Aqueous Fluid Research Articles

Evidence for regional fluid migration in the Eagle Ford Formation, Austin Chalk, and Buda Limestone of south-central and west Texas, USA

Calcite veins hosted by extension fractures and faults are common in the outcrop belt of the Austin Chalk – Eagle Ford – Buda stratigraphic section across south-central and west Texas, and contain aqueous and liquid hydrocarbon fluid inclusions. The hydrocarbon fluid inclusions in these thermally immature rocks indicate long-distance migration of oils from mature source rock down-dip and possibly from deeper units along faults. The widespread spatial distribution and extensive variety of oil types indicated by the fluid inclusion fluorescence suggest a protracted series of migration events – possibly from multiple source areas – rather than a single event. Oil inclusions in fault and fracture hosted calcite veins provide evidence of both strata-bound and cross-stratal oil migration along fault and fracture networks that are pervasive in the Austin Chalk, Eagle Ford, and Buda, as well as stratigraphically deeper units, in the subsurface and outcrop belt.Aqueous fluid inclusion microthermometry of the calcite veins provides evidence for significant exhumation of rocks in the Austin Chalk – Eagle Ford – Buda outcrop belt. Approximately 1.25–1.79 km of overburden was removed along the Balcones fault zone outcrop belt of south-central Texas, while in outcrop belt of the Devils River Uplift as much as 2.44–3.50 km of overburden was removed. In the productive region of the deeper basin down-dip from the outcrop belt, fluid inclusions in a deep core indicate that fluids were trapped during burial, but do not record maximum burial conditions.

Subsurface Transport of Plutonium in Organic and Aqueous Acidic Processing Wastes at the Hanford Site, USA.

Over 4 million liters of mixed acidic (∼pH 2.5), high ionic strength (∼5 M nitrate) plutonium (Pu) processing waste were released into the 216-Z-9 (Z-9) trench at the Hanford Site, USA, and trace Pu has migrated 37 m below the trench. In this study, we used flowthrough columns to investigate Pu transport in simplified processing waste through uncontaminated Hanford sediments to determine the conditions that led to Pu migration. In low pH aqueous fluids, some Pu breakthrough is observed at pH < 4, and increased Pu transport (14% total Pu breakthrough) is observed at pH < 2. However, Pu migrates in organic processing solvents through low pH sediments virtually uninhibited with approximately 94 and 86% total Pu breakthrough observed at pH 1 and pH 3, respectively. This study demonstrates that Pu migration can occur both with and without organic solvents at pH < 4, but significantly more Pu can be transported when partitioned into organic processing solvents. Our data suggest that under acidic conditions (pH < 4) in the vadose zone beneath the Z-9 trench, Pu present in organic processing solvents moved relatively unhindered and may explain the historical downward migration of Pu tens of meters below the Z-9 trench.

Natural hydrogen: sources, systems and exploration plays

Several sources of natural hydrogen are known or postulated but the process of serpentinization, the action of water on ultramafic rocks, is shown to be the most effective. Studies indicate that the rates and volumes generated by high-temperature serpentinization, (i.e. in the temperature range of 200–320°C), could feed a focused hydrogen system potentially capable of sealing and trapping gas-phase hydrogen in commercially-sized accumulations. Natural hydrogen is generated by serpentinization wherever ultramafic rocks can be penetrated by aqueous fluids. This includes diverse geotectonic settings ranging from divergent and convergent plate margins to intra-plate orogenic belts and Precambrian cratons. The ‘hydrogen system’ describes the generation, migration and sealing/trapping of hydrogen. There are two parts to the ‘generic hydrogen system’: the ‘source-generation sub-system’ requires an ultramafic protolith, usually in basement, and a supply of water penetrating basement rocks. In the ‘migration-retention sub-system’ migration, sealing and entrapment of gas-phase hydrogen behaves the same as for hydrocarbon gases. The hydrogen system by serpentinization is used to develop play models to guide exploration in the accessible and exploitable geotectonic settings of continental cratons, ophiolites and convergent margins. Thematic collection: This article is part of the Hydrogen as a future energy source collection available at: https://www.lyellcollection.org/topic/collections/hydrogen

Altered spinels act as a mirror of multi-episodic fluid metasomatism in the forearc mantle: An example from the Minhe ophiolite in Qilian Orogen, NW China

Forearc mantle peridotites commonly undergo complex melt/fluid metasomatism, which inevitably has a considerable influence on their geochemical compositions at the whole-rock scale. Serpentinites predominantly comprise the Minhe ophiolite, which is a fragment of the Proto-Tethys Ocean that outcrops in the Qilian Orogen in NW China. These serpentinites contain zoned spinels that vary compositionally from the centers to the margins, with a spinel core overgrown by ferritchromite layer and magnetite at the outermost rim. The mineral chemistry of the spinel cores (i.e., Cr#, Mg#, Cr2O3, and Al2O3) suggests that the protolith of the serpentinites was an oceanic mantle remnant in a forearc setting. Moreover, the ferritchromite exhibited increases in Fe, Mn, Sc, and Ni contents and decreases in Mg, Cr, Al, V, Zn, and Ga contents. Considering the linear correlation among elements (e.g., Co, Ni, and Zn) and the absence of mineral inclusions, the ferritchromite likely formed through ionic substitutions induced by slab fluids. The magnetite was enriched in Cr, Ni, V, Zn, Co, and Cu, but did not have a magmatic origin owing to low V concentrations. All evidence indicates that the peridotites underwent at least two episodes of fluidic metasomatism in the subduction zone. During early slab subduction, aqueous fluids released from the dehydration of the subducted slab directly serpentinized the forearc mantle peridotites, thereby altering the olivine and orthopyroxene to lizardite/chrysotile. During this process, certain mobile elements (e.g., Fe, Ni, and Mn) in the fluids and/or olivine serpentinization were incorporated into existing spinels, favoring ferritchromite growth. The second fluidic episode was dependent on prograde metamorphism at greater depths in the subduction channel, which not only produced antigorite via the recrystallization of lizardite and chrysotile, but also drove the fluids towards a more oxidizing state, thereby facilitating the growth of Cr-magnetites. Subsolidus re-equilibration controlled by fluid infiltration further promoted the inter-diffusion of elements (e.g., Cr, V, Co, Ni, Cu, and Zn) in the zoned spinels.

Numerical study of hybrid binary Al2O3-Cu-H2O nanofluid coating boundary layer flow from an exponentially stretching/shrinking perforated substrate with Cattaneo-Christov heat flux, heat source, suction and multiple slip effects

Modern coating systems are increasingly deploying nanomaterials which offer improved thermal performance. The optimization of these systems can benefit from more elegant fluid dynamic models of the coating process. Inspired by these advancements, the present investigation introduces a novel mathematical model to analyze the boundary layer transport in Al2O3-Cu-H2O hybrid binary nanofluid coating deposition on an exponentially stretching porous substrate (sheet). Lateral mass flux (suction) at the wall is also considered a heat source (generation) for hot spot manufacturing effects. To add further sophistication to the thermal conduction model, a non-Fourier approach is adopted which accurately incorporates thermal relaxation effects i.e. the Cattaneo-Christov heat flux (CCHF) model. The Tiwari-Das volume fraction nanoscale formulation is implemented for different combinations of Alumina (Al2O3) and Copper (Cu) metallic nanoparticles in an aqueous base fluid (H2O). Hydrodynamic wall and thermal slip are also included as they feature in coating processes. The fundamental equations governing mass, momentum, and energy conservation, along with the corresponding conditions at the wall (substrate) and free stream, are made dimensionless through suitable scaling similarity transformations. The resulting nonlinear coupled ordinary differential boundary value problem is subsequently addressed using the efficient MATLAB bvp4c routine. Special cases of the non-Fourier model are validated against published results, and the general model is further confirmed through validation using an Adams-Moulton 2-step predictor-corrector algorithm (AMPC). Furthermore, dual solutions of the generalized model are extracted and visualized. A comprehensive study of the effects of key thermophysical key parameters on momentum and thermal characteristics (velocity, temperature, skin friction and local Nusselt number) is conducted and solutions are visualized graphically. The computations show that higher temperatures are present with intensification in the thermal relaxation parameter (Cattaneo-Christov hyperbolic model parameter), which predicts therefore larger temperatures than the classical Parabolic heat conduction model using Fourier analysis. Effectively, thermal relaxation is responsible for finite heat wave propagation and produces more accurate estimations of heat transfer than the Fourier model. An increase in stretching parameter enhances the skin friction coefficient and elevates the local Nusselt number. As the thermal relaxation parameter increases, the temperature magnitudes corresponding to the first and second solutions are both enhanced as are thermal boundary layer thicknesses. An increase in wall suction induces an escalation in the first solution for velocity whereas it reduces the second solution velocity. Stronger wall suction suppresses temperatures. With increasing thermal slip, the boundary layer is cooled i.e. temperature plummets and thermal boundary layer thickness is decreased. Strong deceleration is induced with greater hydrodynamic (velocity) slip. Both first and second solutions for skin friction are elevated with shrinking whereas they are depressed with stretching. With greater velocity slip both the first and second solutions for skin friction are depleted with greater velocity slip for the shrinking case, whereas they are generally enhanced for the very strong stretching case. The computations offer some new insights into multi-physical thermal fluid dynamics of nanofluid-based coating systems.

Multiple sulfur isotopes evidence deep intra-slab transport of sulfate-rich fluids

Sub-arc mantle oxidation is often attributed to sulfates from seawater transported in aqueous fluids derived from slab dehydration, but sulfur speciation and origin(s) in high-pressure fluids remain weakly constrained. Here, we use the four sulfur stable isotopes (32S, 33S, 34S, 36S) to decipher processes, e.g. mixing of two end-member reservoirs and open-system reaction occurring during sulfur devolatilization, and deduce the nature and origin of sulfur species in aqueous slab-derived fluids. We analyzed high pressure metamorphic rocks from the Monviso massif Lower Shear Zone (LSZ; Western Alps), recording evidence of an interface-parallel, channelized fluid flow near peak burial metamorphic conditions (∼550 °C and 2.7 GPa). We sampled variably metasomatized Fe-Ti metagabbros, hybrid (talc) schists and serpentinites containing sulfides supposed to preserve the aqueous fluid composition, as well as other alpine metagabbro, metabasalt and serpentinites from greenschist to eclogite-facies devoid of the studied metasomatic overprint.The millimeter to centimeter-sized sulfide crystals found in abundance within LSZ lithologies are mainly pyrites containing inclusions of the peak burial mineral assemblage (e.g. garnet, omphacite, rutile) indicating their crystallization at peak conditions or during incipient exhumation. The sulfides in the non-metasomatic metagabbros and metabasalts cover a narrow range in δ’34S of 0.89 ± 0.63 ‰ and Δ’33S of 0.017 ± 0.01 (n = 6) that could be inherited from hydrothermal sulfides formed on the seafloor. In contrast, the LSZ sulfides from the Fe-Ti metagabbros, serpentinites and hybrid schists (n = 24) are enriched in 34S and 33S (bulk δ’34S from 4.91 to 21.32 ‰ and Δ’33S from 0.02 to 0.06 ‰) compared to the sulfides from the non-metasomatic rocks. Mixing between reduced sulfur species cannot explain all the data without requiring an end-member composition as high as δ34S ∼ 22 ‰ and Δ33S ∼ 0.06 ‰, i.e. values rarely recorded by sulfides in the literature. Instead, we propose that this 33S-34S-enrichment results from open-system sulfate reduction to sulfides in aqueous fluids at 550°C, with an initial δ34S ∼ 12 ± 3 ‰ and Δ33S ∼ 0.025 ± 0.010 ‰. Because this signature is different from seawater sulfate, we suggest that sulfate was produced by hydrothermal sulfide oxidation during antigorite breakdown at 650°C, in agreement with Mg, Ni and Cr enrichments in the metasomatized HP mafic lithologies. This model is consistent with relatively oxidized 34S-enriched arc lavas and can potentially explain recycled sulfur with positive δ34S signature recorded by ocean island basalts.

Decoding degassing modes of magma chamber of arc volcanoes: Insights from CO2/Cl and Cl/H2O ratios of magmatic fluids in groundwater

The H2O-CO2-Cl composition of the fluids released from the magma chambers for arc volcanoes was calculated based on the solubilities of H2O and CO2 in the silicate melt and the partition coefficient of Cl between the aqueous fluid and melt for the stages defined by a simple evolution model of the magma chamber. The degassing modes consisted of mafic bubbling (MB: first boiling) and felsic bubbling (FB: second boiling) releasing fluids as separate bubbles due to the mafic magma supply and felsic magma formation by differentiation, respectively, and felsic solidification (FS) releasing fluid due to felsic pluton formation. The variations in the CO2/Cl and Cl/H2O ratios of the fluids were examined for each degassing mode at pressures ranging from 150 to 400 MPa and were found to have very large variations at 0.00024–845 for CO2/Cl and 0.00043–0.041 for Cl/H2O. The CO2/Cl is concluded to be a good indicator of magma chamber conditions because each mode has a specific ratio distinguished from that of the other modes; i.e., CO2/Cl > 43 for MB, 0.027–23 for FB, and < 0.62 for FS.The alteration of magmatic composition of fluid during ascent was discussed considering the phase separation of fluid, CO2 bubbling in groundwater, dissolution, and deposition of minerals; furthermore, the limitation of the method when applied to natural groundwater systems were outlined. This method was tested for a natural volcanic system, the Kuju volcano in central Kyusyu, Japan, which is an active volcano complex composed of various magma types from rhyolitic to basaltic, replacing the eruption centers from west to east. Groundwater samples from springs and boreholes were collected and analyzed for chemical and isotopic compositions to determine the magmatic H2O, dissolved inorganic carbon (DIC), and Cl concentrations. The new approach to determine the magmatic CO2 concentration in groundwater using 3He concentration proposed herein cancelled the effect of carbonate deposition/dissolution, addition of DIC from organic matter, and bubbling of CO2. The estimated magmatic CO2/Cl ratios were 0.0009–14, which overlapped consistently with the modeled variation in the CO2/Cl ratio. The spatial variation of magmatic CO2/Cl in groundwater showed that higher-CO2/Cl are found near the central part of the volcanic complex which composed of felsic to mafic volcanoes, and low-CO2/Cl are only found around old felsic volcanoes. The CO2 bubbling springs were found to be associated with younger mafic volcanoes. The condition of the magma chambers, as shown by the spatial variation in CO2/Cl, were consistent with the record of the eruptive activities of the Kuju volcano. The CO2/Cl method proposed in this study using groundwater is useful for estimating magmatic conditions in chambers.

Petrogenesis of submarine volcanic arc rocks from Andaman subduction zone, Northeast Indian Ocean: Constraints from slab components and mantle wedge characteristics

The present study provides new petrological and geochemical data of the dredged rocks from submarine volcanoes along the Andaman arc and describes the petrogenetic evolution of the arc system in terms of mantle wedge characteristics, nature and quantitative input of subducted slab components, and fractionation processes of precursor magma. The studied rocks include basaltic andesite, andesite, dacite and rhyolite. These volcanic rocks exhibit LILE, LREE enrichments and HFSE depletion, corroborating their generation through subduction processes. High abundances of Th/Nd, La/Sm(N), LREE/HFSE than LILE/HFSE, LILE/LREE suggest a substantial contribution of sediments from the subducting slab over slab-dehydrated aqueous fluids to the mantle wedge. The 87Sr/86Sr-Ba/La mixing model suggests 0.6–0.8% addition of slab fluid (90:10 AOC: sediment fluid) to account for the fluid signature, whereas the 143Nd/144Nd-La/Sm(N) mixing model envisages ∼3–4% addition of sediment melt to the mantle source, reconciling the sediment signature in Andaman submarine volcanic rocks. The presence of N-MORB type mantle is attributed to the absence and/or inefficient convection of asthenospheric material from the Andaman back-arc basin to the mantle wedge. This ineffective convection can be equated with the flat subduction of the Indian Plate, caused by the convergence of the aseismic Ninety East Ridge. The non-modal batch-melting model suggests that 13–24% partial melting of the spinel lherzolite mantle beneath the Andaman submarine volcanic arc formed the parent magma. The crystallization model invokes up to 60–70% of fractionation of olivine, plagioclase, clinopyroxene, orthopyroxene, sanidine and magnetite in all the rock types with subordinate proportions of amphibole, biotite, apatite, ilmenite, and sanidine in rhyolites. The basaltic andesites, andesites and dacites do not show upper crustal input, while rhyolites indicate crustal contamination from an upper crust and/or arc crust.

Compositional evolution of slab-derived fluids during ascent: implications from trace-element partition between hydrous melts and Cl-free or Cl-rich aqueous fluids

Compositional evolution of slab-derived fluids during ascent: implications from trace-element partition between hydrous melts and Cl-free or Cl-rich aqueous fluids

Fe3O4/CoFe2O4 core-shell nanoparticles with enhanced magnetic properties for hyperthermia application

Fe3O4/CoFe2O4 core/shell nanoparticles with varying shell thickness were fabricated by seed-mediated growth via thermal decomposition method. Ligand exchange process using poly(maleic anhydride-alt-1-octadecene) (PMAO) was performed to prepare the aqueous magnetic fluids from the as-synthesised nanoparticles. X-ray diffraction (XRD), transmission electron microscopy (TEM) and Quantum Design PPMS VersaLab were utilised to characterise morphological and magnetic properties of the sample. XRD results showed that all the particles were single phase with spinel structure and the average crystallite size in the range of 11–17 nm. All particles were spherical in TEM images with similar size compared to results calculated from XRD. Magnetic measurements were performed at different temperatures (50 − 300 K) at 30 kOe. The result showed that the saturation magnetisation (M s) and coercivity (H C) were significantly increased with the formation of hard magnetic shell with varying thickness. The dynamic light scattering (DLS) analysis presented a narrow distribution and zeta potential of −16 to −35 mV, indicating a good stability of the ferrofluids. The cytotoxicity of the FOC3/PMAO ferrofluid, which has the highest SAR value of 372.02 W g−1, was tested on Hep-G2 cell line at different concentrations from 10 to 100 μg ml−1. Less than 30% of the cell was inhibited, indicating that the FOC3/PMAO particles have low toxicity at these tested concentrations. Thus, these as-synthesised core/shell nanoparticles with uniform particle size, high saturation magnetisation, good stability and five-time increased specific absorption rate (SAR) compared to the Fe3O4 core nanoparticles are very promising in hyperthermia and magnetic resonance imaging (MRI) applications.

Oxygen Isotopic Variations in the Calcium, Aluminum-rich Inclusion–forming Region Recorded by a Single Refractory Inclusion from the CO3.1 Carbonaceous Chondrite Dar al Gani 083

Calcium, aluminum-rich inclusions (CAIs) are the oldest solids dated that formed in the solar system. Most CAIs in unmetamorphosed chondritic meteorites (chondrites; petrologic type ≤3.0) have uniform solar-like 16O-rich compositions (Δ17O ∼ −24‰) and a high initial 26Al/27Al ratio [(26Al/27Al)0] of ∼(4–5) × 10−5, consistent with their origin in a gas of approximately solar composition during a brief (<0.3 Ma) epoch at the earliest stage of our solar system. The nature of O-isotope heterogeneity in CAIs (Δ17O range from ∼−24 up to ∼+5‰) from weakly metamorphosed chondrites (petrologic type >3.0) remains an open issue. This heterogeneity could have recorded fluctuations of O-isotope composition of nebular gas in the CAI-forming region and/or postcrystallization O-isotope exchange of CAI minerals with aqueous fluids on the chondrite parent asteroids. To obtain insights into possible processes resulting in this heterogeneity, we investigated the mineralogy, rare-earth element abundances, and O- and Mg-isotope compositions of a CAI from the CO3.1 chondrite Dar al Gani 083. This concentrically zoned inclusion has a Zn-hercynite core surrounded by layers of (from core to edge) grossite, spinel, melilite, and Al-diopside. The various phases have heterogeneous Δ17O (from core to edge): −2.2 ± 0.6‰, −0.9 ± 2.1‰, −13.7 ± 2.1‰, −2.6 ± 2.3‰, and −22.6 ± 2.1‰, respectively. Magnesium-isotope compositions of grossite, spinel, melilite, and Al-diopside define an undisturbed internal Al–Mg isochron with (26Al/27Al)0 of (2.60 ± 0.29) × 10−6. We conclude that the variations in Δ17O of spinel and diopside recorded fluctuations in O-isotope composition of nebular gas in the CAI-forming region prior to injection and/or homogenization of 26Al at the canonical level. The 16O depletion of grossite and melilite resulted from O-isotope exchange with asteroidal fluid, which did not disturb Al–Mg isotope systematics of the CAI primary minerals.

Electrical conductivity of antigorite–olivine aggregates under high temperature and pressure: Implications for the water content in mantle wedges

Antigorite–olivine aggregates were synthesized to serve as representative lithologies of subduction zones, which often suffered serpentinization due to the hydration of the mantle wedge. The electrical conductivities (EC) of antigorite–olivine aggregates with different antigorite proportions before and after dehydration at 2.0 GPa were measured. An increase in electrical conductivity prior to antigorite dehydration was due to Fe and Mg interdiffusion with an activation enthalpy of 130–200 kJ/mol. The electrical conductivity of the aggregates increased to 0.1 S/m due to antigorite dehydration. The electrical conductivity of 0.1 S/m derived from the laboratory experiments is consistent with geophysical observations. Combined cube model and modified Archie's law model with previous studies, the volume fractions of aqueous fluids in the mantle wedge of cold and hot subduction zones were estimated.

Metasomatism of the continental crust and its impact on surface uplift: Insights from reactive‐transport modelling

AbstractHigh‐elevation, low‐relief continental plateaus are major topographic features and profoundly influence atmospheric circulation, sediment transport and storage, and biodiversity. Although orogenic surface‐uplift mechanisms for modern continental plateaus near known plate margins like Tibet are well‐characterized, they cannot account for examples in intracontinental settings like the Colorado Plateau. In contrast to canonical plate‐tectonic uplift mechanisms, broad‐scale hydration‐induced metasomatism of the lower crust has been suggested to reduce its density and increase its buoyancy sufficiently to contribute to isostatic uplift. However, the relationships between key petrophysical properties in these environments are not fully quantified, which limits application of this model. Here, we develop a series of petrological models that describe the petrological and topographic effects of fluid–rock interaction in non‐deforming continental crust of varying composition. We apply an open‐system petrological modelling framework that utilizes reactive‐transport calculations to determine the spatial and temporal scales over which mineralogic transformations take place compared with the magnitude of infiltration of aqueous fluids derived from devolatilization of subducting oceanic lithosphere. The buoyancy effect of hydration‐induced de‐densification is most significant for metabasic lower crust, intermediate for metapelitic crust, and minimal for granodioritic crust. We apply these results to a case study of the ~2 km‐high Colorado Plateau and demonstrate that under ideal conditions, hydration of its lower–middle crust by infiltrating aqueous fluids released by the Farallon slab during Cenozoic low‐angle subduction could have uplifted the plateau surface by a maximum of ~1 km over 16 Myr. However, realistically, although hydration likely has a measurable effect on surface tectonics, the uplift of orogenic plateaus is likely dominantly controlled by other factors, such as lithospheric delamination.

Construction and validation of a neovascular glaucoma nomogram in patients with diabetic retinopathy after pars plana vitrectomy

BACKGROUND Neovascular glaucoma (NVG) is likely to occur after pars plana vitrectomy (PPV) for diabetic retinopathy (DR) in some patients, thus reducing the expected benefit. Understanding the risk factors for NVG occurrence and building effective risk prediction models are currently required for clinical research. AIM To develop a visual risk profile model to explore factors influencing DR after surgery. METHODS We retrospectively selected 151 patients with DR undergoing PPV. The patients were divided into the NVG (NVG occurrence) and No-NVG (No NVG occurrence) groups according to the occurrence of NVG within 6 months after surgery. Independent risk factors for postoperative NVG were screened by logistic regression. A nomogram prediction model was established using R software, and the model’s prediction accuracy was verified internally and externally, involving the receiver operator characteristic curve and correction curve. RESULTS After importing the data into a logistic regression model, we concluded that a posterior capsular defect, preoperative vascular endothelial growth factor ≥ 302.90 pg/mL, glycosylated hemoglobin ≥ 9.05%, aqueous fluid interleukin 6 (IL-6) ≥ 53.27 pg/mL, and aqueous fluid IL-10 ≥ 9.11 pg/mL were independent risk factors for postoperative NVG in patients with DR (P &lt; 0.05). A nomogram model was established based on the aforementioned independent risk factors, and a computer simulation repeated sampling method was used to internally and externally verify the nomogram model. The area under the curve (AUC), sensitivity, and specificity of the model were 0.962 [95% confidence interval (95%CI): 0.932-0.991], 91.5%, and 82.3%, respectively. The AUC, sensitivity, and specificity of the external validation were 0.878 (95%CI: 0.746-0.982), 66.7%, and 95.7%, respectively. CONCLUSION A nomogram constructed based on the risk factors for postoperative NVG in patients with DR has a high prediction accuracy. This study can help formulate relevant preventive and treatment measures.

In-situ forming PLGA implants: Towards less toxic solvents

In-situ forming poly(lactic-co-glycolic acid) (PLGA) implants offer a great potential for controlled drug delivery for a variety of applications, e.g. periodontitis treatment. The polymer is dissolved in a water-miscible solvent. The drug is dissolved or dispersed in this solution. Upon contact with aqueous body fluids, the solvent diffuses into the surrounding tissue and water penetrates into the formulation. Consequently, PLGA precipitates, trapping the drug. Often, N-methyl-2-pyrrolidine (NMP) is used as a water-miscible solvent. However, parenteral administration of NMP raises toxicity concerns. The aim of this study was to identify less toxic alternative solvent systems for in-situ forming PLGA implants. Various blends of polyethylene glycol 400 (PEG 400), triethyl citrate (TEC) and ethanol were used to prepare liquid formulations containing PLGA, ibuprofen (as an anti-inflammatory drug) and/or chlorhexidine dihydrochloride (as an antiseptic agent). Implant formation and drug release kinetics were monitored upon exposure to phosphate buffer pH 6.8 at 37 °C. Furthermore, the syringeability of the liquids, antimicrobial activity of the implants, and dynamic changes in the latter’s wet mass and pH of the release medium were studied. Importantly, 85:10:5 and 60:30:10 PEG 400:TEC:ethanol blends provided good syringeability and allowed for rapid implant formation. The latter controlled ibuprofen and chlorhexidine release over several weeks and assured efficient antimicrobial activity. Interestingly, fundamental differences were observed concerning the underlying release mechanisms of the two drugs: Ibuprofen was dissolved in the solvent mixtures and partially leached out together with the solvents during implant formation, resulting in relatively pronounced burst effects. In contrast, chlorhexidine dihydrochloride was dispersed in the liquids in the form of tiny particles, which were effectively trapped by precipitating PLGA during implant formation, leading to initial lag-phases for drug release.

Colon Drug Delivery Systems Based on Swellable and Microbially Degradable High-Methoxyl Pectin: Coating Process and In Vitro Performance.

Oral colon delivery systems based on a dual targeting strategy, harnessing time- and microbiota-dependent release mechanisms, were designed in the form of a drug-containing core, a swellable/biodegradable polysaccharide inner layer and a gastroresistant outer film. High-methoxyl pectin was employed as the functional coating polymer and was applied by spray-coating or powder-layering. Stratification of pectin powder required the use of low-viscosity hydroxypropyl methylcellulose in water solution as the binder. These coatings exhibited rough surfaces and higher thicknesses than the spray-coated ones. Using a finer powder fraction improved the process outcome, coating quality and inherent barrier properties in aqueous fluids. Pulsatile release profiles and reproducible lag phases of the pursued duration were obtained from systems manufactured by both techniques. This performance was confirmed by double-coated systems, provided with a Kollicoat® MAE outer film that yielded resistance in the acidic stage of the test. Moreover, HM pectin-based coatings manufactured by powder-layering, tested in the presence of bacteria from a Crohn's disease patient, showed earlier release, supporting the role of microbial degradation as a triggering mechanism at the target site. The overall results highlighted viable coating options and in vitro release characteristics, sparking new interest in naturally occurring pectin as a coating agent for oral colon delivery.

Disequilibrium oxygen isotope distribution among aqueously altered minerals in Ryugu asteroid returned samples

AbstractOxygen 3‐isotope ratios of magnetite and carbonates in aqueously altered carbonaceous chondrites provide important clues to understanding the evolution of the fluid in the asteroidal parent bodies. We conducted oxygen 3‐isotope analyses of magnetite, dolomite, and breunnerite in two sections of asteroid Ryugu returned samples, A0058 and C0002, using a secondary ion mass spectrometer (SIMS). Magnetite was analyzed by using a lower primary ion energy that reduced instrumental biases due to the crystal orientation effect. We found two groups of magnetite data identified from the SIMS pit morphologies: (1) higher δ18O (from 3‰ to 7‰) and ∆17O (~2‰) with porous SIMS pits mostly from spherulitic magnetite, and (2) lower δ18O (~ −3‰) and variable ∆17O (0‰–2‰) mostly from euhedral magnetite. Dolomite and breunnerite analyses were conducted using multi‐collection Faraday cup detectors with precisions ≤0.3‰. The instrumental bias correction was applied based on carbonate compositions in two ways, using Fe and (Fe + Mn) contents, respectively, because Ryugu dolomite contains higher amounts of Mn than the terrestrial standard. Results of dolomite and breunnerite analyses show a narrow range of ∆17O; 0.0‰–0.3‰ for dolomite in A0058 and 0.2‰–0.8‰ for dolomite and breunnerite in C0002. The majority of breunnerite, including large ≥100 μm grains, show systematically lower δ18O (~21‰) than dolomite (25‰–30‰ and 23‰–27‰ depending on the instrumental bias corrections). The equilibrium temperatures between magnetite and dolomite from the coarse‐grained lithology in A0058 are calculated to be 51 ± 11°C and 78 ± 14°C, depending on the instrumental bias correction scheme for dolomite; a reliable temperature estimate would require a Mn‐bearing dolomite standard to evaluate the instrumental bias corrections, which is not currently available. These results indicate that the oxygen isotope ratios of aqueous fluids in the Ryugu parent asteroid were isotopically heterogeneous, either spatially, or temporary. Initial water ice accreted to the Ryugu parent body might have ∆17O &gt; 2‰ that was melted and interacted with anhydrous solids with the initial ∆17O &lt; 0‰. In the early stage of aqueous alteration, spherulitic magnetite and calcite formed from aqueous fluid with ∆17O ~ 2‰ that was produced by isotope exchange between water (∆17O &gt; 2‰) and anhydrous solids (∆17O &lt; 0‰). Dolomite and breunnerite, along with some magnetite, formed at the later stage of aqueous alteration under higher water‐to‐rock ratios where the oxygen isotope ratios were nearly at equilibrium between fluid and solid phases. Including literature data, δ18O of carbonates decreased in the order calcite, dolomite, and breunnerite, suggesting that the temperature of alteration might have increased with the degree of aqueous alteration.

Role of polymerase chain reaction from aqueous humor in a suspected case of ocular toxocariasis – A report of a case

An 8-year-old girl presented with unilateral panuveitis with a retinochoroidal lesion superior to disc with overlying vitritis. Laboratory workup was done, and a clinical diagnosis of toxoplasma retinochoroiditis was considered. Based on this initial diagnosis of toxoplasma retinochoroiditis empirically the patient was started on tablet clindamycin along with sulfamethoxazole and trimethoprim and oral steroids. On subsequent follow up, patient developed worsening of lesion. Intraocular fluid was collected from anterior chamber and sample revealed a positive polymerase chain reaction for toxocara canis. The diagnosis of ocular toxocariasis was made. This case highlights the use of aqueous fluid from polymerase chain reaction (PCR) to diagnose ocular toxocariasis.

Deterioration Mechanism and Status Prediction of Hydrocarbon Lubricants under High Temperatures and Humid Environments

In practical engineering applications, high temperatures and water ingress seriously affect the service life of hydrocarbon lubricants. In this study, the deterioration process of hydrocarbon lubricants under high temperatures and humid environments was investigated, and a new health state prediction model was proposed. Simulation of hydrocarbon lubricant Polyalpha−olefin (PAO) molecules used the ReaxFF force field to analyse the high temperature thermal oxidation process of lubricants. The rheological properties of oil−water emulsions were determined by observing the morphology of oil−water two−phase mixtures with different water contents. A multiparameter fusion viscosity prediction model was proposed using a linear model of the viscosity of aqueous fluids, as affected by temperature and water content, and was fitted with the Andrade viscosity−temperature equation to predict lubricant viscosity changes under multiple parameters. Online validation tests were carried out on a compound planetary transmission system, and the surface topographical parameters of the transmission components were further discussed. Experimental results show that the linear correlation with the improved lubricant viscosity prediction model is 0.966, and the surface wear of transmission components is consistent with the trend of lubricant quality change. These findings provide a fundamental basis for the assessment of lubricant service life in high temperatures and humid environments.

Indium partitioning between silicate melts and magmatic fluids: implications for indium ore genesis and the tracing of magma degassing

Most of the global indium resources are from deposits associated with felsic rocks. Considering that the indium concentration in the average upper crust is extremely low, magmatic-hydrothermal processes play a critical role in the enrichment and mineralization of indium. However, the extraction efficiency of indium by magmatic fluids remains unclear. We performed experiments at 800 °C, 150 MPa and oxygen fugacity of Ni-NiO buffer to determine the partition coefficient of indium between aqueous fluids and granitic melts (DInf/m). To counteract the rapid loss of indium into the noble metal container wall, the DInf/m were obtained by the method of local equilibrium between microscopic-sized fluid bubbles and surrounding silicate melt. The results show that indium has the highest fluid-melt partition coefficients of all metals investigated so far. At a constant aluminum saturation index (ASI = 1.07–1.12), DInf/m correlates linearly with the total Cl concentration in the coexisting fluid (mCltotal), increasing from 61 ± 11 (1σ) at mCltotal = 1.0 mol/kg H2O to 895 ± 105 (1σ) at mCltotal = 16 mol/kg H2O. When the HCl concentration in the solution increases from 0.13 to 0.49 mol/kg H2O at a fixed mCltotal = 2 mol/kg H2O, DInf/m increases parabolically from 129 ± 21 to 320 ± 24. The observed partitioning data suggest that indium was dominantly present as In(OH)2Cl in the low-HCl and In(OH)Cl2 in high-HCl aqueous fluid at the experimental conditions. Numerical modeling indicates that the extraction efficiency of indium from S-type felsic magmas is very high (>85 %) and magmatic fluids may be the major source of indium for most indium deposits. Due to the high DInf/m values, fluid saturation and exsolution result in a sharp drop of indium concentration in both the residual melt and crystallized minerals, which makes the indium concentration in whole rock and minerals an indicator of fluid exsolution.