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1.
The release of Pb and rare earth elements (REE) during granitoid weathering was investigated through dissolution experiments of fresh granite and soil samples. Two aliquots of a granite sample from the El-Capitan Granite, Sierra Nevada, California, were leached several times using a dilute acid at pH = 1. The results of the experiment were compared with Pb and REE data from soils developed on the same rock. During the early stages of granitoid dissolution, Pb and REE were preferentially released from some of the accessory phases (i.e., allanite, sphene, and apatite). This caused higher 206Pb/207Pb and 208Pb/207Pb values and different REE patterns in solution compared with the rock values. Based on Pb isotopes and REE patterns, three stages of rock dissolution can be identified. In the first stage the dissolution of allanite dominates the release of Pb and REE from accessory phases, as 208Pb/207Pb, Ce/Pb, and chondrite-normalized Ce/Yb ratios in solution increase and approach the values of allanite. In the second stage, the dissolution of apatite and sphene become more significant. In the third stage, the isotopic ratios of Pb and the normalized-REE patterns reflect the depletion of accessory phases and the increase in the rate of feldspar dissolution. According to our estimate (based on Si release from the rock) all three stages account for the first 500 kyr of granitoid weathering.Using the isotopic ratios of Pb, major elemental compositions, and REE concentrations both in the experimental solutions and in the soil we were able to establish the following order of the weathering rates of accessory phases: allanite > apatite > sphene. In addition, we have demonstrated that biotite is significantly less resistant to weathering than hornblende under acidic conditions, and is probably dissolved completely after approximately 500 kyr of rock weathering. We also suggest that within 500 kyr of granitoid weathering K-feldspar accounts for 15% of the released K.  相似文献   

2.
The concentrations of twenty four chemical elements in the surface layer of natural desert soils and the cultivated farmland soils were measured at a desert-oasis ecotone in the middle of Heihe river basin, north-west China. Background values were estimated for (a) major elements (Si 335.3 g kg− 1, Al 49.4 g kg− 1, Fe 19.1 g kg− 1, Ca 29.4 g kg− 1, Mg 8.9 g kg− 1, K 20.1 g kg− 1, Na 17.5 g kg− 1 and P 0.338 g kg− 1), (b) heavy metals and non-metals (Cr 55.8 mg kg− 1, Mn 404.8 mg kg− 1, Ni 17.7 mg kg− 1, Cu 5.1 mg kg− 1, Zn 33.7 mg kg− 1, Pb 15.5 mg kg− 1 and As 5.2 mg kg− 1) and (c) other trace elements (Ti 2.0 mg kg− 1, V 55.3 mg kg− 1, Co 5.7 mg kg− 1, Rb 82.4 mg kg− 1, Sr 232.9 mg kg− 1, Y 14.7 mg kg− 1, Zr 194.9 mg kg− 1, Nb 7.8 mg kg− 1 and Ba 720.6 mg kg− 1). After natural desert soil was cultivated for agricultural use, significant changes in element concentrations occurred under tillage, irrigation and fertilisation management. Compared to natural soil, the for the levels of Si, K, Na, Sr, Zr and Ba decreased, and no changes were observed for Rb, while the values of the other 17 elements increase in agricultural soil from 1.2 to 3.5 times. However, their absolute concentrations are still low, suggesting that the arable soil in this region remains comparatively a clean soil. The increased silt, clay and organic carbon content, under long-term irrigation, enriched the fine-grained materials, and application of fertilisers and manure contributed to the accumulation of most elements in arable soil. The accumulation of elements in agricultural soil increased with increasing cultivation years and extent of soil development.  相似文献   

3.
《Applied Geochemistry》1997,12(5):607-623
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.  相似文献   

4.
 Mantle peridotites of the Internal Liguride (IL) units (Northern Apennines) constitute a rare example of the depleted lithosphere of the Jurassic Ligurian Tethys. Detailed chemical (ICP-MS and SIMS techniques) and isotopic investigations on very fresh samples have been performed with the major aim to constrain the timing and mechanism of their evolution and to furnish new data for the geodynamic interpretation. The data are also useful to discuss some general geochemical aspects of oceanic-type mantle. The studied samples consist of clinopyroxene-poor spinel lherzolites, showing incipient re-equilibration in the plagioclase-facies stability field. The spinel-facies assemblage records high (asthenospheric) equilibration temperatures (1150–1250° C). Whole rocks, and constituent clinopyroxenes, show a decoupling between severe depletion in highly incompatible elements [light rare earth elements (LREE), Sr, Zr, Na, Ti] and less pronounced depletion in moderate incompatible elements (Ca, Al, Sc, V). Bulk rocks also display a relatively strong M(middle)REE/H(heavy)REE fractionation. These compositional features indicate low-degree (<10%) fractional melting, which presumably started in the garnet stability field, as the most suitable depletion mechanism. In this respect, the IL ultramafics show strong similarity to abyssal peridotites. The Sr and Nd isotopic compositions, determined on carefully handpicked clinopyroxene separates, indicate an extremely depleted signature (87Sr/86Sr=0.702203–0.702285; 143Nd/144Nd=0.513619–0.513775). The Sm/Nd model ages suggest that the IL peridotites melted most likely during Permian times. They could record, therefore, the early upwelling and melting of mid ocean ridge basalt (MORB) type asthenosphere, in response to the onset of extensional mechanisms which led to the opening of the Western Tethys. They subsequently cooled and experienced a composite subsolidus evolution testified by multiple episodes of gabbroic intrusions and HT-LP retrograde metamorphic re-equilibration, prior to their emplacement on the sea floor. The trace element chemistry of IL peridotites also provides useful information about the composition of oceanic-type mantle. The most important feature concerns the occurrence of Sr and Zr negative anomalies (relative to “adjacent” REE) in both clinopyroxenes and bulk rocks. We suggest that such anomalies reflect changes in the relative magnitude of Sr, Zr and REE partition coefficients, depending on the specific melting conditions. Received: 15 February 1995/Accepted: 4 August 1995  相似文献   

5.
Seamount volcanism associated with the Xigaze ophiolite, Southern Tibet   总被引：6，自引：0，他引：6  
Basaltic lavas at Renbu, Southern Tibet are associated with the Xigaze ophiolite in the Yarlung-Zangbo suture zone. They are alkaline lavas rich in large ion lithophile elements (LILE, Ba, Rb and Sr) and high field strength elements (HFSE, Nb, Ta, Zr and Hf), but poor in Cr, Co and Ni. All of the rocks have chondrite-normalized REE patterns enriched in light rare earth elements (LREE), comparable to modern basalts of the Society Islands, Kerguelen Plateau and Broken Ridge. Abundances of some immobile or moderately immobile elements (Nb, Ta, Zr, Hf, Y, Ti and REE) are also comparable to Kerguelen alkaline basalts. The Renbu basalts are geochemically similar to oceanic island basalts (OIB) and have some elemental ratios, such as Nb/Ta ratios = 15.7–18.1, Th/Nb =  0.06–0.10, La/Nb = 0.59–0.83 and Th/Ta = 1.03–1.52, similar to the primitive mantle. Their 87Sr/86Sr ratios (0.70453–0.70602) are relatively high, similar to OIB. In the 87Sr/86Sr vs. εNd(t) diagram, the Renbu basalts plot along a trend from N-MORB to EMII (enriched mantle II), suggesting the involvement of at least two mantle sources in their generation. The Renbu basalts represent seamount volcanism associated with the Xigaze ophiolite. They formed from an OIB-type mantle source within the Neo-Tethyan Ocean that had a composition similar to the modern Indian Ocean mantle.  相似文献   

6.
Studies of hydrothermal circulation within partly buried basement on the eastern flank of the Juan de Fuca Ridge (JFR) have shown that ridge-flank geochemical fluxes are potentially important for the global budgets of some elements. There are major uncertainties in these flux calculations, however, because the composition of these basement fluids is strongly dependent on temperature and because they may be modified by interaction with the overlying terrigenous sediments, either by diffusive exchange with basement or during upwelling to the seafloor. To better understand the nature and temperature control of basalt-fluid and sediment-fluid reactions at the JFR flank, we have conducted laboratory experiments between 51 and 350°C and at 400 bars pressure. K, Rb, and Si are leached from basalt between 150 and 351°C, and Sr and U are taken up. The direction of exchange of Li and Ca with basalt varies with temperature. Li and Sr are removed from fluid at 150°C, but isotope studies show that there is simultaneous release of both elements from basalt, indicating that uptake is controlled by the formation of secondary minerals. Moreover, our experiments confirm that Sr isotope exchange with oceanic crust occurs at moderate temperature and is not confined to high-temperature axial hydrothermal systems. Our data and field data from the JDR flank indicate that uptake of U into basalt at moderate temperature could remove between 9.9 and 15 × 106 mol U yr−1 from the oceans. This is higher than a recent estimate based on measurements of U in altered ocean crust (5.7 ± 3.3 × 106 mol yr−1), which concords with arguments that the Δelement/heat ratios of JDR flank fluids are too large to be representative of average global flank fluids. K, Ca, Sr, Ba, Li, Si, and B are leached from terrigenous sediments between 51 and 350°C, and U is taken up. Cs and Rb are removed from the fluid below 100°C and leached from the sediment at higher temperature. Sr isotope data show that Sr is preferentially mobilised from volcanic components within terrigenous sediments, which may lead to an overestimation of the ridge-flank Sr isotope flux at the JDR if there is exchange of sediment pore fluids with basement.  相似文献   

7.
Major and trace element and modal analyses are presented for unaltered, epidotized, and carbonated tholeiite flows from the Barberton greenstone belt. Au, As, Sb, Sr, Fe+3, Ca, Br, Ga, and U are enriched and H2O, Na, Mg, Fe+2, K, Rb, Ba, Si, Ti, P, Ni, Cs, Zn, Nb, Cu, Zr, and Co are depleted during epidotization. CO2, H2O, Fe+2, Ti, Zn, Y, Nb, Ga, Ta, and light REE are enriched and Na, Sr, Cr, Ba, Fe+3, Ca, Cs, Sb, Au, Mn, and U are depleted during carbonization-chloritization. The elements least affected by epidotization are Hf, Ta, Sc, Cr, Th, and REE; those least affected by carbonization-chloritization are Hf, Ni, Co, Zr, Th, and heavy REE. Both alteration processes can significantly change major element concentrations (and ratios) and hence caution should be used in distinguishing tholeiites from komatiites based on major elements alone. The amount of variation of many of the least mobile trace elements in the altered flows is approximately the same as allowed by magma model calculations. Hence, up to about 10% carbonization and 60% epidotization of tholeiite do not appreciably affect the interpretation of trace-element models for magma generation.  相似文献   

8.
We conducted a modified Bureau Commun Reference (BCR) sequential extraction on a basaltic soil (phono-tephrite) from Mt. Meru in Northern Tanzania in order to determine the relative contribution of water soluble, carbonate and exchangeable, oxide and organic fractions to the bulk composition of the soil. Elemental compositions were determined by ICP-MS and corrected for loss on ignition. Relatively immobile elements, such as Zr, Hf and Al, are enriched by 10–30% compared to the unweathered protolith, consistent with soil formation being accompanied by mass loss due to chemical weathering. However, superimposed on this mass loss appears to be enrichment of elements such as Fe, Ca and Mg, especially towards the surface. In some cases, the bulk concentrations of these elements at the surface exceed that of the protolith. These data suggest that the surface of the Meru soil columns may have experienced “re-fertilization” by the deposition of volcanic ash. From the carbonate and exchangeable extraction, we found evidence of clay rich horizons which may sequester as much as 5% of the bulk K. The concentration of calcium carbonate appears to decrease with depth, but the largest incorporation of Sr and Ba into carbonates occurs below 114 cm. Fe and Mn oxides scavenge more than 10–20% of total Ti, V, Co, Cu, Zr and Pb below 114 cm. The organic fraction sequestered significant fractions of total Al, Cu, REE’s and Pb throughout the soil column.  相似文献   

9.
Partition coefficients (zircon/meltDM) for rare earth elements (REE) (La, Ce, Nd, Sm, Dy, Er and Yb) and other trace elements (Ba, Rb, B, Sr, Ti, Y and Nb) between zircon and melt have been calculated from secondary ion mass spectrometric (SIMS) analyses of zircon/melt inclusion pairs. The melt inclusion-mineral (MIM) technique shows that DREE increase in compatibility with increasing atomic number, similar to results of previous studies. However, DREE determined using the MIM technique are, in general, lower than previously reported values. Calculated DREE indicate that light REE with atomic numbers less than Sm are incompatible in zircon and become more incompatible with decreasing atomic number. This behavior is in contrast to most previously published results which indicate D > 1 and define a flat partitioning pattern for elements from La through Sm. The partition coefficients for the heavy REE determined using the MIM technique are lower than previously published results by factors of ≈15 to 20 but follow a similar trend. These differences are thought to reflect the effects of mineral and/or glass contaminants in samples from earlier studies which employed bulk analysis techniques.DREE determined using the MIM technique agree well with values predicted using the equations of Brice (1975), which are based on the size and elasticity of crystallographic sites. The presence of Ce4+ in the melt results in elevated DCe compared to neighboring REE due to the similar valence and size of Ce4+ and Zr4+. Predicted zircon/meltD values for Ce4+ and Ce3+ indicate that the Ce4+/Ce3+ ratios of the melt ranged from about 10−3 to 10−2. Partition coefficients for other trace elements determined in this study increase in compatibility in the order Ba < Rb < B < Sr < Ti < Y < Nb, with Ba, Rb, B and Sr showing incompatible behavior (DM < 1.0), and Ti, Y and Nb showing compatible behavior (DM > 1.0).The effect of partition coefficients on melt evolution during petrogenetic modeling was examined using partition coefficients determined in this study and compared to trends obtained using published partition coefficients. The lower DREE determined in this study result in smaller REE bulk distribution coefficients, for a given mineral assemblage, compared to those calculated using previously reported values. As an example, fractional crystallization of an assemblage composed of 35% hornblende, 64.5% plagioclase and 0.5% zircon produces a melt that becomes increasingly more enriched in Yb using the DYb from this study. Using DYb from Fujimaki (1986) results in a melt that becomes progressively depleted in Yb during crystallization.  相似文献   

10.
The major element and Sr isotope systematics and geochemistry of coal fly ash and its interactions with environmental waters were investigated using laboratory flow-through column leaching experiments (sodium carbonate, acetic acid, nitric acid) and sequential batch leaching experiments (water, acetic acid, hydrochloric acid). Column leaching of Class F fly ash samples shows rapid release of most major elements early in the leaching procedure, suggesting an association of these elements with soluble and surface bound phases. Delayed release of certain elements (e.g., Al, Fe, Si) signals gradual dissolution of more resistant silicate or glass phases as leaching continues. Strontium isotope results from both column and batch leaching experiments show a marked increase in 87Sr/86Sr ratio with continued leaching, yielding a total range of values from 0.7107 to 0.7138. For comparison, the isotopic composition of fluid output from a fly ash impoundment in West Virginia falls in a narrow range around 0.7124. The experimental data suggest the presence of a more resistant, highly radiogenic silicate phase that survives the combustion process and is leached after the more soluble minerals are removed. Strontium isotopic homogenization of minerals in coal does not always occur during the combustion process, despite the high temperatures encountered in the boiler. Early-released Sr tends to be isotopically uniform; thus the Sr isotopic composition of fly ash could be distinguishable from other sources and is a useful tool for quantifying the possible contribution of fly ash leaching to the total dissolved load in natural surface and ground waters.  相似文献   

11.
Mineral/melt trace element partition coefficients were determined for rutile (TiO2) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found DTa > DNb, DHf > DZr and DU > DTh. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, DNb/DTa and DHf/DZr are not significantly affected by melt composition. Because DU ? DTh, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of 230Th over 238U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of 238U over 230Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed 231Pa-235U disequilibria in certain volcanic rocks.  相似文献   

12.
Bransfield Strait is a narrow basin separating the South Shetland Islands from the Antarctic Peninsula and is attributed to recent back-arc extension behind the South Shetland volcanic arc. The volcanic islands of Deception and Bridgeman are situated close to the axis of spreading, whereas Penguin Island lies slightly to the north of this axis. The mineralogy, petrology and geochemistry of the lavas of the three volcanoes have been studied in order to provide information on the nature of magmatism associated with the initial stages of back-arc spreading.Deception Island lavas range from olivine basalt to dacite, and all are highly sodic, with high Na/K, K/Rb, Ba/Rb and Zr/Nb ratios and with CeN/YbN = 2. Incompatible elements increase systematically between basalt and rhyodacite, while Sr decreases, suggesting that fractional crystallisation is the dominant process relating lava compositions. The rhyodacites have high concentrations of Zr, Y and the REE and negative Eu anomalies and are compositionally similar to oceanic plagiogranite. Bridgeman Island lavas are mostly basaltic andesites, but the levels of many incompatible elements, including REE, are significantly lower than those of Deception lavas, although CeN/YbN ratios and 87Sr/86Sr ratios (0.7035) are the same. Penguin Island lavas are magnesian, mildly alkaline olivine basalts with a small range of composition that can be accommodated by fractional crystallisation of olivine, clinopyroxene and/or chromite. Penguin lavas have higher 87Sr/86Sr (0.7039) and CeN/ YbN (4) ratios than Deception and Bridgeman lavas. The Rb/Sr ratios of Deception and Penguin basalts (ca. 0.01) are much too low to account for their present 87Sr/86Sr ratios.Modelling suggests that the source regions of the lavas of the three volcanoes share many geochemical features, but there are also some significant differences, which probably reflects the complex nature of the mantle under an active island arc combined with complex melting relationships attending the initial stages of back-arc spreading. Favoured models suggest that Bridgeman lavas represent 10–20% melting and the more primitive Deception lavas 5–10% melting of spinel-peridotite, whereas Penguin lavas represent less then 5% melting of a garnet-peridotite source. The mantle source for Bridgeman lavas seems to have undergone short-term enrichment in K, Rb and Ba, possibly resulting from dewatering of the subducted slab. Hydrous melting conditions may also account for the more siliceous, high-alumina nature and low trace element contents of Bridgeman lavas.  相似文献   

13.
Trace elements, including rare earth elements (REE), exhibit systematic variations in plutonic rocks from the Captains Bay pluton which is zoned from a narrow gabbroic rim to a core of quartz monzodiorite and granodiorite. The chemical variations parallel those in the associated Aleutian calcalkaline volcanic suite. Concentrations of Rb, Y, Zr and Ba increase as Sr and Ti decrease with progressive differentiation. Intermediate plutonic rocks are slightly enriched in light REE (La/Yb=3.45–9.22), and show increasing light REE fractionation and negative Eu anomalies (Eu/Eu*=1.03–0.584). Two border-zone gabbros have similar REE patterns but are relatively depleted in total REE and have positive Eu anomalies; indicative of their cumulate nature. Initial 87Sr/86Sr ratios in 8 samples (0.70299 to 0.70377) are comparable to those of volcanic rocks throughout the arc and suggest a mantle source for the magmas. Oxygen isotopic ratios indicate that many of the intermediate plutonic rocks have undergone oxygen isotopic exchange with large volumes of meteoric water during the late stages of crystallization; however no trace element or Sr isotopic alteration is evident.Major and trace element variations are consistent with a model of inward fractional crystallization of a parental high-alumina basaltic magma at low pressures (6 kb). Least-squares approximations and trace element fractionation calculations suggest that differentiation in the plutonic suite was initially controlled by the removal of calcic plagioclase, lesser pyroxene, olivine and Fe-Ti oxides but that with increasing differentiation and water fugacity the removal of sub-equal amounts of sodic plagioclase and hornblende with lesser Fe-Ti oxides effectively drove residual liquids toward dacitic compositions. Major and trace element compositions of aplites which intrude the pluton are not adequately explained by fractional crystallization. They may represent partial melts derived from the island arc crust. Similarities in Sr isotopes, chemical compositions and differentiation trends between the plutonic series and some Aleutian volcanic suites indicates that shallow-level fractional crystallization is a viable mechanism for generating the Aleutian calcalkaline rock series.LDGO Contribution no. 2964  相似文献   

14.
Carbonate, largely in the form of dolomite, is found throughout the host rocks and ores of the Nchanga mine of the Zambian Copperbelt. Dolomite samples from the hanging wall of the mineralization show low concentrations of rare-earth elements (REE) and roof-shaped, upward convex, shale-normalized REE patterns, with positive Eu*SN anomalies (1.54 and 1.39) and marginally negative Ce anomalies (Ce*SN 0.98,0.93). In contrast, dolomite samples associated with copper and cobalt mineralization show a significant rotation of the REE profile, with HREE enrichment, and La/LuSN ratios <1 (0.06–0.42). These samples also tend to show variable but predominantly negative Eu*SN and positive cerium anomalies and an upwardly concave MREE distribution (Gd-Er). Malachite samples from the Lower Orebody show roof-tile-normalized REE patterns with negative europium anomalies (Eu*SN 0.65–0.80) and negative cerium anomalies (Ce*SN 0.86–0.9). The carbonate 87Sr/86Sr signature correlates with the associated REE values. The uppermost dolomite samples show Neoproterozoic seawater-like 87Sr/86Sr ratios ranging from 0.7111 to 0.7116, whereas carbonate from Cu–Co mineralized samples show relatively low concentrations of strontium and more radiogenic 87Sr/86Sr, ranging between 0.7136–0.7469. The malachite samples show low concentrations of strontium, but give a highly radiogenic 87Sr/86Sr of 0.7735, the most radiogenic 87Sr/86Sr ratio. These new data suggest that the origin and timing of carbonate precipitation at Nchanga is reflected in the REE and Sr isotope chemistry. The upper dolomite samples show a modified, but essentially seawater-like signature, whereas the rotation of the REE profile, the MREE enrichment, the development of a negative Eu*SN anomaly and more radiogenic 87Sr/86Sr suggests the dolomite in the Cu–Co mineralized samples precipitated from basinal brines which had undergone significant fluid–rock interaction. Petrographic, REE, and 87Sr/86Sr data for malachite are consistent with the original sulfide Lower Orebody being subject to a later oxidizing event.  相似文献   

15.
Acid mine drainage is a major source of water pollution in the Sarcheshmeh porphyry copper mine area. The concentrations of heavy metals and rare earth elements (REEs) in the host rocks, natural waters and acid mine drainage (AMD) associated with mining and tailing impoundments are determined. Contrary to the solid samples, AMDs and impacted stream waters are enriched in middle rare earth elements (MREEs) and heavy rare earth elements (HREEs) relative to light rare earth elements (LREEs). This behavior suggests that REE probably fractionate during sulfide oxidation and acid generation and subsequent transport, so that MREE and HREE are preferentially enriched. Speciation modeling predict that the dominant dissolved REE inorganic species are Ln3+, Ln(SO4)2−, LnSO4+, LnHCO32+, Ln(CO3)2− and LnCO3+. Compared to natural waters, Sarcheshmeh AMD is enriched in REEs and SO42−. High concentrations of SO42− lead to the formation of stable LnSO4+, thereby resulting in higher concentrations of REEs in AMD samples. The model indicates that LnSO4+ is the dissolved form of REE in acid waters, while carbonate and dicarbonate complexes are the most abundant dissolved REE species in alkaline waters. The speciation calculations indicate that other factors besides complexation of the REE's, such as release of MREE from dissolution and/or desorption processes in soluble salts and poorly crystalline iron oxyhydroxy sulfates as well as dissolution of host rock MREE-bearing minerals control the dissolved REE concentrations and, hence, the MREE-enriched patterns of acid mine waters.  相似文献   

16.
In natural river systems, the chemical and isotopic composition of stream- and ground waters are mainly controlled by the geology and water-rock interactions. The leaching of major cations from soils has been recognized as a possible consequence of acidic deposition from atmosphere for over 30 years. Moreover, in agricultural areas, the application of physiological acid fertilizers and nitrogen fertilizers in the ammonia form may enhance the cation leaching through the soil profile into ground- and surface waters. This origin of leached cations has been studied on two small and adjacent agricultural catchments in Brittany, western France. The study catchments are drained by two first-order streams, and mainly covered with cambisoils, issued from the alteration and weathering of a granodiorite basement. Precipitations, soil water- and NH4 acetate-leachates, separated minerals, and stream waters have been investigated. Chemical element ratios, such as Ba/Sr, Na/Sr and Ca/Sr ratios, as well as Sr isotopic ratios are used to constrain the relative contribution from potential sources of stream water elements.Based on Sr isotopic ratio and element concentration, soil water- and NH4 acetate leaching indicates (1) a dominant manure/slurry contribution in the top soil, representing a cation concentrated pool, with low 87Sr/86Sr ratios; (2) in subsoils, mineral dissolution is enhanced by fertilizer application, becoming the unique source of cations in the saprolite. The relatively high weathering rates encountered implies significant sources of cations which are not accessory minerals, but rather plagioclase and biotite dissolution.Stream water has a very different isotopic and chemical composition compared to soil water leaching suggesting that stream water chemistry is dominated by elements issued from mineral and rock weathering. Agriculture, by applications of chemical and organic fertilizers, can influence the export of major base cations, such as Na+. Plagioclase dissolution, rather than anthropogenically controlled soil water, seems to be the dominant source of Na+ in streams. However, Ca2+ in streams is mostly derived from slurries and manures deposited on top soils, and transferred into the soil ion-exchange pool and stream waters. Less than 10% of Na+, 5-40% of Sr2+ and 20-100% of Ca2+ found in streams can be directly derived from the application of organic fertilizers.  相似文献   

17.
This study characterizes the nature of fluid interaction andmelting processes in the lithospheric mantle beneath the Yingfenglingand Tianyang volcanoes, Leizhou Peninsula, South China, usingin situ trace-element analyses of clinopyroxene, amphibole andgarnet from a suite of mantle-derived xenoliths. Clinopyroxenesfrom discrete spinel lherzolites exhibit large compositionalvariations ranging from extremely light rare earth element (LREE)-depletedto LREE-enriched. Trace-element modelling for depleted samplesindicates that the Leizhou lherzolites are the residues of amantle peridotite source after extraction of 1–11% meltgenerated by incremental melting in the spinel lherzolite fieldwith the degree of melting increasing upwards from about 60km to 30 km. This process is consistent with gradational meltingat different depths in an upwelling asthenospheric column thatsubsequently cooled to form the current lithospheric mantlein this region. The calculated melt production rate of thiscolumn could generate mafic crust 5–6 km thick, whichwould account for most of the present-day lower crust. The formationof the lithospheric column is inferred to be related to Mesozoiclithosphere thinning. Al-augite pyroxenites occur in compositexenoliths; these are geochemically similar to HIMU-type oceanisland basalt. These pyroxenites postdate the lithospheric columnformation and belong to two episodes of magmatism. Early magmatism(forming metapyroxenites) is inferred to have occurred duringthe opening of the South China Sea Basin (32–15 Ma), whereasthe most recent magmatic episode (producing pyroxenites withigneous microstructures) occurred shortly before the eruptionof the host magmas (6–0·3 Ma). Trace-element traversesfrom the contacts of the Al-augite pyroxenite with the spinelperidotite wall-rock in composite xenoliths record gradientsin the strength and nature of metasomatic effects away fromthe contact, showing that equilibrium was not attained. Significantenrichment in highly incompatible elements close to the contacts,with only slight enrichment in Sr, LREE and Nb away from thecontact, is inferred to reflect the different diffusion ratesof specific trace elements. The observed geochemical gradientsin metasomatic zones show that Sr, La, Ce and Nb have the highestdiffusion rates, other REE are intermediate, and Zr, Hf andTi have the lowest diffusion rates. Lower diffusion rates observedfor Nb, Zr, Hf and Ti compared with REE may cause high fieldstrength element (HFSE) negative anomalies in metasomatizedperidotites. Therefore, metasomatized lherzolites with HFSEnegative anomalies do not necessarily require a carbonatiticmetasomatizing agent. KEY WORDS: China; lithosphere; mantle xenoliths; clinopyroxene trace elements; mantle partial melting; mantle metasomatism; trace-element diffusion rates  相似文献   

18.
为了探讨青海软玉的成矿物质来源、成矿环境及成矿年代,对三岔口矿点、拖拉海沟矿点及大灶火矿点的样品进行了主量元素、微量元素、稀土元素及Ar-Ar法定年的测试。结果显示,软玉样品的主量元素变化不大,与透闪石的理论值相符;微量元素差异较大,说明不同矿点成矿环境不同;稀土元素总量较低(0.29×10-6~40.72×10-6),Eu中度负异常(0.49~0.84),除大灶火青玉样品具左倾的重稀土元素富集模式[(La/Yb)N=0.16~0.61]外,其他样品都具有右倾的轻稀土元素富集模式,(La/Yb)N=2.87~6.34。三岔口矿点、拖拉海沟矿点软玉样品的稀土元素分配曲线与纳赤台基性辉长岩相似,大灶火矿点黄玉的稀土元素分配模式与二长花岗岩相似,而青玉的分配模式与斜长花岗岩相似。样品的~TAl~(3+)、~CAl~(3+)和Ti含量变化表明,翠青玉的成矿温度最高、压力最大,黄玉成矿温度较高、压力较大;烟青玉和青玉成矿温度较高、压力较低;白玉、青白玉和糖玉成矿温度较低、压力较低。翠青玉和黄玉中明显较低的Zr/Hf、Nb/Ta和Sr/Ba值提示其成矿环境酸性明显加强。3个矿点样品的成矿年代301.38~237.28 Ma介于晚石炭世—中三叠世之间,属于印支-海西运动阶段。成矿年代均晚于侵入岩形成年代,说明矿体经历了多次热液交代过程。  相似文献   

19.
Sr isotope data from soils, water, and atmospheric inputs in a small tropical granitoid watershed in the Luquillo Mountains of Puerto Rico constrain soil mineral development, weathering fluxes, and atmospheric deposition. This study provides new information on pedogenic processes and geochemical fluxes that is not apparent in watershed mass balances based on major elements alone. 87Sr/86Sr data reveal that Saharan mineral aerosol dust contributes significantly to atmospheric inputs. Watershed-scale Sr isotope mass balance calculations indicate that the dust deposition flux for the watershed is 2100 ± 700 mg cm−2 ka−1. Nd isotope analyses of soil and saprolite samples provide independent evidence for the presence of Saharan dust in the regolith. Watershed-scale Sr isotope mass balance calculations are used to calculate the overall short-term chemical denudation velocity for the watershed, which agrees well with previous denudation rate estimates based on major element chemistry and cosmogenic nuclides. The dissolved streamwater Sr flux is dominated by weathering of plagioclase and hornblende and partial weathering of biotite in the saprock zone. A steep gradient in regolith porewater 87Sr/86Sr ratio with depth, from 0.70635 to as high as 0.71395, reflects the transition from primary mineral-derived Sr to a combination of residual biotite-derived Sr and atmospherically-derived Sr near the surface, and allows multiple origins of kaolinite to be identified.  相似文献   

20.
Appinites are commonly derived from a mantle source and are potentially significant in constraining the tectonic nature and evolution of ancient orogens, yet they have received little attention because of their limited outcrop. Here we investigate the newly identified appinitic rocks from the Laoniushan complex in the eastern Qinling Orogen. The appinites are composed of coarse-grained hornblendite, medium- and fine-grained hornblende-gabbro, and diorite porphyrite in the field occurrence. Winthin the appinitic rocks, the hornblendite displays features of cumulates. This study presents LA-ICP-MS zircon U-Pb data, mineral chemistry and whole rock geochemistry of the appinites. Zircons in the mafic to ultramafic rocks yield a U-Pb age of 152 ± 1Ma. The geochemistry of the rocks displays: lower SiO2, higher Fe2O3T and MgO contents, relatively flat chondrite normalized REE patterns with slight enrichment in light REE and a minor negative Eu anomaly; enrichment in large-ion lithophile elements(LILE, e.g. Rb, Ba, Sr and P), and depletion in high field strength elements(HFSE, e.g. Nb, Zr, Hf and Ti). Such geochemical features, together with crust-like bulk Sr-Nd isotopic compositions(initial 87Sr/86Sr ratios of 0.7057–0.7072, εNd(t) = −17.2 to −9), suggest that the Laoniushan appinites likely originated from an ancient metasomatised mantle, followed by fractional crystallization in the petrogenetic process. The studied appinites were most likely generated in an intracontinental extensional environment in the Late Mesozoic.  相似文献   

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