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.     

Investigating the scale of structural controls on chlorinated hydrocarbon distributions in the fractured-porous unsaturated zone of a sandstone aquifer in the UK

Contaminant migration behaviour in the unsaturated zone of a fractured porous aquifer is discussed in the context of a study site in Cheshire, UK. The site is situated on gently dipping sandstones, adjacent to a linear lagoon historically used to dispose of industrial wastes containing chlorinated solvents. Two cores of more than 100 m length were recovered and measurements of chlorinated hydrocarbons (CHCs), inorganic chemistry, lithology, fracturing and aquifer properties were made. The results show that selecting an appropriate vertical sampling density is crucial both to providing an understanding of contaminant pathways and distinguishing whether CHCs are present in the aqueous or non-aqueous phase. The spacing of such sampling should be on a similar scale to the heterogeneity that controls water and contaminant movement. For some sections of the Permo-Triassic aquifer, significant changes in lithology and permeability occur over vertical distances of less than 1 m and samples need to be collected at this interval, otherwise considerable resolution is lost, potentially leading to erroneous interpretation of data. At this site, although CHC concentrations were high, the consistent ratio of the two main components of the plume (tetrachloroethene and trichloroethene) provided evidence of movement in the aqueous phase rather than in dense non-aqueous phase liquid (DNAPL).     

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.     

Comment on: 'The 3D shear experiment over the Natih field in Oman: the effects of fracture-filling fluids on shear propagation' by C.M. van der Kolk, W.S. Guest and J.H.H.M. Potters

We find errors in theory and application in the paper by van der Kolk et al. (Geophysical Prospecting 49 , 179–197 (2001)) that invalidate their arguments for the cause of the reduction in the velocity of the vertically propagating slower split shear-wave in the gas cap over the Natih field in Oman. We suggest that existing theories are adequate and can explain the anomaly.     

Discrete-element modelling of detachment folding

A two‐dimensional, discrete‐element modelling technique is used to investigate the initiation and growth of detachment folds in sedimentary rocks above a weak décollement level. The model depicts the sedimentary rocks as an assemblage of spheres that obey Newton's equations of motion and that interact with elastic forces under the influence of gravity. Faulting or fracturing between neighbouring elements is represented by a transition from repulsive–attractive forces to solely repulsive forces. The sedimentary sequence is mechanically heterogeneous, consisting of intercalated layers of markedly different strengths and thicknesses. The interlayering of weak and strong layers within the sedimentary rocks promotes the localization of flexural flow deformation within the weak layers. Even with simple displacement boundary conditions, and straightforward interlayering of weak and strong layers, the structural geometries that develop are complex, with a combination of box, lift‐off and disharmonic detachment fold styles forming above the décollement. In detail, it is found that the modelled folds grow by both limb rotation and limb lengthening. The combination of these two mechanisms results in uplift patterns above the folds that are difficult, or misleading, to interpret in terms of simple kinematic models. Comparison of modelling results with natural examples and with kinematic models highlights the complexities of structural interpretation in such settings.     

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.     

A numerical model of the partitioning of trace chemical solutes during drop freezing

Partitioning of volatile chemicals among the gas, liquid, and solid phases during freezing of liquid water in clouds can impact trace chemical distributions in the troposphere and in precipitation. We describe here a numerical model of this partitioning during the freezing of a supercooled liquid drop. Our model includes the time-dependent calculation of the coupled processes of crystallization kinetics, heat transport, and solute mass transport, for a freezing hydrometeor particle. We demonstrate the model for tracer partitioning during the freezing of a 1000 μm radius drop on a 100 μm ice substrate, under a few ambient condition scenarios. The model effectively simulates particle freezing and solute transport, yielding results that are qualitatively and quantitatively consistent with previous experimental and theoretical work. Results suggest that the ice shell formation time is governed by heat loss to air and not by dendrite propagation, and that the location of ice nucleation is not important to freezing times or the effective partitioning of chemical solutes. Even for the case of nucleation at the center of the drop, we found that dendrites propagated rapidly to form surface ice. Freezing then proceeded from the outside in. Results also indicate that the solid-liquid interfacial surface area is not important to freezing times or the effective partitioning of chemical solutes, and that the rate aspects of trapping are more important than equilibrium solid-liquid partitioning to the effective partitioning resulting from freezing.     

Electrodynamic Disaggregation: Does it Affect Apatite Fission-Track and (U-Th)/He Analyses?

Apatite fission-track and (U-Th)/He analyses require the liberation of intact idiomorphic apatite grains from rock samples. While routinely being carried out by mechanical methods, electrodynamic disaggregation (ED) offers an alternative approach. The high-voltage discharges produced during the ED process create localised temperature peaks (10000 K) along a narrow plasma channel. In apatite, such high temperatures could potentially reduce the length of fission tracks, which start to anneal at temperatures > 60 °C, and could also enhance He diffusion, which becomes significant at 30–40 °C over geological time scales. A comparison of fission-track analyses and (U-Th)/He ages of apatites prepared both by mechanical (jaw crusher, disk mill) and ED processing provides a way of determining whether heating during the latter method has any significant effect. Apatites from three samples of different geological settings (an orthogneiss from Madagascar, the Fish Canyon Tuff, and a muscovite-gneiss from Greece) yielded statistically identical track length distributions compared to samples prepared mechanically. Additionally, (U-Th)/He ages of apatites from a leucogranite from Morocco prepared by both methods were indistinguishable. These first results indicated that during electrodynamic disaggregation apatite crystals were not heated enough to partially anneal the fission tracks or induce significant diffusive loss of He.     

Carbonate cements in Miller field of the UK North Sea: a natural analog for mineral trapping in CO<Subscript>2</Subscript> geological storage

Miller field of the North Sea has had high concentrations of natural CO₂ for ~70 Ma. It is an ideal analog for the long-term fate of CO₂ during engineered storage, particularly for formation of carbonate minerals that permanently lock up CO₂ in solid form. The Brae Formation reservoir sandstone contains an unusually high quantity of calcite concretions; however, C and O stable isotopic signatures suggest that these are not related to the present-day CO₂ charge. Margins of the concretions are corroded, probably because of reduced pH due to CO₂ influx. Dispersed calcite cements are also present, some of which postdate the CO₂ charge and, therefore, are the products of mineral trapping. It is calculated that only a minority of the reservoired CO₂ in Miller (6–24%) has been sequestrated in carbonates, even after 70 Ma of CO₂ emplacement. Most of the CO₂ accumulation is dissolved in pore fluids. Therefore, in a reservoir similar to the Brae Formation, engineered CO₂ storage must rely on physical retention mechanisms because mineral trapping is both incomplete and slow.