The reactive transport of Li as a monitor of weathering processes in kinetically limited weathering regimes

Analytical solutions to reactive-transport equations describing the evolution of Li concentrations and isotopic ratios are presented for one-dimensional flow paths where reaction stoichiometry is constant along the flow path. These solutions are considered appropriate for chemical weathering in rapidly eroding catchments. The solutions may be described by two dimensionless numbers; 1) a Damkӧhler number describing the product of reaction rate and fluid residence time, and 2) a net partition coefficient which describes the fraction of Li re-precipitated in secondary minerals as the product of a fluid-secondary mineral partition coefficient and the mass fraction of secondary mineral precipitates. In settings where water entering flow paths is dilute, Li concentrations will increase along the flow path until they reach a limiting value determined by the net partition coefficient. Simultaneously, 7Li/6Li isotopic ratios will increase to a limiting value of the source rock ratio minus the secondary mineral-fluid Li-isotopic fractionation factor. Waters with Li-isotopic ratios in excess of this limiting value must have evolved with a change of reaction stoichiometry and/or partition coefficient along the flow path such that at some point net removal of Li to secondary minerals exceeds that supplied by dissolution of primary minerals. The modelling shows that the multiple controls on chemical weathering rates (temperature, rainfall, erosion rate, hydrology) cannot be inferred from Li concentration and isotopic ratio data alone which only provide two independent constraints. Caution should be exercised in interpretation of oceanic Li records in terms of potential climatic variables. The model is illustrated by a set of Li concentration and isotopic ratio measurements on river waters and bed sands in the Alaknanda river basin which forms the headwaters of the Ganges. This illustrates how values of the Damkӧhler number and net partition coefficient can be used to trace weathering processes. Water samples from catchments with similar lithologies and climates scatter along contours of approximately constant net partition coefficient, reflecting similar reaction stoichiometries, but with more variable Damkӧhler numbers reflecting variations in flow path length, fluid flux and/or reaction rate. Samples from the lower, warmer and less rapidly eroding catchments have high 7Li/6Li isotopic ratios with lower Li concentrations and must reflect at least a two-stage weathering process where reaction stoichiometry and/or Li fluid-mineral partition coefficients change along the flow path so that net Li is removed in the later stages

Fluid Transport in Geological Reservoirs with Background Flow

This paper presents fundamental analysis of the injection and release of fluid into porous media or geological reservoirs saturated by a different fluid undergoing a background flow, and tests the predictions using analogue laboratory experiments. The study reveals new results important for an understanding of the transport of hazardous contaminants through aquifers and the long-term fate of carbon dioxide ( ) in geological sequestration. Using numerical and asymptotic analysis, we describe a variety of flow regimes that arise, and demonstrate an almost instantaneous control of injected fluid by the far field conditions in geological reservoirs. For a continuous input, the flow develops a horizontal interface between the injected and ambient fluids. The background flow thereby effectively caps the height of the injected fluid into a shallower region of vertical confinement. For a released parcel of fluid, gravitational spreading is found to become negligible after a short time. A dominant control of the interface by the background pressure gradient arises, and stems from the different velocities at which it drives the injected and ambient fluids individually. Similarity solutions describing these dynamics show that the parcel approaches a slender triangular profile that grows horizontally as , where is time, a rate faster than relaxation under gravity. Shock layers develop at the front or back of the parcel, depending on whether it is more or less viscous than the ambient fluid. New analytical results describing the long-term effects of residual trapping due to capillary retention are developed, which yield explicit predictions for the time and length scales on which a parcel of becomes retained. We end by applying our results to geological contexts, concluding that even slight background motion can have considerable implications for long-term transport through the subsurface

CO2 Dissolution Trapping Rates in Heterogeneous Porous Media

The rate of carbon dioxide (CO2) dissolution in saline aquifers is the least well‐constrained of the secondary trapping mechanisms enhancing the long‐term security of geological carbon storage. CO2 injected into a heterogeneous saline reservoir will preferentially travel along high permeability layers increasing the CO2‐water interfacial area which increases dissolution rates. We provide a conservative, first‐principles analysis of the quantity of CO2 dissolved and the rate at which free‐phase CO2 propagates in layered reservoirs. At early times, advection dominates the propagation of CO2. This transitions to diffusion dominated propagation as the interfacial area increases and diffusive loss slows propagation. As surrounding water‐filled layers become CO2 saturated, propagation becomes advection dominated. For reservoirs with finely bedded strata, ~10% of the injected CO2 can dissolve in a year. The maximum fraction of CO2 that dissolves is determined by the volumetric ratio of water in low permeability layers and CO2 in high permeability layers

Chemical weathering outputs from the flood plain of the Ganga

Transport of sediment across riverine flood plains contributes a significant but poorly constrained fraction of the total chemical weathering fluxes from rapidly eroding mountain belts which has impor- tant implications for chemical fluxes to the oceans and the impact of orogens on long term climate. We report water and bedload chemical analyses from the Ganges flood-plain, a major transit reservoir of sediment from the Himalayan orogen. Our data comprise six major southern tributaries to the Ganga, 31 additional analyses of major rivers from the Himalayan front in Nepal, 79 samples of the Ganga collected close to the mouth below the Farakka barrage every two weeks over three years and 67 water and 8 bedload samples from tributaries confined to the Ganga flood plain,. The flood plain tributaries are characterised by a shallow d 18 O - dD array, compared to the meteoric water line, with a low dD excess from evaporative loss from the flood plain which is mirrored in the higher dD excess of the mountain rivers in Nepal. The stable-isotope data confirms that the waters in the flood plain tributaries are domi- nantly derived from flood plain rainfall and not by redistribution of waters from the mountains. The flood plain tributaries are chemically distinct from the major Himalayan rivers. They can be divided into two groups. Tributaries from a small area around the Kosi river have 87 Sr/ 86 Sr ratios > 0.75 and molar Na/Ca ratios as high as 6. Tributaries from the rest of the flood plain have 87 Sr/ 86 Sr ratios <0.74 and most have Na/Ca ratios <1. One sample of the Gomti river and seven small adjacent tributaries have elevated Na concentrations likely caused by dissolution of Na carbonate salts. The compositions of the carbonate and silicate components of the sediments were determined from sequential leaches of floodplain bedloads and these were used to partition the dissolved cation load between silicate and car- bonate sources. The 87 Sr/ 86 Sr and Sr/Ca ratios of the carbonate inputs were derived from the ace- tic-acid leach compositions and silicate Na/Ca and 87 Sr/ 86 Sr ratios derived from silicate residues from leaching. Modelling based on the 87 Sr/ 86 Sr and Sr/Ca ratios of the carbonate inputs and 87 Sr/ 86 Sr ratios of the silicates indicates that the flood plain waters have lost up to 70% of their Ca (average ~ 50%) to precipitation of secondary calcite which is abundant as a diagenetic cement in the flood plain sedi- ments. 31% of the Sr, 8% of the Ca and 45% of the Mg are calculated to be derived from silicate miner- als. Because of significant evaporative loss of water across the flood plain, and in the absence of hy- drological data for flood plain tributaries, chemical weathering fluxes from the flood plain are best calculated by mass balance of the Na, K, Ca, Mg, Sr, SO 4 and 87 Sr/ 86 Sr compositions of the inputs, comprising the flood plain tributaries, Himalayan rivers and southern rivers, with the chemical dis- charge in the Ganga at Farakka. The calculated fluxes from the flood plain for Na, K, Ca and Mg are within error of those estimated from changes in sediment chemistry across the flood plain (Lupker et al., 2012, Geochemica Cosmochimica Acta). Flood plain weathering supplies between 33 and 48% of the major cation and Sr fluxes and 58% of the alkalinity flux carried by the Ganga at Farakka which compares with 24% supplied by Himalayan rivers and 18% by the southern tributaries

IFN-gamma is associated with risk of Schistosoma japonicum infection in China.

Before the start of the schistosomiasis transmission season, 129 villagers resident on a Schistosoma japonicum-endemic island in Poyang Lake, Jiangxi Province, 64 of whom were stool-positive for S. japonicum eggs by the Kato method and 65 negative, were treated with praziquantel. Forty-five days later the 93 subjects who presented for follow-up were all stool-negative. Blood samples were collected from all 93 individuals. S. japonicum soluble worm antigen (SWAP) and soluble egg antigen (SEA) stimulated IL-4, IL-5 and IFN-gamma production in whole-blood cultures were measured by ELISA. All the subjects were interviewed nine times during the subsequent transmission season to estimate the intensity of their contact with potentially infective snail habitats, and the subjects were all re-screened for S. japonicum by the Kato method at the end of the transmission season. Fourteen subjects were found to be infected at that time. There was some indication that the risk of infection might be associated with gender (with females being at higher risk) and with the intensity of water contact, and there was evidence that levels of SEA-induced IFN-gamma production were associated with reduced risk of infection

Immune Events Associated with High Level Protection against Schistosoma japonicum Infection in Pigs Immunized with UV-Attenuated Cercariae

BACKGROUND: The vaccination of radiation-attenuated Schistosoma japonicum cercariae can induce effective protection in artiodactyl, but the immune events related to protective immunity are not fully understood. To provide a paradigm for a human recombinant antigen vaccine, we have undertaken a vaccination and challenge experiment in pigs, which was recognized as an appropriate animal model in this type of study because of their similarity to human in immunology, and investigated the relative immune events induced by the radiation-attenuated S. japonicum cercariae. METHODS AND FINDINGS: We found that pigs immunized once with 400 µw UV-irradiated cercariae exhibited 63.84% and 71.82% reductions in worm burden and hepatic eggs respectively. Protective immunity in vaccinated pigs was associated with high level productions of IgM, total IgG, IgG1 and IgG2; IgG2 was significantly increased in the acute infection. IFN-γ levels could be elicited by immunization. At week 6 post-infection, IFN-γ, IL-4 and IL-10 levels also showed a dramatic rise synchronously in vaccinated pigs. Moreover, the granzyme b, nk-lysin, ifnγ, il4 and il10 mRNA levels in early skin-draining lymph nodes of immunized pigs were higher than those in pigs with non-irradiated cercariae infection. In addition, cytotoxicity-related genes in the mesenteric lymph nodes were significantly upregulated in vaccinated pigs in the acute infection. CONCLUSION/SIGNIFICANCE: Our results demonstrated that IFN-γ and IgG2 antibody production, as well as genes related to cytotoxicity are associated with the high level protection induced by UV-irradiated Schistosoma japonicum vaccine. These findings indicated that optimal vaccination against S. japonicum required the induction of IFN-γ, IgG2 antibody related to Th1 responses and cytotoxicity effect

Atmospheric oxygenation caused by a change in volcanic degassing pressure

International audienceThe Precambrian history of our planet is marked by two major events: a pulse of continental crust formation at the end of the Archaean eon and a weak oxygenation of the atmosphere (the Great Oxidation Event) that followed, at 2.45 billion years ago. This oxygenation has been linked to the emergence of oxygenic cyanobacteria1,2 and to changes in the compositions of volcanic gases3,4, but not to the composition of erupting lavas--geochemical constraints indicate that the oxidation state of basalts and their mantle sources has remained constant since 3.5 billion years ago5,6. Here we propose that a decrease in the average pressure of volcanic degassing changed the oxidation state of sulphur in volcanic gases, initiating themodern biogeochemical sulphur cycle and triggering atmospheric oxygenation. Using thermodynamic calculations simulating gas-melt equilibria in erupting magmas, we suggest that mostly submarine Archaean volcanoes produced gases with SO2/H2S,1 and low sulphur content. Emergence of the continents due to a global decrease in sea level and growth of the continental crust in the late Archaean then led to widespread subaerial volcanism, which in turn yielded gases much richer in sulphur and dominated bySO2. Dissolution of sulphur in sea water and the onset of sulphate reduction processes could then oxidize the atmosphere

Electron shuttle-mediated microbial Fe(III) reduction under alkaline conditions

Purpose: Extracellular Fe(III) reduction plays an important role in a variety of biogeochemical processes. Several mechanisms for microbial Fe(III) reduction in pH-neutral environments have been proposed, but pathways of microbial Fe(III) reduction within alkaline conditions have not been clearly identified. Alkaline soils are vastly distributed; thus, a better understanding of microbial Fe(III) reduction under alkaline conditions is of significance. The purpose of this study is to explore the dominant mechanism of bacterial iron reduction in alkaline environments. Materials and methods: We used antraquinone-2,6-disulfonate (AQDS) as a representative of quinone moities of humic substances and elemental sulfur and sulfate as sulfur species to investigate the potential role of humic substances and sulfur species in mediating microbial Fe(III) reduction in alkaline environments. We carried out thermodynamic calculations to predict the ability of bacteria to reduce Fe(III) (oxyhydr)oxides under alkaline conditions and the ability of AQDS and sulfur species to serve as electron acceptors for microbial anaerobic respiration in an assumed alkaline soil environments. A series of incubation experiments with two model dissimilatory metal reducing bacteria, Shewanella oneidensis MR-1 and Geobacter sulfurreducens PCA as well as mixed bacteria enriched from a soil were performed to confirm the contribution of AQDS and sulfur species to Fe(III) reduction under alkaline conditions. Results and discussion: Based on thermodynamic calculations, we predicted that, under alkaline conditions, the enzymatic reduction of Fe(III) (oxyhydr)oxides would be thermodynamically feasible but very weak. In our incubation experiments, the reduction of ferrihydrite by anaerobic cultures of Shewanella oneidensis MR-1, Geobacter sulfurreducens PCA or microbes enriched from a soil was significantly increased in the presence of S0 or AQDS. Notably, AQDS contributed more to promoting Fe(III) reduction as a soluble electron shuttle than S0 did under the alkaline conditions probably because of different mechanisms of microbial utilization of AQDS and S0. Conclusions: These results suggest that microbial reduction of Fe(III) (oxyhydr)oxides under alkaline conditions may proceed via a pathway mediated by electron shuttles such as AQDS and S0. Considering the high ability of electron shuttling and vast distribution of humic substances, we suggest that humic substance-mediated Fe(III) reduction may potentially be the dominant mechanism for Fe(III) reduction in alkaline environments

R-SNARE Homolog MoSec22 Is Required for Conidiogenesis, Cell Wall Integrity, and Pathogenesis of Magnaporthe oryzae

Soluble N-ethylmaleimide-sensitive factor attachment protein receptor (SNARE) proteins mediate intracellular vesicle fusion, which is an essential cellular process of the eukaryotic cells. To investigate the role of SNARE proteins in the rice blast fungus Magnaporthe oryzae, MoSec22, an ortholog of Saccharomyces cerevisiae SNARE protein Sec22, was identified and the MoSEC22 gene disrupted. MoSec22 restored a S. cerevisiae sec22 mutant in resistance to cell wall perturbing agents, and the ΔMosec22 mutant also exhibited defects in mycelial growth, conidial production, and infection of the host plant. Treatment with oxidative stress inducers indicated a breach in cell wall integrity, and staining and quantification assays suggested abnormal chitin deposition on the lateral walls of hyphae of the ΔMosec22 mutant. Furthermore, hypersensitivity to the oxidative stress correlates with the reduced expression of the extracellular enzymes peroxidases and laccases. Our study thus provides new evidence on the conserved function of Sec22 among fungal organisms and indicates that MoSec22 has a role in maintaining cell wall integrity affecting the growth, morphogenesis, and virulence of M. oryzae