Seawater Values Research Articles

High-precision zirconium isotope analysis of Pacific seawater reveals large mass-dependent fractionations in the ocean

Zirconium (Zr) stable isotopes recently emerged as potential tracers of magmatic processes and, as a result, their behavior in high-temperature environments have been the focus of extensive characterization. In contrast, few studies have focused on Zr behavior and isotopic fractionation in low temperature or aqueous environments. Here, we describe a new analytical routine for highly precise and accurate analysis of Zr isotopes of water samples, using a combination of double-spike and iron co-precipitation methods. To assess the impact of potential systematic biases a series of experiments were conducted on natural and synthetic water samples. Our results show that the spike-to-sample ratio, matrix composition, and high field-strength element (HFSE) concentration have negligible effects on measured seawater Zr isotopic compositions, and that the Fe co-precipitation method used yields accurate and precise Zr isotope data. We thus apply this method to natural seawater samples collected from a water column profile in the Pacific Ocean off the coast of California, with depths ranging from 5 to 711 m. We find that the natural seawater samples are highly fractionated relative to solid-Earth values and display marked variability in δ94/90Zr as a function of depth, ranging from ∼ +0.650 ‰ near the surface, to + 1.530 ‰ near the profile bottom, with an analytical uncertainty of ± ∼0.045 ‰ (2 SE, external reproducibility). The δ94/90Zr value of seawater is much higher than that of Earth’s mantle and continental crust, which has a δ94/90Zr value near zero, indicating the presence of processes in the hydrosphere capable of inducing large mass-dependent fractionation. Furthermore, the seawater δ94/90Zr value exhibits systematic variations with respect to water depth and salinity, suggesting that Zr isotopic compositions may be sensitive to seawater chemical properties and source highlighting its potential utility as a tracer of biogeochemical processes within the ocean.

Saline-Tolerant Pathogenic Acanthamoeba spp. Isolated from a Geothermal Power Plant.

Few studies have been conducted in the cooling systems of power plants; they have focused on Naegleria fowleri, leaving a gap in the knowledge of other pathogenic free-living amoebae in this environment. The objective of this study was to determine the occurrence of saline-tolerant pathogenic Acanthamoeba in a geothermal power plant. The identification of isolated amoebae at genus level was carried out, observing their morphological characteristics; the determination of genotype and species of Acanthamoeba was performed via molecular biology (PCR). Water temperature ranged from 18 to 43 °C and conductivity from 4.0 × 104 to 8.7 × 104 μS/cm; this last value was greater than the seawater value. Only five amoeba genera were found. Acanthamoeba was in all the sampling sites, showing high saline tolerance. The high temperature, but mainly high conductivity, were the environmental conditions that determined the presence of pathogenic free-living amoebae in the hot water. All the strains of Acanthamoeba culbertsoni killed the mice, having a mortality of 40 to 100%. Acanthamoeba genotypes T10 and T5 were identified, T10 is rarely isolated from the environment, while T5 is more frequent. This is the first time that genotypes T5 and T10 have been reported in the environment in Mexico.

The application of dual clumped isotope thermometer (Δ47 and Δ48) to the understanding of dolomite formation

Abstract Although several studies have shown the possibility of kinetic isotopic effects during the precipitation of carbonates using the dual clumped isotope proxy (Δ47 and Δ48), this approach has not yet been applied to the study of dolomite. We present Δ47 and Δ48 values of two types of Cenozoic Bahamian dolomites formed by distinctly different mechanisms. One dolomite, present in a core drilled on the island of San Salvador, is believed to have formed from normal seawater in the open system, while the other, taken from the Clino core drilled on the margin of the Great Bahama Bank, was precipitated associated with microbial sulfate reduction in the closed system. The Δ48-derived temperatures of San Salvador dolomites are consistent with their Δ47-temperatures, which are in turn close to the expected value of normal seawater. In contrast, dolomites from Clino show slightly elevated Δ47-derived temperatures (~15 °C higher than the expected) and significantly increased Δ48-temperatures (~145 °C) that are positively correlated with the sulfur isotopes of carbonate associated sulfate, in excess of +30‰. Such an association suggests a non-equilibrium process driven by microbial sulfate reduction, which elevates the alkalinity and depresses the pH of dolomitizing fluids. Notably, the greater amplitude of disequilibrium in Δ48 relative to Δ47 values demonstrates the sensitivity of the Δ48 proxy to kinetic isotope effects in dolomite. Conclusively, this study shows the potential of the dual clumped isotope proxy to identify microbial-mediated dolomitization in modern and ancient records.

Active near-surface mobilisation of slab-derived geochemical signatures by hyperalkaline waters in brecciated serpentinites

Unusual hyperalkaline meteoric groundwaters on Troodos massif, Cyprus, issue from highly deformed and completely serpentinized ultramafic brecciated rock masses of the Artemis Diapir and have high salinity (25–30% seawater total dissolved solids) and some of the highest recorded pH values (11−13) for natural waters. These waters have elevated dissolved Na, K, Li, B, Ba, Rb, Cs, Cl and SO4 with ion/chloride substantially above seawater ratios, overprinting minor contributions from marine aerosols. For example, K concentrations are similar to seawater values. Water stable isotope ratios imply extensive water-rock interaction and 87Sr/86Sr is rock-dominated (0.705) and significantly lower than seawater. These rare fluids contrast with surface and shallow ground waters draining the ultramafic Troodos Mantle Sequence that have pH of 8.5–9, meteoric stable isotope ratios, 87Sr/86Sr similar to early Miocene seawater (0.7085) and low dissolved salts albeit with ion/chloride ratios also greater than seawater. The combination of high pH and salinity is unusual in ophiolites and these hyperalkaline waters are most similar to end-member fluids emanating from serpentine mud volcanoes in the Mariana forearc. Rainwater rapidly transiting terraces of asbestos mine tailings on Troodos mostly resemble the surface waters but show slight contamination by a saline component. We propose that inclusions within the serpentinite that contain highly soluble salts have been made accessible by tectonic deformation during uplift and diapirism, or comminution during mining activity. A multistage process is proposed whereby alkali and other signatures have been released from the stalled subducting slab beneath the Troodos massif and have infused the mantle wedge. Some of these rocks have been carried to the surface by diapiric uplift and erosion, where tectonic deformation or mining activities have enabled the near-surface mobilisation of slab-derived geochemical signatures by modern meteoric waters.

Re-Os, Sr-Nd isotopic and PGE elemental constraints for the formation of mid-Proterozoic ironstones in North China Craton: Implications for the atmospheric oxygen level

The origin (hydrothermal vs. continental Fe source) and environmental implications in particular for the atmospheric oxygen level of mid-Proterozoic ironstones have been widely studied, but remain highly debated. Here, we present Re-Os, Sr-Nd isotopic and PGE elemental data for ironstones from the ∼1.7 Ga Yunmengshan (YMS) Formation in south margin of the North China Craton to address the controversy. The initial 87Sr/86Sr ratios of the YMS ironstones are ∼0.7063, which are roughly comparable with seawater values around that period, suggesting a seawater signal with minor/minimal direct contributions from submarine hydrothermal fluids. The Nd isotopic compositions (εNd(t): −6.6 to −6.0) indicate a dominantly continental crustal signal for the formation of the ironstones. The PGE patterns of the YMS ironstones are distinctly similar to those of hydrogenous Fe-Mn crusts/nodules in modern ocean, also suggesting deposition from normal seawater conditions. Importantly, the YMS ironstones give initial 187Os/188Os ratios of ∼0.6 at ∼1.7 Ga, providing critical constraints for contemporaneous seawater values. This seawater 187Os/188Os value of ∼0.6 strongly suggests a result of oxidative weathering and transportation of Os in continental crust into the ocean, implying a relatively high atmospheric oxygen level at ∼1.7 Ga.

Effect of hybridization on mechanical and water absorption properties of short palmyra palm leaf stalk/carbon fibers reinforced polyester composites

AbstractRecently, there has been interest in the development of hybrid composites for diverse industrial applications. In this aspect, this paper explores the mechanical (tensile, flexural, impact, and dynamic mechanical analysis) and water (distilled and seawater) absorption properties of palmyra palm leaf stalk/carbon fiber‐based composites. Hybrid composites with various reinforcement weight ratios were manufactured for the experiment employing the compression molding procedure. To analyze the hybridization effect, composites with a single reinforcement were also produced and evaluated. The results demonstrated that adding carbon fiber to palmyra fiber in the matrix enhances the composites' overall mechanical properties. Field emission scanning electron microscope (FESEM) was used to assess the broken surface of mechanically tested composites to better comprehend the failure causes. The findings of the moisture absorption test have shown that using carbon fiber in composites reduces moisture absorption due to their hydrophobic behavior. In addition, the specimens dipped in seawater absorbed more water due to the higher pH value of seawater and gained more weight due to salt deposition. The results of this study indicate that the hybrid composite formulation P25C75 exhibits a balance between its mechanical properties and environmental resilience, making it a possible lightweight material for structural applications.Highlights Various properties of palmyra palm/carbon hybrid composites were investigated. Addition of carbon fibers to palmyra palm composites enhanced their properties. Hybrid composites exhibit better‐damping property. Performance, environmental effect, and cost are balanced in hybrid composites.

Diagenetic effect on barium isotope compositions of barites in the lower Cambrian successions

The pelagic barite precipitation in the seawater column is tightly associated with the biological pump, and thus the barite Ba isotope composition (δ138/134Ba) has been advocated as a novel paleo-productivity proxy. However, pelagic barites in sediments are susceptible to diagenetic processes that may modify primary δ138/134Ba signals and hamper the application. To constrain the diagenetic effect, we report δ138/134Ba data of diagenetic barites from the black shales of the lower Cambrian Yurtus Formation in the Aksu area of the Tarim Basin. The δ138/134Ba values vary within a large range from −0.15‰ to +0.49‰ and show a generally positive correlation with the 87Sr/86Sr ratios, indicating the mixing of two end-members. The samples with 87Sr/86Sr ratios close to the coeval seawater value record relatively low δ138/134Ba values from −0.15‰ to +0.14‰, which are inferred to inherit from the primary barites; whereas the samples with 87Sr/86Sr ratios exceeding the coeval seawater value record higher δ138/134Ba values from −0.05‰ to +0.49‰, which may have resulted from the alteration by the host black shales during early diageneses. Based on these investigations, we propose that pore waters below the sulfate-methane transition zone may provide an additional source of Ba (enriched in heavy isotopes) for the formation of diagenetic barites. We suggest to combine barite 87Sr/86Sr ratio with δ138/134Ba value to evaluate diagenetic influence on primary Ba isotope signatures especially for an over-determined system, which is important for applying Ba isotope compositions of barites to understand paleo-oceanic evolution.

Chemical composition of monsoon bulk precipitation in the Salalah area, Oman

Precipitation chemistry data provide important information for environmental studies on large-scale element cycling and anthropogenic impacts on our atmosphere, but also for hydrochemical models and groundwater recharge estimations via the Chloride Mass Balance method. Such recharge data play a crucial role in groundwater management, particularly in (semi-)arid areas. Unfortunately, precipitation analyses are often scarce in such regions. This also applies to the Arabian Peninsula, including southern Oman. To overcome this lack of rain chemistry data, we developed a strategy for automatic weekly bulk precipitation sampling, using recently designed automatic rainwater samplers. The integral samples were gathered along an elevation gradient from the Salalah coast to the Dhofar mountains during the Indian Ocean Monsoon seasons 2017 and 2018.Our major ion analyses of the rainwater samples revealed considerable temporal and spatial heterogeneity, in terms of ion proportions and absolute concentrations. Samples from the coast were relatively salty (EC mostly >3000 μS cm−1) and rich in Na+ and Cl−, reflecting small rain amounts and a sea spray effect. Further inland, solute concentrations were lower, partly due to more precipitation, and ions such as Ca2+ and SO42− gained importance, probably due to calcite and gypsum dust. This pattern reflects the interplay between solute availability (influenced by regional geology, wind direction at different altitudes, and wind speed) and precipitation amounts. Cl−/Br− ratios were fairly uniform and scattered around the seawater value. Combining ion concentrations and rain amounts yielded bulk depositions that showed an erratic pattern along the elevation gradient, i.e., depositions did not decrease steadily in inland direction, as one may assume. This suggests that the occasionally reported approach of collecting a few opportunistic grab samples at a single site is unlikely to yield data that are representative for a larger coastal study area.

Changing Sub‐Surface Chemistry Resulting From a 26‐Million‐Year Unconformity: Porewater Chemistry From IODP Site U1553 in the South Pacific

AbstractWhereas changes in pore water chemistry are known to impact carbonate sediment geochemistry, little is known about the impact of long unconformities on carbonate alteration. IODP Site 378‐U1553 on the southern Campbell Plateau, with a 26‐million‐year, erosional unconformity, provides a key location for examining the impact of long‐term unconformities on sub‐surface chemistry and carbonate archives. This study examined 76 interstitial water samples for sulfate sulfur and oxygen isotopes, as well as 28 bulk carbonate samples for carbonate associated sulfate (CAS) sulfur isotopes, to quantify the effects of this unconformity on the sub‐surface redox chemistry of the Site. The current state of the system suggests limited influence of redox processes on the CAS archive. Manganese reduction reaches 30 mbsf, with a decrease in manganese reduction between 20 and 30 mbsf. Below 30 mbsf, the system transitions to iron reduction to a depth of approximately 140 mbsf where sulfate reduction begins. Dissolved sulfate sulfur and oxygen isotope values suggest repeated oxygenation of sulfides. The CAS record from the Site deviates from previously published seawater values. However, the lack of a relationship between the dissolved sulfate and CAS records suggests most of the alteration of the CAS record likely occurred before the unconformity when the carbonate sediments were more reactive. This further supports the CAS record as a relatively robust archive, withstanding most post‐depositional mechanisms of carbonate alteration.

Early diagenetic mobilization of rare earth elements and implications for the Ce anomaly as a redox proxy

The Rare Earth Elements (REE) archived in carbonate rocks retain a wealth of information on paleo-seawater chemistry and local-regional redox conditions. However, interpretations are often ambiguous due to the potential for REE remobilization in marine environments. In this regard, many carbonate rocks that retain primary seawater isotopic signatures exhibit non-seawater-like REE patterns, implying either unusual REE behaviour in seawater or diagenetic overprinting of otherwise well-preserved rock samples. Here, we apply sequential leaching to constrain the possible effects of different REE-bearing phases on measured carbonate REE patterns in order to address this quandary. Our results show that the exchangeable phase contains negligible REE, but could be an important host phase for other elements such as Sr, Ba and K. The acidified hydroxylamine hydrochloride leach is shown here not only to dissolve Fe–Mn oxides but also phosphate minerals, which induces middle REE enrichment in corresponding leachates of dolostone samples in our study. The demonstrable Fe–Mn oxide phase in limestone samples is characterized by middle and/or light REE enrichment and positive Eu anomalies, which are attributed to hydrothermal processes and continuing exchange with marine fluids after initial precipitation. The non-seawater-like REE patterns observed in the carbonate phase of otherwise well-preserved limestones resemble those of the co-existing Fe–Mn oxide fraction, and are interpreted to reflect the dissolution of REE carrier phases during early diagenesis. This view is supported by fluid-rock interaction modelling, which shows how REE can be mobilized at relatively low fluid/rock ratios in shallow porewaters. Non-seawater-like REE patterns may therefore be caused by the incorporation of REE from shallow porewaters before final lithification due to an elevated flux of particulate REE carrier phases, e.g. Fe–Mn oxides and organic matter, to the seafloor. In spite of the sensitivity of carbonate REE patterns to early diagenetic exchange, the co-occurrence of non-seawater-like patterns with primary strontium and carbon isotope values suggests that REE should not be viewed as a general indicator for the preservation of other geochemical proxies. Importantly, Ce anomalies of the carbonate phase will also be affected by porewaters, masking primary seawater values. Our results favour a reevaluation of redox interpretations by taking into account REE patterns as a whole.

Seawater silica cycling and chert formation at the Neoproterozoic–Cambrian transition: Insights from δ30Si and Ge/Si systematics of hydrothermal cherts from the Bohemian Massif

The genesis of cherts, rocks with >90 wt% SiO2, is suggested to be linked with dissolved seawater silica and its elevated precipitation in the Phanerozoic due to massive biological activity in the Earth's oceans compared to the Precambrian where hydrothermal fluids played a more dominant role. Because cherts may record a history of global seawater Si cycle, their Si isotope systematics may serve as a proxy for their origin and depositional environment. In this study, Si isotope compositions, combined with Ge/Si ratios, were determined for a suite of shallow-water, deep-water and stromatolitic cherts from the Blovice accretionary complex (Bohemian Massif, Czech Republic), representative of deep marine and subduction settings, to establish the nature of cherts and processes of their formation, identify the sources of Si and Ge, and discuss the possible effect of the Neoproterozoic–Cambrian transition. The predominantly high δ30Si values > +0.23‰, associated with low Ge/Si, in deep-water cherts suggest their precipitation from seawater-derived low-temperature fluids at the seawater–sediment interface with subordinate admixture of terrigenous material. Moreover, the tight relationship between δ30Si and organic matter contents in these deep-water cherts is indicative of either equilibrium precipitation of isotopically lighter Si as the organic content of the medium increases or global decrease of δ30Si values of seawater during the Meso–Neoproterozoic related to coupled Si and C cycles. On the other hand, a δ30Si variation of ∼2.5‰ (−0.94‰ to +1.60‰) in shallow-water cherts argues for precipitation from seawater interacting with hydrothermal fluids of variable temperature. Organic matter, Fe-(oxy)-hydroxides and clays represent important sinks for Ge (and Si in case of organic matter) and thus play a determining role in global marine Si−Ge cycling. This, together with the presence of abundant cherts at the Neoproterozoic–Cambrian transition, appears to be associated with redox-controlled Fe cycle which itself is related to microbial reduction and the increasing presence of organic matter towards the Phanerozoic.

Carbonate diagenesis: A celebration of the work of John Anthony Dawson (Tony) Dickson

Carbonate diagenesis: A celebration of the work of John Anthony Dawson (Tony) Dickson

Boron isotope fractionation between B(OH)3 and B(OH)4− in aqueous solution: A theoretical investigation beyond the harmonic and Born−Oppenheimer approximations

Boron isotope fractionation between boric acid and borate ion in aqueous solution (hereafter, α3–4) is a key coefficient for reconstructing paleo-pH and paleo-pCO2 records, and a valuable parameter for understanding boron isotope geochemistry related to mineral-water interactions. Although boron isotopes have wide geologic application, the effect of temperature and ion pairing on boron isotope fractionation is poorly described. Moreover, conventional density functional theory (DFT) calculations do not provide an accurate estimate of the boron isotope fractionation factor. Here, we provide a new strategy to accurately calculate α3–4 values in aqueous solution by evaluating harmonic frequencies, higher-order energy terms, and solvation effects. Using benchmark coupled cluster (CCSD(T)) calculations, our 25 °C results for α3–4 ranges from 1.0259 to 1.0275, which is in good agreement with recent experimental data. Solvation effects reduced the α3–4 value by ∼6‰, while high-order corrections raised the α3–4 value by ∼2‰. Our calculations evaluating the effect of aqueous ion pairs suggest that the α3–4 values in seawater and pure water should be almost identical. Our results provide a reasonable estimation of the partition function ratios of dissolved boron species, which will benefit studies of boron isotope fractionation in aqueous environments.

Oceanic redox conditions during the terminal Cambrian extinction event

Marine animal diversity during the late Cambrian was reduced by a series of extinctions that have generally been attributed to oceanic anoxic events associated with positive carbon isotope excursions. Here we present carbon and uranium isotope ratios (δ13C and δ238U values) as proxies for global carbon cycle and oceanic redox conditions, respectively, from carbonate rocks of the Wa'ergang section, South China. The dataset spans an interval that includes the last major negative δ13C excursion (TOCE) of the Cambrian Period. The TOCE is a globally documented event, recovery from which corresponds to the terminal Cambrian extinction event. The δ13C and δ238U values covary through the section, shifting initially to lower values, with δ238U falling below the modern open-ocean seawater value from the start to the middle of the profile, followed by a shift to higher values towards the end of the Cambrian. Neither the co-occurrence of δ13C and δ238U negative excursions, nor the association of rising δ238U with extinction have been commonly reported. Here we argue that robust positive coupling of δ13C and δ238U relates to the existence of extensive intermediate reducing settings (from low-O2 suboxia to intermittent anoxia) during the late Cambrian alongside low atmospheric pO2 and a greenhouse climate. Similarly, a stepwise increase in the δ238U baseline in carbonates across the Ediacaran−Cambrian boundary is consistent with the growing importance of an intermediate reducing sink through that interval. We propose further that divergent trends in lower and upper ocean redox conditions could have driven the parallel isotope excursions. An expansion of intermediate reducing conditions, rather than persistent anoxic euxinia, is consistent with the recovery of δ13C and δ238U to higher values, as well as the presence of benthic fauna and shoreward extension of deeper-water fauna that may have had a greater tolerance against hypoxia.

A Principal Component Analysis Methodology of Oil Spill Detection and Monitoring Using Satellite Remote Sensing Sensors

Monitoring, assessing, and measuring oil spills is essential in protecting the marine environment and in efforts to clean oil spills. One of the most recent oil spills happened near Port Fourchon, Louisiana, caused by Hurricane Ida (Category 4), that had a wind speed of 240 km/h. In this regard, Earth Observation (EO) Satellite Remote Sensing (SRS) images can effectively highlight oil spills in marine areas as a “fast and no-cost” technique. However, clouds and the sea surface spectral signature complicate the interpretation of oil spill areas in the optical images. In this study, Principal Component Analysis (PCA) has been applied of Landsat-8 and Sentinel-2 SRS images to improve information from the optical sensor bands. The PCA produces an output unrelated to the main bands, making it easier to distinguish oil spills from clouds and seawater due to the spectral diversity between oil, clouds, and the seawater surface. Then, an additional step has been applied to highlight the oil spill area using PCAs with different band combinations. Furthermore, Sentinel-1 (SAR), Sentinel-2 (optical), and Landsat-8 (optical) SRS images have been analyzed with cross-sections to suppress the “look-alike” effect of marine oil spill areas. Finally, mean and high-pass filters were used for Land Surface Temperature (LST) SRS images estimated from the Landsat thermal band. The results show that the seawater value is about −17.5 db and the oil spill area shows a value between −22.5 db and −25 db; the Landsat 8 satellites thermal band 10, depicting contrast at some areas for oil spill, can be determined by the 3 × 3 and 5 × 5 Kernel High pass and the 3 × 3 Mean filter. The results demonstrate that the SRS images should be used together to improve oil spill detection studies results.

Multi-isotope fingerprints of recent environmental samples from the Baltic coast and their implications for bioarchaeological studies

Stable isotopes in coastal regions are influenced by the so-called sea spray effect which masks the actual terrestrial isotope fingerprint with a marine isotope signal. The sea spray impact on plants was investigated by analyzing different stable isotope systems (δ13Ccellulose, δ18Ocellulose, δ18Osulfate, δ34Ssulfate, δ34Stotal S, δ34Sorganic S, 87Sr/86Sr) in recent environmental samples (plants, soil, water) collected close to the Baltic Sea.All these isotopic systems are influenced by the sea spray, either by the uptake of ions (HCO3−, SO42−, Sr2+) of marine origin, thus exhibiting a marine isotopic signature, or by biochemical reactions associated with, e.g., salinity stress. A shift towards seawater values is observed for δ18Osulfate, δ34S, and 87Sr/86Sr. Cellulose becomes enriched in 13C and 18O due to sea spray, further enhanced (δ13Ccellulose) or mitigated (δ18Ocellulose) by salinity stress. The effect differs both regionally and seasonally, probably as a result of, e.g., differences in wind strength or prevailing wind direction, as well as between plants collected only few meters apart, in either the open field or at more wind-protected sites, reflecting samples more or less influenced by sea spray.The stable isotope data of recent environmental samples are compared to previously analyzed archaeological bone samples of animals from the Viking Haithabu and Early Medieval Schleswig sites located close to the Baltic Sea. Potential regions of origin can be predicted based on the magnitude of the (recent) local sea spray effect. This enables the identification of probably non-local individuals.The insights into sea spray mechanisms, biochemical reactions in plants, as well as seasonal, regional, and small-scale differences in stable isotope data will help to interpret multi-isotope fingerprints at coastal sites. Our study demonstrates the usefulness of environmental samples for bioarchaeological studies. Moreover, the detected seasonal and small-scale differences require adjusted sampling strategies for, e.g., isotopic baselines in coastal areas.

In‐Situ and Triple Oxygen Isotope Characterization of Seafloor Drilled Cherts: Marine Diagenesis and Its Bearing on Seawater Reconstructions

AbstractCherts are used to reconstruct the evolution of seawater δ18O and temperature over geological time. However, given the influence of marine diagenesis, reconstructing seawater from the isotope composition of cherts is not straightforward, resulting in ambiguity of interpretation. Here, we present a detailed isotope and petrographic investigation of deep‐sea drilled 135–40 Ma cherts with focus on the effects of marine diagenesis. We combined triple O‐isotope data with in‐situ δ′18O‐16OH/16O measurements using secondary ion mass spectrometry (SIMS). We also provide electron microprobe maps, traditional δ′18O measurements from petrographically diverse domains, and δD and H2O wt.% values. The bulk δ′18O values range between 29‰ and 38‰ in our collection, while SIMS δ′18O data reveal significant intra‐sample heterogeneities up to 6‰ related to distinct petrographic features (e.g., filled radiolarian tests) and to micrometer‐scale variations in silica forms. Further, the δ′18O—Δ′17O values of these seafloor‐drilled cherts plot near and under equilibrium curve. Both triple‐O and SIMS δ′18O results reflect diagenesis in presence of marine pore waters at temperatures higher than ambient seawater, which is especially appreciable in cherts deposited on young oceanic crust. Despite the relatively constant δ18O seawater values over last 135 Ma, the marine silica spanning between 0 and 135 Ma occupies a wide compositional space in the δ′18O—Δ′17O rather than an equilibrium curve. The δ′18O values of cherts from modern‐seafloor positively correlate with the oceanic crustal age at the time of deposition, hinting at the importance of the heat flux in the diagenetic recrystallization of marine silica.

Mollusk Response Under Ocean Acidification in Shallow Marine Settings of Sicily (Central Mediterranean)

Anthropogenic CO2 is a major driver of change in most marine ecosystems, as the consequent ocean acidification is threatening marine calcifying organisms. In this respect, long-term analyses on ocean acidification effects on marine ecosystems acclimated to high pCO2, as found around CO2 vents, are needed. Here we tackle mollusk assemblages from acidified shallow marine settings off the Aeolian archipelago (Central Mediterranean). The detected gradient manifests along a 34 m long transect (9.6 m and 11.4 m water depth), mostly in a Posidonia oceanica matte from normal (site 1) to high levels (site 3) of pCO2 (405 μatm, pH 8.1 and 715 μatm, pH 7.8; respectively). The strongest acidified condition at the vent crater (site 4, pCO2 1110 μatm, pH 7.7). At the vent site gaseous emissions are characterized by ~99% in volume of CO2 and ~0.6% of H2S. However, water dissolved H2S was below detection limit and the sulphate content along the transect does not show significant variations with respect to normal seawater values. Preliminary paleoecologic surveys on diversity structure (diversity profiles) and taphonomic degradation (NMDS, z scored % values) were conducted on mollusk remains collected along the natural pH gradient (sites 1-4). Along the P. oceanica matte (sites 1-3), overall mollusk taxon diversity (alpha and beta) decreased, mollusk in site 3 were mostly juveniles and had higher overall taphonomic damages than those retrieved at normal pH conditions. Within the vent crater only fewer and highly taphonomically altered gastropod specimens were retrieved on the pebbly seafloor, suggesting a very short residence time of shell material and rapid dissolution. Even if vents are not exact predictors of the anthropogenic-designed future of marine settings, due to their limited spatial and temporal extent, they can act as natural laboratories where to evaluate the output of ecosystem processes under rising pCO2 and the effects on the creation of the future fossil record.

Multiphase dolomitization mechanisms of the Cambrian upper Changping Formation, North China Platform, China

The Cambrian dolomite reservoirs of the North China Platform offer good exploration prospects, but their occurrence and the impacts of dolomitization on reservoir quality are not yet clearly understood. The study herein assesses outcrop samples in the Cambrian upper Changping Formation, Dingjiatan area, and highlights the important role of multiphase dolomitization in the formation of paleo-reservoirs of acceptable porosity, where oil pools and fields may be discovered. A combination of petrology, fluid inclusion microthermometry, isotopes, and trace element compositions has been used to explain multiphase dolomitization mechanisms and their impacts on dolomite reservoirs. Five types of dolomites are identified through outcrop observation, thin section identification via transmitted light, and cathodoluminescence. The following geochemical analyses reveal various dolomitization mechanisms. In the (pene) contemporaneous stage, microbial dolomite is commonly related to microbial metabolic activities with significant carbon isotopic depletion compared to the Cambrian seawater values. With the influence of microbial dolomitization, dolomicrite corresponds to the sabkha dolomitization mode in a low-salinity seawater environment and early-stage dolomitization. The structureless dolomite (ssD) in the early highstand systems tract (EHST), characterized by elevated 87Sr/88Sr ratios and low oxygen isotopic values, forms from stratum brine water in the shallow-middle burial stage rather than in the (pene) contemporaneous stage. In contrast, ssD in the late highstand systems tract (LHST) undergoes (pene) contemporaneous dolomitization at salinities between 6% and 28% before later pore water transformation, with the participation of atmospheric freshwater through faults and unconformities exhibiting the lowest inclusion temperature and salinity values. The medium to coarse crystalline dolomite (MCD) in the LHST and the saddle dolomite (SD) in the EHST with low REE values are atypical hydrothermal dolomites caused by a combined superposition of middle-deep burial hydrothermal fluids at temperatures >150°C and stratigraphic brines. The MCD is also influenced by terrigenous water characterized by relatively low Eu anomaly values. Finally, the mechanisms of porosity increase are investigated, and it is concluded that the pore increase caused by the (pene) contemporaneous reflux interaction and the later pore retention both lead to better ssD reservoirs in the LHST than in the EHST.

Phosphate aggregation, diffusion, and adsorption on kaolinite in saline solutions by molecular dynamics simulation

Large amounts of phosphates are required for the survival of cells. However, undesirable algae overgrowth requires phosphorus levels to be kept under control. For large bodies of water, cost-effective and ecosystem-friendly ways to export phosphate are needed. The use of clays appears to be the most promising method in seawater. However, for a broader application, the mechanisms of phosphate adsorption on kaolinite, the conditions for effective flocculation, and the impact of salt must first be addressed. In this study, molecular dynamics simulations are used to determine the adsorption and anchoring mechanisms of two species of phosphates that predominate at neutral pH, the dihydrogen phosphate ion H2PO4− and the hydrogen phosphate ion HPO42−, in a 1:1 ratio, on each of the three kaolinite principal planes, the basal surfaces, octahedral gibbsite (001) and tetrahedral siloxane (001¯), and the edge sites (010), in aqueous NaCl at a concentration of 0.6 M to mimic seawater. Phosphate aggregation is enhanced by Na bridges, although at very high concentrations, the number of aggregates and the size of the largest cluster decrease. Calculated diffusion coefficients for both phosphate species drop sharply in hypersaline solutions, although the decay rate is higher for the HPO42− species. Diffusion results are in close agreement with experimental data. Phosphate adsorption on kaolinite occurs in clusters. The hydrophilic surface (001) adsorbs increasing amounts of each of the phosphate species as the salt concentration increases, more HPO42− than H2PO4−. The hydrophobic (001¯) surface remains non-reactive to any species. The hydrophilic (010) edge surface increases adsorption of H2PO4− and drastically decreases that of HPO42− as salt concentration increases. Bidentate adsorption of HPO42− on the much rougher edge surface, even if saturated with adsorbed Na ions, is sterically impeded. The dominant adsorption mechanism is through cationic bridges on the gibbsite surface and at the edges. The adsorption capacity of kaolinite, including all its surfaces, increases with salt concentration, reaching its highest value in synthetic seawater. The values are of the order, although lower than the experimental ones obtained with less-accessible clays with atomic substitutions. The use of clays to control phosphate content in coastal waters is expected to contribute to public health and sustainability of marine industrial activities.