Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

The persistence of lead from past gasoline emissions and mining drainage in a large riparian system: Evidence from lead isotopes in the Sacramento River, California

Lead concentrations and isotope ratios measured in river water colloids and streambed sediment samples along 426 km of the Sacramento River, California reveal that the influence of lead from the historical mining of massive sulfide deposits in the West Shasta Cu-mining district (at the headwaters of the Sacramento River) is confined to a 60 km stretch of river immediately downstream of that mining region, whereas inputs from past leaded gasoline emissions and historical hydraulic Au-mining in the Sierra Nevadan foothills are the dominant lead sources in the remaining 370 km of the river. Binary mixing calculations suggest that more than 50% of the lead in the Sacramento River outside of the region of influence of the West Shasta Cu-mining district is derived from past depositions of leaded gasoline emissions. This predominance is the first direct documentation of the geographic extent of gasoline lead persistence throughout a large riparian system (>160,000 km²) and corroborates previous observations based on samples taken at the mouth of the Sacramento River. In addition, new analyses of sediment samples from the hydraulic gold mines of the Sierra Nevada foothills confirm the present-day fluxes into the Sacramento River of contaminant metals derived from historical hydraulic Au-mining that occurred during the latter half of the 19th and early part of the 20th centuries. These fluxes occur predominantly during periods of elevated river discharge associated with heavy winter precipitation in northern California. In the broadest context, the study demonstrates the potential for altered precipitation patterns resulting from climate change to affect the mobility and transport of soil-bound contaminants in the surface environment.     

Calcite precipitation instability under laminar, open-channel flow

We present a 2D numerical model for the growth of calcite from supersaturated aqueous solutions under laminar, open-channel flow conditions. The model couples solution chemistry, precipitation at solution/calcite interfaces, hydrodynamics, diffusion and degassing. The model output is compared with experimental results obtained using an oversaturated calcite solution produced by mixing CaCl₂ and Na₂CO₃. The precipitation rate is observed to increase when the supersaturated solution flows over an obstruction, leading to a growth instability that causes the formation of terraces. At relatively high flow rates, the most important mechanism for this behaviour seems to be hydrodynamic advection of dissolved species either towards or away from the calcite surface, depending on location relative to the obstruction, which deforms the concentration gradients. At lower flow rates, steepening of diffusion gradients around protrusions becomes important. Enhanced degassing over the obstruction due to shallowing and pressure drop is not important on small scales. Diffusion controlled transport close to the calcite surface can lead to a fingering-type growth instability, which generates porous textures. Our results are consistent with existing diffusive boundary layer theory, but for flow over non-smooth surfaces, simple calcite precipitation models that include empirical correlations between fluid flow rate and calcite precipitation rate are inaccurate.     

Lateral structural variability in zone of eocene island-arc-continent collision,Kamchatka

The lateral variability of structural elements in the collision zone of the Cretaceous-Paleocene Achaivayam-Valagin island arc with the northeastern Asian margin is considered. The similarity and difference of Eocene collision structural elements in the north and the south of Kamchatka are shown. In northern Kamchatka, the continent-arc boundary is traced along the Lesnaya-Vatyn Thrust Fault, which completed its evolution about 45 Ma ago. The thin, near-horizontal allochthon of this thrust, composed of island-arc rocks, overlies the deformed but unmetamorphosed terrigeneous sequences of the Asian margin. The general structure of this suture in the Kamchatka Isthmus and southern Koryakia is comparable with the uppermost subduction zone, where a thin lithospheric wedge overlaps intensely deformed sediments detached from the plunging plate. In southern Kamchatka (Malka Uplift of the Sredinny Range), the arc-continent collision started 55–53 Ma ago with thrusting of island-arc complexes over terrigenous rocks of continental margin. However, the thickness of the allochthon was much greater than in the north. Immediately after this event, both the autochthon and lower part of allochthon were deformed and subsided to a significant depth. This subsidence gave rise to metamorphism of both the autochthon (Kolpakov and Kamchatka groups, Kheivan Formation) and lower allochthon (Andrianovka and Khimka formations). The anomalously fast heating of the crust was most likely related to the ascent of asthenospheric masses due to slab breakoff, when the Eurasian Plate was plunging beneath the Achaivayam-Valagin arc.     

Trace Element Partitioning and Accessory Phase Saturation during H2O-Saturated Melting of Basalt with Implications for Subduction Zone Chemical Fluxes

Experimental phase equilibrium and trace element partitioningdata are reported for H₂O-saturated mid-ocean ridge basalt at2·5 GPa, 750–900°C and oxygen fugacities atthe nickel–nickel oxide buffer. Garnet, omphacite andrutile are present at all temperatures. Amphibole and epidotedisappear as residual phases above 800°C; allanite appearsabove 750°C. The Na–Al-rich silicate glass presentin all run products is likely to have quenched from a supercriticalliquid. Trace element analyses of glasses demonstrate the importantcontrol exerted by residual minerals on liquid chemistry. Inaddition to garnet, which controls heavy rare earth elements(HREE) and Sc, and rutile, which controls Ti, Nb and Ta, allanitebuffers the light REE (LREE; La–Sm) contents of liquidsto relatively low levels and preferentially holds back Th relativeto U. In agreement with previous experimental and metamorphicstudies we propose that residual allanite plays a key role inselectively retaining trace elements in the slab during subduction.Experimental data and analyses of allanite-bearing volcanicrocks are used to derive a model for allanite solubility inliquids as a function of pressure, temperature, anhydrous liquidcomposition and LREE content. The large temperature dependenceof allanite solubility is very similar to that previously determinedfor monazite. Our model, fitted to 48 datapoints, retrievesLREE solubility (in ppm) to within a factor of 1· 40over a pressure range of 0–4 GPa, temperature range of700–1200°C and for liquids with anhydrous SiO₂ contentsof 50–84 wt %. This uncertainty in LREE content is equivalentto a temperature uncertainty of only ± 27°C at 1000K, indicating the potential of allanite as a geothermometer.Silicic liquids from either basaltic or sedimentary protolithswill be saturated in allanite except for Ca-poor protolithsor at very high temperatures. For conventional subduction geothermsthe low solubility of LREE (+ Th) in liquids raises questionsabout the mechanism of LREE + Th transport from slab to wedge.It is suggested either that, locally, temperatures experiencedby the slab are high enough to eliminate allanite in the residueor that substantial volumes of H₂O-rich fluids must pass throughthe mantle wedge prior to melting. The solubility of accessoryphases in fluids derived from subducted rocks can provide importantconstraints on subduction zone thermal structure. KEY WORDS: subduction; experimental petrology; allanite; solubility; supercritical liquid; eclogite     

Origin of the Oceanic Lithosphere

In a global examination of mid-ocean ridge basalt (MORB) glasscompositions, we find that Na₈–Fe₈–depth variationsdo not support modeling of MORBs as aggregates of melt compositionsgenerated over a large range of temperature and pressure. However,the Na₈–Fe₈ variations are consistent with the compositionalsystematics of solidus melts in the plagioclase–spinellherzolite transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O–FeO(CMASNF) system. For natural compositions, the P–T rangefor melt extraction is estimated to be 1·2–1·5GPa and 1250–1280°C. This P–T range is a closematch with the maximum P–T conditions for explosive pressure-releasevaporization of carbonate-bearing melts. It is proposed thatfracturing of the lithosphere induces explosive formation andescape of CO₂ vapor. This provides the vehicle for extractionof MORBs at a relatively uniform T and P. The upper portionof the CO₂-bearing and slightly melted seismic low-velocityzone flows toward the ridge, rises at the ridge axis to lower-lithospheredepths, melts much more extensively during this rise, and releasesMORB melts to the surface driven by explosively escaping CO₂vapor. The residue and overlying crust produced by this meltingthen migrate away from the ridge axis as new oceanic lithosphere.The entire process of oceanic lithosphere creation involvesonly the upper 140 km. When lithospheric stresses shift fractureformation to other localities, escape of CO₂ ceases, the vehiclefor transporting melt to the surface disappears, and ridgesdie. Inverse correlations of Na₈ vs Fe₈ for MORB glasses areexplained by mantle heterogeneity, and positive variations superimposedon the inverse variations are consistent with progressive extractionof melts from short, ascending melting columns. The uniformlylow temperatures of MORB extraction are not consistent withthe existence of hot plumes on or close to ocean ridges. Inthis modeling, the southern Atlantic mantle from Bouvet to about26°N is relatively homogeneous, whereas the Atlantic mantlenorth of about 26°N shows significant long-range heterogeneity.The mantle between the Charlie Gibbs and Jan Mayen fracturezones is strongly enriched in FeO/MgO, perhaps by a trappedfragment of basaltic crust. Iceland is explained as the productof this enrichment, not a hot plume. The East Pacific Rise,Galapagos Ridge, Gorda Ridge, and Juan de Fuca Ridge samplemantle that is heterogeneous over short distances. The mantlebeneath the Red Sea is enriched in FeO/MgO relative to the mantlebeneath the northern Indian Ocean.     

Late Precambrian rifting in the geological history of the western slope of the South Urals

The rift-related geodynamic setting of the Late Precambrian geological evolution on the western slope of the South Urals is reconstructed on the basis of localization of lithotectonic complexes of this age, their formation conditions, and the geochemistry of rocks. The Early Riphean stage comprises accumulation of coarse-clastic rocks intercalating with alkaline volcanic rocks of the Navysh Complex, which is a constituent of the Ai Formation, and emplacement of doleritic and picritic intrusions of the Shuida Complex and melanocratic dolerite and gabbrodolerite of the Yusha Complex. The Middle Riphean stage is characterized by wide-spread coarse-clastic terrigenous rocks of the Mashak Formation that intercalate with volcanic rocks of the bimodal basalt-rhyolite association, the Berdyaush pluton of rapakivi granite, the Kusa-Kopan layered intrusive complex, the Lapyshta Complex of dolerites and picrites, and numerous occurrences of gabbrodolerites. The terrigenous rocks of the Vendian stage include conglomerate, gravelstone, and sandstone of the Asha Group, while igneous rocks comprise alkaline volcanics of the Arsha Complex, alkali gabbroids of the Miseli Complex, and melanocratic syenite of the Avashla Complex. The geological evolution of the region is distinguished by local (failed or aborted) rifting. The occurrence of lithotectonic complexes is controlled by dynamic conditions of rifting. A certain inheritance in the evolution may be traced for the Early and Middle Riphean and partly for the Late Riphean and Vendian.     

Large and giant hydrocarbon accumulations in the transitional continent-ocean zone

The petroleum resource potential is considered for the Atlantic, West Pacific, and East Pacific types of deepwater continental margins. The most considerable energy resources are concentrated at the Atlantic-type passive margins in the zone transitional to the ocean. The less studied continental slope of backarc seas of the generally active margins of the West Pacific type is currently not so rich in discoveries as the Atlantic-type margin, but is not devoid of certain expectations. In some of their parameters, the margins bounded by continental slopes may be regarded as analogs of classical passive margins. At the margins of the East Pacific type, the petroleum potential is solely confined to transform segments. In the shelf-continental-slope basins of the rift and pull-apart nature, petroleum fields occur largely in the upper fan complex, and to a lesser extent in the lower graben (rift) complex. In light of world experience, the shelf-continental-slope basins of the Arctic and Pacific margins of Russia are evaluated as highly promising.     

Lateral protrusions in the structure of the Earth’s lithosphere

The factual material and modeling results concerning the geology of specific structural elements defined as lateral protrusions, or flowing layers, are considered. The formation of such structural elements is a fundamental phenomenon that controls many features of the structural evolution and geodynamics of platform basement and foldbelts. A lateral protrusion, or flowing layer, is a spatially constrained, nearly horizontal geological body with attributes of 3D tectonic flow (rheid deformation) and lateral transport of rock masses. Flowing layers are large lateral protrusions that play important role in the structure of the continental and oceanic lithosphere. They embody the internal mobility of huge rock bodies and confirm the possibility of their lateral redistribution at different depths of the continental lithosphere. The lateral displacement of rocks within such assemblies may occur in the regime of cold deformation, heating, metamorphism, and ductile flow of rocks under subsolidus conditions or in the process of their partial melting.