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At least 541 records · Page 30

Laboratory Electrical Conductivity of Marine Gas Hydrate

Methane hydrate was synthesized from pure water ice and flash frozen seawater, with varying amounts of sand or silt added. Electrical conductivity was determined by impedance spectroscopy, using equivalent circuit modeling to separate the effects of electrodes and to gain insight into conduction mechanisms. Silt and sand increase the conductivity of pure hydrate; we infer by contaminant NaCl contributing to conduction in hydrate, to values in agreement with resistivities observed in well logs through hydrate–saturated sediment. The addition of silt and sand lowers the conductivity of hydrate synthesized from seawater by an amount consistent with Archie's law. Here, all samples were characterized using cryogenic scanning electron microscopy and energy dispersive spectroscopy, which show good connectivity of salt and brine phases. Electrical conductivity measurements of pure hydrate and hydrate mixed with silt during pressure–induced dissociation support previous conclusions that sediment increases dissociation rate.

58 GEOSCIENCES↗

Methane Plume Emissions Associated With Puget Sound Faults in the Cascadia Forearc

Methane gas plumes have been discovered to issue from the seafloor in the Puget Sound estuary. These gas emission sites are co-located over traces of three major fault zones that fracture the entire forearc crust of the Cascadia Subduction Zone. Multibeam and single-beam sonar data from cruises conducted in 2011, 2018, 2019, 2020 and 2021 identified the acoustic signature of over 330 bubble plumes. Dissolved gas from the plumes combines to elevate seawater methane concentrations of the entire Puget Sound estuary. Fluid samples from adjacent terrestrial hot springs and deep-water wells surrounding the estuary contain a helium-3 isotope signature, indicating a deep fluid source located near the underlying Cascadia Subduction Zone. However, Puget Sound seawater emission sites lack chemical isotope signatures and elevated thermal anomalies expected from association with a deep plate-interface reservoir. The existence of vigorous marine methane plumes located in areas of thin sediment cover and above the traces of deeply-penetrating forearc fault zones – but still presenting no thermal or chemical anomalies that are found in many other similar forearc environments and remain an unresolved paradox.

54 ENVIRONMENTAL SCIENCES↗

Eroding Permafrost Coastlines Release Biodegradable Dissolved Organic Carbon to the Arctic Ocean

Coastal erosion mobilizes large quantities of organic matter (OM) to the Arctic Ocean where it may fuel greenhouse gas emissions and marine production. While the biodegradability of permafrost-derived dissolved organic carbon (DOC) has been extensively studied in inland soils and freshwaters, few studies have examined dissolved OM (DOM) leached from eroding coastal permafrost in seawater. To address this knowledge gap, we sampled three horizons from bluff exposures near Drew Point, Alaska: seasonally thawed active layer soils, permafrost containing Holocene terrestrial and/or lacustrine OM, and permafrost containing late-Pleistocene marine-derived OM. Samples were leached in seawater to compare DOC yields, DOM composition (chromophoric DOM, Fourier transform ion cyclotron resonance mass spectrometry), and biodegradable DOC (BDOC). Holocene terrestrial permafrost leached the most DOC compared to active layer soils and Pleistocene marine permafrost. However, DOC from Pleistocene marine permafrost was the most biodegradable (33 ± 6% over 90 days), followed by DOC from active layer soils (23 ± 5%) and Holocene terrestrial permafrost (14 ± 3%). Permafrost leachates contained relatively more aliphatic and peptide-like formulae, whereas active layer leachates contained relatively more aromatic formulae. BDOC was positively correlated with nitrogen-containing and aliphatic formulae, and negatively correlated with polyphenolic and condensed aromatic formulae. Using estimates of eroding OM, we scale our results to estimate DOC and BDOC inputs to the Alaska Beaufort Sea. While DOC inputs from coastal erosion are relatively small compared to rivers, our results suggest that erosion may be an important source of BDOC to the Beaufort Sea when river inputs are low.

Bristol, Emily M.↗

Hydrological and Thermal Dynamics of a Supra‐Permafrost Subterranean Estuary

Subterranean estuaries (STEs), where groundwater interacts with seawater, influence surface and subsurface coastal ecology and biogeochemistry. In Arctic-STEs overlying permafrost, groundwater flow and heat transport determine the fate of organic matter. Yet, direct observations of groundwater flow and heat and solute transport processes in Arctic STEs remain limited. This study characterized groundwater flow paths and fluxes and heat transport within an Arctic-STE along Alaska's Beaufort Sea coast during thawing, summer, and freeze-up. Intertidal seabed temperature-depth profiles collected along a 10-m transect captured the active groundwater flow period, from thaw and flow onset in mid-June to freeze-up in late-September. During this period, aquifer geometry evolved non-uniformly due to spatially varying thaw rates across the STE (mean (m) thaw depths–beach: 0.25 to 0.55–0.6 m on 20 June, 25 July, 1 October; seabed: 0.6–0.9 m from 25 July to 1 October). Groundwater and surface water levels, salinity, and subsurface temperature profiles measured over tidal time scales were interpreted alongside groundwater flow-heat transport numerical simulations. Fresh groundwater discharge was sporadic during thawing (m: 0.32 m 3 /day/m), abundant in summer (m: 0.45 m 3 /day/m), and was largely absent during freeze-up. During freeze-up, groundwater flow was driven exclusively by seawater recirculation via tidal pumping (from thawing to summer to freeze-up: 0.00025–0.15–0.5 m3/day/m) and convection. Heat advection dominated near aquatic interfaces (shaping intertidal ice), and conduction controlled vertical temperature gradients in low-flow and unsaturated sediments. These findings will help predict how prolonged summers will alter Arctic-STE cryo-hydrology and biogeochemistry.

54 ENVIRONMENTAL SCIENCES↗

Ion sieving and desalination: Energy penalty for excess baggage

Here, more than a billion people do not have access to clean water globally and millions of people die every year from water borne diseases. Human activity has resulted in depletion of groundwater, seawater intrusion in coastal aquifers, pollution of water resources, ecological damage, and resultant threats to the world’s freshwater, food supply, security, and prosperity. To address this challenge, there is a pressing need to produce clean water from seawater, brackish groundwater, and waste water. Current desalination methods are energy intensive and produce adverse environmental impact. At the same time, energy production consumes large quantities of water and creates waste water that needs to be treated with further energy input. Water treatment with membranes that separate water molecules from ions, pathogens and pollutants has been proposed as an energy-efficient solution to the fresh water crisis. Recently, membranes based on carbon nanotubes, graphene and graphene oxide (GO) have garnered considerable interest for their potential in desalination. Of these, GO membranes hold the promise of inexpensive production on a large scale but swell when immersed in water. The swollen membrane allows not only water molecules but also ions, such as Na + and Mg 2+ , to pass through. Abraham and coworkers show that the interlayer spacing in a GO laminar membrane can be tuned to a certain value and then fixed by physically restraining the membrane from swelling. When the authors reduced the spacing systematically in steps from 9.8 Å to 7.4 Å, the ion permeation rate was reduced by two orders of magnitude while the water permeation rate was only halved.

36 MATERIALS SCIENCE↗

Highly active cobalt phosphate and borate based oxygen evolving catalysts operating in neutral and natural waters

A high surface area electrode is functionalized with cobalt-based oxygen evolving catalysts (Co-OEC = electrodeposited from pH 7 phosphate, Pi, pH 8.5 methylphosphonate, MePi, and pH 9.2 borate electrolyte, Bi). Co-OEC prepared from MePi and operated in Pi and Bi achieves a current density of 100 mA cm(-2) for water oxidation at 442 and 363 mV overpotential, respectively. The catalyst retains activity in near-neutral pH buffered electrolyte in natural waters such as those from the Charles River (Cambridge, MA) and seawater (Woods Hole, MA). The efficacy and ease of operation of anodes functionalized with Co-OEC at appreciable current density together with its ability to operate in near neutral pH buffered natural water sources bodes well for the translation of this catalyst to a viable renewable energy storage technology.

Esswein, AJ↗

Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl

Poly(acrylamidoxime)-based fibers bearing random mixtures of carboxylate and amidoxime groups are the most widely utilized materials for extracting uranium from seawater. However, the competition between uranyl (UO 2 2+ ) and vanadium ions poses a significant challenge to the industrial mining of uranium from seawater using the current generation of adsorbents. To design more selective adsorbents, a detailed understanding of how major competing ions interact with carboxylate and amidoxime ligands is required. In this work, we employ density functional theory (DFT) and wave-function methods to investigate potential binding motifs of the dioxovanadium ion, VO 2 + , with water, formate, and formamidoximate ligands. Employing higher level of theory calculations (CCSD(T)) resolve the existing controversy between the experimental results and previous DFT calculations for the structure of the hydrated VO 2 + ion. Consistent with the EXAFS data, CCSD(T) calculations predict higher stability of the distorted octahedral geometry of VO 2 + (H 2 O) 4 compared to the five-coordinate complex with a single water molecule in the second hydration shell, while all seven tested DFT methods yield the reverse stability of the two conformations. Analysis of the relative stabilities of formate-VO 2 + complexes indicates that both monodentate and bidentate forms may coexist in thermodynamic equilibrium in solution, with the equilibrium balance leaning more towards the formation of monodentate species. Investigations of VO 2 + coordination with the formamidoximate anion has revealed the existence of seven possible binding motifs, four of which are within ~ 4.0 kcal/mol of each other. Calculations establish that the most stable binding motif entails the coordination of oxime oxygen and amide nitrogen atoms via a tautomeric rearrangement of amidoxime to imino hydroxylamine. Lastly, the difference in the most stable VO 2 + and UO 2 2+ binding conformation has important implications for the design of more selective UO 2 2+ ligands.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions

Magnetic nanoparticles are well known to possess chemically active surfaces and high surface areas that can be employed to extract a range of ions from aqueous solutions. Additionally, their paramagnetic property provides a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. Herein, two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes, were evaluated for their ability to collect both naturally occurring radioactive isotopes (polonium (Po), radium (Ra), and uranium (U)) as well as the transuranic element americium (Am) from a suite of naturally occurring aqueous matrices. The nanomaterials include commercially available paramagnetic magnetite (Fe3O4) and magnetite that was modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1 (acidified with HCl). Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the aforementioned alpha-emitting radionuclide spikes from Hanford Site ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. The uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified groundwater was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. Overall, the results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions. These applications may include analytical chemistry, waste water treatment and remediation, mining, and in vitro radiobioassay.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly porous CO 2 hydrate generation aided by silica nanoparticles for potential secure storage of CO 2 and desalination

Here in this paper, we report a new way of storing CO 2 in a highly porous hydrate structure, stabilized by silica nanoparticles (NPs). Such a porous CO 2 hydrate structure was generated either by cooling down NP-stabilized CO 2 -in-seawater foams, or by gently mixing CO 2 and seawater that contains silica NPs under CO 2 hydrate-generating conditions. With the highly porous structure, enhanced desalination was also achievable when the partial meltdown of CO 2 hydrate was allowed.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Interactions of vanadium( iv ) with amidoxime ligands: redox reactivity

Vanadium is the main competitor for uranium extraction from seawater, and V( iv ) comprises a minor but important portion of this. V( iv ) undergoes redox reactions with oximes and amidoxime ligands under seawater-relevant conditions, leading to V( v ) complexes and loss of oxime functional groups.

Parker, B. F.↗

Metal–bicarbonate ion pairing in alkaline aqueous solutions from multilevel embedded correlated wavefunction theory and molecular dynamics

In this work, we examine ion-pairing mechanisms of bicarbonates in alkaline aqueous solutions with the divalent metal ions most abundantly present in seawater, namely, Ca 2+ and Mg 2+ . We employ a rare-event enhanced sampling approach within first-principles molecular dynamics to explore regions of phase space spanning solvent-shared to contact ion pairs. Second-order Møller–Plesset perturbation theory (MP2) corrections are subsequently applied in an embedding framework (EMB) to refine the electronic structure of stationary states and associated reaction barriers along the free-energy profiles while retaining the extended solvent effects at the density functional theory (DFT) level. Ca 2+ –HCO 3 − was previously hypothesized to exist in a solvent-shared ion pair (SSHIP) by DFT studies with an endergonic contact ion pair (CIP) formation; however, our EMB-MP2 refinement of the DFT ion-pairing pathways reveals that Ca 2+ and HCO 3 − form a virtually barrier-free CIP in alkaline solutions, with even more energetic ease than the widely studied Ca–CO 3 ion pair. We find qualitative agreement between DFT and EMB-MP2 for Mg 2+ —unlike Ca 2+ , Mg 2+ refuses to shed its strong hydration shell, thereby preferring a SSHIP state with a significant activation barrier to crossover to the CIP forms—a trait reminiscent of ion pairing in Mg–CO 3 and closely related to the kinetic limitations underlying the famous subject of the dolomite problem. Our study highlights the importance of improved electronic structure descriptions of liquids, modeled as a condensed phase of matter lacking in long-range crystalline order. It also strongly suggests that Ca 2+ –HCO 3 − CIPs are likely precursors involved in prenucleation of CaCO 3 mineral formation in seawater.

Sharma, Vidushi [Princeton Plasma Physics Laborato↗

Shape-preserving amorphous-to-crystalline transformation of CaCO3 revealed by in situ TEM

Organisms use inorganic ions and macromolecules to regulate crystallization from amorphous- precursors, endowing natural biominerals with complex morphologies and enhanced properties. The mechanisms by which modifiers enable these shape preserving transformations are poorly understood. We used in situ liquid-phase transmission electron microscopy to follow the evolution from amorphous calcium carbonate to calcite in the presence of additives. A combination of contrast analysis and infrared spectroscopy shows that Mg ions, which are widely present in seawater and biological fluids, alter the transformation pathway in a concentration-dependent manner. The ions bring excess (structural) water into the amorphous bulk so that a direct transformation is triggered by dehydration in the absence of morphological changes. Molecular dynamics simulations suggest Mg-incorporated water induces structural fluctuations, allowing transformation without the need to nucleate a separate crystal. Thus, the obtained calcite retains the original morphology of the amorphous state, biomimetically achieving the morphological control of crystals seen in biominerals

crystallization, biomineralization, calcium carbon↗

Using 81 Kr and isotopic tracers to characterise old groundwater in the Bangkok metropolitan and vicinity areas

Krypton-81 was applied to investigate the age of groundwater in the aquifer system in the Bangkok metropolitan and vicinity areas. Stable ( 2 H, 18 O and 13 C) and radioactive ( 3 H, 85 Kr and 14 C) isotopes and noble gases were applied in parallel. Low levels of 14 C and significant radiogenic 4 He confirm that groundwater in the deep aquifers is older than 30 ka. 81 Kr analysis identified groundwater with ages ranging from 17 to 300 ka. At some sites, large age discrepancies between 81 Kr and 14 C indicated that inter-aquifer mixing is likely occurring. The interpretation of the noble gases suggests that groundwaters in the deeper aquifers, with apparent ages of 300 to 10 ka, have recharged in slightly colder and wetter climates than those found in the upper aquifers with apparent ages < 10 ka. Degradation of water quality from seawater intrusion was identified in the upper four aquifers. This was also evidenced by higher δ 18 O and δ 2 H values, typical of seawater. The four deeper aquifers contain high quality water characterised by less enriched 18 O and 2 H. In conclusion, this work presents new findings of very old groundwater in the Bangkok aquifer system.

54 ENVIRONMENTAL SCIENCES↗

Mixing and dilution controls on marine CO 2 removal using alkalinity enhancement

Marine CO 2 removal (CDR) using enhanced-alkalinity seawater discharge was simulated in the estuarine waters of the Salish Sea, Washington, US. The high-alkalinity seawater would be generated using bipolar membrane electrodialysis technology to remove acid and the alkaline stream returned to the sea. Response of the receiving waters was evaluated using a shoreline resolving hydrodynamic model with biogeochemistry, and carbonate chemistry. Two sites, and two deployment scales, each with enhanced TA of 2997 mmol m -3 and a pH of 9 were simulated. The effects on air-sea CO 2 flux and pH in the near-field as well as over the larger estuary wide domain were assessed. The large-scale deployment (addition of 164 Mmoles TA yr -1 ) in a small embayment (Sequim Bay, 12.5 km 2 ) resulted in removal of 2066 T of CO 2 (45% of total simulated) at rate of 3756 mmol m -2 yr -1 , higher than the 63 mmol m -2 yr -1 required globally to remove 1.0 GT CO 2 yr -1 . It also reduced acidity in the bay, ΔpH ≈ +0.1 pH units, an amount comparable to the historic impacts of anthropogenic acidification in the Salish Sea. The mixing and dilution of added TA with distance from the source results in reduced CDR rates such that comparable amount 2176 T CO 2 yr -1 was removed over >1000 fold larger area of the rest of the model domain. There is the potential for more removal occurring beyond the region modeled. The CDR from reduction of outgassing between October and May accounts for as much as 90% of total CDR simulated. Of the total, only 375 T CO 2 yr -1 (8%) was from the open shelf portion of the model domain. With shallow depths limiting vertical mixing, nearshore estuarine waters may provide a more rapid removal of CO 2 using alkalinity enhancement relative to deeper oceanic sites.

54 ENVIRONMENTAL SCIENCES↗

Use of carbon monoxide and hydrogen by a bacteria-animal symbiosis from seagrass sediments

The gutless marine worm Olavius algarvensis lives in symbiosis with chemosynthetic bacteria that provide nutrition by fixing carbon dioxide (CO 2 ) into biomass using reduced sulfur compounds as energy sources. A recent metaproteomic analysis of the O. algarvensis symbiosis indicated that carbon monoxide (CO) and hydrogen (H 2 ) might also be used as energy sources. We provide direct evidence that the O. algarvensis symbiosis consumes CO and H 2 . Single cell imaging using nanoscale secondary ion mass spectrometry revealed that one of the symbionts, the γ3-symbiont, uses the energy from CO oxidation to fix CO 2 . Pore water analysis revealed considerable in-situ concentrations of CO and H 2 in the O. algarvensis environment, Mediterranean seagrass sediments. Pore water H 2 concentrations (89-2147 nM) were up to two orders of magnitude higher than in seawater, and up to 36-fold higher than previously known from shallow-water marine sediments. Pore water CO concentrations (17-51 nM) were twice as high as in the overlying seawater (no literature data from other shallow-water sediments are available for comparison). Ex-situ incubation experiments showed that dead seagrass rhizomes produced large amounts of CO. Lastly, CO production from decaying plant material could thus be a significant energy source for microbial primary production in seagrass sediments.

54 ENVIRONMENTAL SCIENCES↗

Millennial-scale ocean acidification and late Quaternary

Ocean acidification by atmospheric carbon dioxide has increased almost continuously since the last glacial maximum (LGM), 21 000 years ago. It is expected to impair tropical reef development, but effects on reefs at the present day and in the recent past have proved difficult to evaluate. We present evidence that acidification has already significantly reduced the formation of calcified bacterial crusts in tropical reefs. Unlike major reef builders such as coralline algae and corals that more closely control their calcification, bacterial calcification is very sensitive to ambient changes in carbonate chemistry. Bacterial crusts in reef cavities have declined in thickness over the past 14 000 years with largest reduction occurring 12 000 10 000 years ago. We interpret this as an early effect of deglacial ocean acidification on reef calcification and infer that similar crusts were likely to have been thicker when seawater carbonate saturation was increased during earlier glacial intervals, and thinner during interglacials. These changes in crust thickness could have substantially affected reef development over glacial cycles, as rigid crusts significantly strengthen framework and their reduction would have increased the susceptibility of reefs to biological and physical erosion. Bacterial crust decline reveals previously unrecognized millennial-scale acidification effects on tropical reefs. This directs attention to the role of crusts in reef formation and the ability of bioinduced calcification to reflect changes in seawater chemistry. It also provides a long-term context for assessing anticipated anthropogenic effects.

bacterial crust↗

Analysis of a Wave-Powered, Reverse-Osmosis System and Its Economic Availability in the United States: Preprint

A wave energy converter (WEC) system has the potential to convert the wave energy resource directly into the high-pressure flow that is needed by the desalination system to permeate saltwater through the reverse-osmosis membrane to generate clean water. In this study, a wave-to-water numerical model was developed to investigate the potential use of a wave-powered desalination system (WPDS) for water production in the United States. The model was developed by coupling a time-domain radiation-and-diffraction-method-based numerical tool (WEC-Sim) for predicting the hydrodynamic performance of WECs with a solution-diffusion model that was used to simulate the reverse-osmosis process. To evaluate the feasibility of the WPDS, the wave-to-water numerical model was applied to simulate a desalination system that used an oscillating surge WEC device to pump seawater through the system. The annual water production was estimated based on the wave resource at a reference site on the coast of northern California to investigate the potential cost of water in that area, where the cost of water and electricity is high compared to other regions. In the scenario evaluated, for a 100-unit utility-scale electricity-producing array, the estimated levelized cost of energy for these WECs is about 3-6 times the U.S.'s current, unsubsidized electricity rates. However, with clean water as an end product and by directly producing pressurized water with WECs, rather than electricity as an intermediary, it is presently only 12 percent greater than typical water cost in California. This study suggests that a WEC array that produces water may be a viable, near-term solution to the nation's water supply, and the niche application of the WPDS may also provide developers with new opportunities to further develop technologies that benefit both the electric and drinking water markets.

16 TIDAL AND WAVE POWER↗

A Novel Zero-Discharge Supercritical Water-Based Wave Energy Desalination System

This paper presents a sustainable and innovative wave-energy-based water desalination system combined with an emerging supercritical water process for a zero-liquid-discharge technology. There is growing demand for producing clean water. Within desalination technologies, reverse osmosis, one of the most popular methods, uses a semipermeable membrane that separates fresh water from pressurized seawater. However, this technology produces brine, which is harmful to the environment. Supercritical water desalination is employed here as a means of using the brine to extract more fresh water and eliminate this environmentally toxic output. Wave energy is integrated with reverse osmosis to provide direct seawater pressurization for the first stage in the process. This wave energy converter converts the motion of waves into pressurized water through a power takeoff unit.

reverse osmosis↗