Ivan R. Kennedy, John Runcie, Angus N. Crossan
et al.
Why do atmospheric carbon dioxide levels rise and fall seasonally measured on Mauna Loa? This study explores the thermal acid-calcification (TAC) hypothesis, suggesting that seasonal temperature shifts in surface seawater trigger acid pH-driven CO2 emissions caused by calcification. Using oceanographic data, we modeled how temperature affects dissolved inorganic carbon including CO2, bicarbonate, and carbonate. Our findings reveal that warming waters absorb atmospheric CO2 by promoting calcium carbonate formation, acidifying seawater and boosting CO2 release to the atmosphere in late autumn and winter, when atmospheric CO2 becomes highest. The model predicts a net annual CO2 rise of 2 ppmv, driven by calcification rather than land-based processes. Seasonal pH swings of 0.04 units corroborate this mechanism. The TAC hypothesis indicates that continued ocean warming, not just fossil fuels, contribute to rising CO2 levels, calling for deeper investigation into marine carbon dynamics.
Ifeoluwa Oluwatosin Kunle-John, Segun P. Michaels, Edith N. Okay
Eleyele Lake has enormous economic importance as it is completely surrounded by various communities which discharge their domestic waste directly into the lake. This alters the physical, chemical and biological characteristics of the lake. It is essential to assess the water for its various usage. Twelve (12) samples were collected from various locations of the lake and analysed. Some physical parameters (electrical conductivity, Total Dissolved Solids, Ph and temperature were determined in-situ. The rest of the sample was taken to the laboratory for various chemical analysis and the results were compared to the WHO standards. The chemical extent of the contamination was determined by the contamination factor, degree of contamination and Geo-Accumulation Index. The physical parameters show that the TDS has an average of 122.2ppm and EC was uniform throughout the various points of reading suggesting that the lake is fresh water. The pH averaged at 72, temperature at 27.2 degrees. The selected trace element falls within the WHO acceptable limits. Their contamination indices showed that Ba, Co, Cs, Cu, Mo, Rb, Sr and Zn are generally less than one depicting their geogenic origin. The high degree of contamination is influenced by high levels of Al and Fe due to human activities and industrial waste disposal and can lead to anemia, osteomalacia (brittle or soft bones), cardiac arrest, stomach problems, nausea, and hemochromatosis. Thus, Eleyele lake is not advisable for consumption.
With the advancement of crewed deep-space missions, Bioregenerative Life Support Systems (BLSS) for lunar bases face stresses from lunar environmental factors. While microgravity and radiation are well-studied, the low-magnetic field's effects remain unclear. Earthworms ("soil scavengers") improve lunar soil simulant and degrade plant waste, as shown in our prior studies. We tested earthworms in lunar soil simulant mixed with organic waste (from "Lunar Palace 365" experiment) under three magnetic conditions: lunar-low, Earth, and high. Stronger fields increased earthworm oxidative stress (MDA) and impaired neurotransmitters. Weaker fields enhanced substrate cultivability: neutralized pH, increased nutrients, humus, and wheat seedling rate. Microbial analyses showed: (1) Higher fungal Shannon index under high fields indicated impaired digestion; (2) More positive correlations in gut networks suggested slower microbial cooperation (e.g., lignocellulose degradation); (3) Reduced Network Size, Path Length and Modularity confirmed disrupted interactions. This disproves lunar low-magnetic stress on earthworm-soil-waste systems, aiding deep-space BLSS research.
Convective mixing in porous media is crucial in both geophysical and industrial fields, spanning applications ranging from carbon dioxide sequestration to contaminant transport in groundwater. Key processes are affected by convective heat transport or diffusion of chemical species in porous formations. Intense convection flow and mixing create complex, dynamic patterns that are difficult to predict and measure. The present work focuses on the use of topological data analysis, in particular, the measures emerging from the growing field of persistent homology (PH), to quantify these patterns. These measures are objective and quantify structures across all temperature or concentration values simultaneously. These techniques, when applied to classical porous media setups, such as one-sided and Rayleigh-Bénard flow configurations, provide new insights into the system's structure, flow patterns, and macroscopic mixing properties. Using large datasets we make publicly available, comprising original simulations as well as those presented in previous works, we correlate the behaviour of the heat transport rate (quantified by the Nusselt number) with the evolution of the flow structures (quantified by the PH measures). Finally, we provide a detailed analysis of the flow evolution over a wide range of governing parameters, namely the Rayleigh-Darcy number and the domain size.
This chapter reviews proposed exoplanet biosignatures, including their biological origins, observable features, atmospheric sinks, and potentially confounding abiotic sources. Emphasis is placed on material published since past comprehensive reviews while providing a foundational understanding of each named biosignature. Topics include possible gaseous biosignatures (e.g., O$_2$, O$_3$, CH$_4$, N$_2$O, DMS, CH$_3$Cl, C$_5$H$_8$, NH$_3$, PH$_3$), surface biosignatures (e.g., vegetation red edge, other pigment features, polarization signatures), and temporal biosignatures (e.g., atmospheric seasonality). Potential frameworks for assessing remote biosignatures are described. Text and table summaries provide references to relevant original research articles.
One way in which we can attempt to relate chemical pathways to geochemical environments is by studying the kinetics of a given sequence of reactions and identifying the conditions under which this chemistry is the most productive. Many prebiotic reactions rely on a source of fixed carbon, therefore chemical pathways that suggest prebiotically plausible ways of fixing carbon are of significant interest. One such pathway is the carboxysulfitic reaction network which uses solvated electrons, produced as a result of electron photodetachment from sulfite, to reduce carbon. In this work we explore carboxysulfitic chemistry at three different pH values: 6, 9, and 12. We utilise a new light source, that matches the broadband spectral shape of the young Sun, to irradiate a mixture of bicarbonate and sulfite. We determine the rate equation for the production of formate from these compounds and find the order to be 0.71 $\pm$ 0.12 with respect to bicarbonate and -0.60 $\pm$ 0.10 with respect to sulfite. Following this, we determine rate constants for the production of formate considering two different mechanisms. We find this chemistry to be feasible at all three of the pH values tested, with the magnitude of the rate constants being highly dependent on the assumed mechanism. We suggest that these results may have implications for Mars Sample Return owing to Jezero Crater having had lakes similar to those in which we propose carboxysulfitic chemistry to have been the most productive. Due to Mars' relatively unaltered surface, we propose that Mars Sample Return missions could look for preserved tracers of this chemistry, shedding light on Mars' past conditions and its potential for having hosted life.
Maximilian Weingart, Siyu Chen, Clara Donat
et al.
Alkaline vents (AV) are hypothesized to have been a setting for the emergence of life, by creating strong gradients across inorganic membranes within chimney structures. In the past, 3-dimensional chimney structures were formed under laboratory conditions, however, no in situ visualisation or testing of the gradients was possible. We develop a quasi-2-dimensional microfluidic model of alkaline vents that allows spatio-temporal visualisation of mineral precipitation in low volume experiments. Upon injection of an alkaline fluid into an acidic, iron-rich solution, we observe a diverse set of precipitation morphologies, mainly controlled by flow-rate and ion-concentration. Using microscope imaging and pH dependent dyes, we show that finger-like precipitates can facilitate formation and maintenance of microscale pH gradients and accumulation of dispersed particles in confined geometries. Our findings establish a model to investigate the potential of gradients across a semi-permeable boundary for early compartmentalisation, accumulation and chemical reactions at the origins of life.
Ogochukwu Ozotta, Mohammad Reza Saberi, Oladoyin Kolawole
et al.
Abstract Unconventional geo-resources are critical due to their important contributions to energy production. In this energy transition and sustainability era, there is an increased focus on CO2-enhanced oil recovery (CO2-EOR) and geological CO2 storage (GCS) in unconventional hydrocarbon reservoirs, and the extraction of hot fluid for energy through enhanced geothermal systems. However, these energy solutions can only be achieved through efficient stimulation to develop a complex fracture network and pore structure in the host rocks to extract heat and hydrocarbon, or for CO2 storage. Using Bakken formation well data and rock physics models, this study aimed to identify the post-depositional effect of pore structure on seismic velocity, elastic moduli, and formation fluid; and further predict the best lithofacies interval for well landing, and the implications for fluid (gas, oil, and water) recovery in naturally- and often systematically-fractured geosystems. The KT and DEM models' predictions show distinct formation intervals exhibiting needle-like pores and having higher seismic velocities (Vp and Vs) and elastic moduli (K and µ), relative to other formation intervals that exhibit moldic pores. At the same fluid concentration, the needle-like pores (small aspect ratios) have a higher impact on elastic moduli, Vp, and Vs than on the moldic spherical pores with all other parameters held constant. Vp is affected more than Vs by the properties of the saturating fluid (gas, oil, or water) with Vp being greater in Bakken formation when it is water-saturated than when it is gas-saturated. Vs exhibit the reverse behavior, with Vs greater in the gas-saturated case than in the water-saturated case. Further, analyses suggest that the middle Bakken formation will have a higher susceptibility to fracturing and faulting, and hence will achieve greater fluid (oil and water) recovery. Our findings in this study provide insights that are relevant for fluid production and geo-storage in unconventional reservoirs. Article highlights Integrated well log data and rock physics models. Investigated the effect of changes in pore structure on elastic properties and fluid flow in shale. Increase in porosity causes a reduction in elastic moduli and seismic velocities. Vp is more affected by pore geometry than Vs depending on density and properties of saturating fluid. Lithofacies with needle−like pores are more susceptible to fracturing than lithofacies with intragranular pores.
AbstractAn important question arises in relation to a rock-mass that is disrupted by an array of fractures, namely: how to quantify the evolving spatial arrangement of fracture apertures that are a major factor in bulk fluid flow processes. The approach herein employs a discrete micro-physics model of the rock texture, enabling the formulation of analytical expressions that explicitly define the fluids//geomechanics interactions that occur at the micro-scale. The resulting macro-scale responses of the model define the stress, bulk strain, and pressure states that characterise the porous rock. Via extending the discrete model by introducing a planar discontinuity, the fracture-normal bulk strain determines the status of the fracture aperture, as a consequence of the movement of the rock//fracture interface. The micro-physics model shows that a closed fracture cannot change to an open fracture by pressure changes alone; instead, bulk strain must elongate the porous rock in a direction normal to the fracture. Once opened, fracture apertures respond to changes in fluid pressure. A realistic context, within which the required bulk strain occurs, is the discontinuum geomechanics of fractured rock-mass systems, for which previous simulations exhibit a range of emergent local states that relate to the conditions, identified via the micro-physics, as being the essential controls on aperture evolution.Article highlightsDiscrete rock-texture model underpins micro-physics expressions that lead to macro-scale material response of matrix//fractureClosed fracture cannot open without local elongation normal to fracture; high pressure alone does not open fractureOpen fracture changes aperture with changing pressure
AbstractThere have been significant efforts to transform traditional farming into organic farming practices. It is believed that this transformation would guarantee the long term production while it also maintains the environment. Studying the differences between these two practices in the form of maps can be useful for understanding spatially how effective the transformation has been achieved. This is because soil varies in space. The main aim of this research is to study the spatial variability of Total Nitrogen, pH and Organic Carbon in the soil. Methods used in this study consists of : (a) data capture; (b) data input in GIS; (c) processing data using Kriging: (d) analysis and presentation of results. The results showed that : (a)Soil organic content in the study area was generally low suggesting the future warning; (b) Using pH, Organic Carbon and Total N as indicators of assessing the differences between organic and inorganic practices, indicating that there has not been significant different between these practices; (c)The analysis of spatial variability using Kriging in GIS environment could uncover the spatial variability and suggested the way of managing the study area. Keywords: organic farming, inorganic farming, spatial variability, soil properties
The chemistry of carbon in aqueous fluids at extreme pressure and temperature conditions is of great importance to Earth's deep carbon cycle, which substantially affects the carbon budget at Earth's surface and global climate change. At ambient conditions, the concentration of carbonic acid in water is negligible, so aqueous carbonic acid was simply ignored in previous geochemical models. However, by applying extensive ab initio molecular dynamics simulations at pressure and temperature conditions similar to those in Earth's upper mantle, we found that carbonic acid can be the most abundant carbon species in aqueous CO$_2$ solutions at ~10 GPa and 1000 K. The mole percent of carbonic acid in total dissolved carbon species increases with increasing pressure along an isotherm, while its mole percent decreases with increasing temperature along an isobar. In CO$_2$-rich solutions, we found significant proton transfer between carbonic acid molecules and bicarbonate ions, which may enhance the conductivity of the solutions. The effects of pH buffering by carbonic acid may play an important role in water-rock interactions in Earth's interior. Our findings suggest that carbonic acid is an important carbon carrier in the deep carbon cycle.
Amanda Ramcharan, Tomislav Hengl, Travis Nauman
et al.
With growing concern for the depletion of soil resources, conventional soil data must be updated to support spatially explicit human-landscape models. Three US soil point datasetswere combined with a stack of over 200 environmental datasets to generate complete coverage gridded predictions at 100 m spatial resolution of soil properties (percent organic C, total N, bulk density, pH, and percent sand and clay) and US soil taxonomic classes (291 great groups and 78 modified particle size classes) for the conterminous US. Models were built using parallelized random forest and gradient boosting algorithms. Soil property predictions were generated at seven standard soil depths (0, 5, 15, 30, 60, 100 and 200 cm). Prediction probability maps for US soil taxonomic classifications were also generated. Model validation results indicate an out-of-bag classification accuracy of 60 percent for great groups, and 66 percent for modified particle size classes; for soil properties cross-validated R-square ranged from 62 percent for total N to 87 percent for pH. Nine independent validation datasets were used to assess prediction accuracies for soil class models and results ranged between 24-58 percent and 24-93 percent for great group and modified particle size class prediction accuracies, respectively. The hybrid "SoilGrids+" modeling system that incorporates remote sensing data, local predictions of soil properties, conventional soil polygon maps, and machine learning opens the possibility for updating conventional soil survey data with machine learning technology to make soil information easier to integrate with spatially explicit models, compared to multi-component map units.
The quantification of surface area between mineral and reactive fluid is essential in environmental applications of reactive transport modelling. This quantity evolves with microstructures and is difficult to predict because the mechanisms for the generation and destruction of reactive surface remain elusive. The challenge of accounting for the inherent heterogeneities of natural porous media in numerical simulation further complicates the problem. Here we first show a direct observation of reactive surface generation in chalk under circumneutral to alkaline pH using in situ X-ray microtomography. The momentary increase of reactive surface area cannot be explained by a change in fluid accessibility or by surface roughening stemming from mineralogical heterogeneity. We then combine greyscale nanotomography data with numerical simulations to show that similar temporal behaviour can be observed over a wide range of pH as porous media dissolve in imposed flow field. We attribute the observation to the coupling between fluid flow and mineral dissolution and argue that the extent of surface generation is strongly correlated with the advective penetration depth of reactants. To conclude, we demonstrate the applicability of using a macroscopic Damköhler number as an indicator for the phenomenon and discuss its environmental significance beyond geologic carbon storage.
Dasapta Erwin Irawan, Deny Juanda Puradimaja, Defitri Yeni
et al.
The decreasing of groundwater quality has been the major issue in Tangerang area. One of the key process is the interaction between groundwater and Cisadane river water, which flows over volcanic deposits of Bojongmanik Fm, Genteng Fm, Tuf Banten, and Alluvial Fan. The objective of this study is to unravel such interactions based on the potentiometric mapping in the riverbank. We had 60 stop sites along the riverbank for groundwater and river water level observations, and chemical measurements (TDS, EC, temp, and pH). Three river water gauge were also analyzed to see the fluctuations. We identified three types of hydrodynamic relationships with fairly low flow gradients: effluent flow at Segmen I (Kranggan - Batuceper) with 0.2-0.25 gradient, perched flow at Segmen II (Batuceper-Kalibaru) with gradient 0.2-0.25, and influent flow at Segmen III (Kalibaru-Tanjungburung) with gradient 0.15-0.20. Such low flow gradient is controlled by the moderate to low morphological slope in the area. The gaining and losing stream model were also supported by the river water fluctuation data. TDS and EC readings increased more than 40$\%$ from upstream to downstream. At some points the both measurements were two times higher than the permissible limits, along with the drops of pH values at those areas. This study shows the very close interaction between Cisadane river water and groundwater in the riverbank. Therefore the authorities need to be managed the areas with a very strict regulations related to the small and large scale industries located near by the river.
This note is a companion of Marquet and Geleyn (2013, {arXiv:1401.2379 [ao-ph]}), where adiabatic lapse rates $Γ_{ns}$ and $Γ_{sw}$ are derived for non-saturated ($Γ_{ns}$) or saturated ($Γ_{sw}$) parcel of moist-air. They are computed in terms of the vertical derivative of the moist-air entropy potential temperature $θ_s$ defined in Marquet (2011, {arXiv:1401.1097 [ao-ph]}). The saturated value $Γ_{sw}$ is rewritten in this note so that a more compact formulation is obtained. The new formulation for $Γ_{sw}$ is expressed in term of a weighting factor $C$. This factor may represent the proportion of an air parcel being in saturated conditions.
Brine channels are formed in sea ice under certain constraints and represent a habitat of different microorganisms. The complex system depends on a number of various quantities as salinity, density, pH-value or temperature. Each quantity governs the process of brine channel formation. There exists a strong link between bulk salinity and the presence of brine drainage channels in growing ice with respect to both the horizontal and vertical planes. We develop a suitable phenomenological model for the formation of brine channels both referring to the Ginzburg-Landau-theory of phase transitions as well as to the chemical basis of morphogenesis according to Turing. It is possible to conclude from the critical wavenumber on the size of the structure and the critical parameters. The theoretically deduced transition rates have the same magnitude as the experimental values. The model creates channels of similar size as observed experimentally. An extension of the model towards channels with different sizes is possible. The microstructure of ice determines the albedo feedback and plays therefore an important role for large-scale global circulation models (GCMs).
Gabriela Roman-Ross, Gabriel Cuello, Xavier Turrillas
et al.
Sorption of As(III) by calcite was investigated as a function of As(III) concentration, time and pH. The sorption isotherm, i.e. the log As(III) vs. log [As(OH)3 degrees / Assat] plot is S-shaped and has been modelled on an extended version of the surface precipitation model. At low concentrations, As(OH)3 degrees is adsorbed by complexation to surface Ca surface sites, as previously described by the X-ray standing wave technique. The inflexion point of the isotherm, where As(OH)3 degrees is limited by the amount of surface sites (ST), yields 6 sites nm-2 in good agreement with crystallographic data. Beyond this value, the amount of sorbed arsenic increases linearly with solution concentration, up to the saturation of arsenic with respect to the precipitation of CaHAsO3(s). The solid solutions formed in this concentration range were examined by X-ray and neutron diffraction. The doped calcite lattice parameters increase with arsenic content while c/a ratio remains constant. Our results made on bulk calcite on the atomic displacement of As atoms along [0001] direction extend those published by Cheng et al., (1999) on calcite surface. This study provides a molecular-level explanation for why As(III) is trapped by calcite in industrial treatments.
Roland Hellmann, Damien Daval, Delphine Tisserand
et al.
We are currently measuring the dissolution kinetics of albite feldspar at 100 deg C in the presence of high levels of dissolved CO_2 (pCO_2 = 9 MPa) as a function of the saturation state of the feldspar (Gibbs free energy of reaction, ΔG). The experiments are conducted using a flow through reactor, thereby allowing the dissolution reactions to occur at a fixed pH and at constant, but variable saturation states. Preliminary results indicate that at far-from-equilibrium conditions, the dissolution kinetics of albite are defined by a rate plateau, with R \approx 5.0 x 10^{-10} mol m^{-2} s^{-1} at -70 < ΔG < -40 kJ mol^{-1}. At ΔG > -40 kJ mol^{-1}, the rates decrease sharply, revealing a strong inverse relation between the dissolution rate and free energy. Based on the experiments carried out to date, the dissolution rate-free energy data correspond to a highly non-linear and sigmoidal relation, in accord with recent studies.