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At least 631 records · Page 35

Comments on Fusion Energy and Desalination

A fusion energy reactor is a potential source of electricity and heat for desalination of water. This note discusses the motivation, environmental issues, and a simplified schematic of such a desalination plant. A desalination facility producing ~ 100 million m{sup 3}/day of potable water from seawater is well matched to a compact reactor operating in the hundred MW range.

54 ENVIRONMENTAL SCIENCES↗

Thorium(IV) Recovery from Water and Sea Water Using Surface Modified Nanocellulose/Nanobentonite Composite: Process Design

Thorium(Th) contamination in the ground water an emerging environmental issue and Th recovery from sea water and nuclear wastewater is of high significance, as it is a major player in the energy sector. For the adsorption and recovery of Th, polymer grafted bio materials are reported as most efficient materials. P(IA/MAA)-g-NC/NB was prepared and all the steps in the synthetic routes were monitored using FTIR, SEM–EDS, and XRD, TG. Efficiency in removal of Th(IV) by P(IA/MAA)-g-NC/NB was tested by batch adsorption technique. The pH dependent Th(IV) adsorption process, was optimized at 4.5 and adsorption equilibrium was achieved within 120 min. Experimental kinetic data correlates well with pseudo-second-order equation, indicates adsorption was chemical process via ion exchange followed by complexation reaction, also could explain the film diffusion process of adsorption. Sips isotherm proved to best fit for the adsorption of Th(IV) onto P(IA/MAA)-g-NC/NB with maximum adsorption capacity of 95.19 mg/g. Thermodynamic studies revealed the endothermic nature, feasibility and spontaneity of the adsorption process. ΔHx and ΔSx were decreased to a small extent from −5.567 to −3.439 kJ/mol and increased from 11.18 to 18.39 J/mol, respectively, with increase in surface loading from 50 to 70 mg/g, indicating that the surface of the onto P(IA/MAA)-g-NC/NB is having energetically heterogeneous surface and there may be some lateral interactions between the adsorbed Th(IV) ions Repeated adsorption–desorption study over six cycles, adsorption percentage decreases from 99.0 to 94.6 %, proved the efficiency of P(IA/MAA)-g-NC/NB as an effective adsorbent for the removal and recovery of Th(IV) from aqueous solutions. Complete removal of Th(IV) ions from seawater containing 10 mg/L with a dose of 0.25 g/L P(IA/MAA)-g-NC/NB achieved. Batch adsorption system as double stage reactor designed from the adsorption isotherm data of Th(IV) by constructing operational lines. From these could be concluded that P(IA/MAA)-g-NC/NB is a promising candidate for the effective removal and removal of Th(IV) from industrial effluents phase and sea water. The maximum adsorption capacity Qs for Ceralite IRC-50 calculated which was found to be 179.67 mg/g which are considerably lower than those for P(IA/MAA)-g-NC/NB.

54 ENVIRONMENTAL SCIENCES↗

Influence of Rust Permeability on Corrosion of E690 Steel in Industrial and Non-industrial Marine Splash Zones

The corrosion behaviour of E690 steel in industrial and non-industrial marine splash environments was studied by environmental testing, morphology analysis, electrochemical measurements, and scanning Kelvin probe microscopy. Chloride and sulphide anions were found to diffuse across the rust layer following the evaporation of seawater splashed on the steel’s surface. The cation-selective permeability of the rust layer resulted in an anion concentration gradient across the rust layer, which was more significant in the presence of sulphur dioxide. In addition, sulphur dioxide enhanced the formation of α-FeOOH, which led to the formation of distinct anode and cathode areas at the rust/steel interface.

36 MATERIALS SCIENCE↗

Electrochemical Behavior of Mg-Al-Zn-Ga Alloy as Anode Materials in 3.5 wt.% NaCl Solution

The microstructure and electrochemical behaviors of Mg-Al-Zn and Mg-Al-Zn-Ga alloys as anode materials were investigated by morphology observation, composition analysis, phase identification, and electrochemical tests. The experimental results suggest that Ga alloying can refine the grains of the Mg-Al-Zn alloy by promoting second-phase segregation, which comprises Mg{sub 17}Al{sub 12} and GaMg{sub 2}. The comparison of discharge tests indicates that adding Ga to the Mg-Al-Zn alloy can negatively shift the discharge potential, provide a high current density, promote the formation of tiny and thin products, and improve the utilization efficiency. Meanwhile, the addition of Ga can increase the corrosion resistance of Mg-Al-Zn alloy because the Ga alloying promotes the segregation of the intermetallic phases in the Mg matrix. The intermetallic phases disperse in isolate states in the Mg matrix, resulting in their falling off from the substrate once their adjacent Mg is exhausted and subsequently ceasing the micro-galvanic corrosion. The Mg-Al-Zn-Ga alloy with higher corrosion resistance performs better discharge activity than that of Mg-Al-Zn alloy in 3.5 wt.% NaCl solution, implying that the Mg-Al-Zn-Ga alloy is a promising anode material for seawater-activated battery.

36 MATERIALS SCIENCE↗

Calcium and actin in the saga of awakening oocytes

The interaction of the spermatozoon with the egg at fertilization remains one of the most fascinating mysteries of life. Much of our scientific knowledge on fertilization comes from studies on sea urchin and starfish, which provide plenty of gametes. Large and transparent, these eggs have served as excellent model systems for studying egg activation and embryo development in seawater, a plain natural medium. Starfish oocytes allow the study of the cortical, cytoplasmic and nuclear changes during the meiotic maturation process, which can also be triggered in vitro by hormonal stimulation. These morphological and biochemical changes ensure successful fertilization of the eggs at the first metaphase. On the other hand, sea urchin eggs are fertilized after the completion of meiosis, and are particularly suitable for the study of sperm–egg interaction, early events of egg activation, and embryonic development, as a large number of mature eggs can be fertilized synchronously. Starfish and sea urchin eggs undergo abrupt changes in the cytoskeleton and ion fluxes in response to the fertilizing spermatozoon. The plasma membrane and cortex of an egg thus represent “excitable media” that quickly respond to the stimulus with the Ca{sup 2+} swings and structural changes. In this article, we review some of the key findings on the rapid dynamic rearrangements of the actin cytoskeleton in the oocyte/egg cortex upon hormonal or sperm stimulation and their roles in the modulation of the Ca{sup 2+} signals and in the control of monospermic fertilization. - Highlights: • Besides microtubules, microfilaments may anchor the nucleus to oocyte surface. • The cortical Ca{sup 2+} flash and wave at fertilization mirror electrical membrane change. • Artificial egg activation lacks microvilli extension in the perivitelline space. • Calcium is necessary but not sufficient for cortical granules exocytosis. • Actin cytoskeleton modulates Ca{sup 2+} release at oocyte maturation and fertilization.

60 APPLIED LIFE SCIENCES↗

Tilapia and human CLIC2 structures are highly conserved

Chloride intracellular channels (CLICs) exist in soluble and membrane bound forms. We have determined the crystal structure of soluble Clic2 from the euryhaline teleost fish Oreochromis mossambicus. Structural comparison of tilapia and human CLIC2 with other CLICs shows that these proteins are highly conserved. We have also compared the expression levels of clic2 in selected osmoregulatory organs of tilapia, acclimated to freshwater, seawater and hypersaline water. Structural conservation of vertebrate CLICs implies that they might play conserved roles. Also, tissue-specific responsiveness of clic2 suggests that it might be involved in iono-osmoregulation under extreme conditions in tilapia.

60 APPLIED LIFE SCIENCES↗

Exergy and thermo-economic analysis for MED-TVC desalination systems

An exergo-economic model is used to simulate four different feed configurations of multi-effect desalination with thermal vapor compressor (MED-TVC) system. The feed configurations considered are backward feed (BF), forward feed (FF), parallel feed (PF) and parallel cross feed (PCF). The model results indicate that the PCF configuration has better performance characteristics than the other feed configurations regarding gain output ratio (GOR) and specific heat consumption (SHC), but it has the highest specific cooling seawater flow rate ($sM_{cw}$). On the other hand, the BF configuration has the lowest $sM_{cw}$. The highest exergy destruction (58%) occurs within the TVC unit and this can be reduced by lowering the supplied motive steam pressure. The exergy destructions in the condenser and pumps account for 4 to 6.7% of the total exergy destruction for all feed configurations. The MED-TVC under consideration has a second law efficiency between 3.9 and 4.6%. Lowering the motive steam pressure for the PCF from 2300 to 300 kPa results in a 7.5% reduction in GOR and a 25.4% increase in the second law efficiency. Reducing the exergy destruction in the TVC unit is cost-effective for the entire system even with the increase in capital investment costs. The specific exergy cost flow method is used to estimate the total water price for BF, FF, PF and PCF as 2.12, 2.30, 2.16 and 2.09 $\$/m^3$, respectively.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Transient and thermo-economic analysis of MED-MVC desalination system

An exergo-economic model is used to assess the performance of a multi-effect desalination plant integrated to a mechanical vapor compressor unit (MED-MVC) with a water production capacity of 1500 $m^3$/day. The results show that the second law efficiency ($\eta_{II}$) 2.8%. The MVC and evaporator units are responsible for about 39 and 52% of the total exergy destruction, respectively. The total water price (TWP) is 1.70 $\$/m^3$ when calculated using a simple conventional economic model and 1.63 $\$/m^3$ when calculated using an exergy-based cost model. Increasing the number of effects from 1 to 6 results in a 39% reduction in the specific power consumption (SPC), a 70% increase in $\eta_{II}$ and a 24% decrease in TWP. A dynamic model is developed to investigate the effect of fluctuations of compressor work ($\dot{W}_c$) and inlet seawater temperature ($T_{sw}$) on the plant behavior and performance. The dynamic model results show that the disturbance in $\dot{W}$ has a significant effect on the plant transient behavior and may cause the plant to cease operation while a disturbance in $T_{sw}$ has only a moderate impact. Increasing $T_{sw}$ above a certain value of the steady-state condition without proper control on the plant response could lead to evaporator dry out. In term of performance, a reduction in $\dot{W}_c$ causes a decrease in the plant production capacity and SPC, while it increases the plant performance ratio (PR). On the other hand, a reduction in the inlet $T_{sw}$ causes a reduction in the plant production capacity and PR and an increase in SPC for the same compressor work. Furthermore, a comparison between a MED-MVC system and a MED integrated to a thermal vapor compressor system (MED-TVC) reveals that the latter system is rather sensitive to the reduction in $T_{sw}$ due to the presence of the condenser unit in the MED-TVC. The response of the MED-MVC system is slower than the MED-TVC which is due to the high thermal capacity of the preheaters for the feed in the MED-MVC.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Evaluation of the use of common sculpin (Myoxocephalus scorpius) organ histology as bioindicator for element exposure in the fjord of the mining area Maarmorilik, West Greenland

The former Black Angel lead–zinc mine in Maarmorilik, West Greenland, is a historic example of how mining activity may result in a significant impact on the surrounding fjord system in terms of elevated concentrations of especially lead (Pb) and zinc (Zn) in seawater, sediments and surrounding biota. In order to shed light on the present contamination and possible effects in the fjord we initiated a range of studies including a pilot study on gill and liver morphology of common sculpins (Myoxocephalus scorpius) around Maarmorilik. Sculpins were caught and sampled at five different stations known to represent a gradient of Pb concentrations. Fish livers from all specimens were analyzed for relevant elements in the area: Fe, Zn, As, Cu, Se, Cd, Pb, Ag, Hg, Co and Ni. Lead, As and Hg showed significant differences among the five stations. For 20% of the sculpins, Hg concentrations were in the range of lowest observed effect dose (LOED) of 0.1–0.5 μg/g ww for toxic threshold on reproduction and subclinical endpoints. Likewise LOEDs for tissue lesions, LOEDs for biochemistry, growth, survival and reproduction were exceeded for Cd (0.42–1.8 μg/g ww) and for As (11.6 μg/g ww) in 28% and 85% of the sculpins, respectively. Similar to this, the no observed effect dose (NOED) for biochemistry was exceeded for Pb (0.32 μg/g ww) and for growth, mortality and reproduction for Zn (60–68 μg/g ww) in 33% and 24% of the sculpins, respectively. For all sculpins, females were significantly larger than males and for five of the elements (Fe, Co, Ni, Cu, Se) females had higher concentrations. The chronic lesions observed in liver (mononuclear cell infiltrates, necrosis, vacuolar hepatocytes, portal fibrosis, bile duct hyperplasia, active melanomacrophage centers) and gills (fusion and edema of secondary lamellae, laminar telangiectasis, mononuclear cell infiltrates, blebs) were similar to those in the literature studies for both wild and laboratory exposed sculpins and other fish species carrying similar or higher Hg concentrations. Ignoring sex and size, specimens with hepatic cell infiltrates had the highest concentrations of most elements, a relation that was also found for gill telangiectasis and Hg (all p<0.05). When controlling for sex and size, the prevalence of vacuolar hepatocytes and endoparasites was significantly highest at the three most contaminated stations and similar differences were found for liver necrosis. We suggest that beside exposure to mining-related elements, other environmental factors, such as parasites, might be co-factors in the development of the observed liver and gill lesions. Therefore, sculpin liver and gill pathology are likely to be suitable health indicators when biomonitoring gradients of mining and other element related activity effects; while a larger study is required to fully evaluate the relationships. - Highlights: • Black Angel Pb–Zn mine in West Greenland has led to significant metal pollution. • Gill and liver morphology of common sculpins was evaluated as bioindicators. • Significant pathologies were found and were related to metal concentrations. • Sculpin pathology may be suitable health indicators for mining activity effects. • These should be enrolled in EIAs of raw material industrialization in the Arctic.

54 ENVIRONMENTAL SCIENCES↗

Toxic elements and speciation in seafood samples from different contaminated sites in Europe

The presence of cadmium (Cd), lead (Pb), mercury (THg), methylmercury (MeHg), arsenic (TAs), inorganic arsenic (iAs), cobalt (Co), copper (Cu), zinc (Zn), nickel (Ni), chromium (Cr) and iron (Fe) was investigated in seafood collected from European marine ecosystems subjected to strong anthropogenic pressure, i.e. hotspot areas. Different species (Mytilus galloprovincialis, n=50; Chamelea gallina, n=50; Liza aurata, n=25; Platichthys flesus, n=25; Laminaria digitata, n=15; and Saccharina latissima, n=15) sampled in Tagus estuary, Po delta, Ebro delta, western Scheldt, and in the vicinities of a fish farm area (Solund, Norway), between September and December 2013, were selected to assess metal contamination and potential risks to seafood consumers, as well as to determine the suitability of ecologically distinct organisms as bioindicators in environmental monitoring studies. Species exhibited different elemental profiles, likely as a result of their ecological strategies, metabolism and levels in the environment (i.e. seawater and sediments). Higher levels of Cd (0.15–0.94 mg kg{sup −1}), Pb (0.37−0.89 mg kg{sup −1}), Co (0.48–1.1 mg kg{sup −1}), Cu (4.8–8.4 mg kg{sup −1}), Zn (75–153 mg kg{sup −1}), Cr (1.0–4.5 mg kg{sup −1}) and Fe (283–930 mg kg{sup −1}) were detected in bivalve species, particularly in M. galloprovincialis from Ebro and Po deltas, whereas the highest content of Hg was found in P. flesus (0.86 mg kg{sup −1}). In fish species, most Hg was organic (MeHg; from 69 to 79%), whereas lower proportions of MeHg were encountered in bivalve species (between 20 and 43%). The highest levels of As were found in macroalgae species L. digitata and S. latissima (41 mg kg{sup −1} and 43 mg kg{sup −1}, respectively), with iAs accounting almost 50% of the total As content in L. digitata but not with S. latissima nor in the remaining seafood samples. This work highlights that the selection of the most appropriate bioindicator species is a fundamental step in environmental monitoring of each contaminant, especially in coastal areas. Furthermore, data clearly shows that the current risk assessment and legislation solely based on total As or Hg data is limiting, as elemental speciation greatly varies according to seafood species, thus playing a key role in human exposure assessment via food.

54 ENVIRONMENTAL SCIENCES↗

Combined effects of warming and acidification on accumulation and elimination dynamics of paralytic shellfish toxins in mussels Mytilus galloprovincialis

Highlights: • Impact of warming and acidification on the accumulation/elimination dynamics of HAB-toxins in shellfish. • High toxicity levels were found under current conditions. • Climate change scenarios may lead to lower but prolonged PST contamination. Harmful algal blooms (HAB) have been increasing in frequency and intensity most likely due to changes on global conditions, which constitute a significant threat to wild shellfish and its commercial farming. This study evaluated the impact of increasing seawater temperature and acidification on the accumulation/elimination dynamics of HAB-toxins in shellfish. Mytilus galloprovincialis were acclimated to four environmental conditions simulating different climate change scenarios: i) current conditions, ii) warming, iii) acidification and iv) interaction of warming with acidification. Once acclimated, mussels were exposed to the paralytic shellfish toxins (PSTs) producing dinoflagellate Gymnodinium catenatum for 5 days and to non-toxic diet during the subsequent 10 days. High toxicity levels (1493 µg STX eq. kg{sup −1}) exceeding the safety limits were determined under current conditions at the end of the uptake period. Significantly lower PSP toxicity levels were registered for warming- and acidification-acclimated mussels (661 and 761 µg STX eq. kg{sup −1}). The combined effect of both warming and acidification resulted in PSP toxicity values slightly higher (856 μg STX eq. kg{sup −1}). A rapid decrease of toxicity was observed in mussels at the current conditions after shifting to a non-toxic diet, which was not noticed under the predicted climate change scenarios. Variability of each PST analogue, measured throughout the experiment, highlighted different mechanisms are associated with changes of each environmental factor, although both resulting in lower toxicity. Warming-acclimated mussels showed lower accumulation/elimination rates, while acidification-acclimated mussels showed higher capability to accumulate toxins, but also a higher elimination rate preventing high toxicity levels. As different mechanisms are triggered by warming and acidification, their combined effect not leads to a synergism of their individual effects. The present work is the first assessing the combined effect of climate change drivers on accumulation/elimination of PSTs, in mussels, indicating that warming and acidification may lead to lower toxicity values but longer toxic episodes. PSTs are responsible for the food poisoning syndrome, paralytic shellfish poisoning (PSP) in humans. This study can be considered as the first step to build models for predicting shellfish toxicity under climate change scenarios.

54 ENVIRONMENTAL SCIENCES↗

Application of an in-situ soil sampler for assessing subsurface biogeochemical dynamics in a diesel-contaminated coastal site during soil flushing operations

Subsurface biogeochemistry and contaminant dynamics during the remediation of diesel-contamination by in-situ soil flushing were investigated at a site located in a coastal region. An in-situ sampler containing diesel-contaminated soils separated into two size fractions (<0.063- and <2-mm) was utilized in two monitoring wells: DH1 (located close to the injection and extraction wells for in-situ soil flushing) and DH2 (located beyond sheet piles placed to block the transport of leaked diesel). Total petroleum hydrocarbon (TPH) concentrations and biogeochemical properties were monitored both in soil and groundwater for six months. A shift occurred in the groundwater type from Ca-HCO 3 to Na-CI due to seawater intrusion during intense pumping, while the concentrations of Ni, Cu, Co, V, Cr, and Se increased substantially following surfactant (TWEEN 80) injection. The in-situ sampler with fine particles was more sensitive to variations in conditions during the remedial soil flushing process. In both wells, soil TPH concentrations in the <0.063-mm fraction were much higher than those in the <2-mm fraction. Increases in soil TPH in DH1 were consistent with the expected outcomes following well pumping and surfactant injection used to enhance TPH extraction. However, the number of diesel-degrading microorganisms decreased after surfactant injection. 16S-rRNA gene-based analysis also showed that the community composition and diversity depended on both particle size and diesel contamination. The multidisciplinary approach to the contaminated site assessments showed that soil flushing with surfactant enhanced diesel extraction, but negatively impacted in-situ diesel biodegradation as well as groundwater quality. In conclusion, the results also suggest that the in-situ sampler can be an effective monitoring tool for subsurface biogeochemistry as well as contaminant dynamics.

02 PETROLEUM↗

Selective Capture of Cesium and Thallium from Natural Waters and Simulated Wastes with Copper Ferrocyanide Functionalized Mesoporous Silica

Copper(II) ferrocyanide immobilized inside mesoporous silica MCM-41 supports (Cu-FC-EDA-SAMMSTM) has been evaluated against iron(III) hexacyanoferrate(II) (insoluble Prussian blue) for the sorption of cesium (Cs+) and thallium (Tl+) from natural waters and simulated wastes. The affinities (in term of distribution coefficients, Kd) of both sorbents for Cs and Tl were measured as a function of solution pH, competing cations, and matrices. For the entire pH studied (pH 0.1 to 7.3), Cu-FC-EDA-SAMMS had higher affinities for Cs and Tl (one to two orders of magnitude higher Kd) than Prussian blue and was less negatively impacted by the solution pH, competing cations, and matrices. The adsorption isotherms and kinetics of the two sorbents for Cs and/or Tl were also determined in seawater and simulated acid and alkaline wastes. SAMMS outperformed Prussian blue in terms of maximum adsorption capacity (e.g., 21.7 versus 2.6 mg Cs/g in acid waste stimulant, pH 1.1), and rate (e.g., over 95 wt% of Cs was removed after 2 minutes with SAMMS, while only 75 wt% was removed with Prussian blue). The lower affinity, capacity, and rate of Cs and Tl sorption on Prussian blue than those on Cu-FC-EDA-SAMMS were attributed to the molecular pore sizes, which restrict mass transport, and the insoluble Cs abducts of the Prussian blue, which restrict the ability of neighboring binding sites to further bind Cs ions. On the other hand, the large pores of SAMMS not only enable faster diffusion and faster binding chemistry, but they also allow isolation of binding sites so that one Cs binding event does not impact further Cs binding. In addition, iron (Fe) dissolved from insoluble Prussian blue over 10-fold of that from Cu-FC-EDA-SAMMS after 24 hours of contact time, indicating poorer material stability of Prussian blue.

54 ENVIRONMENTAL SCIENCES↗

Response relationship between loading condition and corrosion fatigue behavior of nickel-aluminum bronze alloy and its crack tip damage mechanism

Highlights: • The differences of corrosion fatigue behavior of NAB alloy in air and in 3.5% NaCl solution are carefully compared. • The corrosion environment significantly accelerates the crack growth of NAB alloy and decreases the fatigue threshold. • The corrosion fatigue crack growth rate increases with the decrease of loading frequency. • The acidification and the dealumination occur in process of corrosion fatigue, resulting in the deterioration of crack tip. - Abstract: Corrosion fatigue is one of the major forms for nickel‑aluminum bronze alloy used in marine propeller. It is greatly important to understand the corrosion fatigue behavior of nickel‑aluminum bronze alloy in seawater for the purpose of improving the service life of marine equipment. In this study, corrosion fatigue crack growth rate of nickel‑aluminum bronze alloy in 3.5% NaCl solution was tested under various stress intensity factors, stress ratios and loading frequencies to reveal its corrosion fatigue mechanism. The results show that corrosion environment significantly accelerates the crack growth and decreases the corrosion fatigue threshold, which is attributed to the corrosion reactions between the metals of crack tip and corrosive medium. Among the various factors, loading frequency has more predominant influence on the corrosion fatigue crack growth rate of nickel‑aluminum bronze alloy, which can be rationally explained by the hydrogen embrittlement mechanism. Additionally, in the process of corrosion fatigue crack growth, the acidification and the dealumination would occur at the crack tip, resulting in the corrosion dissolution of κ phases and the deterioration in mechanical properties of crack tip.

36 MATERIALS SCIENCE↗

Photocatalytic pure water splitting with high efficiency and value by Pt/porous brookite TiO 2 nanoflutes

We report the remarkable production of H 2 and H 2 O 2 from pure water using porous brookite TiO 2 nanoflutes decorated with Pt nanoparticles through two-electron photocatalytic intermediate water splitting (PIWS). The H 2 production rate from deionized water (pH similar to 7.0) was 9.8 +/- 0.6 $\mu$mol mg -1 h -1 , more than 12-fold and 230-fold higher than the reported TiO 2 -based photocatalytic overall water splitting (POWS) and H 2 /H 2 O 2 production systems, respectively. The apparent quantum yields (AQY) value can achieve 43.4%, which is the highest value compared with the reported TiO 2 -based POWS systems and the commercial value for PIWS is similar to 9-fold higher than that for POWS even ignoring the separation cost. The mechanism of the distinct performance was confirmed by DFT and experimental measurements. The present work provides a feasible strategy to significantly improve the process efficiency and value of photocatalytic water splitting in both pure water and seawater using natural sunlight.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ZeroCAL: Eliminating Carbon Dioxide Emissions from Limestone’s Decomposition to Decarbonize Cement Production

Limestone (calcite, CaCO 3 ) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (~800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO 2(g) ) emissions and energy use, i.e., ~1 tonne [t] of CO 2 and ~1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO 3 as a Ca source to make hydrated lime (portlandite, Ca(OH) 2 ) at ambient conditions (p, T) while nearly eliminating process CO 2(g) emissions (as low as 1.5 mol. % of the CO 2 in the precursor CaCO 3 , equivalent to 9 kg of CO 2(g) per t of Ca(OH) 2 ) within an aqueous flowelectrolysis/ pH-swing process that coproduces hydrogen (H 2(g) ) and oxygen (O 2(g) ). Because Ca(OH) 2 is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The Zero CArbon Lime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO 3 and complexation of Ca 2+ under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO 3 – ) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH) 2 from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO 3 ), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO 3 , 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ~2 MWh of electrical energy are required to produce 1 t of Ca(OH) 2 , with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO 2 mineralization via Ca(OH) 2 carbonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cyclic Imide Dioximes: Formation and Hydrolytic Stability

Poly(acrylamidoximes) play an important role in the uranium extraction from seawater. The present work reports solution studies of simple analogs to address the formation and stability of two binding sites present in these polymers, open-chain amidoximes and cyclic imide dioximes, including: 1) conditions that maximize the formation of the cyclic form, 2) existence of a base-induced conversion from open-chain to cyclic form, and 3) degradation under acid and base conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗