Mass Change Calculations Research Articles

Geochemical evolution of the Doushantuo economic phosphorite in Central Guizhou, South China: Quantified multi-stage metallogenic process

Economic phosphorite from Ediacaran Doushantuo Formation is the first true phosphorite giant and represents the onset of the Precambrian-Cambrian global phosphogenic event. The Doushantuo phosphorite may have deposited during the early-middle Ediacaran (ca. 632–574 Ma) according to the latest radiochronological data. Petrographically, in central Guizhou, it can be subdivided into two types of lithofacies: pristine phosphorite (micritic phosphorite, phosphatic shale, banded phosphorites) and reworked phosphorite (intraclastic phosphorite, vuggy intraclastic phosphorite, unconsolidated phosphorite). Geochemical data show that chemical/biochemical enrichment is the most effective process to condense the phosphatic sediments and obviously improve the grade of P2O5 (can reach 38.8 wt%). Hydrodynamic reworking may not play an important role in the further enrichment of P2O5 content but effectively got rid of SiO2 and Al2O3 components in phosphorite by the removal of lighter terrigenous particles and clays. Mass change calculation shows that Ca and Mg are heavily depleted in the chemical leaching process, implying it is a key process to upgrading the quality of phosphorite by separating the carbonate constituents from phosphorite. Therefore, a multi-stage metallogenic model of chemical/biochemical enrichment, hydrodynamic reworking, and chemical leaching is proposed, quantified the composition changes and elucidated the constrained factors in the formation of high-graded phosphorite. Such a metallogenic process effectively produced high-quality phosphorite deposits and bring great benefits to metallurgy.

Mass Change Calculation of Elements in the Khut Cu Deposit, West of Yazd

Mass Change Calculation of Elements in the Khut Cu Deposit, West of Yazd

Hydrothermal alteration, lithogeochemical marker units and vectors towards mineralisation at the Svärdsjö Zn-Pb-Cu deposit, Bergslagen, Sweden

ABSTRACT The Svärdsjö Zn-Pb-Cu deposit is situated in the heavily mineralised Bergslagen lithotectonic unit of the Fennoscandian shield, south-central Sweden. Intense hydrothermal alteration followed by a strong overprint by deformation and metamorphism during the Svecokarelian orogeny complicate interpretation of the local geology. Integration of whole-rock lithogeochemical and petrographic methods has allowed the mainly dacitic volcanic host succession and effects of ore-related hydrothermal alteration to be characterised. Mineralisation is hosted by 2–15 m thick, commonly skarn-altered dolomitic marble interbeds. Zones of strong–intense hydrothermal chlorite-sericite alteration envelop the marble units, recording mass gains of Fe and Mg, as well as Na depletion. Minerals such as cordierite, anthophyllite and sillimanite formed in these rocks during regional metamorphism. Mineralisation via sub-seafloor replacement is suggested for the deposit based on alteration zoning and the irregular, stratabound, marble-hosted style of sulphide lenses. It is inferred that mineralisation formed via neutralisation of hot, acidic metalliferous fluids. Geochemically and lithologically distinct units adjacent to the mineralised zones can serve as marker units to aid further exploration in the area. Mass change calculations reveal that Fe and Mg enrichment, as well as Na depletion exhibit detectable changes extending up to 100 m from the mineralised lenses, providing exploration vectors.

Fluid source, element mobility and physicochemical conditions of porphyry-style hydrothermal alteration-mineralization at Mirkhani, Southern Chitral, Pakistan

The Cretaceous calc-alkaline granodioritic rocks in north-western Kohistan island arc host porphyry-type mineralization at Mirkhani in the Khyber Pakhtunkhwa province of Pakistan. In this paper, we present whole-rock geochemistry, mass-change calculations, and type and degree of element mobility regarding the hydrothermal mineralization-alteration processes. There are two distinct types of pyrite mineralization: (1) euhedral to subhedral pyrite (Py1) and cataclastic pyrite (Py2). To comprehend the source of hydrothermal fluids and their physicochemical conditions, trace element and S (sulfur) isotope compositions of the two types of pyrite were determined. Besides, the pyrite and silicate minerals were investigated through electron probe microanalysis (EPMA).The average low Ni (46), Zn (5), Cd (below detection level), and Bi (1) contents (in ppm), high Co/Ni ratio (>10) of both Py1 and Py2, and the range of sulfur isotope values for Py1 (−0.84‰ to 1.49‰) and Py2 (−0.93‰ to 1.84‰) indicate affiliation of the mineralization with felsic magma-derived hydrothermal fluids. The average low and high contents (ppm) of Se (0.7), As (2.6) and Zn (2), and Co (1089), respectively, in Py1 than Py2 (Se = 1.3, As = 4, Zn = 6 and Co = 747) indicates that former pyrite grains crystallized at a higher temperature than the latter, however, both types of pyrites were formed in medium to high-temperature conditions.The observed strong mobility of REE (rare earth elements) and HFSE (high field strength elements), high La/Yb ratios (avg. 23), and low (<1) Nb/La and Th/La ratios in the altered rocks reflect mobilization by slightly acidic solutions dominated by chloride and fluoride-rich complexes (±SO4 and OH). The gain-loss calculations reveal that SiO2, CaO, and TiO2 were leached out, whereas Al2O3, Fe2O3, MgO, P2O5, K2O, Cu, As, Mo, Ag, Au, Bi, and REE, HFSE, and LILE (large-ion lithophile elements) were variably added to the rocks during the hydrothermal process.Temperature calculation for chlorite formation and the type of gangue and ore mineral assemblage (epidote + sericite + albite + pyrite) implies a mineralization temperature range between ~ 215 °C and ~ 322 °C. The porphyry style of hydrothermal alteration-mineralization, trace element and S isotope composition of pyrite, and elemental gain and loss indicates that the mineralization at Mirkhani could be a part of a major porphyry Cu-Au system.

Metallogenic Characteristics and Formation Mechanism of Naomugeng Clay-Type Lithium Deposit in Central Inner Mongolia, China

A newly discovered Naomugeng lithium mineralization area is located to the east of the Central Asian Orogenic Belt (CAOB). The lithium is hosted in the volcanic rocks of the Manketou’ebo Formation. The altered volcanic rocks mainly consist of quartz, orthoclase, chlorite, montmorillonite, calcite, and dolomite. Here, we present integrated studies of petrography, mineralogy, and geochemistry of the altered volcanic rocks (with an average Li2O content of 0.43 wt.%) collected from the drilling hole and trail trench to systematically investigate the occurrence of lithium, the mineralizing processes, and the metallogenic mechanisms. The secondary minerals of the core samples are montmorillonite, chlorite calcite, and dolomite, while the secondary minerals from the earth surface ones are montmorillonite, chlorite, and calcite. The mass change calculation and isocon analysis show that the rocks received MnO, P2O5, Co, Ni, Cu, and Li and lost Na2O, K2O, MgO, rare earth elements (REE), and Rb in the alteration process. However, other elements such as Fe, V, Co, and Ca of the core samples increased while those of the earth surface ones did not change by much. Hence, there are two zones of alterations, i.e., the montmorillonization-chloritization zone and the montmorillonization-chloritization-carbonatization zone. Lithium enrichment occurs in the zone where montmorillonization and chloritization occur. The lithium is probably enriched in altered minerals such as montmorillonite and chlorite in the forms of interlayered or adsorbed ions. The slightly negative to positive Eu anomalies of the rocks can be explained by the metasomatism of hydrothermal fluid that enriched Eu. We suggest that the Naomugeng deposit is a clay-type lithium deposit and formed under a caldera setting. The meteoric and hydrothermal fluids leach the lithium from the volcanic materials and then alter the host rocks (e.g., tuff or sediments) in the caldera basin, which forms the type of lithium clay deposit. This study analyzed the migration behavior of elements in the Naomugeng lithium deposit during a hydrothermal process, which shows that the mass balance calculation has good application in reflecting the mineralization process of clay type deposit. This study also reveals the great exploration potential of the Naomugeng deposit and has important significance for further prospecting of clay-type lithium deposits in central Inner Mongolia.

Mineralogical and geochemical changes due to hydrothermal alteration of the volcanic rocks at Acoculco geothermal system, Mexico

Most of the volcanic rocks in the Acoculco geothermal system (AGS), near to the surface manifestations, are intensively altered. Thirty‐four surface volcanic rocks and five rocks from outcrop sections are considered in this work. Silica polymorphs (quartz, cristobalite and tridymite) are the dominant hydrothermal minerals in almost all the rock samples. The following other minerals are present in minor concentrations: alkali‐feldspars (sanidine potassic, anorthoclase and microcline), plagioclase feldspars (albite and anorthite), clay minerals (illite, kaolinite and montmorillonite), anhydrite, buddingtonite, titanoaugite, magnetite and anatase. This type of mineral assemblage of the rocks indicates an intensive silicic and argillic alteration. Comparison of the elemental concentrations of the surface acid rocks of the AGS with that of the precursor rock has indicated alteration‐induced changes in (a) chemical mobility in the concentrations of major element oxides, with an increase in the concentrations of SiO2, and TiO2, loss in those of Al2O3, Fe2O3, MnO, MgO, CaO, Na2O and K2O, and no statistically significant changes in those of P2O5, (b) no significant changes in the concentrations of LREE and MREE (except Dy and Ho), however, less but significant loss in the concentrations of Dy and Ho, and HREE, and (c) there is an enrichment in the concentrations of Nd, Sr, Sc, V, Nb, Ag, Sn, Pb, Tl, Ta, U and Th; and depletion in Be, Co, Zn, Ga, Ge, Rb, Y, Zr, Mo, Cs, Ba and Hf compared to those of the precursor rock. This type of distribution of the elements may indicate (a) an intense silicic alteration; and (b) REEs might have been leached from the original rocks because of hydrothermal alteration processes, but only LREEs, and MREEs (except Dy and Ho) can be redistributed and accommodated in the hydrothermal minerals, providing them with somewhat inert (immobile) behaviour. The mass change calculations have indicated that MnO and Sr have experienced the greatest and smallest mass changes, respectively. The identification of outliers in chemical data has revealed the presence of two distinctive groups of rocks. Ten out of the total 27 acid volcanic rocks with several elements as outlier data are negligibly to moderately altered (Group‐1), and the remaining 17 acid rocks without outlier data are intensively altered rocks (Group‐2).

The use of lithogeochemistry in delineating hydrothermal fluid pathways and vectoring towards gold mineralization in the Malartic district, Québec

The world-class, oxidized intrusion-related Canadian Malartic gold deposit, with reserves estimated at 5.56 Moz Au grading 1.10 g/t Au, and a total geological endowment of 16.3 Moz Au, is one of the largest gold deposits in the Archean Superior Province of Canada. The gold mineralization is hosted predominantly by Pontiac Group metasedimentary rocks, Piché Group metavolcanic rocks, and quartz monzodiorite to granodiorite porphyritic intrusions. The ore takes the form of a low-grade envelope of disseminated pyrite (0.35 to 1 g/t Au) grading inwards into higher grade (>1 g/t Au) stockwork and breccia zones. Hydrothermal alteration in the metasedimentary rocks is zonally distributed around the fluid pathways. Proximal alteration is characterized by a microcline±albite-quartz replacement-type assemblage, with lesser phlogopite, calcite±Fe-dolomite, pyrite and rutile. The distal alteration assemblage comprises biotite, microcline±albite, phengite, quartz, calcite, pyrite and rutile.In this study, we assess the magnitude and distribution of fluid-rock interaction in the metasedimentary rocks of the Malartic district. The metaturbidites are separated into four lithotypes based on grain-size to reduce the effects of primary depositional processes on mass change calculations. Despite the variability in protolith composition, the metasedimentary rocks define a geochemically consistent, cogenetic sequence. The results of the mass transfer calculations indicate progressive gains in CO2, S, K2O and LOI, as well as Au, Te, W, Ag, As, Be, Sb, Bi, Mo and Pb, from background, to distal and proximal alteration zones (relative to the least-altered samples). Molar element ratio analysis (alkali/aluminum) indicates an increase in alkali metasomatism (K and Na) adjacent to the main hydrothermal fluid pathways, which is manifested by the progressive stabilization of microcline and albite at the expense of oligoclase, biotite and white mica.Ore-associated pathfinder elements delineate broad enrichment patterns around the deposit, and are used to understand hydrothermal fluid circulation in the Malartic district. A statistical approach based on a comparison of the mass change results with the background composition provides robust constraints on the magnitude and extent of the lithogeochemical haloes. Generally, the alteration forms envelopes that extend along the S2 fabric, with the largest lithogeochemical anomalies (e.g., Au, W, Te and Ag) reaching up to 10 km in length, and 2 km in width. The results of this study demonstrate that whole-rock lithogeochemistry can provide a valuable tool with which to define vectors toward gold mineralization in a regional exploration context.

Geochemical and industrial properties of the Kejal kaolin deposit, NW Iran

The Kejal kaolin deposit, situated in the northwest of Iran, is considered a small part of the Hashtjin hydrothermal zone. The kaolinization process in this deposit has occurred in ignimbritic and volcanic tuff parent rocks in different grades such that severely kaolinized samples can be found in the middle section of the kaolinization profile. Kaolinite is the most abundant clay mineral in the studied samples. Quartz and cristobalite are the main minerals while anatase is the minor mineral of the kaolin samples. Among the major oxides, SiO2, Al2O3, and TiO2 show the highest concentrations in kaolin samples. The mass change calculations based on Ti show enrichment of Si, Al, Sr, and LREEs and depletion of alkali and alkali earth elements, HREEs, and HFSEs. The evaluation of REEs normalized to chondrite represents the higher concentration of LREEs comparing to HREEs. A remarkable positive Gd anomaly is seen in spider diagrams, which can be attributed to the primary CaO in the composition of ignimbritic precursor and also the Gd release due to the decomposition of Gd complexes and adsorption by clay minerals. The Eu negative anomaly is the other obvious characteristic of the studied samples and is most likely related to the alteration of feldspars, decomposition of plagioclase, and Eu liberation from the system. The significant positive correlations between REEs and Al2O3, TiO2, and P2O5 demonstrate the important role of clay minerals, REE-bearing phosphate minerals such as monazite, and titanium minerals like anatase and rutile in the kaolinization process and REE transport and establishment. The performed particle size test based on the hydrometer method shows about 20% of particles <2 μm and 36%-42% of particles <25 μm, which reveals a dominant medium particle size for these kaolin samples. Furthermore, the chemical composition of the analyzed samples represents around 20% alumina. Based on the obtained physicochemical evaluations, the Kejal kaolin deposit is medium- to low-grade kaolin, which is useable after simple processing in the paper industry as filler and in the ceramic industry as floor tiles.

Sea-level fingerprints emergent from GRACE mission data

Abstract. The Gravity Recovery and Climate Experiment (GRACE) mission data have an important, if not revolutionary, impact on how scientists quantify the water transport on the Earth's surface. The transport phenomena include land hydrology, physical oceanography, atmospheric moisture flux, and global cryospheric mass balance. The mass transport observed by the satellite system also includes solid Earth motions caused by, for example, great subduction zone earthquakes and glacial isostatic adjustment (GIA) processes. When coupled with altimetry, these space gravimetry data provide a powerful framework for studying climate-related changes on decadal timescales, such as ice mass loss and sea-level rise. As the changes in the latter are significant over the past two decades, there is a concomitant self-attraction and loading phenomenon generating ancillary changes in gravity, sea surface, and solid Earth deformation. These generate a finite signal in GRACE and ocean altimetry, and it may often be desirable to isolate and remove them for the purpose of understanding, for example, ocean circulation changes and post-seismic viscoelastic mantle flow, or GIA, occurring beneath the seafloor. Here we perform a systematic calculation of sea-level fingerprints of on-land water mass changes using monthly Release-06 GRACE Level-2 Stokes coefficients for the span April 2002 to August 2016, which result in a set of solutions for the time-varying geoid, sea-surface height, and vertical bedrock motion. We provide both spherical harmonic coefficients and spatial maps of these global field variables and uncertainties therein (https://doi.org/10.7910/DVN/8UC8IR; Adhikari et al., 2019). Solutions are provided for three official GRACE data processing centers, namely the University of Texas Austin's Center for Space Research (CSR), GeoForschungsZentrum Potsdam (GFZ), and Jet Propulsion Laboratory (JPL), with and without rotational feedback included and in both the center-of-mass and center-of-figure reference frames. These data may be applied for either study of the fields themselves or as fundamental filter components for the analysis of ocean-circulation- and earthquake-related fields or for improving ocean tide models.

Mineralogical and geochemical features of karst bauxites from Poci (western Henan, China), implications for parental affinity and bauxitization

The Poci bauxite deposits in western Henan, China, are hosted in the lower member of Upper Carboniferous Benxi Formation, unconformably overlying upon the paleokarst surface of the Ordovician Majiagou Formation. The orebodies comprise a high-grade bauxite horizon (characterized by the association of diaspore-illite-anatase) and a basal iron-rich horizon (diaspore-goethite-hematite-illite-anatase), sandwiched between the overlying clayey layer (illite-diaspore-goethite-anatase) and the underlying clayey layer (illite-diaspore-microcline-goethite). Geochemical investigations reveal that Rb, Cs, Ba, Cu, Zn are depleted, while B, Ga, Bi, V, Sc, Zr, Hf, Nb, Ta, W, U and Th are enriched in bauxite horizons. B is highly enriched in bauxite ores and clays (contents 176–1061 ppm) and positively associated with SiO2, indicating B is mainly hosted in clay components, e.g. dominantly illite, which are considered a mixture of authigenic minerals transformed from kaolinites during diagenesis and unaltered detrital minerals. Mass change calculations reveal that Hf, Zr, Nb, Ta, U, Th, Sc, Cr, and Ga are stable relative to TiO2 during the bauxitization process, indicating these elements are mainly associated with anatase and diaspore. The bauxite horizons and the underlying clays are more enriched in total REE contents (ΣREEs) and display more intense LREE/HREE fractionation than the overlying clays. Provenance analysis shows that parental materials of Poci bauxites were mainly derived from felsic-dominated igneous rocks along the southern margins of the North China Craton, with minor contribution from siliciclastic sedimentary rocks and argillaceous components of underlying carbonates. A conceptual model is proposed for the formation and evolution of Poci bauxites. Uplift caused by the North Qinling orogenesis along the southwestern margin of NCC led to the formation of karstic topography, allowing aluminum-rich source materials to be transported to the low karst plain and transformed into incipient bauxites under hot and humid tropical conditions. When the platform was submerged, Fe2+ ions were released from Fe/Al oxides/hydroxides under the reducing conditions associated with bacteria activity in an organic-rich environment, and redeposited as pyrites and siderites, generating a high-grade bauxite horizon and an iron-rich bauxite horizon. This marine modification resulted in further aluminum enrichment of bauxite ores.

Extreme alteration in an acid-sulphate geothermal field: Sulphur Springs, Saint Lucia

Sulphur Springs is a vigorous geothermal field associated with the Soufrière Volcanic Centre in southern Saint Lucia. Intensely altered rocks occur over an area of at least 200 × 400 m, together with bubbling hot pools and fumaroles. The pools are sodium‑calcium-sulphate type, with pHs of 3–7 and temperatures of 41–97 °C. Fumaroles have temperatures up to, and at times above 100 °C. Gases collected from both fumaroles and bubbling pools have high contents of CO2 (601–993 mmol/mol) and commonly high H2S (3–190 mmol/mol).Least-altered host rocks surrounding Sulphur Springs comprise calc-alkaline, feldspar-quartz-porphyritic dacites of near-uniform chemical composition. These rocks, which form massive domes and volcaniclastic units, were emplaced 13–30 ka ago (Lindsay et al., 2013). Within the geothermal field, the dacites have been moderately to highly altered to acid-sulphate assemblages of kaolinite, illite, smectite, alunite, natroalunite, cristobalite, opaline silica, native sulphur, jarosite and amorphous compounds. Muddy sediments from grey to blackish thermal pools additionally contain iron sulphides.Despite intense alteration of the volcanic rocks (and derived volcaniclastic sediments), Zr and Ti have remained essentially immobile, which allows identification of the precursors (dacites) and calculation of mass changes. Many of the altered rocks and sediments show major depletions of Fe, Mg, Ca, Na. Extremely altered samples additionally show notable losses of Al, P, K, REE and Y, implying leaching by highly acidic waters. A few of the highly altered rocks, however, have gained Al, together with P, presumably due to neutralization or evaporation of acidic thermal waters. Also present within the geothermal field are metre-scale zones with very high contents of silica and native sulphur, and <1% Al2O3. Based on mass change results, the silica in the silica-sulphur zones, although recrystallized, was mainly inherited from the precursor dacites, rather than added as new hydrothermal precipitates.Surface thermal waters define a linear trend in a plot of δ18O vs. δD, and reach high levels of isotopic enrichment. The enrichment trend is ascribed to progressive evaporation in the thermal pools. The low slope of the isotopic trend (1.4) is interpreted as being due to surficial mixing between meteoric waters and steam condensates derived at about 230 °C from the deep brine that underlies the geothermal field. The whole-rock O-H-isotopic composition of four highly altered samples (kaolinite-smectite-opal-sulphates) can be accounted for if the alteration fluid was a 50:50 mixture of steam and meteoric water, and alteration occurred at 50–125 °C. Whole-rock δ34S values of samples containing variable amounts of sulphates, sulphides and native S are all notably negative (−5 to −16‰), consistent with derivation of sulphur from volcanic gases such as SO2 and H2S. Altered rocks and thermal pool sediments in the geothermal field are commonly enriched in Hg and Se (up to 50 mg/kg).At Sulphur Springs, primary dacitic rocks have been chemically and mineralogically transformed by reaction with acidic waters that formed when uprising volcanic gases condensed into neutral meteoric waters. In many cases, this has led to substantial mass losses or gains in Al, P and REEs. Regardless of the degree of alteration, however, the precursor rocks can still be identified using Ti-Zr relations.

Hydrothermal fault zones in the lower oceanic crust: An example from Wadi Gideah, Samail ophiolite, Oman

Hydrothermal circulation is a key process for chemical and isotopic exchange between the solid Earth and oceans, and for the extraction of heat from newly accreted crust at mid-ocean ridges. However, due to a dearth of samples from intact oceanic crust, or continuous sample suites from ophiolites, there remain major shortcomings in our understanding of hydrothermal circulation in the oceanic crust, especially in the lower plutonic crust. In particular, it remains unknown whether fluid recharge and discharge occurs pervasively or if it is mainly channelled within discrete zones such as faults.Here, we describe a hydrothermally-altered fault zone that crops out in the Wadi Gideah in the layered gabbro section of the Samail ophiolite of Oman. A one metre thick normal fault comprising deformed chlorite ± epidote fault rock with disseminated chalcopyrite and pyrite, offsets gently dipping layered olivine gabbros. The chlorite-rich fault rocks surround strongly altered clasts of layered gabbro, 50 to 80 cm in size. Layered gabbros in the hanging wall and the footwall are partially altered and abundantly veined by epidote, prehnite, laumontite and calcite veins. In the wall rocks, igneous plagioclase (An82±2%) is partially altered towards more albitic compositions (An75-81), and chlorite + tremolite partially replaces plagioclase and clinopyroxene. Clinopyroxene is moderately overgrown by Mg-hornblende.Whole rock mass change calculations show that the chlorite-rich fault rocks are enriched in Fe, Mn, H2O + CO2, Co, Cu, Zn, Ba, and U, but have lost significant amounts of Si, Ca, Na, Cr, Ni, Rb, Sr, Cs, light rare earth elements (LREE), Eu, and Pb. Gabbro clasts within the fault zone as well as altered rock from the immediate hanging wall show enrichments in Na, volatiles, Sr, Ba and U and depletions of Si, Ti, Al, Fe, Mn, Mg, Ca, Cu, Zn, Rb, Cs, LREE, and Pb. Chlorite thermometry suggests a formation temperature of 300–350 °C for the fault rock and based on the Si loss and solubility of silica in hydrothermal fluids the intensity of alteration requires a fluid to rock ratio of up to 900:1. Strontium isotope whole rock data of the fault rock yield 87Sr/86Sr ratios of 0.7043–0.7048, which is considerably more radiogenic than fresh layered gabbro from this locality (87Sr/86Sr = 0.7030–0.7033), and similar to black smoker hydrothermal signatures based on epidote, measured from epidote veins in the footwall and elsewhere in the ophiolite (87Sr/86Sr = 0.7043–0.7051). Altered gabbro clasts within the fault zone show similar values with 87Sr/86Sr ratios of ~0.7045–0.7050. In contrast, the hanging and footwall gabbros display values only slightly more radiogenic than fresh layered gabbro. The elevated strontium isotope composition of the fault rock and clasts together with the observed secondary mineral assemblages and calculated mass changes strongly supports the intense interaction with seawater-derived up-welling hydrothermal fluids, active during oceanic spreading. Assuming that such a fault zone is globally representative of faulting in the lower crust, an extrapolation of our results from mass change calculations to elemental fluxes, shows a significant contribution to the global hydrothermal budgets of Si, Ti, Fe, Mn, Mg, Ca, H2O, Cu, Zn, Sr and Cs.

Hydrothermal processes at the Axi epithermal Au deposit, western Tianshan: Insights from geochemical effects of alteration, mineralization and trace elements in pyrite

As the largest low-sulfidation (LS) epithermal deposit in the Tulasu basin, western Tianshan, NW China, the Axi gold deposit has a poorly understood geologic history. It is not clear whether hydrothermal mineralization occurred during a single event or multiple events. In this paper, new data consist of whole rock geochemistry and mass-change calculations for hydrothermal alteration. LA-ICP-MS trace element analysis of pyrite was conducted in order to develop a comprehensive metallogenic model. The pyrite-sericite-quartz alteration at the Axi deposit is characterized by replacement of plagioclase and mafic phenocrysts by sericite, quartz, pyrite (py1), smectite, and illite, indicating slightly acidic and reducing conditions during the early ore stage. Medium subhedral pyrite crystals (py1) with porous texture are typically sited adjacent to iron-rich minerals (e.g., hornblende) and are characterized by Co-Ni-Mn enrichment with high ratios of Co/Ni (avg. 1.114) and Cu/As (avg. 0.655), implying preferential sulfidation reactions in magmatic hydrothermal systems. The quartz ± calcite ± pyrite ± adularia assemblages in silicified rocks and the strong mobility of LREE both reflect a slightly acidic chloride-rich solution phase during the later ore stage. Coarse anhedral pyrites with cataclastic texture (py2) and medium euhedral pyrites (py3) have a mixed hydrothermal origin and were deposited with quartz during Au-pyrite-quartz and Au-polysulfide-quartz stages, respectively. Py2 and py3 both have significantly lower Cu/As ratios (avg. 0.103 and avg. 0.088, respectively) than py1, indicating the input of meteoric fluid during the later ore stage. The three generations of pyrite, especially py3, have significant lattice-bound gold contents (py1: 0.01–38.86 ppm, median 1.51 ppm; py2: 0.03–234.37 ppm, median 1.21 ppm; py3: 3.31–231.56 ppm, median 42.72 ppm). Gold precipitation is associated with the destabilization of Au-bearing chlorine (Au(Cl)2−) and bisulfide complexes (Au(HS)2−) via sulfidation and fluid boiling. All of these characteristics indicate the Axi epithermal deposit is the result of two stages of mineralization.

Petrography, mineralogy, geochemistry and genesis of the Balaya bauxite deposits in Kindia region, Maritime Guinea, West Africa

The Balaya bauxite plateau is located in the Kindia bauxite province; where the bauxite ores are found above Ordovician and Silurian formations in the southern part of the Guinean Paleozoic Bove Basin, West African Craton. In this study, petrographical, mineralogical and geochemical investigations were carried out on the different type of bauxites (sedimentary and lateritic) of this plateau. Mineralogical analysis and petrological study revealed that the mineralogy is almost identical in both bauxite types of the Balaya plateau. Gibbsite (ave. 83.90%), goethite and aluminous goethite are the major mineral components; anatase, rutile, diaspore and kaolinite are minor minerals, with zircon and clastic quartz as accessory minerals in the bauxites. Whole rock and trace elements analysis show that the main components of the Balaya bauxites ore are Al2O3 (49.70–61.00 wt%), SiO2 (0.30–5.00 wt%), Fe2O3 (1.60–19.00 wt%), and TiO2 (1.71–3.70 wt%). Trace elements investigation indicates that HFSEs, Ti, Cr, Ga, Sn, HREE were immobile and specifically enriched; whereas alkalis and alkaline earth metals were depleted, in bauxites during lateritization. Geochemical paths of dismantlement, immobile element ratios (Zr vs Hf, Nb vs Ta and Yb vs Lu; and Cr/Ni) and REE patterns of the bauxites indicate that they were all originated from the destruction of the kaolinite by a deep of lateritization, through an indirect bauxitization of the Silurian argillites and siltstones of the Télimélé Suite. Thus, Balaya sedimentary bauxites were further formed by redeposition from these lateritic bauxites, by different mechanical transportation. Pearson correlation and mass change calculations revealed that Ti-bearing and Fe-bearing minerals are the carrier for HREE, HFSE, Sn, U, Ga, W and Y; and Mo, Cu, Pb, As, Sb and Bi respectively. P-bearing minerals and kaolinites could have played signifiquent roles in LREE concentration, but the possible presence of authigenic minerals such as strontianite, celestite or florencite bearing the LREE are expected.

Geology and geochemistry of the Xiaoshanba bauxite deposit, Central Guizhou Province, SW China: Implications for the behavior of trace and rare earth elements

In China, bauxite is mainly of the karst type. Karst bauxite deposits in Central Guizhou are widely distributed in the Qingzhen, Xiuwen, and Zunyi districts. The Xiaoshanba deposit is located in the Xiuwen district and is hosted in the Lower Carboniferous Jiujialu Formation. It shows parallel unconformity with the overlying and underlying strata. The main chemical contents of the bauxite ore in the Xiuwen district is Al2O3 (55.7 to 73.5 wt%), followed by SiO2, Fe2O3, TiO2, CaO, MgO, S, P, etc. There are obvious enrichments in rare earth elements (REEs) and immobile trace elements (such as Ti, Nb, Zr, Hf, Ta, and Th) in the Al-bearing rocks.The mass change calculation (MC) is an effective means of investigating the relative mobility of elements. Here we present the multiples of mass change calculation (MMC), which represents an improvement over the MC, and is effective for element mobile investigations. The MMC results for REEs of the Xiaohsanba Al-bearing rocks showed grouping phenomenon, in which REEs were divided into four groups (Group A: La–Ce–Pr–Nd; Group B: Pm–Sm–Eu–Gd; Group C: Gd–Tb–Dy–Ho, and Group D: Er–Tm–Yb–Lu) and showed different fractionation trends in the MMC curves. The tetrad characteristic of the REEs (tetrad effects) most likely induced the special grouping phenomenon. During bauxite mineralization, REE fractionations caused by mineral control, especially the widespread distribution of accessory minerals that are rich in REEs such as Ti-dioxide minerals (i.e., TiO2 such as rutile and anatase) and zircon, and water–rock interactions resulted in the REE grouping phenomenon in the Xiaoshanba profile.The majority of these immobile elements tend to concentrate in the accessory minerals of bauxite, and barely any elements (except Li and Ga) seem associated with the ore-forming minerals. For instance, Ti-dioxide minerals played an important role in the accumulation of some elements, such as Ti, V, Nb, and Ta. Another important mineral was zircon, which is rich in Zr, Hf, and Th, etc. In general, there were two main factors that influence the content of immobile elements in the karst bauxite profile: (a) the chemical composition of the precursor rock (the higher the content of immobile elements in the parent rock, the higher the content of accessory minerals and immobile elements in bauxite), and (b) the weathering degree of the precursor rock (the stronger the degree of weathering, the higher the content of accessory minerals and immobile elements in bauxite).

Geochemical behavior during mineralization and alteration events in the Baiyinchang volcanic-hosted massive sulfide deposits, Gansu Province, China

The Zheyaoshan deposit is the largest within the Baiyinchang (BYC) volcanic-hosted massive sulfide (VHMS) district, located in the northern Qilian orogenic belt of North China. The deposit is hosted by quartz keratophyre tuffs, with wall-rock alteration mainly comprising chlorite, sericite, quartz, pyrite and epidote. Mineral assemblages within the altered host rocks can be divided into a sericite-quartz-dominant assemblage (sericite-silicified zone), a chlorite-dominant assemblage (chlorite-dominant zone) and a pyrite-dominant assemblage (mineralized zone) based on geochemical analysis and alteration characteristics. We have conducted detailed processing and critical analysis of the geochemical data of both the altered and least-altered host rocks in order to investigate the problem of closure in the geochemical dataset to eliminate the influence that each component has on the other in terms of mass change, and have applied the standardized method of the mass change calculation to analyze this data. The results show that: (1) the sericite-silicified zone formed along fissures due to the ingress of hydrothermal fluids, with MnO2, Na2O and CaO being mobilized into the hydrothermal fluids leached and MgO, Fe2O3, SiO2, K2O, BaO deposited. Additionally, Ag, Cu and chalcophile elements (Ag, As and Bi) were enriched while Pb, Zn and large ion lithophile elements (LILEs) (Cs, Sr, Eu, Be) were mobilized into hydrothermal fluids; (2) the physiochemical conditions and pH levels of the hydrothermal fluids changed during sericitization, with MgO, Fe2O3, BaO being further enriched and MnO, Na2O, CaO further depleted, leading to formation of chlorite and the initial precipitation of metallogenic the (Cu, Zn, Pb) and chalcophile elements (Ag, As, Bi); (3) the negative Eu anomaly was mainly due to its strong activity when Eu is mobilized into the hydrothermal fluids during since plagioclase break-down during the sericite-silicification process; (4) AI and CCPI values gradually increase towards the orebody. The chlorite-dominant assemblage and sericite-quartz-dominant assemblage on the periphery of the chlorite-dominant zone can all be used as vectors towards the volcanic massive sulfide orebody and for regional-scale mineral exploration. Either leached elements or enriched elements can be considered as significant indicator elements and as prospective indicators for geochemical exploration within the BYC district. The Eu anomaly may be especially useful as an indicator for distinguishing the least-altered rocks which has great significance for exploration on the regional scale.

Quantifying weathering on variable rocks, an extension of geochemical mass balance: Critical zone and landscape evolution

AbstractWe present a statistical model of soil and rock weathering in deep profiles to expand the capacity to assess weathering to heterogeneous bedrock types, which are common at the Earth's surface. We developed the Weathering Trends (WT) model by extending the fractional mass change calculation (tau) of the geochemical mass balance model in two important ways. First, WT log transforms the elemental ratio data, to discern the log‐linear patterns that naturally develop from thermodynamic and kinetic laws of chemistry. Second, WT statistically fits log‐transformed element concentration ratio data – log(cj/ci), the only depth‐varying term in tau – as a function of depth to determine characteristic depths of transitions in weathering processes, along with confidence intervals. With no prior assumptions, WT estimates average parent material composition, average composition of the upper weathered zone and mean fractional mass change of each element over the entire weathering profile. WT displays the mean shape of weathering profiles of log‐transformed geochemical data bounded by calculated confidence intervals. We share the WT model code as an open‐source R package (https://github.com/fisherba/WeatheringTrends). The WT model was designed to interpret two 21 m cores from the Laurels Schist bedrock in the Christina River Basin Critical Zone Observatory in the Pennsylvania Piedmont, where our morphological and elemental data provided inconclusive estimates of bedrock depth. The WT model differentiated between rock variability and weathering to delineate the maximum extent of weathering at 12.3 m (CI 95% [9.2, 21.3]) in Ridge Well 1 and 7.2 m (CI 95% [4.3, 13.0]) in Interfluve Well 2. The water table was 5–8 m below fresh rock at Ridge Well 1, but at the same depth as fresh rock at the lower elevation interfluve. We assess statistical approaches to identify the best immobile element for use in WT and tau calculations. Copyright © 2017 John Wiley &amp; Sons, Ltd.

Mineralogical and geochemical evolution of the Bidgol bauxite deposit, Zagros Mountain Belt, Iran: Implications for ore genesis, rare earth elements fractionation and parental affinity

The present study focuses on the Late Cretaceous Bidgol bauxite deposit in the Zagros Simply Fold Belt, SW Iran. The orebody is located in the eroded major NW–SE trending Koh-e-Hosseyn anticline and hosted as discontinuous stratified layers and lenses within the upper member of the Cenomanian–Turonian Sarvak Formation. Detailed mineralogical analysis reveals that diaspore, hematite, goethite, anatase, clinochlore, chamosite, and calcite are the major mineral components accompanied by minor amounts of detrital and REE-bearing minerals such as rutile, zircon and parisite. The ore texture suggest that the bauxite material has an authigenic origin but in some parts it has been transported short distances from a primary in situ environment and redeposited in karstic depressions. The spheroidal pisolites of the Bidgol bauxite formed under conditions of low water activity, favouring the formation of large diaspore cores and a single dry-to-wet climatic fluctuation. The mass change calculations relative to the immobile element Ti show that elements such as Si, Fe, Mg, K, Na and Sr are leached out of the weathered system; Al, Ni, Zr, Ga, Cr and Ba are concentrated in the residual system; and Hf, Ta, Co, Rb, Cs, Be, and U are relatively immobile during the bauxitisation processes. The Nb, Th, Y, V, Sc, Sn and ΣREE are relatively immobile in the initial stage of bauxitisation processes in the bauxite ores, but were slightly mobile at the later stage of bauxitisation. Geochemical data reveal progressive enrichment of the REE and intense LREE/HREE fractionation toward the lower parts of the bauxite profile. Cerium behaves differently from the other REEs (especially LREE) and show positive anomalies in the upper horizons that gradually become negative in the deeper parts of the profile. The distribution and fractionation of trace elements and REEs during the bauxitisation process in the Bidgol deposit are mainly controlled by the presence of REE-bearing minerals, fluctuations in soil solution pH, REE ionization potential and the presence of bicarbonates or organic matter. Geochemical analyses confirm a protolith contribution from the bedrock argillaceous limestone and suggest that the source material for the Bidgol bauxite was provided from a siliciclastic material derived from a continental margin. The mid-Turonian uplift led to the formation of karstic topography, rubbly breccia and a layer of ferruginous–argillaceous debris that was affected by lateritic weathering under humid tropical climate. Subsequently, mobile elements are removed from the profiles, while Al, Fe and Ti are enriched, resulting in the formation of the pristine bauxite materials. When the platform subsided into the water again, the pristine bauxitic materials were partly converted to bauxite. During the exposure of bauxite orebodies on the limbs and crests of anticlines and subsequent eroding and accumulation in the karstic depressions during folding and faulting in Oligocene–Miocene, important factors such as intensity of the weathering, drainage and floating flow may have improved the qualities of the bauxite ores.

Geochemical characteristics of the Arabshah kaolin deposit, Takab geothermal field, NW Iran

The Arabshah kaolin deposit (Takab geothermal field, NW Iran) is the product of alteration of Miocene dioritic rocks. According to mineralogical data, the rock-forming minerals in this deposit include kaolinite, quartz, muscovite-illite, pyrophyllite, accompanied by lesser amounts of rutile, chlorite, anatase, albite, gypsum, nontronite, and pyrite. Consideration of elemental ratios and geochemical indices such as TiO2, Nb + Cr, Ti + Fe, Sr + Ba, and La + Ce + Y demonstrated that both hypogene and supergene processes played a significant role in the development of this deposit. The mass change calculations revealed that elements like Zr, Ga, Hf, REEs, and Th which are normally immobile in ordinary alteration processes had both incremental and decremental trends during the development of this deposit. The Eu and Ce anomaly values (normalized to chondrite) in kaolinized samples vary within the range of 0.65–1.13 and 0.91–1.05, respectively. It seems that the variation of negative Eu anomaly values was controlled by kaolinization of feldspars by hypogene solutions and by scavenging of this element by Fe oxides and hydroxides (formed during oxidation of hypogene pyrite by supergene solutions). Variation of Ce anomalies also unravels the effective role of reducing hypogene fluids and to some extent of supergene solutions during kaolinization. Combination of the results obtained from mineralization considerations, mass change calculations of elements, and correlation coefficients illustrate that distribution and concentration of major, minor, and rare earth elements during kaolinization at Arabshah were affected by the function of factors such as changes in physico-chemical conditions of altering solutions (e.g., Eh and pH), adsorption, accessibility to complex-forming ligands, water-rock ratios, existing in resistant (to alteration) mineral phases, and scavenging by Fe and Mn oxides.

Geology, alteration, and lithogeochemistry of the Hood volcanogenic massive sulfide (VMS) deposits, Nunavut, Canada

The Hood volcanogenic massive sulfide (VMS) deposits are hosted by the ~2.68 Ga Amooga Booga volcanic belt (ABVB) in the northwestern Archaen Slave Craton and consist of three deposits (Hood 10, 41, and 41A) and three occurrences (46, 461, and 462). The mineralized zones consist of massive to semi-massive pyrrhotite, pyrite, chalcopyrite, sphalerite, and galena hosted predominantly by felsic volcanic flows within the predominantly mafic ABVB. The mineralized lenses occur at different stratigraphic levels and have textural, alteration, and stratigraphic features consistent with formation via subseafloor replacement. The felsic volcanic rocks in the Hood deposits can be subdivided into groups based on immobile trace element geochemistry. The main felsic types (A and B) are petrographically indistinguishable. Type A has higher high field strength element (HSFE) and rare earth element (REE) contents than type B, suggesting a higher temperature of formation. Type A rocks also have higher Nb/Ta values indicative of a greater mantle input in their genesis compared to type B rocks. Mineralization is more closely associated with type A than type B rocks. The two mafic volcanic rock types previously identified in the ABVB, type I and type II, both occur within the Hood deposits. The type II mafic group is interpreted to be the result of variable crustal contamination of type I magma. The volcanic rocks of the ABVB are interpreted to have formed in a continental margin arc/back-arc setting. The genesis of these magmatic suites involved magmatic underplating and emplacement through pre-existing sialic basement that resulted in crustal melting, mantle-crust mixing, and contamination leading to the aforementioned geochemical features in both mafic and felsic suites. This type of extensional tectonic environment was likely associated with high heat flow and is similar to global VMS environments proximal to extending continental margins (e.g., Sturgeon Lake, Bathurst, and Finlayson Lake). The similarities of the ABVB to other Slave Craton greenstone belts further highlights the overall potential for greenstone-hosted VMS mineralization in the Slave Craton. Chlorite-sericite (+/− quartz) is the dominant hydrothermal alteration assemblage in the Hood deposits and is typical of VMS-style mineralization. Mass change calculations illustrate that elemental changes are typical of VMS environments with gains in Fe2O3, MgO, and base metals associated with chlorite alteration near mineralized zones; K2O gains associated with sericite alteration; and losses of Na2O in both alteration types.