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Experimental Studies of Brines and Evaporites as Applied to Mars: Initial Results from 1998-1999 Runs

We are performing laboratory experiments to determine the concentrations and rates of dissolution of ions that could occur in closed, juvenile groundwater systems on Mars. Our approach is to incubate unaltered Mars-analog minerals in initially pure liquid water in contact with a Mars gas mixture for one year. At exponentially increasing time intervals, aliquots of the solutions at three different temperatures are extracted and analyzed using standard terrestrial laboratory geochemical techniques. Ultimately, our experiments will produce Mars analog brines which will be freeze dried to create evaporites. The physical and chemical properties of these evaporites will be compared with spacecraft remote sensing and in situ compositional and physical data. Additional information is contained in the original extended abstract.

Moore, J. M.↗

Preliminary Feasibility Testing of the BRIC Brine Water Recovery Concept

The Brine Residual In-Containment (BRIC) concept was developed as a new technology to recover water from spacecraft wastewater brines. Such capability is considered critical to closing the water loop and achieving a sustained human presence in space. The intention of the BRIC concept is to increase the robustness and efficiency of the dewatering process by performing drying inside the container used for the final disposal of the residual brine solid. Recent efforts in the development of BRIC have focused on preliminary feasibility testing using a laboratory- assembled pre-prototype unit. Observations of the drying behavior of actual brine solutions processed under BRIC-like conditions has been of particular interest. To date, experiments conducted with three types of analogue spacecraft wastewater brines have confirmed the basic premise behind the proposed application of in-place drying for these solutions. Specifically, the dried residual mass from these solutions have tended to exhibit characteristics of adhesion and flow that are expected to continue to challenge process stream management in spacecraft brine dewatering system designs. Yet, these same characteristics may favor the development of capillary- and surface-tension-based approaches envisioned as part of an ultimate microgravity-compatible BRIC design. In addition, preliminary feasibility testing of the BRIC pre-prototype confirmed that high rates of water recovery, up to 98% of the available brine water, may be possible while still removing the majority of the brine contaminants from the influent brine stream. These and other observations from testing are reported.

Callahan, Michael R.↗

Treatment of brackish water for fossil power plant cooling

In this study, we evaluated the technical, economic and environmental impacts of retrofitting brackish groundwater treatment systems at existing coal- and gas-fired electric generating units (EGUs) to reduce freshwater consumption in wet cooling towers. Based on fleet averages, retrofitting brackish water treatment systems decreases unit freshwater consumption by 94–100%, while increasing the cost of electricity generation by 8–10%. The unit capacity shortfalls are less than 1.1%. The resulting cost of freshwater consumption savings by brackish water treatment is US$1.7 m -3 and US$2.9 m -3 on average for coal- and gas-fired EGUs, respectively. However, these trade-offs are highly affected by the brine disposal method. The use of thermal zero liquid discharge for brine disposal can roughly double the average cost of freshwater consumption savings. The cost-effectiveness of brackish water treatment compared with dry cooling deployment depends on how concentrated brines are managed. In conclusion, the identified trade-offs and their dependence fill knowledge gaps to better inform water management.

20 FOSSIL-FUELED POWER PLANTS↗

Preliminary Feasibility Testing of the BRIC Brine Water Recovery Concept

The Brine Residual In-Containment (BRIC) concept is being developed as a new technology to recover water from spacecraft wastewater brines. Such capability is considered critical to closing the water loop and achieving a sustained human presence in space. The intention of the BRIC concept is to increase the robustness and efficiency of the dewatering process by performing drying inside the container used for the final disposal of the residual brine solid. Recent efforts in the development of BRIC have focused on preliminary feasibility testing using a laboratory- assembled pre-prototype unit. Observations of the drying behavior of actual brine solutions processed under BRIC-like conditions has been of particular interest. To date, experiments conducted with three types of analogue spacecraft wastewater brines have confirmed the basic premise behind the proposed application of in-place drying. Specifically, the dried residual mass from these solutions have tended to exhibit characteristics of adhesion and flow that are expected to continue to challenge process stream management designs typically used in spacecraft systems. Yet, these same characteristics may favor the development of capillary- and surface-tension-based approaches currently envisioned as part of an ultimate microgravity-compatible BRIC design. In addition, preliminary feasibility testing of the BRIC pre-prototype confirmed that high rates of water recovery, up to 98% of the available brine water, may be possible while still removing the majority of the brine contaminants from the influent brine stream. These and other early observations from testing are reported.

Callahan, Michael R.↗

Evaporation Rates of Brine on Mars

While Mars is now largely a dry and barren place, recent data have indicated that water has flowed at specific locations within the last approx. 10(exp 6) y. This had led to a resurgence of interest in theoretical and experimental work aimed at understanding the behavior of water on Mars. There are several means whereby the stability of liquid water on Mars could be increased, one being the presence solutes that would depress the freezing point. Salt water on Earth is about 0.5M NaCl, but laboratory experiments suggest that martian salt water is quite different. We recently began a program of laboratory measurements of the stability of liquid water, ice and ice-dust mixtures under martian conditions and here report measurements of the evaporation rate of 0.25M brine.

Sears, D. W. G.↗

Global assessment of the carbon–water tradeoff of dry cooling for thermal power generation

Water scarcity and climate change are dual challenges that could potentially threaten energy security. Yet, integrated water–carbon management frameworks coupling diverse water- and carbon-mitigation technologies at high spatial heterogeneity are largely underdeveloped. Here we build a global unit-level framework to investigate the CO 2 emission and energy penalty due to the deployment of dry cooling—a critical water mitigation strategy—together with alternative water sourcing and carbon capture and storage under climate scenarios. We find that CO 2 emission and energy penalty for dry cooling units are location and climate specific (for example, 1–15% of power output), often demonstrating notably faster efficiency losses than rising temperature, especially under the high climate change scenario. Despite energy and CO 2 penalties associated with alternative water treatment and carbon capture and storage utilization, increasing wastewater and brine water accessibility provide potential alternatives to dry cooling for water scarcity alleviation, whereas CO 2 storage can help to mitigate dry cooling-associated CO 2 emission tradeoffs when alternative water supply is insufficient. By demonstrating an integrative planning framework, our study highlights the importance of integrated power sector planning under interconnected dual water–carbon challenges.

42 ENGINEERING↗

A Technical-Economic Assessment of Brackish Water Treatment for Fossil Power Plant Cooling with Reduced Environmental Impact

The power sector accounts for approximately 40% of freshwater use in the U.S. Reusing non-traditional water resources is critical for alleviating water stress in the western United States. The purpose of this study is to conduct a techno-economic system analysis to evaluate the potential of brackish water treatment for wet cooling towers at existing thermo-electric generating units (EGUs). It aims to address current knowledge gaps in support of non-traditional water resources planning and the electric power industry's water decision- and policy making. An engineering-economic model was developed and combined with DuPont's water application value engine (WAVE) v1.82 to evaluate the viability of retrofitting reverse osmosis-based brackish water treatment systems to individual existing EGUs and then aggregating the unit-level results to the fleet level. In the base case, brackish water treatment can reduce freshwater consumption of electric generation units by 94–100% while increasing the cost of electric generation by approximately 10% and have marginal impacts on the units' parasitic loads. When zero liquid discharge systems are applied to brackish water brine treatment, the cost of electric generation and freshwater consumption savings and energy penalty to the power plant significantly increase. These costs are even higher than dry cooling deployment in lieu of wet cooling towers. The choice of freshwater savings between brackish water desalination and dry cooling deployment depends greatly on how the concentrated brines are managed. Multiple factors must be considered when supporting decision-making in water management and planning in power sectors, which include non-traditional water quantity and quality as well as trade-offs among technical performance, economics, and environmental impacts.

Wu, Zitao↗

Gully Formation at the Haughton Impact Structure (Arctic Canada) Through the Melting of Snow and Ground Ice, with Implications for Gully Formation on Mars

The formation of gullies on Mars has been the topic of active debate and scientific study since their first discovery by Malin and Edgett in 2000. Several mechanisms have been proposed to account for gully formation on Mars, from “dry” mass movement processes, release of water or brine from subsurface aquifers, and the melting of near-surface ground ice or snowpacks. In their global documentation of martian gullies, report that gullies are confined to ~27–83°S and ~28–72°N latitudes and span all longitudes. Gullies on Mars have been documented on impact crater walls and central uplifts, isolated massifs, and on canyon walls, with crater walls being the most common situation. In order to better understand gully formation on Mars, we have been conducting field studies in the Canadian High Arctic over the past several summers, most recently in summer 2018 and 2019 under the auspices of the Canadian Space Agency-funded Icy Mars Analogue Program. It is notable that the majority of previous studies in the Arctic and Antarctica, including our recent work on Devon Island, have focused on gullies formed on slopes generated by regular endogenic geological processes and in “regular” bedrock. How-ever, as noted above, meteorite impact craters are the most dominant setting for gullies on Mars. Impact craters provide an environment with diverse lithologies – including impact-generated and impact-modified rocks – and slope angle, and thus greatly variable hill slope processes could occur within a localized area. Here, we investigate the formation of gullies within the Haughton impact structure and compare them to gullies formed in unimpacted target rock in the nearby Thomas Lee Inlet

Osinski, G. R.↗

Chemical and isotopic evolution of flowback fluids from the Utica Gas Shale Play, Eastern Ohio USA

For this work, hydraulic fracturing flowback fluids were collected from two Utica/Point Pleasant well pads in eastern Ohio. One site was in the wet gas zone (UPPW), while the site ~50 km south consisted of four wells on the same pad in the dry gas zone (UPPS). Samples of input fluids also were collected before and during hydraulic fracturing. Flowback fluids are Na-Ca-Cl brines with total dissolved salt (TDS) concentrations that increase over several months from ~100 to 200 g/L. The slightly higher TDS of the dry gas fluids are in part due to recycled flowback used as input fluids, and in part due to lower volume of water used in hydraulic fracturing. Concentrations of most major ions (Ca 2+ , Mg 2+ , Na + , Sr2 + , Fe, Mn, Cl – , Br – ) are similar for the five wells sampled, although small but systematic changes occur in the major element ratios over time. Most notably, an increase in the Sr/Cl ratio corresponds to an increase in the 87 Sr/ 86 Sr ratio in the fluids, suggesting interactions with a more radiogenic Sr source in the subsurface. Dissolved Ba concentrations and Ra activities were different between the two sites, reflecting a high SO 4 2– fluid used at the UPPW site, and water-rock reactions occurring during hydraulic fracturing at the UPPS site. Water oxygen (δ 18 O) and hydrogen (δD) isotopes for input fluids used in the UPPW4 well and fresh water used for the UPPS wells fall on the Global Meteoric waterline (GMWL). Flowback fluids from both sites are relatively enriched in δ 18 O and δD compared to the input, but do not appear to follow a simple mixing trend, suggesting reaction and isotopic exchange with carbonates and fractionation due to imbibition in the rock. Cl isotopes, δ 37 Cl in the FP fluids varied from ~ –0.43 to +0.13‰, the largest variation was observed in the earlier stages of flowback, while in the later stages δ 37 Cl exhibited a small but systematic increase over time, suggesting diffusion control of isotopic composition. Some of the trace species measured (dissolved Fe, Mn, thiosulfate and organic acids) do not follow the same trends as the major ions, suggesting contributions from input fluids, or microbially mediated reactions are exerting control on their concentrations. Input water chemistry exerts an important control on the Sr and Ba concentrations in flowback water. High SO 4 2– in the input fluids used for hydraulically fracturing the wet gas well leads to precipitation of barite-celestite in flowback fluids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Martian Brines in Ancient Salt Lake Beds – A High Priority Target for Mars Sample Return

Mars hosts over 600 chloride deposits as identified from orbital imagery [1-3], including deposits in settings resembling dry, evaporite lacustrine bedforms on Earth. A Mars sample return mission to one of these salt lake beds has a strong potential to directly sample present-day brines originating from ancient martian surface fluids, allowing direct laboratory investigation into fluids, atmosphere, and either potential biology or prebiological conditions on the martian surface at the Noachian through the Hesperian epochs. These sites are extraordinarily well suited for sample return missions because they are favorable for landing and for drill-based sampling, and preserve samples of parent water bodies, including dissolved atmosphere and potential well-preserved biological remains. Such a mission would provide a foundational set of reference samples for understanding Mars’ physiochemical and pre-/biological history, likely to be investigated in depth for generations to come.

brine↗

DECOVALEX-2023: Task E Final Report

This is the Task E final report for DECOVALEX-2023. Task E is focused on understanding thermal, two-phase hydrological, and mechanical (TH2M) processes, especially related to predicting brine migration in the excavation damaged zone around a heated excavation in salt. Salt is attractive as a disposal medium for radioactive waste because it is self-healing and is essentially impermeable and essentially non-porous in the far field (away from excavations). Investigation of the short-term (days to years) near-field (centimeters to tens of meters) behavior of salt is important for radioactive waste disposal because this early period strongly controls the amount of brine in a salt repository. Brine leads to corrosion of waste forms and waste packages, and possible dissolution of radionuclides with brine transport being a potential transport vector to the accessible environment. The main test case used in Task E is the ongoing Brine Availability Test in Salt (BATS) heater test located underground at the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico, USA. The Task was divided into a series of Steps. Step 0 was an introduction to processes in salt, that included matching historical unheated brine inflow data from boreholes at WIPP and matching temperature observations during BATS heater test 1a. Step 1 included validation of models against a thermo-poroelastic analytical solution relevant to heated boreholes in salt, and two-phase flow around an excavation in salt. Step 2 required all the individual components covered in steps 0 and 1 to come together to match observed brine inflow behavior during the BATS 1a heater test. There were a range of approaches from the teams, from mechanistic to prescriptive. Given the uncertainties in the problem, some teams used one- or two-dimensional models of the processes, while other teams included more geometrical complexity in three-dimensional models. The key learning points from Task E have been: • Heat conduction through salt typically requires non-linear thermal conductivity (as a function of temperature), but most models do a good job matching observations, given appropriate adjustments to the applied power and some thermocouple locations. • Thermal pressurization requires coupled thermal-hydrological-mechanical (THM) responses that consider the thermal expansion of the fluid and solid phases. • Initialization of two-phase flow models around a borehole or excavation in salt are more realistically represented as “wetting up”, rather than “drying down” (i.e., the initial state after excavation is mostly dry, rather than mostly wet). • The BATS 1a heater test includes a significant release of brine after the end of heating, which requires a large increase in permeability to recreate. Task E has been a great learning experience for all the teams involved, and feedback from the modeling teams has led to changes in the design of follow-on BATS experiments, which are now ongoing underground at WIPP. There was a balance throughout the task between freedom to model phenomena how each team saw fit, and prescriptiveness in problem design to bring the modeling teams closer together to allow attribution of smaller differences between models to different modeling choices. The modeling approaches seem to go through two phases: an early phase of discovery or testing, and a later phase of refinement and improvement. In future modeling efforts, different field data could be used (e.g., BATS 2) and more time should be included in the processes for teams to make multiple model refinement or even significant changes to their conceptual model or setup, based on lessons learned from the modeling exercise.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Geologic Settings of Martian Gullies: Implications for Their Origins

Martian gullies are found on steep slopes of all origins, on all sorts of terrains of all ages, scattered across nearly all of Mars. Gullies are observed on all manner of substrates (layered, massive, shattered, rubble), with or without nearby mantling deposits. Gullies are most common in the southern midlatitudes but also occur in the northern hemisphere, in near polar terrain, on equatorial volcanoes, and on northern plains. Most gullies in the southern hemisphere are on south-facing slopes, but they occur on slopes of all orientations. Gullies are among the youngest features on Mars but locally are overlain by eolian deposits and cut by faults. Old or eroded gullies are rare, and those found have been partially stripped from slopes, leaving no rock debris behind. Most gully deposits contain no detectable rocks. These data are inconsistent with published hypotheses of gully formation, including seeps and breakouts of water or brine, hydrothermal activity, cryovolcanism, and breakouts from liquid carbon dioxide. The data are consistent with gullies being dry flows of eolian material (dust and silt), comparable to climax snow avalanches on Earth. Eolian sedimentation should be correlated little with underlying geology: cause of slope, age of terrain, type of terrain, or the nature of the rocks. Eolian sedimentation should be correlated with wind deceleration (which will cause suspended sediment to drop), and areas with common gullies are those with strong wind deceleration (predicted by global circulation model). In such areas, sediment will be deposited preferentially in the lee of obstacles; for the gully-rich areas of the southern midlatitudes, winds blow from the NNW, so that sediment is deposited on SSE-facing slopes (i.e., poleward). These predictions are in accord with observations.

Treiman, Allan H.↗

2023 Billion-Ton Report: An Assessment of U.S. Renewable Carbon Resources - Microalgae

Microalgae is a unique biomass resource that does not need to compete for land and water with other biomass feedstocks because it can be cultivated on low-quality unencumbered land using noncompetitive water types including saline and wastewater. It is included as a complementary resource alongside other biomass feedstocks reported in this study, albeit at higher biomass production costs reflective of more capital-intensive farming operations than typical for terrestrial biomass. Higher biomass costs can be offset by the potential to produce value-added coproducts unique to compositional constituents of microalgae. Relative to the 2016 Billion-Ton Report, this chapter reflects the latest analysis from the 2022 Algae Harmonization Update, which uses the latest parameterized and high-performing saline algal strain, second-generation carbon capture of point-source waste CO 2 , and high-pressure pipeline transport resolved to specific point-source types, saline water sourcing up to 40,000 mg/L total dissolved solids for source and makeup water salinity, blowdown water treatment and recycle, and brine disposal handling. National-scale algal biomass availability potential was calculated at 152 million tons/yr ash-free dry weight (AFDW) (191 million tons/yr dry weight) at an average biomass

09 BIOMASS FUELS↗

Chapter 7.1: Microalgae

Microalgae is a unique biomass resource that does not need to compete for land and water with other biomass feedstocks because it can be cultivated on low-quality unencumbered land using noncompetitive water types including saline and wastewater. It is included as a complementary resource alongside other biomass feedstocks reported in this study, albeit at higher biomass production costs reflective of more capital-intensive farming operations than typical for terrestrial biomass. Higher biomass costs can be offset by the potential to produce value-added coproducts unique to compositional constituents of microalgae. Relative to BT16, this chapter reflects the latest analysis from the 2022 Algae Harmonization Update, which uses the latest parameterized and high-performing saline algal strain, second-generation carbon capture of point-source waste CO2 and high-pressure pipeline transport resolved to specific point-source types, saline water sourcing up to 40,000 mg/L total dissolved solids for source and makeup water salinity, blowdown water treatment and recycle, and brine disposal handling. National-scale algal biomass availability potential was calculated at 152 million tons/yr ash-free dry weight (AFDW) (191 million tons/yr dry weight) at an average biomass productivity of 26.2 g/m2 -day AFDW (about 50 tons/acre/yr dry weight).1 The algal biomass was cultivated on 3.9 million acres of multi-criteria screened and potentially available land for CONUS and fixed 268 million tons of waste CO2 based on biomass uptake. The algae biomass can be produced at an average MBSP of $674/ton AFDW ($536/ton dry weight) in 2020 dollars,2 corresponding to a total energy potential of 3.3 quads/yr at an average MBSP of $31.2/MMBtu (higher-heating-value [HHV] basis).

algae↗

Zero Liquid Discharge and Water Reuse in Recirculating Cooling Towers at Power Facilities: Review and Case Study Analysis

Zero liquid discharge (ZLD) systems installed at power facilities with the primary purpose of meeting water discharge regulations have the added benefit of providing high quality effluent that can be reused in the facility. This paper provides a review of water use in power sector recirculating cooling towers and a baseline assessment of on-site water reuse at natural gas combined cycle (NGCC) power facilities. Two NGCC facilities with reverse-osmosis (RO) or brine-concentrator processes followed by evaporation ponds were selected as case studies; data from these facilities were used to quantify the water, energy, and cost implications of implementing conventional and emerging ZLD technologies. At one case study facility, model results show that implementation of ZLD would reduce water withdrawals by 18%, which is less than savings associated with implementation of dry cooling but comparable to current efforts to reduce water withdrawals by increasing cycles of concentration. Implementation of ZLD using high-recovery RO resulted in a doubling of the levelized cost of water (LCOW). LCOW increased more when a brine concentrator was used. For both case studies, the ZLD system using high-recovery RO required less than 0.1% of a facilitiy's annual electricity generation and the ZLD system using a brine concentrator process required less than 0.8%. Additionally, increasing the evaporation pond area to minimize required ZLD system recovery rates and reduce system electricity costs does not reduce the LCOW. Instead, the LCOW increases because less water is recovered and more water is lost to evaporation. Furthermore, if water availability decreases or water competition/cost increases, facilities may be incentivized to maximize water recovery from ZLD systems.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Passive microwave remote sensing of thin sea ice using principal component analysis

The possibility of developing a satellite-based sea-ice-concentration algorithm which solves for the presence of thinner ice is explored on the basis of time sequences of surface-based measurements of passive MW emission from growing saline ice reported by Wensnahan et al. (1993). It is shown that two classes of thinner ice can be distinguished from mixtures of open water, first-year ice, and multiyear ice. Newly formed ice appears to be optically thick at 37 and 90 GHz and has a relatively dry surface. The thin ice spectrum occurs when the ice is greater than 4 cm thick and appears to result from the accumulation of brine at the ice surface. Thin ice has a relatively stable spectrum characterized by high brightness temperatures, a near-zero spectral gradient at vertical polarization, and a large difference between vertical and horizontal polarizations. It is concluded that thin ice can be detected using satellite data.

Wensnahan, Mark↗

Soil developments in polar deserts: Implications for exobiology and future Mars missions

Chemical alterations, weathering, and diagenesis of soil profiles from the dry valleys of Antarctica were studied as analogs of regolith development for the Martian regolith. Chemical weathering processes play an important part in soil development within the dry valleys of Antarctica. A suite of core samples were studied which were taken within the valley floors in addition to samples taken in the vicinity of evaporite and brine ponds. Analysis of water soluable cations and anions from core samples were performed along with petrographic analysis of selected samples. It was shown that ionic transport processes operate primarily above the permafrost zone. Abundances of the water soluable ions reflect the nature of secondary minerals produced by evaporation and weathering. Chloride, calcium, and sodium abundances for soils from the cores within the North and South Forks of Wright Valley, reflect the secondary mineralogy of the soil columns. Calculations for Na, Ca, and Cl abundances reflect the appearance of halite and antarcticite. In areas where excess Ca is present, X-ray diffraction studies show the presence of gypsum. It is well known that the Martian surface conditions may be favorable for chemical weathering. Primary silicates would be expected to be reactive with any ground water. It seems likely that Martian subsurface water is available to assist in the weathering of the primary minerals. Such weathering could result in the formation of clays, sulfates, carbonates, hydrates, halides, and zeolites. The dry valley cores have shown that they maybe excellent analogs to weathering processes on the near-surface of Mars. Since movement of water within the near-surface region clearly results in chemical weathering, leaching, and salt formation in the dry valleys, similar processes are probably operating within the Martian regolith.

Gibson, Everett K., Jr.↗