Fractionation Of Trace Elements Research Articles

Trace element fractionation in magnetite as a function of Fe depletion from ore fluids at the Baijian Fe-(Co) skarn deposit, eastern China: Implications for Co mineralization in Fe skarns

Trace element fractionation in magnetite as a function of Fe depletion from ore fluids at the Baijian Fe-(Co) skarn deposit, eastern China: Implications for Co mineralization in Fe skarns

The effect of grain size on the distribution and fractionation of the major chemical trace and rare earth elements in shale, silt and sand rocks of the Muqdadia formation in north of Iraq

(17) samples were collected from Muqdadia formation from various areas in Erbil governorate and Aqra district north of Iraq, which were represented by the sections (A, B, D, R, W). (10) samples were used in analyzing the element using Plasma–Mass Spectrometry (ICP–MS) Analysis and the Inductive Couple Plasma–Mass Spectrometry (ICP–MS) Analysis for four granule sizes after these granules were separated from each sample. The elements included were Al, Fe, Mg, Ca, Na, K, Ti, P, Rb, Cs, Sr, Ba, Au, Mo, Pb, Cu, Zn, As, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Cr, Ni, Co, Mn, Sc, V, Zr, Hf, Ta, Nb, Th, U, Ga, La, Dy, Ho, Er, Tm, Yb, Lu, Y.The geochemical study revealed that there is no significant variation in the content of the main, trace and rare earth elements in the four sizes of shale, silt, fine sand and coarse sand. Also, it was found that the sizes of silt and fine sand contain the highest portion of the trace elements and the rare earth element.It was also, noticed that the patterns of the rare earth elements in the granule sizes are similar in general with some differences, as these differences were reflected in some changes in the portions of these elements.In general, it was observed that the total content of the rare earth elements in the various sizes is relatively small and this might be due to two main factors; the high decrease by calcite (calcium carbonate) and the free silica (quartz) and the other reason is that the mineral that contain REEs are mostly derived from rock sources (mafic or ultra-mafic), which contain these elements with low concentrations.Patterns of REE in the study samples and the four sizes are similar to the pattern of (PAAS) with slight differences like the presence of LREE and on a lower level in HREE and also the presence of negative anomaly Ce*/Ce in the size of shale, silt, fine sand and coarse sand.Although there are variations in the values of anomaly Eu* /Eu, the values are not far from the acceptable PAAS values and they are, generally, higher than PAAS due to the presence of the mafic and ultra-mafic component in the sediments of the current study. In all the sizes, except the shale size, it was found that ∑ REE varies and increases with the increase of the contents of Al2O3 and Fe2O3.As for the shale size, it was found that the relationship between REE∑, Mn and P2O5 is negative and this is because the shale were sedimented in river environments that don’t permit them to absorb sufficient amounts of REE as is the case with the shale that are sedimented in sea environments where there is a direct contact with the seawater that although contains slight concentrations of REE but they are effective when they are adsorbed on shale particularly when the average sedimentation of the shale is low. But in the current study, the shale is river sediments and the river contains insignificant concentrations of REE and the sediment in the river is faster compared to the sea environment and this case doesn’t permit the shale to adsorb large portions of REE.

Evolution of weathering products over mylonites of the Lom series at Kissi (Bétaré-Oya Gold District, East-Cameroon): Morphological, mineralogical and geochemical mechanisms for trace and rare earth elements enrichment

Weathering and lateritization processes and their implication to the fractionation of trace and rare earth elements (REEs) in soil materials developed upon mylonites in Kissi area of the Bétaré-Oya Gold District (Lom series, East Cameroon) were assessed through morphological (position on the slopes), mineralogical (X-ray diffraction) and geochemical (X-ray fluorescence and Inductively Coupled Plasma-Mass Spectrometry) investigations. Three (03) representative soil profiles were selected and described according to the topography (upslope, mid-slope and downslope). The resulted weathering products are rich in kaolinite (16–49%), gibbsite (3–17%), goethite (5–10%) and hematite (2–10%), with quartz (30–49%) and muscovite (4–31%) as inherited minerals. Geochemical proxies and related ternary diagrams signal an intense chemical weathering (CIA: 43.3–100%; PIA: 41.9–100%), but weak lateritization (IOL: 11.3–40.8%) of parent mylonite under warm and wet tropical climate, that induce the formation of kaolinitic laterites. These processes are characterized by a weak leaching of SiO2 (79.7–52.2%), but strong one of labile elements (WIP: 48.7 to 0.8%; TRB: 228.9 to 15.1 mg kg−1). Al2O3 (16.2–22.8%) and Fe2O3 (4.2–14.0%) are the slightly enriched major oxides in the weathered materials. Some trace elements including Sc, V, Cr, Co, Ni, Cu, Ga, As, Li, Y, Mo, Cs, Hf, W, Pb, Th, Tl, U, Zr and REEs are reported as strongly enriched compared to mylonite, but weak mineralized according to their average contents in the earth's crust (Maximum Enrichment factor: 1.1–38.8). This gives rise of low mining potential of the current weathering products. Nevertheless, Ce (37.8–453.6 ppm), Ba (34.2–379.6 ppm), Cr (100.0–270.0 ppm), V (108.9–215.0 ppm), Zn (23.4–192.0 ppm), Ni (29.3–170.0 ppm) and Rb (2.5–140.0 ppm) are the most abundant in the soil profiles. Topographically, trace and REEs are preferentially enriched and mineralized at mid-slope and downslope of the interfluve. But, the overall behavior and enrichment of elements in Kissi are controlled by the dissolution of rock-forming minerals and their release in the residual soil system, their incorporation into the crystalline structure of newly formed secondary minerals and the lateral water runoff along the slope gradient.

Robust dating of Pb–Zn skarn systems by LA–ICP–MS garnet U–Pb geochronology

Lawu and Yaguila are two Pb–Zn skarn deposits in the eastern Nyainqêntanglha metallogenic belt, central Lhasa subterrane, Tibet. The genesis of Pb–Zn deposits in this belt and the crustal processes leading to their formation remain ill-constrained, mostly because of the lack of precise mineralization ages. We integrate textural information, geochemistry, and in-situ garnet U–Pb geochronology to constrain the timing and genesis of Pb–Zn mineralization. Garnets from the two deposits display oscillatory compositional zoning (And14Gr86 to And100) and contain variable U contents (0.07–5.3 ppm). Aluminum-rich garnet displays a chondrite-normalized rare earth element (REE) fractionation pattern in which LREEs are depleted relative to flattish HREE segments. In contrast, Fe-rich garnet shows LREE-enriched, relatively HREE-poor patterns with positive Eu-anomalies. Uranium concentration is correlated with total REE and Fe components in garnets, implying that U incorporation is largely controlled by coupled substitution mechanisms. The same garnets also contain measurable contents of other metals (up to hundreds of ppm), such as Sn, W, and In. The distribution and fractionation of major and trace elements in zoned garnets record periodic fluid pluses with different compositions during hydraulic fracturing. The new garnet U–Pb data show that the Yaguila deposit formed between 68.5 ± 3.4 and 65.0 ± 4.7 Ma, and the Lawu deposit formed at 54.6 ± 2.9 Ma. Within the geochronological framework of igneous rocks and Pb–Zn mineralization in the Nyainqêntanglha metallogenic belt, the new garnet ages suggest a magmatic-hydrothermal origin for related mineralization, with the causative magma likely derived from partial melting of ancient continental material due to rollback and subsequent breakoff of the Neo-Tethys oceanic slab during India–Asia continental collision. This study highlights the opportunities offered by garnet U–Pb dating for elucidating the formation age and ore genesis of base metal skarn systems.

Recycling of eroded crust by mélange diapirs evidenced from the Early Cretaceous arc magmatism in southern Tibet

Crustal material recycling in a subduction factory increases the diversity and complexity of arc magma. However, the exact origin and mechanism of its contribution to arc magma are not fully understood. Here, we present new data on the Molang basaltic rocks from the southern Lhasa terrane to gain an in-depth-understanding of the mechanisms of crustal recycling. The zircon UPb ages indicate that these rocks were emplaced at 128 Ma. They display characteristics ranging from forearc basalts to tholeiitic arc basalts with depleted mantle isotope compositions (εNd(t) = +4.58 to +4.86) and zircon ɛHf(t) values (+7.3 to +8.7). The uniform isotopic composition (SrNd) and fractionation of trace elements show that crustal materials could have been added to the magma source in the form of bulk sediment. Therefore, we have proposed an argument supporting the mélange diapirs model. The age spectra of the inherited zircons are consistent with those of the detrital zircons from the subduction hanging wall. This implies that the inherited zircons may be unmolten residues of eroded forearc crust that survived erosion and subduction from the slab in well-mixed mélange diapirs that passed through a comparatively hot mantle wedge and occur as key evidence for crustal recycling in the arc magma. Based on a synthesis of earlier research, we suggest that the Molang basaltic rocks were derived from the partial melting of the mélange diapirs in a steep subduction setting during a new subduction initiation event involving the Neo-Tethyan oceanic slab.

Geochemical Aspects of the Frictional Melting of Metapsammites during Seismic Slips (with Reference to Pseudotachylytes of the Ladoga Region)

Based on analytical data on the geochemistry of tectonic pseudotachylytes and their host rocks, the specific trends of redistribution of major, trace, and rare earth elements in the course of seismogenic frictional melting of the arkosic metaterrigenous rocks from three zones of regional metamorphism with different temperatures (greenschist, amphibolite, and granulite) in the Northern Ladoga region are discussed. Oppositely directed trends of changes in the contents of the oxides of major elements in the protolith–blastocataclasite–pseudotachylyte triad were revealed, and a unidirectional increase in the basicity of the frictional melt as compared with the protolith was established at the same time. Geochemical evidence for partial selective melting of the protoliths is discussed. The specific features of the fractionation of trace and rare-earth elements during the transition of the protolith into the melt, as well as during its subsequent partial recrystallization, are shown. The emergence of a peak of elevated europium contents relative to the protolith in the melt matrix of all three sampling points is noted. Based on changes in the concentrations of these elements in the zones of pseudotachylyte substrate generation and in the areas of its moving and injection, the estimates of their differential mobility during frictional melting in a dynamic slip zone are given.

Elemental Fractionation in Sabellariidae (Polychaeta) Biocement and Comparison with Seawater Pattern: A New Environmental Proxy in a High-Biodiversity Ecosystem?

The polychaete worm Sabellaria alveolata builds shallow-water aggregates of tubes by agglutinating sands using a secreted glue. Sabellarid bioconstructions represent fragile and dynamic habitats that host numerous associated organisms, playing a key ecological role. A two-year study on bioconstructions from three Sicilian sites (Simeto, Portopalo, and Falconara) investigated the balance between reef status and environmental parameters through a geochemical comparison of biocement tube portions and the surrounding waters. Water pollution by heavy metals, which is monitored in marine waters, is a result of river, domestic, and industrial discharges. The major constituents from the biocements of the three sites showed concentrations comparable to those in the seawater, while trace elements (Cr, Ni, Cu, Zn, and As) showed concentrations significantly higher than the mean seawater composition. These similar trends confirm a close dependence between the presence of trace elements (metals) in the seawater and the subsequent bioaccumulation in the biocement produced by the worm. The results also showed that Ca and Mg are fractionated by biocement independent of their water concentrations, in contrast to the trace elements. Further studies addressing the biomineralization processes and the relative fractionation of trace elements in Sabellaria biocement will allow it to be validated as a valuable proxy for short- and long-term environmental studies.

Changes in Speciation and Bioavailability of Trace Elements in Sewage Sludge after the Ozonation Process

This work aimed to detect changes in trace element chemical speciation in sewage sludge (SS) after the ozonation process. The modified Community Bureau of Reference (BCR) sequential extraction procedure was performed to determine the chemical speciation of trace elements in SS after the ozonation process. To assess potential soil contamination with trace elements from sewage sludge after the ozonation process, the risk assessment code (RAC) coefficient was used. The bioaccumulation factor (BAF) and translocation factor (TF) values were also calculated to characterize the efficiency of trace element accumulation in the studied plant species from soil fertilized with sludges after the ozonation process. Generally, the mean concentration of total trace elements in the SS after the ozonation process was higher, but the differences were statistically significant only in the case of Mn, Cu, Pb, and Cd. The dominant fraction of Fe, Cr, Pb, and Cd was the residual fraction F4, while the extractable/exchangeable fraction F1 was present in the smallest amount. Therefore, in the case of Mn, Zn, and Ni, the ozonation process had a significant impact on the increase in the content of these elements in the F1 fraction. The application of the SS stabilized by ozonation process for maize and wheat fertilization did not significantly affect the bioaccumulation of most of the analyzed metals in aboveground biomass. Higher values of BAF coefficients after the application of ozonated SS were found only in the case of Cu and Ni. In turn, the determined TF coefficients were lower than 1 in most cases. The obtained results showed that the slight change in the concentration of Zn, Mn, and Ni in fraction F1 causes a specific risk of their mobility in the soil environment. It should be noted that due to the variable composition of sewage sludge, an analysis of the content of individual trace elements in chemical fractions should be carried out to assess its actual impact on the environment. This can help to indicate further actions that should be undertaken to limit their negative impact on the environment.

Chemical Speciation of Trace Elements in Soil Fertilized with Biomass Combustion Ash and Their Accumulation in Winter Oilseed Rape Plants

The impact of fertilization of fly ashes from biomass combustion (BAs) on the changes in the chemical speciation of trace elements (Zn, Cu, Cr, Ni, Pb, Cd) in Gleyic Chernozem soil was analyzed in field-experiment conditions, under cultivation of winter oilseed rape plants. The three-year field experiment was carried out in southeastern Poland (50°3′ N, 22°47′ E). The three-stage sequential extraction procedure developed by the Measurements and Testing Program (BCR) was used for the fractionation of trace elements in BAs and soil. The risk assessment code (RAC) coefficient was used to assess potential soil contamination with trace elements from Bas. The total content of Zn, Cu, Cr, Ni, Pb, and Cd in BAs used in the experiment was 470, 311, 29, 78, 38, and 3.7 mg kg−1, respectively. The present study showed that the application of BAs significantly increased the total concentration of Zn and Cu in the surface layer of the Gleyic Chernozem soil, and did not significantly increase the concentration of Cr, Ni, Pb, and Cd. Generally, using BAs does not significantly change the chemical speciation of trace elements in soil. Regardless of the applied fertilization, residual fraction (F4) was the most abundant, whereas the exchangeable/extractable (F1) fraction and reducible (F2) fraction were present in the smallest amounts. Due to the low share of exchangeable/extractable fraction (F1), the BAs used in the experiment were characterized by a low RAC coefficient; hence, their use as a soil fertilizer is relatively safe for the environment. The BAs fertilization did not cause significant changes in the content of trace elements in the different parts of the winter oilseed rape plants. Due to the relatively high content of trace elements in fly ashes from biomass combustion, an analysis of the content of individual trace element fractions should be carried out to assess their actual impact on the environment. This can help indicate further actions that should be taken to limit their negative environmental impact.

A peridotite source for strongly alkalic ultrabasic HIMU lavas of the Oslo Rift, Norway

High alkali (Na2O + K2O) low SiO2 lavas generally have highly fractionated trace element compositions and their petrogenesis is debated. Both pyroxene-rich (pyroxenite) and olivine-rich (peridotite) mantle sources have been proposed for such lavas. HIMU (high 238U/204Pb) lavas usually have such compositions and are often interpreted as being derived from garnet-pyroxenite (eclogite) residue of subducted recycled oceanic crust, possibly including a carbonate component. In some cases, an origin from a garnet peridotite source has also been considered.We present new Mg, Pb, Nd, and Sr isotopic data and elemental data for alkalic ultrabasic lavas (melilitites, nephelinites) from the Oslo Rift, Norway. The magmatic province of the Permo-Carboniferous Oslo Rift is interpreted as part of the much larger Skagerrak-Centered Large Igneous Province (SCLIP) which may be related to a mantle plume source originating from the African Large Low Shear Velocity Province (LLSVP) at the core-mantle boundary. The range of δ26Mg is narrow (−0.32 to −0.28) and is similar to typical mantle values, and therefore is inconsistent with a carbonated source as has been suggested for other similar lavas. The 206Pb/204Pb values of all the lavas are high, which identifies them as HIMU lavas. The εNd of +1 to +2 are substantially lower than for typical HIMU lavas, and in the εNd-εSr diagram they plot on the LoNd array between HIMU and EMI. The lavas are more like archetypal kimberlites (formerly, Group I kimberlites), as these also have εNd slightly higher than the chondritic value and Pb isotopes consistent with a HIMU source. The REE patterns of the lavas are also almost as fractionated as in Group I kimberlites.We used major and trace elements to infer the primary magma composition of these lavas. This primary magma composition is compared with experimental melts of both carbonated peridotite and carbonated eclogite source compositions and shows that their major element compositions are only consistent with either a very high degree of melting of eclogite or a very low degree melting of garnet peridotite. The strongly fractionated REE patterns of the lavas can only be made by low-degree melting of either eclogite or garnet peridotite, which therefore effectively rules out eclogite as a major component of the mantle source of these lavas. Further trace element modeling points to a mantle source composition with >97% garnet peridotite that was lightly carbonated (<0.5 wt% CO2) and melted to a very low degree (∼0.4%) to produce these lavas. The modeled source trace element pattern was constrained by the Nd, Sr, and Pb isotopic compositions of the lavas. The measured high Ti contents of these lavas (3.8–6 wt%) are quantitatively shown to be the result of enrichment by both partial melting and fractional crystallization, using experimentally determined DTi for melting of this type of source. We also show that a low degree of melting of a slightly carbonated source is sufficient to result in the likely very high CO2 content (10–15 wt%) of the primary magma.The rather uniform Pb isotope composition of HIMU magmas suggests that the HIMU source is rather uniform in composition, but the Pb isotope composition requires this source to form late in Earth's history. The similarity of these lavas and kimberlites suggests a very deep source, possibly in the LLSVP that gave origin to the SCLIP. This means that LLSVPs do not represent some primordial layer around the core that escaped homogenization of the mantle by the Moon-forming giant impact. Instead, this layer must have formed late in Earth's history. The constraint that this source contains <3% of garnet-pyroxenite (eclogite) residue of recycled basaltic oceanic crust shows that this layer is primarily not a subducted slab graveyard. The process by which the LLSVPs formed, however, remains obscure.

Partitioning and Migration of Trace Elements during Coal Combustion in Two Coal-Fired Power Plants in Hefei City, Anhui Province, Eastern China

Coal-fired thermal power plants that meet the huge energy demand of China largely contribute to carbon emissions, environmental pollution, and human health issues. To investigate the impact of coal-fired power plants on the environment in the most developed region of eastern China, samples of feed coal, limestone, slag, fly ash, and flue gas desulfurization (FGD) gypsum were collected from two coal-fired power plants in Hefei City, Anhui Province, China. The concentrations of trace elements in these samples were determined using inductively coupled plasma mass spectrometry (ICP-MS). The results show that the feed coal was slightly rich in V, Cr, Se, In, Sb, Pb, and Ga compared to common Chinese coal. Most trace elements were concentrated in fly ash, especially in the fine particles. Only Sc, Cr, Rb, and Ba were enriched in slag. The smaller the particle size of the fly ash, the higher the fraction of volatile trace elements. The elemental concentrations of old fly ash, which was precipitated in the well of the flue gas pipeline, did not show noticeable differences from fresh fly ash. In addition, the short-time storage of fly ash did not influence the trace elements. To understand the possibility of recovering rare earth elements from coal combustion by-products, the outlook coefficients (Coutl) of coal combustion by-products for the Wanneng (WN) and Tianyuan (TY) power plants were calculated, and they were found to be promising for rare earth elements plus yttrium (REY) recovery. However, as per the evaluation diagram of cut-off grade and Coutl values, all feed coal and its by-products from these two coal-fired power plants are projected to be ‘unpromising’. Therefore, the coal combustion by-products from the WN and TY coal-fired power plants were not candidates for REY recovery.

A novel strategy to reduce trace element supplementation in the semi-solid anaerobic digestion with gradient ammonia concentration: the role of biochar

Solid anaerobic digestion of chicken manure is prone to the accumulation of volatile fatty acids (VFAs). Addition of trace elements (TEs) is an effective way to stabilize the digestion system. However, excessive supplementation of TEs may eventually cause environmental pollution. Therefore, it is necessary to develop an environmentally friendly method to reduce the addition for TEs. In this study, we explored the possibility of reducing the supplement for TEs with the assistance of biochar. The results showed that addition of biochar resulted in a 50 % decrease in the need for TE supplementation when the organic loading rate (OLR) was 5 g TS−1 d−1. Biochar increased the relative (+0.67–8.5 folds) and absolute amounts (0.1–104.6 mg kg−1 total solid (TS)) of the highly-bioavailable fraction of TEs (exchangeable fraction (F2)) by chemical adsorption. The conductivity of biochar increased from 4.2 to 38.4 mS m−1 after adsorbing TEs, which might explain the enrichment of conductive microorganisms (+16 folds) in the digestion system, such as Geobacter (34-fold increase). Substitution of TEs with biochar increased the absolute amounts of Methanosaeta, Mathanosarcina, Methanoculleus, and Methanospirillum by 72.7 %, 5.7 %, 46.1 % and 2.7 %, respectively, and propionate and butyrate oxidizing bacteria (Syntrophomonas, Syntrophobacter, and Smithella) had the highest abundance. In summary, beneficial interactions between biochar and TEs makes biochar an ideal material for reducing the amounts of TEs needed to stabilize the semi-solid anaerobic digestion (SSAD) system.

Redistribution and fractionation of trace and rare earth elements during weathering and lateritization of orthogneiss in Ndokayo (Bétaré-Oya Gold District, South East Cameroon)

Ferralsols in the transitional zone between the Adamaoua and the South Cameroonian plateaus provided evidence of significant economical and scientific interests, but they have received very little attention over the last decades. Thus, macroscopic, mineral and geochemical investigations of two residual soil profiles from orthogneiss in the Bétaré-Oya Gold District (BOGD) with significant morphological differences were conducted in order to assess weathering and lateritization processes and their significance to the occurrence of mineralized trace and rare earth elements. Macroscopically, soil profile in upslope is deep weathered and thick (> 8.0 m thick), exhibiting a 5.1 m thick encrusted mineral level. Inversely, the downslope soil profile is moderately weathered and marked by a near surface water table that partly affects the mineral horizon B. These studied ferralsols result from an intense weathering but weak to moderate lateritization as revealed by the Chemical Index of Alteration (CIA: 87 to 99%), the Plagioclase Index of Alteration (PIA: 98 to 100%) and the Index of Lateritization (IOL: 31.48 to 60.83%). The two soil profiles have a similar mineralogical content characterized by the predominance of newly-formed secondary minerals such as kaolinite (12–40%), gibbsite (12–27%), goethite (7–15%), hematite (2–15%), maghemite (6–10%) and anatase (1–2%). However, a considerable amount of residual quartz (16–56%) and muscovite (3–15%) is evidenced in the weathering products. Geochemically, the weathering products of Ndokayo show weak to moderate depletion of SiO2 (77.26–31.82%), strong depletion of alkali and alkaline earths (Weathering Index of Parker or WIP: 56.73 to 1.56), and moderate enrichment of Al2O3 (12.43–29.20%), Fe2O3 (1.26–23.45%) and TiO2 (0.11–1.77%). V (64.67–210 ppm) and Cr (25.81–720 ppm) are the most enriched trace elements in this area, with their respective maximum enrichment factor of 2 and 7, and display similar geochemical patterns with Fe2O3, suggesting their adsorption or incorporation into the crystalline structure of Fe-oxides. Some others mineralized trace elements (Sc, Ga, As, Mo, Sn, Cs, Pb, Bi, Th and U) exhibit low to moderate contents, even if their mineralization indices range between 1 and 81. This is indicative of low mining potential of the Ndokayo weathering products. Finally, the deep and intense weathering of orthogneiss, coupled with weak to moderate lateritization of the weathering products in the study area is controlled by rock type involving the formation of kaolinitic laterites and bauxitious kaolins with weak mineralization indices of some trace and rare earth elements.

Experimental Crystallization of the Beauvoir Granite as a Model for the Evolution of Variscan Rare Metal Magmas

Abstract New experiments on the strongly peraluminous, Li-, P- and F-rich Beauvoir granite (Massif Central, France) provide a basis for understanding crystallization and chemical fractionation in Variscan rare metal magmas. Crystallization experiments were performed on two natural granite compositions under H2O-saturated conditions at 100, 200, and 300 MPa, from 540°C to 700°C and between ~NNO + 3 and NNO-1.4. Experimental charges were examined by SEM and their products (glasses and crystals) analyzed for major elements by EMPA. Trace element concentrations in selected glasses were determined by LA ICP-MS. Despite experimental durations commonly exceeding 1000 h and some up to 4000 h, kinetic problems were encountered in particular in the 100 MPa charges whereas, at 200 and 300 MPa, results consistent with previous melting experiments were obtained. Beauvoir melts crystallize quartz, plagioclase, K-feldspar and mica as major phases. At NNO-1.4, mica is a biotite, whereas it is a Li-mica between ~NNO+3 and NNO-1. Apatite, Fe-Ti oxides, either hematite or magnetite, topaz, amblygonite, cassiterite and columbite-tantalite appear as accessory phases between ~NNO + 3 and NNO + 1. Experimental plagioclases are albitic (An &amp;lt;4.5 mol%) and more Ca and K-rich than natural albites in the granite whereas experimental K-feldspars are more sodic (Ab &amp;lt;45 mol%) than the natural crystals. The less evolved starting melt crystallized Li phengites whereas the most evolved yielded Li-, F-rich micas near the polylithionite-zinnwaldite series, similar to natural micas in the granite. Equilibrium crystallization increases A/CNK, F and P and concentrates Li, Be, B, Rb, Cs, W, U in the melt. Nb and Ta are also enriched, their behavior being controlled by the solubility of columbite-tantalite in the melt. Other elements are either unchanged (Mn, Zn, Ti) or depleted (Sr, Pb) during magmatic fractionation. Sn is concentrated in Li-mica and hematite, and it behaves compatibly at high fO2. Beauvoir melts crystallize at very low temperatures, below 670°C for the two compositions studied and solidus temperatures, determined from previous melting experiments and confirmed by the new crystallization experiments, are near 550°C. The experiments demonstrate that most of the mineralogical and geochemical characteristics that make the Beauvoir granite distinctive result from magmatic rather than hydrothermal post-magmatic processes. Albitic plagioclase, Li-mica, topaz, and amblygonite are of magmatic origin. Glass major element compositions suggest that the two granite samples represent crystallized liquids. Trace element fractionations for most elements at Beauvoir can be accounted for by magmatic crystallization–differentiation processes. Implications for the mineralogy, fO2, volatile concentrations, crystallization and conditions of emplacement, fractionation mechanisms and origin of the Beauvoir granite are discussed.

The petrogenesis of chemically zoned, phonolitic, Plinian and sub-Plinian eruptions of Somma-Vesuvius, Italy: Role of accessory phase removal, independently filled magma reservoirs with time, and transition from slightly to highly silica undersaturated magmatic series in an ultrapotassic stratovolcano

A mineralogical, major, LA-ICP-MS trace element mineral chemistry and bulk-rock geochemical study of juvenile samples of the Mercato, Avellino, Pompeii and Pollena eruptions, collected in stratigraphically and volcanologically well-characterized sections of the Somma-Vesuvius stratovolcano (Roman Magmatic Province), along with reference data on the 1944 CE and the Pomici di Base eruptions, highlights the compositional variability of bulk-rock and glass from leucite phonotephrite to garnet-bearing phonolite . The latter products have extreme fractionation of trace elements (e.g., La/Yb n = 126, Zr/Y = 89, Zr/Hf =78, Nb/Ta = 40; Th/U = 2.3), very low Sc, V, Y, HREE and very high As, Tl, Cs, Pb, Th and U. The Pomici di Base products, older than the eruptions described above, range from leucite-bearing shoshonites to trachytes , are devoid of garnet and belong to an independent liquid-line-of-descent, having also different fractionation between trace elements (e.g., La/Yb n = 15; Zr/Y = 12.4, Zr/Hf = 50, Nb/Ta = 15.6; Th/U = 3 in the Pomici di Base trachytes). A marked chemical variability of the observed phases is found. The geochemistry of garnet, amphibole , clinopyroxene and other phases shows wide variations of concentrations and elemental ratios (e.g., La/Yb n up to 520 in the sadanagaite coexisting with garnet). The magmatic evolution is dominated by low-pressure, oxidized, nearly closed-system fractional crystallization of clinopyroxene, plagioclase , leucite, ±magnetite, ±biotite, ±olivine and apatite in the transition tephrite-phonotephrite, and of potassic sanidine (±hyalophane), Fe-clinopyroxene, melanite garnet±Fe-amphibole in the transition tephriphonolite-phonolite. Mineralogic and geochemical evidence and modelling points out the existence of independent, zoned magma batches throughout the activity of the stratovolcano, which possibly started to crystallize at similar depths. The Somma-Vesuvius magmas thus evolved in shallow independent reservoirs with respect to those of the neighbouring volcanic complexes (Campi Flegrei, Ischia) as shown, for instance, by the contrasting compositional trends of clinopyroxene and amphibole, and have very limited evidence of crustal contamination (and/or carbonate assimilation). • Pollena, Pompeii, Avellino and Mercato are zoned eruptions with phonolites • The magmas which formed the various eruptions evolved independently • Different garnets dominate HREE, Y and HFSE; amphibole is strongly HREE-poor • The phonolites and their mineral compositions have no tendency to become peralkaline • F, Cl and H 2 O dominate the volatile budget

Metalloenzyme signatures in authigenic carbonates from the Chukchi Borderlands in the western Arctic Ocean

Migration of methane-rich fluids at submarine cold seeps drives intense microbial activity and precipitation of authigenic carbonates. In this study, we analyzed microbially derived authigenic carbonate samples recently recovered from active gas hydrate mounds on the southwestern slope of the Chukchi Borderlands (CB), western Arctic Ocean. Our main aim was to characterize the distribution patterns of trace elements in carbonate-hosted lipid fractions to assess metalloenzyme requirements of microbes involved in anaerobic oxidation of methane (AOM). We measured stable isotopes, trace elements, lipid biomarkers, and genomic DNA, and results indicate the dominance of AOM-related lipid biomarkers in studied carbonate samples, as well as a predominant occurrence of the anaerobic methanotrophic archaea (ANME)-1. We also report evidence for significant preferential enrichments of various trace elements (Li, Ni, Co, Cu, Zn, and Mo) in the total lipid fractions of CB carbonates, relative to elemental compositions determined for corresponding carbonate fractions, which differ from those previously reported for other seep sites. We hypothesize that trace element enrichments in carbonate-hosted lipid fractions could vary depending on the type of AOM microbial assemblage. Additional work is required to further investigate the mechanisms of lipid-bound trace elements in cold seep carbonates as potential metalloenzymes in AOM.

Stagnated eclogitic slab-related shoshonitic series volcanic rocks in West Tianshan, Xinjiang, China: Insights from Li-B-Sr-Nd-Hf-Pb isotope and trace element compositions

This study presents major, trace element and Li-B-Sr–Nd–Pb-Hf isotope compositions of post-collisional (Permian) shoshonitic volcanic rocks (SVRs) from West Tianshan, NW China. Zircon U Pb dating indicates that the West Tianshan SVRs were mainly formed in the late Early Permian (272–279 Ma). They include absarokites, shoshonites and banakites, which have variable SiO 2 (46–63 wt%) and K 2 O (2.12–8.12 wt%) contents. They display enrichment in light rare earth elements (LREE) and depletion in heavy rare earth elements. They are enriched in large ion lithophile elements (e.g., La, Rb and Ba) and depleted in high field strength elements (e.g., Nb, Ta and Ti) with slightly negative to negligible Eu anomalies, pronounced positive Pb anomalies and low Nb/U (9.32 ± 6.54), Ce/Pb (0.14–10.0, average 5.03 ± 3.02), relatively high Nb/Ta (16.74 ± 2.72) and Zr/Hf (39.56 ± 6.06) ratios. They have relatively high Li contents (26.0–93.0 ppm) and B contents (6.19–84.7 ppm), and low but variable δ 7 Li (−4.0‰ to +2.4‰). They are characterized by low ( 87 Sr/ 86 Sr) i (0.7045–0.7068), positive ε Nd (t) values (+0.31 − +5.53), relatively low 206 Pb/ 204 Pb (18.16–18.65), 207 Pb/ 204 Pb (15.51–15.63) and 208 Pb/ 204 Pb (37.97–39.22) and positive ε Hf (t) (+5.4 − +12.5). These features consistently suggest a metasomatized enriched mantle source having affinities with an EM I-like reservoir for the SVRs. Source enrichment was generated dominantly by subducted slab related aqueous fluid and altered oceanic crust (AOC) melts. Dehydration modeling of Li and B isotopes and Li, Y, B, Nb trace element fractionation collectively show that the flat, deeply subducted and stagnated, eclogitic slab suffered progressive dehydration(~5–12%)and was distinctly 7 Li-depleted. Based on these compositional features and model calculations, we suggest that West Tianshan SVRs had an enriched mantle source metasomatised by aqueous fluid and hydrous slab melt, and their parental magmas were derived from variable mixing of spinel and garnet peridotite (60Gt:40Sp − 80Gt:20Sp). Taking into account petrogenetic and regional tectonic data, we suggest that the West Tianshan SVRs developed in an intraplate setting during the late Early Permian. It is most probable that the Early Permian Tarim mantle plume, located in the south side of the study area, promoted Early Permian asthenospheric upwelling that resulted in melting of a fossil subduction-enriched source to produce shoshonitic volcanic rocks in the West Tianshan. • Lower δ7Li and wider range are evidently lighter than most volcanic suites world-wide. • A deeply subducted and stagnated eclogitic slab is one end-member of enriched source. • Parental magmas were from mixing of garnet and spinel peridotite (60/40–80/20). • SVRs formed in post-collision transition from subduction-related to intraplate setting.

The A B C's of metasomatism in the North Atlantic Craton during Pangea breakup; characterized by fluid inclusions in Chidliak diamonds

Here we report the nitrogen characteristics and composition of high-density fluid (HDF) trapped in microinclusions in a suite of fibrous diamonds from the ~142 Ma Chidliak CH-7 kimberlite pipe, the Hall Peninsula, southern Baffin Island, Nunavut. Within these diamonds, we observe three populations based on the chemistry of the encapsulated HDFs, the diamond's nitrogen aggregation states, and the diamond color. ‘Chidliak C' diamonds contain highly silicic HDFs, have nitrogen in A- and C-centers (with 5–20% in C-centers), and a characteristic intense yellow color. ‘Chidliak A' diamonds contain silicic to low-Mg carbonatitic HDFs, carry nitrogen solely in A-centers, and are mostly colorless. A third population, ‘Chidliak B', has grey color and distinctive low-K2O silicic to low-Mg carbonatitic HDF compositions and overall smoother and less fractionated trace element pattern relative to ‘Chidliak C' and ‘Chidliak A' diamonds; they carry nitrogen in A- and B-centers (with ~15% in B-centers) and are characterized by a grey hue. An eclogitic paragenesis of all diamonds is evident by the HDF compositional variation as well as the presence of omphacitic clinopyroxene inclusions. The appearance of a diamond with A- and B-centers in its octahedral core and A- and C-centers in its coat suggests formation at two distinct events at a similar depth. Combined with pressure and mantle residence estimates based on nitrogen aggregation considerations, we argue that the three diamond populations formed at the relatively shallow region of the lithosphere (likely <180 km) during distinct metasomatic events in the North Atlantic Craton (NAC) since the Proterozoic. The youngest event by silicic HDFs took place close in time to kimberlite activity at 142–157 Ma, as evident by the preservation of nitrogen C-centers in ‘Chidliak C' diamonds. A link between this event and the mid-lithosphere discontinuity (MLD) in eclogitic portions of the cratonic lithosphere in Chidliak is plausible. The timing of ‘Chidliak A' diamonds formation by more carbonatitic HDFs is less well constrained, but can be related to Ca-rich metasomatism observed in local peridotite xenoliths and/or alkaline magmatism between 610 and 550 Ma. A possible link between the formation of ‘Chidliak B' diamonds and the timing of Mesoproterozoic olivine lamproite magmatism ca. 1400 Ma is suggested based on the HDF trace element composition and the aggregated nature of nitrogen in these diamonds. The nitrogen systematics and eclogitic source of the fibrous diamonds are comparable with those observed for previously studied gem-quality diamonds from Chidliak. We suggest that these similarities show a temporal connection and mutual crystallization of the two diamond types. This strengthens the involvement of HDFs in the formation of gem-quality diamonds.

Genesis of Chaoshan skarn Au deposit, Tongling, eastern China: Insights from mineral geochemistry

Skarn Au deposits are particularly developed along Middle and Lower Yangtze River region, eastern China, but gold behavior and genesis of the skarn Au deposits remain unclear. Whole-rock geochemical, sulfur isotopic and in-situ mineralogical data from the mineralized alteration stages of Chaoshan skarn Au deposit in Tongling region are systemically investigated to reveal Au distribution and precipitation, and useful information for ore-forming process. The altered rocks and ores in the Chaoshan deposit have total REE contents of 7.81–226 ppm and show LREE enrichment patterns with weak negative to positive Eu (δEu = 0.71–2.24) anomalies. Electron probe microanalysis results indicate that garnet and pyroxene of the Chaoshan deposit are grossular-andradite and diopside-hedenbergite series, respectively. In situ elemental compositions of the euhedral pyrite analyzed show that invisible Au is mainly of lattice-bound Au+ in As-bearing pyrite. The studied pyrite samples also have high Co/Ni (mainly >1) and Se/Tl (>10) ratios, highly variable Pb and As contents, low Se content (<5.00 ppm), low Tl/Pb and Sb/Pb ratios, and relatively consistent sulfur isotopic compositions (5.0–8.3 ‰). The distinctly geochemical characteristics indicate that the Chaoshan skarn Au mineralization was likely derived from a magmatic-hydrothermal system. A comprehensive discriminant analysis shows that the Au precipitation and enrichment of the Chaoshan deposit are a result of boiling-induced trace element fractionation resulted from fluid boiling during the skarn formation process.

Fractionation of trace and platinum-group elements during metamorphism of komatiitic chromites from the early Archean Gorumahishani greenstone belt, Singhbhum Craton (eastern India)

It is well established that the major and minor element contents of chromites are subject to change during greenschist to amphibolite facies metamorphism. During upper amphibolite facies metamorphism, chromite can be completely converted to chrome magnetite. However, not all elements are affected to the same degree, the concentrations of +2 ions (e.g. Zn, Co, Mn) being particularly vulnerable to modification. The degree to which trace elements, particularly the platinum-group elements (PGE), are affected has not been closely examined. The compositions and textures of chromites from komatiites of the Gorumahishani greenstone belt of the Singhbhum Craton (India) have experienced a range of metamorphic conditions from greenschist to amphibolite facies, providing the opportunity to study the changes of trace and platinum-group element composition with metamorphic grade. Five types of altered chromites are identified from the komatiitic suite of rocks in the ~120-km-long greenstone belt. The type-I chromites are non-porous and characterized by the least modified cores. These chromites are mostly present in the northern Maharajgunj-Tua Dungri section where rocks show metamorphism from greenschist to greenschist-amphibolite transition facies. The type-II and type-III chromites are porous and mostly found in the southern Kapili section of the greenstone belt where rocks show metamorphism up to the mid-amphibolite facies. Type-IV and type-V chromites are completely modified to ferritchromit and chrome magnetite, respectively, and are present in the komatiitic rocks from the entire greenstone belt. The central cores of the type-I and type-II grains have relatively higher concentrations of mobile trace elements (e.g. Zn, Co, and Mn) with higher Mg# [Mg/(Mg + Fe2+)], lower Cr# [Cr/(Cr + Al)], and lower Fe3+/R3+ (R3+ = Fe3+ + Cr3+ + Al3+) ratios than their respective rims. Significantly higher concentrations of the immobile trace elements (e.g. Ti and V) in the cores of the type-II grains relative to their chrome magnetite rims from the Kapili section and to the type-I varieties from other sections might be due to the metamorphism of the komatiitic rocks under higher-grade conditions (amphibolite facies). In situ LA-ICPMS analysis for PGE reveals a relatively higher concentration of Ru and Rh in the rims of the type-I chromites than in the cores which is due to the diffusion of these elements from the normal spinel structure of the cores towards the bivalent octahedral sites of the inverse spinel structure of the chrome magnetite rims during metamorphic processes. The lower concentrations of Os, Ir, Ru, and Rh in the cores of the type-II chromites from the Kapili section might be related to the metamorphism of the rocks under higher-grade conditions that facilitated the diffusion of these elements to associated sulphide or platinum-group mineral or alloy phases. The calculated partition coefficients of Sc, Ti, V, Mn, Ni, Ga, Os, Ir, Ru, and Rh from the least altered chromite cores assuming equilibrium with the parental komatiitic melt also suggest the variable effects of metamorphism when compared with global experimental and empirical values of the natural samples.