Geochemical challenges of diverse regolith-covered terrains for mineral exploration in China

In recent years mineral exploration has concentrated on concealed deposits in regolith-covered terrains. In China, the regolith-covered landscapes mainly include desert windblown sand basins, desert peneplains, semi-arid grassland, loess plateaus, forestry land, alluvial plains and laterite terrains. These diverse regolith-covered areas represent geochemical challenges for mineral exploration in China. This paper provides an overview of recent progress on mechanisms of metal dispersion from the buried ore deposits through the transported cover to the surface and penetrating geochemical methods to detect the anomalies. Case studies show that, in arid and semi-arid desert sand-covered terrains, sampling of fine-fraction (− 120 mesh, < 0.125 mm) clay-rich horizon soil is cost-effective for regional geochemical surveys for sandstone-type uranium, gold, and base metal deposits. Fine-fraction sampling, selective-leaching and overburden drilling geochemical methods can effectively indicate the 210 gold ore body at Jinwozi goldfield. In alluvium-covered terrains, fine-grained soil sampling (− 200 mesh, < 0.074 mm) combined with selective leaching geochemistry shows clear ring-shaped anomalies of Cu and Ni over the Zhouan concealed Cu–Ni deposit. In laterite-covered terrains, the anomalies determined by the fine-fraction soils and selective leaching of absorbed metals on coatings of Fe–Mn oxides coincide well with the concealed deposit over the Yueyang ore deposits at the Zijin Au–Cu–Ag field. Nanoparticles of hexagonal crystals mainly native copper, gold and alloys of Cu–Fe, Cu–Fe–Mn, Cu–Ti, and Cu–Au were observed in gases, soils and ores using a transmission electron microscope (TEM). The findings imply that nanoparticles of gold and copper may migrate through the transported cover to the surface. Uranium is converted to uranyl ions [UO₂^2 +] under oxidizing conditions when migrating from ore bodies to the surface. The uranyl ions are absorbed on clay minerals, because clay layers have a net negative charge, which needs to be balanced by interlayer cations. Nanoparticles of Au and Cu and ion complexes of U are more readily absorbed onto fine fractions of soils containing clays, colloids, oxides and organic matters. Thus, fine-grained soils enriched with clays, oxides and colloids are useful media for regional geochemical surveys in regolith-covered terrains and in sedimentary basins. Fine-fraction soil sampling combined with selective leaching geochemistry is effective for finding concealed ore bodies in detailed surveys. Penetrating geochemistry at surface sampling provides cost-effective mineral exploration methods for delineation of regional and local targets in transported cover terrains.     

Electron probe microanalysis and microscopy: Principles and applications in characterization of mineral inclusions in chromite from diamond deposit

Electron probe microanalysis and microscopy is a widely used modern analytical technique primarily for quantifying chemical compositions of solid materials and for mapping or imaging elemental distributions or surface morphology of samples at micrometer or nanometer-scale. This technique uses an electromagnetic lens-focused electron beam, generated from an electron gun, to bombard a sample. When the electron beam interacts with the sample, signals such as secondary electron, backscattered electron and characteristic X-ray are generated from the interaction volume. These signals are then examined by detectors to acquire chemical and imaging information of the sample. A unique part of an electron probe is that it is equipped with multiple WDS spectrometers of X-ray and each spectrometer with multiple diffracting crystals in order to analyze multiple elements simultaneously. An electron probe is capable of analyzing almost all elements (from Be to U) with a spatial resolution at or below micrometer scale and a detection limit down to a few ppm.Mineral inclusions in chromite from the Wafangdian kimberlite, Liaoning Province, China were used to demonstrate the applications of electron probe microanalysis and microscopy technique in characterizing minerals associated with ore deposits, specifically, in this paper, minerals associated with diamond deposit. Chemical analysis and SE and BSE imaging show that mineral inclusions in chromite include anhydrous silicates, hydrous silicates, carbonates, and sulfides, occurring as discrete or single mineral inclusions or composite multiple mineral inclusions. The chromite–olivine pair poses a serious problem in analysis of Cr in olivine using electron probe. Secondary fluorescence of Cr in chromite by Fe in olivine drastically increases the apparent Cr₂O₃ content of an olivine inclusion in a chromite. From the chemical compositions obtained using electron probe, formation temperatures and pressures of chromite and its mineral inclusions calculated using applicable geothermobarometers are from 46 kbar and 980 °C to 53 kbar and 1130 °C, which are within the stability field of diamond, thus Cr-rich chromite is a useful indication mineral for exploration of kimberlite and diamond deposit. A composite inclusion in chromite composed of silicate and carbonate minerals has a bulk composition of 33.2 wt.% SiO₂, 2.5 wt.% Al₂O₃, 22.0 wt.% MgO, 7.5 wt.% CaO, 2.5 wt.% BaO, 0.8 wt.% K₂O, 25.5 wt.% CO₂, and 0.8 wt.% H₂O, similar to the chemical composition of the Wafangdian kimberlite, suggesting that it is trapped kimberlitic magma.     

Metallogeny,structural evolution,post-mineral cover distribution and exploration in concealed areas of the northern Chilean Andes

Mineral exploration of prospective areas concealed by extensive post-mineralization cover is growing, being very complex and expensive. The projection of rich and giant Paleocene to early Oligocene porphyry-Cu-Mo belts in northernmost Chilean Andes (17.5–19.5°S) has major exploration potential, but only a few minor deposits have been reported to date, due to the fact that the area is largely covered by post-mineral strata. We integrate the Cenozoic stratigraphic, structural and metallogenic evolution of this sector, in order to identify the most promising regions related to lesser post-mineral cover and the projection of different metallogenic belts. The Paleocene to early Eocene metallogenic belt extends along the Precordillera, with ca. 30 km wide, and includes porphyry-Cu prospects and small Cu (±Mo-Au-Ag) vein and breccia-pipe deposits. Geochronological data indicate an age of 55.5 Ma for an intrusion related to one deposit and ages from 69.5 to 54.5 Ma for hydrothermal alteration in one porphyry-Cu prospect and largest known Cu deposits. The middle Eocene to early Oligocene porphyry belt, in the Western Cordillera farther east, is associated with 46–44 Ma intrusions. It is estimated to be 40-km wide, but is largely concealed by thick post-mineral cover. The youngest Miocene to early Pliocene metallogenic belt, also in the Western Cordillera, is well-exposed and includes Au-Ag epithermal and polymetallic veins and manto-type deposits.The Oligocene-Holocene cover consists of a succession of continental sedimentary and volcanic rocks that overall increase in thickness from 0 to 5000 m, from west to east. These strata are subhorizontal in the west and folded-faulted towards the east. Miocene gentle anticlines and monocline flexures extend along strike for 30–60 km in the Precordillera and were generated by propagation of high-angle east-dipping blind reverse faults with at least 300–900 m of Oligocene bedrock offset. The thickness of cover exceeds 2000 m in the eastern Central Depression, whereas it is generally less than 1000 m in the Precordillera along the Paleocene to early Eocene porphyry-Cu belt and it can reach locally up to 5000 m in the Western Cordillera, above the middle Eocene to early Oligocene belt.In the studied Andean segment, the Miocene to early Pliocene metallogenic belt is superimposed on the Paleocene to Oligocene belts in a 40–50 km wide zone. This overlap may be explained by an accentuated migration of the magmatic front, from east to west, since ca. 25 Ma, as a consequence of subduction slab steepening after a period of magmatic lull and flat subduction from ca. 30–35 to 25 Ma. The identified areas of lesser cover thickness are prone to exploration for concealed deposits, especially along the projection of major porphyry-Cu-Mo belts.     

Metal binding to dissolved organic matter and adsorption to ferrihydrite in shallow peat groundwaters: Application to diamond exploration in the James Bay Lowlands,Canada

The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSI_ferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSI_ferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.     

Volcanological and environmental controls on the Snowdon mineralization,North Wales,UK: A failed volcanogenic massive sulfide system in the Avalon Zone of the British Caledonides

The Snowdon caldera of North Wales is host to base metal sulfide-bearing veins and stockworks, mineralized breccias, disseminated sulfides, and localized zones of semi-massive to massive sulfide, with subordinate magnetite-rich veins. The late Ordovician host volcanic sequence accumulated in a shallow marine, back-arc environment in the Welsh Basin, which forms part of the Avalon Zone of the British and Irish Caledonides. New field evidence, sulfur isotopes, and U-Pb dating indicate that the Snowdon mineralization is genetically and temporally related to Late Ordovician magmatism and caldera formation. It is interpreted to represent volcanogenic pipe-style sulfide mineralization, resulting from focused hydrothermal fluids moving along caldera-related faults and simultaneous dispersal of fluids through the volcaniclastic pile. Sulfur isotope data suggest that, whilst a limited contribution of magmatic S cannot be ruled out, thermochemical reduction of contemporaneous Ordovician seawater sulfate was the dominant mechanism for sulfide production in the Snowdon system, resulting in a mean value of about 12‰ in both the host volcanic strata and the mineralized veins. Despite the tectonic setting being prospective for VMS deposits, strata-bound sulfide accumulations are absent in the caldera. This is attributed to the shallow water depths, which promoted boiling and the formation of sub-seafloor vein-type mineralization. Furthermore, the tectonic instability of the caldera and the high energy, shallow marine environment would have limited preservation of any seafloor deposits. The new U-Pb dates for the base (454.26 ± 0.35 Ma) and top (454.42 ± 0.45 Ma) of the host volcanic rocks, indicate that the Snowdon magmatic activity was short lived, which is likely to have limited the duration and areal extent of the ore-forming system. The absence of massive sulfide mineralization is consistent with the general paucity of economic VMS deposits in the Avalon Zone. Despite the highly prospective geological setting this study further illustrates the importance of volcanic facies mapping and associated paleo-environmental interpretations in VMS exploration.     

Nickel sulfide deposits in Australia: Characteristics,resources, and potential

Australia's nickel sulfide industry has had a fluctuating history since the discovery in 1966 of massive sulfides at Kambalda in the Eastern Goldfields of Western Australia. Periods of buoyant nickel prices and high demand, speculative exploration, and frenetic investment (the ‘nickel boom’ years) have been interspersed by protracted periods of relatively depressed metal prices, exploration inactivity, and low discovery rates. Despite this unpredictable evolution, the industry has had a significant impact on the world nickel scene with Australia having a global resource of nickel metal from sulfide ores of ∼ 12.9 Mt, five world-class deposits (> 1 Mt contained Ni), and a production status of number three after Russia and Canada. More than 90% of the nation's known global resources of nickel metal from sulfide sources were discovered during the relative short period of 1966 to 1973. Australia's nickel sulfide deposits are associated with ultramafic and/or mafic igneous rocks in three major geotectonic settings: (1) Archean komatiites emplaced in rift zones of granite–greenstone belts; (2) Precambrian tholeiitic mafic–ultramafic intrusions emplaced in rift zones of Archean cratons and Proterozoic orogens; and (3) hydrothermal-remobilized deposits of various ages and settings. The komatiitic association is economically by far the most important, accounting for more than 95% of the nation's identified nickel sulfide resources. The ages of Australian komatiitic- and tholeiitic-hosted deposits generally correlate with three major global-scale nickel-metallogenic events at ∼ 3000 Ma, ∼ 2700 Ma, and ∼ 1900 Ma. These events are interpreted to correspond to periods of juvenile crustal growth and the development of large volumes of primitive komatiitic and tholeiitic magmas caused by large-scale mantle overturn and mantle plume activities. There is considerable potential for the further discovery of komatiite-hosted deposits in Archean granite–greenstone terranes including both large, and smaller high-grade (5 to 9% Ni) deposits, that may be enriched in PGEs (2 to 5 g/t), especially where the host ultramafic sequences are poorly exposed.Analysis of the major komatiite provinces of the world reveals that fertile komatiitic sequences are generally of late Archean (∼ 2700 Ma) or Paleoproterozoic (∼ 1900 Ma) age, have dominantly Al-undepleted (Al₂O₃/TiO₂ = 15 to 25) chemical affinities, and often occur with sulfur-bearing country rocks in dynamic high-magma-flux environments, such as compound sheet flows with internal pathways facies (Kambalda-type) or dunitic compound sheet flow facies (Mt Keith-type). Most Precambrian provinces in Australia, particularly the Proterozoic orogenic belts, contain an abundance of sulfur-saturated tholeiitic mafic ± ultramafic intrusions that have not been fully investigated for their potential to host basal Ni–Cu sulfides (Voisey's Bay-type mineralization). The major exploration challenges for finding these deposits are to determine the pre-deformational geometries and younging directions of the intrusions, and to locate structural depressions in the basal contacts and feeder conduits under cover. Stratabound PGE–Ni–Cu ± Cr deposits hosted by large Archean–Proterozoic layered mafic–ultramafic intrusions (Munni Munni, Panton) of tholeiitic affinity have comparable global nickel resources to many komatiite deposits, but low-grades (< 0.2% Ni). There are also hydrothermal nickel sulfide deposits, including the unusual Avebury deposit in western Tasmania, and some potential for ‘Noril'sk-type’ Ni–Cu–PGE deposits associated with major flood basaltic provinces in western and northern Australia.     

Controls on chemistry during fracture-hosted flow of cold CO2-bearing mineral waters,Daylesford, Victoria,Australia: Implications for resource protection

Mineral springs from Daylesford, Australia discharge at ambient temperatures, have high CO₂ contents, and effervesce naturally. Mineral waters have high HCO₃ and Na concentrations (up to 4110 and 750 mg/L, respectively) and CO₂ concentrations of 620–2520 mg/L. Calcium and Mg concentrations are 61–250 and 44–215 mg/L, respectively, and Si, Sr, Ba, and Li are the most abundant minor and trace elements. The high P_CO2 of these waters promotes mineral dissolution, while maintaining low pH values, and geochemical modelling indicates that the CO₂-rich mineral water must have interacted with both sediments and basalts. Amorphous silica concentrations and silica geothermometry indicate that these waters are unlikely to have been heated above ambient temperatures and therefore reflect shallow circulation on the order of several hundreds of metres. Variations in minor and trace element composition from closely adjacent spring discharges indicate that groundwater flows within relatively isolated fracture networks. The chemical consistency of individual spring discharges over at least 20 a indicates that flow within these fracture networks has remained isolated over long periods. The mineral water resource is at risk from mixing with potentially contaminated surface water and shallow groundwater in the discharge areas. Increased δ²H values and Cl concentrations, and lower Na concentrations indicate those springs that are most at risk from surface contamination and overpumping. Elevated NO₃ concentrations in a few springs indicate that these springs have already been contaminated during discharge.     

Gold and platinum group minerals in placers of the South Urals: Composition,microinclusions of ore minerals and primary sources

Gold and platinum group minerals from the gold placers of the South Urals are studied in order to identify the metal sources. In placers from the Main Uralian fault zone (MUF), the primary gold contains Ag (up to 29 wt.%), Cu (up to 2 wt.%) and Hg (up to 4 wt.%) and its fineness ranges from 538 to 997‰. Tetra-auricupride and cupriferous gold (up to 20 wt.% Cu) are common for the Nizhny Karabash placer of the MUF zone. In the eastern part of the South Urals, the placer gold is mainly characterized by high fineness of 900–1000‰ and low Cu contents (max 1.38 wt.%). Most of the placer gold grains consist of the primary domains, which are rimmed by secondary high-fineness gold with diffuse and clear boundaries. The secondary gold also develops along the shear dislocations of primary gold. Gold contains microinclusions of geerite, balkanite, chalcopyrite, Se-bearing galena, sphalerite, pyrite, pyrrhotite, arsenopyrite and hematite.Twenty four (including five unnamed) platinum group minerals (PGMs) were found in 28 placers; those from the Kialim and Maly Iremel placers of the Miass placer zone were studied in details. In the Kialim placer, ruthenium is most abundant PGM, which hosts microinclusions of isoferroplatinum, ferroan platinum, laurite, cupriferous gold, a mineral similar in composition to tolovkite, heazlewoodite and unnamed RhSbS phase. The osmium contains microinclusions of erlichmanite and laurite. The iridium grains hosts various sulfides and arsenides of platinum group elements (PGEs). The inclusion-free PGMs form Ru compositional trend in contrast to Os–Ru trend of the Ir-depleted inclusion-hosted PGMs. The isoferroplatinum from the Maly Iremel placer hosts laurite, rhodarsenite, bowieite, a mineral similar in composition to miassite and unnamed sulfide of Pt (Pt_1.11S_2.00) and antimonide of Pd ((Pd_2.41Rh_0.43Fe_0.17)_3.01(Sb_0.91Te_0.09)_1.00). Ruthenium is a host to isoferroplatinum, PGE sulfides and arsenides, and heazlewoodite. Osmium contains microinclusions of ferroan platinum; iridium is a host to a mineral similar in composition to hongshiite. Three types of PGM intergrowths were identified in the Maly Iremel samples: (1) the intergrowths of platy grains of ruthenium with isoferroplatinum and a mineral similar in composition to tulameenite; (2) the open-latticework intergrowths of platy crystals of ruthenium with interstitial aggregates made up of gold, isoferroplatinum and a mineral similar in composition to xingzhongite and (3) the intergrowths of osmium and irarsite and iridarsenite, which are developed along cleavage of the osmium grains. Nickel sulfides associated with some PGMs contain Ru (11.32 wt.%) and Rh (2.21 wt.%) in millerite and Ir (31.00 wt.%), Ru (5.81 wt.%) and Rh (2.87 wt.%) in vaesite.The primary metal sources were determined on the basis of the mineral assemblages and composition of minerals, taking into account the nearby mineral deposits and directions of rivers. The rodingite-associated gold, gold-bearing massive sulfide and chromite deposits are major sources of gold and PGMs in placers of the Miass placer zone confined to the MUF structure of the South Urals. In the southern part of this structure, gold was mainly originated from orogenic gold–sulfide deposits associated with volcanic/volcaniclastic rocks and listvenite-associated gold deposits. The placer PGMs were derived from the adjacent ultramafic massifs of ophiolitic origin. The distance between the placers and primary deposits varies from 2 to 5 km (up to 20 km in the extended valley of the Miass River). Usage of ore microinclusions and associated PGMs in study of placer gold is far more advanced than an ordinary consideration of gold composition alone. This approach allowed us to identify the concrete sources for individual placers and to predict some mineralogical findings in already known primary occurrences.     

In-situ SIMS uraninite U–Pb dating and genesis of the Xianshi granite-hosted uranium deposit,South China

The southeastern part of the Nanling metallogenic province, China is host to numerous granite-hosted vein-type hydrothermal uranium deposits. The geology and geochemistry of these deposits have been extensively studied. However, accurate and precise ages for the uranium mineralization are scarce because the uranium minerals in these deposits are usually fine grained, and may have formed in several stages. Therefore, the ages previously obtained by the bulk dating techniques are possibly a mixed age.The Xianshi uranium deposit, located in the southeastern part of the Guidong granite complex, is a major uranium deposit in South China. The uranium mineralization from this deposit is mainly fine grained uraninite in quartz or calcite veins which are spatially associated with the Cretaceous mantle-derived mafic dykes. Micro-Raman spectroscopy and X-ray diffraction analyses indicate that the dominant uranium mineral occurs as a rare form of uraninite (U₃O₇). Three distinct generations of uranium minerals have been identified based on petrographic and field relations. Stage 1 uraninite has the lowest UO₂ and highest PbO contents whereas Stage 3 uraninite has the highest UO₂ and lowest PbO contents.Uraninite from the Xianshi deposit was dated using an in-situ SIMS U–Pb dating technique. The results show three distinct age groups: 135 ± 4 Ma, 113 ± 2 Ma and 104 ± 2 Ma, which are in excellent agreement with the ages of three episodes of mantle-derived mafic dykes. Therefore, the Xianshi uranium deposit has experienced at least three hydrothermal events that are responsible for the deposition of uranium ores, which are genetically related to the emplacement of three sets of mafic dykes.     

Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO₂/g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C₂₇–C₃₁) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are inconsistent with diagenetic degradation of terrigenous OM in oxic depositional environments and cannot be associated with thermal breakdown due to the relatively low thermal maturity of the deposits (R_r = 0.26%). It is assumed that the intimate spatial association of high U concentrations resulted in breakdown via radiolytic cracking of recalcitrant polyaliphatic macromolecules (spores, pollen, cuticles, or algal cysts) yielding medium chain length n-alkanes (C₁₃–C₂₄). Reactions of n-alkenes with OH⁻ radicals from water hydrolysis produced alcohols that dehydrogenated to alkanones or through carbonylation formed alkanones. Rapid reactions with hydroxyl radicals likely decreased the isomerization of n-alkenes and decreased alkanone diversity, such that the alkan-2-one isomer is predominant. This specific distribution of components generated by natural radiolysis enables their application as “radiolytic molecular markers”. Breaking of C–C bonds through radiolytic cracking at temperatures much lower than the oil window (<50 °C) can have profound implications on initiation of petroleum formation, paleoenvironmental reconstructions, mineral exploration and in tracking radiolysis of OM.     

Mineral chemistry of high-Mg diorites and skarn in the Han-Xing Iron deposits of South Taihang Mountains,China: Constraints on mineralization process

The Han-Xing region is located in the south Taihang Mountains (TM) in the central part of the North China Craton, and is an important iron producing area. The iron deposits in this region are of skarn type, related to an Early Cretaceous high-Mg diorite complex, including gabbro diorite, hornblende diorite, diorite, diorite porphyrite, and monzonite. In this study we report the detailed mineral chemistry of the high-Mg diorites and skarn rocks. The olivine in the gabbro diorite shows chemical composition similar to that in mantle peridotite xenoliths. Clinopyroxene in the gabbro diorite is dominantly augite, with only minor diopside, whereas the clinopyroxenes in the diorite and monzonite are diopside. Amphiboles in the high-Mg diorites show compositional range from magnesiohornblende to magnesiohastingsite, with minor pargasite and tschermakite. Most plagioclase in the high-Mg diorite is andesine and oligoclase. The magnesio-biotite in gabbro diorites shows chemical characteristics of re-equilibrated primary biotites and those in calc-alkaline rocks. In the diorite and diorite porphyrite, plagioclase shows complex chemical zoning. Clinopyroxene and garnet in skarn rocks show varying FeO contents, the former containing low FeO (< 9 wt.%) and occurring as the major skarn mineral in large-scale iron deposits, and the latter within small-scale iron deposits with high FeO (mostly > 25 wt.%) content. We computed the pressure, temperature, oxygen fugacity and water contents based on the mineral chemistry of amphibole and biotite. Based on the results, the magma crystallization can be divided into two stages, one within the deep magma chamber, forming clinopyroxene, amphibole and plagioclase phenocrysts; the other after emplacement, forming the rim of phenocrysts and matrix minerals. The magma during the early stage shows high temperature (~ 900 °C–950 °C), pressure (~ 300 MPa–500 MPa), relatively high logfO₂ (NNO–NNO + 2), and H₂O content in melt (4%–8%). During the late stage, the magma temperature dropped to about 750 °C, and pressure came down to less than 100 MPa, with the logfO₂ rising to NNO + 1–NNO + 2.The zoning of amphibole and plagioclase records the process of magma mixing and crystallization, with injection of mafic magma into the felsic magma chamber. The relatively high logfO₂ and H₂O content inhibited partitioning of iron into mafic minerals and favored concentration of Fe in the melt. Iron ore precipitation occurred when the magma was emplaced at shallow level, and was principally controlled by the chemical composition of carbonate wall rocks. The high logfO₂, Fe^3 + rich ore-forming fluid generated andradite and clinopyroxene when it reacted with limestone and dolomitic limestone respectively.     

Geochemical constraints on Cu–Fe and Fe skarn deposits in the Edong district,Middle–Lower Yangtze River metallogenic belt,China

Copper and iron skarn deposits are economically important types of skarn deposits throughout the world, especially in China, but the differences between Cu and Fe skarn deposits are poorly constrained. The Edong ore district in southeastern Hubei Province, Middle–Lower Yangtze River metallogenic belt, China, contains numerous Fe and Cu–Fe skarn deposits. In this contribution, variations in skarn mineralogy, mineralization-related intrusions and sulfur isotope values between these Cu–Fe and Fe skarn deposits are discussed.The garnets and pyroxenes of the Cu–Fe and Fe skarn deposits in the Edong ore district share similar compositions, i.e., dominantly andradite (Ad_29–100Gr_0–68) and diopside (Di_54–100Hd_0–38), respectively. This feature indicates that the mineral compositions of skarn silicate mineral assemblages were not the critical controlling factors for variations between the Cu–Fe and Fe skarn deposits. Intrusions associated with skarn Fe deposits in the Edong ore district differ from those Cu–Fe skarn deposits in petrology, geochemistry and Sr–Nd isotope. Intrusions associated with Fe deposits have large variations in their (La/Yb)_N ratios (3.84–24.6) and Eu anomalies (δEu = 0.32–1.65), and have relatively low Sr/Y ratios (4.2–44.0) and high Yb contents (1.20–11.8 ppm), as well as radiogenic Sr–Nd isotopes (εNd(t) = − 12.5 to − 9.2) and (⁸⁷Sr/⁸⁶Sr)_i = 0.7067 to 0.7086. In contrast, intrusions associated with Cu–Fe deposits are characterized by relatively high Sr/Y (35.0–81.3) and (La/Yb)_N (15.0–31.6) ratios, low Yb contents (1.00–1.62 ppm) without obvious Eu anomalies (δEu = 0.67–0.97), as well as (⁸⁷Sr/⁸⁶Sr)_i = 0.7055 to 0.7068 and εNd(t) = − 7.9 to − 3.4. Geochemical evidence indicates a greater contribution from the crust in intrusions associated with Fe skarn deposits than in intrusions associated with Cu–Fe skarn deposits. In the Edong ore district, the sulfides and sulfates in the Cu–Fe skarn deposits have sulfur isotope signatures that differ from those of Fe skarn deposits. The Cu–Fe skarn deposits have a narrow range of δ³⁴S values from − 6.2‰ to + 8.7‰ in sulfides, and + 13.2‰ to + 15.2‰ in anhydrite, while the Fe skarn deposits have a wide range of δ³⁴S values from + 10.3‰ to + 20.0‰ in pyrite and + 18.9‰ to + 30.8‰ in anhydrite. Sulfur isotope data for anhydrite and sedimentary country rocks suggest that the formation of skarns in the Edong district involved the interaction between magmatic fluids and variable amounts of evaporites in host rocks.     

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH₄ gas content and its C isotopes (δ¹³C_CH4), and select isotope tracers (δ¹¹B, ⁸⁷Sr/⁸⁶Sr, δ²H, δ¹⁸O, δ¹³C_DIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH₄ was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH₄/L. The δ¹³C_CH4 of dissolved CH₄ ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH₄ concentrations, with a possible minor contribution of trace amounts of thermogenic CH₄. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ¹³C_CH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO₃ dominated, (3) TDS > 100 mg/L and Na–HCO₃ dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (⁸⁷Sr/⁸⁶Sr = 0.7097–0.7166), C (δ¹³C_DIC = −21.3‰ to −4.7‰), and B (δ¹¹B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO₃, and higher-mineralized Na–HCO₃ composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH₄ and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.     

3D geological modeling for prediction of subsurface Mo targets in the Luanchuan district,China

Three-dimensional (3D) district-scale geoscience information for the Luanchuan Mo district was integrated for understanding the development of its regional geology and ore-forming processes and for decision-making about potential targets for mineral exploration. The methodology and datasets used were: (1) construction of an initial geological model (25 km × 20 km × 2.5 km) using 1:10,000 scale geological map, nine geological cross-sections and gravity and magnetic data; (2) construction of three large-scale Mo deposits model (5 km × 4 km × 2.5 km) using 1:2000 scale geological and topographic maps, 288 boreholes (total core length of 158,700 m), and 32 1:2000 scale cross-sections; (3) 3D inversion of 1:25,000 scale gravity and magnetic data for identification metallogenic anomaly zones which are associated with Jurassic intrusions; (4) extraction of ore-controlling formation and sequence of the Luanchuan Group using the large-scale 3D models of Mo deposits and results of analysis of lithogeochemical samples from outcrops and borehole cores; (5) identification of ore-forming and ore-controlling faults using the large-scale 3D model of Mo deposits and mineralized Jurassic granite porphyry stocks; (6) boost weights-of-evidence and concentration–volume (C–V) fractal analyses to integrate metallogenic information and to identify and classify potential Mo targets. Four classes of exploration targets were identified using C–V modeling and 3D known orebodies model: the first and second class targets are mainly located in three large magma-skarn type deposit camps, occupying ~ 1.4 km³ with total estimated reserve of ~ 2.3 Mt; the third class targets, which are mainly located in Huangbeiling and Yuku deposit camps comprising concealed magma-skarn type deposits, occupy ~ 2.8 km³ and represent a new target exploration zone in the Luanchuan district; the fourth class targets, which are located in the Huoshenmiao, Majuan, and Daping zones, occupy ~ 15 km³ and represent potential mineral resources with likely similar orebody features as the Yuku deposit.     

CO2 leakage impacts on shallow groundwater: Field-scale reactive-transport simulations informed by observations at a natural analog site

It is challenging to predict the degree to which shallow groundwater might be affected by leaks from a CO₂ sequestration reservoir, particularly over long time scales and large spatial scales. In this study observations at a CO₂ enriched shallow aquifer natural analog were used to develop a predictive model which is then used to simulate leakage scenarios. This natural analog provides the opportunity to make direct field observations of groundwater chemistry in the presence of elevated CO₂, to collect aquifer samples and expose them to CO₂ under controlled conditions in the laboratory, and to test the ability of multi-phase reactive transport models to reproduce measured geochemical trends at the field-scale. The field observations suggest that brackish water entrained with the upwelling CO₂ are a more significant source of trace metals than in situ mobilization of metals due to exposure to CO₂. The study focuses on a single trace metal of concern at this site: U. Experimental results indicate that cation exchange/adsorption and dissolution/precipitation of calcite containing trace amounts of U are important reactions controlling U in groundwater at this site, and that the amount of U associated with calcite is fairly well constrained. Simulations incorporating these results into a 3-D multi-phase reactive transport model are able to reproduce the measured ranges and trends between pH, pCO₂, Ca, total C, U and Cl⁻ at the field site. Although the true fluxes at the natural analog site are unknown, the cumulative CO₂ flux inferred from these simulations are approximately equivalent to 37.8E−3 MT, approximately corresponding to a .001% leak rate for injection at a large (750 MW) power plant. The leakage scenario simulations suggest that if the leak only persists for a short time the volume of aquifer contaminated by CO₂-induced mobilization of U will be relatively small, yet persistent over 100 a.     

Zircon Hf–isotopic mapping for understanding crustal architecture and metallogenesis in the Eastern Qinling Orogen

The Eastern Qinling Orogen (EQO) is a major composite collisional zone located between the North China and the Yangtze cratons. This contribution combines geological and Hf–isotopic data from magmatic rocks associated with mineralization to gain insights into links between the crust architecture and metallogeny, and to focus exploration in the orogen.The new zircon U–Pb dates reported in this study are 434 ± 2 Ma for diorite, 433 ± 2 and 436 ± 2 Ma for monzogranite, and 454 ± 2 Ma for granodiorite in the Nanzhao area; 225 ± 2 Ma for syenite and 160 ± 1 Ma for monzogranite at Songxian; and 108 ± 1 and 102 ± 1 Ma for syenogranite in eastern Fangcheng. Combining our data with those from the entire EQO reveals seven major magmatic events since the Cambrian. These magmatic events took place during the Cambrian–Silurian associated with subduction, Early Devonian magmatism related to a collisional event, Early Permian to Late Triassic magmatism related to subduction, Late Triassic collisional magmatism, Late Triassic to Early Jurassic post–collision magmatism, and Jurassic–Cretaceous magmatism during intra–continental subduction.Lu-Hf isotopic data collected from granitic rocks for this study give εHf(t) values of: − 1.4 to 10.9 for diorite and monzogranite at Nanzhao; − 27.1 to − 15.6 for syenite and − 27.5 to − 25.1 for monzogranite at Songxian; and − 12.9 to − 3.4 for syenogranite in the eastern Fangcheng. Combining Hf isotopic data for the EQO from previous studies, we have evaluated the spatio–temporal distribution of Hf isotopic compositions. The resultant Hf isotopic maps highlight the location of the Kuanping Suture as an important tectonic boundary between the North China and the Yangtze cratons, which separates the EQO into a north part with an old and reworked lower crust and a southern part representing a juvenile lower crust.The Hf isotopic mapping of the EQO also provides information on the distribution of mineral deposits. Porphyry and porphyry–skarn Mo(–W) deposits are associated with magmatic rocks were emplaced in zones with low–εHf and high T_DM^c values representing old and reworked crustal components. In contrast, porphyry and porphyry–skarn Cu(–Mo) deposits are associated with magmatic rocks emplaced in domains with variable εHf and T_DM^c values characterized by dominantly reworked old crustal components with minor juvenile material. The magmatic source for the intrusions is characterized by low–εHf and high T_DM^c values, which are granite–related Mo or Pb–Zn–Ag mineralization.     

Arsenic and other drinking water quality issues,Muzaffargarh District,Pakistan

In 49 samples of groundwater, sampled in Muzaffargarh District of south-western Punjab, central Pakistan, concentrations of As exceeded the World Health Organisation provisional guideline value, and United States Environmental Protection Agency (USEPA) Maximum Contaminant Level (MCL), of 10 μg L⁻¹ in 58% of samples and reached up to 906 μg L⁻¹. In this semi-arid region canal irrigation has lead to widespread water-logging, and evaporative concentration of salts has the potential to raise As concentrations in shallow groundwater well above 10 μg L⁻¹. In fact, in rural areas, concentrations stay below 25 μg L⁻¹ because As in the oxic shallow groundwater, and in recharging water, is sorbed to aquifer sediments. In some urban areas, however, shallow groundwater is found to contain elevated levels of As. The spatial distribution of As-rich shallow groundwater indicates either direct contamination with industrial or agricultural chemicals, or some other anthropogenic influence. Geochemical evidence suggests that pollutant organics from unconfined sewage and other sources drives reduction of hydrous ferric oxide (HFO) releasing sorbed As to shallow groundwater. The situation is slightly less clear for seven wells sampled which tap deeper groundwater, all of which were found with >50 μg L⁻¹ As. Here As concentrations seem to increase with depth and differing geochemical signatures are seen, suggesting that As concentrations in older groundwater may be governed by different processes. Other data on parameters of potential concern in drinking water are discussed briefly at the end of the paper.     

Uraniferous paleoplacers of the Mesoarchean Mahagiri Quartzite,Singhbhum craton,India: Depositional controls,nature and source of > 3.0 Ga detrital uraninites

The quartz-pebble conglomerate (QPC)-hosted detrital uranium mineralization is unique in character in terms of their restricted distribution before 2.2 Ga atmosphere during pre-Great Oxidation Event (pre-GOE). Such QPC paleoplacer deposits over the world are good targets for moderate to high tonnage and low grade uranium deposits and more importantly for their gold content. The Mahagiri Quartzite, dated c. 3.02 Ga for their youngest detrital zircon population, is developed unconformably over the Mesoarchean Singhbhum Granite (3.44 Ga to 3.1 Ga). The Mahagiri Quartzite includes a conglomerate-pebbly sandstone dominated subaerial alluvial fan to coastal braided plain sequence in the lower parts and shallow marine mature quartz arenite in the upper parts. The alluvial fan-braided plain deposits in the lower parts host a number of pyritiferous and uraniferous conglomerate and pebbly sandstone beds. The uraninite grains are rounded to subrounded in outline suggesting mechanical transport and detrital origin. Together with detrital pyrite and uraninite constitute the example of > 3.0 Ga paleoplacer closely comparable to the Witwatersrand Au–U deposits. EPMA and SEM-EDS studies suggest that the uraninite grains are rich in Th (> 4 wt.%), S and REE-Y. Chemical formula calculations from EPMA analyses suggest uraninite grains belong to two populations with different oxidation states as revealed from Y/REE and cation U^4 +: U^6 + [apfu] ratios. The U contents of the detrital uraninite grains from Mahagiri are significantly lower than that of the ideal stoichiometric composition of UO₂. This is mainly due to higher amount of heterovalent cationic substitution by Th, REE, Y, Pb, and Ca in Mahagiri QPC uraninite structures, and partial alteration and metamictization of uraninites. Alteration due to metamictization resulted in elevated concentration of Si, Al, P, and Ca in more altered and metamict uraninite grains. The REE pattern is typically flat with comparable LREE–HREE concentration. The high Th content flat REE-pattern suggests that the uraninitere presents high temperature phases (> 350 °C) and are magmatic in origin. The Mahagiri detrital uraninite grains suggest existence of highly felsic and K-rich (richer than TTG) granodiorite–granite–monzogranite suites (GGM) of rocks older than 3.1 Ga in the Singhbhum craton.     

Origin,distribution and hydrogeochemical controls on methane occurrences in shallow aquifers,southwestern Ontario,Canada

Natural gas reservoirs in organic-rich shales in the Appalachian and Michigan basins in the United States are currently being produced via hydraulic fracturing. Stratigraphically-equivalent shales occur in the Canadian portion of the basins in southwestern Ontario with anecdotal evidence of gas shows, yet there has been no commercial shale gas production to date. To provide baseline data in the case of future environmental issues related to hydraulic fracturing and shale gas production, such as leakage of natural gas, saline water, and/or hydraulic fracturing fluids, and to evaluate hydrogeochemical controls on natural gas accumulations in shallow groundwater in general, this study investigates the origin and distribution of natural gas and brine in shallow aquifers across southwestern Ontario. An extensive geochemical database of major ion and trace metal chemistry and methane concentrations of 1010 groundwater samples from shallow, domestic wells in bedrock and overburden aquifers throughout southwestern Ontario was utilized. In addition, select wells (n = 36) were resampled for detailed dissolved gas composition, δ¹³C of CH₄, C₂, C₃, and CO₂, and δD of CH₄. Dissolved gases in groundwater from bedrock and overburden wells were composed primarily of CH₄ (29.7–98.6 mol% of total gas volume), N₂ (0.8–66.2 mol%), Ar + O₂ (0.2–3.4 mol%), and CO₂ (0–1.2 mol%). Ethane was detected, but only in low concentrations (<0.041 mol%), and no other higher chain hydrocarbons were present, except for one well in overburden overlying the Dundee Formation, which contained 0.81 mol% ethane and 0.21 mol% propane. The highest methane concentrations (30 to >100 in situ % saturation) were found in bedrock wells completed in the Upper Devonian Kettle Point Formation, Middle Devonian Hamilton Group and Dundee Formation, and in surficial aquifers overlying these organic-rich shale-bearing formations, indicating that bedrock geology is the primary control on methane occurrences. A few (n = 40) samples showed Na–Cl–Br evidence of brine mixing with dilute groundwater, however only one of these samples contained high (>60 in situ % saturation) CH₄. The relatively low δ¹³C values of CH₄ (−89.9‰ to −57.3‰), covariance of δD values of CH₄ and H₂O, positive correlation between δ¹³C values of CH₄ and CO₂, and lack of higher chain hydrocarbons (C₃₊) in all but one dissolved gas sample indicates that the methane in groundwater throughout the study area is primarily microbial in origin. The presence or absence of alternative electron acceptors (e.g. dissolved oxygen, Fe, NO₃, SO₄), in addition to organic substrates, controls the occurrence of microbial CH₄ in shallow aquifers. Microbial methane has likely been accumulating in the study area, since at least the Late Pleistocene to the present, as indicated by the co-variance and range of δD values of CH₄ (−314‰ to −263‰) and associated groundwater (−19‰ to −6‰ δD-H₂O).