Aqueous Fluid Research Articles

Sublithospheric Diamonds: Plate Tectonics from Earth's Deepest Mantle Samples

Sublithospheric diamonds and the inclusions they may carry crystallize in the asthenosphere, transition zone, or uppermost lower mantle (from 300 to ∼800 km), and are the deepest minerals so far recognized to form by plate tectonics. These diamonds are distinctive in their deformation features, low nitrogen content, and inclusions of these major mantle minerals: majoritic garnet, clinopyroxene, ringwoodite, CaSi perovskite, ferropericlase, and bridgmanite or their retrograde equivalents. The stable isotopic compositions of elements within these diamonds (δ11B, δ13C, δ15N) and their inclusions (δ18O, δ56Fe) are typically well outside normal mantle ranges, showing that these elements were either organic (C) or modified by seawater alteration (B, O, Fe) at relatively low temperatures. Metamorphic minerals in cold slabs are effective hosts that transport C as CO3 and H as H2O, OH, or CH4 below the island arc and mantle wedge. Warming of the slab generates carbonatitic melts, supercritical aqueous fluids, or metallic liquids, forming three types of sublithospheric diamonds. Diamond crystallization occurs by movement and reduction of mobile fluids as they pass through host mantle via fractures—a process that creates chemical heterogeneity and may promote deep focus earthquakes. Geobarometry of majoritic garnet inclusions and diamond ages suggest upward transport, perhaps to the base of mantle lithosphere. From there, diamonds are carried to Earth's surface by eruptions of kimberlite magma. Mineral assemblages in sublithospheric diamonds directly trace Earth's deep volatile cycle, demonstrating how the hydrosphere of a rocky planet can connect to its solid interior. ▪Sublithospheric diamonds from the deep upper mantle, transition zone, and lower mantle host Earth's deepest obtainable mineral samples.▪Low-temperature seawater alteration of the ocean floor captures organic and inorganic carbon at the surface eventually to become some of the most precious gem diamonds.▪Subduction transports fluids in metamorphic minerals to great depth. Fluids released by slab heating migrate, react with host mantle to induce diamond crystallization, and may trigger earthquakes.▪Sublithospheric diamonds are powerful tracers of subduction—a plate tectonic process that deeply recycles part of Earth's planetary volatile budget.

Thermal stability and vapor-liquid equilibrium of aqueous solutions of choline and tetramethylammonium taurate

The thermal degradation of tetramethylammonium taurate and choline taurate and aqueous solutions of these compounds were examined. The thermal degradation products for each of the solid compounds are identified and the data show that the compounds lose less than 1 % of their mass when heating is below 85 °C for 10 h. However, it is difficult to distinguish between the degradation of the compounds and the loss of strongly retained water. The degradation products of the compounds in aqueous solution are also identified and a degradation pathway is proposed. Additionally, the vapor–liquid equilibrium of the compounds in aqueous solutions was measured and the data was fit to the non-random two-liquid (NRTL) model. The data indicate significant deviations from ideality as described by the activity coefficients of the solutions. The results provide insight into the selection of absorber stripping temperatures, the modeling of absorber columns that utilize aqueous ionic absorber fluids, and how these properties are impacted by different cations.

Strontium concentration spikes as evidence for fluid-driven carbonate dissolution during subduction

Carbonate dissolution, the process by which carbonate minerals are stoichiometrically dissolved by an aqueous fluid, likely plays an important role in liberating carbon from subducting slabs and may thus make significant contributions to global carbon fluxes. It is therefore necessary to understand the fluid infiltration and flow geometries associated with this process. Despite its widespread use as a powerful tracer of fluid-rock interaction, strontium (Sr) has yet to be widely applied to carbonate dissolution scenarios. Previous work has identified a partially altered metacarbonate layer from Syros, Greece, that has undergone significant carbonate dissolution leading to ∼90% CO2 loss (Ague and Nicolescu, 2014). A bulk-rock compositional profile along this layer has a distinctive spike-shaped Sr profile. Sr concentrations are uniform in the altered region behind the reaction front, increase to form a spike just ahead of the front, and taper off to a baseline value moving farther into the unaltered metacarbonate rock. The origin of this type of spike shape and its potential utility for better understanding carbonate dissolution processes remain unaddressed. Here, we present a numerical diffusion-reaction model which demonstrates that both carbonate dissolution and multidimensional transport of Sr, in which the primary advective flow direction is perpendicular to the propagation of the diffusion front, are required to produce this shape. This model, as well as newly acquired Sr concentration data for calcite (former aragonite) and epidote, also indicate that the infiltration of a fluid with an elevated Sr concentration is necessary. We suggest that such spike-shaped features may aid in identifying carbonate dissolution in other settings, such as vein-selvage systems in metacarbonate rocks or reaction rinds on carbonate-bearing mélange blocks.

Methane-hydrogen-rich fluid migration may trigger seismic failure in subduction zones at forearc depths

Metamorphic fluids, faults, and shear zones are carriers of carbon from the deep Earth to shallower reservoirs. Some of these fluids are reduced and transport energy sources, like H2 and light hydrocarbons. Mechanisms and pathways capable of transporting these deep energy sources towards shallower reservoirs remain unidentified. Here we present geological evidence of failure of mechanically strong rocks due to the accumulation of CH4-H2-rich fluids at deep forearc depths, which ultimately reached supralithostatic pore fluid pressure. These fluids originated from adjacent reduction of carbonates by H2-rich fluids during serpentinization at eclogite-to-blueschist-facies conditions. Thermodynamic modeling predicts that the production and accumulation of CH4-H2-rich aqueous fluids can produce fluid overpressure more easily than carbon-poor and CO2-rich aqueous fluids. This study provides evidence for the migration of deep Earth energy sources along tectonic discontinuities, and suggests causal relationships with brittle failure of hard rock types that may trigger seismic activity at forearc depths.

Origin of Zn-Pb Mineralization of the Vein Bt23C, Bytíz Deposit, Příbram Uranium and Base-Metal Ore District, Czech Republic: Constraints from Occurrence of Immiscible Aqueous–Carbonic Fluids

The mineralogical, fluid inclusion, and stable isotope (C, O) study was conducted on a Late Variscan Zn-Pb vein Bt23C, Příbram uranium and base-metal district, Bohemian Massif, Czech Republic. The vein is hosted by folded Proterozoic clastic sediments in exo-contact of a Devonian-to-Lower-Carboniferous granitic pluton. Siderite, dolomite-ankerite, calcite, quartz, baryte, galena, sphalerite, V-rich mica (roscoelite to an unnamed V-analogue of illite), and chlorite (chamosite) form the studied vein samples. The banded texture of the vein was modified by the episodic dissolution of earlier carbonates and/or sphalerite. Petrographic, microthermometric, and Raman studies of fluid inclusions proved a complicated fluid evolution, related to the activity of aqueous fluids and to an episode involving an aqueous–carbonic fluid mixture. Homogenization temperatures of aqueous inclusions decreased from ~210 to ~50 °C during the evolution of the vein, and salinity varied significantly from pure water up to 27 wt.% NaCl eq. The aqueous–carbonic fluid inclusions hosted by late quartz show highly variable phase compositions caused by the entrapment of accidental mixtures of a carbonic and an aqueous phase. Carbonic fluid is dominated by CO2 with minor CH4 and N2, and the associated aqueous solution has a medium salinity (6–14 wt.% NaCl eq.). The low calculated fluid δ18O values (−4.7 to +3.6‰ V-SMOW) suggest a predominance of surface waters during the crystallization of dolomite-ankerite and calcite, combined with a well-mixed source of carbon with δ13C values ranging between −8.2 and −10.5‰ V-PDB. The participation of three fluid endmembers is probable: (i) early high-temperature high-salinity Na>Ca-Cl fluids from an unspecified “deep” source; (ii) late low-salinity low-temperature waters, likely infiltrating from overlying Permian freshwater partly evaporated piedmont basins; (iii) late high-salinity chloridic solutions with both high and low Ca/Na ratios, which can represent externally derived marine brines, and/or local shield brines. The source of volatiles can be (i) in deep crust, (ii) from interactions of fluids with sedimentary wall rocks and/or (iii) in overlying Permian piedmont basins containing, in places, coal seams. The event dealing with heterogeneous CO2-bearing fluids yielded constraints on pressure conditions of ore formation (100–270 bar) as well as on the clarification of some additional genetic aspects of the Příbram’s ores, including the reasons for the widespread dissolution of older vein fill, the possible re-cycling of some ore-forming components, pH changes, and occasionally observed carbon isotope shift due to CO2 degassing.

Silicon ring resonator with ZIF-8/PDMS cladding for sensing dissolved CO2 gas in perfluorocarbon solutions

Precise measurement of dissolved CO2 gas concentration in perfluorocarbon (PFC) solution is essential to the implementation and understanding of extra-pulmonary gas exchange with liquid ventilation. While electrochemical and optochemical sensing methods are widely used for dissolved CO2 sensing in aqueous solution, dissolved CO2 sensing in the PFC solution remains largely unexplored. We report a refractive index-based silicon photonic sensor for monitoring dissolved CO2 gas in the PFC solution. The sensor employs a high-Q silicon ring resonator with ZIF-8 cladding for selective and sensitive detection of dissolved CO2 gas. Further, a gas-permeable PDMS coating layer is applied to the ZIF-8 cladding for enabling gas diffusion between the PFC solution and the ZIF-8. The PDMS layer does not dissolve in PFC and its hydrophobic properties help protect the ZIF-8 from potential damage caused by aqueous body fluids in the PFC solution during the liquid ventilation process. The fabricated sensor exhibits stable and repeatable responses in the PFC solution with a fine resolution of ∼0.16 CO2 vol%, good selectivity for dissolved CO2 over dissolved O2, and a fast response time of ∼1.9 min, enabling reliable monitoring of dissolved CO2 gas level changes in the PFC solution.

Reaction path model of the formation of abiotic immiscible hydrocarbon fluids in subducted carbonated serpentinites, Lanzo Massif (Western Italian Alps)

Fluids generated from subducted slabs participate in the cycling of deep carbon in the crust and upper mantle. In these fluids, aqueous carbon species vary in oxidation state between +IV and -IV depending on whether the fluids are oxidizing or reducing, respectively. Most studies of subduction-zone fluids have focused on oxidized carbon species. However, recent studies of natural samples have demonstrated the occurrence of deep, reducing fluids, generated in both subducted oceanic upper mantle and crustal rocks. CH4-H2-rich fluid inclusions in subducted carbonated serpentinites have demonstrated the existence of abiotic, immiscible, hydrocarbon fluids at upper mantle conditions. To investigate the formation of such immiscible hydrocarbon fluids during the evolution of subducted carbonated serpentinites, we used equilibrium constants from the Deep Earth Water model to carry out predictive chemical mass transfer modeling to simulate the alteration reactions. A novel feature of the models was the inclusion of an immiscible hydrocarbon fluid containing six components (CH4,f,C2H6,f,C3H8,f,isoC4H10,f,CO2,f,H2,f). This feature enabled prediction of the formation of a separate immiscible fluid in equilibrium with aqueous species and minerals.We developed a predictive reaction path model of invasive H2,f reacting with carbonated serpentinites and interstitial aqueous fluids for comparison with the natural samples from the Lanzo Massif, western Italian Alps. Over a range of temperatures and pressures, immiscible hydrocarbon fluids formed in association with altered mineral assemblages. Reaction progress caused the transformation of carbonated serpentinites and the formation of clinopyroxene, brucite, graphite, and hydrocarbon fluids, along with changes of pH, logfO2, and aqueous species. CH4,f was the most abundant hydrocarbon species in all the models. The overall results at 2.0 GPa and 400 to 450 °C were consistent with the natural samples from the Lanzo Massif. Interestingly, large amounts of H2O formed due to oxidation of H2. More hydrocarbons and H2O formed in models with lower fluid/rock mass ratios or with more reactant H2. Models at different pressure and temperature conditions showed similar results with some variation in the relative stabilities of aragonite, graphite and olivine solid solution, and associated differences in mineral sequences, hydrocarbon fluids, values of aqueous species, and the final logfO2 and pH. Our models strongly support the laboratory and field evidence that reduction of carbonated serpentinites by infiltrating H2 fluids can cause the formation of immiscible, abiotic hydrocarbon fluids in subduction zones.

Nature, source, and evolution of the ore-forming fluids in the Dunbasitao gold deposit, East Junggar, China: Constraints from geology, fluid inclusions, and C-H-O isotopes

The origin of CO2-dominated fluids in orogenic gold deposits is usually mired in controversy. The Dunbasitao gold deposit is the largest among several gold deposits along the Armantai suture zone, East Junggar, China. Orebodies are hosted in volcano-sedimentary rocks of the Lower Carboniferous Jiangbasitao Formation and porphyritic quartz diorite and are controlled by shear zones. Based on the cross-cutting relationship of veins, the hydrothermal process can be divided into the early, middle, and late stages and the gold only occurred in the middle stage. Seven types of fluid inclusions (FIs) were identified in the Dunbasitao deposit: Type-1 FIs (LH2O + LCO2 or LH2O + LCO2 + VCO2) that homogenized to H2O phase or show critical homogenization; Type-2 FIs (LH2O + LCO2 or LH2O + LCO2 + VCO2) that homogenized to CO2 phase; CO2-dominated Type-3 FIs (LCO2 or LCO2 + VCO2); Two-phase aqueous Type-4 FIs (LH2O + VH2O) that homogenized to liquid phase; Type-5 FIs are composed of three phases (LH2O + VH2O + Solid), which homogenized to liquid phase; Type-6 and Type-7 FIs refers to FIs composed of a single liquid or vapor H2O phase, respectively.Microthermometry and laser Raman spectroscopy (LRS) analyses show that the initial ore-forming fluids in the early stage were moderate-Th (326–342 °C), low salinity (2.4 to 4.7 wt% NaCl equiv), and homogenous H2O−CO2−NaCl liquid fluids, containing 13–33 mol% CO2 and a small amount of CH4, H2S, and N2. The calculated δ18OH2O (V-SMOW) values are 7.5–8.5 ‰, δ18DH2O (V-SMOW) values range from −100 to −96 ‰, and δ13Cfluid (PDB) range from −3.8 to −2.5 ‰. In the middle stage, two typical immiscible fluid inclusion assemblages (FIA.18 and FIA. 27) composed of both Type-1 and Type-2 FIs were measured. The salinity of FIA.18 is 3.3 wt% NaCl equiv. and Th is 320 °C. For FIA.27, the salinity is 2.2 wt% NaCl equiv. and Th is 298 °C. The salinities of Type-4 FIAs vary from 5.9 to 14.4 wt% NaCl equiv., significantly higher than Type-1 and Type-2 FIs (1.7 to 3.5 wt% NaCl equiv). The salinities of three isolated Type-5 FIs (halite-bearing) range from 30.3 to 32.9 wt% NaCl equiv. and Th vary from 257 to 277 °C. These facts indicate extreme unmixing between carbonic and aqueous fluids in the middle stage, which led to gold precipitation. The Type-3 FIs represent the salt-free, H2O-lost, CO2 end-member composition, whilst the Type-5 FIs and high-salinity Type-4 FIs represent the highly saline aqueous end-member composition. Late-stage fluids are initially liquid, very low-salinity (1.4 to 2.6 wt% NaCl equiv), and low-Th (176–233 °C) aqueous fluids.Two immiscible carbonic FIAs from the middle stage yield a trapping pressure (Pt) of 86.9–133.9 MPa. Considering the rapid pressure fluctuations during fluid immiscibility, using hydrostatic or lithostatic pressure alone cannot get the real mineralization depth, Therefore, we use the lithostatic pressure for the Pt maximum and hydrostatic pressure for the Pt minimum and calculated a mineralization depth of 5.3–8.9 km, which doesn't represent the change but uncertainty for depth. Combining the characteristics of ore-forming fluids with the hydrothermal alteration and mineral compositions of ores, the Dunbasitao gold deposit is determined as a mesozonal orogenic gold deposit and there is considered to be prospecting potential in the deep.

Novel Crushing Technique for Measuring δ18O and δ2H Values of Fluid Inclusions (H2O) in Quartz Mineral Veins Using Cavity Ring‐Down Spectroscopy

Fluid inclusions in mineralized fracture infillings (i.e., veins) could preserve information about subsurface fluids like temperature and salinity. The isotopic composition of water in these fluid inclusions could provide direct evidence of the provenance of these mineral‐forming fluids. So far, the isotope compositions of fluid inclusions have been mainly derived from carbonate veins and other precipitates, like speleothems. The aim of this study is to analyse the δ18O and δ2H isotopic compositions of aqueous fluid inclusions of quartz veins using a cavity ring‐down spectroscopy (CRDS) analyser in combination with a moisturized nitrogen background and mechanical crusher. For this study, we analysed δ18O and δ2H values of fluid inclusions in quartz veins from three north‐western European locations formed during the Variscan orogeny. Prior to crushing, the fluid‐rich quartz fraction was separated from the pure quartz fraction, from other mineral phases and host rock by using conventional heavy liquids and magnet separation. Raman spectrometry detected some rare occurrences of hydrocarbon, methane, and nitrogen in the fluid inclusions. The samples were sequentially crushed to elucidate the potential impact of different fluid inclusion assemblages (FIA) on the δ18O and δ2H values. The results from single and sequential mechanical crushing, together with interlaboratory comparisons, exhibit reliable and consistent isotopic patterns across locations with high precision (for δ18O: 1σ SD < 0.8‰; for δ2H: 1σ SD < 1.5‰). The obtained data occur in three different clusters for three study zones, providing evidence for the presence of meteoric‐derived fluids in the fold‐and‐thrust belts of the Variscan orogeny. These findings demonstrate that the CRDS approach can be successfully applied to quartz minerals, investigating fluid pathways within the upper crust and the formation of these secondary minerals.

Emergency treatment approaches for central retinal artery occlusion

Aims/Purpose: Central retinal artery occlusion (CRAO), which can be likened to a stroke in the eye, is considered a critical condition requiring immediate attention. The aim of this case was to assess whether anterior chamber paracentesis has a notable impact on the ultimate visual acuity in eye experiencing acute CRAO.Methods: We present the case of a 62‐year‐old man with no significant ophthalmological history, only hypertension under treatment. Presented to the emergency care within an hour after experiencing a sudden decrease in visual acuity in his left eye, whose visual prognosis improved after an urgent ocular chamber paracentesis.Results: The ophthalmological examination revealed a visual acuity of 10/10 on the right (OD) and positive light perception/10 on his left eye (OS). The intraocular pressure was normal in both eyes. Slit lamp and fundus examination showed on OS a positive reflex afferent pupillary defect and a whitish appearance of the retina, with narrowed retinal blood vessels and a cherry red spot in the macula while all was normal on OD. In this case an anterior chamber paracentesis was conducted, involving the removal of 0.3 mL of aqueous fluid from the anterior chamber using a small (30 gauge) needle. By decreasing the intraocular pressure through medical means (acetazolamide 250 mg 1cp 3 times a day for 7 days) and performing the anterior chamber paracentesis, the aim is to optimize the conditions for promoting the movement of any potential embolus away from the central retina and along the vessel. After one week, significant improvement was observed. The visual acuity in the OS was measured at 9/10, and the intraocular pressure was 10 mmHg. Ophthalmoscopic examination revealed the disappearance of the previously observed whitish retina, with a granular appearance of the macula. Despite these positive changes, impairment in the visual field has been noted and still persistent even after six months of follow‐up.Conclusions: Paracentesis, by reducing intraocular pressure, can enhance retinal arterial perfusion pressure, vasodilatation and the dislodgement of thrombi or emboli. Despite the prognosis often being poor, it is essential to take quick action and implement appropriate management strategies to prevent permanent vision loss.

Pulse power plasma stimulation: A technique for waterless fracturing, enhancing the near wellbore permeability, and increasing the EUR of unconventional reservoirs

The inherent characteristic of unconventional and ultra-low permeability reservoirs is a small drainage area that negatively affects the production rate and ultimate recovery (UR). Drilling horizontal wells, coupled with a stimulation process such as hydraulic fracturing, are applied to wells in these reservoirs to enhance well productivity. Although hydraulic fracturing has been the most famous stimulation technique in these reservoirs and has contributed to the increased US oil and gas production during the last several years, other stimulation techniques may be competitive with (or complementary to) hydraulic fracturing. This is because the main contribution to production in these reservoirs would be from complex fracture networks (often micro-cracks) combined with enhanced formation permeability rather than the classical two-wing fractures. Hence, a near-wellbore stimulation technique for improving the permeability of these reservoirs by activating the existing natural fractures and creating secondary microfractures would be highly desired. This paper investigates the pulse plasma stimulation technique to investigate such an approach of waterless stimulation/fracturing that creates multiple fractures and is also a permeability enhancement method. In this method, plasma is generated by discharging a high voltage and high current electrical energy in a very short time into two electrodes submerged in a wellbore filled with aqueous fluid. This study is divided into two sections. The first part presents experimental and numerical examples of stimulation/fracturing induced by pulse plasma in different rocks. Several parameters, including the effect of discharge with and without wire, input energy, confining stress, and rock type, on the induced fractures are studied. The second part uses the insights and results from the first part to numerically investigate pulse plasma's effects on production. Measurement of the formation permeability around the generated fractures indicated that the shock wave generated multiple fractures and increased the rock permeability by more than one or two orders of magnitude. The second part of the numerical section discusses the increased estimated rate and ultimate recovery (EUR) of horizontal wellbores due to fracturing and modified permeability resulting from pulse plasma. We present a sensitivity analysis on the magnitude and extent of the improved permeability region and its impact on EUR.

Growing diamonds in the laboratory to investigate growth, dissolution, and inclusions formation processes

Replicating lithospheric diamonds experimentally helps reveal their histories at depth, which may be complicated by successive growth and dissolution episodes. Here, we present diamond growth and dissolution experiments to constrain the conditions of diamond formation and residence in the Earth’s lithosphere before their transport to the surface. Experiments were performed on mixtures of carbonates, natural lherzolite or MORB, water, diamond seeds, and with or without graphite using multi-anvil presses over a few hours to more than a day at conditions relevant to the lithosphere (7 GPa, 1300–1670 °C). We observed growth within a volatile-rich melt resulting from the miscibility of silicate-carbonate melt and aqueous fluid via the reaction: Carbonate minerals + Silicate minerals/glasses + H2O = [volatile-rich melt] ± minerals + Cdiamond + O2. In the absence of graphite, we observed diamond dissolution within the same hydrous-carbonate–silicate-bearing melts and under similar pressure and temperature conditions used to grow diamond, indicating that diamond formation requires an oxygen sink (graphite, metallic and/or sulphide melts). In dissolution experiments, we also observed resorption features similar to those described in lithospheric monocrystalline diamonds, which we thus attribute to mantle fluids and not to kimberlite-induced resorption during magma ascent. We show that dissolution and growth may alternate in the mantle, and that protracted periods are not necessary to explain natural diamond histories. During experimental growth, inclusions were trapped in diamonds as they are in nature. We observed both syngenetic (formed during growth, representing the parental fluid) and protogenetic inclusions (here particles from the capsule), indicating that both kinds of inclusions can be trapped within a single growth event. Our experiments confirm that inclusions trapped in natural diamonds do not necessarily represent remnants of their parental fluids and are not necessarily contemporaneous: two inclusions near each other within a single monocrystalline diamond may have different histories, and inclusions must be shown to have achieved chemical and isotopic equilibrium before being considered synchronous.

Zapalenie przedniego odcinka błony naczyniowej spowodowane infekcją cytomegalowirusem u immunokompetentnych pacjentów – diagnostyka i leczenie na przykładzie przypadków klinicznych

Uveitis caused by reactivation of cytomegalovirus appears to be a rare disease that usually affects immunocompromised patients, but a recent review of the literature provides us with more and more examples of its occurrence in immunocompetent individuals as well. With the widespread use of polymerization chain reaction tests from the aqueous fluid, it has been demonstrated that cytomegalovirus may be responsible for most cases of the infectious iritis. The variable clinical course of cytomegalovirus anterior uveitis can make it difficult to provide an appropriate diagnosis. The key is to promptly initiate appropriate treatment and effectively prevent recurrence, as the reis a very high risk of complications, i.e. glaucoma or macular edema. Based on exemplary clinical cases, the different forms of inflammation, diagnosis and treatment are discussed.

The cytologic analysis of aqueous humor in eyes with uveitis

Purpose: The purpose of this study was to evaluate the cytologic analysis of aqueous humor (AH) of the eyes with Fuchs uveitis (FU) and idiopathic anterior uveitis (IAU). Methods: AH of 25 uveitic eyes (12 FU and 13 IAU) were evaluated cytologically. The samples of the anterior chamber were taken before cataract surgery. Aqueous fluid samples were evaluated by applying a Giemsa stain. Results: The 12 patients with FU and 13 patients with IAU were included in this study. In AH, the number of lymphocytes was similar in eyes with FU and IAU (the number of lymphocytes: min:1 and max:7). The acellular amorphous structures were detected in eyes with FU, and the same finding was not observed in the eyes with IAU. In addition, any pigmented cells or accumulation were not detected in any of the eyes. Conclusion: The acellular amorphous structures were the remarkable finding of this study. It has been considered that amorphous structures in the AH of the eyes with FU could be related to chronic, low-grade anterior chamber inflammation and responsible for several complications of uveitis. FU is a uveitic entity with mysterious findings that await clarifications in its etiopathogenesis.

High Performance Aqueous Fluids in Deepwater Operation

An exploration drilling in Gambia deepwater with water depth of 965m. well total depth drilled at measured depth 3,457m, the maximum inclination angle 34.6º and the horizontal section depth 1000m. The top-hole section was drilled with seawater and Guar GUM Sweep and the conductor casing set at 1053m. After the 26’’ hole was drilled with seawater and GUAR GUM sweep at TD the well was displaced to pad mud (KCl/polymer Mud) the 20’’ casing run and cemented. The intermediate and landing section was drilled with High Performance Water-based mud which was provide by one of leading servicing provider. This is where it was first deployed in Deepwater operation in West Africa (Gambia) and it shows good cutting and shale inhibitive performance, good hole cleaning, and wellbore stability, it allows the MWD tools to performed at high ROP, the rheological properties were stable with little treatment, the gives good lubrication and good cutting carrying to surface. According to Pearson, J.R.A [1], that the important rheological requirements are that they should have a low an apparent viscosity as possible, consistent with drilled cutting back to the surface during circulation.
 In deepwater operation we may encountered some extremely reactive formations that can incur lot of cost, well lost hole pack off and lost of drilling tools (BHA) which will require sidetrack. Also, with the glamour for the clean energy in the world, there are a lot of environmental restriction now and high cost of waste disposal. This high-performance Water based mud is an option to address the above concerns much attractive in drilling operation.
 In this study, the rheological preparties of the mud will be compare with Oil based mud to see the way they performed downhole. The hole cleaning ability and the number of cutting waste that will be generated which will translate to the cost of disposal.
 This result show that high performance water-based mud is more effective in term of cost, solved environmental concern and performed as oil – based mud that is wildly used in the region.

What do we know about the natural sources, transport and sinks of antimony in the environment?

Limited attention has been given to antimony present in detrital form in the different environmental compartments except for highly polluted systems related in some way to ore deposits. In highly polluted systems, the ultimate sinks of Sb may be the minerals tripuhyite (FeSbO4) or perhaps schafarzikite (FeSb2O4) but how about Sb dynamics in the much more abundant, weakly polluted or ‘non-polluted’ systems? This deficiency in our knowledge is probably related to the perception that the element is mostly present ‘dissolved’ in waters and to a focus on the role of its binding to iron oxyhydroxides in solid phases. Here we evaluate the state of our knowledge in the Sb journey from geological matrices to detrital forms in soils and waters and identify key aspects that require further investigation. In high-temperature environments, Sb demonstrated its striking incompatibility by fractionation into aqueous fluids or sulfide/metallic melts, or by uptake in a few common minerals that accept this element (e.g., rutile or pyrite). In low-temperature environments, Sb enters the structures of minerals with different formation rates and solubilities, creating a confusing impression of being mobile and immobile at the same time. The estimates of Sb concentration in the upper continental crust are scattered and the Sb-bearing mineral(s) there have not yet been identified. Given that sedimentary rocks are consistently enriched in Sb, the carriers could be the clay minerals. In surface water bodies, Sb could be carried predominantly in the particulate fraction, despite the popular belief of the opposite. An important point to consider is the transport of Sb within the suspended particulate matter, not on its surface. In soils, many studies employed sequential extractions to show that Sb accumulates in the ‘residual’ fraction, without ever asking what the nature of this fraction is. Based on these facts (i.e., knowns), we have identified the unknowns regarding detrital Sb on our planet that should preferentially be addressed by future projects if our understanding is to improve.

Complexation of Zr and Hf in fluoride-rich hydrothermal aqueous fluids and its significance for high field strength element fractionation

Zirconium and hafnium behave nearly identically in most geological processes due to their identical nominal ionic charge and similar radius. Some of the most pronounced exceptions from this rule are observed in fluoride-rich aqueous systems, suggesting that aqueous fluoride complexation may be involved in Zr/Hf fractionation. To understand the mechanisms causing this phenomenon, we investigated complexation of Zr4+ and Hf4+ in fluoride-rich (1.0 mol/kg HF) aqueous solutions at 40 MPa and 100–400 °C, using synchrotron X-ray absorption spectroscopy (X-ray absorption near edge structure and extended X-ray absorption fine structure) combined with classical and ab initio molecular dynamics simulations. The dominant experimentally observed complexes are [Zr(F,OH)4·2H2O]0 and [Hf(F,OH)4·2H2O]0, respectively. The first coordination shell comprises a distorted octahedron, with fluoride and hydroxide ligands at a similar mean radial distance (1.9–2.0 Å) from the central cation, and H2O ligands at a slightly greater distance (>2.1 Å). With increasing temperature, the H2O ligands move further out, causing first an increasing distortion of the octahedron and subsequently a partial transition to less hydrated complexes as a certain fraction of the H2O molecules move to the second shell at > 3 Å. As a consequence, the radial distance of the F- and OH– anions from the central cation, as well as the overall average radial distance of the first shell decreases due to decreased steric repulsion from the H2O ligands. Both experiments and simulations agree in that Hf forms slightly shorter bonds to its nearest neighbors than Zr. The results suggest two hypotheses for the mechanism of Zr/Hf fractionation during precipitation of minerals from fluoride-rich hydrothermal solutions: 1) The heavy twin (Hf) prefers the lower coordination (shorter bonds) and is thus less likely to enter into the higher coordination found in the solids. This mechanism would be analogous to equilibrium isotope fractionation. 2) The change of Hf into a higher coordination environment (e.g., from solution to solid) is slower because it forms stronger ligand-bonds than Zr. This would be analogous to reactive kinetic isotope fractionation. In either case mass dependent fractionation qualitatively matches the observations but mass independent effects on bond strength may also be significant. Quantitative investigations of these effects are needed and may also shed light on the currently still somewhat enigmatic fractionation behavior of Zr isotopes.

A novel polyionic liquid with lubricity and viscosity-increasing dual functionalities as the additive in aqueous lubrication system

The polyionic liquid poly-PEGMA-r-METAC (PPM) with quaternary ammonium has been synthesized and evaluated as additive in aqueous lubricating fluids. The rheological behavior of aqueous lubricating fluids with PPM has been characterized to confirm PPM’s function as a viscosity modifier. The tribological behavior of aqueous lubricating fluids with PPM has been investigated on SRV-V and MTM testing machines. It was found that PPM has excellent viscosity-increasing, lubricating, and anti-wear properties as an additive for aqueous, which can be attributed to the ability of PPM to form the protective film and boundary tribofilm generated from complex tribochemical reaction on rubbing surface. The obtained PPM with dual functions of anti-corrosion additives and viscosity index improver can play an important role in diverse lubrication regimes.

Aqueous Macrophages Contribute to Conserved CCL2 and CXCL10 Gradients in Uveitis

Uveitis is a heterogenous group of inflammatory eye disease for which current cytokine-targeted immune therapies are effective for only a subset of patients. We hypothesized that despite pathophysiologic nuances that differentiate individual disease states, all forms of eye inflammation might share common mechanisms for immune cell recruitment. Identifying these mechanisms is critical for developing novel, broadly acting therapeutic strategies. Experimental study. Biospecimens from patients with active or inactive uveitis and healthy controls. Protein concentration and single cell gene expression were assessed in aqueous fluid biopsies and plasma samples from deidentified patients with uveitis or healthy controls. The concentration of 31 inflammatory proteins was measured in all aqueous samples, as well as plasma samples from patients with active uveitis. Chemokine and cytokine ligand and receptor expression were assessed in individual cell types from aqueous biopsies obtained from patients with active uveitis. We identified 6 chemokines that were both elevated in active uveitis compared with controls and enriched in aqueous compared with plasma during active uveitis (C-C motif chemokine ligand [CCL]2, C-X-C motif chemokine ligand [CXCL]10, CXCL9, CXCL8, CCL3, and CCL14), forming potential gradients for migration of immune cells from the blood to the eye. Of these, CCL2 and CXCL10 were consistently enriched in the aqueous of all patients in our cohort, as well as in a larger cohort of patients from a previously published study. These data suggest that CCL2 and CXCL10 are key mediators in immune cell migration to the eye during uveitis. Next, single cell RNA sequencing suggested that macrophages contribute to aqueous enrichment of CCL2 and CXCL10 during human uveitis. Finally, using chemokine ligand and receptor expression mapping, we identified a broad signaling network for macrophage-derived CCL2 and CXCL10 in human uveitis. These data suggest that ocular macrophages may play a central role, via CCL2 and CXCL10 production, in recruiting inflammatory cells to the eye in patients with uveitis. Proprietary or commercial disclosure may be found in the Footnotes and Disclosures at the end of this article.

Algama Gold Ore Cluster (Aldan–Stanovoi Shield): Mineralogy, Formation Conditions, Sources of Ore Matter, and Age of Mineralization

Abstract —The paper presents results of research into the conditions of formation of ores in the poorly studied Algama ore cluster (Bodorono deposit and Dyvok ore occurrence) located at the junction of the Aldan Shield and the Stanovoi area. We have established that Bi and Se minerals (bismuthinite, lillianite, native bismuth, tellurobismuthite, tetradymite, hedleyite, pilsenite, and laitakarite) are present in the ores of the Bodorono deposit. Two successive productive stages of mineral formation have been distinguished: Au–polymetallic and Au–Bi–Te. The corresponding minerals are products of the evolution of a hydrothermal system, during which a gradual decrease in fluid temperature (from 300 to 145 °C) and salinity (from 5 to 1.9 wt.% NaCl equiv.) took place. The fineness of native gold gradually increases from early (~840‰) to late (~940‰) stages and changes in passing from simple sulfides to sulfosalts. The evolution of the ore system is accompanied by a change in the composition of the vapor phase of fluid inclusions from CH4–CO2 to CO2 with an impurity of N2 and CH4. The results of 40Ar/39Ar dating of pre-ore metasomatites point to ore-forming processes at the Bodorono deposit ca. 150 ± 1.8 Ma. Analysis of the isotopic composition of lead in galena shows the leading role of the ancient crustal source of ore matter. The calculated isotopic composition of oxygen (δ18OH2O) in ore-bearing quartz varies from 1.0 to 7.3‰, which corresponds to an aqueous fluid of a mixed source. The Dyvok ore occurrence differs from the Bodorono deposit in the mineral composition of ores and the physicochemical parameters of ore formation. Four mineral stages have been established within the ore occurrence: gold–arsenopyrite–pyrite–quartz, pyrite–chalcopyrite–sphalerite, quartz–boulangerite, and telluride. The telluride stage is represented by hessite, altaite, volynskite, merenskyite, melonite, and rucklidgeite. Gold-bearing mineralization formed from a fluid of medium salinity (0.9–9.2 wt.% NaCl equiv.) with a predominance of CO2 and an impurity of CH4 in the vapor phase at moderate temperatures (310–360 °C). The calculated values of δ34S and δ18O varied from 2.2 to 3.0‰ and from 0.6 to 12.0‰, respectively. The 40Ar/39Ar age of gold mineralization is 124.0 ± 1.5 Ma, which corresponds to the stage of tectonomagmatic activity in the Aldan Shield.