas

Recent experimental evidence is used to assess the conditions under which fluorite forms an early crystallising phase in silicic magmas. Fluorite solubility primarily depends on the (Na + K)/Al balance in the coexisting silicic melt, reaching a minimum in metaluminous melts. It can display reaction relationships with topaz and titanite, depending on changes in melt composition during crystallisation. An empirical model of fluorite stability in Ca-poor peralkaline rhyolite melts is derived and applied to selected rocks:

Peralkaline syenite autoliths from Kilombe volcano, Kenya Rift Valley: Evidence for subvolcanic interaction with carbonatitic fluids

Mineral chemistry, textures and geochemistry of syenite autoliths from Kilombe volcano indicate that they crystallized in the upper parts of a magma chamber from peralkaline trachytic magmas that compositionally straddle the alkali feldspar join in the “residuum system” (ne = 0–1.03; qz = 0–0.77). Mineral reaction and/or overgrowth processes were responsible for the replacement of (i) Mg–hedenbergite by aegirine–augite, Ca–aegirine and/or aegirine, (ii) fayalite by amphiboles, and (iii) magnetite by aenigmatite. Ti–magnetite in silica-saturated syenites generally shows ilmenite exsolution, partly promoted by circulating fluids.

By contrast, the Fe–Ti oxides in the silica-undersaturated (sodalite-bearing) syenites show no signs of deuteric alteration. These syenites were ejected shortly after completion of crystallization. Ilmenite–magnetite equilibria indicate fO₂ between − 19.5 and − 23.1 log units (T 679–578 °C), slightly below the FMQ buffer. The subsequent crystallization of aenigmatite and Na-rich pyroxenes suggests an increase in the oxidation state of the late-magmatic liquids and implies the influence of post-magmatic fluids.

Irrespective of silica saturation, the syenites can be divided into (1) “normal” syenites, characterized by Ce/Ce ratios between 0.83 and 0.99 and (2) Ce-anomalous syenites, showing distinct negative Ce-anomalies (Ce/Ce 0.77–0.24). “Normal” silica-saturated syenites evolved towards pantelleritic trachyte. The Ce-anomalous syenites are relatively depleted in Zr, Hf, Th, Nb and Ta but, with the exception of Ce, are significantly enriched in REE.

The silica-saturated syenites contain REE–fluorcarbonates (synchysite-bastnaesite series) with negative Ce-anomalies (Ce/Ce 0.4–0.8, mean 0.6), corroded monazite group minerals with LREE-rich patches, and hydrated, Fe- and P-rich phyllosilicates. Each of these is inferred to be of non-magmatic origin. Fractures in feldspars and pyroxenes contain Pb-, REE- and Mn-rich cryptocrystalline or amorphous material. The monazite minerals are characterized by the most prominent negative Ce-anomalies (Ce/Ce_mean = 0.5), and in the most altered and Ca-rich areas (depleted in REE), Ce/Ce is less than 0.2.

It is inferred that carbonatitic fluids rich in F, Na and lanthanides but depleted in Ce by fractional crystallization of cerian pyrochlore, percolated into the subvolcanic system and interacted with the syenites at the thermal boundary layers of the magma chamber, during and shortly after their crystallization.

Chevkinite–(Ce), pyrochlore, monazite and synchysite-bastnaesite, occurring as accessory minerals, have been found for the first time at Kilombe together with eudialyte, nacareniobsite–(Ce) and thorite. These latter represent new mineral occurrences in Kenya.     

‘Natural’ rivers, ‘hydromorphological quality’ and river restoration: a challenging new agenda for applied fluvial geomorphology

Fluvial geomorphology is rapidly becoming centrally involved in practical applications to support the agenda of sustainable river basin management. In the UK its principal contributions to date have primarily been in flood risk management and river restoration. There is a new impetus: the European Union's Water Framework and Habitats Directives require all rivers to be considered in terms of their ecological quality, defined partly in terms of ‘hydromorphology’. This paper focuses on the problematic definition of ‘natural’ hydromorphological quality for rivers, the assessment of departures from it, and the ecologically driven strategies for restoration that must be delivered by regulators under the EU Water Framework Directive (WFD). The Habitats Directive contains similar concepts under different labels. Currently available definitions of ‘natural’ or ‘reference’ conditions derive largely from a concept of ‘damage’, principally to channel morphology. Such definitions may, however, be too static to form sustainable strategies for management and regulation, but attract public support. Interdisciplinary knowledge remains scant; yet such knowledge is needed at a range of scales from catchment to microhabitat. The most important contribution of the interdisciplinary R&D effort needed to supply management tools to regulators of the WFD and Habitats regulations is to interpret the physical habitat contribution to biodiversity conservation, in terms of ‘good ecological quality’ in rivers, and the ‘hydromorphological’ component of this quality. Contributions from ‘indigenous knowledge’, through public participation, are important but often understated in this effort to drive the ‘fluvial hydrosystem’ back to spontaneous, affordable, sustainable self‐regulation. Copyright © 2006 John Wiley & Sons, Ltd.     

Assessment of chemical water types and their spatial variation using multi-stage cluster analysis, Queensland, Australia

A multivariate assessment has been adapted to the classification of a large, irregular dataset of approximately 34,000 surface water samples accumulated over more than 30 years. A two-stage K-means clustering method was designed to analyse chemical data in the form of percentages of major ions (Na, Mg, Ca, Cl, HCO₃ and SO₄); the first stage of clustering produced 347 groups, which were then re-clustered to generate the final nine water types. The analysis enabled the definition of provinces of water composition and highlighted natural processes influencing the surface water chemistry. On a statewide basis, sodium is the dominant cation and around 50% at all stream flows, while proportions of calcium and magnesium are about equal. Chloride and bicarbonate constitute the bulk of anions present, while sulfate occurs occasionally and tends to be localised. On a global basis, Queensland surface waters are relatively high in sodium, chloride and magnesium, and low in calcium and sulfate. It was also found that the geographical location has a greater impact on major ion ratios than does the stage of stream flow.

The regional chemical trends are consistent with geology and climate. Streams in northeast Queensland, with short, steep catchments and high rainfall, yield low salinity, sodium-dominated water; this is also the case for sandy southern coastal catchments. Both also reflect an oceanic influence. The proportions of sodium and chloride decrease westward; streams draining the western side of the Great Dividing Range or flowing into the Gulf of Carpentaria have low salinity but relatively hard water. Streams in western Queensland are higher in calcium and bicarbonate. In the large catchments flowing from Queensland into central Australia, the water composition is highly variable, commonly with elevated sulfate. Also in Queensland, there are several other clearly definable water provinces such as the high magnesium waters of basaltic areas.

The findings of this study confirm that the application of such analytical methods can provide a useful assessment of controls over water composition and support management at regional level; the approach used is shown and are applicable to large, disparate datasets.     

Stable isotope analysis of the Cenomanian–Turonian (Late Cretaceous) oceanic anoxic event in the Crimea

Carbon and oxygen isotope data from Cenomanian–Turonian sediments from the southwest of the Crimea are presented. The sediments consist of limestones, marls and organic-rich claystones, the latter with total organic carbon values up to 2.6 wt. %, representing Oceanic Anoxic Event 2. A shift to more negative δ¹⁸O values through the uppermost Cenomanian into the lowermost Turonian may be the result of warming; however, petrographic analysis shows that the samples have undergone a degree of diagenetic alteration. The carbon isotope data reveal a positive excursion from 2.7‰ to a peak of 4.3‰ at the Cenomanian/Turonian boundary; values then decrease in the early Turonian. This excursion is comparable to those of other Cenomanian–Turonian sections, such as those seen in the Anglo-Paris Basin, and is thought to be due to global changes in the oceanic carbon reservoir. On this curve are a number of negative δ¹³C excursions, just below the Cenomanian/Turonian boundary. It is suggested that these negative excursions are associated with the uptake of light carbon derived from the oxidation and deterioration of organic material during localised exposure of the sediments to oxic or meteoric diagenetic conditions, possibly during sea-level fluctuations.