Rare earth element abundances and distribution patterns in hydrothermally altered basalts: Experimental results

Oceanic tholeiites that have been experimentally reacted with seawater at 500–600° C, 800–1000 bars, have rare earth element (REE) abundances and distribution patterns that are essentially identical to those of the unaltered basalts. Although the data indicate the possibility of some REE leaching and redistribution, the net effects are small and the REE patterns of basalts affected by submarine hydrothermal processes may still be valid petrogenetic indicators.     

Rare earth element partitioning between titanite and silicate melts: Henry’s law revisited

We present detailed experimental results on the partitioning of rare earth elements (REE) between titanite and a range of different silicate melts. Our results show that Henry’s law of trace element partitioning depends on bulk composition, the available partners for heterovalent substitution, crystal composition, and melt composition. We illustrate that the partition coefficients for Sm depend very strongly on the bulk concentration of Sm in the system. The substitution mechanism, by which rare earth elements are incorporated into the crystal structure, plays an important role for trace element partitioning and also for the onset of Henry’s law. Our data show that there are clear differences between substitution mechanisms of major elements compared to elements which are present only as traces. Our experiments also clearly show that the onset of Henry’s law depends on the concentrations of the sum of all trace elements which are incorporated into the crystal by the same substitution mechanism. For geochemical modelling of magmatic processes involving titanite, and indeed other accessory phases, it is of crucial importance to first evaluate whether the REE, and other trace elements, are present as traces or as major elements, only then appropriate D values may be chosen.     

河南周庵铂族-铜镍矿床的稀土和铂族元素地球化学特征: 热液成矿的证据

河南周庵超基性岩体蕴含大型Ni-Cu-(PGE)硫化物矿床,矿化带位于超基性岩体边缘与围岩的接触带.周庵超基性岩体轻稀土富集,其La/Sm_N比值为1.3～4.7,Sm/Yb_N比值为1.9～4.4,显示一定程度的LREE/HREE分异.原始地幔标准化的微量元素配分型显示弱的负Nb异常.岩体的M含量为70×10~(-60～2120×10~(-6),Cu含量为15×10~(-6)～1056×10~(-6);矿石的Ni含量为2592×10~(-6)～6549×10~(-6),Cu含量为1147×10~(-6)～3239×10`(-6).矿石的Ni/Cu比值(2.0～2.3)低于岩石样品(5-83).强蚀变矿化样品的PGE元素含量高于弱蚀变样品约一个数量级,所有样品的Pd/Ir和Pt/Ir比值高,Pd/Ir=1.4～21,Pt/Ir=2.4～22,表明PPGE相对IPGE富集.上述特征显示周庵岩体是构造侵位的地幔岩,岩体与围岩发生了较强烈的物质交换,含水流体交代作用导致了岩体-围岩物质交换和岩体边缘矿化.     

Rare earth element sources and modification in the Lower Kittanning coal bed, Pennsylvania: implications for the origin of coal mineral matter and rare earth element exposure in underground mines

In this study, we examine the variations in rare earth elements (REE) from the Lower Kittanning coal bed of eastern Ohio and western Pennsylvania, USA, in an attempt to understand the factors that control mineral matter deposition and modification in coal, and to evaluate possible REE mixed exposure hazards facing underground mine workers. The results of this study suggest that the Lower Kittanning coal mineral matter is derived primarily from a clastic source similar to that of the shale overburden. While highly charged cations like silicon, aluminum, and titanium remained relatively immobile within the coal mineral matter, iron (primarily as pyrite) was added from nonclastic sources, either during deposition of the coal mire vegetation or subsequent to burial. Other mobile cations (e.g., alkali and alkaline earth elements) appear to have been added to and/or leached from the originally deposited clastic mineral matter. Most of the sulfur in the Lower Kittanning coal bed is bound as FeS₂ in the mineral matter, but a majority of samples contain a small excess of S that is most likely organically bound.In general, the total rare earth element content (TREE) in coal ash is greater than that in the shale overburden. If the primary source of mineral matter is the same as that for the overlying shale, then REE must have been enriched in the coal mineral matter subsequent to deposition. The total rare earth element content of Lower Kittanning coals correlates strongly with Si concentration ([TREE]≈0.0024 [Si]), which provides a threshold for evaluating possible mixed exposure health effects. Chondrite-normalized REE patterns reveal a shale-like light rare earth element (LREE) enrichment for the coal, similar to that of the shale overburden, again suggesting a primarily clastic REE source. However, when normalized to the shale overburden, most of the coal ash samples display a small but distinct heavy rare earth element (HREE) enrichment. We surmise that the HREE were added and/or preferentially retained during epigenesis, possibly associated with groundwater flow through the coal unit, but not necessarily in close association with the addition of iron. At least some of the “excess” HREE could be organically bound within the Lower Kittanning coal.     

Experimental and discrete element modeling studies of the trapdoor problem: influence of the macro-mechanical frictional parameters

Granular soils have the inherent ability to develop load transfers in their mass. Mechanisms of load transfers are used as a basic principle of many civil and geotechnical engineering applications. However, their complexity makes it difficult to formulate relevant design methods for such works. The trapdoor problem is one of the ways to reproduce load transfers by the arching effect in a granular layer in non-complex conditions. In addition, many analytical solutions for the prediction of load transfer mechanisms are based on the trapdoor problem. However, some of the parameters required are still being widely discussed, in particular the ratio of horizontal stress to vertical stress. For this paper, an experimental device for trapdoor tests in plane strain conditions was created and several geomaterials were tested. Three phases in the response of the materials were consistently observed. Each of these phases corresponded to a specific displacement of the trapdoor. A first phase of high load transfer was observed followed by a transition phase which was followed by a critical phase for which the load transfer amplitude increased and stabilized. Analytical solutions and experimental values of load transfers were compared. Considerable differences between the stress ratio needed to fit the experimental data and the stress ratio proposed in the analytical models were noted. Based on the conclusions of the experimental study, the discrete element method was used to model the same trapdoor problem. A wide range of granular materials was modeled and tested in the trapdoor problem. The three phases in the response of the layer were also observed in the numerical modeling. In addition, it was shown that the shear strength of the material is the key parameter of load transfers: peak shear resistance for the small displacements of the trapdoor and critical shear strength for the larger displacements. A micro-mechanical analysis showed that the effective stress ratio in the sheared zone does not vary as much with shear strength. Stress ratios here were again greater than those proposed in the analytical solutions. Nevertheless, the relevance of the solution of Terzaghi was confirmed as soon as the stress ratio was correctly chosen.     

Delimitation of ground failure zones due to land subsidence using gravity data and finite element modeling in the Querétaro valley, México

Sedimentary basins of arid and semiarid zones are often subject to regimes of intense ground-water withdrawal as it is normally the only source of water for development of communities. An associated phenomenon is land subsidence, which can develop to ground failures, and consequently, damage to infrastructure. Aquifer deformation can be analyzed using a stress–strain or a flux–force approach depending on the aquifer material (compact or loose) and on whether the water withdrawal forms a predominant flow direction toward a cone of depression. Geometry of the aquifer system also plays an important role as uneven thickness induces differential compaction and hence, tensional and shear stresses on the ground mass. In this work we present a stress–strain approach to analyze subsidence for an unconfined aquifer of varying thickness; this is done in two steps, namely when the aquifer is in equilibrium, and when it is totally depleted. Using this scheme in a region where ground failure is evident, a portion of the aquifer system of the Querétaro valley is analyzed. The geometry of the hydrologic basement is first modeled using gravity measurements properly correlated with wells and field data. Then a stress analysis is implemented using the finite element method in order to identify probable zones of ground weakness, which are calibrated with known ground failures. The results indicate that both, tensional and shear stress are present, which induce ground failure in the form of surface faults.     

Finite element modeling approach to assess the stability of debris and rock slopes: a case study from the Indian Himalayas

Landslides and slope failures are recurrent phenomena in the Indian Himalayas. The study area comprises the hill slopes along a road stretch of 1.5 km at a distance of 9 km from Pipalkoti on Chamoli–Badrinath highway (NH-58) in the Garhwal Himalayas, India. Based on the field survey, contour map, and the hillshade, the study area has been divided into different zones. Three different zones/slopes in this study area including one potential debris slide, one stable debris slope, and one potential rock slide have been undertaken for investigation and modeling. Field mapping, data collection related to slope features and soil/rock sample collection, and discontinuity mapping for all the slopes have been carried out in field. Soil samples have been tested in the laboratory to determine the physico-mechanical properties. These properties along with some material properties from the literature have been used as input parameters for the numerical simulation. To investigate the failure process in the debris/rock slides as well as stable debris slope, the slopes were modeled as a continuum using 2D finite element plain strain approach. Shear strength reduction analysis was performed to determine the critical strength reduction factor. The computed deformations and the stress distributions, along the failure surface, have been compared with the field observations and found to be in good agreement. The analysis results indicated rock/debris slide slopes to be highly unstable. The debris slide modeling depicted failures both above and below road levels as observed in field. The rock slide modeling could depict the exact pattern of failure involving 3 sets of discontinuities simultaneously as observed in real-field scenario which is a major limitation in case of limit equilibrium analysis. The field-observed stable slope comes to be stable through FE analysis also. Based on these analyses, landslide hazard assessment of the study area could be done.     

Rare earth element geochemistry of the Permo-Carboniferous clastic sedimentary rocks from the Spiti Region,Tethys Himalaya: significance of Eu and Ce anomalies

Acta Geochimica - Siliciclastic sedimentary rocks, including sandstones and associated shales, from the Permo-Carboniferous Kanawar Group of NW Tethys Himalaya, Spiti Region, India were examined...     

Rare earth element geochemistry and strontium isotopic composition of a massif-type anorthositic-charnockitic body: the Hidra Massif (Rogaland,SW Norway)

The Hidra Massif (Rogaland Complex, SW Norway) mainly consists of plagioclase cumulates (anorthosites and leuconorites), which grade progressively into a fine-grained (200 μm). locally porphyritic, jotunitic rock towards the contact with the granulite facies gneisses. The massif is cross-cut by thin (10 cm up to 1 m) charnockitic dykes.The petrographical and geochemical evolution of the Hidra Massif can be explained by fractional crystallization of a jotunitic parental magma. Major and trace element constraints indicate that mafic phases are underabundant in the exposed levels of the massif, most likely as a result of plagioclase flotation in the early stages of solidification. Partitioning into the cumulate minerals (mainly plagioclase and orthopyroxene) governs the trace element contents of the leuconoritic adcumulates. However, the trace element geochemistry of the apparently early formed anorthositic orthocumulates largely depends upon the amount of a trapped intercumulus liquid. On the basis of trace element abundances (high REE, Rb, Th, U; negative Eu anomalies) the silicic charnockitic dykes can be considered as the residual liquid of the anorthositic fractionation trend. The higher initial ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios (0.7086 ± 0.0006 vs 0.7055 ± 0.0004 for the plagioclase cumulates and jotunites) point to contamination of the charnockitic liquids by surrounding gneissic material.     

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 element and strontium isotope geochemistry in Dujiali Lake,central Qinghai-Tibet Plateau,China: Implications for the origin of hydromagnesite deposits

Rare earth element (REE) and strontium isotope data (⁸⁷Sr/⁸⁶Sr) are presented for hydromagnesite and surface waters that were collected from Dujiali Lake in central Qinghai-Tibet Plateau (QTP), China. The goal of this study is to constrain the solute sources of hydromagnesite deposits in Dujiali Lake. All lake waters from the area exhibit a slight LREE enrichment (average [La/Sm]_PAAS = 1.36), clear Eu anomalies (average [Eu/Eu*]_PAAS = 1.31), and nearly no Ce anomalies. The recharge waters show a flat pattern (average [La/Sm]_PAAS = 1.007), clear Eu anomalies (average [Eu/Eu*] _PAAS = 1.83), and nearly no Ce anomalies (average [Ce/Ce*]_PAAS = 1.016). The REE+Y data of the surface waters indicate the dissolution of ultramafic rock at depth and change in the hydrogeochemical characteristics through fluid-rock interaction. These data also indicate a significant contribution of paleo-groundwater to the formation of hydromagnesite, which most likely acquired REE and Sr signatures from the interaction with ultramafic rocks. The ⁸⁷Sr/⁸⁶Sr data provide additional insight into the geochemical evolution of waters of the Dujiali Lake indicating that the source of Sr in the hydromagnesite does not directly derive from surface water and may have been influenced by both Mg-rich hydrothermal fluids and meteoric water. Additionally, speciation modeling predicts that carbonate complexes are the most abundant dissolved REE species in surface water. This study provides new insights into the origins of hydromagnesite deposits in Dujiali Lake, and contributes to the understanding of hydromagnesite formation in similar modern and ancient environments on Earth.     

Rare earth and other trace element mobility during mylonitization: a comparison of the Brevard and Hope Valley shear zones in the Appalachian Mountains, USA

In progressing from a granitoid mylonite to an ultramylonite in the Brevard shear zone in North Carolina, Ca and LOI (H₂O) increase, Si, Mg, K, Na, Ba, Sr, Ta, Cs and Th decrease, while changes in Al, Ti, Fe, P, Sc, Rb, REE, Hf, Cr and U are relatively small. A volume loss of 44% is calculated for the Brevard ultramylonite relative to an Al–Ti–Fe isocon. The increase in Ca and LOI is related to a large increase in retrograde epidote and muscovite in the ultramylonite, the decreases in K, Na, Si, Ba and Sr reflect the destruction of feldspars, and the decrease in Mg is related to the destruction of biotite during mylonitization. In an amphibolite facies fault zone separating grey and pink granitic gneisses in the Hope Valley shear zone in New England, compositional similarity suggests the ultramylonite is composed chiefly of the pink gneisses. Utilizing an Al–Ti–Fe isocon for the pink gneisses, Sc, Cr, Hf, Ta, U, Th and M-HREE are relatively unchanged, Si, LOI, K, Mg, Rb, Cs and Ba are enriched, and Ca, Na, P, Sr and LREE are lost during deformation. In contrast to the Brevard mylonite, the Hope Valley mylonite appears to have increased in volume by about 70%, chiefly in response to an introduction of quartz. Chondrite-normalized REE patterns of granitoids from both shear zones are LREE-enriched and have prominent negative Eu anomalies. Although REE increase in abundance in the Brevard ultramylonites (reflecting the volume loss), the shape of the REE pattern remains unchanged. In contrast, REE and especially LREE decrease in abundance with increasing deformation of the Hope Valley gneisses. Mass balance calculations indicate that ≥95% of the REE in the Brevard rocks reside in titanite. In contrast, in the Hope Valley rocks only 15–40% of the REE can be accounted for collectively by titanite, apatite and zircon. Possible sites for the remaining REE are allanite, fluorite or grain boundaries. Loss of LREE from the pink gneisses during deformation may have resulted from decreases in allanite and perhaps apatite or by leaching ofy REE from grain boundaries by fluids moving through the shear zone. Among the element ratios most resistant to change during mylonitization in the Brevard shear zone are La/Yb, Eu/Eu*, Sm/Nd, La/Sc, Th/Sc, Th/Yb, Cr/Th, Th/U and Hf/Ta, whereas the most stable ratios in the Hope Valley shear zone are K/Rb, Rb/Cs, Th/U, Eu/Eu*, Th/Sc, Th/Yb, Sm/Nd, Th/Ta, Hf/Ta and Hf/Yb. However, until more trace element data are available from other shear zones, these ratios should not be used alone to identify protoliths of deformed rocks.     

三维AMT正反演技术对贵州马坪含金刚石岩体探测的精细解释

贵州镇远马坪"东方一号"岩体是我国首次发现的含金刚石原生矿母岩,马坪地区发现的岩体属于金伯利岩浆体系的浅部相,其深部可能存在规模较大的隐伏岩管或岩筒。为揭示马坪地区深部含金刚石隐伏岩管或岩筒的空间展布特征,在区内开展了80 mx40 m高密集网度的音频大地电磁勘探工作;利用三维正演技术模拟研究区纯地形响应并在实测数据中去除,得到的定性解释结果在一定程度上恢复了被静态效应扭曲的AMT阻抗相位不变量分布形态;使用AR-QN拟牛顿反演方法对数据进行三维反演,根据研究区岩性统计结果设定地下单元的电阻率变化区间,获得了可靠的三维电性结构;最后依据地表发现的岩筒、钻孔揭露的多条岩脉等地质资料对该地电模型进行精细解释,勾画出了隐伏岩管(岩筒)的形态,为区内下一步金刚石原生矿找矿方向及预测提供了地球物理依据。     

Rare earth elements in three fluorites: graphical comparison of data and model Comment to “Mathematical analysis of rare earth element patterns of fluorites from the Ehrenfriedersdorf tin deposit, Germany: evidence for a hydrothermal mixing process of lanthanides from two different sources” by T. Monecke et al.

Summary A graphical method is proposed for comparing the data reported by Monecke et al. (2000) with their mathematical model. Received August 9, 2001; accepted October 25, 2001     

An improved description of the interactions between rare earth elements and humic acids by modeling: PHREEQC-Model VI coupling

The Humic Ion Binding Model VI (Model VI) - previously used to model the equilibrium binding of rare earth elements (REE) by humic acid (HA) - was modified to account for differences in the REE constant patterns of the HA carboxylic and phenolic groups, and introduced into PHREEQC to calculate the REE speciation on the HA binding sites. The modifications were shown to greatly improve the modeling. They allow for the first time to both satisfactorily and simultaneously model a large set of multi-REE experimental data with the same set of equations and parameters. The use of PHREEQC shows that the light rare earth elements (LREE) and heavy rare earth elements (HREE) do not bind to HA by the same functional groups. The LREE are preferentially bound to carboxylic groups, whereas the HREE are preferentially bound to carboxy-phenolic and phenolic groups. This binding differentiation might lead to a fractionation of REE-HA patterns when competition between REE and other metals occur during complexation. A survey of the available data shows that competition with Al³⁺ could lead to the development of HREE-depleted HA patterns. This new model should improve the hydrochemical modeling of the REE since PHREEQC takes into account chemical reactions such as mineral dissolution/precipitation equilibrium and redox reactions, but also models kinetically controlled reactions and one-dimensional transport.     

Rare earth element and Pb isotope variations in a 52 kyr peat core from Lynch’s Crater (NE Queensland, Australia): Proxy development and application to paleoclimate in the Southern Hemisphere

Accurate prediction of future climate scenarios is contingent on our understanding of past and present climate mechanisms. This is done in part through the reconstruction of historical climate changes using proxy records from terrestrial and marine archives. Terrestrial archives covering the Holocene and late Pleistocene are limited, most acutely in the Southern Hemisphere. Here, Rare earth elements (REE) and Pb isotopes are developed as inorganic geochemical proxies of mineral dust source changes and, by extension, climate change. Using a peat core from Lynch’s Crater in NE Queensland, Australia, we present the first long-term (c. 52 kyr) terrestrial record of atmospheric REE and Pb deposition (with the exception of four wet events which represent periods of erosion from the crater itself) in the Southern Hemisphere covering both glacial and interglacial times. Based on a combination of correlation analyses, Al and Ti normalised profiles and elemental patterns, we establish REE are immobile within the peat deposit and not subject to significant post depositional diagenetic changes (important particularly for Ce). This is vital as REE can be mobile under acid and organic rich conditions like those that can occur during the development of a peat deposit. The volcanic provinces of eastern Australia have characteristic Eu anomaly signatures, which allowed their use in a novel way to detect changes in dust source to Lynch’s Crater. Between 41,095 and 52,505 BP the deposit was under the influence of dust carried by long distance transport (>1500 km) from SE Australia. From 8525 to 40,815 BP regional sources (100-1500 km) dominated the deposited signals while between 1740 and 8390 BP the dust signal was controlled by local sources (<100 km). These findings were also confirmed by Pb isotope data. Changepoint modelling refined the timing of these changes in dust source, recognizing concurrent shifts in our tracing tools ((Eu/Eu^∗)_PAAS and ²⁰⁶Pb/²⁰⁷Pb). These changepoints were then compared to other palaeoenvironmental records (pollen, lake levels and dune building) from eastern Australia and found to be similar. Our results demonstrate that REE and Pb isotopes are effective tools for tracing past changes in atmospheric dust sources and to the study of climate change using minerotrophic peat deposits.