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At least 19 records

Delivery of a Solar-Powered Forward Osmosis Seawater Desalination Plant: Trevi’s 500 m3/day Zero-Carbon FO Seawater Desalination Plant at NELHA

This paper presents an account of Trevi’s delivery of a 500 m3/day solar powered forward osmosis (FO) seawater desalination plant at the Ocean Science and Technology Park of the Natural Energy Laboratory of Hawaii Authority (NELHA). The project aimed to demonstrate the viability of solar thermal-powered desalination for agricultural applications through the integration of a 2MW micro-dish solar thermal array with a state-of-the-art FO system. Highlighted in the paper are the three distinct project phases; Planning and Design, System Construction, Installation & Testing followed finally by System Operation and Optimization. Results and decisions which led to the final plant design will be shared, highlighting how Trevi Systems succeeded in producing a zero-carbon FO seawater desalination plant with a projected Levelized Cost of Water (LCOW) estimate competitive with existing carbon-intensive RO technologies (based on some assumptions and the cost of heat which is required for FO.

14 SOLAR ENERGY↗

Predictability of Seawater DMS During the North Atlantic Aerosol and Marine Ecosystem Study (NAAMES)

This work presents an overview of a unique set of surface ocean dimethylsulfide (DMS) measurements from four shipboard field campaigns conducted during the North Atlantic Aerosol and Marine Ecosystem Study (NAAMES) project. Variations in surface seawater DMS are discussed in relation to biological and physical observations. Results are considered at a range of timescales (seasons to days) and spatial scales (regional to sub-mesoscale). Elevated DMS concentrations are generally associated with greater biological productivity, although chlorophyll a (Chl) only explains a small fraction of the DMS variability (15%). Physical factors that determine the location of oceanic temperature fronts and depth of vertical mixing have an important influence on seawater DMS concentrations during all seasons. The interplay of biomass and physics influences DMS concentrations at regional/seasonal scales and at smaller spatial and shorter temporal scales. Seawater DMS measurements are compared with the global seawater DMS climatology and predictions made using a recently published algorithm and by a neural network model. The climatology is successful at capturing the seasonal progression in average seawater DMS, but does not reproduce the shorter spatial/temporal scale variability. The input terms common to the algorithm and neural network approaches are biological (Chl) and physical (mixed layer depth, photosynthetically active radiation, seawater temperature). Both models predict the seasonal North Atlantic average seawater DMS trends better than the climatology. However, DMS concentrations tend to be under-predicted and the episodic occurrence of higher DMS concentrations is poorly predicted. The choice of climatological seawater DMS product makes a substantial impact on the estimated DMS flux into the North Atlantic atmosphere. These results suggest that additional input terms are needed to improve the predictive capability of current state-of-the-art approaches to estimating seawater DMS.

54 ENVIRONMENTAL SCIENCES↗

Measurement of the Dielectric Constant of Seawater at L-Band: Techniques and Measurements

Satellite instruments, that will monitor salinity from space in the near future, require an accurate relationship between salinity/temperature and seawater dielectric constant. This paper will review measurements that were made of the dielectric constant of seawater during the past several years. The objective of the measurements is to determine the dependence of the dielectric constant of seawater on salinity and on temperature, more accurately than in the past. by taking advantage of modem instrumentation. The measurements of seawater permittivity have been performed as a function of salinity and temperature using a transmission resonant cavity technique. The measurements have been made in the salinity range of 10 to 38 psu and in the temperature range of IOU C to 35 C. These results will be useful in algorithm development for sensor systems such as SMOS and Aquarius. The measurement system consists of a brass microwave cavity that is resonant at 1.413 GHz. The seawater is introduced into the cavity through a capillary glass tube having an inner diameter of 0.1 mm. The diameter of the tube has been made very small so that the amount of seawater introduced in the cavity is small - thus maintaining the sensitivity of the measurements and allowing the use of perturbation theory predicting the seawater permittivity. The change in resonant frequency and the change in cavity Q can be used to determine the real and imaginary pare of the dielectric constant of seawater introduced into the slender tube. The microwave measurements are made by an HPS722D network analyzer. The cavity has been immersed in a u~ateriethylene-glycol bath which is connected to a Lauda circulator. The circulator keeps the brass cavity at a temperature constant to within 0.01 degrees. The system is automated using a Visual Basic program to control the analyzer and to collect the data. The results of the dielectric constant measurements of seawater will be presented. The measurement results will be compared with permittivity values generated from the Kline and Swift relationship. Two methods of calibration will be discussed, The errors that each technique introduces into the measurement resulls will be reviewed. Temperature stability, frequency drift and the effect of increasing cavity transmission loss on the unloaded cavity Q will also be discussed.

Lang, R.↗

Mn(II)-induced phase transformation of Mn(IV) oxide in seawater

Manganese (Mn) oxides are key components of oceanic and lacustrine Mn nodules and influence metal cycling through oxidation and adsorption processes. Layered Mn oxides (LMOs) are the most common minerals in these nodules and the immediate products of microbially mediated Mn(II) oxidation by O 2 . LMOs can transform into tunneled Mn oxides (TMOs), Mn oxyhydroxides (MnOOH), or Mn(II,III) phase (Mn 3 O 4 ). LMOs often concur with Mn(II) in the environment and the adsorption and oxidation of Mn(II) by LMOs can greatly promote the transformation of LMOs to those phases. However, the Mn(II)-promoted transformation of LMOs in seawater—rich in various cations (300 mM Na + , 10 mM K + , 50 mM Ca 2+ , and 10 mM Mg 2+ ) remains poorly understood. We examined the transformation of δ-MnO 2 in artificial seawater (pH 8.2) under anoxic conditions with the Mn(II)/MnO 2 ratio (r) ranging from 0.08 to 3.83. To assess the effect of ionic strength (IS), parallel experiments were conducted in a mixed 530 mM NaCl and 10 mM KCl solution (having seawater ionic strength but without Ca 2+ and Mg 2+ ) and in 100 mM NaCl solution as a control. At low r (0.08), δ-MnO 2 transformed into triclinic birnessite and a 4 × 4 TMO in 100 mM NaCl solution, which, however, was suppressed in seawater due to strong interactions of Ca 2+ /Mg 2+ with δ-MnO 2 . In the mixed 530 mM NaCl and 10 mM KCl solution (the same ionic strength as of seawater), the transformation occurred extensively but the products had lower crystallinity compared to in 100 mM NaCl solution. At the high Mn(II)/MnO 2 ratios (0.5 ≤ r ≤ 3.83), δ-MnO 2 transformed extensively into MnOOH phases and hausmannite (Mn 3 O 4 ) in 100 mM NaCl solution. The seawater suppressed the transformation, but the suppression became weaker with increasing Mn(II)/MnO 2 ratio. For example, the transformation was completely suppressed at r = 0.5 but essentially negligible at r = 3.83. The suppression at these high Mn(II)/MnO 2 ratios was mainly ascribed to the influence of Ca 2+ and Mg 2+ rather than of the high IS, and the weaker suppression at the higher Mn(II)/MnO 2 ratio suggests stronger competition of Mn(II) with Ca 2+ /Mg 2+ for interacting with δ-MnO 2 . Moreover, the composition and crystallinity of the transformation products (i.e., the relative abundance of MnOOH (α, β, and γ) and Mn 3 O 4 ) were influenced by both the high ionic strength and the presence of Ca 2+ and Mg 2+ . Therefore, even though Ca 2+ and Mg 2+ concentrations are much lower than Na + in seawater, their impacts on the transformation are dominant. Our study explains why MnOOH phases, hausmannite, and TMOs are less common than LMOs in oceanic environments, partially because seawater chemistry suppresses their formation. LMOs are the most reactive for metal adsorption and oxidation among all Mn oxides. Thus, the high stability of LMOs in an oceanic environment confers the high impacts of Mn oxides on metal cycling in the ocean.

Divalent manganese↗

Cutting-edge methods for amplifying the oxygen evolution reaction during seawater electrolysis: a brief synopsis

Electrochemical water splitting has been considered a clean and continual way for hydrogen (H 2 ) production. Direct seawater electrolysis is a potentially attractive technology due to the ample access to seawater and scarce freshwater resources in some regions. However, the presence of impurities (e.g., Cl - , Mg 2+ ) and the resulting corrosion and side reactions, such as the chloride oxidation reaction (ClOR), makes seawater electrocatalysis more challenging than that of fresh or alkaline water due to competition with the oxygen evolution reaction (OER) at the anode. Consequently, much effort has been devoted to developing approaches to enhance OER performance and suppress the ClOR. In this minireview, we summarize three general strategies for enhancing OER activity and selectivity in seawater electrolysis based on three different concepts: (1) the sole development of robust and high-performance OER catalysts in pure seawater electrolytes, (2) the introduction of additives to seawater electrolytes (e.g., alkalis and/or salts without chloride) to enhance the potential equilibrium gap between the ClOR and OER in combination with regular highly active OER catalysts, and (3) a combination of approaches (1) and (2). Finally, the current challenges and potential opportunities for green H 2 production from seawater electrolysis are briefly presented.

08 HYDROGEN↗

Disentangling the effects of sulfate and other seawater ions on microbial communities and greenhouse gas emissions in a coastal forested wetland

Seawater intrusion into freshwater wetlands causes changes in microbial communities and biogeochemistry, but the exact mechanisms driving these changes remain unclear. Here we use a manipulative laboratory microcosm experiment, combined with DNA sequencing and biogeochemical measurements, to tease apart the effects of sulfate from other seawater ions. We examined changes in microbial taxonomy and function as well as emissions of carbon dioxide, methane, and nitrous oxide in response to changes in ion concentrations. Greenhouse gas emissions and microbial richness and composition were altered by artificial seawater regardless of whether sulfate was present, whereas sulfate alone did not alter emissions or communities. Surprisingly, addition of sulfate alone did not lead to increases in the abundance of sulfate reducing bacteria or sulfur cycling genes. Similarly, genes involved in carbon, nitrogen, and phosphorus cycling responded more strongly to artificial seawater than to sulfate. These results suggest that other ions present in seawater, not sulfate, drive ecological and biogeochemical responses to seawater intrusion and may be drivers of increased methane emissions in soils that received artificial seawater addition. A better understanding of how the different components of salt water alter microbial community composition and function is necessary to forecast the consequences of coastal wetland salinization.

54 ENVIRONMENTAL SCIENCES↗

The influence of increasing atmospheric CO 2 , temperature, and vapor pressure deficit on seawater-induced tree mortality

We report increasing seawater exposure is killing coastal trees globally, with expectations of accelerating mortality with rising sea levels. However, the impact of concomitant changes in atmospheric CO 2 concentration, temperature, and vapor pressure deficit (VPD) on seawater-induced tree mortality is uncertain. We examined the mechanisms of seawater-induced mortality under varying climate scenarios using a photosynthetic gain and hydraulic cost optimization model validated against observations in a mature stand of Sitka-spruce (Picea sitchensis) trees in the Pacific Northwest, USA, that were dying from recent seawater exposure. The simulations matched well with observations of photosynthesis, transpiration, nonstructural carbohydrates concentrations, leaf water potential, the percentage loss of xylem conductivity, and stand-level mortality rates. The simulations suggest that seawater-induced mortality could decrease by ~16.7% with increasing atmospheric CO 2 levels due to reduced risk of carbon starvation. Conversely, rising VPD could increase mortality by ~5.6% because of increasing risk of hydraulic failure. Across all scenarios, seawater-induced mortality was driven by hydraulic failure in the first two years after seawater exposure began, with carbon starvation becoming more important in subsequent years. Changing CO 2 and climate appear unlikely to have a significant impact on coastal tree mortality under rising sea levels.

54 ENVIRONMENTAL SCIENCES↗

Assessing the fidelity of shallow-water carbonates as records of the Ni isotope composition of surface seawater

Nickel is a bioessential metal that is used in enzymes important to the C, N, and O cycles, and changes in its marine abundance and bioavailability may have affected the evolutionary trajectory of early life. Changes over time in the Ni isotope composition (δ 60 Ni) of surface seawater, which reflects biological demand for Ni, could allow for the reconstruction of the dynamics of Ni demand over Earth’s history, but this approach would require geologic records of surface seawater. Here, we investigate the fidelity of shallow-water carbonates as a record of the Ni isotope composition of surface seawater by determining how Ni is first partitioned into natural carbonates and then how post-depositional processes influence the Ni signal. Our samples come from the Great Bahama Bank, which is a well-studied, modern carbonate platform often used to study ancient platforms. We found that Ni is fractionated from seawater upon incorporation into carbonates capturing shallow (<18 cm), recent deposition (0.1 ‰–0.4 ‰ lighter than seawater). Variation among these [Ni] and δ 60 Ni values may be controlled by variation in mineral proportions. Meteoric diagenesis shifts δ 60 Ni to lower values, which we attribute to isotopically light meteoric fluids. In contrast, carbonates that experienced sediment-buffered marine diagenesis with respect to Ca isotopes and Sr/Ca ratios do not appear to differ in δ 60 Ni values from sediments generally representative of their initial deposition. The sensitivity of δ 60 Ni to diagenetic reset in these samples appears comparable to the sensitivities of Ca isotopes and Sr/Ca ratios, to first order. Thus, in general, carbonates that experienced sediment-buffered marine diagenesis with respect to these elements may hold the most promise as a record of the δ 60 Ni of coeval surface seawater. Additionally, we use our results to infer that the fraction of Ni removed from seawater into carbonates is less than 10 % of the total Ni output from the global oceans and incorporation of this Ni sink into global biogeochemical models will only have a minor impact on the modeled modern Ni budget.

Great Bahama Bank carbonates↗

Coastal Forest Seawater Exposure Increases Stem Methane Concentration

Methane (CH 4 ) exchange between trees and the atmosphere has recently emerged as an important, but poorly quantified process regulating global climate. The sources (soil and/or tree) and mechanisms driving the increase of CH 4 in trees and degassing to the atmosphere are inadequately understood, particularly for coastal forests facing increased exposure to seawater. Here, we investigated the eco-physiological relationship between tree stem wood density, soil and stem oxygen saturation (an indicator of redox state), soil and stem CH 4 concentrations, soil and stem carbon dioxide (CO 2 ) concentrations, and soil salinity in five forests along the United States coastline. We aim to evaluate the mechanisms underlying greenhouse gas (GHG) increase in trees and the influence of seawater exposure on stem CH 4 accumulation. Seawater exposure corresponded with decreased tree survival and increased tree stem methane. Tree stem wood density was significantly correlated with increased stem CH4 in seawater exposed gymnosperms, indicating that dying gymnosperm trees may accumulate higher levels of CH 4 in association with seawater flooding. Further, we found that significant differences in seawater exposed and unexposed gymnosperm tree populations are associated with increased soil and stem CH 4 and CO 2 , indicating that seawater exposure significantly impacts soil and stem greenhouse gas abundance. Our results provide new insight into the potential mechanisms driving tree CH 4 accumulation within gymnosperm coastal forests.

54 ENVIRONMENTAL SCIENCES↗

High salinity seawater boiling point elevation: Experimental verification

Boiling point elevation (BPE) for high salinity solutions is a crucial parameter that significantly affects the overall thermal efficiency of desalination, water treatment, and many other industrial processing systems, especially when minimum or zero liquid discharge is a key requirement. This paper addresses the discrepancies among the empirical correlations reported in the literature that were commonly used to determine BPE for seawater solutions. An evaluation of the experimental data with low solution concentration reveals that the data cannot be extrapolated to determine the BPE at high concentration (X > 140 ppt or g/kg). Besides, disparities are established within different equations used to determine the BPE for high salinity seawater. As a result of the minimal availability of experimental data of BPE for X > 140 ppt and the need to eliminate the discrepancies, an experimental setup was built, which can produce reliable and repeatable BPE data for any solution concentration. Boiling points were obtained experimentally for seawater solutions with a wide range of salinity (X between 20 and 280 ppt) and brine solution temperature (t b between 20 and 80°C). The experimental results of boiling point elevations for seawater are further compared with the experimental data and analytical results reported in the literature. The newly obtained experimental results show that the minimum and maximum BPE values for the brine solutions tested are 0.175°C at t b = 80°C and X = 20 ppt, and 11.6°C at t b = 80°C and X = 280 ppt, respectively. Furthermore, the measured BPE data for seawater concentration over 80 ppt are fitted and presented using an appropriate fitting model. The new correlation can accurately predict the BPE for high salinity seawater brines and thus should be very helpful in the design of high-energy-efficient evaporation systems.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Investigation of MO x (M = Cr, Mn, Re, and Mo) coated stainless-steel electrodes for oxygen evolution reaction in natural seawater electrolysis

Seawater electrolysis is considered a potential strategy for large-scale of affordable H 2 production. However, poor durability of the anode for oxygen evolution reaction (OER) in natural seawater is a remaining concern due to chloride-induced reaction. Herein, the effect of various MO x (M = Mn, Cr, Re, and Mo) coated stainless steel (SS) electrodes on OER in direct natural seawater electrolysis was comprehensively studied. It is found that the Mo-coated SS electrode is superior to all others in terms of durability, followed by Re-coated SS, while the Cr and Mn-coated SS electrodes show the poorest durability. Additionally, the durability and activity of the Mo/SS electrode can be boosted remarkably in 1 M KOH/seawater compared to the natural seawater, resulting in an overpotential at 10 mA cm −2 decrease from 830 to 399 mV. Meanwhile, no degradation is observed at 1000 mA cm −2 for 100 h in 1 M KOH seawater, which is among the best stability, based on the literature review. Moreover, the improved durability and activity with Mo coating were extended to the Inconel 718 substrate, and around 40 % improvement in durability and 25 mV overpotential decrease at 10 mA cm −2 are observed, which indicates that Mo coating can be considered as a universal approach to improve the anode durability and activity. The improved performance with Mo coating may be attributed to the continuous Mo oxide layer formation or in situ generated MoO 4 2− in the OER process. In conclusion, this work provides a holistic strategy to enhance the anode durability and activity under harsh conditions, offering valuable insights for designing corrosion-resistant electrodes in direct seawater electrolysis.

Direct seawater electrolysis↗

Impact of inland boundary conditions on seawater intrusion modeling in stratified coastal aquifers under sea-level rise

This study systematically examines the impact of inland boundary conditions on seawater intrusion modeling in general stratified coastal aquifers under sea-level rise (SLR). We derived analytical solutions for seawater wedge toe positions in stratified aquifers with general head boundary (GHB) conditions and compiled solutions for constant head boundary (CHB), constant flux boundary (CFB), and GHB conditions in both homogeneous and stratified aquifers. Additionally, we introduced the concept of equivalent boundary conditions and developed equations to ensure consistent steady-state toe positions across different boundary types. Unlike previous studies focusing on specific layering configurations, we conducted a comprehensive sensitivity analysis of seawater intrusion in general stratified aquifers using transmissivity centroid elevation (TCE). Our results show that SLR generally exacerbates seawater intrusion, with unconfined aquifers exhibiting higher sensitivity across all boundary conditions. Among boundary types, CHB conditions were the most sensitive to SLR, CFB the least, and GHB showed an intermediate response depending on its distance from the model boundary. Furthermore, seawater intrusion increases with the TCE of the stratified aquifer under SLR, suggesting that high-permeability or preferential flow layers near the surface amplify the impact of SLR. These findings emphasize the importance of selecting appropriate boundary conditions when evaluating SLR-driven seawater intrusion in stratified coastal aquifers.

Boundary condition↗

Predicting the Seawater Chemistry of an Ocean World Using Machine Learning on Isotopic Measurements of Volatile CO2

Introduction: Given the long time intervals required for data transmission to and from ocean worlds targets, low bandwidth for data transmission, time required for data processing and analysis, and potentially extreme radiation environments (e.g., Europa), it is clear that ocean worlds missions will need more autonomous flight instruments and software in order to achieve established science goals. Protracted time intervals for data analysis (e.g., Europa Lander) strongly motivates the development of rapid, consistent and streamlined methods for interpreting data from flight mass spectrometers to e.g., determine how mass spectra from a plume or surface liquid/ice relates to the surface/subsurface. Since mass spectrometry also has the potential to correctly identify biosignatures[1], it is imperative that such methods for interpreting data are consistent and accurate. We used 848 isotope ratio mass spectra from laboratory analyses of CO2 that interacted with ocean worlds-relevant seawaters as a ‘training’ dataset for ‘unsupervised’ machine learning. In unsupervised learning, characteristics of the data are not labeled or linked, and any similarities found only result from the neural network. CO2 isotopologues analyzed for this dataset mimic the remote measurements of CO2 by a flight mass spectrometer, and are detailed in Theiling [2]. From this dataset, we used measured features of the spectra, such as retention time, intensity, and (isotopologue) mass ratios as inputs for our autoencoder neural network. Our neural network was trained to find similarities in these and other spectral features for seawaters of a particular composition and amount of initial CO2. Successful training then created an output of these similarities for various seawaters, which included MgSO4, Na2SO4, NaCl, MgCl2, KCl, and NaHCO3, and combinations of these salts. We then applied dimensionality reduction techniques such as Principal Component Analysis (PCA), T-Distributed Stochastic Neighbor Embedding (TSNE), and Uniform Manifold Approximation and Projection (UMAP) to demonstrate latent data features as a two-dimensional projection in a unitless, high-dimensional space. In this projection, a data point represents the combined effect of spectral features such as intensity, retention time, and isotope ratio. Our initial UMAP demonstrates data clustering (organization of the data by the neural network) based on the amount of CO2 that had initially interacted with each seawater. Further training using more ‘supervised’ learning techniques demonstrate strong clustering of preliminary data based on initial CO2 concentration, seawater chemical composition, and ionic strength (salinity). Our preliminary work therefore suggests that machine learning has the potential to identify compositional variants of an ocean world seawater based on mass spectra from volatile CO2 measurements. Acknowledgments: This work was funded through a Strategic Task Group at NASA Goddard Space Flight Center. The training dataset was collected through funding from the Oklahoma Space Grant Consortium. References: [1] Pappalardo, R. et al. (2013) Astrobiology, 13, 740–773. [2] Theiling (2020) Icarus, 114216.

Europa↗

Declining carbohydrate content of Sitka-spruce treesdying from seawater exposure

Abstract Increasing sea levels associated with climate change threaten the survival of coastal forests, yet the mechanisms by which seawater exposure causes tree death remain poorly understood. Despite the potentially crucial role of nonstructural carbohydrate (NSC) reserves in tree survival, their dynamics in the process of death under seawater exposure are unknown. Here we monitored progressive tree mortality and associated NSC storage in Sitka-spruce (Picea sitchensis) trees dying under ecosystem-scale increases in seawater exposure in western Washington, USA. All trees exposed to seawater, because of monthly tidal intrusion, experienced declining crown foliage during the sampling period, and individuals with a lower percentage of live foliated crown (PLFC) died faster. Tree PLFC was strongly correlated with subsurface salinity and needle ion contents. Total NSC concentrations in trees declined remarkably with crown decline, and reached extremely low levels at tree death (2.4% and 1.6% in leaves and branches, respectively, and 0.4% in stems and roots). Starch in all tissues was almost completely consumed, while sugars remained at a homeostatic level in foliage. The decreasing NSC with closer proximity to death and near zero starch at death are evidences that carbon starvation occurred during Sitka-spruce mortality during seawater exposure. Our results highlight the importance of carbon storage as an indicator of tree mortality risks under seawater exposure.

59 BASIC BIOLOGICAL SCIENCES↗

Production of Uranium from Seawater Using a Novel Polymer Adsorbent – Process Development and Cost Analysis (Final Scientific/Technical Report SBIR Phase II)

Research in developing techniques for extracting uranium from seawater is of considerable current interest. One reason which drives scientists to develop techniques of sequestering uranium from ocean is the prediction that the land-based uranium reserves would be depleted by the end of this century based on the current production rate. Uranium exists in seawater at a very low concentration (about 3 ppb) and as highly stable uranyl tris-carbonato complexes, primarily in the form Ca 2 [UO 2 (CO 3 ) 3 ]. Because of the enormous volume of seawater, the total amount of uranium in ocean is estimated to be a thousand times greater than the land-based uranium resources. As early as 1964, the idea of extracting uranium from seawater was discussed by Davies et al. in a Nature paper. In the past decades, many different materials were tested to evaluate their ability for sequestering uranium from seawater. Among them, amidoxime and carboxylate containing polymer fiber adsorbents appear most promising because of their high uranium adsorption capacity and stability in seawater. The carboxylate groups are necessary to make the polymer adsorbent hydrophilic whereas the amidoxime groups provide strong coordination sites for uranyl ions. Moreover, according to theoretical analysis, the adsorbability of uranium may involve synergistic effects of both amidoxime and carboxyl groups in the fiber adsorbent.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The evaporation path of seawater and the coprecipitation of Br- and K+ with halite

Brines and salt were sampled at the Morton Bahamas solar salt production facility on Great Inagua Island in the Bahamas. The brines were analyzed by ion chromatography to define more precisely than heretofore the evaporation path of seawater to the end of the halite facies. At Inagua, calcium carbonate begins to precipitate at a brine concentration factor of 1.8 times that of seawater. Gypsum begins to precipitate at a brine concentration of 3.8 times seawater, and halite at a concentration factor of 10.6. Three of the most concentrated brines from Inagua (40 times seawater) were evaporated further in the laboratory. Magnesium sulfate first precipitated at brine concentrations about 70 times those of seawater, and potassium-bearing phases began to precipitate for these brines at concentrations greater than 90 times those of seawater. The distribution of coefficients of Br- and K+ between brines and halite were determined by combining analytical data for the Inagua brines with measurements of the Br- and K+ content of halites from Inagua and of halite which had precipitated from Inagua brines during storage. The observed average value of DBr- is 0.032, in good agreement with some of the previous measurements. The measured values of DK+ are highly variable (0.001 to 0.021); DK+ for halite precipitated early in the halite facies is in the vicinity of 0.015.

NASA Discipline Exobiology↗

Investigation of oxygen evolution reaction with 316 and 304 stainless-steel mesh electrodes in natural seawater electrolysis

Here, two commercially available stainless steel mesh substrates (316 SS and 304 SS) were evaluated as electrodes for oxygen evolution reaction (OER) in natural seawater electrolysis. The results show the 304 SS is less stable against corrosion under neutral (pH of 8.5) and low alkaline (0.1 M NaOH, pH of 12.8) seawater electrolytes because of the direct metal dissolution and chlorine evolution reaction (CER), and the 316 SS is superior to 304 SS in terms of electrocatalytic activity and resistance to corrosion under the same media. The performance of 304 SS is comparable to 316 SS under the high alkaline (1 M NaOH, pH of 13.7) seawater electrolyte, where the CER and metal dissolution are suppressed by OER. The overpotential for 304 and 316 SS is around 430 mV at 10 mA cm -2 , and the Tafel slopes are below 50 mV dec -1 under the high alkaline (1 M NaOH) seawater electrolyte, showing promising performance. The poor resistance to corrosion of 304 SS is attributed to the low Mo content, and it is supposed that the stability of both 304 and 316 SS can be improved further with the addition of Mo content. This work expands on promising substrates for natural seawater electrolysis, with cost and performance advantages.

Stainless-steel mesh↗

Correlating surface adsorbate configuration and electrochemical performance of IrO 2 during seawater-relevant electrolysis

Seawater electrolysis alleviates freshwater demand to produce clean hydrogen while eliminating the need for water purification steps. The anodic process, seawater oxidation, typically requires high overpotentials and yields low selectivity to oxygen via the oxygen evolution reaction (OER), primarily due to the competing chlorine evolution reaction (CER) and hypochlorite evolution reaction (HCER) in pH-neutral conditions. Here, combining in situ surface-enhanced Raman characterization, grand canonical density functional theory-based calculations, and kinetic Monte Carlo simulations, we report the evolution of surface adsorbate configurations driven by applied potential and pH during seawater-relevant OER over IrO 2 , a highly OER-active and chloride-corrosion-resistant catalyst. As a result, the chemical properties of active sites, and thereby the kinetics of OER and CER/HCER, are effectively tuned. However, it is revealed that there is no optimal combination of potential and pH to achieve both high activity and high selectivity for seawater-relevant OER. To address this limitation, we establish a correlation between activity/selectivity and surface adsorbate configurations, enabling the optimization of highly active and OER-selective IrO 2 -based catalysts in seawater-relevant oxidation by modulating the local adsorbate environment of active sites.

08 HYDROGEN↗