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1.
The dissolution kinetics of carbonate rocks sampled from the Keg River Formation in Northeast British Columbia were measured at 50 bar pCO2 and 105 °C, in both natural and synthetic brines of 0.4 M ionic strength. Natural brines yielded reaction rates of −12.16 ± 0.11 mol cm−2 s−1 for Log RCa, and −12.64 ± 0.05 for Log RMg. Synthetic brine yielded faster rates of reaction than natural brines. Experiments performed on synthetic brines, spiked with 10 mmol of either Sr or Zn, suggest that enhanced reaction rates observed in synthetic brines are due to a lack of trace ion interaction with mineral surfaces. Results were interpreted within the surface complexation model framework, allowing for the discrimination of reactive surface sites, most importantly the hydration of the >MgOH surface site. Dissolution rates extrapolated from experiments predict that CO2 injected into the Keg River Formation will dissolve a very minor portion of rock in contact with affected formation waters. 相似文献
2.
《Journal of South American Earth Sciences》2007,24(4):271-289
The major and trace element characteristics of black shales from the Lower Cretaceous Paja Formation of Colombia are broadly comparable with those of the average upper continental crust. Among the exceptions are marked enrichments in V, Cr, and Ni. These enrichments are associated with high organic carbon contents. CaO and Na2O are strongly depleted, leading to high values for both the Chemical Index of Alteration (77–96) and the Plagioclase Index of Alteration (86–99), which indicates derivation from a stable, intensely weathered felsic source terrane. The REE abundances and patterns vary considerably but can be divided into three main groups according to their characteristics and stratigraphic position. Four samples from the lower part of the Paja Formation (Group 1) are characterized by LREE-enriched chondrite-normalized patterns (average LaN/YbN = 8.41) and significant negative Eu anomalies (average Eu/Eu1 = 0.63). A second group of five samples (Group 2), also from the lower part, have relatively flat REE patterns (average LaN/YbN = 1.84) and only slightly smaller Eu anomalies (average Eu/Eu1 = 0.69). Six samples from the middle and upper parts (Group 3) have highly fractionated patterns (average LaN/YbN = 15.35), resembling those of Group 1, and an identical average Eu/Eu1 of 0.63. The fractionated REE patterns and significant negative Eu anomalies in Groups 1 and 3 are consistent with derivation from an evolved felsic source. The flatter patterns of Group 2 shale and strongly concave MREE-depleted patterns in two additional shales likely were produced during diagenesis, rather than reflecting more mafic detrital inputs. An analysis of a single sandstone suggests diagenetic modification of the REE, because its REE pattern is identical to that of the upper continental crust except for the presence of a significant positive Eu anomaly (Eu/Eu1 = 1.15). Felsic provenance for all samples is suggested by the clustering on the Th/Sc–Zr/Sc and GdN/YbN–Eu/Eu1 diagrams. Averages of unmodified Groups 1 and 3 REE patterns compare well with cratonic sediments from the Roraima Formation in the Guyana Shield, suggesting derivation from a continental source of similar composition. In comparison with modern sediments, the geochemical parameters (K2O/Na2O, LaN/YbN, LaN/SmN, Eu/Eu1, La/Sc, La/Y, Ce/Sc) suggest the Paja Formation was deposited at a passive margin. The Paja shales thus represent highly mature sediments recycled from deeply weathered, older, sedimentary/metasedimentary rocks, possibly in the Guyana Shield, though Na-rich volcanic/granitic rocks may have contributed to some extent. 相似文献
3.
The giant sediment-hosted Jinding zinc-lead deposit is located in the Lanping Basin, northwestern Yunnan Province, China. The genesis of the deposit has long been debated and the sources of the ore-forming fluids and metals are controversial. This study presents rare earth element (REE) and noble gas isotope data that constrain the origins of the ore fluids and the heat source driving the hydrothermal circulation. The early-stage sulfides are enriched in light REEs and have high ∑REE values (30.8–94.8 ppm) and weakly negative Eu (δEu 0.85–0.89) and Ce anomalies (δCe 0.84–0.95), suggesting that the fluids were likely derived from dissolution of Upper Triassic marine carbonates with input of REEs from aluminosilicate rocks in the basin. In contrast, the late-stage sulfides have irregular REE patterns, generally low ∑REE values (0.24–10.8 ppm) and positive Eu (δEu 1.22–10.9) and weakly negative Ce anomalies (δCe 0.53–0.90), which suggest that the ore-forming fluids interacted with evaporite minerals. The 3He/4He (0.01–0.04 Ra) and 40Ar/36Ar values (301–340) of the ore-forming fluids indicate crustal and atmospheric origins for these noble gases. These findings are in agreement with the published fluid inclusion microthermometry data and the results of H, O, C, S, Pb and Sr isotope studies. Our data, in combination with published results, support a two-stage hydrothermal mineralization model, involving early-stage basinal brines and late-stage meteoric water that acquired metals and heat from crustal sources. 相似文献
4.
The Ranger 1 unconformity-related uranium deposit in the Northern Territory of Australia is one of the world's largest uranium deposits and has ranked in the top two Australian producers of uranium in recent years. Mineralisation at the Ranger, Jabiluka and other major unconformity-related deposits in the Alligator Rivers Uranium Field (ARUF) occurs in Paleoproterozoic metamorphic basement rocks immediately beneath the unconformity with the Paleo- to Mesoproterozoic McArthur Basin.The sites of uranium mineralisation and associated alteration at the Ranger 1 deposit (Number 3 orebody) were fundamentally controlled by reactivated shear zones that were initiated during the regional Nimbuwah tectonothermal event. The timing of shearing at medium metamorphic grade was constrained by ion microprobe U–Pb dating of zircons in two pegmatites, one weakly foliated (1867.0 ± 3.5 Ma) and another that is unfoliated and cuts the shear fabric (1862.8 ± 3.4 Ma). The younger age of ~ 1863 Ma represents the minimum age of D1 shearing during the Nimbuwah event at the Ranger 1 deposit (Number 3 orebody). Titanite within veins of amphibole-plagioclase-apatite yielded an ion microprobe U–Pb age of 1845.4 ± 4.2 Ma, which represents a previously unrecognised hydrothermal event in the ARUF. Based on previous data, retrograde hydrothermal alteration during D2 reactivation of D1 shear zones is interpreted to have occurred at ~ 1800 Ma during the regional Shoobridge tectonothermal event.Detailed paragenetic observations supported by whole-rock geochemical data from the Ranger 1 deposit (Number 3 orebody) reveal a sequence of post-D2 hydrothermal events, as follows. (1) Intense magnesium-rich chlorite alteration and brecciation, focussed within schists of the Upper Mine Sequence in the Cahill Formation. (2) Silicification of Lower Mine Sequence carbonate rock units and overlying schist units, comprising quartz ± Mg-foitite (tourmaline) ± muscovite ± pyrite ± marcasite, and rare uraninite (early U1). (3) Formation of main stage uranium ore and heterolithic breccias including clasts of olivine–phyric dolerite, with breccia matrix composed of uraninite (U1), Mg-chlorite ± Mg-foitite and minor pyrite and chalcopyrite. (4) A second generation of uraninite (U2) veinlets with disordered graphitic carbon and quartz of hydrothermal origin. (5) Late-stage veinlets of massive uraninite (U3). As inferred in a previous study and confirmed herein, olivine–phyric dolerite dykes at Ranger are mineralised and chloritised, and are geochemically similar to the regional Oenpelli Dolerite. A maximum age for uranium mineralisation at the Ranger 1 deposit is therefore set by the age of the Oenpelli Dolerite (~ 1723 Ma).In-situ ion microprobe U–Pb analysis of texturally oldest U1 uraninite yielded a discordia array with a 206Pb/238U-207Pb/235U upper intercept age of 1688 ± 46 Ma. The oldest individual ion microprobe 207Pb–206Pb age is 1684 ± 7 Ma whereas the oldest age determined by in-situ electron microprobe chemical dating of U1 uraninite is ~ 1646 Ma. Another sample containing both U1 and U2 uraninite yielded discordant data with a 206Pb/238U–207Pb/235U upper intercept age of 1421 ± 68 Ma. When the 207Pb/206Pb ages are considered the data are suggestive of U2 uraninite formation and possible resetting of the U1 age between ~ 1420 Ma and ~ 1040 Ma. All ion microprobe analyses of U1 and U2 uraninite indicate variable and possibly repeated lead loss. In contrast ion microprobe U–Pb dating of the third generation of uraninite (U3) yielded several near-concordant analyses and a 206Pb/238U–207Pb/235U upper intercept age of 474 ± 6 Ma. This age is supported by electron microprobe chemical ages of U3 uraninite between 515 Ma and 385 Ma.The new results constrain the timing of initial uranium mineralisation at the Ranger 1 deposit (Number 3 orebody) to the period ~ 1720 Ma to ~ 1680 Ma, which just overlaps with a previous U–Pb age of 1737 ± 20 Ma for uraninite-rich whole-rock samples. Our results are consistent with individual laser-ICPMS 207Pb/206Pb and chemical ages of uraninite as old as 1690–1680 Ma reported from other deposits and prospects in the ARUF.Whole-rock geochemical data in this study of the Ranger 1 deposit (Number 3 orebody) and in other studies in the ARUF demonstrate that zones of intense chloritisation associated with uranium mineralisation experienced large metasomatic gains of Mg, U, Co, Ni, Cu and S and losses of Si, Na, Ca, Sr, Ba, K, Rb, Y and the light REE. More broadly in the ARUF, a regionally extensive illite–hematite ± kaolinite-bearing ‘paleoregolith’ zone in basement beneath the McArthur Basin exhibits depletion of about half of its uranium as well as major losses in Na, Sr, Pb, Ba and minor losses of Mg. These features together with new petrographic observations suggest this zone is a regional sub-McArthur Basin alteration zone produced by interaction with diagenetic or hydrothermal fluids of primary basinal origin, rather than representing a low-temperature paleo-weathering zone before the deposition of the McArthur Basin, as previously suggested.Based on these results and a synthesis of previous work, a new multi-stage model is proposed for the Ranger 1 ore-forming mineral system that may apply to other major unconformity-related uranium deposits in the ARUF and which may be used for targeting new deposits in the region. As in most recent models, oxidised diagenetic brines within the McArthur Basin are envisaged as crucial in mobilising uranium. However, a different architecture of fluid flow is proposed involving the sub-unconformity regional basement alteration zone as a preferential source of leached uranium. Possibly driven by convection during regional magmatism at ~ 1725–1705 Ma, oxidised basinal brines were drawn downwards and laterally through fault networks and fractures in the regional sub-unconformity alteration zone, leaching uranium from hematite-altered basement rocks. Simultaneously within deeper and lateral parts of the hydrothermal system, Mg-metasomatism produced chloritic alteration and brines with increased acidity and silica content (from the desilicification of the basement rock), analogous to processes described in sub-seafloor hydrothermal systems. Silicification occurred locally (e.g., Ranger deposit) within upflow zones of convective systems due to decreases in temperature and/or pressure of the brines and/or CO2 generation during carbonate dissolution. Interruptions to convection during transient regional extensional or strike-slip tectonic events resulted in generalised lateral and downwards flow of fluids from the McArthur Basin through deepened zones of sub-unconformity alteration, transferring leached uranium into reactivated shear zones within the basement. The main stage of uraninite precipitation at the Ranger deposit and elsewhere in the ARUF is proposed to have occurred between ~ 1720 Ma and ~ 1680 Ma as a result of reduction of oxidised and evolved basin-derived ore fluids during reaction with pre-existing Fe2 +-bearing minerals and/or mixing of the ore fluids with basement-reacted silica-rich brines.A second, volumetrically minor but locally high-grade, stage of uraninite mineralisation was associated with hydrothermal disordered carbon and quartz of presently unknown origin. Available data suggest formation between ~ 1420 Ma and ~ 1040 Ma. Almost a billion years later at ~ 475 Ma, fluids capable of mobilising uranium again resulted in uraninite (U3) deposition as sparse veinlets in the Ranger deposit, representing the first documentation of uranium mineralisation of this age in the region. 相似文献
5.
《Applied Geochemistry》1998,13(5):651-671
Highly saline fluids were encountered during the German Continental Deep Drilling Project (KTB) from depths ranging between 2 and 3 km to about 9 km. The most reliable data were obtained from samples extracted during a long-term pumping test in the 4000-m deep KTB pilot hole. Some 460 m3 Ca–Na–Cl brines with about 68 g l−1 total dissolved solids (TDS) and some 270 m3 associated gases, mainly N2 and CH4 were pumped to the surface from the main fracture system situated near the bottom of the pilot hole. Geochemical and isotopic data support the hydraulic tests which suggest the presence of an open and large fluid reservoir at depth. The pumped fluids from this main fracture system were released from a deep reservoir situated at more than 5500 m depth which is hydraulically connected with the 9101 m deep KTB main hole, drilled some 250 m to the northeast of the pilot hole.While Ca and Sr contents of the extracted brines may be the result of water–rock interaction, Cl is most likely of external origin. The Cl is hypothesized to derive from geotectonic processes rather than to descending infiltration of paleo-seawater (evaporitic brines). The sampled fluids have probably migrated from a deeper reservoir to their present position since the Cretaceous–Tertiary period due to tectonic activity. However, several isotopic studies have identified an admixture of descending paleowaters down to more than 4000 m depth. The high 36Cl/Cl ratio of the fluids sampled during the long-term pumping test point to a host rock highly enriched in U–Th, unlike the sampled KTB country rocks. The fluid reservoir is believed to be in contact with the Falkenberg granite massif situated about 2 km to the E of the KTB holes, capable of supplying sufficient neutron flux for considerable subsurface production of 36Cl. The Na–Cl–(K-, SO4) precursor fluids of the Ca–Na–Cl brines were produced in the course of extensive tectonic processes since the Late Caledonian within the Bohemian Massif. 相似文献
6.
The response to CO2 exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO2 injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO2 injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO2 and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO2; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO2, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions. 相似文献
7.
The Dalucao deposit, located in western Sichuan Province, southwestern China, in the western part of the Yangtze Craton, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE belt. Moreover, the Dalucao deposit is the only deposit identified in the southern part of the belt. The Dalucao deposit contains the No. 1, 2, and 3 orebodies; the No. 1 and 3 orebodies are both hosted in two breccia pipes, located in syenite–carbonatite host rocks. Both pipes have elliptical cross-sections at the surface, with long-axis diameters of 200–400 m and short-axis diameters of 180–200 m; the pipes extend downwards for > 450 m. No. 1 and No. 3 have total thickness varying between 55 and 175 m and 14 to 58 m respectively. The REE mineralization is associated with four brecciation events, which are recorded in each of the pipes. The ore grades in the No. 1 and 3 orebodies are similar, and consist of 1.0%–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a Type I mineral assemblage (fluorite + barite + celestite + bastnäsite), whereas the No. 3 orebody is characterized by a Type II assemblage (fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite). Argon (40Ar/39Ar) dating of hydrothermal muscovite intergrown with REE minerals in typical ores from the No. 1 and 3 orebodies yielded similar ages of 12.69 ± 0.13 and 12.23 ± 0.21 Ma, respectively, which suggest that both mineral assemblages formed coevally, rather than in paragenetic stages. Both ages are also similar to the timing of intrusion of the syenite–carbonatite complex (12.13 ± 0.19 Ma). The ore-mineral assemblages occur in breccias, veinlets, and in narrow veins. The ore veinlets, which usually show a transition to mineralized breccia or brecciated ores, are commonly enveloped by narrow veins and stringer zones with comparable mineral assemblages. The brecciated ores form 95% of the volume of the deposit, whereas brecciated ores are only a minor constituent of other deposits in the Mianning–Dechang REE belt. The carbonatite in the syenite–carbonatite complexes contains high concentrations of S (0.07–2.32 wt.%), Sr (16,500–20,700 ppm), Ba (3600–8400 ppm), and light REEs (LREE) (2848–10,768 ppm), but is depleted in high-field-strength elements (HFSE) (Nb, Ta, P, Zr, Hf, and Ti). The syenite is moderately enriched in large-ion lithophile elements (LILE), Sr (155–277 ppm), and Ba (440–755 ppm). The mineralized, altered, and fresh syenites and carbonatites exhibit similar trace element compositions and REE patterns. Brecciation events, and the Dalucao Fault and its secondary faults around the deposit, contributed to the REE mineralization by facilitating the circulation of ore-forming fluids and providing space for REE precipitation. Some hydrothermal veins composed of coarse-grained fluorite and quartz are distributed in the syenite–carbonatite complex. The oxygen isotope compositions of ore-forming fluids in equilibrium with quartz at 215 °C are − 4.95‰ to − 7.45‰, and the hydrogen isotope compositions of fluid inclusions in coarse-grained quartz are − 88.4‰ to − 105.1‰. The syenite–carbonatite complex and carbonatite are main contributors to the mineralization in the geological occurrence. Thus, the main components of the ore-forming fluids were magmatic water, meteoric water, and CO2 derived from the decarbonation of carbonatite. According to the petrographic studies, bastnäsite mineralization developed during later stages of hydrothermal evolution and overprinted the formation of the brecciated fluorite–quartz hydrothermal veins. As low-temperature isotope exchange between carbonates of the carbonatite and water-rich magmatic fluids will lead to positive shifts in δ18O values of the carbonates, C–O isotopic compositions from the bulk primary carbonatite to hydrothermal calcite and bastnäsite changed (δ18OV-SMOW from 8.0‰ to 11.6‰, and δ13C V-PDB from − 6.1 to − 8.7‰). According to the chemical composition of syenite and carbonatite, REE chloride species are the primary complexes for the transport of the REEs in the hydrothermal fluids, and the presence of bastnäsite and parisite means the REE were precipitated as fluorocarbonates. High contents of Sr, Ba and S in the syenite–carbonatite complex led to the deposition of large amount of barite and celestite. 相似文献
8.
Large quantities of highly saline brine flow from gas wells in the Marcellus Formation after hydraulic stimulation (“fracking”). This study assesses the composition of these flowback waters from the Marcellus shale in Pennsylvania, USA. Concentrations of most inorganic components of flowback water (Cl, Br, Na, K, Ca, Mg, Sr, Ba, Ra, Fe, Mn, total dissolved solids, and others) increase with time from a well after hydraulic stimulation. Based on results in several datasets reported here, the greatest concentration of Cl− in flowback water is 151,000 mg/L. For total Ra (combined 226Ra and 228Ra) in flowback, the highest level reported is 6540 pCi/L. Flowback waters from hydraulic fracturing of Marcellus wells resemble brines produced from conventional gas wells that tap into other Paleozoic formations in the region. The Br/Cl ratio and other parameters indicate that both types of brine formed by the evaporation of seawater followed by dolomitization, sulfate reduction and subsurface mixing with seawater and/or freshwater. Trends and relationships in brine composition indicate that (1) increased salt concentration in flowback is not mainly caused by dissolution of salt or other minerals in rock units, (2) the flowback waters represent a mixture of injection waters with highly concentrated in situ brines similar to those in the other formations, and (3) these waters contain concentrations of Ra and Ba that are commonly hundreds of times the US drinking water standards. 相似文献
9.
The Eocene (ca. 55–38 Ma) Bear Lodge alkaline complex in the northern Black Hills region of northeastern Wyoming (USA) is host to stockwork-style carbonatite dikes and veins with high concentrations of rare earth elements (e.g., La: 4140–21000 ppm, Ce: 9220–35800 ppm, Nd: 4800–13900 ppm). The central carbonatite dike swarm is characterized by zones of variable REE content, with peripheral zones enriched in HREE including yttrium. The principle REE-bearing phases in unoxidized carbonatite are ancylite and carbocernaite, with subordinate monazite, fluorapatite, burbankite, and Ca-REE fluorocarbonates. In oxidized carbonatite, REE are hosted primarily by Ca-REE fluorocarbonates (bastnäsite, parisite, synchysite, and mixed varieties), with lesser REE phosphates (rhabdophane and monazite), fluorapatite, and cerianite. REE abundances were substantially upgraded (e.g., La: 54500–66800 ppm, Ce: 11500–92100 ppm, Nd: 4740–31200 ppm) in carbonatite that was altered by oxidizing hydrothermal and supergene processes. Vertical, near surface increases in REE concentrations correlate with replacement of REE(±Sr,Ca,Na,Ba) carbonate minerals by Ca-REE fluorocarbonate minerals, dissolution of matrix calcite, development of Fe- and Mn-rich gossan, crystallization of cerianite and accompanying negative Ce anomalies in secondary fluorocarbonates and phosphates, and increasing δ18O values. These vertical changes demonstrate the importance of oxidizing meteoric water during the most recent modifications to the carbonatite stockwork. Scanning electron microscopy, energy dispersive spectroscopy, and electron probe microanalysis were used to investigate variations in mineral chemistry controlling the lateral complex-wide geochemical heterogeneity. HREE-enrichment in some peripheral zones can be attributed to an increase in the abundance of secondary REE phosphates (rhabdophane group, monazite, and fluorapatite), while HREE-enrichment in other zones is a result of HREE substitution in the otherwise LREE-selective fluorocarbonate minerals. Microprobe analyses show that HREE substitution is most pronounced in Ca-rich fluorocarbonates (parisite, synchysite, and mixed syntaxial varieties). Peripheral, late-stage HREE-enrichment is attributed to: 1) fractionation during early crystallization of LREE selective minerals, such as ancylite, carbocernaite, and Ca-REE fluorocarbonates in the central Bull Hill dike swarm, 2) REE liberated during breakdown of primary calcite and apatite with higher HREE/LREE ratios, and 3) differential transport of REE in fluids with higher PO43−/CO32− and F−/CO32− ratios, leading to phosphate and pseudomorphic fluorocarbonate mineralization. Supergene weathering processes were important at the stratigraphically highest peripheral REE occurrence, which consists of fine, acicular monazite, jarosite, rutile/pseudorutile, barite, and plumbopyrochlore, an assemblage mineralogically similar to carbonatite laterites in tropical regions. 相似文献
10.
《Chemie der Erde / Geochemistry》2016,76(3):353-362
Active and abandoned mine activities constitute the sources of deterioration of water and soil quality in many parts of the world, particularly in the African Copperbelt regions. The accumulation in soils and the release of toxic substances into the aquatic ecosystem can lead to water resources pollution and may place aquatic organisms and human health at risk. In this study, the impact of past mining activity (i.e., abandoned mine) on aquatic ecosystems has been studied using ICP-MS analysis for trace metals and Rare Earth Elements (REE) in sediment samples from Lubumbashi River (RL) and Tshamilemba Canal (CT), Katanga, Democratic Republic of the Congo (DRC). Soil samples from surrounding CT were collected to evaluate trace metal and REE concentrations and their spatial distribution. The extent of trace metal contamination compared to the background area was assessed by Enrichment Factor (EF) and Geoaccumulation Index (Igeo). Additionally, the trace metal concentrations probable effect levels (PELs) for their potential environmental impact was achieved by comparing the trace metal concentrations in the sediment/soil samples with the Sediment Quality Guidelines (SQGs). Spearman's Rank-order correlation was used to identify the source and origin of contaminants. The results highlighted high concentrations of trace metals in surface sediments of CT reaching the values of 40152, 15586, 610, 10322, 60704 and 15152 mg kg−1 for Cu, Co, Zn, Pb, Fe and Mn, respectively. In the RL, the concentrations reached the values of 24093, 2046, 5463, 3340, 68290 and 769 mg kg−1 for Cu, Co, Zn, Pb, Fe and Mn, respectively. The ΣREE varied from 66 to 218 and 142–331 mg kg−1 for CT and RL, respectively. The soil samples are characterized by variable levels of trace metals. The EF analysis showed “extremely severe enrichment” for Cu and Co. However, no enrichment was observed for REE. Except for Mo, Th, U, Eu, Mo, Ho and Tm for which Igeo is classified as “moderately polluted and/or unpolluted”, all elements in different sites are classified in the class 6, “extremely polluted”. The trace metal concentrations in all sampling sites largely exceeded the SQGs and the PELs for the Protection of Aquatic Life recommendation. Cu and Co had positive correlation coefficient values (r = 0.741, P < 0.05, n = 14). This research presents useful tools for the evaluation of water contamination in abandoned and active mining areas. 相似文献
11.
《Chemie der Erde / Geochemistry》2014,74(4):545-555
The abandoned Sn-W Ribeira mine, northeast of Portugal, contained quartz veins with cassiterite, wolframite, scheelite, pyrite, arsenopyrite, sphalerite, chalcopyrite, manganocolumbite, bismuthinite, native bismuth, phosphates and carbonates. The exploration took place on the northern slope of the Viveiros stream, which is an affluent of the Sabor River. The waste-rock dumps and tailings were deposited on the hillside, close to the mine and are nowadays exposed to significant weathering and erosion, as they are not vegetated. The eroded material is transported by the Viveiros stream toward the Sabor River. A seasonal stream drains the tailings. The stream sediments samples were collected along the Viveiros stream, in the seasonal stream, in a seasonal spring at the bottom of the tailings, in the Sabor River and in other streams not affected by mine workings, following the mine influence along the Viveiros stream and in the Sabor River (1.2 km away from the mine workings). The data show that the degree of pollution increases along the Viveiros stream, especially in winter. The highest degree of pollution is for As, In, W, Sn and Bi. The sediments from the drainage of the main tailings are particularly polluted during winter, by Bi, In and Sn. The sedimentary precipitate from the spring is polluted in Cu, As, In, Sn, Ta, W, Bi, Zn, Nb, Ag, Sb and Ta. The sediments from the Sabor River are significantly polluted by As, Ag, In, Sn, W and Bi. The sediments from the regional streams, Viveiros stream and Sabor River have similar REE (NASC normalized) patterns (ΣREE = 131.7–185.9 mg/kg, LaN/LuN = 1.23–1.42 and Eu/Eu* = 1.02), while those from the seasonal stream, crossing the main tailings, are enriched in REE (ΣREE = 250.3–283.6 mg/kg, LaN/LuN = 1.6–2.09 and Eu/Eu* = 0.96). The general decrease in LaN/LuN values with increase in total Fe2O3 can be explained by the partitioning of HREE to the solid Fe-oxides phase. The sedimentary precipitate and coatings, which are mainly formed by Fe-oxy-hydroxides, but also contain jarosite, are impoverished in all REE. The impoverishment can be explained by the release of REE from the surface of the Fe-oxy-hydroxides, which occurs due to a local lowering of pH, caused by jarosite dissolution. During successive alternate cycles of wet and dry conditions, takes place the formation of Fe-oxy-hydroxides and jarosite in the sedimentary precipitate and coatings. The subsequent dissolution of jarosite releases acidity, thus promoting de-sorption of REE from the Fe-oxy-hydroxides mineral phases. 相似文献
12.
The Wulaga gold deposit, located in Heilongjiang province, NE China, is a subvolcanic rock-hosted, low-sulfidation epithermal gold deposit, and has an Au reserve of about 84 tons. The gold mineralization occurs in a crypto-explosive breccia, and is spatially and temporally associated with an Early Cretaceous granodioritic porphyry. Three individual stages of mineralization have been identified in the Wulaga gold deposit: an early white quartz-euhedral vein stage, a fine-grained pyrite–marcasite–stibnite–chalcedony stage, and a late calcite–pyrite stage. The sulfur isotopic values of sulfide minerals vary in a wide range from − 4 to 4.9‰, but are concentrated in the range of − 3 to 0‰, implying that sulfur in the hydrothermal fluids was derived from magmatic volatiles. Lead isotopic results of the granodioritic porphyry (206Pb/204Pb = 18.341–18.395, 207Pb/204Pb = 15.507–15.523, 208Pb/204Pb = 38.174–38.251) and sulfide minerals (206Pb/204Pb = 18.172–18.378, 207Pb/204Pb = 15.536–15.600, 208Pb/204Pb = 38.172–38.339) are comparatively consistent and clustered together between the orogenic and upper mantle lines, indicating the lead in the ores is closely related to the parent magma of the granodioritic porphyry. The REE patterns of fluid inclusions trapped in sulfides are similar to those of the granodioritic porphyry, which confirms the magmatic origin of the REE in the hydrothermal fluids. The characteristics of S and Pb isotopes and REE suggest that the ore-forming materials of the Wulaga gold deposit are partly magmatic in origin, and related to a high-level hydrous granodioritic magma. 相似文献
13.
The Borborema Province, northeastern Brazil, occupies a central position in pre-drift reconstructions of western Gondwana, making an understanding of its geological evolution crucial for Neoproterozoic reconstructions. In recent years, it has been proposed that the Borborema Province grew by accretion of distinct tectonic terranes. In order to test this hypothesis, we compare here the geochemistry of orthogneisses and metasedimentary rocks across a proposed terrane boundary in the Central Domain of the province. Orthogneiss samples show smooth trends in Harker diagrams and similar rare earth element (REE) patterns, characterized by sharp decreases from La to Sm (chondrite-normalized La/Sm = 3–6) and flat heavy REE profiles (chondrite-normalized Tb/Yb = 1.5–2.5), with small or no Eu anomalies. In primitive mantle-normalized multi-element diagrams, all samples show parallel patterns characterized by sharp negative anomalies of U, Ta, Nb, P and Ti. The metasedimentary samples show little scatter of the major elements in Harker diagrams, suggesting that their chemistry was little affected by post-depositional diagenesis and metamorphism. They have indistinguishable chondrite-normalized REE patterns, characterized by light REE enrichment, flat heavy REE (normalized Tb/Y = 1–2) and small or no negative Eu anomalies, and similar ratios of immobile trace elements (e.g., Th/Sc, Zr/Sc). The geochemistry of the metasedimentary samples is comparable in many ways to those of the orthogneisses, suggesting that these may have been an important source of the precursor sedimentary rocks. These data do not support the terrane accretion hypothesis, rather suggesting the existence of a continuous basement that became available for erosion during intraplate continental extension in the late Neoproterozoic. Comparisons of the studied sequences with those present in the Northern Domain suggest that most, if not all of the Neoproterozoic geodynamic evolution of Borborema Province, occurred in an intracontinental setting. 相似文献
14.
Karstic bauxites in western Guangxi, China, comprise two subtypes: Permian bauxite and Quaternary bauxite. The Quaternary bauxite originated from the breaking up, rolling, and accumulating of Permian bauxite in karstic depressions in Quaternary. Various types of rare earth element (REE) minerals were discovered during the formation of the Permian and Quaternary bauxites from the Xinxu, Longhe, and Tianyang bauxite deposits in this study. Five types of REE minerals, including bastnäsite, parisite, cerianite, rhabdophane, and churchite, were identified. Bastnäsite and parisite are the most abundant, and they are widely developed in the Permian ore and also present in the Quaternary ore. Obvious variations in bastnäsite and parisite REE compositions were observed, which is ascribed to distinctions in the source materials in the primary weathering profile from different areas. The mode of occurrence of bastnäsite and parisite suggests they were mainly precipitated under alkaline and reducing conditions during the Permian bauxite-forming stage and underwent intensive corrosion in the Quaternary. Churchite was formed during the Permian weathering stage under acidic condition. Both cerianite and rhabdophane occur in fractures within the Permian bauxite ore, indicating that both formed during the Quaternary weathering stage. It is considered that the rhabdophane enriched in Ce have formed locally, in the process of that the Ce3 +, released from bastnäsite rapidly, entered the rhabdophane lattice before being oxidized to Ce4 +. Cerianite was mainly found in association with Mn–Al hydroxides, suggesting that the released Ce3 + was oxidized into Ce4 + and precipitated cerianite in fractures within the Permian bauxite ore. Mass balance equations reveal a depletion in nearly all REEs during the transformation from the Permian to the Quaternary bauxite ore, mainly caused by the dissolution of bastnäsite and parisite. The genesis of the REE minerals, together with the occurrence of other minerals, indicates that intensively acidic and oxidizing conditions developed before the formation of the Permian bauxite ore. Towards the end of the Permian, the conditions became reducing and alkaline, favorable for the large-scale bauxitization. The Quaternary bauxite-forming stage was characterized by variable pH and Eh conditions, with acidic (pH = 4–6) and oxidizing (Eh > 2) conditions at the surface of the exposed Permian bauxite ore. 相似文献
15.
Lithium-rich brine within the sub-surface of the Salar del Hombre Muerto (SHM) salt pan in the Andes of northwestern Argentina has a chemical and isotopic composition which is consistent with Li derived from several sources: the modern halite saturated lagoon, Li-rich salts and brines formed recently, and dissolution of halite which precipitated from ancient saline lakes. SHM lies in the closed basin that includes part of the massive Cerro Galán caldera which is drained by the Río los Patos, which is responsible for 90% of surface runoff into the salar. The low Li isotope composition, +3.4‰, of this river is consistent with significant contributions of geothermal spring water. As water drains through the volcaniclastic deposits which cover a large proportion of the basin, Li removal, as indicated by decreasing Li/Na, occurs but without significant isotope fractionation. This indicates a mechanism of surface sorption onto smectite or ferrihydrite rather than Li incorporation into octahedral structural sites of clays. These observations suggest that conditions in this high altitude desert have limited the dilution of hydrothermal spring water as well as the formation of clay minerals, which jointly have allowed the Li resource to accumulate rapidly. Changes in climate on a multi-millennial time scale, specifically in the hydrologic budget, have resulted in solute accumulation rates that have been variable through time, and decoupled Li and Na fluxes. Inflow to the salar under modern conditions has high Li/Na (7.9 × 10−3 by wt) with δ7Li indistinguishable from basement rocks (−0.3‰ to +6.4‰), while under pluvial climate conditions the Li/Na of the saline lake was 40 times lower than the modern lagoon (0.1–0.3 × 10−3 compared to 10.6–13.4 × 10−3) with slightly higher δ7Li, +6.9‰ to +12.3‰, reflecting the uptake of 6Li into secondary minerals which formed under a wetter climate. 相似文献
16.
《Chemie der Erde / Geochemistry》2016,76(1):13-37
The Mombi bauxite deposit is located in 165 km northwest of Dehdasht city, southwestern Iran. The deposit is situated in the Zagros Simply Fold Belt and developed as discontinuous stratified layers in Upper Cretaceous carbonates (Sarvak Formation). Outcrops of the bauxitic horizons occur in NW-SE trending Bangestan anticline and are situated between the marine neritic limestones of the Ilam and Sarvak Formations. From the bottom to top, the deposit is generally consisting of brown, gray, pink, pisolitic, red, and yellow bauxite horizons. Boehmite, diaspore, kaolinite, and hematite are the major mineral components, while gibbsite, goethite, anatase, rutile, pyrite, chlorite, quartz, as well as feldspar occur to a lesser extent. The Eh–pH conditions during bauxitization in the Mombi bauxite deposit show oxidizing to reducing conditions during the Upper Cretaceous. This feature seems to be general and had a significant effect on the mineral composition of Cretaceous bauxite deposits in the Zagros fold belt. Geochemical data show that Al2O3, SiO2, Fe2O3 and TiO2 are the main components in the bauxite ores at Mombi and immobile elements like Al, Ti, Nb, Zr, Hf, Cr, Ta, Y, and Th were enriched while Rb, Ba, K, Sr, and P were depleted during the bauxitization process. Chondrite-normalized REE pattern in the bauxite ores indicate REE enrichment (ΣREE = 162.8–755.28 ppm, ave. ∼399.36 ppm) relative to argillic limestone (ΣREE = 76.26–84.03 ppm, ave. ∼80.145 ppm) and Sarvak Formation (ΣREE = 40.15 ppm). The REE patterns also reflect enrichment in LREE relative to HREE. Both positive and negative Ce anomalies (0.48–2.0) are observed in the Mombi bauxite horizons. These anomalies are related to the change of oxidation state of Ce (from Ce3+ to Ce4+), ionic potential, and complexation of Ce4+ with carbonate compounds in the studied horizons. It seems that the variations in the chemistry of ore-forming solutions (e.g., Eh and pH), function of carbonate host rock as a geochemical barrier, and leaching degree of lanthanide-bearing minerals are the most important controlling factors in the distribution and concentration of REEs. Several lines of evidences such as Zr/Hf and Nb/Ta ratios as well as similarity in REE patterns indicate that the underlying marly limestone (Sarvak Formation) could be considered as the source of bauxite horizons. Based on mineralogical and geochemical data, it could be inferred that the Mombi deposit has been formed in a karstic environment during karstification and weathering of the Sarvak limy Formation. 相似文献
17.
《Chemie der Erde / Geochemistry》2016,76(4):659-676
The Hercynian late-orogenic granites from the Gerês massif, northern Portugal, underwent intense hydrothermal activity along tectonic structures striking N-S and NE-SW. The first hydrothermal stage is characterized by the albitization of feldspars (primary K-feldspar and plagioclase) followed by the dissolution of magmatic quartz, the chloritization of biotite, and the muscovitization of magmatic biotite and feldspars and occasionally of authigenic albite. Whole-rock geochemistry shows a decrease of SiO2, K2O and Rb and an increase of Na2O, Al2O3 and Sr amounts during the albitization. The second hydrothermal stage is characterized by a mineral assemblage consisting of secondary quartz, albite, chlorite, hematite, apatite, muscovite, epidote, sphene and carbonates, which infilled the cavities produced by the early quartz leaching.Mass balance calculations demonstrate a noticeable element mobilization during the granite alteration. The average ∑REE of the Gerês granite is nearly constant at 154 ppm, but ranges from 91 to 163 ppm in the altered rocks. A relative LREE depletion and a slight HREE enrichment associated with a negative Eu anomaly characterize the feldspathization process of Gerês granite. The average ∑REE of the Carris granite is at 159 ppm but in the altered epidote + chlorite + hematite assemblage it reaches about 201 ppm with a slight HREE increase.Two different fluids were involved in the hydrothermal alteration. A first aqueous fluid (Lw1), with a low to intermediate salinity (<10 wt.% eq. NaCl) circulated along the main structures (N-S, NE-SW and NW-SE), characterized by entrapment temperature lower than 350 °C and maximum pressure of 115 MPa followed by a later colder and more saline fluid (Lw2) under a temperature of 220 °C and a pressure of about 27 MPa.Oxygen isotope data obtained on magmatic quartz indicate δ18Oquartz of + 9.3 and + 11.0‰, pointing to an interaction of magmatic fluids with others of meteoric origin. For the secondary quartz, δ18Owater of +0.5 and +0.7‰ were calculated for a temperature of 250 °C, suggesting a meteoric fluid with a possible seawater signature.The K-Ar data of K-feldspar from the altered rocks confirm an age of 273.6 ± 11.7 Ma, attributed to the first alteration process. Younger K-Ar ages between 155.8 ± 6.7 Ma and 124 ± 5.3 Ma were also obtained in the feldspathized rocks, confirming the late hydrothermal activity.Albitization and quartz dissolution of granitic rocks from the Gerês massif occurred at depths shallower than 5 km, induced by the circulation of fluids along brittle structures, during the orogenic uplift and extensional tectonics which affected the Iberian Massif in the Early Permian. A second major event is attributed to late hydrothermal circulations of aqueous brines until a depth of about 3 km, presumably derived from interaction with sub-surface evaporites throughout Late Jurassic to Early Cretaceous. These late hydrothermal events probably reflect the rifting episodes and the rising of geothermal gradient, associated with the opening of the Atlantic Ocean and Gulf of Biscay, respectively. 相似文献
18.
The Pan-African Lufilian belt (Zambia and Democratic Republic of Congo) is known for its world-class copper and cobalt deposits. In addition, the Lufilian Copperbelt hosts several uranium occurrences concentrated within deformed siliciclastic rocks of the basal Neoproterozoic Katanga Supergroup. We report LA-ICPMS and EMP analyses of the rare earth element (REE) and yttrium (Y) abundances (designated as the REY signatures) of uranium oxides from two uranium mineralizing events of the Lufilian belt previously dated at 652 ± 8 Ma and 530 ± 6 Ma by the U–Pb method on uraninite. Uranium oxides dated at ca. 650 Ma from the External fold-and-thrust belt are characterized by (i) bell shape REE patterns centered on middle REE (MREE), (ii) positive europium (Eu) anomalies and (iii) relatively low Y contents. In contrast, uranium oxides dated at ca. 530 Ma from the Domes region are characterized by (i) REE patterns but with a less pronounced light REE (LREE) fractionation, (ii) negative Eu anomalies and (iii) higher Y contents. Moreover, the External fold-and-thrust belt also contains uranium mineralization dated at ca. 530 Ma having the same characteristics as the ca. 530 Ma uranium oxides from the Domes region (a moderately fractionated REE pattern and a negative Eu anomaly).As REY signatures are known to reflect mineralizing processes, the distinct geochemical signatures of the two uranium oxide generations (ca. 650 Ma and ca. 530 Ma) provide meaningful information about the uranium cycle during the Pan-African orogeny. Compared to the REY signatures of the known worldwide uranium deposit types, the REY signature of uranium oxides dated at ca. 650 Ma of the External fold-and-thrust belt is similar to the REE patterns from unconformity-related U deposits (Athabasca in Canada and Kombolgie in Australia). Uranium oxides of the Domes region and some of the External fold-and-thrust belt display similar characteristics to syn-metamorphic U deposit (Mistamisk in Canada). Accordingly, we propose that the two stages of uranium oxide crystallizations within the Lufilian belt, at ca. 650 and ca. 530 Ma, occurred under distinct physico-chemical conditions. The first stage, at ca. 650 Ma, may be related to late diagenesis hydrothermal processes, at the basement/cover interface, with the circulation of highly saline basinal brines linked to evaporites of the Roan Group. This Pan-African unconformity-related uranium deposit is the youngest of this type described to date. The second stage may be connected to metamorphic fluid circulations, at about 530 Ma, during the Lufilian orogeny in the Domes region and also in the External fold-and-thrust belt. 相似文献
19.
The Vergenoeg fluorite deposit in the Bushveld Complex in South Africa is hosted by a volcanic pipe-like body. The distribution characteristics, composition and formation conditions of high-field-strength element (HFSE)-rich minerals in different lithological units of the deposit were investigated by optical and cathodoluminescence microscopy, scanning electron microscopy, X-ray fluorescence, inductively-coupled plasma mass-spectrometry and electron-probe microanalysis. The Vergenoeg host rocks comprise a diverse silica-undersaturated assemblage of fayalite–magnetite–fluorite with variably subordinate apatite and mineral phases enriched in rare-earth elements (REEs). The Sm–Nd isotope systematics of the fluorite from the various lithological units of the pipe support the model that the HFSE budget of the Vergenoeg pipe was likely derived from a Lebowa-type granitic magma. Isotopically, there is no evidence for other REE sources. Formation of the pipe, including development of the fluorite mineralization, occurred within the same time frame as the emplacement of other magmatic rock units of the Bushveld Complex (Sm–Nd isochron age for fluorite separates: 2040 ± 46 Ma). Hydrothermal alteration is manifested in strongly disturbed Rb–Sr isotope systematics of the Vergenoeg deposit, but did not affect its HFSE and REE budget. Whole-rock chondrite-normalized REE + Y distribution patterns of two types were observed: (i) flat patterns characteristic of magnetite–fluorite unit, gossan, metallurgical-grade fluorite (“metspar”) plugs and siderite lenses, and (ii) U-shaped patterns showing enrichment towards the heaviest REE (Tm–Lu) observed in the fayalite-rich units. Common HFSE minerals are complex Nb-rich oxides (samarskite, fergusonite), REE phosphates and fluorocarbonates. Additionally, fluocerite and REE silicates, whose identification requires further work, were found. Most of the HFSE-rich minerals are spatially associated with Fe-rich phases (e.g., pyrite, magnetite, greenalite and hematite). To a smaller extent, they are found finely disseminated or healing micro-fractures in fluorite. The whole-rock REE + Y distribution patterns of the individual lithological units are mainly controlled by the distribution of Yb-rich and Y-rich xenotime in these rocks. The common occurrence of bastnäsite-(Ce) in the gossan, “metspar” plugs and especially in the rhyolitic carapace at the pipe–wall-rock contact, controls the REE + Y distribution patterns of these rocks. HFSE minerals in the Vergenoeg pipe rocks have formed in several stages. Samarskite and coarse fluorapatite belong to the primary mineral assemblage. Fergusonite and Yb-rich xenotime formed during high- to moderate-temperature hydrothermal activity. Significant remobilization of the HFSE from the early-crystallized minerals (breakdown of fluorapatite and possibly allanite with release of REE + Y) and subsequent partial redistribution of these elements into near surface rocks are inferred. The late-stage assemblages are characterized by the presence of fine-grained REE fluorocarbonates, monazite-(Ce), monazite-(La) and xenotime-(Y). 相似文献
20.
The F–(Ba–Pb–Zn) ore deposits of the Zaghouan District, located in NE Tunisia, occur as open space fillings or stratabound orebodies, hosted in Jurassic, Cretaceous and Tertiary layers. The chondrite-normalized rare earth element (REE) patterns may be split into three groups: (i) “Normal marine” patterns characterizing the wallrock carbonates; (ii) light REE (LREE) enriched (slide-shaped) patterns with respect to heavy REE (HREE), with small negative Ce and Eu anomalies, characteristic of the early ore stages; (iii) Bell-shaped REE patterns displaying LREE depletion, as well as weak negative Ce and Eu anomalies, characterizing residual fluids of subsequent stages. The 87Sr/86Sr ratios (0.707654–0.708127 ± 8), show that the Sr of the epigenetic carbonates (dolomite, calcite) and ore minerals (fluorite, celestite) are more radiogenic than those of the country (Triassic, Jurassic, Cretaceous, lower Miocene) sedimentary rocks. The uniformity of this ratio, throughout the District, provides evidence for the isotopic homogeneity and, consequently, the identity of the source of the mineralizing fluids. This signature strongly suggests that the radiogenic Sr is carried by Upper Paleozoic basinal fluids.The δ34S values of barite, associated to mineralizations, are close to those of the Triassic sea water (17‰). The δ34S values of sulfide minerals range from − 13.6‰ to + 11.4‰, suggesting two sulfur-reduced end members (BSR/TSR) with a dominant BSR process.Taking account of the homogeneity in the Pb-isotope composition of galenas (18.833–18.954 ± 0.001, 15.679–15.700 ± 0.001 and 38.690–38.880 ± 0.004, for the 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios respectively), a single upper crustal source for base-metals is accepted. The Late Paleozoic basement seems to be the more plausible source for F–Pb–Zn concentrated in the deposits. The genesis of the Zaghouan District ore deposits is considered as the result of the Zaghouan Fault reactivation during the Late Miocene period. 相似文献