Renewable Ocean Thermal Energy for Low-Pressure Desalination of Seawater with Co-Production of Ammonia (Final Report)
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25 ENERGY STORAGE↗
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Making lithium metal—seawater battery cells having protected lithium electrodes
Active metal and active metal intercalation electrode structures and battery cells having ionically conductive protective architecture including an active metal (e.g., lithium) conductive impervious layer separated from the electrode (anode) by a porous separator impregnated with a non-aqueous electrolyte (anolyte). This protective architecture prevents the active metal from deleterious reaction with the environment on the other (cathode) side of the impervious layer, which may include aqueous or non-aqueous liquid electrolytes (catholytes) and/or a variety electrochemically active materials, including liquid, solid and gaseous oxidizers. Safety additives and designs that facilitate manufacture are also provided.
Visco, Steven J.↗
Seawater electrolysis enables Mg(OH) 2 production and CO 2 mineralization
A method for producing one or more hydroxide solids includes providing a catholyte comprising an electrolyte solution; contacting the catholyte with an electroactive mesh cathode to electrolytically generate hydroxide ions, thereby precipitating the one or more hydroxide solid(s); and removing the one or more hydroxide solids from the surface of the mesh where they may deposit.
Chen, Xin↗
The Brachiopod δ 11 B Record Across the Carboniferous-Permian Climate Transition
In this work, we present the δ 11 B of well-preserved brachiopod fossils coupled with geochemical modeling to examine how seawater boron responded to abrupt and dynamic climate changes in the Late Paleozoic. The Late Carboniferous, a time of major coal formation and glacioeustatic sea level changes, is characterized by relatively stable brachiopod δ11B of 15–17‰, similar to values seen in modern brachiopods. Brachiopod δ 11 B dropped by ~5‰ in the early Permian and then restabilized at a new value of 10‰ within a few million years. Mass balance models of seawater δ 11 B reproduced the overall trends in our brachiopod data but failed to capture the large drop in δ11B in the early Permian. Published seawater 87 Sr/ 86 Sr and δ 44 / 40 Ca data based on brachiopod shells also shift to lower values in the early Permian, suggesting a common control on all three seawater isotope systems. The Permian terrestrial record of evaporites and eolian deposits suggests a prolonged reduced delivery of dissolved weathering products to the ocean, accounting for the change in seawater 87 Sr/ 86 Sr. This reduced weathering, in turn, led to increased atmospheric CO 2 and lowered seawater pH, which may have significantly decreased major removal mechanisms for seawater calcium and boron leading to declines in both isotope systems. We propose that boron removal via coprecipitation in carbonates and adsorption onto clay minerals was significantly diminished due to a reduction in the availability of the borate aqueous species caused by lowered seawater pH.
54 ENVIRONMENTAL SCIENCES↗
Impacts of Sea‐Level Rise on Coastal Groundwater Table Simulated by an Earth System Model With a Land‐Ocean Coupling Scheme
Abstract Sea‐level rise (SLR) poses a severe threat to the coastal environment through seawater intrusion into freshwater aquifers. The rising groundwater table also exacerbates the risk of pluvial, fluvial, and groundwater flooding in coastal regions. However, current Earth system models (ESMs) commonly ignore the exchanges of water at the land‐ocean interface. To address this gap, we developed a novel land‐ocean hydrologic coupling scheme in a state‐of‐the‐science ESM, the Energy Exascale Earth System Model version 2 (E3SMv2). The new scheme includes the lateral exchange between seawater and groundwater and the vertical infiltration of seawater driven by the SLR‐induced inundation. Simulations were performed with the updated E3SMv2 for the global land‐ocean interface to assess the impacts of SLR on coastal groundwater under a high CO 2 emission scenario. By the middle of this century, seawater infiltration on the inundated areas will be the dominant component in the land‐ocean coupling process, while the lateral subsurface flow exchange will be much smaller. The SLR‐induced seawater infiltration will raise the groundwater levels, enhance evapotranspiration, and increase runoff with distinct spatial patterns globally in the future. Although the coupling process is induced by SLR, we found topography and warming temperature have more control on the coupling impacts, probably due to the relatively modest magnitude of SLR during the selected future period. Overall, our study suggests significant groundwater and seawater exchange at the land‐ocean interface, which needs to be considered in ESMs.
54 ENVIRONMENTAL SCIENCES↗
An assessment of ocean alkalinity enhancement using aqueous hydroxides: kinetics, efficiency, and precipitation thresholds
Abstract. Ocean alkalinity enhancement (OAE) is a promising approach to marine carbon dioxide removal (mCDR) that leverages the large surface area and carbon storage capacity of the oceans to sequester atmospheric CO2 as dissolved bicarbonate (HCO3-). One OAE method involves the conversion of salt in seawater into aqueous alkalinity (NaOH), which is returned to the ocean. The resulting increase in seawater pH and alkalinity causes a shift in dissolved inorganic carbon (DIC) speciation toward carbonate and a decrease in the surface ocean pCO2. The shift in the pCO2 results in enhanced uptake of atmospheric CO2 by the seawater due to gas exchange. In this study, we systematically test the efficiency of CO2 uptake in seawater treated with NaOH at aquarium (15 L) and tank (6000 L) scales to establish operational boundaries for safety and efficiency in advance of scaling up to field experiments. CO2 equilibration occurred on the order of weeks to months, depending on circulation, air forcing, and air bubbling conditions within the test tanks. An increase of ∼0.7–0.9 mol DIC per mol added alkalinity (in the form of NaOH) was observed through analysis of seawater bottle samples and pH sensor data, consistent with the value expected given the values of the carbonate system equilibrium calculations for the range of salinities and temperatures tested. Mineral precipitation occurred when the bulk seawater pH exceeded 10.0 and Ωaragonite exceeded 30.0. This precipitation was dominated by Mg(OH)2 over hours to 1 d before shifting to CaCO3,aragonite precipitation. These data, combined with models of the dilution and advection of alkaline plumes, will allow the estimation of the amount of carbon dioxide removal expected from OAE pilot studies. Future experiments should better approximate field conditions including sediment interactions, biological activity, ocean circulation, air–sea gas exchange rates, and mixing zone dynamics.
Ringham, Mallory C. (ORCID:0000000348020185)↗
Mining waste-driven carbon capture via ocean alkalinity enhancement
Ocean alkalinity enhancement (OAE) has emerged as a promising strategy to mitigate ocean acidification and reduce global warming. Traditional metal (e.g., critical materials) mining industries release alkaline waste via mining tailings with high concentrations (99.2%) of calcium and magnesium oxide (CaO, MgO). Incorporating mining waste into OAE processes is less energy intensive than processes relying on calcination of limestone for CaO production. The solubility limit of simulated mining waste in American Society for Testing and Materials (ASTM) seawater is 75 mg⋅L -1 , which can sequester 118 mg of carbon dioxide (CO 2 ). The solubility in seawater retrieved from Sunset Beach, FL was 25 mg⋅L -1 . Changes in pH, total alkalinity, and total inorganic carbon were analyzed to confirm the successful addition of simulated alkaline mining waste without the formation of secondary precipitation. This study proposes a new OAE strategy where a facility is developed nearby ocean waters that mixes alkaline waste with seawater. Subsequently, the seawater is met with previously captured, pure CO 2 to bring the pH back to 8.2 and eliminate the risks of pH shock and secondary precipitation. Technoeconomic analysis estimated an energy requirement of 1.4 GJ per ton of CO 2 stored that resulted in a processing cost of $\$$266 per ton of CO 2 sequestered (4.2 GJ per ton, $\$$807 per ton of CO 2 for real seawater). Results from this study underscore the potential for utilizing mining waste in OAE processes and provide a pathway for practical deployment.
Absorption↗
CFD modeling of crystallization fouling with CO 2 desorption incorporated for a falling-film evaporator in thermal desalination
Seawater flowing around horizontal tubes in falling-film evaporators is a common configuration for thermal desalination. Heat is transferred from in-tube steam condensation to the shell-side seawater by conduction through the tube wall and scaling layer, and conduction and convection to the evaporating liquid film. CO 2 is simultaneously released from seawater and mixed with the produced vapor. Fouling coupled with CO 2 desorption has deleterious impacts on both evaporation and condensation. The evaluation of spatiotemporal dependent crystallization fouling and CO 2 desorption is vital to selecting optimal operating conditions. Here, in this work, a CO 2 desorption model is integrated into CFD modeling for predictions of coupled heat and mass transfer, to understand and predict scale formation and CO 2 desorption with local and transient profiles of temperature, carbonate species concentrations, pH, and total alkalinity. The porosity of the scale layer is experimentally determined as 67.7% and invoked in the calculation of effective thermal conductivity. The simulation results reveal that high steam temperatures increase seawater total alkalinity and accelerate scale formation. The scale thickness on the bottom tube reaches 0.30 μm and 5.24 μm for steam temperatures of 60 °C and 80 °C, respectively. High salinity leads to a large CO 2 desorption rates. The CO 2 desorption rate increases 43% when the seawater salinity increases from 35 to 55 g/kg. The effects of operating conditions on carbonate speciation and pH have been compared and analyzed. This model can serve as a comprehensive tool for the design of thermal desalination systems and optimal operation.
42 ENGINEERING↗
Prediction of the Inter-Tube Flow Mode Transitions in the Evaporators of Multi-Effect Thermal Desalination Plants
Water is one of the most stressed resources on the planet. The limited availability of fresh water and the high cost of transportation have led to an increased interest in water desalination technologies. The two main categories of desalination techniques are membrane desalination and thermal desalination. Membrane technologies include pressure driven and electrical driven membranes. On the other hand, thermal desalination includes: multi-effect desalination (MED), multi-stage flash (MSF) desalination, and mechanical vapor compression desalination. Multi-effect desalination plants are usually made of a series of evaporators (also known as effects). In each effect, hot steam flows inside the tubes and evaporates the seawater that falls on the outside of the tubes. The vapor formed at each effect flows to the next effect and acts as the heating medium for the falling seawater. The prevailing flow mode of the falling seawater (i.e. droplet, jet, or sheet) influences heat and mass transfer as well as dry out in the evaporators of Multi-Effect Desalination (MED) plants. The objective of this paper is to predict and discuss the prevailing falling film flow modes in the evaporators of MED plants, under different operating conditions. The paper demonstrates the transitional Reynolds numbers between the main falling film modes for seawater. This closes a gap in the literature where there is a dearth of mode transition data for seawater. The effect of fluid properties and tube geometry on the transitions is discussed in details. As a result, the accuracy of the predicted transitional Reynolds numbers is evaluated via uncertainty quantification techniques.
availability↗
Co-Located Wave Energy Converter (WEC) and Aquaculture System Annotated Bibliography
This annotated bibliography includes references that could aid in the design of a co-located WEC and aquaculture system off the coast of Guam. The breadth of this work covers multiple co-location archetypes such as: 1. WEC seawater desalination system a) Nearshore and deepwater WEC deployment b) Onshore and offshore aquaculture 2. WEC powering an offshore aquaculture platform a) Nearshore or deepwater WEC deployment 3. WEC powering an onshore aquaculture system a) Nearshore WEC deployment 4. Wave powered seawater pump a) Nearshore WEC deployment b) Onshore aquaculture There are two archetypes that may be of immediate interest to the community in Guam are to service the existing Fadian Hatchery (Mangilao) and to support freshwater aquaculture activities. First, the seawater pump at the hatchery that fills the facility’s seawater storage unit is broken. A nearshore seawater pumping WEC could be a solution to this issue. In addition, due to the high frequency of typhoons/extreme conditions and the island’s bathymetry, the likelihood of community support for an offshore aquaculture platform or WEC deployed in deepwater is low. Proactive and resilient solutions not just for power, but for freshwater are of interest as well to support any freshwater aquaculture activities. Therefore, a nearshore WEC desalination system is another archetype to consider.
16 TIDAL AND WAVE POWER↗
Godzilla mineral dust and La Soufrière volcanic ash fallout immediately stimulate marine microbial phosphate uptake
During the “Godzilla” dust storm of June 2020, unusually high fluxes of mineral dust traveled across the Atlantic from the Sahara Desert, reaching the Caribbean Basin, Gulf Coast, and southeastern United States. Additionally, an eruption of the La Soufrière volcano on St. Vincent in April 2021 generated substantial ashfall in the southeastern Caribbean. While many studies have analyzed mineral dust’s ability to relieve nutrient limitation of phosphorus (P) in the P-stressed North Atlantic, less is known about the impact of extreme events and other natural aerosols on fluxes of P into seawater and from seawater into marine microbial cells. We quantified P and iron (Fe) content in mineral dust from the Godzilla dust storm and volcanic ash from the La Soufrière eruption collected at Ragged Point, Barbados. We also performed seawater incubations to assess the marine microbial response to aerosol deposition. Using environmentally-relevant concentrations of atmospheric particles for within the ocean’s mixed layer allowed us to draw realistic conclusions about how these deposition events impacted P cycling in situ. Volcanic ash has lower P content than mineral dust, and P in volcanic ash is far less soluble (~1%) than assumed in current atmospheric deposition models. Adding mineral dust and the volcanic ash leachate in concentrations representing different deposition scenarios increased soluble reactive phosphorus (SRP) concentrations in coastal seawater by ~7-32 nM. Phosphate uptake rate was stimulated in coastal seawater after either mineral dust or volcanic ash deposition at aerosol concentrations relevant to the Godzilla dust event, with ash eliciting the fastest uptake rate. Furthermore, high concentrations of both the mineral dust and volcanic ash led to slightly elevated alkaline phosphatase activity (APA) compared to the relevant controls, indicating higher potential for use of dissolved organic phosphorus (DOP) as a P source. Quantifying these aerosols’ impacts on P cycling is a significant step towards achieving a better understanding of their potential roles in relieving nutrient limitation and fueling the biological carbon pump.
54 ENVIRONMENTAL SCIENCES↗
Sustainable ammonia synthesis from nitrogen wet with sea water by single-step plasma catalysis
Ammonia synthesis at ambient conditions employing intermittent distributed green sources of energy and feedstocks is globally sought to replace the centralized Haber-Bosch (H-B) process operating at high temperature and pressure. We report herein for the first time an effective and sustainable ammonia synthesis pathway from N 2 wet with seawater vapor over spherical SiO 2 and M/SiO 2 (M: Ag, Cu, and Co) catalysts driven by non-thermal plasma (NTP). Experimental results indicate that the presence of a catalyst is required for ammonia production from seawater vapor and N 2 . The Co/SiO 2 catalyst delivered the highest ammonia synthesis rate (r NH 3 ) of 3.7 mmol g cat -1 h -1 and energy yield of 3.2 g NH 3 ∙kW -1 ∙h -1 at a relatively low input power of 2 W. The extraction of H atoms from H 2 O molecules plays an important role in the ammonia synthesis from seawater vapor. Finally, this work unfolds a novel platform for the subsequent optimization of sustainable ammonia production from endless resources such as seawater and N 2 through catalytic non-thermal plasma potentially powered by renewable sources.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Sequestration and release of nitrite and nitrate in alkali-activated slag: A route toward smart corrosion control
Intercalating the corrosion inhibitive ions in hydrotalcite is a promising approach to improve the long-term efficiency of inhibitors in corrosion protection of steel in reinforced concrete. In this work, the potential of autogenously generating nitrite- and nitrate-intercalated hydrotalcite in alkali-activated slag (AAS) is investigated. The results show that the added nitrite and nitrate ions are preferably uptaken in the interlayer structure of hydrotalcite in AAS, and the sequestered nitrite and nitrate are released upon chloride exposure in seawater and NaCl solution. The incorporation of nitrite and nitrate has little detrimental effects on the chloride binding capacity of AAS but slightly enhances the chloride ingress due to the pore coarsening effect. Similar to ordinary Portland cement (OPC), AAS is more permeable to the chloride in seawater than NaCl solution. However, unlike the release of bound chloride contributed by ettringite formation in seawater-exposed OPC, the enhanced chloride ingress in seawater-exposed AAS is primarily attributed to the aggravated pH reduction at the exposure front due to brucite formation. This study contributes to the design of alkali-activated binders with a smart inhibitor releasing ability for mitigating corrosion of steel in concrete.
36 MATERIALS SCIENCE↗
Origin of water masses in Floridan Aquifer System revealed by 81 Kr
Groundwater in coastal aquifers serves as an essential resource in densely populated areas throughout the world. However, hydrological connection to the ocean leaves it at risk of salinization via changes in climate and hydrological cycles. Therefore, an accurate hydrological characterization of coastal aquifers is of the utmost importance. Although localized salinization of shallow aquifers has commonly been studied, geochemical constraints on the time scale of regional freshwater and seawater in coastal aquifers are limited especially in carbonate aquifers. Such information is not only crucial for water resource management, but also for understanding solute flux over the land-ocean boundary and for interpreting the geochemical signatures that each water mass carries. Toward this goal, we report tracer-based, subsurface residence times of groundwater in the Floridan Aquifer System in southern Florida, which is one of the most productive aquifers on Earth. The first application of Kr 81-an emerging tracer of old groundwater-to this aquifer has identified freshwater recharge during the last glacial period as anticipated from previous studies using other geochemical tools including radiocarbon, stable isotopes and noble gas concentrations. Moreover, freshwater of Holocene age was also detected at 100 km-distance from the recharge area, suggesting the possibility of an active flow system in the upgradient region. A contribution of fossil seawater that predates the last glacial maximum was locally identified, suggesting slow seawater circulation and limited but significant solute flux from the ocean into the aquifer for dolomitization. This also implies that the deep saline coastal groundwater can potentially serve as a paleo-seawater archive.
58 GEOSCIENCES↗
The Storage of Marine Hydrokinetic Power through Hydrogen Production
Marine hydrokinetic (MHK) power is likely to play a crucial role in future energy diversification and remote energy supply efforts. Providing a means of direct energy storage for MHK power would provide additional benefits to applications in ship microgrids and remote communities. Hydrogen (H 2 ) has long been pursued as a means of green energy storage and can be generated through electrolysis of water in an electrolyzer. However, electrolyzer technology for H 2 production is currently only possible on the commercial scale using fresh water, also a precious resource in our society. The direct electrolysis of seawater would alleviate the fresh water constraints for a new H 2 feedstock and a seawater-fed electrolyzer could be powered locally at a MHK platform. Several technical challenges exist before efficient direct seawater electrolysis can be realized. This project was designed as a demonstration of efficient direct seawater electrolysis that limits chlorine evolution, avoids use of platinum (Pt) group metals and overcomes cathode fouling over long service times.
08 HYDROGEN↗
Cadmium isotope systematics in sedimentary carbonate: Extending the utility of the cadmium isotope palaeo-productivity proxy
The cadmium (Cd) isotope compositions of seven Holocene (<11.7 ka) carbonate sediments, including the bulk carbonate, as well as the > 140 μm (zooplankton), <63 μm and < 20 μm (phytoplankton) fractions, and individual species of foraminifera isolated from the bulk carbonate were obtained for sub-samples processed using the Cd-cleaning and Mg/Ca cleaning methods. The respective Cd isotope systematics of each carbonate archive were then compared with the Cd isotope signature within the ocean using modern seawater data. We show that a constant Cd isotope fractionation factor of -0.25 ± 0.03 ‰ (2SE, n = 4) describes the partitioning of Cd from seawater into the carbonate phase ($Δ^{114}Cd_{CdC O_3 - seawater}$), allowing for accurate reconstructions of the past seawater nutrient regime. The Cd isotope signature of the < 63 µm and < 20 µm (phytoplankton) fractions can display comparable values to those recorded in the modern surface ocean, and can be used to model the magnitude of Cd uptake and utilisation in the past ocean. Individual species of planktic and benthic foraminifera, which inhabit different depths of the water column, can provide a full surface to deep water column reconstruction of the Cd nutrient regime, while infaunal benthic foraminifera can be used to interrogate the Cd isotope systematics of sediment porewaters. Bulk sediment and the > 140 µm (zooplankton) fraction also retain important information relating to the overlying water column Cd isotope systematics and can serve as essential archives for palaeo-productivity reconstructions where the separation of individual components from the bulk sediment is not possible. This new Cd isotope palaeo-productivity toolkit can considerably aid reconstruction efforts and vastly improves the ability to quantify the role of phytoplankton in modulating carbon sequestration through transitions in Earth’s climate evolution.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Surface Reactivity Analysis of the Crude Oil–Brine–Limestone Interface for a Comprehensive Understanding of the Low-Salinity Waterflooding Mechanism
Low-salinity waterflooding (LSWF) has proven to improve oil recovery in carbonate formations through rock wettability alteration, although the underlying mechanism remains elusive. Multivalent ionic exchange and calcite dissolution have usually been investigated using geochemical analysis in secondary coreflooding. In this work, coreflooding, in tertiary mode, coupled with a surface reactivity analysis approach was employed to investigate the interplay of wettability alteration mechanisms such as mineral dissolution, electrostatic bond attraction, and the effect of pH at in situ conditions. Improved oil recovery (IOR) in tertiary mode observed by coreflooding in Indiana limestone rocks showed an ionic strength dependence, that is, reducing brine ionic strength resulted in an increase in oil recovery. Coreflooding results showed that the seawater and low-salinity brines deprived of Mg 2+ ions resulted in the lowest IOR in tertiary mode, indicating the significance of Mg 2+ on IOR in limestone rocks. Similar results were observed through the contact angle measurement showing the limestone rock wettability state dependence on ionic strength and the effect of Mg2+ ions. Surface reactivity analysis showed an increase in solution pH, Ca 2+ and Mg 2+ ions concentration in the effluent solution from the coreflooding in tertiary mode using low salinity brines (about 40 and 20% increase in the effluent composition for Ca 2+ and Mg 2+ , respectively). These changes in solution composition were used to calculate the in situ oil–brine and rock–brine zeta potential using a validated surface complexation model, showing the changes of zeta potential as brine is injected into limestone rocks. The results show that using seawater-like brine in tertiary mode resulted in no mineral dissolution or ionic exchange. However, improved oil recovery (IOR) using such seawater-like brine was due to wettability alteration caused by reduced electrostatic bond attraction associated with Mg 2+ ions [from 2.6 × 10 –13 (mol/m 2 ) 2 for formation water salinity to 1.5 × 10 –13 (mol/m 2 ) 2 for seawater salinity]. Using low-salinity brines in tertiary mode improved oil recovery by mineral dissolution, resulting in oil desorption and an increase in solution pH. Finally, the increase in solution pH also resulted in reduced electrostatic bond attraction which lead to rock wettability alteration using low-salinity brines.
04 OIL SHALES AND TAR SANDS↗
Solar-driven selective conversion of millimolar dissolved carbon to fuels with molecular flux generation
Abstract The direct utilization of dissolved inorganic carbon in seawater for CO 2 conversion promises chemical production on-demand and with zero carbon footprint. Photoelectrochemical (PEC) CO 2 reduction (CO 2 R) devices promise the sustainable conversion of dissolved carbon in seawater to carbon products using sunlight as the only energy input. However, the diffusion-dominant transport mechanism and the near-zero concentration of CO 2 (aq) (CO 2 dissolved in aqueous solution) in static seawater has made it extremely challenging to achieve high solar-to-fuel (STF) efficiency and high carbon-product selectivity. Here, where CO 2 (aq) as a reactant generated in situ by acidification of HCO 3 - flows continuously from BiVO 4 photoanodes to Si photocathodes, enabling a single-step conversion of dissolved carbon into products. Our PEC device significantly increases the CO selectivity from 3% to 21%, which approaches the 30% theoretical limit according to multi-physics modeling. Meanwhile, the Si/BiVO 4 PEC CO 2 R device achieved a STF efficiency of 0.71%. Such flow engineering achieves flow-dependent selectivity, rate, and stability in simulated seawater, thus promising practical solar fuel production at scale.
Liu, Bin↗