Dolomitization of the Waulsortian Limestone (Lower Carboniferous) in the Irish Midlands

The Waulsortian Limestone (Lower Carboniferous) of the southern Irish Midlands is dolomitized pervasively over a much larger region than previous studies have documented. This study indicates a complex, multistage, multiple fluid history for regional dolomitization. Partially and completely dolomitized sections of Waulsortian Limestones are characterized by finely crystalline (0·01–0·3 mm) planar dolomite. Planar replacive dolomite is commonly followed by coarse (≥0·5 mm) nonplanar replacive dolomite, and pervasive void‐filling saddle dolomite cement is frequently associated with Zn–Pb mineralization. Planar dolomite has average δ¹⁸O and δ¹³C values (‰ PDB) of –4·8 and 3·9 respectively. These are lower oxygen and slightly higher carbon isotope values than averages for marine limestones in the Waulsortian (δ¹⁸O=–2·2, δ¹³C=3·7). Mean C and O isotope values of planar replacive dolomite are also distinct from those of nonplanar and saddle dolomite cement (–7·0 and 3·3; –7·4 and 2·4 respectively). Fluid inclusions indicate a complex history involving at least three chemically and thermally distinct fluids during dolomite cementation. The petrography and geochemistry of planar dolomites are consistent with an early diagenetic origin, possibly in equilibrium with modified Carboniferous sea water. Where the Waulsortian was exposed to hydrothermal fluids (70–280 °C), planar dolomite underwent a neomorphic recrystallization to a coarser crystalline, planar and nonplanar dolomite characterized by lower δ¹⁸O values. Void‐filling dolomite cement is isotopically similar to nonplanar, replacive dolomite and reflects a similar origin from hydrothermal fluids. This history of multiple stages of dolomitization is significantly more complex than earlier models proposed for the Irish Midlands and provides a framework upon which to test competing models of regional vs. localized fluid flow.     

Implications of Nb/U, Th/U and Sm/Nd in plume magmas for the relationship between continental and oceanic crust formation and the development of the depleted mantle

The Nb/U and Th/U of the primitive mantle are 34 and 4.04 respectively, which compare with 9.7 and 3.96 for the continental crust. Extraction of continental crust from the mantle therefore has a profound influence on its Nb/U but little influence on its Th/U. Conversely, extraction of midocean ridge-type basalts lowers the Th/U of the mantle residue but has little influence on its Nb/U. As a consequence, variations in Th/U and Nb/U with Sm/Nd can be used to evaluate the relative importance of continental and basaltic crust extraction in the formation of the depleted (Sm/Nd enriched) mantle reservoir.This study evaluates Nb/U, Th/U, and Sm/Nd variations in suites of komatiites, picrites, and their associated basalts, of various ages, to determine whether basalt and/or continental crust have been extracted from their source region. Emphasis is placed on komatiites and picrites because they formed at high degrees of partial melting and are expected to have Nb/U, Th/U, and Sm/Nd that are essentially the same as the mantle that melted to produce them. The results show that all of the studied suites, with the exception of the Barberton, have had both continental crust and basaltic crust extracted from their mantle source region. The high Sm/Nd of the Gorgona and Munro komatiites require the elevated ratios seen in these suites to be due primarily to extraction of basaltic crust from their source regions, whereas basaltic and continental crust extraction are of subequal importance in the source regions of the Yilgarn and Belingwe komatiites. The Sm/Nd of modern midocean ridge basalts lies above the crustal extraction curve on a plot of Sm/Nd against Nb/U, which requires the upper mantle to have had both basaltic and continental crust extracted from it.It is suggested that the extraction of the basaltic reservoir from the mantle occurs at midocean ridges and that the basaltic crust, together with its complementary depleted mantle residue, is subducted to the core-mantle boundary. When the two components reach thermal equilibrium with their surroundings, the lighter depleted component separates from the denser basaltic component. Both are eventually returned to the upper mantle, but the lighter depleted component has a shorter residence time in the lower mantle than the denser basaltic component. If the difference in the recycling times for the basaltic and depleted components is ∼1.0 to 1.5 Ga, a basaltic reservoir is created in the lower mantle, equivalent to the amount of basalt that is subducted in 1.0 to 1.5 Ga, and that reservoir is isolated from the upper mantle. It is this reservoir that is responsible for the Sm/Nd ratio of the upper mantle lying above the trend predicted by extraction of continental crust on the plot of Sm/Nd against Nb/U.     

Early Carboniferous (Viséan) emplacement of the collisional Kłodzko–Złoty Stok granitoids (Sudetes, SW Poland): constraints from geochemical data and zircon U–Pb ages

Sensitive high-resolution ion microprobe zircon U–Pb dating and geochemical data of igneous rocks from the composite K?odzko–Z?oty Stok (KZS) Granite Pluton, Sudetic Block, indicate that the granitoids represent an Early Carboniferous Viséan phase of Variscan metaluminous, high-K, I-type, syn-collisional granite magmatism within the Saxothuringian Zone of the Central European Variscides. Igneous zircon records hypabyssal magmatism that produced various granitoids and lamprophyre (spessartite) emplaced from ca. 340 to 331 Ma. The KZS granitoids have compositions ranging from granodiorite to monzonite, low A/CNK ratios (<1), and are associated with abundant mafic members. Most of them are alkaline, highly potassic, and moderately evolved. The major and trace element contents of the KZS granitoids suggest geochemical heterogeneity, and the hybrid nature of magmas derived from a range of sources in the middle crust, with a strong input of material from the upper mantle. Mixing of magmas of mantle origin with high-K material from partly melted continental crust was probably a more important factor than fractional crystallization, in controlling the evolution of the magmas. The mean Pb–U ages of the main population of igneous zircon from a quartz monzodiorite (?elazno) and hornblende monzonite (Droszków) are 340.2 ± 2.5 Ma and 339.5 ± 3.1 Ma, respectively. A slightly younger biotite-hornblende granodiorite from Chwalis?aw, 336.7 ± 2.5 Ma, was cut by a spessartite dyke at 333.1 ± 3.1 Ma. This indicates that mafic magmas were immediately intruded into fractured, probably incompletely solidified, granodiorites. The lamprophyric dyke also contains igneous zircon of Neoproterozoic age, 566.3 ± 6.4 Ma, typical of the crust in the Saxothuringian Zone. Tonalite from Ptasznik Hill near Droszków is of similar age to the spessartite, 331.5 ± 2.6 Ma. High REE contents in the tonalite and its igneous zircon indicate advanced differentiation of granitic magma, producing a more leucocratic melt associated with post-magmatic activity including abundant late crosscutting pegmatites and quartz veins, and contact metasomatic mineralization. The KZS granitoids have rather similar petrographic and geochemical characteristics to granitoids from other parts of the Central European Variscides, where a thickened orogenic root caused a substantial rise in crustal temperatures, producing granitoid magmas closely correlated with regional tectonic activity between the Saxothuringian and Brunovistulia Terranes at the NE margin of the Bohemian Massif.     

Iron(III) accumulations in inland saline waterways,Hunter Valley,Australia: Mineralogy,micromorphology and pore-water geochemistry

Discharge of Fe(II)-rich groundwaters into surface-waters results in the accumulation of Fe(III)-minerals in salinized sand-bed waterways of the Hunter Valley, Australia. The objective of this study was to characterise the mineralogy, micromorphology and pore-water geochemistry of these Fe(III) accumulations. Pore-waters had a circumneutral pH (6.2–7.2), were sub-oxic to oxic (Eh 59–453 mV), and had dissolved Fe(II) concentrations up to 81.6 mg L⁻¹. X-ray diffraction (XRD) on natural and acid-ammonium-oxalate (AAO) extracted samples indicated a dominance of 2-line ferrihydrite in most samples, with lesser amounts of goethite, lepidocrocite, quartz, and alumino-silicate clays. The majority of Fe in the samples was bound in the AAO extractable fraction (Fe^Ox) relative to the Na-dithionite extractable fraction (Fe^Di), with generally high Fe^Ox:Fe^Di ratios (0.52–0.92). The presence of nano-crystalline 2-line ferrihydrite (Fe₅HO₃·4H₂O) with lesser amounts of goethite (α-FeOOH) was confirmed by scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX), and transmission electron microscopy (TEM) coupled with selected area electron diffraction (SAED). In addition, it was found that lepidocrocite (γ-FeOOH), which occurred as nanoparticles as little as ∼5 lattice spacings thick perpendicular to the (0 2 0) lattice plane, was also present in the studied Fe(III) deposits. Overall, the results highlight the complex variability in the crystallinity and particle-size of Fe(III)-minerals which form via oxidation of Fe(II)-rich groundwaters in sand-bed streams. This variability may be attributed to: (1) divergent precipitation conditions influencing the Fe(II) oxidation rate and the associated supply and hydrolysis of the Fe(III) ion, (2) the effect of interfering compounds, and (3) the influence of bacteria, especially Leptothrix ochracea.     

The stability of a remediated bed in Hamilton Harbour,Lake Ontario,Canada

ABSTRACT In situ measurements of lakebed sediment erodibility were made on three sites in Hamilton Harbour, Lake Ontario, using the benthic flume Sea Carousel. Three methods of estimating the surface erosion threshold (τ_c(0)) from a Carousel time series were evaluated: the first method fits measures of bed strength to eroded depth (the failure envelope) and evaluates threshold as the surface intercept; the second method regresses mean erosion rate (E_m) with bed shear stress and solves for the floc erosion rate (E_f) to derive the threshold for E_m = E_f = 1 × 10^?5 kg m^?2 s^?1; the third method extrapolates a regression of suspended sediment concentration (S) and fluid transmitted bed shear stress (τ₀) to ambient concentrations. The first field site was undisturbed (C) and acted as a control; the second (W) was disturbed through ploughing and water injection as part of lakebed treatment, whereas the third site (OIP) was disturbed and injected with an oxidant used for remediation of contaminated sediment. The main objectives of this study were: (1) to evaluate the three different methods of deriving erosion threshold; (2) to compare the physical behaviour of lacustrine sediments with their marine estuarine counterparts; and (3) to examine the effects of ploughing and chemical treatment of contaminated sediment on bed stability. Five deployments of Sea Carousel were carried out at the control site. Mean erosion thresholds for the three methods were: τ_c(0) = 0·5 (±0·06), 0·27 (±0·01) and 0·34 (±0·03) Pa respectively. Method 1 overpredicted bed strength as it was insensitive to effects in the surface 1–2 mm, and the fit of the failure envelope was also highly subjective. Method 2 exhibited a wide scatter in the data (low correlation coefficients), and definition of the baseline erosion rate (E_f) is largely arbitrary in the literature. Method 3 yielded stable (high correlation coefficients), reproducible and objective results and is thus recommended for evaluation of the erosion threshold. The results of this method correlated well with sediment bulk density and followed the same trend as marine counterparts from widely varying sites. Mass settling rates, expressed as a decay constant, k, of S(t), were strongly related to the maximum turbidity at the onset of settling (S_max) and were also in continuity with marine counterparts. Thus, it appears that differences in salinity had little effect on mass settling rates in the examples presented, and that biological activity dominated any effects normally attributable to changes in salinity. Bedload transport of eroded aggregates (2–4 mm in diameter) took place by rolling below a mean tangential flow velocity (U_y) of 0·32 ms^?1 and by saltation at higher velocities. Mass transport as bedload was a maximum at U_y = 0·4 ms^?1, although bedload never exceeded 1% of the suspended load. The proportion of material moving as bedload was greatest at the onset of erosion but decreased as flow competence increased. Given the low bulk density and strength of the lakebed sediment, the presence of a bedload component is notable. Bedload transport over eroding cohesive substrates should be greater in estuaries, where both sediment density and strength are usually higher. Significant differences between the ploughed and control sites were apparent in both the erosion rate and the friction coefficient (φ), and suggest that bed recovery after disruption is rapid (< 24 h). τ_c(0) increased linearly with time after ploughing and recovered to the control mean value within 3 days. The friction coefficient was reduced to zero by ploughing (diagnostic of fluidization), but increased linearly with time, regaining control values within 6 days. No long‐term reduction in bed strength due to remediation was apparent.     

Eastern Laurentia in Rodinia: constraints from whole-rock Pb and U/Pb geochronology

Whole-rock Pb isotopic signatures and U/Pb geochronology refute a Rodinian correlation of northeastern Laurentia and proto-Andean Amazonia. According to this previously proposed model, the Labrador–Scotland–Greenland Promontory (LSGP) of northeastern Laurentia collided with the proto-Andean margin of Amazonia, at the Arica Embayment, during the Grenville/Sunsás Orogeny (ca. 1.0 Ga). Links between the two margins were based upon the correlation of the LSGP with Arequipa-Antofalla Basement (AAB), a Proterozoic block along the proto-Andean margin of Amazonia adjacent to the Arica Embayment. Specifically, similarities in 1.8–1.0 Ga basement rocks in both regions suggested that the AAB was originally a piece of the LSGP. Furthermore, similarities in unique, post-collisional, but pre-rift, glacial sedimentary sequences also supported a link between the AAB and LSGP.Tests of these apparent similarities fail to support correlation of the AAB and the LSGP and, thus, eliminate a direct link between northeastern Laurentia and southwestern Amazonia in Rodinia. However, Pb isotopic compositions and U/Pb geochronology provide the basis for two new correlations, namely, (1) the ca. 1.3–1.0 Ga basement in the central and southern Appalachians may be an allochthonous block that was transferred to Laurentia from Amazonia at ca. 1.0 Ga, and (2) an allochthonous AAB may be a piece of the Kalahari Craton that was transferred to Amazonia at ca. 1.0 Ga. Based on these new correlations and a previously proposed Grenvillian connection between southern Laurentia (Llano) and Kalahari, we propose that Amazonia may have collided with a contiguous southeastern Laurentia/Kalahari margin at ca. 1.0 Ga.     

Geochemical Correlation Between Metasediments of the Mfongosi Group of the Natal Sector of the Namaqua-Natal Metamorphic Province, South Africa and the Ahlmannryggen Group of the Grunehogna Province, Antarctica

The whole-rock geochemistry of metamorphosed greywackes, arenites and arkoses within the Mesoproterozoic Namaqua-Natal-Maudheim Province is interpreted with the aim of establishing geochemical correlations and defining common sediment source terrains. Metasediments of the Mfongosi Group of the Natal Sector of the Namaqua-Natal Metamorphic Province were sampled from their type area in the Mfongosi Valley. Metagreywackes from the northern limits of the Mfongosi Valley, directly adjacent to the Kaapvaal Craton, show ocean island arc signatures while metagreywackes from the southern limits of the Mfongosi Valley, near the contact with the Madidima Thrust of the Natal nappe zone, show mainly active continental margin signatures. Interleaved, geochemically distinct low-Ca+Na, high-K metamorphosed arkoses to lithic arkoses indicate a minor passive margin sediment component. Geochemical classification of low-grade Ahlmannryggen Group greywackes, arenites and arkoses of the Grunehogna Province, Antarctica, indicates both active and passive continental margin sediment sources. An oceanic island arc signature is not evident in Ahlmannryggen Group data. The active continental margin signature in both Natal Sector and Grunehogna Province metasediments potentially provides for a common link between these terranes. Discriminant Function Analysis, using three pre-defined provenance sub-sets within the Mfongosi Group and two pre-defined provenance sub-sets within the Ahlmannryggen Group, indicate that metasediments with active continental margin signatures from both groups are geochemically identical, implying that the active continental margin of the Grunehogna Province shed immature sediments westwards (African azimuths) into the developing, narrow or restricted Mesoproterozoic ‘Mfongosi Basin.’ This was accompanied by minor sediment influx from a stable continental platform, potentially the Kaapvaal Craton. Oblique and diachronous collision, initiated in the southwestern portions of the combined Natal Sector/Grunehogna Province system produced a laterally variable Mfongosi Group, which formed in the ‘Mfongosi Basin’. Coarse-grained sediments dominated in its eastern portions while basalts with thin sapropelite units dominated in its western portions.     

Mass-independent fractionation of oxygen isotopes in the mesostasis of a chondrule from the Semarkona LL3.0 ordinary chondrite

A large chondrule from Semarkona, the most primitive ordinary chondrite known, has been discovered to contain a record of mass transport during its formation. In most respects, it is a normal Type I, group A1, low-FeO chondrule that was produced by reduction and mass-loss during the unidentified flash-heating event that produced the chondrules, the most abundant structural component in primitive meteorites. We have previously measured elemental abundances and abundance profiles in this chondrule. We here report oxygen isotope ratio abundances and ratio abundance profiles. We have found that the mesostasis is zoned in oxygen isotope ratio, with the center of the chondrule containing isotopically heavier oxygen than the outer regions, the outer regions being volatile rich from the diffusion of volatiles into the chondrule during cooling. The δ¹⁷O values range from −2.0‰ to 9.9‰, while δ¹⁸O range from −1.9‰ to 9.6‰. More importantly, a plot of δ¹⁷O against δ¹⁸O has a slope of 1.1 ± 0.2 (1σ) and 0.88 ± 0.10 (1σ) when measured by two independent methods. Co-variation of δ¹⁷O with δ¹⁸O that does not follow mass-dependent fractionation has often been seen in primitive solar system materials and is usually ascribed to the mixing of different oxygen reservoirs. We argue that petrographic and compositional data indicate that this chondrule was completely melted at the time of its formation so that relic grains could not have survived. Furthermore, there is petrographic and compositional evidence that there was no aqueous alteration of this chondrule subsequent to its formation. Although it is possible to formulate a series of exchanges between the chondrule and external ¹⁶O-rich and ¹⁶O-poor reservoirs that may explain the detailed oxygen isotope systematics of this chondrule, such a sequence of events looks very contrived. We therefore hypothesize that reduction, devolatilization, and crystallization of the chondrule melt may have produced ¹⁶O-rich olivines and ¹⁶O-poor mesostasis plotting on a slope-one line as part of the chondrule-forming process in an analogous fashion to known chemical mass-independent isotopic fractionation mechanisms. During cooling, volatiles and oxygen near the terrestrial line in oxygen isotope composition produced the outer zone of volatile rich and ¹⁶O-rich mesostasis. The chondrule therefore not only retains a record of considerable mass transport accompanying formation, but also may indicate that the isotopes of oxygen underwent mass-independent fractionation during the process.