Trace Element Proxies Research Articles

The relationship between total organic carbon and bottom water redox state in North American black shales

It is clear from modern analogue studies that O2-deficient conditions favor preservation of organic matter (OM) in fine-grained sedimentary rocks (black shales). It is also clear that appreciable productivity and OM flux to the sediment are required to establish and maintain these conditions. However, debates regarding redox controls on OM accumulation in black shales have mainly focused on oxic versus anoxic conditions, and the implications of different anoxic redox states remain unexplored. Here, we present detailed multi-proxy sedimentary geochemical studies of major Paleozoic and Mesozoic North American black shale units to elucidate their depositional redox conditions. This is the first broad-scale study to use a consistent geochemical methodology and to incorporate data from Fe-speciation – presently the only redox proxy able to clearly distinguish anoxic depositional conditions as ferruginous (H2S-limited) or euxinic (H2S-replete, Fe-limited). These data are coupled with total organic carbon (TOC), programmed pyrolysis, and redox-sensitive trace element proxies, with almost all measurements analyzed using the same geochemical methodology. Consistent with expectations based on previous geochemical and paleontological/ichnological studies, these analyses demonstrate that the study units were almost exclusively deposited under anoxic bottom waters. These analyses also demonstrate that there is wide variance in the prevalence of euxinic versus ferruginous conditions, with many North American black shale units deposited under predominantly ferruginous or oscillatory conditions. TOC is significantly higher under euxinic bottom waters in analyses of both preserved (present day) TOC and reconstructed initial TOC values, although sediments deposited under both redox states do have economically viable TOC content. While this correlation does not reveal the mechanism behind higher organic enrichment in euxinic environments, which may be different in different basins, it does open new research avenues regarding resource exploration and the biogeochemistry of ancient reducing environments.

Geochemical and mineralogical features as indicators of sulfate-methane transition zones in shallow gas-bearing offshore sediments from Zhoushan

Subsurface shallow gas, primarily composed of biogenic methane (>95%), is highly-enriched in global offshore sediments. The redox conditions of methane-rich pore fluid play a crucial role in shaping the geochemical signatures associated with the anaerobic oxidation of methane (AOM) and vertical displacement of sulfate-methane transition zones (SMTZs) within deep sedimentary records. However, long-period, and continuous records of AOM and SMTZs in shallow gas-bearing offshore sediments are sparse. Here, we employed a comprehensive analyses of iron sulfide, elemental, and stable isotopies on a 63-m drilled sediment core (JC-1) from offshore Zhoushan. Four different layers U1–U4 were identified in 11.5–24 mbsf, 24−42 mbsf, 42−51 mbsf, and 51−63 mbsf, respectively, as revealed by the lithofacies and sedimentary structures. By comparing the pyrite contents, total sulfur to total organic carbon ratios, and δ34S-chromium-reducible sulfur values, the commonly seen organoclastic sulfate reduction occurred in U1 and U2, whereas significant AOM activities were found in U1 and U4. Further, the peaks of total sulfur to total organic carbon ratios, sulfur contents, and multiple positive δ34S-chromium-reducible sulfur values indicated the presence of AOM in SMTZs at 18.3, 52, and 59 mbsf. These intervals were featured by a sub-oxic or anoxic condition with strong methane seepages, evident from the scarcity of metals and the enrichment of Mo/Al and U/Al ratios. The presence of multiple SMTZs was consistent with the pore-water data of the adjacent YS4 and YS7 cores. In light of these findings, it is prudent to exercise caution when utilizing geochemical indicators, such as trace element proxies and the δ34S values of sulfide minerals, to comprehend the progression of fluctuating depositional settings in reaction to sea-level fluctuations and shallow gas reservoirs. This study provides a new perspective to better understand the evolution of unsteady depositional environments in response to sea-level changes and shallow gas reservoirs.

Marine anoxia events across the upper Cambrian (stage 10) of eastern Gondwana: Implications from paleoenvironmental geochemical proxies

The uppermost Cambrian succession (Stage 10) of the Wa'ergang section (∼300 m of rhythmites, South China) records three globally correlated negative δ13Ccarb excursions (N1, N2, and the HERB- Helenmaria – Red Tops Boundary), overlying the SPICE event (Steptoean Positive Carbon Isotope Excursion), indicating perturbations in the global carbon cycle. The trigger and process of these events still remain elusive. The petrographic and chemical screening of the investigated carbonates proves well preservation of sedimentary fabrics and at least near-primary geochemical signatures. The paleoredox proxy (UEF/TOC, VEF/TOC, and MoEF/TOC) and δ15Norg profiles exhibit positive excursions that correlate with the negative δ13Ccarb excursions, indicating pulses of expanded oceanic anoxia potentially resulted from anoxic deep-water upwelling. The correlated negative shifts in TOC and paleoproductivity proxy (NiEF and CuEF) profiles suggest suppressed primary productivity, possibly by upwelling-induced oceanic toxic events, aligning with mass extinctions particularly during the HERB event. Independently, the paired δ13Ccarb and δ13Corg (Δ13C) variations reveal decreased biological fractionation that aligns with the δ13Ccarb excursions, implying pulses of declining atmospheric O2 levels, which are consistent with the suggested expanded oceanic anoxia and suppressed primary productivity. The peaks of the negative δ13Ccarb excursions are correlated with the base of upward-shallowing sequences, consistent with the evidence from TOC, δ13Corg, δ15Norg, and trace element proxies, support a scenario of upwelling deep toxic waters during sea-level rise that likely resulted in expanded oceanic anoxia, and ultimately led to the negative excursions in δ13Ccarb values and mass extinction.

Response of trace and rare earth elements to environmental changes in a stalagmite from southern India for the last deglaciation

Speleothems, particularly stalagmites are extensively used to reconstruct paleoclimatic and paleomonsoon changes by using stable oxygen and carbon isotopes along the growth profile of a stalagmite sample. Trace and rare earth elements (REEs) variations in stalagmites are widely recognized as indicators of past precipitation and local hydrology. The amalgamation of isotopic and trace element proxies in speleothems has been regarded as an important tool to infer past climate and hydro-chemical fluctuations. Current advancements in geochemical techniques have enabled us to generate high-resolution paleo-records of almost all trace and REEs from stalagmites. However, their assessment is dependent on numerous factors that control the formation of a stalagmite.Here we present a geochemical record from a well dated stalagmite (VSPM1) from a cave located in the southern India. The stalagmite grew between 15,610 and 13,160 yr BP as revealed by its StalAge modelled ages from eight U–Th dates. This study demonstrates significant variations in trace and REEs during the last deglacial time interval of 2100 years and suggests variations in drip water chemistry. The relative amount of trace elements in colloidal solutions originating from the soil organics and weathered particles of host dolomitic rock may have altered with climatic changes. It appears that trace and REEs of VSPM1 stalagmite have responded to fluctuations in Indian Summer Monsoon (ISM) intensity during the time interval of this study.

Reducing-condition reworked phosphorite sedimentary model: Petrographic and geochemical evidence from the Lower Cretaceous in the Thaniyat area, northern Saudi Arabia

The Thaniyat phosphorite, occurred in northern Saudi Arabia, is a component of a massive phosphorite deposit that was formed in the Late Cretaceous to Paleogene era within the southern Neo-Tethys Ocean. To gain insights into the sedimentary environments and formation processes of these phosphorites, samples were collected from the Thaniyat Phosphorite Member in northern Saudi Arabia and analyzed using petrological and geochemical methods. To ensure a comprehensive understanding, the obtained results were compared with results from nearby sites. The Thaniyat phosphorite is composed of phosphatic grains and quartz grains with distinctive granular textures. The phosphatic grains were derived from pristine phosphorite present along the shelf margin, while the quartz grains were supplied by terrestrial input. The presence of this dual provenance is furtherly supported by the negligible correlation observed between P2O5 content and the content of Al2O3 and TiO2. Trace element proxies provide additional insights into the sedimentary setting of the phosphorite, indicating that it occurred in an upwelling environment, which caused relative enrichment of Cr and a positive correlation between the value of Co × Mn and Al2O3 content of the phosphorite. Proxies related to Fe and Mn were found to be unsuitable for predicting the redox conditions in this area. A combination of V, Mo, and U proxies suggests a prevailing suboxic environment during the deposition of the Thaniyat phosphorite. A comparative analysis with contemporaneous phosphorite samples from Jordan and Iran demonstrated consistent characteristics of the sedimentary environment. Building upon these findings, a sedimentary model was proposed to elucidate the depositional processes of the phosphorite in a suboxic environment, where an upwelling with an extensive oxygen minimum zone dominated the sedimentary environment. The extensive reducing sedimentary environment likely facilitated carbon fixation and subsequently climate change. These findings contributed to a better understanding of the role of phosphorite in the paleoenvironmental context of the southern Neo-Tethys Ocean.

Organic matter preservation conditions in the third member of the Shahejie Formation (Dongpu Depression, China)

The third member of the Paleogene Shahejie Formation (Es3) in the Dongpu Depression, China, was studied to interpret its paleoenvironment through a series of trace element proxies, to reveal paleosalinity conditions, to elucidate on the hydrological conditions of the paleolake using carbon and oxygen stable isotopes, and to investigate the effects of paleoredox conditions on organic matter preservation. Most of the redox-sensitive proxies, such as U/Th, V/Cr, Ni/Co, Uauth, (Cu + Mo)/Zn, Cu/Zn, Th/U, and V/Sc, indicate that the Es3 was deposited under predominantly oxic and oxic/suboxic conditions, while V/(V + Ni) and δU and previous studies suggested that the formation was deposited under mainly anoxic conditions. Oxygen levels agreed with the trace element ratios and showed a decrease from the lower to the upper part of the Es3 and an increase in paleoproductivity in the same direction. Salt rocks interbedded within the formation were shown to have overall lower oxygen levels than their neighboring organic-rich layers, black shale, and mudstone intervals, thus have likely altered the paleoredox proxies to oxygen consumption. Although Sr/Ba values point to a saline lake environment, the relative fluctuations seen suggest that the above ratio is not an appropriate indicator of paleosalinity in salt-bearing strata and that the variations in paleoredox conditions in the formation are not a function of paleosalinity. Based on the negative δ13C and δ18O stable isotopic values, it is inferred that the shales in the Es3 were deposited in a hydrologically open lake environment. However, the presence of palynomorphs such as dinoflagellate cysts that are typically found in middle to outer neritic and open marine environments reinforces the assumption of a sea level transgression and inundation of the lake basin and mixing with freshwater algae and rare terrigenous phytoclasts such as cuticles, wood fragments, and suberin. The higher paleoproductivity and lower oxygen levels in the upper Es3 have contributed to greater OM preservation conditions in the absence of any variations in salinity or freshwater influx. The study also demonstrates that many of the paleoredox proxies and thresholds established are not valid to properly characterize certain formations deposited in lacustrine lake paleoenvironments such as the Shahejie, thus their applicability in certain situations must be re-evaluated.

Evaluating novel trace element proxies for oil-source rock correlations

油源对比微量元素地球化学示踪是油气地球化学领域的前沿科学问题。以准噶尔盆地二叠系风城组碱湖含油气系统为例，对此进行了探索研究。通过对烃源岩和原油样品的微量元素组成进行电感耦合等离子体质谱（ICP–MS）分析和系统对比，发现检出的33个常见微量元素中，过渡族金属元素（Ti、V、Cr、Ni、Cu、Zn、Mn和Zr）、碱土金属元素（Sr和Ba）和非金属元素（B和As）在烃源岩与原油间具有较好的继承性，展示出油源对比意义，但由源到油，元素浓度下降0.3–1141倍，差异富集特征显著，表明不能直接简单应用于油源对比。分析认为，微量元素在从源到油的差异富集主要受控于微量元素以有机（螯）络合物或无机盐离子形式在有机质成烃演化与成藏过程中的动态分配。具体而言，Ni和部分V以N-Ni/V键合于卟啉化合物，受油气运移影响小，相对稳定；大部分V以难溶矿物相赋存，油气初次运移时优先富集于烃源岩；Cr、Cu和Zn与有机酸中O/S原子络合，但在油气二次运移过程中化学键容易破裂；Mn、Zr、Ti、Sr和Ba主要以矿物相赋存于烃源岩中，在油气运移中以离子形式存在，易受油-岩相互作用发生离子交换；B以矿物相赋存于烃源岩中，但在初次运移时易与有机酸络合且受二次运移影响有限；As主要以砷化物或砷酸根离子赋存，受二次运移影响较大。据此，Ni、V、B、Cr、Cu、Zn和As具有较好的示踪意义，形成了4组参数：Ni浓度进行油源对比、Cr–Cu+Zn–As三端元图示踪二次运移、V/Ni和Ni/B示踪初次运移。油气形成演化过程中的元素地球化学行为复杂，可在深入剖析后遴选有效参数应用于油气示踪，是经典有机地球化学方法的有效补充。

Multi-isotopic and trace element evidence against different formation pathways for oyster microstructures

Shells of oysters (Ostreidae) are predominantly composed of foliated and chalky calcite microstructures. The formation process of the more porous chalky structure is subject to debate, with some studies suggesting that it is not formed directly by the oyster but rather through microbial mineralization within the shell. Here, this hypothesis is tested in modern shells of the Pacific oyster (Crassostrea gigas) from coastal regions in France and the Netherlands. We combine measurements of stable carbon, oxygen, nitrogen, sulfur, and clumped isotope ratios with high-resolution spatially resolved element (Na, Mg, Cl, S, Mn and Sr) data and microscopic observations of chalky and foliated microstructures in the oyster shells. Our results show no isotopic differences between the different microstructures, arguing against formation of the chalky calcite by microorganisms. However, we observe a small difference in the oxygen isotope ratio (0.32‰) and clumped isotope composition (0.017‰) between the microstructures, which is likely caused by sampling biases due to seasonal differences in growth rate and the short timespan over which the chalky microstructure forms. We therefore recommend sampling profiles through the foliated microstructure to control for strong seasonal variability recorded in the shell which can bias environmental reconstructions. High-resolution (25–50 µm) Na, Mg, Cl, S, Mn and Sr profiles yield empirical distribution coefficients between seawater and shell calcite for these elements. Significant differences in element concentrations and distribution coefficients were confirmed between the two microstructures, likely reflecting differences in mineralization rates or inclusion of non-lattice-bound elements. Only Mg/Ca ratios in the foliated microstructure vary predictably with growth seasonality, and we show that these can be used to establish accurate oyster shell chronologies. The observed effect of mineralization rate on element incorporation into oyster shells should be considered while developing potential element proxies for paleoclimate reconstructions. Trace element proxies in oyster shells should be interpreted with caution, especially when element chemical properties were measured in different microstructures.

Trace element proxies and stable isotopes used to identify water quality threats to elkhorn coral (Acropora palmata) at two national parks in St. Croix, USVI

Biological impairments have been documented on reefs at two national parks in St. Croix, USVI. Although several water quality parameters have been out of compliance with USVI criteria, whether these parameters or other pollutants are responsible for coral health impacts is unknown. Trace elements quantified in sediment showed four sites at SARI, which is closer than BUIS to settlements and land-derived anthropogenic outflows, had Cu mass fractions above sediment quality guidelines for invertebrate toxicity. Trace elements were also analyzed in the skeleton of threatened elkhorn coral, Acropora palmata, to evaluate potential exposure. Heavy metals (Pb, Zn) were significantly greater in coral skeleton at SARI than BUIS. Cu, Pb, and Zn may be impacting coral health in these parks. Potential anthropogenic sources of these metals were revealed by the coral tissue stable isotope levels (δ13C and δ15N). These findings provide a framework for determining heavy metal impacts on these invaluable reefs.

Trace elements in olivine: Proxies for petrogenesis, mineralization and discrimination of mafic-ultramafic rocks

Olivine is a ubiquitous mineral in mafic-ultramafic rocks and has been widely used as a mineral marker in various geological processes. However, its development of trace elements is limited. Here we present newly-obtained trace element data 7Li, 27Al, 29Si, 31P, 43Ca, 45Sc, 49Ti, 51V, 53Cr, 55Mn, 59Co, 60Ni, and 66Zn of olivine in typical mantle xenoliths, mantle peridotites in ophiolites, and plutonic rocks from layered and Alaskan-type intrusions to develop trace element proxies for the petrogenesis, mineralization and discrimination of various mafic-ultramafic rocks. Residual olivine grains in mantle xenoliths and ophiolitic peridotites, which represent residues of mantle melting, have higher Ni/Co (>20) and Ni/Mn (>2) ratios than magmatic olivine (Ni/Co < 20, Ni/Mn < 2), which are consistent with the compatibilities of these elements during partial melting and magma differentiation. Lower Ni content, and lower Ni/Co and Ni/Mn ratios at a given Fo content can distinguish olivine in Alaskan-type intrusions from layered intrusions, reflecting the nature of their mantle sources. The V and Sc contents and V/Sc ratios in olivine can distinguish mantle xenoliths (V > 2 ppm, V/Sc > 0.5) from ophiolitic peridotites (V < 2 ppm, V/Sc < 0.5), indicating a more reduced state of continental lithospheric mantle compared to the oceanic lithospheric mantle. As a consequence, the four occurrences of mafic-ultramafic rocks can be distinguished by olivine with (Sc × 10)-(Ti × 2)-Zn and V/Sc-(Co/Ni × 2)-(Zn/Mn × 5) ternary diagrams. In addition, Li, Ti and P contents in olivine are good tracers of melt/fluid metasomatism, whereas Ni/Co, Ni/Mn and Mn/Zn ratios are indicators of chromite mineralization. Therefore, trace elements in olivine can be used as chemical proxies to distinguish the origin of various mafic-ultramafic rocks, as well as the processes by which they evolved.

Spatiotemporal variation of rare earth elements from river to reef continuum aids monitoring of terrigenous sources in the Great Barrier Reef

Degradation of inshore water quality associated with catchment modification is threatening global coral reef ecosystems. Coral trace element proxies are widely applied to document the magnitude and timing of historical changes in river runoff and other disturbances. However, conflicting interpretations of commonly used coral proxies (Ba/Ca, Y/Ca and Mn/Ca) complicate their application for examining historical changes in coastal water quality. The exploration of other coral trace element proxies (such as rare earth elements, REE) is limited in space and time, and to few coral genera. This study examined the dynamics of dissolved REE and yttrium (REEY) in the Fitzroy and Burdekin river tributaries and estuaries, Queensland, Australia. In addition, monthly-resolution long-term temporal records of Ba/Ca, Mn/Ca, Y/Ca and REEY proxies were investigated in two Porites and one Cyphastrea coral colonies from the central and southern Great Barrier Reef in order to test the reliability of these proxies to record the variability of river runoff and local anthropogenic disturbances. The results showed large scale removal of REEY (55–86%) in the low salinity mixing zones of both estuaries with significant fractionation of Nd-Yb and Y-Ho, confirming the ability of coral REEY to act as a terrestrial runoff proxy. Coralline Ba/Ca, Y/Ca and Mn/Ca records generally lack coherence with proximal discharge. However, temporal fluctuations of REEY proxies, irrespective of geographic location and coral genus, showed consistent behaviour relative to regional discharge with progressive increase of total REE/Ca and shale normalized Nd/Yb and decrease of Y/Ho during high-flow summer periods. The shifting baselines of REEY proxies in Cyphastrea grown in the turbid water setting of Rat Island effectively captured the timing of Gladstone Port dredging activities. Our findings suggest that shale normalized coral REEY distributions outperformed other commonly used trace element proxies and are robust indicators of changing inshore water quality. Longer-term records of coral REEY, even covering the period before European settlement from the 1850s, may provide a means to identify shifting baselines and evaluate and quantify the impacts of catchment alteration on coastal water quality and specific coral reef communities.

Unusually heavy stable Mo isotope signatures of the Ottawa River: Causes and implications for global riverine Mo fluxes

The accurate use of Mo isotope mass balance modelling of ancient oceans relies on the assumption that the δ98Mo of modern riverine inputs represents a reasonable estimate of the past. A growing number of studies of global rivers have demonstrated significant variation in δ98Mo from the bedrock sources of Mo. The Ottawa River, Canada, was previously identified as having an anomalously heavy Mo isotope composition, with a δ98Mo signature close to seawater (2.3‰), for a seemingly pristine natural river. To further explore this unusual signature, we collected and filtered 29 water samples from the Ottawa River, tributaries, and small lakes, and analysed them for Mo isotopes as well as major and trace elements. Here, we fully document heavy δ98Mo signatures throughout the Ottawa River and its absence in surrounding areas of the wider Ottawa River basin (ORB). Our results reveal a progressive upstream increase in both Mo concentration and δ98Mo signatures in the Ottawa River towards values even heavier than seawater, up to 3.13‰ – the heaviest Mo isotopic signature of river water measured to date. In contrast, the tributaries and lakes display far lighter and more consistent δ98Mo signatures within the range previously found in other rivers. Weathering of an isotopically heavy bedrock source, fractionation during weathering and retention of light isotopes in soils have all been proposed as sources of heavy δ98Mo in rivers; however, none of these mechanisms can satisfactorily explain our new observations. Colloidal and particulate processes that remove elements downstream, as inferred from some trace element proxies, also cannot explain the decreasing δ98Mo, since the preferential removal of light Mo isotopes is predicted from these processes. Similarly, the downstream trends show no apparent relationships with constructed dams or known potential industrial sources. Therefore, our findings from the Ottawa River are best explained as the dilution of a yet unidentified point source of heavy Mo upstream of sampling, or a significant permanent sink for light isotopes existing only in the upper reaches of the catchment. In both cases, anthropogenic contribution from a large mining district in the headwaters of the river must be considered and should be explored further. Fractionation of Mo in waste rock storage facilities has been previously identified and may provide an unnatural sink for isotopically light Mo through the Rayleigh-type fractionation of dissolved Mo on oxyhydr(oxide) mineral surfaces. The implied anthropogenic alteration of the natural Mo cycle highlights the significant and wide-reaching effects of unnatural point sources of Mo on the cumulative δ98Mo signatures of the catchment, and emphasises the necessity for detailed geochemical screening of anomalous river water isotope signatures before natural isotope compositions are inferred.

Provenance and tectonic implications of the Carboniferous sediments in the Bainaimiao arc belt, northern margin of the North China Craton: evidence from detrital zircon U–Pb–Hf isotopes and trace elements

Sedimentological and zircon U–Pb–Hf isotopic analyses of the Carboniferous strata in the Bainaimiao arc belt (BAB) provide provenance information for the northern margin of the North China Craton (NCC). The late Carboniferous strata in the eastern BAB were dominantly shallow marine carbonate-clastic deposits. Detrital zircon data show that: (1) sandstone from lower Sidaozhangpeng Formation displays two major age peaks of 369 Ma and 2522 Ma, with eHf (t) values of − 25.9 to − 20.4 and 2.2–6.4, respectively; (2) sandstone from upper Sidaozhangpeng Formation shows a significant age peak at 384 Ma, with eHf (t) values of − 25.3 to − 14.5. Determination of detrital zircon parent rock types based on trace element proxies suggests that the protolith rock types consist of felsic (73%) and mafic rocks (22%), with minor alkaline rocks (5%), implying a continental arc setting. The U–Pb–Hf dating of the Carboniferous strata in the western and eastern BAB shows different provenances: the Carboniferous sediments in the western BAB were derived from early Paleozoic magmatic rocks, micro-block (Hunshandake Block) and the NCC basement; the provenances of the Carboniferous strata from the eastern BAB were mainly local Devonian magmatic rocks, with subordinate input of the Neoarchean NCC basement rocks. The early Paleozoic zircon grains recorded by the early Devonian rhyolitic tuff and late Carboniferous sandstone indicate that the early Paleozoic arc magmatic activities also occurred in the eastern BAB.

Multi-proxy stalagmite records from northern California reveal dynamic patterns of regional hydroclimate over the last glacial cycle

Despite its importance for California’s water resources, little is known about how precipitation has varied in far northern California beyond the historical record. We present a new, multi-proxy paleoclimate record derived from two coeval stalagmites from Lake Shasta Caverns (LSC), California that covers the end of Marine Isotope Stage 3 through Heinrich Stadial 1 (∼35,000 to 14,000 years BP). At 40.8°N, LSC is situated within the transition zone between regions in the northwestern and southwestern United States that demonstrate different precipitation responses to both modern and paleoclimatic drivers. Stable isotope and trace element proxies from LSC stalagmites indicate the region experienced wet conditions during interstadials (warm periods) associated with Dansgaard-Oeschger cycles, similar to proxy records from southern Oregon and the northern Great Basin, but in contrast to records from the desert southwest. Similar to the northern Cascades and Rocky Mountains, LSC was drier during the Last Glacial Maximum. However, proxies indicate increased rainfall throughout Heinrich Stadial 1, similar to the Great Basin and southwest. Thus, the LSC record demonstrates the non-stationarity of the transition zone location and illustrates a complex pattern of precipitation response to global climate change in the western United States. Covariation of speleothem δ18O, an indicator of moisture source, with δ13C and trace elements, indicators of moisture amount, suggest a higher proportion of Central Pacific precipitation during the Last Glacial Maximum, despite the enhanced aridity. In contrast, periods characterized by increased precipitation amounts, such as early Heinrich 1, are associated with enhanced moisture from the Northern Pacific.

Shell chemistry of the boreal Campanian bivalve &amp;lt;i&amp;gt;Rastellum diluvianum&amp;lt;/i&amp;gt; (Linnaeus, 1767) reveals temperature seasonality, growth rates and life cycle of an extinct Cretaceous oyster

Abstract. The Campanian age (Late Cretaceous) is characterized by a warm greenhouse climate with limited land-ice volume. This makes this period an ideal target for studying climate dynamics during greenhouse periods, which are essential for predictions of future climate change due to anthropogenic greenhouse gas emissions. Well-preserved fossil shells from the Campanian (±78 Ma) high mid-latitude (50∘ N) coastal faunas of the Kristianstad Basin (southern Sweden) offer a unique snapshot of short-term climate and environmental variability, which complements existing long-term climate reconstructions. In this study, we apply a combination of high-resolution spatially resolved trace element analyses (micro-X-ray fluorescence – µXRF – and laser ablation inductively coupled plasma mass spectrometry – LA-ICP-MS), stable isotope analyses (IRMS) and growth modeling to study short-term (seasonal) variations recorded in the oyster species Rastellum diluvianum from the Ivö Klack locality. Geochemical records through 12 specimens shed light on the influence of specimen-specific and ontogenetic effects on the expression of seasonal variations in shell chemistry and allow disentangling vital effects from environmental influences in an effort to refine paleoseasonality reconstructions of Late Cretaceous greenhouse climates. Growth models based on stable oxygen isotope records yield information on the mode of life, circadian rhythm and reproductive cycle of these extinct oysters. This multi-proxy study reveals that mean annual temperatures in the Campanian higher mid-latitudes were 17 to 19 ∘C, with winter minima of ∼13 ∘C and summer maxima of 26 ∘C, assuming a Late Cretaceous seawater oxygen isotope composition of −1 ‰ VSMOW (Vienna standard mean ocean water). These results yield smaller latitudinal differences in temperature seasonality in the Campanian compared to today. Latitudinal temperature gradients were similar to the present, contrasting with previous notions of “equable climate” during the Late Cretaceous. Our results also demonstrate that species-specific differences and uncertainties in the composition of Late Cretaceous seawater prevent trace element proxies (Mg∕Ca, Sr∕Ca, Mg∕Li and Sr∕Li) from being used as reliable temperature proxies for fossil oyster shells. However, trace element profiles can serve as a quick tool for diagenesis screening and investigating seasonal growth patterns in ancient shells.

Geochemistry and palynology of the upper Albian at the Abu Gharadig Basin, southern Tethys: Constraints on the oceanic anoxic event 1d

The mid‐Cretaceous period was a time of abnormal polar temperature warming and consequent global oceanic anoxia that enhanced the widespread accumulation of organic matter‐rich marine sediments. The current contribution focuses on the late Albian oceanic anoxic subevent 1d (OAE 1d) that represents a period of increased perturbation of the global carbon cycle. Palynological and geochemical investigations, including TOC/Rock‐Eval pyrolysis and stable carbon isotope of organic matter (δ13CTOC), were conducted for the upper part of the Kharita Formation from the Abu Gharadig Basin, north Western Desert, Egypt, to (a) confirm the age of this unit, (b) assess the depositional environments and prevalent redox conditions, and (c) confirm the occurrence of the OAE 1d within the sedimentary record in this part of the southern Tethys. Based on the TOC content and Rock‐Eval pyrolysis parameters, the organic matter in the upper Kharita Formation is expected to have a limited hydrocarbon generation potential consisting of gas only. The sedimentation patterns and role of continental weathering and runoff influx were assessed through trace element ratios and relationships. Redox conditions were interpreted based on Stotal–TOC relationship, Stotal–TOC–Fetotalternary plot, Rock‐Eval S2, trace element proxies and relationships (including Cr vs. V + Ni, V/Cr vs. Stotal, and Stotal/Fe vs. Mn/Stotal). The ratio of TOC/Ptotalwas implemented to assess both marine primary productivity and oceanic anoxia during this period. Biostratigraphic constraints showed that the upper part of the Kharita Formation spanned a late Albian age (Cretacaeiporites densimurusInterval Zone). Results showed that the OAE 1d was characterized by organic matter deposition during dysoxic‐suboxic to anoxic redox conditions in a fluvio‐deltaic to shallow marine depositional environment in this part of the Tethys. A low to moderate primary productivity was also prevalent during a fairly high rate of sediment accumulation. Regional correlation of positiveδ13CTOCexcursion during the OAE 1d throughout the Tethys and Atlantic oceans matched well, in several parts, with the current study interval that confirm the global distribution of the OAE 1d. In this region of the southern Tethys, an overall collapse of water column stratification during the OAE 1d principally related to decreased terrestrial input at low relative sea level, as evidenced from freshwater algaePediastrumand pteridophyte sporeCrybelosporites pannuceus; however, orbital forcing likely induced monsoonal activity at low‐latitudes in the SE, N, and W Tethys.

Environmental fluctuation impacted the evolution of Early Pleistocene non-human primates: Biomarker and geochemical evidence from Mohui Cave (Bubing, Guangxi, southern China)

Quaternary climate variability, profoundly impacting the evolution and distribution of plants and animals across the globe, has been reconstructed by many sediment archives. Here, we track past changes of temperature, rainfall and plant type by using the n-alkane and glycerol dialkyl glycerol tetraethers (GDGTs), as well as weathering and pedogenesis by mineralogical and geochemical proxies from a 250 cm deep soil sediment profile from the Early Pleistocene deposits in Mohui Cave, southern China. Indices for weathering intensity such as mineral composition (quartz, feldspar and calcite), major element proxies (Ti/Na, Al/Na, Al/Mg, Ti/Mg, CIW, PIA, CPA, CIA), trace element proxies (Ba/Sr and Rb/Sr), and biomarker proxies (OEP, LSR and CPI) show similar secular trends, revealing a three-stage historical accumulation. The high long-chain n-alkane ratios (C31/C29 and (C31+C33)/(C27+C29)) indicate that the vegetation in the region had increases in percentage of woody plants and decreases in herbs during periods of relatively lower temperature and less precipitation, which evidenced from GDGTs, consistent with a weak weathering process influenced by summer monsoon strength. Further, we compared the distribution of these plant types with the taxonomic variation in the vertebrate paleontological fossils excavated from the same profile in Mohui Cave. The distribution of Lufengpithecus appears in only one interval but Gigantopithecus blacki appears throughout the profile, despite an environment that experienced transitional stages from grassland to woodland in relatively cooler and drier conditions. We infer that in face of these climatic changes Lufengpithecus may have preferred to emigrate from the region, while Gigantopithecus blacki may have stayed given that it was limited to staying in its core area.

Deposition conditions of the Jurassic lacustrine source rocks in the East Fukang Sag, Junggar Basin, NW China: Evidence from major and trace elements

The Fukang Sag hosts prolific Jurassic lacustrine source rocks, which include the Badaowan (J1b), Sangonghe (J1s), and Xishanyao (J2x) formations in the Junggar Basin. Depositional conditions were reconstructed based on various major and trace element proxies for the East Fukang Sag during the Jurassic. The palaeowater depth in the sag was shallow and did not display a great change during the deposition of the J1b, J1s, and J2x formations, as indicated by lithological composition and the widespread ripple cross‐beddings. The oxic to dysoxic and fresh‐water conditions were postulated to prevail in the sag during the deposition of these source rocks, as revealed by concentrations of salinity‐ and redox‐sensitive trace elements [i.e., V/Cr, Ni/Co, (Cu+Mo)/Zn, Sr/Ba ratios, and Sr, Mn, Ga contents] derived from the source rocks. The seasonal salinity stratification superposed on preexisting thermal stratification led to the appearance of the chemocline in the J1b Formation. The palaeoclimate regime was humid and warm during the depositions of the J1b and the upper J1s formations, and warmer and drier during the deposition of the lower J1s Formation, but the palaeoclimate gradually became semi‐arid and semi‐cold during the deposition of the upper J2x Formation, as implied by various proxies (i.e., Sr/Cu ratio, C‐value, and CIA value). Despite the fact that the oxic to dysoxic conditions were not conducive for organic matter (OM) preservation, the significantly moderate‐high palaeoproductivity (suggested by, i.e., Ba content and Ba/Al ratio), which was promoted by a suitable supply of nutrient from terrestrial inputs in the shallow water was the controlling factorfor the OM accumulation on the margin of the sag, but the low OM concentration was controlled by the palaeoredox conditions in the central area, which was far from the OM input source [suggested by the relationship between total organic carbon content and stable carbon isotope composition of OM (δ13Corg)]. The analyses based on Rock‐Eval pyrolysis, maceral composition, C/N ratio of isolated kerogen, and δ13Corg value showing the OM was derived from terrestrial higher plants with C3 plants (type III kerogen) are consistent with the palaeoenvironmental analysis.

Trace element proxies of seafloor hydrothermal fluids based on secondary ion mass spectrometry (SIMS) of black smoker chimney linings

Sampling of paired black smoker chimney linings and seafloor hydrothermal vent fluids supports the development of trace element proxies for sulfide mineral deposition environments by facilitating analyses of trace element partitioning between mineral and fluid phases under well-constrained physiochemical conditions. Here, concentrations of Co, Ni, Ga, Ag, and In in chalcopyrite lining 22 black smoker chimneys (29 for Co, Ag, and In) are measured using secondary ion mass spectrometry (SIMS) calibrated against inductively coupled plasma mass spectrometry (ICP-MS) and NIST-traceable reference solutions. To provide additional data on the trace element concentrations of vent fluid pairs for 19 of the 29 black smoker chimney linings investigated, this paper also presents new ICP-MS data for 33 hydrothermal vent fluids collected from the Tahi Moana-1, ABE, Tu’i Malila, and Mariner vent fields on the Eastern Lau Spreading Center and Valu Fa Ridge.The chalcopyrite black smoker chimney linings investigated represent a variety of temperature (269–395 °C), chemical (e.g., pH (at 25 °C) = 2.3–4.4), and geologic conditions. Electron microprobe results indicate that mineral stoichiometry ranges from stoichiometric chalcopyrite to mol Cu : mol Fe = 0.65. Trace element concentrations obtained by SIMS are: Co (<2 ng/g–760 μg/g), Ni (<17 ng/g–454 μg/g), Ga (<0.9 ng/g–48 μg/g), Ag (60 μg/g–3800 μg/g), In (<0.5 ng/g–270 μg/g). Concentrations of Ag in chalcopyrite strongly correlate with the free ion activity ratio of {Ag+}:{Cu+} in paired vent fluids, with high Ag concentrations in chalcopyrite indicating formation from near neutral vent fluids containing low Cu concentrations or low-pH vent fluids with high Ag concentrations attributable to subsurface Ag remobilization. Chalcopyrite with low Ag precipitates from low-pH Cu-rich fluids unaffected by extensive Ag remobilization. Concentrations of Ga and In in chalcopyrite exhibit a negative trend with vent fluid pH, possibly reflecting the strength of Ga and In OH− complexes. Thus, Ga and In concentrations differentiate Ag-rich chalcopyrite formed from near-neutral Cu-poor vent fluids or that formed from Ag-rich low-pH vent fluids. In contrast, Co and Ni exhibit no trend with fluid data, but correlate with mineral Cu:Fe ratios, possibly reflecting the greater availability of Fe(II) lattice sites or paired substitution of 2+ ions.Overall, this study demonstrates the potential of paired vent fluid and black smoker chimney samples to provide insight into the partitioning of trace elements in sulfide mineral deposition environments and related proxies of important fluid parameters such as pH and metal concentrations. This study also demonstrates the utility of SIMS to precisely analyze trace elements in chalcopyrite at high spatial resolutions and low detection limits.

Trace element and isotope proxies in paleoceanography: Starting a new synergic effort around marine geochemical proxies

Trace element and isotope proxies in paleoceanography: Starting a new synergic effort around marine geochemical proxies