Rare earth element behavior and Pb,Sr, Nd isotope systematics in a heavy metal contaminated soil

The aim of this study is to characterize the processes and phases which control migration and retention of rare earth elements (REE) in a heavy metal contaminated soil. In addition to concentration data, we used Pb, Sr and Nd isotopic compositions in order to distinguish between natural and anthropogenic trace metals and to characterize the phases leached away during the sequential extraction procedure.The samples were sequentially extracted in 3 steps with 1 N acetic acid (HAc), 1 N HCl and 1 N HNO₃. The Pb isotope data showed that anthropogenic Pb had mainly been retained in the uppermost 10 cm by the organic matter of the topsoil. The⁸⁷Sr/⁸⁶Sr ratios of the HAc extracts are almost constant and indicate that soil carbonate is derived from regionally outcropping carbonate-rich sediments. Most HCl and HNO₃ extracts have more radiogenic Sr isotopic compositions, but it is unclear whether this reflects a growing influence of anthropogenic or silicate-derived Sr.The depth distribution of the REE is mainly controlled by two different parameters: soil pH for the HAc extractable REE and FeMn oxides for the REE in the HCl and HNO₃ extracts. A part of the HNO₃ extractable REE was also bound to the organic matter of the topsoil. The REE concentrations in the HAc extractable phase increase with depth and increasing soil pH, which indicates that they are derived from the surface and hence are of anthropogenic origin. This is confirmed by¹⁴³Nd/¹⁴⁴Nd isotope ratios which show a mixing between a natural end-member at the top and an anthropogenic end-member at the base of the profile. We assume that the anthropogenic REE were transported in dissolved form as carbonate complexes and then precipitated during downward migration as soil pH increased.     

Rare earth element variations resulting from inversion of pigeonite and subsolidus reequilibration in lunar ferroan anorthosites

We present results of a secondary ion mass spectrometry study of the rare earth elements (REEs) in the minerals of two samples of lunar ferroan anorthosite, and the results are applicable to studies of REEs in all igneous rocks, no matter what their planet of origin. Our pyroxene analyses are used to determine solid-solid REE distribution coefficients (D = C_REE in low-Ca pyroxene/C_REE in augite) in orthopyroxene-augite pairs derived by inversion of pigeonite. Our data and predictions from crystal-chemical considerations indicate that as primary pigeonite inverts to orthopyroxene plus augite and subsolidus reequilibration proceeds, the solid-solid Ds for orthopyroxene-augite pairs progressively decrease for all REEs; the decrease is greatest for the LREEs. The REE pattern of solid-solid Ds for inversion-derived pyroxene pairs is close to a straight line for Sm-Lu and turns upward for REEs lighter than Sm; the shape of this pattern is predicted by the shapes of the REE patterns for the individual minerals.Equilibrium liquids calculated for one sample from the compositions of primary phases, using measured or experimentally determined solid-liquid Ds, have chondrite-normalized REE patterns that are very slightly enriched in LREEs. The plagioclase equilibrium liquid is overall less rich in REEs than pyroxene equilibrium liquids, and the discrepancy probably arises because the calculated plagioclase equilibrium liquid represents a liquid earlier in the fractionation sequence than the pyroxene equilibrium liquids. “Equilibrium” liquids calculated from the compositions of inversion-derived pyroxenes or orthopyroxene derived by reaction of olivine are LREE depleted (in some cases substantially) in comparison with equilibrium liquids calculated from the compositions of primary phases. These discrepancies arise because the inversion-derived and reaction-derived pyroxenes did not crystallize directly from liquid, and the use of solid-liquid Ds is inappropriate. The LREE depletion of the calculated liquids is a relic of formation of these phases from primary LREE-depleted minerals. Thus, if one attempts to calculate the compositions of equilibrium liquids from pyroxene compositions, it is important to establish that the pyroxenes are primary. In addition, our data suggest that experimental studies have underestimated solid-liquid Ds for REEs in pigeonite and that REE contents of liquids calculated using these Ds are overestimates.Our results have implications for Sm-Nd age studies. Our work shows that if pigeonite inversion and/or subsolidus reequilibration between augite and orthopyroxene occurred significantly after crystallization, and if pyroxene separates isolated for Sm-Nd studies do not have the bulk composition of the primary pyroxenes, then the Sm-Nd isochron age and ε_Nd will be in error.     

The use of principle component analyses in characterising trace and major elemental distribution in a 55 kyr peat deposit in tropical Australia: Implications to paleoclimate

The Lynch’s Crater peat deposit in NE-Australia is a sensitive environmental archive located in the tropical Southern Hemisphere. This unique deposit illustrates that local and regional changes had a profound effect on the local Australian ecosystem over the past 55 kyr. To obtain a proxy of past climate changes, trace and major element geochemistry analyses were applied to a 13 m peat core from the crater. Principle component analysis (PCA) was used to identify the main factors that control elemental distribution in the peat and to add interpretative strength to the geochemical behavior of selected major and trace elements. For example, Sc, Al, Cu, and Pb were found to be related to increased erosion of the basin soils, and from this, several periods of significant flux from atmospheric input and/or terrigenous run-off were identified. Geochemically mobile elements during rock weathering and pedogenesis, such as Mg, Ca, and Sr helped to identify the peat ombrotrophic-minerotrophic boundary at ∼1.5 m depth and offered important information about fluxes of these nutrients to the mire and their dynamics within the deposit. Arsenic and V comparisons between the peat record (high concentrations in some peat sections) and in local basin rocks (very low concentrations), suggested the presence of a long range, atmospheric dust source early in the formation of the mire. The Lynch’s Crater peat record presents a continuous record of environmental change in tropical Australia and contributes new understanding to geochemical processes in peatlands.     

Continentally-derived solutes in shallow Archean seawater: Rare earth element and Nd isotope evidence in iron formation from the 2.9 Ga Pongola Supergroup, South Africa

The chemical composition of surface water in the photic zone of the Precambrian ocean is almost exclusively known from studies of stromatolitic carbonates, while banded iron formations (IFs) have provided information on the composition of deeper waters. Here we discuss the trace element and Nd isotope geochemistry of very shallow-water IF from the Pongola Supergroup, South Africa, to gain a better understanding of solute sources to Mesoarchean shallow coastal seawater. The Pongola Supergroup formed on the stable margin of the Kaapvaal craton ∼2.9 Ga ago and contains banded iron formations (IFs) that represent the oldest documented Superior-type iron formations. The IFs are near-shore, pure chemical sediments, and shale-normalized rare earth and yttrium distributions (REY_SN) exhibit positive La_SN, Gd_SN, and Y_SN anomalies, which are typical features of marine waters throughout the Archean and Proterozoic. The marine origin of these samples is further supported by super-chondritic Y/Ho ratios (average Y/Ho = 42). Relative to older Isua IFs (3.7 Ga) from Greenland, and younger Kuruman IFs (2.5 Ga) also from South Africa, the Pongola IFs are depleted in heavy rare earth elements (HREE), and appear to record variations in solute fluxes related to sea level rise and fall. Sm-Nd isotopes were used to identify potential sediment and solute sources within pongola shales and IFs. The ?_Nd(t) for Pongola shales ranges from −2.7 to −4.2, and ?_Nd(t) values for the coeval iron-formation samples (range −1.9 to −4.3) are generally indistinguishable from those of the shales, although two IF samples display ?_Nd(t) as low as −8.1 and −10.9. The similarity in Nd isotope signatures between the shale and iron-formation suggests that mantle-derived REY were not a significant Nd source within the Pongola depositional environment, though the presence of positive Eu anomalies in the IF samples indicates that high-T hydrothermal input did contribute to their REY signature. Isotopic mass balance calculations indicate that most (?72%) of the Nd in these seawater precipitates was derived from continental sources. If previous models of Fe-Nd distributions in Archean IFs are applied, then the Pongola IFs suggest that continental fluxes of Fe to Archean seawater were significantly greater than are generally considered.     

Rare earth elements, yttrium and H, O, C, Sr, Nd and Pb isotope studies in mineral waters and corresponding rocks from NW-Bohemia, Czech Republic

The sparkling waters from the area of Kyselka near Karlovy Vary at the western slope of the Doupovske hory, Bohemia (Czech Republic), and CO₂-poor waters from two underground boreholes at Jachymov, Krusne hory, Bohemia, have been studied with the aim of characterizing the distribution of rare earth elements, yttrium, and H, O, C, Sr, Nd, Pb isotopes during the low-temperature alteration processes of the host rocks. Additionally, leaching experiments were performed at pH 3 on the granitic and basaltic host rocks from Kyselka and the granite of Jachymov. All REE patterns of the granite- and the basalt-derived waters from the Kyselka area are different from those of their source rocks and the leachates of the latter. This elucidates the inhomogeneous distribution of REE and Y among the solid phases in the altered magmatic rocks. The Eu and Ce anomalies in granite-derived waters are inherited, the Y anomaly is achieved by fluid migration. Yttrium is always preferentially leached by mineral waters, whereas Y/Ho ratios of rocks and their leachates are very similar. The REE abundances in waters from the wells in Jachymov are derived from rocks intensely leached and depleted in easily soluble REE-bearing minerals, whereas the granites and basalts from Kyselka still contain soluble, REE-bearing minerals. A comparison of REE/Ca patterns of the experimental leachates with those of the mineral waters elucidate the high retention of REE in rocks during water–rock interaction. In strongly altered rocks Sr isotope ratios of mineral waters and rocks differ widely, whereas the corresponding Nd isotope ratios are very similar. ²⁰⁷Pb/²⁰⁸Pb, ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb ratios in mineral waters are independent from U/Th ratios in the rocks. ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb are lower in mineral waters than in their source rocks and their leachates, which indicates that Pb is primarily derived from solid phases that do not contain significant contents of leachable U and Th. Thus, mineral waters, although CO₂ rich, only interact with surface films on minerals and not with the bulk of the minerals as in the leaching experiments.Calculation of mixing ratios of waters from the granitic and basaltic sources of the waters from the Kyselka area yield about 40% of water from the underlying granite in water recovered from the basalt, whereas the granite-derived water is mixed with only about 5% of the water from the basalt.     

Age and duration of ultrahigh-temperature metamorphism in the Anápolis–Itauçu Complex, Southern Brasília Belt, central Brazil – constraints from U–Pb geochronology, mineral rare earth element chemistry and trace-element thermometry

Integrated petrographic and chemical analysis of zircon, garnet and rutile from ultrahigh‐temperature (UHT) granulites in the Anápolis–Itauçu Complex, Brazil, is used to constrain the significance of zircon ID‐TIMS U–Pb geochronological data. Chondrite‐normalized rare earth element (REE) profiles of zircon cores have positive‐sloping heavy‐REE patterns, commonly inferred to be magmatic, whereas unambiguous metamorphic grains and overgrowths have flat to slightly negatively sloping heavy‐REE patterns. However, in one sample, a core of zircon interpreted as having formed prior to garnet crystallization and a metamorphic zircon formed within microstructures involving garnet breakdown both display elevated heavy‐REE (and Y) with positive‐sloping patterns. D_REE(zrc/grt) partition coefficients suggest an approximation to equilibrium between zircon and garnet cores, although progressive enrichment in heavy REE towards garnet rims occurs in two of the samples investigated. Titanium‐in‐zircon thermometry indicates zircon growth during both the prograde and post‐peak evolution, but not at peak temperatures of the UHT metamorphism. By contrast, zirconium‐in‐rutile thermometry of inclusions armoured by garnet records crystallization temperatures, based on the upper end of the interquartile range of the data, of ～890 to 870 °C and maximum temperature around 980 °C, indicating prograde and retrograde growth close to and after peak conditions. Rutile located in retrograde microstructures records crystallization temperatures of 850 to 820 °C. Rutile intergrown with ilmenite and included within orthopyroxene, which is associated with exsolved zircon, records temperatures ～760 °C, consistent with Ti‐in‐zircon crystallization temperatures. ID‐TIMS U–Pb geochronological data from two of the four samples investigated define upper intercept ages of 641.3 ± 8.4 Ma (MSWD 0.91) and 638.8 ± 2.5 Ma (MSWD 1.03) that correlate with periods of zircon growth along the prograde segment of the P–T path. Individual zircon U–Pb dates retrieved from all samples range from 649 to 634 Ma, indicating a maximum duration of c. 15 Myr for the UHT event. This period is interpreted as recording modest thickening of hot backarc lithosphere located behind the Arenópolis Arc at the edge of the São Francisco Craton consequent upon terminal collision of the Parána Block with the arc during the amalgamation of West Gondwana.     

Paleoproterozoic subduction-related metasomatic signatures in the lithospheric mantle beneath NE Brazil: inferences from trace element and Sr–Nd–Pb isotopic compositions of Neoproterozoic high-K igneous rocks

Late Neoproterozoic (ca. 580 Ma), high-K, mafic-intermediate rocks represent voluminous bimodal magmatism in the Borborema Province, northeast Brazil. These rocks show the following chemical signatures that reflect derivation from a subduction-modified lithospheric mantle source: (1) enrichment in large ion lithophile elements (Rb, Ba, K, Th) and light rare-earth elements (REE) (La/Yb_CN=11–70), (2) pronounced negative Nb anomalies, and (3) radiogenic Sr (0.71202–0.7059) and unradiogenic Nd (_Nd from −9.3–−20.1) isotopic compositions. T_DM model ages suggest that modification of the lithospheric mantle source (metasomatised garnet lherzolite) may have occurred in the Paleoproterozoic during the Transamazonian/Eburnean tectonics that affected the region. Interaction with asthenospheric fluids is believed to have partially melted this enriched source in the Neoproterozoic, probably as a result of asthenosphere-derived fluid percolation in the Brasiliano/Pan-African shear zones that controlled the emplacement of these mafic-intermediate magmas. The involvement of this asthenospheric component is supported by the nonradiogenic Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb=16–17.3, ²⁰⁷Pb/²⁰⁴Pb=15.1–15.6, ²⁰⁸Pb/²⁰⁴Pb=36–37.5), which contrast with the enriched Sr and Nd compositions and thereby suggest the decoupling of Rb–Sr, Sm–Nd, and U–Pb systems at the time of intrusion of the mafic-intermediate magmas in the crust.     

Post-collisional granitoids from the Dabie orogen in China: Zircon U–Pb age, element and O isotope evidence for recycling of subducted continental crust

While recycling of subducted oceanic crust is widely proposed to be associated with oceanic island, island arc, and subduction-related adakite magmatism, it is less clear whether recycling of subducted continental crust takes place in continental collision belts. A combined study of zircon U–Pb dating, major and minor element geochemistry, and O isotopes in Early Cretaceous post-collisional granitoids from the Dabie orogen in China demonstrates that they may have been generated by partial melting of subducted continental crust. The post-collisional granitoids from the Dabie orogen comprise hornblende-bearing intermediate rocks and hornblende-free granitic rocks. These granitoids are characterized by fractionated REE patterns with low HREE contents and negative HFSE anomalies (Nb, Ta and Ti). Although zircon U–Pb dating gives consistent ages of 120 to 130 Ma for magma crystallization, occurrence of inherited cores is identified by CL imaging and SHRIMP U–Pb dating; some zircon grains yield ages of 739 to 749 Ma and 214 to 249 Ma, in agreement with Neoproterozoic protolith ages of UHP metaigneous rocks and a Triassic tectono-metamorphic event in the Dabie–Sulu orogenic belt, respectively. The granitoids have relatively homogeneous zircon δ¹⁸O values from 4.14‰ to 6.11‰ with an average of 5.10‰ ± 0.42‰ (n = 28) similar to normal mantle zircon. Systematically low zircon δ¹⁸O values for most of the coeval mafic–ultramafic rocks and intruded country rocks preclude an AFC process of mafic magma or mixing between mafic and felsic magma as potential mechanisms for the petrogenesis of the granitoids. Along with zircon U–Pb ages and element results, it is inferred that the granitic rocks were probably derived from partial melting of intermediate lower crust and the intermediate rocks were generated by amphibole-dehydration melting of mafic rocks in the thickened lower crust, coupled with fractional crystallization during magma emplacement. The post-collisional granitoids in the Dabie orogen are interpreted to originate from recycling of the subducted Yangtze continental crust that was thickened by the Triassic continent–continent collision. Partial melting of orogenic lithospheric keel is suggested to have generated the bimodal igneous rocks with the similar crustal heritage. Crustal thinning by post-collisional detachment postdated the onset of bimodal magmatism that was initiated by a thermal pulse related to mantle superwelling in Early Cretaceous.