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.     

In situ sampling reveals rapid uptake and depuration of polycyclic aromatic hydrocarbons by surf clams (Paphies subtriangulata) affected by the Rena oil spill

ABSTRACT

To investigate the uptake and depuration of polycyclic aromatic hydrocarbons associated with the Rena oil spill we sampled the surf clam Paphies subtriangulata at two open coast locations (6?km apart) just prior to oil coming ashore (7 October 2011), then at 1–3 week intervals for the next 4 months. Total polycyclic aromatic hydrocarbons (tPAH) increased at both sites from 1 to 96–124?µg?kg^?1 (wet weight) by 18 October before declining to low levels (<4?µg?kg^?1) by February 2012. Ongoing sampling throughout 2012–2014 included three additional sites to the north east (up to 30?km away) and a site 5?km to the south east revealing tPAH levels generally <10?µg?kg^?1 except in October 2013 where levels ranged between 39–45?µg?kg^?1 at all sites. A comparison of PAH component profiles with oil-contaminated beach sediment indicated that the high levels observed in surf clams between October–December 2011 were clearly associated with the Rena spill. However, the October 2013 peak had a PAH profile inconsistent with weathered Rena oil, suggesting an alternative source of contamination. Our results highlight the potential for P. subtriangulata as a PAH monitoring tool but recognise more study is needed to better quantify baseline levels and uptake and depuration dynamics.     

Lead and Mg isotopic age constraints on the evolution of the HED parent body

The large collection of howardite‐eucrite‐diogenite (HED) meteorites allows us to study the initial magmatic differentiation of a planetesimal. We report Pb‐Pb ages of the unequilibrated North West Africa (NWA) 4215 and Dhofar 700 diogenite meteorites and their mass‐independent ²⁶Mg isotope compositions (²⁶Mg*) to better understand the timing of differentiation and crystallization of their source reservoir(s). NWA 4215 defines a Pb‐Pb age of 4484.5 ± 7.9 Myr and has a ²⁶Mg* excess of +2.3 ± 1.6 ppm whereas Dhofar 700 has a Pb‐Pb age of 4546.4 ± 4.7 Myr and a ²⁶Mg* excess of +25.5 ± 1.9 ppm. We interpret the young age of NWA 4215 as a thermal overprint, but the age of Dhofar 700 is interpreted to represent a primary crystallization age. Combining our new data with published Mg isotope and trace element data suggests that approximately half of the diogenites for which such data are available crystallized within the first 1–2 Myr of our solar system, consistent with a short‐lived, early‐formed magma ocean undergoing convective cooling. The other half of the diogenites, including both NWA 4215 and Dhofar 700, are best explained by their crystallization in slowly cooled isolated magma chambers lasting over at least ~20 Myr.     

Uranium-lead isotope systematics of Mars inferred from the basaltic shergottite QUE 94201

Uranium-lead ratios (commonly represented as ²³⁸U/²⁰⁴Pb = μ) calculated for the sources of martian basalts preserve a record of petrogenetic processes that were active during early planetary differentiation and formation of martian geochemical reservoirs. To better define the range of μ values represented by the source regions of martian basalts, we completed U-Pb elemental and isotopic analyses on whole rock, mineral and leachate fractions from the martian meteorite Queen Alexandra Range 94201 (QUE 94201). The whole rock and silicate mineral fractions have unradiogenic Pb isotopic compositions that define a narrow range (²⁰⁶Pb/²⁰⁴Pb = 11.16-11.61). In contrast, the Pb isotopic compositions of weak HCl leachates are more variable and radiogenic. The intersection of the QUE 94201 data array with terrestrial Pb in ²⁰⁶Pb/²⁰⁴Pb-²⁰⁷Pb/²⁰⁴Pb-²⁰⁸Pb/²⁰⁴Pb compositional space is consistent with varying amounts of terrestrial contamination in these fractions. We calculate that only 1-7% contamination is present in the purified silicate mineral and whole rock fractions, whereas the HCl leachates contain up to 86% terrestrial Pb. This terrestrial Pb contamination generated a ²⁰⁶Pb-²⁰⁷Pb array in the QUE fractions that appears to represent an ancient age, which contrasts with a much younger crystallization age of 327 ± 10 Ma derived from Rb-Sr and Sm-Nd isochrons (Borg L. E., Nyquist L. E., Taylor L. A., Wiesmann H. and Shih C. -Y. (1997) Constraints on Martian differentiation processes from Rb-Sr and Sm-Nd isotopic analyses of the basaltic shergottite QUE 94201. Geochim. Cosmochim. Acta61, 4915-4931). Despite the contamination, and accepting 327 ± 10 Ma as the crystallization age, we use the U-Pb data to determine the initial ²⁰⁶Pb/²⁰⁴Pb of QUE 94201 to be 11.086 ± 0.008 and to calculate the μ value of its mantle source to be 1.82 ± 0.01. The μ value calculated for the QUE 94201 source is the lowest determined for any martian basalt source, and, when compared to the highest values determined for martian basalt sources, indicates that μ values in martian source reservoirs vary by at least a factor of two. Additionally, the range of source μ values indicates that the μ value of bulk silicate Mars is approximately three. The amount of variation in the μ values of the mantle sources (μ ∼ 2-4) is greater than can be explained by igneous processes involving silicate phases alone. We suggest the possibility that a small amount of sulfide crystallization may generate greater extents of U-Pb fractionation during formation of the mantle sources of martian basalts.     

Testing accretion mechanisms of the H chondrite parent body utilizing nucleosynthetic anomalies

Planetary bodies a few hundred kilometers in radii are the precursors to larger planets but it is unclear whether these bodies themselves formed very rapidly or accreted slowly over several millions of years. Ordinary H chondrite meteorites provide an opportunity to investigate the accretion time scale of a small planetary body given that variable degrees of thermal metamorphism present in H chondrites provide a proxy for their stratigraphic depth and, therefore, relative accretion times. We exploit this feature to search for nucleosynthetic isotope variability of ⁵⁴Cr, which is a sensitive tracer of spatial and temporal variations in the protoplanetary disk's solids, between 17 H chondrites covering all petrologic types to obtain clues about the parent body accretionary rate. We find no systematic variability in the mass‐biased corrected abundances of ⁵³Cr or ⁵⁴Cr outside of the analytical uncertainties, suggesting very rapid accretion of the H chondrite parent body consistent with turbulent accretion. By utilizing the μ⁵⁴Cr–planetary mass relationship observed between inner solar system planetary bodies, we calculate that the H chondrite accretion occurred at 1.1 ± 0.4 or 1.8 ± 0.2 Myr after the formation of calcium‐aluminum‐rich inclusions (CAIs), assuming either the initial ²⁶Al/²⁷Al abundance of inner solar system solids determined from angrite meteorites or CAIs from CV chondrites, respectively. Notably, these ages are in agreement with age estimates based on the parent bodies’ thermal evolution when correcting these calculations to the same initial ²⁶Al/²⁷Al abundance, reinforcing the idea of a secular evolution in the isotopic composition of inner disk solids.     

Hydrothermal activity on the southern Mid-Atlantic Ridge: Tectonically- and volcanically-controlled venting at 4–5°S

We report results from an investigation of the geologic processes controlling hydrothermal activity along the previously-unstudied southern Mid-Atlantic Ridge (3–7°S). Our study employed the NOC (UK) deep-tow sidescan sonar instrument, TOBI, in concert with the WHOI (USA) autonomous underwater vehicle, ABE, to collect information concerning hydrothermal plume distributions in the water column co-registered with geologic investigations of the underlying seafloor. Two areas of high-temperature hydrothermal venting were identified. The first was situated in a non-transform discontinuity (NTD) between two adjacent second-order ridge-segments near 4°02′S, distant from any neovolcanic activity. This geologic setting is very similar to that of the ultramafic-hosted and tectonically-controlled Rainbow vent-site on the northern Mid-Atlantic Ridge. The second site was located at 4°48′S at the axial-summit centre of a second-order ridge-segment. There, high-temperature venting is hosted in an  18 km² area of young lava flows which in some cases are observed to have flowed over and engulfed pre-existing chemosynthetic vent-fauna. In both appearance and extent, these lava flows are directly reminiscent of those emplaced in Winter 2005−06 at the East Pacific Rise, 9°50′N and reference to global seismic catalogues reveals that a swarm of large (M 4.6−5.6) seismic events was centred on the 5°S segment over a  24 h period in late June 2002, perhaps indicating the precise timing of this volcanic eruptive episode. Temperature measurements at one of the vents found directly adjacent to the fresh lava flows at 5°S MAR (Turtle Pits) have subsequently revealed vent-fluids that are actively phase separating under conditions very close to the Critical Point for seawater, at  3000 m depth and 407 °C: the hottest vent-fluids yet reported from anywhere along the global ridge crest.     

Contamination of the coastal waters of Bermuda by organotins and the triazine herbicide Irgarol 1051.

A study of the distribution of the 'booster' biocide 2-methylthio-4-tert-butylamino-6-cyclopropyl amino-s-triazine (Irgarol 1051) was carried out in the coastal waters of Bermuda. Irgarol 1051 concentrations (as determined by GC/MS) up to 590 ng l-1 have been measured within Hamilton Harbour. The data presented herein unequivocally demonstrate contamination of the coastal system of Bermuda by Irgarol 1051. Concurrently, TBT concentrations were measured and results indicate that levels are falling through legislated changes in antifouling treatments, from 220 ng l-1 in 1990 to < 20 ng l-1 (as Sn) by 1995, in the open water area of Hamilton Harbour. Concentrations of TBT immediately offshore from a boatyard were found to be > 600 ng l-1 (Sn), indicating continuing release due to painting operations and sediments in the area.     

Contrasting response of monazite and zircon to a high-T thermal overprint

Contact metamorphism in the aureole of the 1322 Ma Makhavinekh Lake Pluton, northern Labrador, affected monazite and zircon in the adjacent 1850 Ma metapelitic gneisses. Transformation of regional garnet and sillimanite to lower-pressure symplectitic intergrowths of cordierite, orthopyroxene, and spinel was accompanied by resorption of inherited monazite inclusions in garnet coupled with the appearance of coronitic high-Y monazite rims. In situ ion-microprobe dating is used to show that high-Y rims formed during contact metamorphism. Liberation of Y and HREE from garnet also gave rise to new xenotime growth. The coronitic nature of monazite overgrowths reflects the diffusion-controlled nature of net-transfer reactions whereas its higher Y composition reflects equilibration with xenotime at peak T (> 800 °C) conditions in the inner aureole. Very thin overgrowths on inherited zircon were also encountered, but only where zircon is surrounded by the symplectitic assemblage, reflecting liberation of Zr from garnet. Although these overgrowths are too thin to date using conventional ion-microprobe techniques, well-developed triple junctions between zircon and orthopyroxene suggests that they grew in textural equilibrium with the contact metamorphic assemblage.

In contrast to monazite, inherited zircon remained intact during contact metamorphism, exhibiting no change in morphology (other than the growth of thin rims) or internal zoning throughout the aureole. However, inherited sector-zoned zircons of anatectic origin display evidence for intracrystalline Pb redistribution in the inner aureole. In these samples, ion-microprobe analyses encountered heterogeneous Pb signals and a dispersion of ²⁰⁷Pb / ²⁰⁶Pb dates away from the well constrained 1850 Ma age of regional metamorphism. Whereas analyses from the outer aureole faithfully record the age of regional metamorphism, those from the inner aureole are normally and reversely discordant and distributed along a line collinear with a 1850 to 1322 Ma discordia. This disturbance is correlated with proximity to the pluton implying that Pb was mobile in the zircon lattice during contact metamorphism. Most grains are characterized by apparent Pb loss from low-U domains and apparent Pb gain in higher-U domains. These data are interpreted to reflect recovery of strained crystalline domains leading to expulsion of Pb* that was able to efficiently diffuse into higher-U domains that were partly amorphous prior to rapid reheating in the inner aureole.     

Convex profiles from asteroid lightcurves

Integral geometry is used to solve a two-dimensional simplification of the three-dimensional lightcurve inversion problem, and a method is introduced for obtaining a convex profile, $\text{P}$, from asteroid lightcurve data. Whenever four ideal conditions are satisfied, $\text{P}$ is an estimator for the asteroid's “mean cross section,” $\text{C}$, a convex set defined as the average of all cross sections $\text{C}$ cut by planes a distance z above the asteroid's equatorial plane. $\text{C}$ is therefore a two-dimensional average of the asteroid's three-dimensional shape. The ideal conditions are that (A) each curve $\text{C}\text{(z)}$ is convex. (B) the asteroid's scattering law is uniform and geometric, (C) the astrocentric declinations of the Sun and Earth are zero, and (D) the solar phase angle θ ≠ 0. If Condition C is known to hold, the extend to which the lightcurve can be accounted for by a geometrically scattering convex object can be quantified in terms of an appropriate “goodness-of-fit” static. If the solar phase angle is zero, as for radar “lightcurve,” then (i) method yields a profile $\text{P}{}_{\mathrm{<mtext>s</mtext>}}$ the symmetrization $\text{C}{}_{\mathrm{<mtext>s</mtext>}}$ of $\text{C}$; (ii) Condition A need not hold and if it does not, then the inversion yields the symmetrization of the asteroid's mean convex hull; and (iii) Fourier analysis of the lightcurve can reveal violation of Condition B. Doppler-frequency resolution of radar echoes at several rotational phases adds information by constraining the convex hull $\text{H}{}_{\mathrm{<mtext>p</mtext>}}$ of the asteroid's (not necessarily convex) polar silhouette. Estimation of a convex profile from a photoelectric or radar lightcurve is a problem in weighted-least-squares optimization subject to inequality constraints. The solution uses a recursive quadratic programming algorithm to derive a Fourier parameterization for $\text{P}$ from the coefficients in the lightcurve's Fourier expansion. The method has been tested by inverting analytically generated lightcurves for geometrically scattering ellipsoids with semiaxes a ? b ? c, and the inversion yields $\text{P}\text{=}\text{P}{}_{\mathrm{<mtext>s</mtext>}}\text{?}\text{C}\text{=}\text{C}{}_{\mathrm{<mtext>s</mtext>}}\text{=}\text{H}{}_{\mathrm{<mtext>p</mtext>}}$ when the viewing geometry (Condition C) is close to ideal. For situations when the asteroid's pole direction is unknown, a test is offered of the hyphothesis that a given lightcurve can be due to a geometrically scattering ellipsoid with $\text{a}\text{c}\text{? ?}$, where ? is an priori upper bound on the maximum axis ratio. Convex profiles are presented for 15 Eunomia, 118 Peitho, 246 Asporina, 281 Lucretia. 790 Pretoria, 1685 Toro, and 1978 CA.     

A high-resolution analyser for the measurement of ammonium in oligotrophic seawater

In this work, we describe a high-resolution fluorometric shipboard analyser and an improved method to determine NH₄⁺ in oligotrophic seawater. The limit of detection is <5 nM, calculated with 95% confidence level using the weighted regression line applied to the standard addition method using real samples prepared with low nutrient seawater from the Atlantic. The results are summarised and cross-compared with spiked artificial seawater (ASW) and spiked Milli-Q water samples. The analyser has a precision of ±1–4% with a high performance over a wide range from 5 nM to 25 μM. The methodology of NH₄⁺ analysis is based on the fluorescent product formed between o-pthaldialdehyde and NH₄⁺ in the presence of sulfite. Due to the high resolution of the developed system, we were able to study in depth the sensitivity of the method to salinity, amines, amino acids and potential interferences from particles/algae. The method was found to be sensitive to salinity variations, reducing the signal by up to 85% at 5 nM; this effect decreased at higher concentrations of ammonium. It was noted that the interference from amines at low concentrations was negligible; however, at either high amino acid or high amine concentrations, the signal was depressed. To test for the effect of particles on the system, the system was tested with samples containing phytoplankton (Dunaliella primolecta) cells at different concentrations prepared with ASW to simulate the effect of a phytoplankton bloom. This experiment assessed the potential impact of both particles and other potential fluorescence interferences from cells and/or ammonium leaching from cells. This experiment showed that a phytoplankton bloom could potentially have an impact of up to 12% on the signal of interest. Thus, we propose that this method is suitable for oligotrophic environments rather than coastal and eutrophic environments. The reagent was found to be stable for 17 days and standards of 1 μM were stable for 6 days under laboratory conditions. The developed analyser was successfully demonstrated in the North Atlantic Ocean, in an area of oligotrophic, low NH₄⁺ oceanic waters.