A refined solution to the first terrestrial Pb-isotope paradox

The first terrestrial Pb-isotope paradox refers to the fact that on average, rocks from the Earth's surface (i.e. the accessible Earth) plot significantly to the right of the meteorite isochron in a common Pb-isotope diagram. The Earth as a whole, however, should plot close to the meteorite isochron, implying the existence of at least one terrestrial reservoir that plots to the left of the meteorite isochron. The core and the lower continental crust are the two candidates that have been widely discussed in the past. Here we propose that subducted oceanic crust and associated continental sediment stored as garnetite slabs in the mantle Transition Zone or mid-lower mantle are an additional potential reservoir that requires consideration. We present evidence from the literature that indicates that neither the core nor the lower crust contains sufficient unradiogenic Pb to balance the accessible Earth. Of all mantle magmas, only rare alkaline melts plot significantly to the left of the meteorite isochron. We interpret these melts to be derived from the missing mantle reservoir that plots to the left of the meteorite isochron but, significantly, above the mid-ocean ridge basalt (MORB)-source mantle evolution line. Our solution to the paradox predicts the bulk silicate Earth to be more radiogenic in Pb-207/Pb-204 than present-day MORB-source mantle, which opens the possibility that undegassed primitive mantle might be the source of certain ocean island basalts (OIB). Further implications for mantle dynamics and oceanic magmatism are discussed based on a previously justified proposal that lamproites and associated rocks could derive from the Transition Zone.

Geochemical and Sr, Nd, Pb isotope investigation of the New Caledonia ophiolite

The New Caledonia ophiolite hosts one of the largest obducted mantle section in the world, hence providing a unique insight for the study of upper mantle processes. These mantle rocks belong to an “atypical” ophiolitic sequence, which is dominated by refractory harzburgites but it also includes minor spinel and plagioclase lherzolites. Upper crust is notably absent in the ophiolite, with the exception of some mafic-ultramafic cumulates cropping out in the southern part of the island. Although the New Caledonia ophiolite has been under investigation for decades, its ultra-depleted nature has made its characterization an analytical challenge, so that few trace element data are available, while isotopic data are completely missing. In this thesis a comprehensive geochemical study (major, trace element and Sr-Nd-Pb isotopes) of the peridotites and the associated intrusive mafic rocks from the New Caledonia ophiolite has been carried out. The peridotites are low-strain tectonites showing porphyroclastic textures. Spinel lherzolites are undepleted lithotypes, as attested by the presence of 7-8 vol% of Na2O and Al2O3-rich clinopyroxene (up to 0.5 wt% Na2O; 6.5 wt% Al2O3), Fo content of olivine (88.5-90.0 mol%) and low Cr# of spinel (13-17). Conversely, harzburgites display a refractory nature, proven by the remarkable absence of primary clinopyroxene, very high Fo content in olivine (90.9-92.9 mol%), high Mg# in orthopyroxene (89.8-94.2) and Cr# in spinel (39-71). REE contents show abyssal-type patterns for spinel lherzolites, while harzburgites display U-shaped patterns, typical of fore-arc settings. Spinel lherzolites REE compositions are consistent with relatively low degree (8-9%) of fractional melting of a DMM source, starting in the garnet stability field. Conversely, REE models for harzburgites indicate high melting degrees (20-25%) of a DMM mantle source under spinel faies conditions, consistent with hydrous melting in forearc setting. Plagioclase lherzolites exhibit melt impregnation microtextures, Cr- and TiO2-enriched spinels and REE, Ti, Y, Zr progressive increase with respect to spinel lherzolites. Impregnation models indicate that plagioclase lherzolites may derive from spinel lherzolites by entrapment of highly depleted MORB melts in the shallow oceanic lithosphere. Mafic intrusives are olivine gabbronorites with a very refractory composition, as attested by high Fo content of olivine (87.3-88.9 mol.%), very high Mg# of clinopyroxene (87.7-92.2) and extreme anorthitic content of plagioclase (An = 90-96 mol%). The high Mg#, low TiO2 concentrations in pyroxenes and the anorthitic composition of plagioclase point out an origin from ultra-depleted primitive magmas in a convergent setting. Geochemical trace element models show that the parental melts of gabbronorites are primitive magmas with striking depleted compositions, bearing only in part similarities with the primitive boninitic melts of Bonin Islands. The first Sr, Nd and Pb isotope data obtained for the New Caledonia ophiolite highlight the presence of DM mantle source variably modified by different processes. Nd-Sr-Pb isotopic ratios for the lherzolites (+6.98≤epsilon Ndi≤+10.97) indicate a DM source that suffered low-temperature hydrothermal reactions. Harzburgites are characterized by a wide variation of Sr, Nd and Pb isotopic values, extending from DM-type to EM2 compositions (-0.82≤ epsilon Ndi≤+17.55), suggesting that harzburgite source was strongly affected by subduction-related processes. Conversely, combined trace element and Sr-Nd-Pb isotopic data for gabbronorites indicate a derivation from a source with composition similar to Indian-type mantle, but affected by fluid input in subduction environment. These geochemical features point out an evolution in a pre-Eocenic marginal basin setting, possibly in the proximity of a transform fault, for the lherzolites. Conversely, the harzburgites acquired their main geochemical and isotopic fingerprint in subduction zone setting.

Victoria Land Antarctica Pb and Ba concentrations and Pb isotope ratios 1872-1994 CE

Pb and Ba concentrations and Pb isotopic compositions are reported for firn core and snow pit samples from Victoria Land, Antarctica, dating from 1872 AD to 1994 AD. From variations in Pb/Ba ratios and Pb isotopic compositions, two periods of major Pb enhancements were identified, from 1891 to 1908 AD and from 1948 to 1994 AD. The earlier pollution event is attributed to Pb emissions from non-ferrous metal production and coal combustion in the Southern Hemisphere and is in excellent agreement with coincident pollution inputs reported in firn/ice cores from two other regions of Antarctica, at Coats Land and Law Dome. Using Pb isotopic systematics, it was calculated that ~50% of Pb deposited in Victoria Land in 1897 originated from anthropogenic emission sources. The more recent period of Pb enhancements, from 1948 to 1994 AD, corresponds to the introduction and widespread use of gasoline alkyl Pb additives in automobiles in the Southern Hemisphere, with anthropogenic Pb inputs averaging 60% of total Pb but with large uncertainty. Intra- and inter-annual variations in Pb concentrations and isotopic compositions were evaluated in snow pits samples corresponding to the period 1991-1994. Substantial variations in Pb/ Ba and 206Pb/207Pb ratios were detected but the absence of a regular seasonal pattern for these parameters suggests that the transport and deposition of aerosols to the Antarctic ice sheet are complex and vary from year to year.

Pb and Ba concentrations and Pb isotope ratios in EPICA Dome C ice 2-217 ky BP

A record of Pb isotopic compositions and Pb and Ba concentrations are presented for the EPICA Dome C ice core covering the past 220 ky, indicating the characteristics of dust and volcanic Pb deposition in central East Antarctica. Lead isotopic compositions are also reported in a suite of soil and loess samples from the Southern Hemisphere (Australia, Southern Africa, Southern South America, New Zealand, Antarctica) in order to evaluate the provenance of dust present in Antarctic ice. Lead isotopic compositions in Dome C ice support the contention that Southern South America was an important source of dust in Antarctica during the last two glacial maxima, and furthermore suggest occasional dust contributions from local Antarctic sources. The isotopic signature of Pb in Antarctic ice is altered by the presence of volcanic Pb, inhibiting the evaluation of glacial-interglacial changes in dust sources and the evaluation of Australia as a source of dust to Antarctica. Consequently, an accurate evaluation of the predominant source(s) of Antarctic dust can only be obtained from glacial maxima, when dust-Pb concentrations were greatest. These data confirm that volcanic Pb is present throughout Antarctica and is emitted in a physical phase that is free from Ba, while dust Pb is transported within a matrix containing Ba and other crustal elements.

Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures

Methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Delta(47)), as much as similar to 0.2 parts per thousand lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 degrees C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings.