Time scales and length scales in magma flow pathways and the origin of magmatic Ni–Cu–PGE ore deposits

Ore forming processes involve the redistribution of heat, mass and momentum by a wide range of processes operating at different time and length scales. The fastest process at any given length scale tends to be the dominant control. Applying this principle to the array of physical processes that operate within magma flow pathways leads to some key insights into the origins of magmatic Ni–Cu–PGE sulfide ore deposits. A high proportion of mineralised systems, including those in the super-giant Noril'sk-Talnakh camp, are formed in small conduit intrusions where assimilation of country rock has played a major role. Evidence of this process is reflected in the common association of sulfides with vari-textured contaminated host rocks containing xenoliths in varying stages of assimilation. Direct incorporation of S-bearing country rock xenoliths is likely to be the dominant mechanism for generating sulfide liquids in this setting. However, the processes of melting or dissolving these xenoliths is relatively slow compared with magma flow rates and, depending on xenolith lithology and the composition of the carrier magma, slow compared with settling and accumulation rates. Chemical equilibration between sulfide droplets and silicate magma is slower still, as is the process of dissolving sulfide liquid into initially undersaturated silicate magmas. Much of the transport and deposition of sulfide in the carrier magmas may occur while sulfide is still incorporated in the xenoliths, accounting for the common association of magmatic sulfide-matrix ore breccias and contaminated “taxitic” host rocks. Effective upgrading of so-formed sulfide liquids would require repetitive recycling by processes such as re-entrainment, back flow or gravity flow operating over the lifetime of the magma transport system as a whole. In contrast to mafic-hosted systems, komatiite-hosted ores only rarely show an association with externally-derived xenoliths, an observation which is partially due to the predominant formation of ores in lava flows rather than deep-seated intrusions, but also to the much shorter timescales of key component systems in hotter, less viscous magmas. Nonetheless, multiple cycles of deposition and entrainment are necessary to account for the metal contents of komatiite-hosted sulfides. More generally, the time and length scale approach introduced here may be of value in understanding other igneous processes as well as non-magmatic mineral systems.     

Temporal and spatial controls on the formation of magmatic PGE and Ni–Cu deposits

Magmatic PGE and Ni–Cu deposits form in contrasting geologic environments and periods. PGE deposits predominantly occur in large layered intrusions emplaced during the late Archean and early Proterozoic into stabilized, relatively S-poor cratonic lithosphere that provides enhanced preservation potential. The magmas ascend through intracratonic sutures where extension and rifting is limited. Crystallization under conditions of low regional stress, with limited magma-induced sagging due to underlying thick buoyant sub-continental mantle lithosphere, is consistent with their laterally continuous layering. Most of the global resources occur in three large intrusions: Bushveld, Great Dyke and Stillwater. Due to the large size (tens of kilometres) and limited complexity of the deposits, they are relatively easy to locate and delineate. As a result, the search space is relatively mature and few new discoveries have been made in the last few decades. The parental magmas to the intrusions are predominantly derived from the convecting mantle but, in addition, the involvement of the sub-continental lithospheric mantle is suggested by the relative Pt enrichment of most of the major deposits. In contrast to the PGE deposits, Ni–Cu deposits form throughout geologic time, but with the largest deposits being younger than ca. 2 Ga. The sulfide ores are concentrated under highly dynamic conditions within lava channels and magma conduits. The deposits are preferentially located near craton margins towards which mantle plumes have been channelled and where mantle magmas can readily ascend through abundant trans-lithospheric structures. Magma flow is focused and locally enhanced by shifting compressive–extensional tectonic regimes, and abundant S-rich crustal rocks provide an external S source that is required for the majority of deposits. The igneous bodies hosting the deposits tend to be irregular and small, tens to hundreds of metres in width and height, and are difficult to locate. As a result, the search space remains relatively immature. Understanding their tectonic setting helps reduce the prospective search space for world-class examples.     

The record of temperature, wind velocity and air humidity in the δD and δO of water inclusions in synthetic and Messinian halites

Deuterium and oxygen isotope fractionations between liquid and vapor water were experimentally-determined during evaporation of a NaCl solution (35 g L⁻¹) as a function of water temperature and wind velocity. In the case of a null wind velocity, slopes of δD-δ¹⁸O trajectories of residual waters hyperbolically decrease with increasing water temperatures in the range 23-47 °C. For wind velocities ranging from 0.8 to 2.2 m s⁻¹, slopes of the δD-δ¹⁸O trajectories linearly increase with increasing wind velocity at a given water temperature. These experimental results can be modeled by using Rayleigh distillation equations taking into account wind-related kinetics effects. Deuterium and oxygen isotope compositions of water inclusions trapped by the precipitated halite crystals were determined by micro-equilibration techniques.These isotopic compositions accurately reflect those of the surrounding residual waters during halite growth. Isotopic compositions of water inclusions in twenty natural halites from the Messinian Realmonte mine in Sicily suggest precipitation temperatures of that match the homogenization temperatures obtained by microthermometry (median = 34 ± 5 °C). The similarity between the measured and experimental slopes of the δD-δ¹⁸O evaporation trajectories suggests that the effect of wind was negligible during the genesis of these halite deposits. Hydrogen and oxygen isotope compositions of water inclusions from Realmonte halite also define a linear trend whose extrapolation until intersection with the Mediterranean Meteoric Water Line allows the characterization of the water source with δD and δ¹⁸O values of −70 ± 10‰ and −11.5 ± 1.5‰, respectively. These results reveal that the huge amounts of salts deposited in Sicily result from the evaporation of seawater mixed with a dominant fraction (?50%) of meteoric waters most likely deriving from alpine fluvial discharge.     

Palaeozoic porphyry Cu–Au and ultramafic Cu–Ni deposits in the eastern Tianshan orogenic belt: temporal constraints from U–Pb geochronology

During late Palaeozoic time, extensive magmatism and associated ore deposits were developed in the eastern Tianshan orogenic belt (ETOB), Northwest China, which is part of the Central Asian Orogenic Belt. To understand the petrogenesis of the intrusions in this area, we performed in situ zircon U–Pb and Hf isotopic analyses on the Tuwu–Yandong (TW–YD) stocks and the Xianshan, Hulu, Luodong, and Poshi batholiths. Two major suites of intrusive rocks have been recognized in the ETOB: (1) 338–339 Ma plagiogranite porphyries and 265–300 Ma ultramafic and mafic rocks, of which the former are associated with 323 Ma porphyry Cu–Mo deposits and have enriched radiogenic Hf isotopic compositions (?_Hf(t) = +11.5 to +15.6), which were derived from a depleted mantle source, whereas the latter are associated with 265–300 Ma magmatic Ni–Cu deposits and have variable Hf isotopic compositions (?_Hf(t) = ?10.3 to +14.3), indicating an origin via the hybridization of depleted mantle magma and variable amounts of ancient lower-crustal components. The proposed magma sources, combined with the geochemical differences between these two suites of intrusive rocks, indicate that in the lower to middle Carboniferous, a N-dipping subduction zone beneath the Dananhu arc triggered the emplacement of granitic porphyries in the Tousuquan and Dananhu island arc belt in the east Tianshan, leading to the formation of the TW and YD porphyry Cu–Mo deposits. In the Upper Carboniferous to Lower Permian, large mafic–ultramafic complexes were emplaced during the closure of the ancient Tianshan Ocean, resulting in the formation of several magmatic Cu–Ni sulphide deposits.     

Can in situ geochemical measurements be more fit-for-purpose than those made ex situ?

It is argued that the selection of the most appropriate geochemical measurement technique should be based upon the fitness of its measurement results for any specified purpose, regardless of whether the measurement are made in situ or ex situ. Using this approach, in situ measurements made in the field are shown to have some definite advantages over those made ex situ in a laboratory. A case study is used to show that there are cases where in situ measurements can be more fit-for-purpose than their ex situ equivalents. This is primarily because the uncertainty of both types of measurement is usually limited by the uncertainty arising from the field sampling process. That uncertainty is mainly caused by small-scale heterogeneity (in space or time) in the analyte concentration within the environmental material (e.g. soil, water or air).     

Can sedimentary leaf waxes record D/H ratios of continental precipitation? Field, model, and experimental assessments

D/H ratios of leaf waxes (δD_wax) derived from terrestrial plants and preserved in lake sediments can provide important information on past continental hydrology. Ideally, δD_wax can be used to reconstruct precipitation D/H ratios (δD_P) which is a well-established paleoclimate proxy. However, many other factors, such as vegetation and relative humidity (RH), also affect δD_wax variation. How the combination of these factors affects sedimentary δD_wax is unclear. Here, we use a transect of 32 lake surface sediments across large gradients of precipitation, relative humidity, and vegetation composition in the southwestern United States to study the natural factors affecting sedimentary δD_wax. δD values of C₂₈n-alkanoic acids show significant correlation with δD_P values (R² = 0.76) with an apparent isotopic enrichment of ∼99 ± 8‰, indicating that sedimentary δD_wax values track overall δD_P variation along the entire transect. Leaf waxes produced by plants grown under controlled conditions (RH = 80%, 60%, 40%) show a small increase in D/H ratios as RH decreases, consistent with prediction from the Craig-Gordon model. However, the isotopic effect of RH on δD_wax along the natural transect is partially countered by the opposing influence of vegetation changes. The correlation between δD_wax and δD_P values is significantly higher (R² = 0.84) in the drier portions of the transect than in the wetter regions (R² = 0.64). This study suggests that D/H ratios of sedimentary leaf waxes can be used as a proxy for precipitation δD variations, with particularly high fidelity in dry regions, although more studies in other regions will be important to further test this proxy.     

Prediction of hidden Au and Cu–Ni ores from depleted mines in Northwestern China: four case studies of integrated geological and geophysical investigations

Integrated geological and geophysical investigations were carried out in 26 active mines in Northwestern China during the period 2001–2006 to explore for hidden extensions of known ore bodies and to search for new mineralization. This paper presents four case studies from northwest China: the Kuoerzhenkuoa volcanogenic hydrothermal gold deposit, the Nanjinshan breccia-associated gold deposit, the Duolanasayi deposit, associated with a ductile–shear zone, and the Hulu magmatic Cu–Ni sulfide deposit. In these studies, detailed mine-scale geological studies were carried out to determine the location and controls on ore formation. Based on these investigations and a review of previous exploration data, genetic models for the deposits were evaluated, and specific new targets were generated. These target areas were tested with surface geophysical surveys using the Stratagem EH4 system, a hybrid-source magnetotellurics (MT) method. Analysis of the data obtained in the surveys identified geophysical target anomalies that were subsequently drilled. Many of these test holes demonstrate the presence of Au and Cu–Ni mineralization. Evaluation of the geological models was crucial in developing conceptual targets as a basis for surface geophysical surveys. These models established the most likely target areas where Au and Cu–Ni mineralization could occur, but they did not define the limits or the geometries of the mineralized zones. Hybrid MT surveys played an important role in defining the location of buried mineralized systems and in testing the validity of the conceptual targets. The resistivity cross-sections obtained by imaging the MT data established the boundaries and geometries of the host rocks, including the distribution of lithology, structures, alteration, and mineralization. The four case studies in this paper show how this integrated geological and geophysical approach was used successfully to discover hidden mineral deposits.

About the variability in thunderstorm and rainfall activity over India and its association with El Niño and La Niña

Thunderstorms are of much importance in tropics, as this region is considered to have central role in the convective overturn of the atmosphere and play an important role in rainfall activity. It is well known that El Niño and La Niña are well associated with significant climate anomalies at many places around the globe. Therefore, an attempt is made in this study to analyze variability in thunderstorm days and rainfall activity over Indian region and its association with El Niño and La Niña using data of thunderstorm day’s for 64 stations well distributed all over India for the period 1981–2005 (25 years). It is seen that thunderstorm activity is higher and much variable during pre-monsoon (MAM) and southwest monsoon (JJAS) than the rest of the year. Positive correlation coefficients (CCs) are seen between thunderstorms and rainfall except for the month of June during which the onset of the southwest monsoon sets over the country. CCs during winter months are highly correlated. Composite anomalies in thunderstorms during El Niño and La Niña years suggest that ENSO conditions altered the patterns of thunderstorm activity over the country. Positive anomalies are seen during pre-monsoon (MAM) and southwest monsoon months (JAS) during La Niña years. Opposite features are seen in southwest monsoon during El Niño periods, but El Niño favors thunderstorm activity during pre-monsoon months. There is a clear contrast between the role of ENSO during southwest monsoon and post-monsoon on thunderstorm activity over the country. Time series of thunderstorms and precipitation show strong association with similarities in their year-to-year variation over the country.     

Response of the coccolithophores Emiliania huxleyi and Coccolithus braarudii to changing seawater Mg and Ca concentrations: Mg/Ca, Sr/Ca ratios and δCa, δMg of coccolith calcite

Calcium and magnesium concentrations in seawater have varied over geological time scales. On short time scales, variations in the major ion composition of seawater influences coccolithophorid physiology and the chemistry of biogenically produced coccoliths. Validation of those changes via controlled laboratory experiments is a crucial step in applying coccolithophorid based paleoproxies for the reconstruction of past environmental conditions. Therefore, we examined the response of two species of coccolithophores, Emiliania huxleyi and Coccolithus braarudii, to changes in the seawater Mg/Ca ratio (≈0.5 to 10 mol/mol) by either manipulating the magnesium or calcium concentration under controlled laboratory conditions. Concurrently, seawater Sr/Ca ratios were also modified (≈2 to 40 mmol/mol), while keeping salinity constant at 35. The physiological response was monitored by measurements of the cell growth rate as well as the production rates of particulate inorganic and organic carbon, and chlorophyll a. Additionally, coccolithophorid calcite was analyzed for its elemental composition (Sr/Ca and Mg/Ca) as well as isotope fractionation of calcium and magnesium (Δ^44/40Ca and Δ^26/24Mg). Our results reveal that physiological rates were substantially influenced by changes in seawater calcium rather than magnesium concentration within the range estimated to have occurred over the past 250 million years when coccolithophores appear in the fossil record. All physiological rates of E. huxleyi decreased at a calcium concentration above 25 mmol L⁻¹, whereas C. braarudii displayed a higher tolerance to increased seawater calcium concentrations. Partition coefficient of Sr was calculated as 0.36 ± 0.04 (±2σ) independent of species. Partition coefficient of Mg²⁺ increased with increasing seawater Ca²⁺ concentrations in both coccolithophore species. Calcium isotope fractionation was constant at 1.1 ± 0.1‰ (±2σ) and not altered by changes in seawater Mg/Ca ratio. There is a well-defined inverse linear relationship between calcium isotope fractionation and partition coefficient of Sr²⁺ in all experiments, suggesting similar controls on both proxies in the investigated species. Magnesium isotope ratios were relatively stable for seawater Mg/Ca ratios ranging from 1 to 5, with a higher degree of fractionation in Emiliania huxleyi (by ≈0.2‰ in Δ^26/24Mg). Although Mg/Ca ratios in the calcite of coccolithophores and foraminifera are similar, the former have considerably higher Δ^26/24Mg (by >+3‰), presumably due to differences in calcification mechanisms between the two taxa. These observations suggest, a physiological control over magnesium elemental and isotopic fractionation during the process of calcification in coccolithophores.     

Micro-Fourier Transform Infrared (FT-IR) and δD value investigation of hydrothermal vein quartz: Interpretation of fluid inclusion δD values in hydrothermal systems

Some recent studies have suggested that the hydrogen isotopic composition (δD) of hydrothermal fluids, released in vacuo by thermal decrepitation of quartz, are not always accurately revealed. We report the results of a step-heating δD value study of vein quartz, hosted by Lower Palaeozoic rocks in SW England, which was analyzed by micro-FT-IR for hydrogen speciation, before and after fluid extraction at temperatures between 750 and 1500 °C. The δD values of individual aliquots of released water vary between −3‰ and −208‰, with the lowest values generally corresponding to the highest temperature fractions and samples of relatively low yield. The data show significant departures from geologically reasonable δD. Micro-FT-IR analyses show that a variety of OH species are present within the vein quartz, with significant intra and inter sample variation. Typically a broad absorption due to molecular water, in the region 3400 cm⁻¹ is observed, along with bands attributed to Li-OH and Al-OH. On heating, the broad absorption due to molecular water is reduced, accompanied by a measurable loss of Li-OH species. The latter becomes more pronounced in the higher temperature fractions (>750 °C). These data support earlier studies which indicated that contributions from the contrasting OH reservoirs in quartz can significantly influence the reported δD values. These new data also suggest that the incorporation of OH released from Li-OH sites in the quartz may be the most important factor in the generation of the anomalous values for these samples.     

The Permian Huangshanxi Cu–Ni deposit in western China: intrusive–extrusive association,ore genesis,and exploration implications

The Permian Huangshanxi Cu–Ni deposit is the second largest magmatic sulfide deposit discovered to date in a major Ni–Cu province related to protracted basaltic magmatism in eastern Xinjiang, China. It is hosted by a small mafic–ultramafic intrusion comprised predominantly of lherzolites, olivine websterites, gabbronorites, and gabbros. The Huangshanxi intrusion is coeval with Permian basalts of tholeiitic and alkaline affinities in the Tuha and Tarim basins, respectively. To evaluate a possible genetic relationship between the Huangshanxi intrusion and a specific type of coeval basalt in the region, as well as ore genesis in the intrusion, we have carried out an integrated mineralogical, petrological, and geochemical study. Our data reveal that the Huangshanxi intrusive rocks are characterized by relatively flat chondrite-normalized REE patterns, depletion in Nb and Ta, and elevated εNd values varying between 6 and 10. These features are similar to those of coeval tholeiitic basalts in the nearby Tuha basin, but are significantly different from those of coeval alkaline basalts in the relatively remote Tarim basin. The geochemical similarities and differences suggest that the Huangshanxi intrusion is genetically related to the tholeiitic basalts in the Tuha basin, not to the alkaline basalts in the Tarim basin, as suggested previously by some researchers. This implies that regional exploration for the Huangshanxi-type Cu–Ni deposits should be centered in the Tuha basin instead of the Tarim basin. More specifically, the uplifted areas around the Tuha basin where similar intrusions may have been brought close to the surface should be carefully examined for mineralization potential. Intrusive relations and mass balance constraints from incompatible trace elements and sulfide abundances suggest that the Huangshanxi intrusion represents a dynamic magma conduit through which multiple pulses of magma ascended to higher levels or to the surface. Numerical simulation of magma evolution and mixing calculations using Sr–Nd isotopes indicate that selective assimilation of S-bearing crustal materials is important for sulfide saturation during the early stages of magma evolution when lherzolites formed. Fractional crystallization may have also played a role in the attainment of sulfide saturation during the later stages of magma evolution when olivine websterites and gabbronorites formed. In both cases, immiscible sulfide droplets were retained in the conduit to form disseminated sulfide lenses while the fractionated silicate liquids and buoyant phases such as plagioclase continued to ascend. Extremely low PGE tenors in the sulfide ores of the Huangshanxi deposit suggest that the parental magma was highly depleted in chalcophile elements possibly due to previous sulfide segregation at depth.     

The composition of magmatic Ni–Cu–(PGE) sulfide deposits in the Tati and Selebi-Phikwe belts of eastern Botswana

We studied a number of magmatic Ni–Cu–(PGE) sulfide deposits in two distinct belts in eastern Botswana. The Tati belt contains several relatively small deposits (up to 4.5 Mt of ore at 2.05% Ni and 0.85% Cu) at Phoenix, Selkirk and Tekwane. The deposits are hosted by ca 2.7 Ga, low- to medium-grade metamorphosed gabbroic–troctolitic intrusions situated within or at the periphery of a greenstone belt. The deposits of the Selebi-Phikwe belt are larger in size (up to 31 Mt of ore grade). They are hosted by high-grade metamorphosed gabbronorites, pyroxenites and peridotites believed to be older than ca 2.0 Ga that intruded gneisses of the Central Zone of the Limpopo metamorphic belt. The composition of the sulfide mineralisation in the two belts shows systematic variation. Most of the mineralisation in the Tati belt contains 2–9% Ni and 0.05–4% Cu (Cu/Cu + Ni = 0.4–0.7), whereas most of the mineralisation in the Selebi-Phikwe belt contains 1–3% Ni and 0.1–4% Cu (Cu/Cu + Ni = 0.4–0.9). The Cu–Ni tenors of the ores in both belts are consistent with crystallization from a basaltic magma. The Tati ores contain mostly >3 ppm Pt + Pd (Pt/Pd 0.1–1), with Pd/Ir = 100–1,000, indicative of a differentiated basaltic magma that remained S-undersaturated before emplacement. Most of the Selebi-Phikwe ores have <0.5 ppm Pt + Pd (Pt/Pd < 0.1–1), with Pd/Ir = 10–500. This suggests a relatively less differentiated magma that reached S saturation before emplacement. The Tati rocks show flat mantle-normalised incompatible trace element patterns (average Th/Yb_N = 1.57), except for strong enrichments in large ion lithophile elements (Cs, Rb, Ba, U, K). Such patterns are characteristic of relatively uncontaminated oceanic arc magmas and suggest that the Tati intrusions were emplaced in a destructive plate margin setting. Most of the Selebi-Phikwe rocks (notably Dikoloti) have more fractionated trace element signatures (average Th/Yb_N = 4.22), possibly indicating digestion of upper crustal material during magma emplacement. However, as there are also samples that have oceanic arc-like signatures, an alternative possibility is that the composition of most Selebi-Phikwe rocks reflects tectonic mingling of the intrusive rocks with the country rocks. The implication is that orogenic belts may have a higher prospectivity for magmatic Ni–Cu ores than presently recognised. The trigger mechanism for sulfide saturation and segregation in all intrusions remains unclear. Whereas the host rocks to the intrusions appear to be relatively sulfur poor, addition of crustal S to the magmas is suggested by low Se/S ratios in some of the ores (notably at Selebi-Phikwe). External S sources may thus remain unidentified due to poor exposure and/or S mobility in response to metamorphism.     

δB, Sr, Mg and B in a modern Porites coral: the relationship between calcification site pH and skeletal chemistry

Sr/Ca, B/Ca, Mg/Ca and δ¹¹B were determined at high spatial resolution across ∼1 year of a modern Hawaiian Porites lobata coral by secondary ion mass spectrometry (SIMS). We observe significant variations in B/Ca, Mg/Ca, Sr/Ca and δ¹¹B over short skeletal distances (nominally equivalent to periods of <20 days). This heterogeneity probably reflects variations in the composition of the extracellular calcifying fluid (ECF) from which the skeleton precipitates. Calcification site pH (total scale) was estimated from skeletal δ¹¹B and ranged from 8.3 to 8.8 (± ∼0.1) with a mean of ∼8.6. Sr/Ca and B/Ca heterogeneity is not simply correlated with calcification site pH, as might be expected if Ca-ATPase activity increases the pH and decreases the Sr/Ca and B(OH)₄⁻/CO₃²⁻ ratios of the ECF. We produced a simple model of the ECF composition and the skeleton deposited from it, over a range of calcium transport and carbonate scenarios, which can account for these observed geochemical variations. The relationship between the pH and Sr/Ca of the ECF is dependent on the concentration of DIC at the calcification site. At higher DIC concentrations the ECF has a high capacity to buffer the [H⁺] changes induced by Ca-ATPase pumping. Conversely, at low DIC concentrations, this buffering capacity is reduced and ECF pH changes more rapidly in response to Ca-ATPase pumping. The absence of a simple correlation between ECF pH and skeletal Sr/Ca implies that calcification occurred under a range of DIC concentrations, reflecting variations in the respiration and photosynthesis of the coral and symbiotic zooxanthellate in the overlying coral tissues. Our observations have important implications for the use of coral skeletons as indicators of palaeo-ocean pH.     

东昆仑夏日哈木超大型铜镍钴矿床Ni/Cu比值的地质意义

<正>夏日哈木超大型铜镍钴硫化物矿床位于青海省格尔木市以西120 km处,东昆仑中带内。探明的金属镍储量已经超过100万吨,平均品位为镍~0.65wt%,铜~0.14wt%,钴~0.013wt%(青海五院内部资料),成为仅次于金川超大型铜镍(铂族元素)矿床的我国第二大岩浆硫化物矿床,也是近年来我国     

Origin of ultra-nickeliferous olivine in the Kevitsa Ni–Cu–PGE-mineralized intrusion, northern Finland

The 2,058 ± 4 Ma mafic–ultramafic Kevitsa intrusion is located in the Central Lapland greenstone belt, northern Finland. It is hosted by a Paleoproterozoic volcano–sedimentary sequence that contains komatiitic volcanic rocks and sulfide- and graphite-rich black schists. Economic Ni–Cu–(PGE) sulfide mineralization occurs in the middle part of the ultramafic lower unit of the intrusion. Two main types of ore are distinguished, “normal” and “Ni–PGE” ores. The normal ore is characterized by ~2 to 6 vol% disseminated sulfides and average Ni and Cu grades of 0.3 and 0.42 wt %, respectively (Ni/Cu < 1). The Ni–PGE ore has broadly similar sulfide contents, but a higher Ni grade and lower Cu grade. As a result, the Ni/Cu ratio reaches 15, much higher than in the normal ore. The Ni–PGE ores occur as irregular, discontinuous, lense-like bodies in the ultramafic rocks. Notably, the olivines in the Ni–PGE ore contain extremely high Ni contents of up to 14,000 ppm, which is significantly higher than the Ni content of olivine in other mafic–ultramafic igneous rocks globally (up to ~5,000 ppm) and in harmony with the associated Ni-rich sulfide assemblage containing pentlandite, millerite and pyrite. Microprobe mapping of olivine from the Ni–PGE ore suggests relatively low and homogeneous S contents and homogeneous distribution of Ni, Mg, Fe, which is inconsistent with the presence of sulfide inclusions in the olivine grains, or diffusion of Ni from interstitial sulfides into the olivine grains. We therefore conclude that Ni substitutes for Mg in the olivine lattice. The clinopyroxenes from the Ni–PGE ore also have unusually high Ni concentrations reaching 1,500 ppm and show a positive correlation with the nickel content of the associated olivine. The Ni_cpx/Ni_olivine is ~0.1 to 0.2 corresponding to high T partitioning of Ni between clinopyroxene and olivine. K _D of 20 can account for the partitioning of nickel between olivine and the sulfide phase, consistent with magmatic equilibration. These data suggest that the olivine, clinopyroxene, and sulfides all crystallized from a basaltic magma with an unexceptionally high Ni content ranging from 300 to 1,100 ppm. The Ni–PGE ores are spatially associated with ultramafic xenoliths. Olivine in these ultramafic xenoliths have relatively high Fo contents (up to 90 mol %) and high Ni contents (up to 5,200 ppm) suggesting that the xenoliths formed from a komatiitic parental magma. It is proposed that assimilation by the Kevitsa magma of massive or semi-massive sulfides associated with komatiitic rocks elevated the Ni content of the magma and resulted in the formation of Ni–PGE ores and related extremely Ni-rich olivines.     

Dechlorination of trichloroethylene in solution over supported nano zero valent Fe and Cu/Fe bimetal on exfoliated graphite

Degradation of organic halides by reductive dehalogenation promoted by zerovalent metals is a very active research area. The use of nano-sized particles of zero valent iron （ZVI） or bimetallic combinations of ZVI currently attracts the most attention due to their high surface areas and high reactive activity. The introduction of second catalytic metals, such as Pd, Pt, Cu, or Ni, results in an even higher dehalogenation rate. The supported zero-valent iron materials have higher activity and greater flexibility for environmental remediation applications than other forms of ZVI. Nano ZVI supported on micro-scale exfoliated graphite was prepared by using KBH4 as the reducing agent in the H2O/ethanol solution of Fe^2＋ in the laboratory. Then the ethanol solution of Cu^2＋ was added to the fleshly prepared wet supported nano ZVI. The Fe/Cu bimetallic particles supported on the graphite were obtained because of the reduction and deposition of Cu on the Fe surface. The TEM image showed that iron particles were highly dispersed on the surface of graphite. In this study, supported zero valent Cu/Fe bimetallic nanoparticles were used for the dehalogenation of trichloroethylene （TCE） in batch experiments. The dechlorination rate of supported zero valent Fe/Cu bimetallic nanoparticles was greater than the supported nano ZVI. Supported Cu/Fe bimetal with 4 wt% Cu had the fastest dehalogenation rate than that with different content of Cu. When the nana FeO dosage was 5 g/L in the dehalogention system, 8 mg/L of TCE was completely dechlorinated within 4 hours. Increasing or decreasing the FeO dosage, the dechlorination rate could be worse. When the concentration of Fe^2＋ was 0.05 mol/L during the preparation by KBH4 reduction, the nano Cu/Fe particles exhibited the spheral shape with 50-80 nm in size. When the concentration of Fe^2＋ was higher （0.2 mol/L）, the nano particles were the palpus structure and had the poor dehalogenation effect on the TCE.