Bulk Geochemical Data Research Articles

Insights on the formation of layered ferromanganese precipitates from the southern Mariana Arc, West Pacific, from micron-scale major, minor, and trace element variations

A combined laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and energy dispersive X-ray spectroscopy (EDS) study was used to map 49 elements in four FeMn precipitates produced from three different genetic processes (hydrogenetic, hydrothermal, and mixed-type hydrogenetic-hydrothermal) in samples obtained from the southern Mariana Arc. Results show Mn-oxide minerals are consistently found to be associated with Ba, Mo, Sb, V, Zn, and the rare earth elements and yttrium (REY), excluding Ce, whereas Fe-oxyhydroxide minerals are primarily associated with Ti, Co, Cr, Cu, Nb, and Pb. Element distributions in FeMn precipitates from the southern Mariana Arc differ from deposits formed in other environments; notably, there is a decoupling of As and Sb, and redox-sensitive elements are more variable than non-redox-sensitive elements. Samples previously classified as either hydrogenetic or hydrothermal in origin, based on bulk geochemical data, show characteristics of both at higher resolution. Combining high resolution in-situ data with genetic classification discrimination diagrams reveals more ambiguity in metal and metalloid origin than previously thought. Mariana Arc FeMn precipitates can be separated into two formation sub-types (hydrothermal or mixed hydrothermal/hydrogenetic) based on textural and compositional differences, e.g., differences in Ce/Ce and Y/Ho values and relative variations in (Zr + Y + Ce) versus (Co + Ni) versus (Mn + Fe). Improved classification and knowledge of how fast-growing hydrothermal FeMn precipitates form may help us identify a relatively renewable critical metal resource.

Metal impact and vaporization on the Moon's surface: Nano‐geochemical insights into the source of lunar metals

AbstractMillimeter‐to‐nanometer‐sized iron‐ and nickel‐rich metals are ubiquitous on the lunar surface. The proposed origin of these metals falls into two broad classes which should have distinct geochemical signatures—(1) the reduction of iron‐bearing minerals or (2) the addition of metals from meteoritic sources. The metals measured here from the Apollo 16 regolith possess low Ni (2–6 wt%) and elevated Ge (80–350 ppm) suggesting a meteoritic origin. However, the measured Ni is lower, and the Ge higher than currently known iron meteorites. In comparison to the low Ni iron meteorites, the even lower Ni and higher Ge contents exhibited by these lunar metals are best explained by impact‐driven volatilization and condensation of Ni‐poor meteoritic metal during their impact and addition to the lunar surface. The presence of similar, low Ni‐bearing metals in Apollo return samples from geographically distant sites suggests that this geochemical signature might not be restricted to just the Apollo 16 locality and that volatility‐driven modification of meteoritic metals are a common feature of lunar regolith formation. The possibility of a significant low Ni/high Ge meteoritic component in the lunar regolith, and the observation of chemical fractionation during emplacement, has implications for the interpretation of both lunar remote‐sensing data and bulk geochemical data derived from sample return material. Additionally, our observation of predominantly meteoritic sourced metals has implications for the prevalence of meteoritic addition on airless planetary bodies.

Controls on Quaternary geochemical and mineralogical variability in the Koora Basin and South Kenya Rift

The South Kenya Rift is comprised of a series of N-S-oriented grabens with sediments that preserve an approximate one-million-year environmental history that reflects the interplay of climate, tectonism and volcanism. This study attempts to disentangle the relative roles of these major controls by comparing the geochemical records preserved in three sedimentary basins. The study focuses on the Koora Basin using bulk geochemical data in a 139-m-long core. This record is then compared with geochemical data and environmental histories from a 196-m-long core at Magadi and outcrops in the Olorgesailie Basin. Four climatic phases (1000–850; 850–470; 470–400; 400–0 ka) are recognised at Koora, which can also be distinguished in the Magadi and Olorgesailie Basins. However, inter-basin contrasts also suggest that additional, non-climatic factors influenced these geochemical histories, particularly during four intervals. These include 1) the Magadi Transition (MT; ∼770–700 ka), 2) the Magadi Tectonic Event (MTE; ∼540 ka), 3) the Koora Instability Period (KIP; ∼325–180 ka), and 4) the Trona Precipitation Period (TPP; ∼105–0 ka). Prior to the MT, Zr/TiO2, La/Lu, Mo, As, V and Na/Ca in Magadi and Koora cores were similar but afterwards diverged. Major reductions in transition metals at Magadi during the MTE reflect tectonically-induced cross-rift drainage diversion. This contrasts with the Koora and Olorgesailie basins where these metals were constant from ∼1000 to 300 ka. The KIP represents a significant increase in volcanic inputs to the Koora Basin and increased geochemical variability. Bromine (Br), which reflects peralkaline volcanic activity and/or evaporative concentration, is elevated during the KIP at Koora but is below detection limits in the rest of the Koora core. Br in the Magadi core does not correlate with that in the Koora record, suggesting contrasting accumulation processes. The TPP represents a phase of trona precipitation at Magadi but not at Koora. This difference partly reflects increased magmatic CO2 rising along faults in the Magadi basin during a period of increasing aridity. Rare-earth element patterns indicate a major change at Magadi with many anomalies after about 325 ka to the present, caused by the development of hypersaline waters, which did not occur at Koora or Olorgesailie. The geochemical data from the three basins help to partially separate climatic controls from those related to volcanism, tectonism and local geomorphology.

Cryptic trans-lithospheric fault systems at the western margin of South America: implications for the formation and localization of gold-rich deposit superclusters

We present a review of frontier research advances in the investigation of cryptic structures that transect the South American Andes at oblique strike directions. The intersections between these cryptic structures and the superimposed Andean belt correlate with the spatial distribution of gold-rich mineral deposit clusters. The deposit clusters can be described as superclusters, as they comprise various gold deposit types that formed at multiple times throughout the Phanerozoic, impinging repeatedly on the structural intersections. However, the cryptic inherited fault structures are difficult to detect, because their deeper-seated roots are often overlain by younger supracrustal successions, and/or their exposed surface manifestations are structurally obscured by subsequent tectonic-magmatic activity. Thus, it also remains a challenge to constrain the nature and timing of formation, and the respective subsequent evolutionary path, of these proposed pre-Andean structures. Based on various case studies, we demonstrate that the localization of identified Phanerozoic gold deposit superclusters along the western South American margin is fundamentally controlled by structural inheritance often dating back to at least the Mesoproterozoic. Integration of multi-approach observations and datasets allows insights into a larger-scale tectonic history that showcases the successive inheritance of major structures originating from the Amazonian Craton, over the Paleozoic Gondwana margin, into the Cenozoic magmatic belts of the Andes, and even into recent fractures within the subducting oceanic Nazca plate, recording >1.2-billion-years of progressive structural inheritance and growth at one of the longest-lived tectonic margins in Earth history. In contrast to previous models of the spatial distribution of gold deposits, based on statistical approaches and spatial periodicity in self-organized systems focusing on single subduction and/or accretion episodes and belts, we propose that the structural inheritance and intersections are key to the localization of gold deposits in the Andes. In combination with bulk-geochemical data from magmatic rocks, we suggest that inherited structures maintained a trans-lithospheric connectivity to pre-fertilized gold enriched upper mantle reservoirs, which were tapped during multiple tectono-magmatic reactivation episodes.

What do dust sinks tell us about their sources and past environmental dynamics? A case study for oxygen isotope stages 3–2 in the Middle Rhine Valley, Germany

Abstract. The study of geological archives of dust is of great relevance as they are directly linked to past atmospheric circulation and bear the potential to reconstruct dust provenance and flux relative to climate changes. Among the dust sinks, loess–palaeosol sequences (LPSs) represent the only continental and non-aquatic archives that are predominantly built up by dust deposits close to source areas, providing detailed information on Quaternary climatic and terrestrial environmental changes. Upper Pleistocene LPSs of western central Europe have been investigated in great detail showing their linkage to millennial-scale northern hemispheric climate oscillations, but comprehensive data on dust composition and potential source–sink relationships as well as inferred past atmospheric circulation patterns for this region are still fragmentary. Here, we present an integrative approach that systematically combines sedimentological, rock magnetic, and bulk geochemical data, as well as information on Sr and Nd isotope composition, enabling a synthetic interpretation of LPS formation. We focus on the Schwalbenberg RP1 profile in the Middle Rhine Valley in Germany and integrate our data into a robust age model that has recently been established based on high-resolution radiocarbon dating of earthworm calcite granules. We show that Schwalbenberg RP1 is subdivided into a lower section corresponding to late oxygen isotope stage 3 (OIS; ∼ 40–30 ka) and an upper section dating into the Last Glacial Maximum (LGM; ∼ 24–22 ka), separated by a major stratigraphic unconformity. Sedimentological proxies of wind dynamics (U ratio) and pedogenesis (finest clay) of the lower section attest to comparable and largely synchronous patterns of northern hemispheric climatic changes supporting the overall synchronicity of climatic changes in and around the North Atlantic region. The anisotropy of magnetic susceptibility (AMS) reveals a clear correlation between finer grain size and increasing AMS foliation within interstadials, possibly owing to continuous accumulation of dust during pedogenic phases. Such a clear negative correlation has so far not been described for any LPS on stadial–interstadial scales. Distinct shifts in several proxy data supported by changes in isotope composition (87Sr/86Sr and εNd) within the lower section are interpreted as changes in provenance and decreasing weathering simultaneously with an overall cooling and aridification towards the end of OIS 3 (after ∼ 35 ka) and enhanced wind activity with significant input of coarse-grained material recycled from local sources related to increased landscape instability (after ∼ 31.5 ka). We find that environmental conditions within the upper section, most likely dominated by local to regional environmental signals, significantly differ from those in the lower section. In addition, AMS-based reconstructions of near-surface wind trends may indicate the influence of north-easterly winds beside the overall dominance of westerlies. The integrative approach contributes to a more comprehensive understanding of LPS formation including changes in dust composition and associated circulation patterns during Quaternary climate changes.

INTEGRATED ANALYSIS FOR ASSESSMENT OF DEEPER HYDROCARBON PLAY POTENTIAL IN REBAB-1, CENTRAL LUCONIA PROVINCE, SARAWAK

The basin history, thermal maturity, and hydrocarbon entrapments of Rebab-1 Well in Central Luconia have been relooked through the study of seismic, well log, and geochemical data to find new hydrocarbon potential in the deeper section of the well. The quality of source rocks in this area was based on assumptions, and hydrocarbon exploitation only occurs on shallow hydrocarbon plays making the potential for deeper plays difficult to ascertain. This study was conducted based on two 2D seismic lines, integrated with well lithological and stratigraphy data and geochemical data such as total organic carbon, pyrolysis, and vitrinite reflectance. Integration of these data was used to determine the deeper hydrocarbon play of Rebab-1 in Central Luconia Province. The seismic data were interpreted using Petrel software with validation from the report. Cross-plots from bulk geochemical analysis data were interpreted for the source rock's organic richness, kerogen quality, hydrocarbon-generating potentials, and thermal maturation levels. The results of seismic interpretations showed that extensional and compressional tectonics shaped the field of Rebab-1, with structures mainly trending to the NW-SE and NE-SW directions. Geochemical analysis showed that the total organic carbon content (TOC) of the samples analysed ranges between 0.06 and 2.98 wt.% indicating fair to very good source rocks producing mainly type II and mixed type II-III kerogen as the dominant kerogen. These types can generate mainly gas and mixed oil and gas accumulations upon attaining thermal maturation level. Also, Rebab-1 shows fair to very good hydrocarbon-generating potentials. The vitrinite reflectance (Ro) and Tmax results showed that the analysed samples are generally plotted in the immature, mature, and post-mature stages of oil generation but still within the gas generation window. Overall, source rocks from Rebab-1 can be said to have attained maturity at the youngest during depositions of Cycle III to older than that, and faulting and folding serves as hydrocarbon trap systems, indicative of potential in having deeper hydrocarbon plays in Rebab-1 well.

The early opening of the Equatorial Atlantic gateway and the evolution of Cretaceous peak warming

Abstract The Cretaceous opening of the Equatorial Atlantic gateway (EAG) is considered a driver of major changes in global oceanography, carbon cycling, and climate. However, the early stages of EAG opening are poorly understood. We present seawater Nd-isotope, bulk geochemical, and micropaleontological data from two South Atlantic drill cores that constrain the onset of shallow (<500 m) and intermediate (<~1000 m) water mass exchange across the EAG to 113 Ma and 107 Ma, respectively. Deep water mass exchange (>2000 m) was enabled by at least ca. 100 Ma, as much as 10 m.y. earlier than previously estimated. In response to EAG opening, deep-water ventilation in the South Atlantic, North Atlantic, and Tethys basins intensified, thereby triggering basin-scale reductions in organic carbon burial. We propose that the consequent drop in carbon sequestration in concert with increased atmospheric CO2 fluxes from subduction zones acted as major amplifiers of global warming that culminated in peak greenhouse conditions during the mid-Cretaceous.

Stratigraphy of the Cenozoic succession in eastern Azerbaijan: Implications for petroleum systems and paleogeography in the Caspian basin

The Cenozoic succession in the Lower Kura Basin includes largely uniform, often carbonate-free mudstones. Because age dating of these sediments has proved difficult, the stratigraphy of the Cenozoic succession and the distribution of organic-rich strata are poorly known. A better understanding of the Cenozoic succession is not only important for petroleum-systems-analysis, but also for the understanding of the Cenozoic evolution of the Caucasus region. Therefore, bulk geochemical data (carbonate, TOC, sulphur, Rock-Eval) of 885 samples and biostratigraphic data were collected along seven outcrop profiles. This enabled the establishment of a continuous stratigraphic record from the Middle Eocene to the Late Miocene (Pontian). The study results show that potential source rocks are present in three stratigraphic units: the Middle Koun (Middle Eocene), Maikop Group (Oligo-Miocene) and Diatom Formation (Upper Miocene). The Middle Koun is about 100 m thick near the Caspian Sea and contains highly oil-prone sediments (2–24 wt% TOC; HI 300–577 mgHC/gTOC), which may generate 1.5 tHC/m2. The Maikop Group contains on average 1.8 wt% TOC, but is often gas-prone. Highly oil prone layers (2–5 wt% TOC; HI 300–450 mgHC/gTOC) are rare. Nevertheless, the Upper Maikop Formation may generate ∼2 tHC/m2. The Diatom Formation contains paper shales with high TOC contents (3–22 wt%) and HI values (350–770 mgHC/gTOC). The paper shale unit is more than 60 m thick near the Caspian Sea and can generate 3.8 tHC/m2. Previously it was thought that the Maikop Group had the highest petroleum potential, whilst Upper Miocene and Middle Eocene source intervals were overlooked. The Middle Eocene to Lower Oligocene succession in the Kura Basin is largely carbonate-free. In contrast, coeval successions elsewhere in the Caucasus region contain sediments with varying, but often high carbonate contents. Differences in carbonate content imply greater water depth during deposition in the Kura Basin.

Generation and Field Relations of Low-δ18O Silica-Undersaturated and Mildly Saturated Alkaline Magmas: a Case Study from the Fataga Group, Gran Canaria

Abstract The origins of felsic low-δ18O melts (< +5.5‰) are usually attributed to assimilation of high-temperature hydrothermally altered (HTHA) rocks. Very few alkaline (silica-undersaturated and/or peralkaline) examples are known. Here, we classify the Miocene Fataga Group in Gran Canaria, a silica-undersaturated to mildly saturated alkaline volcanic sequence consisting of trachytic to phonolitic extra-caldera ignimbrites and lavas, as a new low-δ18O felsic locality. We provide new mineral, glass, and bulk geochemical data linked to a well-constrained stratigraphy to assess the processes involved in the magma reservoir that fed the Fataga eruptions. New high-precision single crystal feldspar 40Ar/39Ar ages of the study area span 13.931 ± 0.034 Ma to 10.288 ± 0.016 Ma. Fractional crystallization at shallow depths of sanidine/anorthoclase, biotite, augite/diopside, titanite, ilmenite, and titanomagnetite is the main driving process to produce phonolitic magmas from trachytic melts. Evidence of mafic hotter recharge is not found in the field, but some units exhibit trachytic compositions characterized by positive Eu/Eu* anomalies and high Ba contents, interpreted as melts of feldspar-dominated cumulates, the solid remnants of fractional crystallization. Hence, recharge magmas halted in the crystal mush and provided the heat needed to sustain cumulate melting and volcanic activity. This cumulate signature might be lost if fractional crystallization continues before the eruption. The interplay among meteoric water, the caldera-fault system, intra-caldera ignimbrites (Mogán Group), and the Fataga magma reservoir favoured assimilation of up to ca. 30% of HTHA rocks. Such assimilation is variable through time and recorded by δ18Omelt values down to +4.73‰. We did not find any direct relation between assimilation and silica saturation of the Fataga volcanic deposits.

Geochemical and Sr-Isotopic Study of Clinopyroxenes from Somma-Vesuvius Lavas: Inferences for Magmatic Processes and Eruptive Behavior

Somma-Vesuvius is one of the most dangerous active Italian volcanoes, due to the explosive character of its activity and because it is surrounded by an intensely urbanized area. For mitigating the volcanic risks, it is important to define how the Somma-Vesuvius magmatic system worked during the past activity and what processes took place. A continuous coring borehole drilled at Camaldoli della Torre, along the southern slopes of Somma-Vesuvius, allowed reconstructing its volcanic and magmatic history in a previous study. In this work, the wide range of chemical (Mg# = 92–69) and isotopic (87Sr/86Sr = 0.70781–0.70681) compositions, collected on single clinopyroxene crystals separated from selected lava flow units of the Camaldoli della Torre sequence, have been integrated with the already available bulk geochemical and Sr-isotopic data. The detected chemical and isotopic signatures and their variation through time allow us to better constrain the behavior of the volcano magmatic feeding system, highlighting that mixing and/or assimilation processes occurred before a significant change in the eruptive dynamics at Somma-Vesuvius during a period of polycyclic caldera formation, starting with the Pomici di Base Plinian eruption (ca. 22 ka).

Geochemistry of Mafic-Intermediate Intrusive Rocks from the Twangiza-Namoya Gold Belt, Eastern Democratic Republic of Congo: Trace Element Constraints on their Origin, Petrogenesis and Tectonic Setting

Bulk geochemical data for the Twangiza-Namoya Gold Belt, Democratic Republic of Congo, are presented in order to classify the rock assemblages, elucidate their petrogenesis and tectonic settings. Nb/Yb and Zr/Ti constraints reveal two suites for the rocks: sub-alkaline to andesitic basalts (Suite-1); and alkaline basalts (Suite-2). Ratios of Ti/Zr = 22–70; Zr/Hf = 35–42; Nb/Ta = 12–13; Nb/Th = 1–2 and La/Nb = 2.4–3.8 suggest arc-generated mantle melts with crustal inputs and arc-fluids metasomatism for Suite-1. The samples have positive LILE and negative Nb, Ta, Ti anomalies, enrichments in the LREE over middle and HREE (La/Yb)CN = 3.6–8.9 with negative Eu anomalies (0.7–0.9) in Chondrite-normalized diagrams. Yb-Th/Ta and Ta/Yb-Th/Yb ratios suggest active continental margin settings, whereas Ta/Hf-Th/Ta and Nb/Yb-Th/Yb diagrams suggest a depleted MORB source. Ti/Zr, Zr/Hf, Nb/Ta, Nb/Th and La/Nb constraints for Suite-2 suggest MORB and oceanic plateau basaltic sources. REE patterns show enrichments in the LREE with negative to positive Eu anomalies (0.7– 1.3). Yb-Th/Ta and Ta/Yb-Th/Yb ratios suggest a within plate tectonic setting. It is suggested that Suite-2 rocks were sourced from mantle-derived melts with a composition between an enriched MORB to OIB.
 Keywords: Twangiza-Namoya; Petrogenesis; Tectonic setting; Trace element ratios

Lateral changes of organic matter preservation in the lacustrine Qingshankou Formation (Cretaceous Songliao Basin, NE China): Evidence for basin segmentation

Organic matter-rich intervals in the Cretaceous succession of the large non-marine Songliao Basin in northeastern China (covered area ~ 87 × 103 km2), including the Turonian–Coniacian Qingshankou Formation (K2qn), offer unique records to study the role of global (e.g., climate, “limno-eustasy”) and regional (tectonics, basin geometry) controls on organic matter accumulation. A wealth of scientific papers concentrate on the vertical variations in organic matter (OM) preservation along the Southeastern Uplift of the basin, which hosts its most prolific source rock intervals. However, the corresponding K2qn interval in the Central Depression is less well studied, and no lateral correlation between both parts of the basin based on direct information from well logs and drill cores exists to date. Hence, the dominant influencing factors causing lateral changes organic-richness and source potential are not yet fully understood. Basin geometry effects in particular could not be evaluated in detail, as highly resolved seismic data is lacking for the transitional zone between the Southeastern Uplift and Central Depression. This paper uses Integrated Prediction Error Filter Analysis of wireline logs together with petrographical and geochemical data from drill cores of two key wells in the Central Depression and Southeastern Uplift areas for a detailed correlation of the K2qn1 interval and its three sub-units (Sq1 to Sq3). Bulk geochemical (e.g., total organic carbon vs. total sulphur), biomarker (ratios of pristane vs. phytane, dibenzothiophene vs. phenanthrene, and total steroid vs. hopanoid compounds; Gammacerane Index; abundance of 4-methylsteranes and C29 steranes), and petrographical (e.g., maceral composition; framboidal pyrite size) data to trace changes in the depositional conditions. All data sources support a higher degree of salinity stratification and more intense anoxia at the Southeastern Uplift compared to the Central Depression particularly during accumulation of the lowermost and most organic-rich Sq1 sub-unit. These observations indicate that two depocenters may have existed during times of Sq1 deposition, and that the pronounced basin separation inhibited marine incursions from the Southeastern Uplift to the Central Depression. During deposition of the overlying Sq2 and Sq3 sub-units, a low relative lake level and dry climatic conditions likely prevailed. The geochemical data suggest similar dysoxic brackish-fresh water conditions in both depocenters. Moreover, the well log correlation indicates that a gradually connected basin may have formed at this time, reducing the effects of two separate depocenters on sediment accumulation and organic matter preservation. Thus, this study provides the first direct evidence that apart from global factors, basin segmentation strongly controlled the distribution of organic matter-rich rocks within the Qingshankou Formation.

NEOCOMIAN – BARREMIAN LACUSTRINE SHALES IN THE MAYO OULO‐LERE BASIN, NORTH CAMEROON: DEPOSITIONAL ENVIRONMENT AND PETROLEUM POTENTIAL

The synrift Mayo Oulo‐Léré Basin in Northern Cameroon is located in the transition zone between the West and Central African Rift Systems. Structural and stratigraphic elements of the basin resemble those of the Yola Basin in NE Nigeria, an extension of the Upper Benue Trough. The Lower Cretaceous lacustrine shales with source rock potential which occur in nearby rift basins are also present in the Mayo Oulo‐Léré Basin. These shales were investigated at two outcrop locations (Badesi and Tchontchi), and samples collected (n = 60) were subjected to palynofacies and bulk geochemical analyses to evaluate their petroleum generation potential and to interpret their depositional environment. At the studied locations, shales were divided into two lithofacies: grey to black laminated shales containing algal‐bacterial OM together with common woody (phytoclast) debris (“facies Fml”); and cm‐bedded shales which had a higher content of algal‐bacterial OM but a lower phytoclast content (“facies Fmlc”).Palynological and bulk geochemical data indicate that the shales contain well‐preserved organic matter (OM) and locally display good to excellent oil generation potential. Average TOC contents are 2.7% and 1.4% for samples of the Fmlc and Fml facies shales respectively. HI values (94‐889 mg HC/g TOC and 131‐638 mg HC/g TOC respectively) suggest that the shales contain Types I to III kerogen. Organic material in the Fmlc facies shales is dominated by amorphous organic matter (AOM: 90% on average) with a low phytoclast content (6% on average); whereas samples of the Fml facies shales contain less AOM (74% on average) and have a higher phytoclast content (23% on average). AOM in the Fmlc shales is highly fluorescent; these shales are interpreted to have been deposited in dysoxic to anoxic conditions. The AOM in the Fml shales is weakly fluorescent and the shales were deposited under more oxic conditions. The kerogen in the shales ranges from immature to early oil window mature. Average values of the pyrolysis S2 yield are 15.5 mg HC/g of rock and 7 mg HC/g of rock for samples from Fmlc and Fml facies shales respectively. The shales increase in thickness northwards towards the Logone Birni Basin where they may have reached the oil window, as in neighbouring basins. The results of this study of lacustrine shales from the Mayo Oulo‐Léré Basin suggests that there may be potential for oil exploration in northern Cameroon.

Co-genetic formation of scheelite- and wolframite-bearing quartz veins in the Chuankou W deposit, South China: Evidence from individual fluid inclusion and wall-rock alteration analysis

The large-scale Chuankou W deposit is located in the north part of the Nanling metallogenic belt, South China. It comprises independent quartz vein-type scheelite and wolframite mineralization, both associated with the underlying granitic intrusion spatially. The scheelite-bearing quartz veins occur invariably in sandstone and slate to the west, whereas the wolframite-bearing quartz veins are mainly hosted by the granite to the east. To reveal the fluid characteristics of the two mineralizing vein systems, detailed petrography, microthermometry, and Raman spectroscopic analyses were carried out on fluid inclusions in scheelite, wolframite and their coexisting quartz. Major and trace element concentrations of fluids were obtained from individual fluid inclusions in quartz via LA-ICP-MS analysis. Wall-rock alteration of both vein systems were evaluated by TESCAN Integrated Mineral Analyser (TIMA) analysis, and based on which the bulk geochemical data of wall-rock as a function of distance from the vein were obtained for scheelite-bearing quartz vein. These data aid elucidation on the nature of fluids in the two types of W mineralization. Fluid inclusions in quartz and its coexisting tungsten minerals share similar homogenization temperature and salinity, suggesting near concurrent formation of quartz and ore minerals. LA-ICP-MS analyses on pseudosecondary fluid inclusions in quartz associated with ore minerals show considerable concentrations of W in both mineralizing fluids, whereas Fe, Mn and Ca are generally absent irrespective of their higher detection limits. This may imply that Ca, Fe, and Mn were not initially derived from the granitic magma. The fluid compositions of both types of W mineralization display similar Rb/Na, K/Na, and Rb/Cs ratios, indicating a similar initial fluid source. The TIMA image shows that the host rock (sandstone) of scheelite-bearing quartz vein contains abundant Ca-rich minerals, such as apatite and calcium feldspar, indicating wall-rock as potential source providing Ca for the precipitation of scheelite. This assumption is strongly supported by bulk geochemical data of wall rock as a function of distance from hydrothermal quartz vein. In contrast, the tourmaline-rich granite hosting wolframite quartz veins may be a potential source of Fe for the precipitation of wolframite. Study on fluid composition combined with wall rock alteration suggest that the magmatic-sourced fluids and fluid–wall-rock interactions exerted primary control on the large-scale variations in mineralization types in the deposit, with scheelite- and wolframite-bearing quartz veins being both genetically and spatially related. Results of this study provide new guidelines for mineral exploration, suggesting a homologous scheelite-dominated deposit being likely to exist in association with a wolframite-dominated deposit, where the lithology of Ca-bearing formations may indicate potential prospecting areas.

In situ chemical and isotopic analyses and element mapping of multiple-generation pyrite: Evidence of episodic gold mobilization and deposition for the Qiucun epithermal gold deposit in Southeast China

Abstract Gold deposits are often the result of complex mineralization and remobilization processes. Interpretation of bulk geochemical and sulfur isotope data of the gold deposits is frequently hampered by complex zoning in pyrite, which calls for in situ determination of geochemical and sulfur isotope composition of sulfide minerals. The Qiucun deposit is a good representative of epithermal gold deposits in the Mesozoic Coastal Volcanic Belt of southeastern China. It represents a complex mineralization history, comprising three hydrothermal stages: (I) early stage of pyrite-quartz-chalcedony; (II) main ore stage of quartz-polymetallic sulfide; and (III) post-ore stage of quartz-carbonate. Detailed backscattered electron imaging (BSE) and in situ trace element and sulfur isotope analyses using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and LA-multicollector (MC)-ICP-MS were applied to reveal the gold mineralization and remobilization history of this deposit. Four texturally distinct generations of pyrite were identified, all of which host invisible gold: Py1a and Py1b in Stage I and Py2a and Py2b in Stage II. A detailed study of the texture, chemistry, and sulfur isotopic composition as well as hydrothermal evolution of auriferous pyrite from the Qiucun deposit revealed the behavior of gold in the course of pyrite evolution. Pyrite of Stages I and II contains invisible gold, whereas later-stage visible native gold and re-enrichment in invisible gold is associated with alteration rims around the primary pyrite grains. Py1a is rich in silicate inclusions, enriched in Co and Ni, and depleted in As and Au relative to later pyrite generations. This redistribution is attributed to the alteration of biotite in the sub-volcanic host rocks that effectively destabilized gold in the ore fluid during Py1a deposition. Py1b and Py2a show oscillatory zoning with bright bands having elevated As and Au contents. The oscillatory zoning is interpreted to reflect pressure fluctuations and repeated local fluid boiling around the pyrite crystals. These three pyrite generations (Py1a, Py1b, Py2a) record a narrow range of δ34SV-CDT values between –3.6 and 4.6‰, consistent with a magmatic sulfur source. Gold and some trace elements (As, Ag, Sb, Pb, Tl, and Cu) that were initially incorporated into Py2a became partially exsolved and remobilized during the replacement of porous and invisible gold-rich Py2b. This replacement was likely due to coupled dissolution and re-precipitation reactions triggered by oxidation of the mineralizing fluids. Fluid oxidation is further supported by a general decrease trend of δ34SV-CDT from Py2a (–3.2 to 4.6‰) to Py2b (–15.2 to –2.3‰). Last, previously formed auriferous pyrite underwent post-mineralization fracturing, causing local pulverization of pyrite. Thus, newly created porosity facilitated fluid circulation, hydrothermal alteration of the pyrite, and remobilization of invisible gold, which re-precipitated with pyrite in the form of electrum as small inclusions or as larger grains within fractures. Our study emphasizes that pressure-driven hydrothermal processes play a vital role in the initial enrichment and re-concentration of gold and some other trace metals during episodic deposition, replacement, and hydrothermal alteration of gold-bearing pyrite in epithermal gold deposits, ultimately forming visible gold and high-grade ore shoots as exemplified by the Qiucun deposit.

Contribution of an Eastern Indochina-derived fragment to the formation of island arc systems in the Philippine Mobile Belt

AbstractThe Philippine Mobile Belt is a complex plate boundary with multiple terranes in Southeast Asia, yet its early tectonic evolution is still not fully understood due to a scarcity of solid evidence. Here we report new whole rock geochemical, Sr-Nd isotopic, and zircon U-Pb-Hf isotopic data for Cretaceous-Miocene arc magmatic rocks from the Cebu and Bohol Islands, Philippine Mobile Belt. Bulk geochemical data display arc affinities with enriched large ion lithophile elements (e.g., Sr and Ba) and depleted high field strength elements (e.g., Nb, Ta, and Ti). The high positive εNd(t) (+4.6 to +9.1) values and low initial 87Sr/86Sr ratios (0.7032–0.7048) suggest that these igneous rocks were generated by partial melting of mantle wedge in an arc setting. U-Pb dating of zircons revealed Cretaceous (ca. 120–90 Ma), middle Eocene to early Oligocene (ca. 43–30 Ma), and middle Miocene (ca. 14 Ma) crystallization ages for the arc magmatism with abundant Permian-Triassic zircon xenocrysts clustering at ca. 250 Ma. The Permian-Triassic grains show dominantly negative εHf(t) values ranging from −16.2 to −6.6, which are similar to those of coeval rocks in Eastern Indochina. Combined with previous paleomagnetic studies, we propose that an Eastern Indochina-derived continental fragment was involved during the formation of arcs in the Cebu and Bohol Islands, which highlights the potential contribution of ancient continental materials in the formation of intra-oceanic arcs. This scenario does not support the previously proposed model that the Cretaceous arc in the Philippine Mobile Belt formed in the northern margin of the proto-Philippine Sea Plate and Australian margin.

Characteristics and genesis of lacustrine laminar coal and oil shale: A case study in the Dachanggou Basin, Xinjiang, Northwest China

Lacustrine laminar coal is an unusual and rare sedimentary deposit, especially when it coexists with oil shale; this combination has special significance for indicating the evolution of the paleoenvironment. The coal-bearing and oil shale strata of the Early Jurassic Badaowan Formation in the Dachanggou Basin, Xinjiang Uygur Autonomous Region, present an ideal example to reveal the evolution of high-frequency environmental changes in the Early Jurassic. Based on bulk geochemical data, the paleoenvironmental, paleoclimatic and genetic differences between lacustrine laminar coal and oil shale were studied. The Badaowan Formation oil shale has high organic matter abundance and hydrocarbon-generating potential and contains type I and type II1 organic matter. However, compared with oil shale, interlayered laminar coal has higher organic matter abundance and hydrocarbon-generating potential, and the type of organic matter is II1. Various environmental geochemical indicators suggest that oil shale formed in a warm and humid climate and was deposited in fresh water under oxic-suboxic conditions and that algae were the main source of organic matter, followed by terrigenous organic matter. Laminar coal formed in relatively high-temperature periods and accumulated in suboxic-euxinic saline lakes. The source of organic matter was mainly higher plants or hydrophilic plants around the basin, followed by algae. Short-term thermal events swamped the lake margins and increased the input of terrigenous organic matter, which promoted the formation of thin laminar coal interbedded with oil shale.

Integrated isotopic and organic geochemical constraints on the depositional controls and source rock quality of the Neogene Kalamaki sedimentary successions (Zakynthos Island, Ionian Sea)

This study investigates the oxygen and carbon (δ18O, δ13C) stable isotope ratios, as well as the organic geochemical features of the 146-m-thick composite Kalamaki section located in the southwest margin of the Hellenic Fold and Thrust Belt (Zakynthos Island). The section includes Late Miocene–Pliocene pre-evaporitic, evaporitic, and post-evaporitic deposits. The obtained bulk geochemical data (Rock–Eval II, bitumen extraction, and fractionation) and biomarker compositions indicate poor–fair source-rock potential predominantly promising for gas production. TOC values indicate the presence of samples that might be of slight interest (0.50–0.95%) in the evaporitic interval and samples that are worthy of further investigation (up to 1.31%) in the pre-evaporitic sequence. The organic matter type (type III kerogen), along with the presence of plant remains (leaves) in the studied deposits reflect the mainly terrestrial origin of the organic material. Tmax and Production Index values further indicate that most of the sediments (138 out of 195 samples) are immature for oil generation and were not under high temperature conditions during burial, whereas 29 of them correspond to the mature oil stage. Oil generation requires deeper burial, which may have occurred offshore in the Ionian Sea. A marine paleoenvironment is indicated that received organic material from both marine and terrigenous sources. Isotopic values imply influence of continental fresh-water inputs in a high salinity, evaporative depositional setting. Furthermore, our findings provide evidence that the climate has favored the development of these source rocks by triggering relative sea-level fall, which in turn enhanced the preservation of organic matter by increasing sea-water salinity and suppressing carbonate deposition.

Geochemical characterization of hydrocarbon source rocks of the Triassic-Jurassic time interval in the Mandawa basin, southern Tanzania: Implications for petroleum generation potential

Abstract Triassic to mid-Jurassic core samples of the Mandawa basin, southern Tanzania (western coast of the Indian Ocean), were geochemically analyzed in order to constrain source rock potentials and petroleum generation prospects of different stratigraphic formations within the coastal basin complex. The samples were collected from the Mihambia, Mbuo and Nondwa Formations in the basin. Geochemical characterization of source rocks intersected in exploration wells drilled between 503 to 4042 m below surface yielded highly variable organic matter contents (TOC) rated between fair and very good potential source rocks (0.5 to 8.7 wt%; mean ca. 2.3 wt%). Based on bulk geochemical data obtained in this study, the Mandawa source rocks are mainly Type I, Type II, Type III, mixed Types II/III and Type IV kerogens, with a predominance of Type II, Type III and mixed Type II/III. Based on pyrolysis data (Tmax 417 to 473oC; PI = 0.02 to 0.47; highly variable HI = 13 to 1 000 mg/gTOC; OI = 16 to 225 mg/g; and VR values of between 0.24 to 0.95% Ro) we suggest that the Triassic Mbuo Formation and possibly the mid-Jurassic Mihambia Formation have a higher potential for hydrocarbon generation than the Nondwa Formation as they are relatively thermally mature.

Eocene Basins on the SE Tibetan Plateau: Markers of Minor Offset along the Xuelongshan–Diancangshan–Ailaoshan Structural System

AbstractThe offset of geological bodies provides robust evidence of displacement along a fault or ductile shear zone. The amount of displacement along the Xuelongshan–Diancangshan–Ailaoshan structural system, southeastern Tibetan Plateau, is uncertain because of the lack of offset geological markers. This NNW–SSE‐trending system is developed in three isolated metamorphic complexes and interjacent nonmetamorphosed rocks. They are expected to record similar post‐Eocene strain, although their structural patterns should be distinct. Geological mapping in the area between the Xuelongshan and Diancangshan metamorphic complexes has revealed a small Eocene basin, the Madeng Basin, located to the west of the structural system. The sedimentary and volcanic successions of the Madeng Basin are comparable to those of the Jianchuan Basin, which is located to the east of the structural system. Zircon U–Pb geochronological and bulk geochemical data demonstrate that the volcanic rocks of both basins formed during 37–34 Ma and share the same geochemical features. These data suggest that the Madeng and Jianchuan basins previously constituted a single basin, with the distribution of high‐K volcanic rocks in the basins defining an ENE–WSW‐trending volcanic belt that shows a limited dextral offset of ≤20 km across the Xuelongshan–Diancangshan–Ailaoshan structural system. Therefore, the northern segment of the structural system records no evidence of large‐scale lateral movement/displacement. The results suggest that the Indochina block, which is bounded by the Xuelongshan–Diancangshan–Ailaoshan structural system to the east and the Sagaing Fault to the west, has not extruded southward as a whole but rather has been deformed by pervasive crustal shortening.