Ce Anomalies Research Articles

Potential effects of the Emeishan large igneous province on Capitanian marine anoxia in the Upper Yangtze region

The widespread Capitanian (late Guadalupian) marine anoxia/euxinia has long been regarded as a key driver of the end-Guadalupian (middle Permian) biotic crisis. However, the cause of this marine anoxia is debated, particularly regarding the influence of the Emeishan large igneous province (ELIP). To investigate the contribution of the ELIP to marine anoxia and the possible causal mechanisms, we undertook a conodont biostratigraphic and geochemical study of the middle Permian Maokou Formation in a platform-to-trough transect in the Upper Yangtze region, South China. Our results show that the depositional facies of the Maokou Formation changed from a carbonate ramp to an intra-platform trough within the Jinogondolella (J.) altudaensis zone in the northwestern Yangtze region, which can be attributed to the initial activity of the ELIP. Mantle-derived Sr inputs in the initial and main stages of the ELIP led to two decreases in 87Sr/86Sr during the Capitanian, in the J. shannoni–J. altudaensis and J. prexuanhanensis–J. xuanhanensis zones. The elevated 87Sr/86Sr values during the late Capitanian may have been due to enhanced continental weathering caused by rapid climate warming in response to subaerial eruptions of the ELIP. The deep-water anoxia–euxinia expanded during the middle Capitanian, as indicated by increased MoEF/UEF and V/(V + Ni) values, along with the disappearance of burrows and appearance of small pyrite framboids in the J. altudaensis zone in the Cheng 20 well. However, shallow-water anoxia occurred during the late Capitanian (i.e., J. prexuanhanensis–J. xuanhanensis zone), as evidenced by positive Ce anomalies and losses of aerobic benthic species in the Erya section. Importantly, marine anoxia and negative δ13Ccarb excursions occurred synchronously, but earlier in deep water than in shallow water, potentially indicating an expansion of the oxygen minimum zone (OMZ). The deep-water anoxia corresponded to a decrease in 87Sr/86Sr ratios and the appearance of an intra-platform trough in the J. altudaensis zone, whereas the shallow-water anoxia in the late Capitanian coincided with elevated 87Sr/86Sr ratios. This suggests that the initial activity of the ELIP promoted the development of the OMZ in deep waters during the middle Capitanian, while the subaerial eruptions of the ELIP drove climate warming that led to the expansion of the OMZ into shallow-water platforms during the late Capitanian.

Apatite as an archive of pegmatite-forming processes: An example from the Berry-Havey pegmatite (Maine, U.S.A.)

Abstract Apatite is an accessory phase in all the units of the internally zoned Berry-Havey complex pegmatite. This body presents a highly fractionated core zone, enriched in Li, F, B, Be, and P, which hosts three different types of pockets, some of them often containing tens to hundreds of gemmy euhedral Li-rich tourmaline crystals, together with other mineral phases such as lepidolite. Processes involved in the complex internal evolution of pegmatitic melts that give rise to zoned bodies containing pockets are not completely understood. To shed light on these processes, apatite from all the different units of the Berry-Havey pegmatite (wall zone, intermediate zone, core margin, and core zone pods) and from the three pocket types (Li-poor, Li-rich, and apatite seams) has been characterized petrographically and later analyzed for major (electronic microprobe) and trace elements (LA-ICP-MS). Results indicate that apatite chemistry changed significantly during the crystallization of the Berry-Havey pegmatite, reflecting the conditions at each stage and mainly depending on the fractionation degree, fO2, and paragenetic association. Fluorapatite is found in all the units except the core margin, the Li-poor pockets, and the seams, where Mn-bearing fluorapatite is present. A gradual increase of the Mn content in apatite from the pegmatite border (wall zone) inward, up to the formation of subrounded masses of Mn-Fe phosphate in the core zone pods, parallels the increasing fractionation of the melt. Phosphate crystallization would deplete the residual melt in Mn, probably causing the significant Mn-decrease observed in apatite from the core zone pods and Li-rich pockets. The late depletion of Mn could also be related to an increase of fO2 in the melt during the later stages of its evolution. Main trace element variations in apatite at both pegmatite and crystal scales correspond to REE, Y, and Sr. Yttrium and REE behave in a very similar way, decreasing inward, i.e., with fractionation of the pegmatitic melt (ΣREE from 1796 ppm in the apatite from the wall zone to 0 ppm in the core zone; and Y from 1503 ppm in the apatite from the wall zone to 0 ppm in the core zone); which could be due to early crystallization of REE-bearing phosphates such as monazite and xenotime. Strontium shows a more complex trend, with an initial depletion in apatite from the wall zone (52 ppm) to the intermediate zone (3 ppm) and a pronounced increase from the core margin (23–87 ppm) up to the core zone and pockets (up to 2.87 wt%). This increase of Sr at the latest fractionation stages of the pegmatite is interpreted to be associated with a late, incompatible character of this element in highly fractionated melts, related to the composition of feldspars from the core margin (mainly pure albite). The lack of Ca in feldspars would decrease affinity for Sr incorporation into their structure and, consequently, Sr would go preferentially to apatite in the core zone pods and, more markedly, in the pockets. Apatite also records changes in the redox conditions during crystallization, with the highest fO2 at the end of the crystallization, mainly reflected in the Eu and Ce anomalies. The chemistry of apatite also reflects the evolution of the pegmatitic melt during crystallization regarding the fluids saturation and pockets generation. Accordingly, at least two exsolution events took place during the Berry-Havey crystallization history: (1) at the beginning of the core zone crystallization, giving rise to the Li-poor pockets, and (2) after the crystallization of the Li-rich pods of the core zone, resulting in the Li-rich pockets. The apatite-rich seams may have crystallized between these two exsolution events or later, at a subsolidus stage, after a Na-autometasomatism episode. This study shows how a detailed petrographic and chemical characterization of apatite associated with different units of a highly fractionated, internally zoned pegmatite may help understand the crystallization history of pegmatitic melts. It is also evidenced that during the internal evolution of pegmatites, apatite chemistry records variations in the fO2, elemental fractionation, interaction with competing mineral phases, fluids activity and exsolution events. In addition, it is shown how apatite chemistry may be useful as an exploration tool for pegmatites.

Oxidative weathering on the continent and seawater upwelling along the passive continental margin promoted widespread phosphorite formation at the Neoproterozoic-Cambrian boundary in South China

The latest Proterozoic to early Cambrian is characterized by major global phosphogenic events and the diversification of complex multicellular life. However, the feedback mechanism of atmospheric oxidation and upwelling processes to form voluminous phosphorite deposits is unclear. South China is a key example of the sedimentary spectrum related to the Neoproterozoic to Early Cambrian bloom of oxygenic photosynthesis, with alginite deposits (sapropelite; “stone coal”), barite, polymetallic black shales and phosphorites along the passive continental paleo-margin of the Yangtze craton. Here, we present a comprehensive geochemical analysis of drill core samples from the Zhijin phosphorite deposit, including Cr isotope, Fe speciation, and bulk elemental composition of dolostone, phosphorite and black shale from the Ediacaran to Early Cambrian sequence. The positively fractionated δ53Cr values of 0.11 to 1.81 ‰ of leachates from Ediacaran dolostone and Terreneuvian phosphorite indicate intensive oxidative terrestrial weathering. The phosphorite samples exhibit REE distribution patterns similar to modern seawater and strongly negative Ce anomalies (0.47–0.61), suggesting an oxic, open ocean environment. In contrast, the absence of Ce anomaly, high FeHR/FeT, and Fepy/FeHR ratios, enhanced redox-sensitive element concentrations, high Mo/TOC and TS/TOC, and high molar Corg:P ratios suggest euxinic to anoxic conditions for the overlying black shale sedimentation in a restricted sedimentary marine environment. Bulk-rock shale samples retain the positively fractionated Cr isotope pattern. The dramatic change from oxic to anoxic conditions aligns with the fossil record, which shows a proliferation of small shelly fossils in the phosphorite and their extinction in the overlying black shales, likely by hydrogen sulfide poisoning. We infer that nutrient-rich, oxidized upwelling seawater transported phosphorus and other nutrients to the photic zone, from where organic matter settled down to the seafloor and formed thick phosphorite beds at the oxic-anoxic boundary at and below the seafloor. Our study highlights that atmospheric and seawater oxygenation accelerated the Early Cambrian bio-diversification, and the subsequent restricted basin situation is responsible for the extinction at the Neoproterozoic-Cambrian boundary.

Intense intrusion of low-oxygen waters into mid-Cambrian surface ocean carbonate factories

The Phanerozoic surface ocean is characterized by its high dissolved oxygen content owing to mixing with the atmosphere. However, atmospheric oxygen levels varied in the early Paleozoic and it remains unclear whether the surface ocean was susceptible to significant redox fluctuations in response to extreme environmental events. In this study, we probed the redox structures of shallow middle Cambrian marine depositional environments across the North China Platform, ranging from open tidal flats to relatively deep subtidal environments. We utilized a combination of least diagenetically altered carbonate materials (such as ooid cortices, calcimicrobes, and their fringing cements), as well as in situ element measurement and imaging techniques. By analyzing a set of redox-related elements (e.g., Ce anomaly, Zn/Fe molar ratio, Mn and Cr) and mineralogical proxies (hydrogenetic Fe oxides), we revealed a stratified redox structure in the Drumian surface oceans. Compared to earlier Drumian conditions, late Drumian surface oceans experienced significant intrusions of ferruginous waters, probably reaching into shallow subtidal environments with water depths less than 10 m. Furthermore, we identified shallow subtidal microbial O2-producing factories, characterized by dendritic Epiphyton thalli. These calcimicrobes exhibited more oxygenated signatures (negative Ce anomalies and enrichment of hydrogenetic Fe oxides) relative to contemporaneous less oxic shallower and deeper environments. This finding indicates that they produced oxygen oases or refuges during periods of both normal and poor dissolved O2 conditions. This study has the potential to broaden our understanding of redox conditions and microbial oxygen-producing mechanisms in the surface ocean, particularly during intervals characterized by low atmospheric oxygen levels or episodic anoxic events.

The yengejeh diasporic karst bauxite deposit, NW Iran: Constraints on distribution and fractionation of major and rare earth elements

The Yengejeh diasporic karst bauxite deposit (NW Iran) was developed as discontinuous layers and lenses along the contact of dolomitic limestone of the Ruteh Formation (middle-upper Permian) and dolomite of the Elika Formation (Triassic). This deposit is constituted by two conspicuous subset layers, (1) green bauxite (GB) and (2) red bauxite (RB). The XRD analytic data revealed that diaspore is accompanied by chlorite and anatase in the GB subset and by hematite in the RB subset. Minerals such as pyrophyllite, kaolinite, illite, and rutile are present within the both subsets. The antithetical distributions of Al with Fe and Al with Ti in the deposit are indicative of the controlling role of climatic changes of the depositional environment and the function of post-formation diagenetic processes. The increment in certain geochemical ratios like La/Y, (La/Yb)N, and (LREE/HREE)N from the top toward the bottom of the horizon is designative of pH increase in depositional milieu by buffering of the percolating solutions, and of preferential scavenging of LREE by hematite. The positive Ce anomaly in the GB subset took place as the result of change in the oxidation state of this element from Ce3+ to Ce4+. However, the positive Ce anomalies in the RB subset implicates preferential scavenging of Ce onto hematite. The marked variation range in anomaly values of Eu/Eu* (0.38–1.01) at Yengejeh reveals that this index acted as non-conservative during the evolution of this deposit, and this behavior is related most likely to influences of post-formation diagenetic processes.

Marine Fe cycling linked to dynamic redox variability, biological activity and post-depositional mineralization in the 1.1 Ga Mesoproterozoic Taoudeni Basin, Mauritania

The concentration of redox sensitive trace metals (RSTEs) and their isotopic composition preserved in Precambrian marine sediments, are critical for the reconstruction of ocean–atmosphere oxygenation history. Particularly, the concentration of Fe, its redox speciation, and isotopic distribution, have gained widespread use for inferring the biogeochemical processes that controlled Fe cycling in Precambrian oceans linked to the reconstruction of Earth surface redox budget. However, questions remain about the biotic and abiotic processes involved in Fe cycling in these ancient oceans, including the impact of post-depositional alterative processes on the reliability of the Fe redox proxy. Here we present a multi-proxy mineralogical and geochemical study of the ∼1.1 Ga Atar and El Mreiti strata of the Taoudeni Basin in Mauritania, to better constrain pathways involved in Fe cycling, linked to Fe mineralogy, redox speciation, isotopic ratios during this time and metamorphism. We compare unmetamorphosed sedimentary deposits with facies metamorphosed by dolerite sill intrusion. The results reveal the occurrence of diagenetic Fe minerals in the basal unmetamorphosed samples associated with light δ56Fe signatures, reflecting dominant anoxic conditions that promoted microbial dissimilatory Fe reduction. Notably, δ56Fe composition of these rocks reveal several fluctuations in evolving seawater redox state from oxic to anoxic/sulfidic conditions associated with changes in sea level stand and periods of full bottom water oxygenation and redox stratification. Overall, Ce anomalies suggest a general up sequence increase in seawater oxygen content. Metamorphosed rocks display heterogeneous δ56Fe distribution, consisting of light and heavy signatures associated with secondary Fe-bearing minerals produced by metamorphic and metasomatic overprinting of carbonated rocks by hot circulating fluids. The results thus indicate metamorphic overprinting of primary seawater δ56Fe promoted by increased mobility of reactive Fe during post-depositional metamorphic transformation. They show that post-depositional metamorphic/metasomatic overprinting complicates direct reconstruction of seawater biogeochemical Fe cycling and redox state using δ56Fe systematics.

Ce anomaly in hemiboreal headwater streams: An indicator of dominant groundwater flow paths through the catchment

The water quality in headwater streams depends on the groundwater origin and its transport pathways before it eventually discharges as surface water. In this case study, we present the Ce anomaly of over 100 hemiboreal headwater streams in Sweden and discuss the potential of the Ce anomaly to define two stream end members as proxies for the stream origin. The data show a relation between topography and the Ce anomaly, with more negative values (−0.8 to −0.4) in hilly catchments with distinct slopes, defined as an oxidized groundwater end member. The second end member is dominated by groundwater discharge from reduced, organic-rich riparian and wetland soils (reduced groundwater) having small Ce anomalies (−0.3 to zero). Element concentrations show a wide range, depending on the end member of the stream. For example, redox elements (Fe, Mn, S and N) show concentrations up to five times in streams with small negative Ce anomalies (reduced groundwater) compared to the concentrations in streams with large negative Ce anomalies. While element concentrations (of the classic redox elements Fe, Mn, S, N) show seasonal variations due to a summer drought period and the resulting reduced conditions, the Ce anomaly is constant, offering an excellent indicator of the dominant groundwater flow paths regardless of seasonal variations.

The formation of tubular seep carbonate deciphered from mineralogical and geochemical characteristics: an example from the South China Sea

As a special type of seep carbonate, the many details concerning the formation mode and mechanism of tubular seep carbonates are rarely reported. Here, new geochemical and mineralogical data regarding tubular seep carbonate (SQW-65) are reported. Sample SQW-65 had anomalously negative δ13C values and positive δ18O values, which suggested the dissociation of gas hydrate. Additionally, almost all the sub-samples showed no Ce anomaly (Ce/Ce*average = 0.93), with obvious U enrichment (21.3< UEF <240.3), which indicates that the studied tubular seep carbonate was formed in an anoxic environment. Subsequently, the formation process of the studied tubular seep carbonate is further discussed according to the variability of mineralogical and geochemical characteristics from the rim to the core of the tubular formation. In the early stage of the studied tubular seep carbonate (periphery), owing to the influence of terrigenous components, the quartz and Ti content and Y/Ho ratio were high. However, with the formation of the periphery, the influence of terrigenous components was gradually weakened. In addition, from the rim to the core, the carbon and oxygen isotope values showed a “covariation” coupling relationship, an enrichment of U, and a reduction in total rare earth element content. This is because as the outer wall thickens and the internal fluid channel narrows, the intensity of the sulphate-driven anaerobic oxidation of methane and the associated precipitation rate of carbonate also increase.

Busting the dust: Evaluating local vs distal sources in Quaternary sediments at Thirlmere Lakes

The Quaternary sediments preserved within the Thirlmere Lakes system, Greater Blue Mountains World Heritage Area, Australia, are an important regional environmental record representing at least the last two interglacials. Understanding the source and evolution of these sediments, both temporally and spatially, is an essential component of the site's reconstruction. In this study, we evaluate this question using physical, mineralogical, elemental, and isotopic analytical techniques. Four distinct lake sediment facies all show bi-modal distributions of coarse sand and clay to fine silts, representing various mixtures of catchment Hawkesbury Sandstone and Ashfield Shale. Clays are predominantly kaolinite-dickite, however, the 7 Å dehydrated form of halloysite is prominent in an orange-yellow oxidised lake facies unit. The relative distribution and concentration of rare earth elements, including yttrium (REY), is heterogeneous across all the lake facies, varying between both lakes and with depth. This variability suggests a geochemical signature reflecting a combination of mixed sources and secondary mineral precipitation, driven by catchment geomorphology and specific site conditions. Slightly positive Ce anomalies in the oxidised lake facies, combined with the greater halloysite representation, represents a period of dry conditions and sub-aerial exposure. Evaluation of catchment, regional and continental REY ratios, Eu anomalies and εNd data implies a predominant internal catchment source signature, with any external contributions restricted to the local Bringelly Shale and the immediate south-eastern Australia, including the Murray River Basin. Geochemical and isotopic values for these proposed internal and external sediment sources predicts that an aeolian source from outside the immediate catchment represents a maximum of 30% of the fine-grained sediment fraction.

Syndepositional and diagenetic processes in the pigmentation of Middle Ordovician carbonate red beds in South China

Marine red beds (MRBs) are often attributed to specific redox environments during syndepositional and early diagenetic phases. During the Middle Ordovician, a succession of reddish, deeper-water nodular argillaceous limestones (i.e., Zitai and Kuniutan formations) were deposited along the margin of Yangtze Platform in South China. However, the origin of their color remains enigmatic. In this study, we investigated the Middle Ordovician MRBs from a borehole core newly drilled in the Lower Yangtze area of South China whose stratigraphy frameworks are constrained by carbon isotope and biostratigraphy. This study investigates the pigmentation of these MRBs by integrating petrographic observations, elemental geochemistry, diffusive reflectance spectrometry (DRS), and scanning electron microscope (SEM) coupled with energy dispersive X-ray spectrometry (EDS). DRS results show that the red pigment is caused by hematite particles in submicron- to micron-level size. SEM demonstrates that the hematite grains are either detrital grains with traces of physical transport from terrestrial source, or flaky amorphous hematite aggregates situated within the calcite crystal interstices, implicating both syndepositional and early diagenetic origins, respectively. In terms of the geochemical result of the bulk rocks, the close positive correlation between Al2O3 and Fe2O3 indicates that the iron pigment materials may mainly originate from terrestrial Fe-bearing phyllosilicates. These observations are also consistent with the distribution patterns of rare earth elements (REEs) in carbonate leachates. The MRB limestones are characterized by MREE-bulged patterns and close to ~1 Ce anomalies, suggesting active reductive dissolution and subsequent reprecipitation of iron oxides during diagenesis in pore systems. This study proposes that the coloration of Middle Ordovician MRBs in Lower Yangtze Platform was linked to the enhanced input of terrestrial clay minerals rich in iron. The reductive dissolution released iron ions from terrestrial detrital and allowed subsequent reprecipitation of iron-oxides in pore water system during the fluid-buffered diagenesis. In this light, hematites formed during both the syndepositional and diagenetic processes thus could have involved the coloration of the Middle Ordovician carbonate red beds in this case.

Genesis of the Neoarchean Algoma-type banded iron formation: constraints from Fe isotope and element geochemistry of the Qian’an iron deposit, eastern North China craton

The Neoarchean Qian’an BIF deposit in eastern Hebei, eastern North China Craton has attracted extensive attention of study in the last decades, but the genesis, e.g., Fe sources, metallogenic mechanism, as well as tectonic attributes of the BIFs remains highly disputed. Based on field investigations, microscopic observations and geochemical analysis, this study tries to unravel the source characteristics of ore-forming materials in the Qian’an deposit. The results show that the chemical compositions of the BIF ore samples are mainly composed of TFe2O3 and SiO2, with minor Al2O3 and TiO2. The total trace element contents of the samples are relatively low. The PAAS-normalized REE distribution patterns of the ores show LREE depletion and HREE enrichment, with robust positive anomalies of Eu, Y and La. These characteristics indicate that the BIFs are attributed to dominant chemical precipitation originated from paleo-ocean with obvious volcanic hydrothermal contributions and minor clastic input. Their positive to no Ce anomalies and positive δ56Femagnetite values unveil that the iron was precipitated at low oxygen fugacity. These results, in collaboration with evidence from previous lithological, structural geology, metamorphic P-T paths, geochemistry, geochronology and numerical modeling studies, support a mantle plume model to explain the complicated tectono-thermal processes, and the sources of BIFs in Eastern Hebei, eastern North China Craton.

Amphibole geochemistry in the Haobugao skarn Zn-Fe-Sn deposit in the southern Great Xing’an Range: Implications for the ore-forming process

The Haobugao Zn-Fe-Sn deposit is a typical skarn deposit in the southern Great Xing’an Range of NE China. Despite many advances in understanding its genesis, the detailed ore-forming processes of Zn, Fe and Sn are still unclear. Amphibole, a rock-forming mineral, has been well studied as an indicator of diverse magmatic and metamorphic processes; however, the geochemistry of hydrothermal amphibole has previously received less attention. The Haobugao deposit contains two generations of hydrothermal amphibole (Amp-I and Amp-Ⅱ), which provides a good opportunity to use amphibole geochemistry to trace the mineralization process. Early Amp-I coexists with cassiterite, magnetite and quartz, whereas late Amp-II coexists with quartz and sulfides and can be further divided into two subgroups: Amp-Ⅱa (in skarn) and Amp-Ⅱb (in the country rocks of siltstone). The oxygen isotopic compositions of the fluid (δ18Ofluid 2.9‰) responsible for the Amp-I formation indicate that the amphiboles formed from mixed magmatic fluid with meteoric water. Amp-I is LREE-depleted and HREE-enriched with obvious negative Eu anomalies. Amp-Ⅱ is generally slightly LREE-depleted with negative or positive Eu anomalies and positive Ce anomalies. The incorporation of trace and rare elements is mainly controlled by the fluid composition. Detailed petrological observations and amphibole geochemistry, combined with previous research results, confirm that Sn, Fe, Pb and Zn mineralization occurred during a single mineralization event. From the oxide to the quartz sulfide stage, the ore-forming fluid evolved from high-temperature and oxidized conditions with enrichment of Sn, Li, Be and REEs to low-temperature and reduced or oxidized conditions with enrichment of Cu, Co and Zn. The concentrations of Cu, Co and Zn in different amphiboles vary with the mineral crystallization sequence. This study shows that amphibole geochemistry can be useful for tracing fluid evolution and mineralization processes in hydrothermal systems.

Geochemistry of Pelites at Chengmen Area: Implications for Sediments Resource and Tectonic Environment.

The pelite samples were collected from drillholes from the Chengmen area of the Fuzhou Basin of Fujian, China to reveal the sediments resource and tectonic environment of these pelites via an analysis of its lithology and geochemistry. The rare earth element distribution pattern of the pelites exhibited a high degree of fractionation between light and heavy rare earth elements, moderate negative Eu anomalies, and positive Ce anomalies, which are consistent with the rare earth element distribution pattern of Minjiang sediments and Fujian soils. Moreover, the variations in trace elements are also generally consistent, indicating a common provenance. The extremely high chemical index of alteration (CIA) and index of chemical variability (ICV) values of the pelites suggest that the source area experienced intense weathering, indicating a subtropical hot and humid climate environment in the source area and the Fuzhou Basin at that time. The source rock attribute discrimination diagrams show that the main source of pelites is felsic igneous rocks. The ratios of REDOX parameters show that during the sedimentary period, the water body in the study area was predominantly in an oxidizing environment. Furthermore, the tectonic background diagrams reveal that the source area underwent geological tectonic evolution processes of active and passive continental margins, marking the transition from the continental margin above the subduction of the ancient Pacific plate to the continental margin extension after subduction cessation.

Quantitative evaluation of anthropogenic sources and health risks of rare earth elements in airborne particulate matter

Rare earth elements (REEs) have emerged as contaminants in airborne particulate matter (PM); however, their anthropogenic sources remain poorly quantified, and associated health risks are unknown. This study investigates the REE distribution across eight sizes of airborne PM during July and December in Qingdao, a major Chinese port city. Our results reveal a single coarse-mode distribution with REE concentrations. In contrast, fine PM (size: 0.43–2.1 μm) exhibits notable enrichment of La and Ce compared to Al and other REEs. This study traces La and Ce enrichment to fluid catalytic cracking catalysts (FCCC)-related sources, including refinery and ship emissions, by comparing the REE fractionation in samples with potential sources. We quantify the contributions from FCCC-related sources to La (July: 33.6 % ± 3.2 %, Dec.: 46.4 % ± 5.2 %) and Ce (July: 16.5 % ± 14.3 %, Dec.: 30.3 % ± 12.2 %) by comparing measured concentrations with predictions derived from neighboring REEs, a method previously used exclusively in aquatic systems. For the first time, supply ratios of refinery and ship to FCCC-related La are calculated using a two-component mixing model based on the [La]FCCC/[V]anth, revealing the dominance of refinery emissions (July: 97.3 % ± 0.6 %, Dec.: 99.6 % ± 0.1 %). Furthermore, a global review of La and Ce anomalies that integrates published REE data with our findings reveals a widespread distribution of positive anomalies. The significantly positive correlation between La and Ce anomalies underscores FCCC-related emissions as a global source in fine PM, contributing 0–92 % (mean: 35 % ± 33 %) for La and 0–72 % (mean: 21 % ± 24 %) for Ce. Although the non-carcinogenic health risks of Ce are generally low globally, concerns should be raised in areas near source emissions, where Ce health risks sharply increased along with its concentrations. There is urgently need to establish a threshold value for La, owing to its global enrichment. This study provides novel insights into the sources and health implications of REEs in airborne PM.

Coupled δ56Fe and δ18O analysis of the Frere iron formation, Western Australia, and Paleoproterozoic ocean circulation

The Paleoproterozoic (ca.1.89 Ga) Frere Formation is a ca. 300-m-thick sedimentary succession of five stacked, Fe- and silicate-rich shallowing upwards cycles or parasequences that were deposited during marine transgression. Deposition in an oxygen-stratified water column is supported by the occurrence of magnetite-rich mudstones (anoxic and distal) beneath shallower, hematite- and chert-rich grainstones (suboxic and proximal). Minor (LREE/HREE)PAAS depletion and positive Ce anomalies in grainstones support this interpretation. Sequence stratigraphic relationships suggest that the Frere Formation accumulated on an unrimmed continental shelf associated with coastal upwelling of Fe.Large variations in oxygen isotope ratios (δ18O) of magnetite (–0.6 ‰ ≤ δ18O ≤ +2.8 ‰, n = 12) and quartz (+8.8 ‰ ≤ δ18O ≤ +20.1 ‰, n = 11) from lithofacies composing the Frere Formation indicate that pristine δ18O of minerals were overprinted by diagenesis. Highly variable δ18O values calculated at 200 °C in equilibrium with quartz (–3.0 to + 8.3 ‰) and magnetite (+8.0 to + 12.7 ‰) suggest that fluids with heterogeneous δ18O evolved through oxygen isotope exchange between minerals and porewater in accumulating sediment during diagenesis.The Fe isotope ratios (δ56Fe) of bulk rock (–0.50 ‰ ≤ δ56Fe ≤ +1.55 ‰, n = 20) and magnetite separates (–0.09 ‰ ≤ δ56Fe ≤ +2.06 ‰, n = 11) from deeper anoxic and shallow suboxic paleoenvironments define a decreasing trend through stratigraphically stacked parasequences. The high δ56Fe values of magnetite (+0.7 ‰ to + 2.06 ‰) characterizing the base of the Frere Formation is interpreted to reflect equilibrium isotopic fractionation between dissolved Fe2+aq and freshly precipitated Fe-(oxyhydr)oxide (Fe(OH)3) resulting from sluggish recharge of Fe2+aq from deeper shelf environments. These high δ56Fe values of magnetite from shallow paleoenvironments may also reflect microbial dissimilatory Fe reduction at the seafloor. As sea level rose, continued deepening and encroachment of a well-mixed water mass increased the oxidation of Fe2+aq, which ultimately increased the influence of kinetic isotopic fractionation between Fe2+aq and Fe(OH)3. Such a process produced δ56Fe compositions of magnetite that gradually decrease through the stratigraphic thickness of the Frere Formation (+2‰ to −0.1 ‰). Thus, Fe isotopic data framed in a sequence stratigraphic context provides greater insight into water column processes on Fe-rich, oxygen stratified Paleoproterozoic and Mesoproterozoic shelves, as well as geologically younger restricted basins with a redox gradient.

A supergene-hydrothermal origin of the itabirite-hosted high-grade iron ores in the Mbarga prospect, Mbalam iron ore district, southern Cameroon, Congo Craton

The Mbarga itabirite deposit in the Mbalam iron district on the northwest edge of the Congo Craton (CC) hosts two main types of iron ore enrichments: supergene and specularite ores. This study presents mineralogical, geochemical, and isotopic datasets on these ores to determine their genesis.Ore microscopic studies indicate that the itabirites are of the oxide facies type, with magnetite showing partial to extensive alteration to hematite-martite. The supergene ores consist of hematite + martite + goethite ± gibbsite ± magnetite ± quartz, while the specularite ores are mainly composed of hematite + martite ± quartz. Magnetite microchemistry suggests formation under low-T hydrothermal conditions (~200–300 °C) with high fO2. Geochemical analyses show that the supergene and specularite ores have higher Fe2O3 (88.27 to ~100 wt%) and lower SiO2 (<0.01 to 0.18 wt%) contents than the itabirites (31.95 wt% Fe2O3, 67.16 wt% SiO2). The enrichment of Fe in the supergene ores is attributed to the depletion of major oxides and trace elements due to weathering and supergene enrichment, while the high Fe content in the specularite ores stems from the precipitation of iron-rich, but trace- and rare earth elements (REE)-deficient hydrothermal fluids. The slightly higher Al2O3 content and positive Ce anomalies in the supergene ores suggest the retention of Al-bearing minerals (gibbsite) and reveal highly oxidative conditions during martitization. Stable isotope analyses reveal that the supergene and specularite ores have δ18O values of −2.5 to −0.3 ‰ and − 2.0 to −3.4 ‰, and δ2H values of −75 to −123 ‰ and − 70 to −119 ‰, respectively, suggesting the involvement of isotopically light-evolved meteoric water in their formation. In contrast, the itabirites exhibit heavier δ18O (8.5 to 10.2 ‰) and δ2H (−85 to −91 ‰) values, suggesting formation from mixed magmatic and metamorphic fluid sources. A “polygenic-supergene-hydrothermal” model is suggested for the formation of the Mbarga itabirite-hosted iron ores.

Geochemical constrains for unravelling the condition of sedimentation, provenance, paleoclimate variation, and metallogenic implication of the cretaceous deposits of Mayo Oulo Basin (North Cameroon, Africa)

The sediments from the Mayo Oulo intracontinental Basin, along the N–S cross section between the Gadavou and Lombel localities in central part of the basin, were investigated through major and trace elements geochemistry associated with palynological analysis to determine their condition of sedimentation, paleoclimate evolution and metallogenic implication along the Cretaceous sequence from the N–S cross section of the central part of this basin. From bottom to top of this sequence there are various types of facies with various concentrations of carbonate. Based on their major oxides compositions, the sediments were classified as Shales associated with Fe-shales, Fe-sands, Wacke and Litharenite. The CIX (Chemical Index of Alteration, 62.65 to 98.14) and PIX (Plagioclase Index of Alteration, 65.00 to 99.13) sediments underwent a various chemical weathering; little chemical weathering in the middle to the upper part of the sequence and moderate to high chemical weathering in the lower part. The discriminant function-based multidimensional tectonic diagrams indicate mainly and respectively arc-collisional and Island arc-active continental margin settings which are consistent with the Precambrian geological history of the study area. The SiO2 vs. Al2O3+K2O + Na2O, C-values, associated with trace elements plots such as Sr/Ba, and Rb/Sr, and palynological content (continental or terrestrial species exclusively, dominated by Gymnosperm pollens such as. Inaperturopollenites sp., Araucariacites sp. and Classopollis sp, associated with spores such as Cicatricosisporites sp) indicate mainly arid to semi-arid climate with periodic humid to semi-humid conditions. The Sr/Ba values ranging from 0.084 to 6.408 suggest a fluctuating and sometimes high salinity (Hypersaline milieu). The rare earth elements data show high LREE/HREE ratios (2.86–13.31); high negative and positive Eu anomaly (Eu/Eu∗ = 0.33 to 1.38) and no Ce anomaly (Ce/Ce∗ = 0.94 to 1.02); these features, together with mixed major and trace element ratios and plots such as, Al2O3/TiO2 ratios (14.31–54.26); Th/Co ratios (0.30–14.58); Ce vs La/Yb, Zr vs TiO2 and La/Sc vs Th/Co plots, indicate that the sediments are derived mainly from felsic to intermediate or mafic rock composition. Ni/Co (1.86–3.59) and U/Th (0.03–0.76) ratios are consistent with oxic conditions from bottom to top of the sequence. The Al/Si ratio shows positive correlation with CIA, Th, Zr, Hf, Na, K and negative correlation with Ca and Mg. The positive correlation with K, Hf, Na, Zr, and Th from detrital origin and negative correlation with Ca and Mg from chemical origin could suggest the geochemical composition control of grain size. According to the ternary Al–Fe–Mn diagram metallogenic classification, the studied samples are essentially terrigenous and partially weakly metalliferous, close to those from the Babouri –Figuil and Mamfe Basins (Cameroon) and contrary to those from the Sob area (Polar Urals). No marine or transitional fossil species are recorded. The presence of numerous tetrads to dyads indicate a lacustrine or swampy environment surrounded by vegetation.

Exploring Rare Earth Element behavior in the Mount Etna volcanic aquifers (Sicily)

This study presents the first data on REY (Rare Earth Elements plus Yttrium) in the aquifer of Mount Etna (Sicily, Italy). Patterns normalized to chondrites indicate strong water–rock interaction, facilitated by a slightly acidic pH resulting from the dissolution of magma-derived CO2. REY patterns provide insights into the processes of both mineral dissolution and the formation of secondary phases. The relative abundance of light to heavy rare earth elements is compatible with the prevailing dissolution of ferromagnesian minerals (e.g., olivine or clinopyroxenes), reinforced by its strong correlation with other proxies of mineral dissolution (e.g., Mg contents). Pronounced negative Ce anomalies and positive Y anomalies demonstrate an oxidizing environment with continuous formation of secondary iron and/or manganese oxides and hydroxides. The Y/Ho fractionation is strongly influenced by metal complexation with bicarbonate complexes, a common process in C-rich waters. In the studied system, the measured REY contents are always below the limits proposed by Sneller et al. (2000, RIVM report, Issue 601,501, p. 66) for surface water and ensure a very low daily intake from drinking water.

Hydrological dynamics and manganese mineralization in the wake of the Sturtian glaciation

The Cryogenian Sturtian and Marinoan glaciations stand as the most extreme climate events in Earth history. Intriguingly, large-scale Mn carbonates characterize the nonglacial interlude of this period in South China. The formation mechanism of Mn carbonates and the potential correlation underlying this temporal association remain elusive. Here, we present an integrated petrographic and geochemical study of drill core materials intercepting the Mn-bearing Datangpo Formation. Rare earth element patterns of these Mn carbonates exhibit positive Ce anomalies and a lack of Y anomalies, which differ from those of modern seawater but resemble marine Mn-Fe oxides. These features, combined with negative carbonate carbon isotope compositions (δ13Ccarb as light as −9.9 ‰ VPDB), indicate the presence of oxide precursors and the incorporation of light carbon during Mn-carbonate precipitation. Phosphate oxygen isotope ratios (δ18Op) of HCl-extractable apatite reveal a ∼4 ‰ difference in the average δ18Op between Mn-rich and Mn-poor rocks. We propose that the more positive δ18Op of Mn-rich samples may result from the dominance of phosphate released by reductive dissolution of metal oxides or a heavier oxygen isotope signal of surrounding waters with which isotopic equilibrium has been reached. We further illustrate how marine invasions into coastal anoxic basins could have triggered the formation of Mn oxides and highlight the role of glaciation–deglaciation in the development of giant Mn deposits.

The adsorption of cerium on synthetic δ-MnO2: Implications for Ce uptake behavior of hydrogenetic and early diagenetic ferromanganese nodules from the Western Pacific

Cerium (Ce) anomalies can be used to distinguish diagenetic and hydrogenetic nodules, making them an important discriminator for the genesis of marine ferromanganese nodules. To understand the enrichment and adsorption mechanisms of Ce in different types of ferromanganese nodules, we conducted mineralogical and geochemical studies on ferromanganese nodule layers formed through both hydrogenetic and early diagenetic processes as well as adsorption experiments on synthetic δ-MnO2 to monitor the Ce uptake during the different processes. The major and trace element contents of natural ferromanganese nodule layers were investigated by SEM, EPMA and LA-ICP-MS analysis. The marine nodule studied in this study consisted of a core of fish tooth and a rim that could be divided into the hydrogenetic (type I) and early diagenetic (type II) layers based on their mineralogy and Mn/Fe ratios. The Mn oxide mineral assemblage is composed of todorokite, buserite, birnessite, and vernadite (δ-MnO2) and occurred in both type I and II layers. The type I layer has laminated structures with a low Mn/Fe ratio (1.1–3.2; averaging at 1.7), and low Cu, Ni and Mg contents consistent with a hydrogenetic genesis. The type II layer has a columnar and stromatolitic structure with a high Mn/Fe ratio (5.1–54.0; averaging at 23.3) and high Cu, Ni and Mg contents that are similar to early diagenetic nodules. The ΣREE contents in type I and type II layers are 1405–3506 ppm (averaging at 2091 ppm) and 199–1232 ppm (averaging at 674 ppm), respectively, indicating that the REE is enriched in the hydrogenetic type I layers. Strong positive Ce anomalies are present type I layers ranging from 1.2 to 2.5 (averaging 1.9), but only slightly positive are seen in type II ranging from 0.4 to 2.4 (averaging at 1.0). Synthetic experiments to monitor the Ce uptake process show that Ce can be adsorbed onto δ-MnO2 with the XRD and FTIR patterns suggesting that the structure of δ-MnO2 did not change significantly, consistent with Ce behavior in hydrogenetic nodules. The results suggest that Ce is predominantly concentrated in hydrogenetic nodules in an oxic environment, whereas in the early diagenetic layer, there is less oxidation and fixation of Ce due to the suboxic conditions. Our findings are consistent with Ce anomalies in marine Fe-Mn nodules being the result of Mn oxide oxidation adsorption and then fixation (oxidation) after adsorption.