WO2025101950A1 - Products of manufacture for exporting atmospheric carbon dioxide into long-term water storage reservoirs - Google Patents
Products of manufacture for exporting atmospheric carbon dioxide into long-term water storage reservoirs Download PDFInfo
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- WO2025101950A1 WO2025101950A1 PCT/US2024/055195 US2024055195W WO2025101950A1 WO 2025101950 A1 WO2025101950 A1 WO 2025101950A1 US 2024055195 W US2024055195 W US 2024055195W WO 2025101950 A1 WO2025101950 A1 WO 2025101950A1
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B41/00—Equipment or details not covered by groups E21B15/00 - E21B40/00
- E21B41/005—Waste disposal systems
- E21B41/0057—Disposal of a fluid by injection into a subterranean formation
- E21B41/0064—Carbon dioxide sequestration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/95—Specific microorganisms
Definitions
- This invention generally relates to environmental engineering and aquaculturing.
- products of manufacture designed as a Floater- Coupled-to-Sinker (so called “FloCS”) that can export CO2, methane, inorganic and organic nutrients, pollutants, metals and/or plastics into aqueous storage reservoirs, optionally long-term water or aqueous storage reservoirs.
- Fossil fuel usage and the subsequent feedback systems for example, increased release of organic carbon in Arctic peat lands, are leading to an accelerated generation of greenhouse gasses like carbon dioxide (CO2) and methane.
- CO2 carbon dioxide
- the accumulation of these gasses in the atmosphere influence local weather and the greater climate regime of Earth.
- Other effects include acidification, the lowering of pH driven by CO2 dissolving into water. Cost effective solutions are needed to mitigate these problems to avoid an environmental disaster.
- Floater-Coupled-to-Sinker for exporting or sequestering atmospheric carbon dioxide (CO2), methane, an inorganic or an organic nutrient, a pollutant, a metal, a plastic, or a combination thereof, from an aquatic or an ocean environment to an aqueous storage reservoir, wherein the carbon dioxide (CO2), methane, an inorganic or an organic nutrient, a pollutant, a metal, a plastic, or a combination thereof is degraded, modified or digested by an organism and exported or sequestered into or adherent to or attached to an aqueous storage reservoir, optionally a long-term aqueous storage reservoir, the products of manufacture comprising:
- a floater component attached to or operatively attached to the aqueous storage reservoir, wherein the floater comprises at least one organism, optionally at least one plant, macroalgae or algae, and the floater is capable of or fabricated for:
- a sinker component attached or adherent to the aqueous storage reservoir and/or the floater component, wherein the sinker comprises or has contained therein any organism or man-made material that is denser than water (optionally between about 1% and 100% denser than water), and when in an aqueous environment the sinker componenet is able to grow or expand or modify itself such that over time it becomes sufficiently negatively buoyant to the degree that the product of manufacture sinks, and optionally the sinker component comprises a polymer material that undergoes an increase in density when immersed in seawater, and this increase in density can be achieved by the polymer selectively absorbing divalent cations, optionally calcium (Ca 2+ ) and magnesium (Mg 2+ ) ions, and optionally the polymer matrix comprises: polyacrylate or polyacrylic acid, poly(methacrylic acid) (PMAA), divinylbenzene (DVB), PMAA-DVB, styrene-divinylbenzene (S-DVB),
- the density -increasing property or properties of the polymer material controls buoyancy, stability, and/or enhanced durability in an aqueous environment, optionally a marine environment, an underwater structure, a buoyancy control systems or a marine sensor housing.
- the floater component comprises or has contained therein:
- Rhodophyta an organism of the division Rhodophyta (red algae), for example, a plant of the genus Porphyra (such as Porphyra umbilicalis or Porphyra purpurea), Gelidium, Audouinella or I.emanea:
- an organism of the phylum Chlorophyta (green algae), such as a plant of the clades Chlorophyta, Streptophyta, Mesostigmatophyceae Chlorokybophyceae or Viridiplantae , or a plant of the genus Halimeda such as Halimeda tuna,
- halophyte for example, a plant of the family Poaceae or the genus Spartina such as Spartina alterniflora, or plant of the genus Salicornia such as a Salicornia bigelovir, a mangrove, for example, a plant of the genus Rhizophora, for example, a Rhizophora mangle, R.
- the sinker component comprises or has contained therein:
- a bryozoan an invertebrate animal of the phylum Bryozoa, such as an animal of the class Gymnolaemata or order Cheilostomata
- an ascidian an animal of the class Ascidiacea, such as a sea squirt
- a coral or an animal of the class Anthozoa, including sea anemones, stony corals, soft corals and gorgonians
- an animal of the phylum Mollusca for example, a bivalve mollusk such as a clam (for example, of the family Veneridcte.
- the genus Spisula such as a Spisula solidissima; or a Ruditapes decussatus or Venerupis decussatus) or a mussel
- animal of the subclass Pteriomorphia including Arcida, Ostreida, Pectinida, Limida, Mytilida and Pleriidci). or including animals of the family Pectinoidea (scallops), or animals of the subclass Palaeohelerodonla. including Unionida (freshwater mussels) and Trigoniida an animal of the genus Haliolis. such as abalone, for example, Haliotis asinina: and, animals of the genus Dreissena. such as the zebra mussel or Dreissena polymorpha
- any bio-mineralizating organisms including, but not limited to, corals, mollusks like snails, abalone, bryozoans, macroalgae like Halimeda spp. and coralline crustose algae (CCA), microalgae like coccolithophores; or
- a man-made or an inorganic component for example, concrete, metal, wood, an organic polymer such as plastic, or rock, or any material that can gain density through a chemical process.
- the sinker is attached to or adherent to the floater by a natural or a man-made process or material.
- the product of manufacture in an aquatic or ocean environment, and optionally the aquatic or ocean environment is a lake (optionally a deep lake with low oxygen bottom waters); a peat-land; a swamp; a man-made dump; a man-made reservoir; a flooded quarry; or a volcanic crater or a caldera.
- a lake optionally a deep lake with low oxygen bottom waters
- peat-land a swamp
- man-made dump a man-made reservoir
- a flooded quarry or a volcanic crater or a caldera.
- the product of manufacture or the sequestered, degraded or digested atmospheric carbon dioxide (CO2), methane, the inorganic or organic nutrient, the pollutant, the metal, the plastic or the combination thereof is periodically collected or harvested, or the product of manufacture or the sequestered, degraded or digested atmospheric carbon dioxide (CO2), methane, the inorganic or organic nutrient, the pollutant, the metal, the plastic or the combination thereof is collected or harvested about every week, about every month or about every year, or between about one week to one year or more
- polymer materials that increase in density upon immersion in seawater, wherein the increase in density results from or through selective absorption of divalent cations
- the polymer material comprises polyacrylate or polyacrylic acid, poly(methacrylic acid) (PMAA), divinylbenzene (DVB), PMAA-DVB, styrene-divinylbenzene (S-DVB), styrene, polydopamine, polyvinyl alcohol, chitosan, activated carbon, or a polyelectrolyte complex or a combination thereof, wherein the density increase occurs without substantial volumetric expansion, thus enhancing stability and functionality in marine environments.
- the polymer material comprises polyacrylate or polyacrylic acid, poly(methacrylic acid) (PMAA), divinylbenzene (DVB), PMAA-DVB, styrene-divinylbenzene (S-DVB), styrene, polydopamine, polyvinyl alcohol, chitosan, activate
- the polymer material further comprises one or more or a plurality of functional groups that selectively bind to one or more divalent cations, optionally calcium (Ca 2+ ) and/or magnesium (Mg 2+ ) ions, and optionally the one or more functional groups comprise barium hydroxide, strontium hydroxide, calcium hydroxide or a combination thereof, thus promoting crosslinking or structural contraction that results in an increase in density.
- one or more functional groups comprise barium hydroxide, strontium hydroxide, calcium hydroxide or a combination thereof, thus promoting crosslinking or structural contraction that results in an increase in density.
- products of manufacture comprising or having contained therein a polymer material as provided herein, and optionally the products of manufacture further comprise or having contained therein a polymer material as contained herein.
- FIG. 1 is a scatter plot of the density of local organisms that graphically illustrates mass in grams as a function of volume in mis for algae versus (vs) calcifying organism densities, as described in detail in Example 1, below.
- FIG. 2 is a scatter plot of deep sea chamber that graphically illustrates density (in g/ml) as a function of depth of pressurized sample (in meters) for Macrocystis pyrfiera and Mytilus californianus density at different depths in and ex situ pressure chamber, as described in detail in Example 1, below.
- FIG. 3 schematically illustrates a biological and microbial carbon pump energy diagram displaying the movement of carbon from the atmosphere to the deep ocean, as described in detail in Example 1, below.
- FIG. 4 illustrates a table (Table 2) with data collected after collecting field samples, as described in detail in Example 1, below.
- FIG. 5 illustrates a table (Table 3) that provides an overview of the equations used in the GOLDSIMTM modeling software, which includes growth rates, volumetric changes, and buoyant force calculations for both floaters and sinkers, as described in further detail in Example 2, below.
- Table 3 provides an overview of the equations used in the GOLDSIMTM modeling software, which includes growth rates, volumetric changes, and buoyant force calculations for both floaters and sinkers, as described in further detail in Example 2, below.
- FIG. 6 schematically illustrates modeling of Macrocystis pyrifera growth and buoyancy in GOLDSIMTM: This figure shows the relationships between key parameters affecting growth rate, mass, buoyant force, and density of M. pyrifera, as described in further detail in Example 2, below.
- FIG. 7 graphically illustrates simulation of exemplary Force FloCS over 400 days using the GOLDSIMTM model, representing the combined effect of Ostrea gigas oysters and Macrocystis pyrifera kelp on the exemplary FloCS system, as described in further detail in Example 2, below.
- FIG. 8A-D graphically illustrate changes in microbial biomass over time using 1 gram of kelp and 7 grams of mussel shell:
- FIG. 8A Average microbial biomass per cell over time
- FIG. 8B Mean microbial volume
- FIG. 8C Total microbial biomass subset
- FIG. 8D Total microbial biomass; and each treatment is shown for both pressurized (dashed line) and unpressurized (solid line) conditions, as described in further detail in Example 2, below.
- FIG. 9A-F graphically illustrates Virus-to-Microbe Ratio (VMR), Virus-Like Particles (VLPs), and Microbial counts over time under pressurized and unpressurized conditions:
- FIG. 9A VMR over time (pressurized).
- FIG. 9B VLPs per mL (pressurized)
- FIG. 9C Number of microbes per mL (pressurized),
- FIG. 9D VMR over time (unpressurized).
- FIG. 9E VLPs per mL (unpressurized).
- FIG. 9F Number of microbes per mL (unpressurized), as described in further detail in Example 2, below.
- FIG. 10A schematically illustrates an exemplary rosette design showing the arrangement of Niskin bottles, glass sphere, and rosette structure
- FIG. 10B schematically illustrates an individual Niskin bottle assembly and configuration
- FIG. IOC schematically illustrates a fully assembled exemplary system as provided herein integrated with the ocean lander, demonstrating the compact design and ability for small boat deployment, as described in further detail in Example 2, below.
- FIG. 11A-D illustrate picture of stages of kelp spore development
- FIG. 11 A Kelp spores immediately post-release observed under a hemocytometer
- FIG. 11B Gametophytes at 7 days post-release
- FIG. 11C Juvenile kelp 33 days after release
- FIG. 11D Mature kelp after 52 days of growth in a tumble culture tank, as described in further detail in Example 2, below.
- FIG. 12 illustrates the number of kelp settled per image on various material types; materials are categorized by treatment type: smooth, rough, and unmodified, as described in further detail in Example 2, below.
- FIG. 13 A illustrates an image showing oyster larvae settled on a test surface
- FIG. 13B graphically illustrates the total count of oyster larvae settled on different materials, categorized by rough, smooth, and unmodified treatments, as described in further detail in Example 2, below.
- FIG. 14A-C illustrate images of Co-settlement of kelp spores onto pre-settled oysters over time:
- FIG. 14 A Image of settled kelp spores on oysters at 14 days post spore release
- FIG. 14B Image of kelp spores growing on oysters at 21 days post spore release.
- FIG. 14C Image showing the al gale attatched to the sheel at 28 days post spore release, as described in further detail in Example 2, below.
- FIG. 15 graphically shows results illustrating the search for materials that can optimize the ratio of oysters to kelp necessary for successful settlement and growth, as described in further detail in Example 2, below.
- FIG. 16 illustrates a diagram of exemplary methods for co settlement of FloCS devices in suspension, as described in further detail in Example 2, below.
- FIG. 17A-C illustrates linear regression analysis showing the relationship between algal biomass and:
- FIG. 17A Virus-to-Microbe Ratio (VMR);
- FIG. 17B Viral -Like Particles (VLPs), and
- FIG. 18A-D illustrates linear regression analysis showing the relationship between microbial biomass and algal biomass across pressurized and unpressurized treatments:
- FIG. 18 A Average microbial biomass per cell
- FIG. 18B Mean microbial volume
- FIG. 18C Total microbial biomass subset
- FIG. 18D Total microbial biomass over time; as described in further detail in Example 2, below.
- FIG. 19A-D illustrates images comparing VMR samples with 20 grams algae:
- FIG. 19 A Normal Virus-to-Microbe Ratio (VMR),
- FIG. 19B exemplary FloCS unpressurized after 2 weeks, showing an overload of microbial growth
- FIG. 19C exemplary FloCS unpressurized after 4 weeks, exhibiting a higher density of smaller microbes
- FIG. 19D exemplary FloCS pressurized after 2 weeks, demonstrating a significantly reduced microbial population due to pressure constraints, as described in further detail in Example 2, below.
- aqueous storage reservoirs optionally long-term aqueous storage reservoirs.
- CO2 atmospheric carbon dioxide
- FloCS Floater-Coupled-to-Sinker
- the long-term water or aqueous storage reservoir (for example, a CCh-sequestering environment) is the ocean, for example, the deep ocean, where organic carbon - the photosynthetic product of light, water, and CO2 - will be sequestered for hundred's to hundreds-of-thousands of years.
- the long-term water or aqueous storage reservoir (for example, a CCh-sequestering environment) is a lake, for example, a deep lake with low oxygen bottom waters; a peat-land; a swamp; a man-made dump; a manmade reservoir; a flooded quarry, volcanic crater or caldera; and the like.
- products of manufacture designed as FloCSs to be used to remove unwanted materials, including by not limited to, for example, inorganic and organic nutrients, pollutants, metals, plastics, and the like.
- products of manufacture as provided herein comprise at least two components: one floater that accumulates CO2, methane, inorganic and organic nutrients, pollutants, metals, plastics, and the like; and one sinker, which subsequently delivers these materials into (for example, to the bottom of) the long-term water or aqueous storage reservoir.
- the floater and/or sinker is natural or man-made. In alternative embodiments, the floater and/or sinker are directly or indirectly coupled to each other through natural or man-made connection systems or linking agents.
- the floater is a plant or a macroalgae such as (or comprising):
- an organism of the division Phaeophyta (brown algae) or family Phaeophyceae such as a plant of the genus Ascophyllum such as an Ascophyllum nodosum, a plant of the genus Macrocystis such as a Macrocystis pomifera or a giant kelp (Macrocystis pyrifera),' a plant of the genus Laminariales such as kelp, for example, Laminaria setchellii, Laminaria hyperborean, Saccharina japonica or Nereocystis lueteana, or, a plant of the genus Sargassum such as Sargassum muticunr, or
- an organism of the phylum Chlorophyta (green algae), such as a plant of the clades Chlorophyta, Streptophyta, Mesostigmatophyceae Chlorokybophyceae or Viridiplantae , or a plant of the genus Halimeda such as Halimeda tuna.
- the floater is a plant such as: a halophyte, for example, a plant of the family Poaceae or the genus Spartina such as Spartina alterniflora, or plant of the genus Salicornia such as a Salicornia bigelovir, a mangrove, for example, a plant of the genus Rhizophora, for example, a Rhizophora mangle, R.
- a halophyte for example, a plant of the family Poaceae or the genus Spartina such as Spartina alterniflora, or plant of the genus Salicornia such as a Salicornia bigelovir, a mangrove, for example, a plant of the genus Rhizophora, for example, a Rhizophora mangle, R.
- racemosa or R mucronate a plant of the genus Atriplex, a plant of the genus Panicum, or Anemopsis californica,' or, seagrass, for example, including any marine flowering plant or angiosperm such as a plant of order Alismatales, or of the family Posidoniaceae, Zosteraceae, Hydrocharitaceae or Cymodoceaceae .
- the floater can comprise, or further comprise, a non-plant composition, for example, a buoyant non-plant material
- the floater can comprise a man-made floater such as for example, a degradable floater such as a foam; or a non-degradable floater such as a glass; or a low density, buoyant material.
- the genus Spisula such as a Spisula solidissima; or a Ruditapes decussatus or Venerupis decussatus) or a mussel
- animal of the subclass Pteriomorphia including Arcida, Ostreida, Pectinida, Limida, Mytilida and Pleriidci). or including animals of the family Pectinoidea (scallops), or animals of the subclass Palaeohelerodonla. including Unionida (freshwater mussels) and Trigoniida an animal of the genus Haliolis. such as abalone, for example, Haliotis asinina: and, animals of the genus Dreissena. such as the zebra mussel or Dreissena polymorpha.
- the sinker comprises any bio-mineralizating organisms or microorganisms, including, but not limited to, corals, mollusks like snails, abalone, bryozoans, macroalgae like Halimeda spp. and coralline crustose algae (CCA), microalgae like coccolithophores.
- the sinker comprises a genetically engineered organism or microorganism or algae engineered to be a bio-mineralizating organism.
- the sinker can further comprise, or be attached to, a man-made or an inorganic component, for example, concrete, metal, wood, an organic polymer such as plastic, or rock, or any material that can gain density through a chemical process.
- a man-made or an inorganic component for example, concrete, metal, wood, an organic polymer such as plastic, or rock, or any material that can gain density through a chemical process.
- the sinker is attached, bound or coupled a floater, for example, the sinker is coupled to a spore or early developmental stage of a floater.
- the sinker is attached, bound or coupled to a floater by a natural process, for example, by the holdfast of a sporophyte phase.
- the floater When released into an aquatic environment, the floater will keep the product of manufacture (including the sinker) in the photic or euphotic, or epipelagic or sunlit, zone; or at least above the mesopelagic zone.
- the floater and/or sinker Through photosynthesis and photosynthesis-supported metabolisms, the floater and/or sinker will grow and accumulate CO2 and other materials.
- the sinker accumulates CO2 and other materials through autotrophic and heterotrophic feeding. Over time the sinker increases in mass and/or weight, or will also build structures, thus eventually overwhelming the positive buoyancy of the floater component(s), resulting in the product of manufacture, or FloCS, to sink.
- the increasing in mass and/or weight can be according to plan and design by the manufacturer of the product of manufacture, or FloCS, and also can be influenced by natural conditions.
- the positive buoyance of the floater eventually is overwhelmed by the negative buoyance of the sinker, and at this point the product of manufacture, or FloCS system, will sink into or to the bottom of the storage reservoir, for example, will sink into the ocean below the thermocline.
- advantages of the products of manufacture, or FloCS systems, as provided herein include:
- sinkers for example, bivalve, crustaceans or coral larva
- floaters for example, floater spores and seeds such as macroalgae including kelp and Sargassum, as well as plants like mangroves and seagrasses
- FloCS system as provided herein can be very small, both in terms of weight (mgs) and volume (for example, pls or mis);
- one meter of piece of kelp has about 1 gram of carbon
- each gram of carbon in the kelp represents approximately 4 grams of CO2
- the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. About (use of the term “about”) can be understood as within 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12% 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from the context, all numerical values provided herein are modified by the term “about.”
- the terms “substantially all”, “substantially most of’, “substantially all of’ or “majority of’ encompass at least about 75%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or 99.5%, or more of a referenced amount of a composition.
- Example 1 Exemplary Floater-Coupled-to-Sinker (so called “FloCS”) Systems
- the ocean is a carbon sink removes 2.3 Gt C annually (ref. 2).
- a method to increase the ocean’s carbon dioxide removal (CDR) potential can sink macroalgae to the deep ocean.
- CDR carbon dioxide removal
- most of the organic carbon assimilated in the photic zone does not make it to the deep ocean due to grazing, remineralization, and different carbon pumps in the ocean(biological, microbial, etc. (refs. 3, 4, 5).
- Floaters Coupled to Sinkers (FloCS) devices as provided herein can export different carbon forms (for example, particulate organic carbon (POC), dissolved organic carbon (DOC), recalcitrant DOC (RDOC), etc.) to the deep ocean more quickly.
- FloCS as provided herein are “floaters” (comprising photosynthetic organisms that capture CO2 and convert into biomass) physically coupled to “Sinkers” (comprising calcifying organisms that gain mass and drag floater to deep ocean).
- FIG. 1 is a scatter plot of the density of local organisms that graphically illustrates mass in grams as a function of volume in mis for algae versus (vs) calcifying organism densities. Local/Native San Diego Calcifying and Algae species and their physical densities are displayed. Wet weight (mass) measurement on the y- axis and volume of the object (mL) on the x-axis. FloCS need to have a positively buoyant "initial phase” and a negatively buoyant "terminal” phase. Therefore, we need to understand how density changes throughout the life history of organisms.
- This figure displays how juvenile (small mass) densities are extremely close to that of large adults (large mass), insinuating that density may be isometric throughout an organism's life. This will provide us insight as to what organisms we select when we later place them in a modeling system. Less dense floaters may be selected to increase CO2 drawdown time while the most dense sinker may be selected to increase the likelihood the FloCS system eventually sinks.
- FIG. 2 is a scatter plot of deep sea chamber that graphically illustrates density (in g/ml) as a function of depth of pressurized sample (in meters) for Macrocystis pyrfiera and Mytilus californianus density at different depths in and ex situ pressure chamber; we selected one species of floaters and sinkers to simulate deep ocean conditions by subjecting them to pressurization within a chamber. By observing the changes in their density as they traverse the water column, we gain insights into their behavior during the sinking process. Our focus includes identifying the critical points of pneumatocyst implosion/extrusion, which directly influence the buoyancy within the FloCS system. Additionally, we examined whether the organisms' volume undergoes alterations under these pressure conditions.
- FIG. 3 is a graphic illustrating deep-sea carbon cycling: biological and microbial carbon pump energy diagram displaying the movement of carbon from the atmosphere to the deep ocean.
- the left side of the figure depicts the biological carbon pump and how only little bits of carbon actually get stored in the deep ocean.
- the right side of the figure displays FloCS systems accelerating the export of carbon biomass to the deep ocean to prevent getting remineralized and grazed at shallow depths.
- FIG. 4 illustrates a table (Table 2) with data collected after collecting field samples.
- Algae (floater) samples can degrade more or less quickly depending on how long they are in a bag, if the sun is in direct contact with your sample bag, certain species degrade more quickly. *Prioritize collecting your algae (floater) samples last, with your most sensitive species (i.e., Sargassum sp.) closest to you leaving your collection site to minimize any degradation.
- Example 2 Exemplary Floater-Coupled-to-Sinker (so called “FloCS”) Systems
- This example described exemplary advancements of Floater-Coupled-to- Sinker products of manufacture as provided herein, describing methods, data, and modeling results that enhance the scalability and effectiveness of exemplary FloCS system for deep-sea carbon sequestration.
- GOLDSIMTM software (a Monte Carlo simulation software solution for dynamically modeling complex systems) (GoldSim Technology Group LLC, Seattle, WA) to predict the buoyancy dynamics of an exemplary product of manufacture (a so-called FloCS system) by incorporating density data and growth rates from the Metabolic Theory of Ecology (MTE) (see, e.g., Brown, J. H., et al (2004) "Toward a metabolic theory of ecology”. Ecology 85(7): 1771-89).
- MTE Metabolic Theory of Ecology
- This model allowed us to visualize the growth and buoyant forces of both floaters and sinkers over time, indicating that the exemplary FloCS remains buoyant for 250-300 days before transitioning to a sinking phase as the macroalgae ceases growing and becomes negatively buoyant.
- This approach optimizes carbon sequestration by ensuring the material passes through the pycnocline and sinks into the deep sea.
- Table 3 (FIG. 5) provides an overview of the equations used in the GOLDSIMTM modeling software, which includes growth rates, volumetric changes, and buoyant force calculations for both floaters and sinkers; the equations used in GOLDSIMTM are listed in FIG. 5.
- GOLDSIMTM is an advanced Monte Carlo simulation software tailored for dynamic and probabilistic modeling. We used GOLDSIMTM to have a user interface with the mathematical equations in Table 3 and to simulate scenarios across a timeline. GOLDSIMTM allows inputting data, functions and manipulate pools to generate graphs of the functions, which provides a better visualization of how the system was functioning, as illustrated in FIG. 6. By leveraging these capabilities, GOLDSIMTM can be used to identify optimal species combinations that maximize floating duration for floater biomass while ensuring a dense sinker with high growth rates to ensure effective transport beyond the thermocline.
- FIG. 6 schematically illustrates modeling of Macrocystis pyrifera growth and buoyancy in GOLDSIMTM: This figure shows the relationships between key parameters affecting growth rate, mass, buoyant force, and density of M. pyrifera. It includes factors like growth coefficients, carrying capacity, fluid density, and gravity, leading to calculations of mass, weight, and buoyancy, as derived from equations in Table 3 (FIG. 5).
- FIG. 7 graphically illustrates simulation of exemplary Force FloCS over 400 days using the GOLDSIMTM model, representing the combined effect of Ostrea gigas oysters and Macrocystis pyrifera kelp on the exemplary FloCS system.
- the force remains positive during the algae’s growth phase for the first 250-300 days, turning negative as the algae decays, triggering the system to sink at day 363.
- the force exerted by the exemplary FloCS system remains positive for the first 250-300 days, during which time the Macrocystis pyrifera is actively growing. Beyond this period, the force gradually turns negative, reaching a tipping point around day 265, the end of the kelps seasonal cycle, as the algae decays and loses buoyancy.
- the total system becomes negatively buoyant and sinks on day 363. This result aligns with our expectations that the exemplary FloCS system will remain buoyant during the growth phase of the algae, before sinking when the algae degrades, and weight of the sinker takes over.
- a key challenge in marine carbon sequestration is the risk of algal degradation leading to microbialization and acidification at intermediate depths.
- Our findings show that the exemplary FloCS helps buffer against acidification and reduces the risk of microbial degradation by ensuring rapid sinking of algae to deeper ocean layers.
- VMR virus-to-microbe ratios
- This equation represents the rate at which CO2 is removed from the water via photosynthesis by macroalgae, where k is the rate constant for CO2 uptake.
- This equation models the change in carbonate ion concentration, where the conversion of bicarbonate to carbonate is represented by k 2 accounts for the uptake of carbonate ions by calcifiers to produce calcium carbonate.
- This equation describes the rate at which calcium carbonate is formed by calcifiers, where k 3 is the rate constant for calcification.
- Exemplary FloCS systems as provided herein can leverage the synergistic interaction between macroalgae and calcifying organisms to promote a long-term increase in total alkalinity.
- macroalgae consume CO2
- bicarbonate ions are converted into additional CO2, driving the production of carbonate ions.
- calcifying organisms uptake these carbonate ions to form calcium carbonate, further stabilizing the system's alkalinity. This process helps buffer against acidification and improves the resilience of marine ecosystems by reducing the acidifying potential of the water.
- exemplary FloCS systems as provided herein provide a sustainable approach to increasing oceanic alkalinity and promoting marine ecosystem health.
- the experiment included four treatment groups: Control, Algae, Sinker, and exemplary FloCS systems as provided herein, with each group tested under both pressurized (50 MPa) and unpressurized conditions.
- the chambers were stored at 4°C for the duration of the experiment.
- 1 mL water samples were collected from each chamber for both viral and microbial biomass analysis.
- VMR virus- to-microbe ratio
- samples were fixed with 66 pL of 32% paraformaldehyde (2% final concentration) and filtered through 0.02 pm ANODISCTM filters (aluminum oxide membranes having a high level of particle removal efficiency, and having a non-deformable honeycomb pore structure with no lateral crossovers between individual pores) (Whatman).
- Viral particles were stained with SYBR gold (an asymmetrical cyanine dye) and imaged using epifluorescent microscopy, capturing at least 20 images per sample.
- Virus-to-microbe ratio was calculated by dividing the number of viral-like particles (VLPs) by the number of bacterial cells, analyzed using IMAGEPRO PLUSTM software.
- Microbial biomass was measured from the same samples, with 20 pL of 25% glutaraldehyde (2% final concentration) added before filtering through 0.2 pm ANODISCTM filters. The filters were stained with DAPI and imaged using epifluorescent microscopy. Microbial biomass was quantified by calculating cell counts and size measurements using IMAGEPRO PLUSTM software. Viral and microbial responses were measured together to assess the impact of exemplary FloCS as provided herein and other treatments under both pressurized and unpressurized conditions.
- FIG. 8A-D graphically illustrate changes in microbial biomass over time using 1 gram of kelp and 7 grams of mussel shell: FIG. 8 A: Average microbial biomass per cell over time, FIG. 8B: Mean microbial volume, FIG. 8C: Total microbial biomass subset, FIG. 8D: Total microbial biomass.
- FIG. 9A-F graphically illustrates Virus-to-Microbe Ratio (VMR), Virus-Like Particles (VLPs), and Microbial counts over time under pressurized and unpressurized conditions: FIG. 9 A: VMR over time (pressurized), FIG.
- FIG. 9B VLPs per mL (pressurized)
- FIG. 9C Number of microbes per mL (pressurized)
- FIG. 9D VMR over time (unpressurized)
- FIG. 9E VLPs per mL (unpressurized)
- FIG. 9F Number of microbes per mL (unpressurized).
- the pressurized systems consistently exhibited lower biomass across all metrics (FIG. 9A-D) compared to unpressurized treatments, indicating that pressure may inhibit microbial growth and activity.
- the VMR data show higher ratios under pressurized conditions, likely due to the decreased number of microbes experienced in pressurized treatments (FIG. 9C-F). These results may indicate that pressure could be affecting the microbes present where they cannot handle the pressure.
- the CO2 DS 4 system is equipped with 10 Niskin bottles (a water sampling device that's used to collect water samples from the ocean; it is a cylindrical, non-metallic tube with stoppers at both ends that can be opened and closed to collect samples at different depths), each with a 1.5 liter (L) capacity, to capture water samples at depth (FIG. 10).
- the system includes an insert for holding samples and glass vials, expanding its utility in deep-sea sampling.
- a key feature of the design is a glass sphere that houses a camera, enabling real-time imaging during deployment. The camera works alongside planar optodes that measure pH and dissolved oxygen (DO) levels, providing direct, in situ data on environmental conditions at the sampling site.
- DO dissolved oxygen
- the system is durable yet lightweight, ensuring ease of deployment. Its compact design and reliance on accessible materials make it not only cost-effective but also feasible for deployment from smaller vessels.
- the Niskin bottles are triggered to close either via an acoustic signal or a galvanic timed release, allowing for precise, timed sampling without the need for large-scale redeployment equipment.
- This integration of real-time measurements with sample collection offers a novel approach to understanding how algae-driven carbon sequestration impacts microbial communities at depth.
- the ability to capture pH and DO data in conjunction with imaging allows for a more comprehensive assessment of environmental changes in deep-sea ecosystems.
- the CO2 DS 4 system represents a significant advancement in deep-sea research, combining innovation, efficiency, and scalability.
- FIG. 10A schematically illustrates a rosette design showing the arrangement of Niskin bottles, glass sphere, and rosette structure
- FIG. 10B schematically illustrates an individual Niskin bottle assembly and configuration
- FIG. IOC schematically illustrates a fully assembled system integrated with the ocean lander, demonstrating the compact design and ability for small boat deployment.
- This system will help us gain valuable data and information to the viability of the product and verify the product functions how we hypothesize.
- Fertile blades of Macrocystis pyrifera were collected from the base of the kelp plant, where dark spots indicated spore presence. The blades were layered in a Pyrex dish with damp paper towels separating each layer (approximately 10 blades per layer), and the dish was stored in a refrigerator for at least 24 hours. 3. After refrigeration, the blades were transferred to a dish with filtered seawater at 12-15°C. The blades (10-15 at a time) were stirred using a serological pipette to release the spores, and the mixture was allowed to sit for 30 minutes.
- the dishes were incubated at 15°C, and ALGA GROWTM solution was added weekly to maintain nutrient levels.
- the settlement process was monitored for 4 weeks, with weekly imaging using a microscope.
- the materials for oyster larvae settlement were prepared in the same way as for the kelp spore experiment. Different plastics and substrates were tested, with both rough (sanded with 120-grit sandpaper) and smooth (untreated) surface treatments. The materials were placed in 150-300 mL crystallizing dishes, which were then placed onto stones in an indoor recirculating system simulating water maintained at 15°C. Each dish was aerated with an air stone to ensure proper oxygen levels.
- Oyster larvae provided by the Hawaiian Shellfish Hatchery, were shipped in a coffee filter containing 1 million larvae (20 mL volume). The larvae were first diluted by placing the filter into 1 liter of filtered seawater. From this solution, 50 mL was taken and further diluted in a flask containing 950 mL of filtered seawater, resulting in a concentration of 50 larvae/mL
- FIG. 11A-D illustrate picture of stages of kelp spore development: FIG. 11 A: Kelp spores immediately post-release observed under a hemocytometer;
- FIG. 11B Gametophytes at 7 days post-release
- FIG. 11C Juvenile kelp 33 days after release
- FIG. 11D Mature kelp after 52 days of growth in a tumble culture tank.
- FIG. 12 illustrates the number of kelp settled per image on various material types; materials are categorized by treatment type: smooth, rough, and unmodified.
- FIG. 13 A illustrates an image showing oyster larvae settled on a test surface
- FIG. 13B graphically illustrates the total count of oyster larvae settled on different materials, categorized by rough, smooth, and unmodified treatments.
- FIG. 14A-C illustrate images of Co-settlement of kelp spores onto pre-settled oysters over time:
- FIG. 14 A Image of settled kelp spores on oysters at 14 days post spore release
- FIG. 14B Image of kelp spores growing on oysters at 21 days post spore release.
- FIG. 14C Image showing the al gale attatched to the sheel at 28 days post spore release
- FIG. 15 graphically shows results illustrating the search for materials that can optimize the ratio of oysters to kelp necessary for successful settlement and growth.
- FIG. 16 An alternative exemplary method for suspension co-settlement is depicted in Figure 16. This exemplary approach enables the sequential or simultaneous settlement of kelp spores and oyster larvae onto a shared substrate in a controlled, conical hatchery system equipped with an air bubbler and a banjo filter for water exchange.
- Kelp Spore Settlement Kelp spores are first inoculated into petri dishes containing 1 cm 2 coupler substrates. These dishes are monitored until spore settlement is confirmed on the substrates.
- Oyster larvae are introduced into the conical hatchery system. With the water movement and suspended state of the substrates, larvae have the opportunity to encounter and settle on the same coupler substrates where the kelp has already settled.
- This co-settlement system also supports flexibility in the order of introduction. Oyster larvae can be settled first onto the coupler substrates, followed by the kelp spores, or both can be introduced simultaneously, allowing them to settle concurrently while suspended in the water column.
- FIG. 16 illustrates a diagram of exemplary methods for co settlement of FloCS devices in suspension.
- Bio-based and Biodegradable Materials Bioplastics (PL A, PHB), Algal Biomass, Chitin, chitosan, activated carbon,
- Wood-Based Materials Balsa Wood, bamboo, Cork, Oak, Cedar, Teak,
- Clay and Earthen Materials Terracotta, Natural Clay, Kaolinite, Bentonite, Ceramic Tiles, Zeolite,
- Biofilm Growth Encouraging the growth of biofilms on the coupler surface can serve as an attractant for larvae and spores. Biofilms often produce chemical signals that promote larval attachment.
- pH Buffers Some calcifying invertebrates require a stable, slightly basic environment to calcify properly. Incorporating pH-buffering materials (such as calcium carbonate or bioactive ceramics) can help create favorable conditions for these species.
- Bioactive Ceramics These materials can slowly release calcium and other trace minerals, providing essential nutrients for calcification. Incorporating bioactive ceramics into the coupler design could enhance long-term settlement and growth.
- the geometric design of the couplers can significantly influence the success of co-settlement. Designs can be tailored to provide sheltered spaces, increase surface area, or encourage water flow. Some potential designs include:
- Honeycomb structures lattice structures, curved surfaces, concave surfaces, hollow chambers, grooved patterns, ridged patterns, 3D-printed designs, spiral designs, mesh grids, dome-shaped structures, porous blocks, stepped surfaces, interlocking tiles, multi-layered plates, modular cubes, staggered stacking systems, slotted panels, textured spheres, wave patterns, undulating surfaces, hexagonal cells, perforated sheets, coral-like skeletons, cylinder tubes, funnel shapes, baffles for water circulation, concave and convex alternating surfaces, fluted columns.
- Examplary sinkers are: Diadema antillarum ,Echinometra viridis, Lytechinus variegatus, Arbacia patheticate, Strongylocentrotus purpuratus, Tripneustes ventricosus, Tripneusteus gratilla
- exemplary FloCS systems incorporate engineered, non-pathogenic marine viruses as an enhancement mechanism for algal degradation. These viruses would be selectively designed to infect and degrade specific types of algae and their associated microbial communities, thereby accelerating biomass breakdown in the exemplary FloCS unit. Rather than acting as a traditional sinker that adds weight and sinks the exemplary FloCS, these viruses would facilitate the release of dissolved organic carbon (DOC) and particulate organic carbon (POC) from the algae, which can be transported more readily into deep-sea layers through natural carbon cycling processes.
- DOC dissolved organic carbon
- POC particulate organic carbon
- Added essential nutrients for macroalgae and calcifying invertebrates including calcium carbonate, phosphate, ammonia, nitrate, dissolved inorganic carbon (DIC), magnesium, iron, and other trace elements.
- FloCS systems as provided herein are adaptable for specific geographic and environmental conditions, allowing customization of floaters and sinkers based on local water temperature, nutrient availability, and ocean currents.
- thermocline • FloCS systems as provided herein enhance carbon sequestration by sinking organic material beyond the thermocline, with its effectiveness validated through modeling and experimental trials.
- FIG. 17A-C illustrates linear regression analysis showing the relationship between algal biomass and: FIG. 17A Virus-to-Microbe Ratio (VMR);
- VMR Virus-to-Microbe Ratio
- FIG. 17B Viral -Like Particles (VLPs), and
- FIG. 17C microbial counts across pressurized and unpressurized treatments, where VMR and VLPs remained higher under pressure, while microbial counts increased significantly with algal biomass, particularly in unpressurized conditions.
- Table 4 shows P-values from regression analysis assessing the effects of algal biomass and pressure on viral and microbial metrics. Significant p-values are indicated with asterisks: * for p ⁇ 0.05, ** for p ⁇ 0.01 :
- FIG. 18A-D illustrates linear regression analysis showing the relationship between microbial biomass and algal biomass across pressurized and unpressurized treatments:
- FIG. 18 A Average microbial biomass per cell
- FIG. 18B Mean microbial volume
- FIG. 18C Total microbial biomass subset
- FIG. 18D Total microbial biomass over time; treatments are standardized by algal biomass to account for variable amounts of algae across experiments.
- Table 5 shows P-values showing the significance of the effects of algal biomass and pressure on different microbial metrics. Significant values are indicated with asterisks
- FIG. 19A-D illustrates images comparing VMR samples with 20 grams algae:
- FIG. 19B exemplary FloCS unpressurized after 2 weeks, showing an overload of microbial growth
- FIG. 19C exemplary FloCS unpressurized after 4 weeks, exhibiting a higher density of smaller microbes
- FIG. 19D exemplary FloCS pressurized after 2 weeks, demonstrating a significantly reduced microbial population due to pressure constraints.
- Ciais, P., et al, 2013 Carbon and Other Biogeochemical Cycles.
- climate Change 2013 The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change; Stocker, T.F., et al (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA.
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Abstract
In alternative embodiments, provided are products of manufacture and methods for exporting or sequestering atmospheric carbon dioxide (CO2), methane, inorganic and organic nutrients, pollutants, metals, plastics, and the like into an aqueous storage reservoir, optionally a long-term aqueous storage reservoir. In alternative embodiments, provided are products of manufacture designed as a Floater-Coupled-to-Sinker (so called "FloCS") that can export CO2, methane, inorganic and organic nutrients, pollutants, metals and/or plastics into or adherent to or attached to a water or aqueous storage reservoir, optionally long-term water or aqueous storage reservoirs.
Description
PRODUCTS OF MANUFACTURE FOR EXPORTING ATMOSPHERIC CARBON DIOXIDE INTO LONG-TERM WATER STORAGE RESERVOIRS
RELATED APPLICATIONS
This Patent Convention Treaty (PCT) International Application claims the benefit of priority under 35 U.S.C. §119(e) of U.S. Provisional Patent Application Serial No. (USSN) 63/547,920, November 09, 2023. The aforementioned application is expressly incorporated herein by reference in its entirety and for all purposes. All publications, patents, patent applications cited herein are hereby expressly incorporated by reference for all purposes.
TECHNICAL FIELD
This invention generally relates to environmental engineering and aquaculturing. In alternative embodiments, provided are products of manufacture and methods for exporting or sequestering atmospheric carbon dioxide (CO2), methane, inorganic and organic nutrients, pollutants, metals, plastics, and the like into an aqueous storage reservoir, optionally a long-term aqueous storage reservoir. In alternative embodiments, provided are products of manufacture designed as a Floater- Coupled-to-Sinker (so called “FloCS”) that can export CO2, methane, inorganic and organic nutrients, pollutants, metals and/or plastics into aqueous storage reservoirs, optionally long-term water or aqueous storage reservoirs.
BACKGROUND
Fossil fuel usage and the subsequent feedback systems, for example, increased release of organic carbon in Arctic peat lands, are leading to an accelerated generation of greenhouse gasses like carbon dioxide (CO2) and methane. The accumulation of these gasses in the atmosphere influence local weather and the greater climate regime of Earth. Other effects include acidification, the lowering of pH driven by CO2 dissolving into water. Cost effective solutions are needed to mitigate these problems to avoid an environmental disaster.
SUMMARY
In alternative embodiments, provided are products of manufacture (so-called Floater-Coupled-to-Sinker, or “FloCS” systems) for exporting or sequestering atmospheric carbon dioxide (CO2), methane, an inorganic or an organic nutrient, a pollutant, a metal, a plastic, or a combination thereof, from an aquatic or an ocean
environment to an aqueous storage reservoir, wherein the carbon dioxide (CO2), methane, an inorganic or an organic nutrient, a pollutant, a metal, a plastic, or a combination thereof is degraded, modified or digested by an organism and exported or sequestered into or adherent to or attached to an aqueous storage reservoir, optionally a long-term aqueous storage reservoir, the products of manufacture comprising:
(a) an aqueous storage reservoir operatively connected to, or attached to, a floater component;
(b) a floater component attached to or operatively attached to the aqueous storage reservoir, wherein the floater comprises at least one organism, optionally at least one plant, macroalgae or algae, and the floater is capable of or fabricated for:
(i) sequestering, degrading or digesting atmospheric carbon dioxide (CO2), methane, an inorganic or an organic nutrient, a pollutant, a metal, a plastic, or a combination thereof, and
(ii) exporting (or transporting, or moving) the sequestered, degraded or digested atmospheric carbon dioxide (CO2), methane, the inorganic or organic nutrient, the pollutant, the metal, the plastic or the combination thereof to or into the aqueous storage reservoir, wherein the floater component comprises or has contained therein (or has attached thereon) an organism (or at least one organism, or a plurality of organisms), and the atmospheric carbon dioxide (CO2), methane, the inorganic or organic nutrient, the pollutant, the metal, the plastic or the combination thereof is degraded, modified or digested or structurally altered by the organism, wherein the floater component is sufficiently buoyant to keep or maintain the aqueous storage reservoir in the photic or euphotic, or epipelagic or sunlit, zone of an aquatic or ocean environment, or at least keep or maintain the aqueous storage reservoir above the mesopelagic zone of the aquatic or ocean environment (or substantially most of the time keep or maintain the aqueous storage reservoir above the mesopelagic zone of the aquatic or ocean environment, or between about 50% to 99% of the time keep or maintain the aqueous storage reservoir above the mesopelagic zone of the aquatic or ocean environment),
wherein optionally the aqueous storage reservoir, optionally a long-term aqueous storage reservoir, is adapted or fabricated to be in an aquatic or ocean environment, wherein optionally the aquatic or ocean environment is a lake (optionally a deep lake with low oxygen bottom waters); a peat-land; a swamp; a man-made dump; a man-made reservoir; a flooded quarry; or a volcanic crater or a caldera; and
(c) a sinker component attached or adherent to the aqueous storage reservoir and/or the floater component, wherein the sinker comprises or has contained therein any organism or man-made material that is denser than water (optionally between about 1% and 100% denser than water), and when in an aqueous environment the sinker componenet is able to grow or expand or modify itself such that over time it becomes sufficiently negatively buoyant to the degree that the product of manufacture sinks, and optionally the sinker component comprises a polymer material that undergoes an increase in density when immersed in seawater, and this increase in density can be achieved by the polymer selectively absorbing divalent cations, optionally calcium (Ca2+) and magnesium (Mg2+) ions, and optionally the polymer matrix comprises: polyacrylate or polyacrylic acid, poly(methacrylic acid) (PMAA), divinylbenzene (DVB), PMAA-DVB, styrene-divinylbenzene (S-DVB), styrene, polydopamine, polyvinyl alcohol, chitosan, activated carbon, a polyelectrolyte complex and/or a mixture thereof, and optionally the polymer composition is modified with one or more functional groups to promote targeted ion absorption (and optionally the functional groups selectively bind to one or more divalent cations, optionally calcium (Ca2+) and/or magnesium (Mg2+) ions) , and optionally the one or more functional groups comprise barium hydroxide, strontium hydroxide, calcium hydroxide or a combination thereof, and optionally this selective absorption induces localized crosslinking or structural contraction within the polymer resulting in a higher-density material without significant expansion in volume. In alternative embodiments, the density -increasing property or properties of the polymer material controls buoyancy, stability, and/or enhanced durability in an aqueous environment, optionally a marine environment, an underwater structure, a buoyancy control systems or a marine sensor housing.
In alternative embodiments of products of manufacture as provided herein, the floater component comprises or has contained therein:
- an organism of the division Rhodophyta (red algae), for example, a plant of the genus Porphyra (such as Porphyra umbilicalis or Porphyra purpurea), Gelidium, Audouinella or I.emanea:
- an organism of the division Phaeophyta (brown algae) or family Phaeophyceae , such as a plant of the genus Ascophyllum such as an Ascophyllum nodosum, a plant of the genus Macrocystis such as a Macrocystis pomifera or a giant kelp (Macrocystis pyrifera ,' a plant of the genus Laminariales such as kelp, for example, Laminaria setchellii, Laminaria hyperborean, Saccharina japonica or Nereocystis lueteana, or, a plant of the genus Sargassum such as Sargassum muticunr,
- an organism of the phylum Chlorophyta (green algae), such as a plant of the clades Chlorophyta, Streptophyta, Mesostigmatophyceae Chlorokybophyceae or Viridiplantae , or a plant of the genus Halimeda such as Halimeda tuna,
- a halophyte, for example, a plant of the family Poaceae or the genus Spartina such as Spartina alterniflora, or plant of the genus Salicornia such as a Salicornia bigelovir, a mangrove, for example, a plant of the genus Rhizophora, for example, a Rhizophora mangle, R. racemosa or R mucronate, a plant of the genus Atriplex, a plant of the genus Panicum, or Anemopsis californica,' or, seagrass, for example, including any marine flowering plant or angiosperm such as a plant of order Alismatales, or of the family Posidoniaceae, Zosteraceae, Hydrocharitaceae or Cymodoceaceae,' or a non-plant composition, for example, a buoyant non-plant material, for example, the floater can comprise a man-made floater such as for example, a degradable floater such as a foam; or a non-degradable floater such as a glass; or a low density, buoyant material.
In alternative embodiments of products of manufacture as provided herein, the sinker component comprises or has contained therein:
- any organism that is denser than water, or has overall negative buoyancy;
- a sponge, a bryozoan (an invertebrate animal of the phylum Bryozoa, such as an animal of the class Gymnolaemata or order Cheilostomata), an ascidian (an animal of the class Ascidiacea, such as a sea squirt), a coral (or an animal of the class Anthozoa, including sea anemones, stony corals, soft corals and gorgonians), an
animal of the phylum Mollusca, for example, a bivalve mollusk such as a clam (for example, of the family Veneridcte. or of the genus Spisula, such as a Spisula solidissima; or a Ruditapes decussatus or Venerupis decussatus) or a mussel, for example, and animal of the subclass Pteriomorphia, including Arcida, Ostreida, Pectinida, Limida, Mytilida and Pleriidci). or including animals of the family Pectinoidea (scallops), or animals of the subclass Palaeohelerodonla. including Unionida (freshwater mussels) and Trigoniida an animal of the genus Haliolis. such as abalone, for example, Haliotis asinina: and, animals of the genus Dreissena. such as the zebra mussel or Dreissena polymorpha
- any bio-mineralizating organisms, including, but not limited to, corals, mollusks like snails, abalone, bryozoans, macroalgae like Halimeda spp. and coralline crustose algae (CCA), microalgae like coccolithophores; or
- a man-made or an inorganic component, for example, concrete, metal, wood, an organic polymer such as plastic, or rock, or any material that can gain density through a chemical process.
In alternative embodiments of products of manufacture as provided herein, the sinker is attached to or adherent to the floater by a natural or a man-made process or material.
In alternative embodiments, provided herein are methods for exporting or sequestering or degrading or digesting atmospheric carbon dioxide (CO2) into a longterm aqueous storage reservoir, comprising:
(a) providing a product of manufacture as provided herein;
(b) and placing the product of manufacture in an aquatic or ocean environment, and optionally the aquatic or ocean environment is a lake (optionally a deep lake with low oxygen bottom waters); a peat-land; a swamp; a man-made dump; a man-made reservoir; a flooded quarry; or a volcanic crater or a caldera.
In alternative embodiments of methods as provided herein the product of manufacture or the sequestered, degraded or digested atmospheric carbon dioxide (CO2), methane, the inorganic or organic nutrient, the pollutant, the metal, the plastic or the combination thereof is periodically collected or harvested, or the product of manufacture or the sequestered, degraded or digested atmospheric carbon dioxide (CO2), methane, the inorganic or organic nutrient, the pollutant, the metal, the plastic
or the combination thereof is collected or harvested about every week, about every month or about every year, or between about one week to one year or more
In alternative embodiments provided are uses of products of manufacture as provided herein for exporting or sequestering or degrading or digesting atmospheric carbon dioxide (CO2) into a long-term aqueous storage reservoir.
In alternative embodiments provided are polymer materials that increase in density upon immersion in seawater, wherein the increase in density results from or through selective absorption of divalent cations, wherein the polymer material comprises polyacrylate or polyacrylic acid, poly(methacrylic acid) (PMAA), divinylbenzene (DVB), PMAA-DVB, styrene-divinylbenzene (S-DVB), styrene, polydopamine, polyvinyl alcohol, chitosan, activated carbon, or a polyelectrolyte complex or a combination thereof, wherein the density increase occurs without substantial volumetric expansion, thus enhancing stability and functionality in marine environments.
In alternative embodiments the polymer material further comprises one or more or a plurality of functional groups that selectively bind to one or more divalent cations, optionally calcium (Ca2+) and/or magnesium (Mg2+) ions, and optionally the one or more functional groups comprise barium hydroxide, strontium hydroxide, calcium hydroxide or a combination thereof, thus promoting crosslinking or structural contraction that results in an increase in density.
In alternative embodiments provided are products of manufacture comprising or having contained therein a polymer material as provided herein, and optionally the products of manufacture further comprise or having contained therein a polymer material as contained herein.
The details of one or more exemplary embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
All publications, patents, patent applications cited herein are hereby expressly incorporated by reference for all purposes.
DESCRIPTION OF DRAWINGS
The drawings set forth herein are illustrative of exemplary embodiments provided herein and are not meant to limit the scope of the invention as encompassed by the claims.
FIG. 1 is a scatter plot of the density of local organisms that graphically illustrates mass in grams as a function of volume in mis for algae versus (vs) calcifying organism densities, as described in detail in Example 1, below.
FIG. 2 is a scatter plot of deep sea chamber that graphically illustrates density (in g/ml) as a function of depth of pressurized sample (in meters) for Macrocystis pyrfiera and Mytilus californianus density at different depths in and ex situ pressure chamber, as described in detail in Example 1, below.
FIG. 3 schematically illustrates a biological and microbial carbon pump energy diagram displaying the movement of carbon from the atmosphere to the deep ocean, as described in detail in Example 1, below.
FIG. 4 illustrates a table (Table 2) with data collected after collecting field samples, as described in detail in Example 1, below.
FIG. 5 illustrates a table (Table 3) that provides an overview of the equations used in the GOLDSIM™ modeling software, which includes growth rates, volumetric changes, and buoyant force calculations for both floaters and sinkers, as described in further detail in Example 2, below.
FIG. 6 schematically illustrates modeling of Macrocystis pyrifera growth and buoyancy in GOLDSIM™: This figure shows the relationships between key parameters affecting growth rate, mass, buoyant force, and density of M. pyrifera, as described in further detail in Example 2, below.
FIG. 7 graphically illustrates simulation of exemplary Force FloCS over 400 days using the GOLDSIM™ model, representing the combined effect of Ostrea gigas oysters and Macrocystis pyrifera kelp on the exemplary FloCS system, as described in further detail in Example 2, below.
FIG. 8A-D graphically illustrate changes in microbial biomass over time using 1 gram of kelp and 7 grams of mussel shell:
FIG. 8A: Average microbial biomass per cell over time,
FIG. 8B: Mean microbial volume,
FIG. 8C: Total microbial biomass subset, and
FIG. 8D: Total microbial biomass; and each treatment is shown for both pressurized (dashed line) and unpressurized (solid line) conditions, as described in further detail in Example 2, below.
FIG. 9A-F graphically illustrates Virus-to-Microbe Ratio (VMR), Virus-Like Particles (VLPs), and Microbial counts over time under pressurized and unpressurized conditions:
FIG. 9A: VMR over time (pressurized),
FIG. 9B: VLPs per mL (pressurized),
FIG. 9C: Number of microbes per mL (pressurized),
FIG. 9D: VMR over time (unpressurized),
FIG. 9E: VLPs per mL (unpressurized), and
FIG. 9F: Number of microbes per mL (unpressurized), as described in further detail in Example 2, below.
FIG. 10A schematically illustrates an exemplary rosette design showing the arrangement of Niskin bottles, glass sphere, and rosette structure;
FIG. 10B schematically illustrates an individual Niskin bottle assembly and configuration; and
FIG. IOC schematically illustrates a fully assembled exemplary system as provided herein integrated with the ocean lander, demonstrating the compact design and ability for small boat deployment, as described in further detail in Example 2, below.
FIG. 11A-D illustrate picture of stages of kelp spore development:
FIG. 11 A: Kelp spores immediately post-release observed under a hemocytometer;
FIG. 11B Gametophytes at 7 days post-release;
FIG. 11C Juvenile kelp 33 days after release; and
FIG. 11D Mature kelp after 52 days of growth in a tumble culture tank, as described in further detail in Example 2, below.
FIG. 12 illustrates the number of kelp settled per image on various material types; materials are categorized by treatment type: smooth, rough, and unmodified, as described in further detail in Example 2, below.
FIG. 13 A illustrates an image showing oyster larvae settled on a test surface; and
FIG. 13B graphically illustrates the total count of oyster larvae settled on different materials, categorized by rough, smooth, and unmodified treatments, as described in further detail in Example 2, below.
FIG. 14A-C illustrate images of Co-settlement of kelp spores onto pre-settled oysters over time:
FIG. 14 A: Image of settled kelp spores on oysters at 14 days post spore release;
FIG. 14B: Image of kelp spores growing on oysters at 21 days post spore release; and
FIG. 14C: Image showing the al gale attatched to the sheel at 28 days post spore release, as described in further detail in Example 2, below.
FIG. 15 graphically shows results illustrating the search for materials that can optimize the ratio of oysters to kelp necessary for successful settlement and growth, as described in further detail in Example 2, below.
FIG. 16 illustrates a diagram of exemplary methods for co settlement of FloCS devices in suspension, as described in further detail in Example 2, below.
FIG. 17A-C illustrates linear regression analysis showing the relationship between algal biomass and:
FIG. 17A Virus-to-Microbe Ratio (VMR);
FIG. 17B Viral -Like Particles (VLPs), and
FIG. 17C microbial counts across pressurized and unpressurized treatments, where VMR and VLPs remained higher under pressure, while microbial counts increased significantly with algal biomass, particularly in unpressurized conditions, as described in further detail in Example 2, below.
FIG. 18A-D illustrates linear regression analysis showing the relationship between microbial biomass and algal biomass across pressurized and unpressurized treatments:
FIG. 18 A: Average microbial biomass per cell;
FIG. 18B: Mean microbial volume,
FIG. 18C: Total microbial biomass subset,
FIG. 18D: Total microbial biomass over time;
as described in further detail in Example 2, below.
FIG. 19A-D illustrates images comparing VMR samples with 20 grams algae:
FIG. 19 A: Normal Virus-to-Microbe Ratio (VMR),
FIG. 19B: exemplary FloCS unpressurized after 2 weeks, showing an overload of microbial growth,
FIG. 19C: exemplary FloCS unpressurized after 4 weeks, exhibiting a higher density of smaller microbes, and
FIG. 19D: exemplary FloCS pressurized after 2 weeks, demonstrating a significantly reduced microbial population due to pressure constraints, as described in further detail in Example 2, below.
Like reference symbols in the various drawings indicate like elements.
DETAILED DESCRIPTION
In alternative embodiments, provided are products of manufacture and methods for exporting or sequestering or degrading or digesting atmospheric carbon dioxide (CO2), methane, inorganic and organic nutrients, pollutants, metals, plastics, and the like into aqueous storage reservoirs, optionally long-term aqueous storage reservoirs.
In alternative embodiments, provided are products of manufacture designed as a Floater-Coupled-to-Sinker (so called “FloCS”) that can export CO2 into long-term water or aqueous storage reservoirs.
In alternative embodiments, the long-term water or aqueous storage reservoir (for example, a CCh-sequestering environment) is the ocean, for example, the deep ocean, where organic carbon - the photosynthetic product of light, water, and CO2 - will be sequestered for hundred's to hundreds-of-thousands of years.
In alternative embodiments, the long-term water or aqueous storage reservoir (for example, a CCh-sequestering environment) is a lake, for example, a deep lake with low oxygen bottom waters; a peat-land; a swamp; a man-made dump; a manmade reservoir; a flooded quarry, volcanic crater or caldera; and the like.
In alternative embodiments, provided are products of manufacture designed as FloCSs to be used to remove unwanted materials, including by not limited to, for example, inorganic and organic nutrients, pollutants, metals, plastics, and the like.
In alternative embodiments, products of manufacture as provided herein comprise at least two components: one floater that accumulates CO2, methane, inorganic and organic nutrients, pollutants, metals, plastics, and the like; and one sinker, which subsequently delivers these materials into (for example, to the bottom of) the long-term water or aqueous storage reservoir.
In alternative embodiments, the floater and/or sinker is natural or man-made. In alternative embodiments, the floater and/or sinker are directly or indirectly coupled to each other through natural or man-made connection systems or linking agents.
Floaters
In alternative embodiments, the floater is a plant or a macroalgae such as (or comprising):
- as an organism of the division Rhodophyta (red algae), for example, a plant of the genus Porphyra (such as Porphyra umbilicalis or Porphyra purpurea), Gelidium, Audouinella or I.emanea:
- an organism of the division Phaeophyta (brown algae) or family Phaeophyceae , such as a plant of the genus Ascophyllum such as an Ascophyllum nodosum, a plant of the genus Macrocystis such as a Macrocystis pomifera or a giant kelp (Macrocystis pyrifera),' a plant of the genus Laminariales such as kelp, for example, Laminaria setchellii, Laminaria hyperborean, Saccharina japonica or Nereocystis lueteana, or, a plant of the genus Sargassum such as Sargassum muticunr, or
- an organism of the phylum Chlorophyta (green algae), such as a plant of the clades Chlorophyta, Streptophyta, Mesostigmatophyceae Chlorokybophyceae or Viridiplantae , or a plant of the genus Halimeda such as Halimeda tuna.
In alternative embodiments, the floater is a plant such as: a halophyte, for example, a plant of the family Poaceae or the genus Spartina such as Spartina alterniflora, or plant of the genus Salicornia such as a Salicornia bigelovir, a mangrove, for example, a plant of the genus Rhizophora, for example, a Rhizophora mangle, R. racemosa or R mucronate, a plant of the genus Atriplex, a plant of the genus Panicum, or Anemopsis californica,' or, seagrass, for example, including any marine flowering plant or angiosperm such as a plant of order Alismatales, or of the family Posidoniaceae, Zosteraceae, Hydrocharitaceae or Cymodoceaceae .
In alternative embodiments, the floater can comprise, or further comprise, a non-plant composition, for example, a buoyant non-plant material, for example, the floater can comprise a man-made floater such as for example, a degradable floater such as a foam; or a non-degradable floater such as a glass; or a low density, buoyant material.
Sinkers
In alternative embodiments, the sinker comprises or has contained therein (for example, the sinker is fabricated to contain) any organism that is denser than water, for example, a sponge, a bryozoan (an invertebrate animal of the phylum Bryozoa, such as an animal of the class Gymnolaemata or order Cheilostomata), an ascidian (an animal of the class Ascidiacea, such as a sea squirt), a coral (or an animal of the class Anthozoa, including sea anemones, stony corals, soft corals and gorgonians), an animal of the phylum Mollusca, for example, a bivalve mollusk such as a clam (for example, of the family Veneridcte. or of the genus Spisula, such as a Spisula solidissima; or a Ruditapes decussatus or Venerupis decussatus) or a mussel, for example, and animal of the subclass Pteriomorphia, including Arcida, Ostreida, Pectinida, Limida, Mytilida and Pleriidci). or including animals of the family Pectinoidea (scallops), or animals of the subclass Palaeohelerodonla. including Unionida (freshwater mussels) and Trigoniida an animal of the genus Haliolis. such as abalone, for example, Haliotis asinina: and, animals of the genus Dreissena. such as the zebra mussel or Dreissena polymorpha.
In alternative embodiments, the sinker comprises any bio-mineralizating organisms or microorganisms, including, but not limited to, corals, mollusks like snails, abalone, bryozoans, macroalgae like Halimeda spp. and coralline crustose algae (CCA), microalgae like coccolithophores. In alternative embodiments, the sinker comprises a genetically engineered organism or microorganism or algae engineered to be a bio-mineralizating organism.
The sinker can further comprise, or be attached to, a man-made or an inorganic component, for example, concrete, metal, wood, an organic polymer such as plastic, or rock, or any material that can gain density through a chemical process.
In alternative embodiments, the sinker is attached, bound or coupled a floater, for example, the sinker is coupled to a spore or early developmental stage of a floater.
In alternative embodiments, the sinker is attached, bound or coupled to a floater by a natural process, for example, by the holdfast of a sporophyte phase.
When released into an aquatic environment, the floater will keep the product of manufacture (including the sinker) in the photic or euphotic, or epipelagic or sunlit, zone; or at least above the mesopelagic zone. Through photosynthesis and photosynthesis-supported metabolisms, the floater and/or sinker will grow and accumulate CO2 and other materials. In alternative embodiments, the sinker accumulates CO2 and other materials through autotrophic and heterotrophic feeding. Over time the sinker increases in mass and/or weight, or will also build structures, thus eventually overwhelming the positive buoyancy of the floater component(s), resulting in the product of manufacture, or FloCS, to sink. At some time point, the increasing in mass and/or weight can be according to plan and design by the manufacturer of the product of manufacture, or FloCS, and also can be influenced by natural conditions. In other words, the positive buoyance of the floater eventually is overwhelmed by the negative buoyance of the sinker, and at this point the product of manufacture, or FloCS system, will sink into or to the bottom of the storage reservoir, for example, will sink into the ocean below the thermocline.
In alternative embodiments, advantages of the products of manufacture, or FloCS systems, as provided herein include:
- they can be inexpensive: it is relatively easy and inexpensive to raise billions of sinkers (for example, bivalve, crustaceans or coral larva) and floaters (for example, floater spores and seeds such as macroalgae including kelp and Sargassum, as well as plants like mangroves and seagrasses);
- they can be small and transportable, for example, a pre-deployment FloCS system as provided herein can be very small, both in terms of weight (mgs) and volume (for example, pls or mis);
- they can be modular, for example, different combinations of natural and man-made floaters, sinkers, and couples can be used for different biogeochemical conditions;
- they can have carbon dioxide drawdown potential; for example, a large bull kelp uses about 5 kilogram of carbon in the form of CO2. Humans are currently releasing about 38 gigatonnes of carbon dioxide per year and are projected to release more than 50 gigatonnes of carbon dioxide per year by 2030. A gigatonne is equal to
1,000,000,000,000 kilograms (1012) kg. Therefore, 50 gigatonnes of carbon dioxide per year would require producing 1013 bull kelp FloCS to counter this production and mitigate the problems of carbon dioxide release.
Humans are releasing about 38 billion tons of carbon dioxide (3.8 x 1010 tons; 1 metric ton is 106 grams; 3.8 x 1016 grams). To counter this production and mitigate the problems of climate change, it will be necessary to produce and deploy over 1015 FloCS every year, see for example, Table 1, below. If the targeted total annual cost of the FloCS is $100 million, then the target production cost per FloCS unit is
$0.00000001.
Table 1. Size and cost of exemplary floater-sinker coupled systems (FloCSs) as provided herein to counter human production of CO2.
*10 meters kelp
The assumptions for Table 1 :
1) one meter of piece of kelp has about 1 gram of carbon,
2) each gram of carbon in the kelp represents approximately 4 grams of CO2,
3) humans are releasing about 38 billion tons of carbon dioxide (4 x 1010 tons; 1 metric ton is 106 grams; 4 x 1016 grams).
Any of the above aspects and embodiments can be combined with any other aspect or embodiment as disclosed here in the Summary, Figures and/or Detailed Description sections.
As used in this Specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise.
Unless specifically stated or obvious from context, as used herein, the term “or” is understood to be inclusive and covers both “or” and “and”.
Unless specifically stated or obvious from context, as used herein, the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. About (use of the term “about”) can be
understood as within 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12% 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from the context, all numerical values provided herein are modified by the term “about.”
Unless specifically stated or obvious from context, as used herein, the terms “substantially all”, “substantially most of’, “substantially all of’ or “majority of’ encompass at least about 75%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or 99.5%, or more of a referenced amount of a composition.
The entirety of each patent, patent application, publication and document referenced herein hereby is incorporated by reference. Citation of the above patents, patent applications, publications and documents is not an admission that any of the foregoing is pertinent prior art, nor does it constitute any admission as to the contents or date of these publications or documents. Incorporation by reference of these documents, standing alone, should not be construed as an assertion or admission that any portion of the contents of any document is considered to be essential material for satisfying any national or regional statutory disclosure requirement for patent applications. Notwithstanding, the right is reserved for relying upon any of such documents, where appropriate, for providing material deemed essential to the claimed subject matter by an examining authority or court.
Modifications may be made to the foregoing without departing from the basic aspects of the invention. Although the invention has been described in substantial detail with reference to one or more specific embodiments, those of ordinary skill in the art will recognize that changes may be made to the embodiments specifically disclosed in this application, and yet these modifications and improvements are within the scope and spirit of the invention. The invention illustratively described herein suitably may be practiced in the absence of any element(s) not specifically disclosed herein. Thus, for example, in each instance herein any of the terms "comprising", "consisting essentially of', and "consisting of' may be replaced with either of the other two terms. Thus, the terms and expressions which have been employed are used as terms of description and not of limitation, equivalents of the features shown and described, or portions thereof, are not excluded, and it is recognized that various modifications are possible within the scope of the invention. Embodiments of the invention are set forth in the following claims.
The invention will be further described with reference to the examples described herein; however, it is to be understood that the invention is not limited to such examples.
EXAMPLES
Example 1 : Exemplary Floater-Coupled-to-Sinker (so called “FloCS”) Systems
The world emits over 34 Gigatons (Gt C) of CO2 per year (ref. 1). The ocean is a carbon sink removes 2.3 Gt C annually (ref. 2). A method to increase the ocean’s carbon dioxide removal (CDR) potential can sink macroalgae to the deep ocean. However, most of the organic carbon assimilated in the photic zone does not make it to the deep ocean due to grazing, remineralization, and different carbon pumps in the ocean(biological, microbial, etc. (refs. 3, 4, 5).
In alternative embodiments, Floaters Coupled to Sinkers (FloCS) devices as provided herein can export different carbon forms (for example, particulate organic carbon (POC), dissolved organic carbon (DOC), recalcitrant DOC (RDOC), etc.) to the deep ocean more quickly. In alternative embodiments, FloCS as provided herein are “floaters” (comprising photosynthetic organisms that capture CO2 and convert into biomass) physically coupled to “Sinkers” (comprising calcifying organisms that gain mass and drag floater to deep ocean).
FIG. 1 is a scatter plot of the density of local organisms that graphically illustrates mass in grams as a function of volume in mis for algae versus (vs) calcifying organism densities. Local/Native San Diego Calcifying and Algae species and their physical densities are displayed. Wet weight (mass) measurement on the y- axis and volume of the object (mL) on the x-axis. FloCS need to have a positively buoyant "initial phase" and a negatively buoyant "terminal" phase. Therefore, we need to understand how density changes throughout the life history of organisms. This figure displays how juvenile (small mass) densities are extremely close to that of large adults (large mass), insinuating that density may be isometric throughout an organism's life. This will provide us insight as to what organisms we select when we later place them in a modeling system. Less dense floaters may be selected to increase CO2 drawdown time while the most dense sinker may be selected to increase the likelihood the FloCS system eventually sinks.
FIG. 2 is a scatter plot of deep sea chamber that graphically illustrates density (in g/ml) as a function of depth of pressurized sample (in meters) for Macrocystis
pyrfiera and Mytilus californianus density at different depths in and ex situ pressure chamber; we selected one species of floaters and sinkers to simulate deep ocean conditions by subjecting them to pressurization within a chamber. By observing the changes in their density as they traverse the water column, we gain insights into their behavior during the sinking process. Our focus includes identifying the critical points of pneumatocyst implosion/extrusion, which directly influence the buoyancy within the FloCS system. Additionally, we examined whether the organisms' volume undergoes alterations under these pressure conditions.
FIG. 3 is a graphic illustrating deep-sea carbon cycling: biological and microbial carbon pump energy diagram displaying the movement of carbon from the atmosphere to the deep ocean. The left side of the figure depicts the biological carbon pump and how only little bits of carbon actually get stored in the deep ocean. The right side of the figure displays FloCS systems accelerating the export of carbon biomass to the deep ocean to prevent getting remineralized and grazed at shallow depths.
FIG. 4 illustrates a table (Table 2) with data collected after collecting field samples.
Exemplary Procedures for Density Measurements (Archimedes Principle):
Materials Density Control:
An Archimedes Principle experiment, or a materials density experiment, is performed prior to taking samples. This involves verifying the density of 15 different materials of known densities and measuring their mass, volume displacement, and thus density:
1) On sheet 5 in the master data sheet labeled, ‘Materials Validation’ you will find a list of 20 1cm3 cubes of different materials/densities.
2) Place each material on a tared scale and record the mass.
Since it is 1 cm3, this should be the density of that material.
3) Using a small Eureka beaker, fill with seawater until the downspout begins to flow. Once it stops, place a graduated cylinder on a tared scale underneath the downspout.
4) Place your cube in the beaker and record the volume displaced in the cylinder and the mass of that displaced water on the scale.
5) Verify that the mass measurement and volume displaced gets you within the known density range of that material.
Collection:
1) Identify species of interest and check with local standards to ensure it is not a protected species or in a reserve/protected area. Have necessary permits or collect with a lab member who has one. a) Intertidal zones at low tide are an ample place to collect benthic invertebrates (Sinkers) and gather a few pelagic/drifting algal species (Floaters).
2) Collect enough samples of each species. Aim to collect different life stages, to obtain an accurate density curve between life stages. Aim for a few juveniles (approximately2-3), majority of mid-life or not fully grown samples (approximately 4-5), a few fully grown adults (approximately2-3). a) For algae (Floaters) it may be difficult to find juveniles, depending on season, you can use a small amount of mass to ‘mimic’ a juvenile life stage. Use a piece of algae with only 1-2 pneumatocysts and small over mass(grams).
3) Properly transport organisms a) Separate your species (both floaters and sinkers) into their own ziplock bags. Wet the bag with fresh sea water prior to putting your samples in the ziplock. Do not leave large amounts of water in the bag. b) Make sure there is a pocket of air in the ziplock and seal it shut. c) Identify and write species names on the outside of the ziplock bag. d) Place all samples in a styrofoam container with ice packs and a lid to prevent the sun from hitting algae and to keep the contents cold until you arrive to where you will be taking your measurements.
Note: Algae (floater) samples can degrade more or less quickly depending on how long they are in a bag, if the sun is in direct contact with your sample bag, certain species degrade more quickly. *Prioritize collecting your algae (floater) samples last,
with your most sensitive species (i.e., Sargassum sp.) closest to you leaving your collection site to minimize any degradation.
Wet Weight Measurements:
Scale Calibration:
1) Before recording any measurements, you need to calibrate your scale by using the standard weights. Record your measurements in the 4th sheet labeled
‘ Scale Calibration’
2) For good measure, also record the temperature, salinity and density before and after you have collected your measurements.
Algae(Floaters)
*Note: Measure your items in order of the most sensitive species. Certain species of algae are prone to quick decay which can impact your results (i.e., Sargassum) Validation:
Before measuring, you must complete a weight validation table for each species
1) Use a medium sized sample for your validation table, grab your sample from a bin with fresh seawater and place into a salad spinner.
2) Spin your sample 10+ times to ensure any excess water has been spun off.
3) Remove algae from salad spinner and place base of spinner on a scale and tare.
4) Once tared, place algae back into spinner and record the value in sheet three labeled, ‘Weight and Volume validations’
5) Repeat steps 1-4 using the same sample you just measured until 5 measurements have been recorded. Then proceed to wet weight measurement steps.
*Note: you will repeat this for each species you have, Validate and record all volumes for one species, then repeat all steps for the next species.
Wet Weight Measurement:
1) Have a bin with fresh seawater on your lab bench to store your samples you will be measuring.
2) For simplicity, record measurements in size order starting with smallest(juveniles) to largest (adults)
3) Spin your sample 10 + (plus) times to ensure any excess water has been spun off.
4) Remove algae from salad spinner and place base of spinner on a scale and tare.
5) Once zeroed, place algae back into spinner and record the value in sheet 1 labeled ‘Floaters’
6) Repeat steps 3-5 until all samples of that species have been collected then proceed to the next species until all floaters have been recorded.
7) Then move to the floaters volume displacement methods on page .
Calcifying Invertebrates(Sinkers)
*Dip & Shake Method
Validation:
Before measuring, you must complete a weight validation table for each species
1) Use a medium sized sample for your validation table, grab your sample from a bin with fresh seawater and shake your sample gently 10+ times to ensure any excess water has been thrown off.
2) Dry and tare your scale, once zeroed, place your sample on the scale
3) Record the value in sheet three labeled, ‘Weight and Volume validations’ and label your sinker species name
4) Repeat steps 1-3 using the same sample you just measured until 5 measurements have been recorded. Then proceed to wet weight measurement steps.
*Note: you will repeat this for each species you have, Validate and record all volumes for one species, then repeat all steps for the next species.
Wet Weight Measurement:
1) Have your bin of fresh seawater on your lab bench to store your samples you will be measuring.
2) For simplicity, record measurements in size order starting with smallest(juveniles) to largest (adults)
3) Shake your sample 10+ times to ensure any excess water has been thrown off.
4) Dry and tare your scale, once zeroed, place your sample on the scale
5) Record the value in sheet two labeled, ‘Sinkers’
6) Repeat steps 3-5 until all samples of that species have been collected then proceed to the next species till all sinkers have been recorded.
7) Then move to the sinkers volume displacement methods.
Volume Displacement Measurements:
Algae (Floaters):
Validation:
Before measuring, you must complete a volume displacement validation table.
1) Use a medium sized sample for your validation table, preferably the same one you used for the wet weight validation.
2) Place the correctly sized Eureka beaker on an elevated surface with a graduated cylinder on top of a scale underneath the spout of the beaker.
3) Fill the Eureka beaker with fresh seawater until water starts exiting the downwards spout.
4) Once water stops dripping from the spout, empty graduated cylinder, replace graduated cylinder and tare the scale. *Ensure that the graduated cylinder is situated to collect all water coming from the spout.
5) While plugging the end of the spout, place your sample in the Eureka beaker and situate it to be completely submerged.
6) Once it is submerged and the water is still, remove your finger from covering the spout to allow the overflow of water to be emptied into the graduated cylinder.
7) Measure the volume of overflow collected in the graduated cylinder and record this value in the sheet labeled, ‘Weight and Volume Validations’
8) Replace the water from the graduated cylinder back into the Eureka beaker and fill up if needed.
9) Repeat steps 4-8 using the same sample until 5 measurements are recorded for that species. Then proceed to the volume displacement steps below for the rest of your species samples.
*Note: you will repeat this for each species you have, Validate and record all volumes for one species, then repeat all steps for the next species.
Volume Displacement:
1) Have multiple beakers appropriate for the size of your sample. Smaller pieces may require a 100 mL Eureka beaker while larger pieces will need to be placed in a 2000mL Eureka beaker.
2) Place the Eureka beaker on an elevated surface with a graduated cylinder on top of a scale underneath the spout of the beaker. *See image above
3) Fill the Eureka beaker with fresh seawater until water starts exiting the downwards spout.
4) Once water stops dripping from the spout, empty graduated cylinder, replace graduated cylinder and tare the scale. *Ensure that the graduated cylinder is situated to collect all water coming from the spout.
5) While plugging the end of the spout, place your sample in the Eureka beaker and situate it to be completely submerged.
6) Once it is submerged and the water is still, remove your finger from covering the spout to allow the overflow of water to be emptied into the graduated cylinder.
7) Measure the volume of overflow collected in the graduated cylinder and record this value in the sheet labeled, ‘Weight and Volume Validations’
8) Replace the water from the graduated cylinder back into the Eureka beaker and fill up if needed.
9) Repeat steps 4-8 until all samples recorded for that species. Proceed back to the validation steps for the next algae species.
10) Once all algae volume displacement measurements have been taken, proceed to Volume displacement measurement for sinkers steps.
Calcifying Invertebrates (Sinkers)
Validation:
1) Use a medium sized sample for your validation table, preferably the same one you used for the wet weight validation.
2) Place the correctly sized Eureka beaker on an elevated surface with a graduated cylinder on top of a scale underneath the spout of the beaker.
3) Fill the Eureka beaker with fresh seawater until water starts exiting the downwards spout.
4) Once water stops dripping from the spout, empty graduated cylinder, replace graduated cylinder and tare the scale. *Ensure that the graduated cylinder is situated to collect all water coming from the spout.
5) Wrap a string around the sinker, once secure, slowly lower the sinker into the Eureka beaker until it is submerged. *Must go very slow, if you lower too quickly or forcefully you may get an inaccurate reading.
6) Allow the overflow to pour into the graduated cylinder, once water stops coming out of the spout, remove the sinker from the beaker.
7) Measure the volume of overflow collected in the graduated cylinder and record this value in the sheet labeled, ‘Weight and Volume Validations’
8) Replace the water from the graduated cylinder back into the Eureka beaker and fill up if needed.
9) Repeat steps 4-8 using the same sample until 5 measurements are recorded for that species. Then proceed to the volume displacement steps below for the rest of your species samples.
*Note: you will repeat this for each species you have, Validate and record all volumes for one species, then repeat all steps for the next species.
Volume Displacement:
1) Have multiple beakers appropriate for the size of your sample. Smaller pieces may require a 100 mL Eureka beaker while larger pieces will need to be placed in a 2000mL Eureka beaker.
2) Place the Eureka beaker on an elevated surface with a graduated cylinder on top of a scale underneath the spout of the beaker.
3) Fill the Eureka beaker with fresh seawater until water starts exiting the downwards spout.
4) Once water stops dripping from the spout, empty graduated cylinder, replace graduated cylinder and tare the scale. *Ensure that the graduated cylinder is situated to collect all water coming from the spout.
5) Wrap a string around the sinker, once secure, slowly lower the sinker into the Eureka beaker until it is submerged. *Must go very slow, if you lower too quickly or forcefully you may get an inaccurate reading.
6) Allow the overflow to pour into the graduated cylinder, once water stops coming out of the spout, remove the sinker from the beaker.
7) Measure the volume of overflow collected in the graduated cylinder and record this value in the sheet labeled, ‘Weight and Volume Validations’
8) Replace the water from the graduated cylinder back into the Eureka beaker and fill up if needed.
9) Repeat steps 4-8 until all samples recorded for that species. Proceed back to the validation steps for the next sinker species.
10) Once all sinker volume displacement measurements have been taken, proceed to Data analysis steps below.
Once you have recorded everything for the day, do the ‘after’ portion of the scale calibration on sheet 4 of the master data sheet. As well as recording the temperature, density, and salinity of seawater.
Example 2: Exemplary Floater-Coupled-to-Sinker (so called “FloCS”) Systems
This example described exemplary advancements of Floater-Coupled-to- Sinker products of manufacture as provided herein, describing methods, data, and modeling results that enhance the scalability and effectiveness of exemplary FloCS system for deep-sea carbon sequestration.
Methods same as described in Example 1.
Exemplary Modeling Methods and Results
We used GOLDSIM™ software (a Monte Carlo simulation software solution for dynamically modeling complex systems) (GoldSim Technology Group LLC, Seattle, WA) to predict the buoyancy dynamics of an exemplary product of manufacture (a so-called FloCS system) by incorporating density data and growth rates from the Metabolic Theory of Ecology (MTE) (see, e.g., Brown, J. H., et al (2004) "Toward a metabolic theory of ecology". Ecology 85(7): 1771-89). This model allowed us to visualize the growth and buoyant forces of both floaters and sinkers over time, indicating that the exemplary FloCS remains buoyant for 250-300 days before transitioning to a sinking phase as the macroalgae ceases growing and becomes negatively buoyant. This approach optimizes carbon sequestration by ensuring the material passes through the pycnocline and sinks into the deep sea.
Table 3 (FIG. 5) provides an overview of the equations used in the GOLDSIM™ modeling software, which includes growth rates, volumetric changes, and buoyant force calculations for both floaters and sinkers; the equations used in GOLDSIM™ are listed in FIG. 5.
For the equations in FIG. 5, Table 3:
• rF and rs. Growth rates (1/day) for floater and sinker, respectively.
• and ^7^: Power ratio of floater and sinker from MTE. fR s R
• pF and ps: Density of floater and sinker (g/mL).
• Psw Density of seawater (g/mL).
• ff. Acceleration due to gravity (m/s2).
GOLDSIM™ is an advanced Monte Carlo simulation software tailored for dynamic and probabilistic modeling. We used GOLDSIM™ to have a user interface with the mathematical equations in Table 3 and to simulate scenarios across a timeline. GOLDSIM™ allows inputting data, functions and manipulate pools to generate graphs of the functions, which provides a better visualization of how the system was functioning, as illustrated in FIG. 6. By leveraging these capabilities, GOLDSIM™ can be used to identify optimal species combinations that maximize floating duration for floater biomass while ensuring a dense sinker with high growth rates to ensure effective transport beyond the thermocline.
FIG. 6 schematically illustrates modeling of Macrocystis pyrifera growth and buoyancy in GOLDSIM™: This figure shows the relationships between key parameters affecting growth rate, mass, buoyant force, and density of M. pyrifera. It includes factors like growth coefficients, carrying capacity, fluid density, and gravity, leading to calculations of mass, weight, and buoyancy, as derived from equations in Table 3 (FIG. 5).
Results:
We modelled how the exemplary FloCS system behaves over time simulating the two organisms being coupled together. Using the GOLDSIM™ model, we simulated the dynamics of the exemplary FloCS system, incorporating the combined effect of Ostrea gigas oysters and Macrocystis pyrifera kelp. This simulation was designed to explore how the forces generated by the exemplary FloCS system evolve as the algae grows, reaches its peak, and then decays, ultimately allowing the weight of the sinker to take over and cause the system to sink.
Applying the exemplary Force FloCS equation (Equation 7, Table 3), we modeled the system over 400 days, aiming to determine the timeline for buoyancy loss and eventual sinking, as illustrated in FIG. 7.
FIG. 7 graphically illustrates simulation of exemplary Force FloCS over 400 days using the GOLDSIM™ model, representing the combined effect of Ostrea gigas oysters and Macrocystis pyrifera kelp on the exemplary FloCS system. The force remains positive during the algae’s growth phase for the first 250-300 days, turning negative as the algae decays, triggering the system to sink at day 363.
As shown in Figure 7, the force exerted by the exemplary FloCS system remains positive for the first 250-300 days, during which time the Macrocystis pyrifera is actively growing. Beyond this period, the force gradually turns negative, reaching a tipping point around day 265, the end of the kelps seasonal cycle, as the algae decays and loses buoyancy. The total system becomes negatively buoyant and sinks on day 363. This result aligns with our expectations that the exemplary FloCS system will remain buoyant during the growth phase of the algae, before sinking when the algae degrades, and weight of the sinker takes over.
By using this model, we can identify optimal combinations of floaters and sinkers tailored to specific geographical regions based on local environmental factors such as water temperature, nutrient availability, and ocean currents. The growth rates of both organisms, derived from the Metabolic Theory of Ecology (MTE), can be adjusted within the model to reflect region-specific conditions, allowing for precise predictions of when the exemplary FloCS system will transition from buoyant to sinking. This customization enables us to estimate the duration of photosynthetic activity and carbon uptake by the macroalgae before it sinks. Additionally, by calculating the amount of biomass and its carbon content at the time of sinking, the model provides a detailed assessment of how much atmospheric carbon is ultimately sequestered in the deep ocean. This approach ensures that exemplary FloCS deployments are regionally optimized for maximum efficiency in removing carbon dioxide from the atmosphere, aligning the system's performance with the specific ecological and physical characteristics of the deployment area.
Microbialization Prevention and Algal-Induced Acidification
A key challenge in marine carbon sequestration is the risk of algal degradation leading to microbialization and acidification at intermediate depths. To address this, we investigated whether an exemplary FloCS system as provided herein could mitigate these effects. Our findings show that the exemplary FloCS helps buffer against acidification and reduces the risk of microbial degradation by ensuring rapid sinking of algae to deeper ocean layers. We tested this using deep-sea pressure chambers to track microbial responses, measuring virus-to-microbe ratios (VMR) and microbial biomass under controlled conditions.
Kinetic Equations Governing Carbon Utilization (Buffering Algal Induced Acidification) Methods:
To describe the chemical interactions involved in carbon utilization, we modeled the rates of change in CO2, bicarbonate, and carbonate ion concentrations, as well as the formation of calcium carbonate by calcifiers, using the following kinetic equations:
1. CO2 Uptake by Macroalgae: d[CO2]
= -fcx [CO2]
This equation represents the rate at which CO2 is removed from the water via photosynthesis by macroalgae, where k is the rate constant for CO2 uptake.
2. Conversion of Bicarbonate to CO2: d[HCO3 - ]
= -k2[HCO3~] + k1[CO2] dt
T T d\HCO3 —
Here, — - - reflects the rate of change in bicarbonate concentration, with the term
— k2 [HCO3 ]representing the conversion of bicarbonate to CO2 to replenish what was absorbed by the macroalgae.
This equation models the change in carbonate ion concentration, where the conversion of bicarbonate to carbonate is represented by k2
accounts for the uptake of carbonate ions by calcifiers to produce calcium carbonate.
4. Calcium Carbonate Formation by Calcifiers: d[CaCO3]
— ^3 [£^3 ] dt
This equation describes the rate at which calcium carbonate is formed by calcifiers, where k3 is the rate constant for calcification.
Mechanistic Synergy and Long-term Alkalinity Enhancement
Exemplary FloCS systems as provided herein can leverage the synergistic interaction between macroalgae and calcifying organisms to promote a long-term increase in total alkalinity. As macroalgae consume CO2, bicarbonate ions are converted into additional CO2, driving the production of carbonate ions. Simultaneously, calcifying organisms uptake these carbonate ions to form calcium carbonate, further stabilizing the system's alkalinity. This process helps buffer against
acidification and improves the resilience of marine ecosystems by reducing the acidifying potential of the water. By enhancing natural carbon cycling processes, exemplary FloCS systems as provided herein provide a sustainable approach to increasing oceanic alkalinity and promoting marine ecosystem health.
Measuring Microbialization with Epifluorescent Microscopy Methods:
The experiment included four treatment groups: Control, Algae, Sinker, and exemplary FloCS systems as provided herein, with each group tested under both pressurized (50 MPa) and unpressurized conditions. The chambers were stored at 4°C for the duration of the experiment. At the T 14 timepoint, 1 mL water samples were collected from each chamber for both viral and microbial biomass analysis. For virus- to-microbe ratio (VMR) measurements, samples were fixed with 66 pL of 32% paraformaldehyde (2% final concentration) and filtered through 0.02 pm ANODISC™ filters (aluminum oxide membranes having a high level of particle removal efficiency, and having a non-deformable honeycomb pore structure with no lateral crossovers between individual pores) (Whatman). Viral particles were stained with SYBR gold (an asymmetrical cyanine dye) and imaged using epifluorescent microscopy, capturing at least 20 images per sample. Virus-to-microbe ratio (VMR) was calculated by dividing the number of viral-like particles (VLPs) by the number of bacterial cells, analyzed using IMAGEPRO PLUS™ software.
Microbial biomass was measured from the same samples, with 20 pL of 25% glutaraldehyde (2% final concentration) added before filtering through 0.2 pm ANODISC™ filters. The filters were stained with DAPI and imaged using epifluorescent microscopy. Microbial biomass was quantified by calculating cell counts and size measurements using IMAGEPRO PLUS™ software. Viral and microbial responses were measured together to assess the impact of exemplary FloCS as provided herein and other treatments under both pressurized and unpressurized conditions.
FIG. 8A-D graphically illustrate changes in microbial biomass over time using 1 gram of kelp and 7 grams of mussel shell: FIG. 8 A: Average microbial biomass per cell over time, FIG. 8B: Mean microbial volume, FIG. 8C: Total microbial biomass subset, FIG. 8D: Total microbial biomass. Each treatment is shown for both pressurized (dashed line) and unpressurized (solid line) conditions.
FIG. 9A-F graphically illustrates Virus-to-Microbe Ratio (VMR), Virus-Like Particles (VLPs), and Microbial counts over time under pressurized and unpressurized conditions: FIG. 9 A: VMR over time (pressurized), FIG. 9B: VLPs per mL (pressurized), FIG. 9C: Number of microbes per mL (pressurized), FIG. 9D: VMR over time (unpressurized), FIG. 9E: VLPs per mL (unpressurized), FIG. 9F: Number of microbes per mL (unpressurized).
As shown in FIG. 9A-F, the pressurized systems consistently exhibited lower biomass across all metrics (FIG. 9A-D) compared to unpressurized treatments, indicating that pressure may inhibit microbial growth and activity. In contrast, the VMR data show higher ratios under pressurized conditions, likely due to the decreased number of microbes experienced in pressurized treatments (FIG. 9C-F). These results may indicate that pressure could be affecting the microbes present where they cannot handle the pressure.
Deep-Sea Sampling System CO2 DS4
Now that we understand that we will not be directly transplanting algal- associated microbes to the deep ocean, we need to understand how we will affect the deep sea microbes. The CO2 DS4 system is equipped with 10 Niskin bottles (a water sampling device that's used to collect water samples from the ocean; it is a cylindrical, non-metallic tube with stoppers at both ends that can be opened and closed to collect samples at different depths), each with a 1.5 liter (L) capacity, to capture water samples at depth (FIG. 10). In addition to the Niskin bottles, the system includes an insert for holding samples and glass vials, expanding its utility in deep-sea sampling. A key feature of the design is a glass sphere that houses a camera, enabling real-time imaging during deployment. The camera works alongside planar optodes that measure pH and dissolved oxygen (DO) levels, providing direct, in situ data on environmental conditions at the sampling site.
Constructed primarily from polycarbonate and high-density polyethylene (HDPE), the system is durable yet lightweight, ensuring ease of deployment. Its compact design and reliance on accessible materials make it not only cost-effective but also feasible for deployment from smaller vessels. The Niskin bottles are triggered to close either via an acoustic signal or a galvanic timed release, allowing for precise, timed sampling without the need for large-scale redeployment equipment.
This integration of real-time measurements with sample collection offers a novel approach to understanding how algae-driven carbon sequestration impacts microbial communities at depth. The ability to capture pH and DO data in conjunction with imaging allows for a more comprehensive assessment of environmental changes in deep-sea ecosystems. The CO2 DS4 system represents a significant advancement in deep-sea research, combining innovation, efficiency, and scalability.
FIG. 10A schematically illustrates a rosette design showing the arrangement of Niskin bottles, glass sphere, and rosette structure;
FIG. 10B schematically illustrates an individual Niskin bottle assembly and configuration; and
FIG. IOC schematically illustrates a fully assembled system integrated with the ocean lander, demonstrating the compact design and ability for small boat deployment.
This system will help us gain valuable data and information to the viability of the product and verify the product functions how we hypothesize.
FloCS Development and Settlement Trials
Methods and Results of Settlement Trials
We conducted settlement trials using Macrocystis pyrifera kelp spores and oyster larvae. These trials tested various material surfaces (smooth, rough, and untreated) to optimize co-settlement.
Kelp Spores Methods
1. Various materials, including different plastics, ropes, and other substrates, were prepared to evaluate kelp spore settlement. Each plastic material was treated with either a smooth (untreated) or rough (sanded with 120-grit sandpaper) surface. These materials were placed in 150-300 mL crystallizing dishes filled with filtered seawater and ALGA GROW™ solution (Plagron) (20 mL ALGA GROW™ per 1 L of seawater).
2. Fertile blades of Macrocystis pyrifera were collected from the base of the kelp plant, where dark spots indicated spore presence. The blades were layered in a Pyrex dish with damp paper towels separating each layer (approximately 10 blades per layer), and the dish was stored in a refrigerator for at least 24 hours.
3. After refrigeration, the blades were transferred to a dish with filtered seawater at 12-15°C. The blades (10-15 at a time) were stirred using a serological pipette to release the spores, and the mixture was allowed to sit for 30 minutes.
4. Spore viability and density were assessed using a hemocytometer under a microscope. Spores that were swimming or spinning were considered viable. Based on spore density, 5 mL of spore suspension was added to the 150 mL dishes, and 10 mL to the 300 mL dishes using a serological pipette.
5. The dishes were incubated at 15°C, and ALGA GROW™ solution was added weekly to maintain nutrient levels. The settlement process was monitored for 4 weeks, with weekly imaging using a microscope.
6. After 4 weeks, samples were imaged using a dissecting microscope. For plastics, a standardized imaging pattern was followed with five images per sample: one in the center, two turns upward for the next image, two turns right for the third, two turns down for the fourth, and two turns left for the final image. For nonstandard materials like ropes, images were taken as uniformly as possible. The number of settled blades in the five images was averaged to assess settlement success.
Oyster Larvae
1. The materials for oyster larvae settlement were prepared in the same way as for the kelp spore experiment. Different plastics and substrates were tested, with both rough (sanded with 120-grit sandpaper) and smooth (untreated) surface treatments. The materials were placed in 150-300 mL crystallizing dishes, which were then placed onto stones in an indoor recirculating system simulating water maintained at 15°C. Each dish was aerated with an air stone to ensure proper oxygen levels.
2. Oyster larvae, provided by the Hawaiian Shellfish Hatchery, were shipped in a coffee filter containing 1 million larvae (20 mL volume). The larvae were first diluted by placing the filter into 1 liter of filtered seawater. From this solution, 50 mL was taken and further diluted in a flask containing 950 mL of filtered seawater, resulting in a concentration of 50 larvae/mL
3. To distribute the larvae evenly across the experimental dishes, 10-20 mL of the 50 larvae/mL solution was pipetted into each dish (achieving a concentration of 3.33 larvae/mL in both dish sizes). The flask was stirred between each pipetting step to maintain homogeneity in the larvae suspension.
4. Larvae were fed daily using ISO 1800 (Reed Mariculture), a microalgae concentrate made from T. isochrysis. Each dish was fed 150,000 cells per day by adding 2.56 pL of ISO 1800 to a 100 mL flask of filtered seawater, and 1.5 mL of this solution was pipetted into each dish. This feeding regimen was repeated daily until the end of the experiment.
5. After six days of settlement, larvae counts were performed on the seventh day. To count only the settled larvae, the tiles were gently shaken in seawater to dislodge any larvae that were not fully settled. Images of the entire tile were taken using an IPHONE™, and each settled larvae visible on the material was manually counted. This process was repeated for each material, and the total number of settled larvae was recorded to assess which materials provided the best settlement conditions.
FloCS Methods
1. Oyster larvae that had already settled on tiles (following the methods described for larvae settlement) were used for this experiment. These pre-settled oysters were placed into new dishes, and the kelp spore settlement protocol was followed, displacing kelp spores into the dishes containing the pre-settled oyster larvae.
2. Weekly water changes were performed throughout the experiment to maintain optimal conditions. Additionally, ALGA GROW™ solution was added weekly to maintain nutrient levels, and ISO 1800™ (whole-cell concentrate of Isochrysis microalgae) microalgae concentrate was fed daily at a concentration of 150,000 cells per day to sustain the oyster larvae.
3. A weekly microscope check was conducted to monitor potential kelp spore settlement onto the oyster larvae. The focus was on observing whether the kelp spores could successfully couple with the larvae rather than measuring spore density or total counts.
4. After 4-6 weeks, a detailed inspection was performed using a dissecting microscope to determine whether kelp spores had successfully settled onto the oyster larvae. Earlier observations were focused on gametophytes and initial signs of settlement, while the final inspection aimed to confirm successful co-settlement of kelp spores onto the oysters.
FIG. 11A-D illustrate picture of stages of kelp spore development:
FIG. 11 A: Kelp spores immediately post-release observed under a hemocytometer;
FIG. 11B Gametophytes at 7 days post-release;
FIG. 11C Juvenile kelp 33 days after release; and
FIG. 11D Mature kelp after 52 days of growth in a tumble culture tank.
FIG. 12 illustrates the number of kelp settled per image on various material types; materials are categorized by treatment type: smooth, rough, and unmodified.
FIG. 13 A illustrates an image showing oyster larvae settled on a test surface; and
FIG. 13B graphically illustrates the total count of oyster larvae settled on different materials, categorized by rough, smooth, and unmodified treatments.
FIG. 14A-C illustrate images of Co-settlement of kelp spores onto pre-settled oysters over time:
FIG. 14 A: Image of settled kelp spores on oysters at 14 days post spore release;
FIG. 14B: Image of kelp spores growing on oysters at 21 days post spore release; and
FIG. 14C: Image showing the al gale attatched to the sheel at 28 days post spore release,
FIG. 15 graphically shows results illustrating the search for materials that can optimize the ratio of oysters to kelp necessary for successful settlement and growth.
Exemplary Methods for Suspension Co-Settlement
An alternative exemplary method for suspension co-settlement is depicted in Figure 16. This exemplary approach enables the sequential or simultaneous settlement of kelp spores and oyster larvae onto a shared substrate in a controlled, conical hatchery system equipped with an air bubbler and a banjo filter for water exchange.
1. Kelp Spore Settlement: Kelp spores are first inoculated into petri dishes containing 1 cm2 coupler substrates. These dishes are monitored until spore settlement is confirmed on the substrates.
2. Transfer to Hatchery System: Once kelp spores have settled onto the couplers, the substrates are transferred into a conical hatchery system. Here, the air
bubbler creates gentle water movement, keeping the substrates in suspension while allowing for even distribution of larvae and spores in the water column.
3. Introduction of Oyster Larvae: Oyster larvae are introduced into the conical hatchery system. With the water movement and suspended state of the substrates, larvae have the opportunity to encounter and settle on the same coupler substrates where the kelp has already settled.
4. Alternative Approaches: This co-settlement system also supports flexibility in the order of introduction. Oyster larvae can be settled first onto the coupler substrates, followed by the kelp spores, or both can be introduced simultaneously, allowing them to settle concurrently while suspended in the water column.
FIG. 16 illustrates a diagram of exemplary methods for co settlement of FloCS devices in suspension.
Alternative Versions of Exemplary FloCS Couplers: Materials, Settlement Factors, and Nutrients
1. Materials for Couplers
Plastics Already Tested in Experiments:
Acrylic, Cast Acrylic, Cellulose, PETG, Polycarbonate, ABS Plastic, Delrin® Acetal Plastic, HDPE, LDPE, Noryl PPO Plastic, Nylon, Polyester, Polystyrene, Rexolite Polystyrene, styrene-divinylbenzene (S-DVB), styrene, UHMW, CPVC, FEP, Polypropylene, PPS, PVC, PVDF, Teflon® PTFE, Polypropylene Rope, Nylon Rope, Manila Rope, Sisal Rope, Microscope Slides, Aragonite Plugs, Other Calcium Carbonate Plugs, Oyster Shells.
Exemplary Materials to Manufacture Products as provided herein :
PEEK Plastic, PFA Plastic, Polyimide Plastic, Tori on PAI Plastic, Ultem PEI Plastic, Fiberglass (GP03), Garolite (CE, G-3, G-7, G-9, G-10, G-ll, LE, XX, XXX), Carbon Fiber, Various types of wood, Basalt, Volcanic Rock, Stainless Steel, Titanium, Aluminum, Bioactive Glass, Concrete, Marine-Grade Cement, Geopolymer Concrete, Biofilm-Encouraging Materials, Calcium Carbonate-Based Materials, Zeolite, Geotextiles, Bone-Based Materials, Rubber (Vulcanized), Clay, Quartz Sand Coated Materials, Marine Epoxy, Graphene-Coated Materials, Copper Alloys, Magnesium Alloys, Natural Fibers (Hemp, Coconut Coir), Bioplastics, Silicone, Stainless Steel, Titanium, Aramid Fiber (Kevlar).
Additional Natural Materials:
Natural Fibers: Hemp, Coconut Coir, Jute, Flax, Cotton,
Bio-based and Biodegradable Materials: Bioplastics (PL A, PHB), Algal Biomass, Chitin, chitosan, activated carbon,
Wood-Based Materials: Balsa Wood, Bamboo, Cork, Oak, Cedar, Teak,
Natural Stones: Limestone, Marble, Granite, Slate, Sandstone, Basalt, Volcanic Rock,
Clay and Earthen Materials: Terracotta, Natural Clay, Kaolinite, Bentonite, Ceramic Tiles, Zeolite,
Marine-Based Substrates: Coral Skeletons, Oyster Shells, Mussel Shells, Coral Rubble,
Other Natural Substrates: Seaweed Matting, Peat Moss, Biochar, Soil Aggregates, Kelp-Based Mats, Bark,
Mineral-Based Materials: Pumice, Diatomaceous Earth, Shale, Quartz Sand, Silica-Based Substrates,
Other Potential Materials: Cork, Reclaimed Timber, Coconut Shells, Sawdust Composite, Recycled Paper.
2. Settlement Cues and Enhancers
Different species of calcifying invertebrates and macroalgae require specific settlement cues to optimize attachment and growth. Below are some of the most common settlement cues and enhancers that can be incorporated into FloCS couplers:
• Surface Texture: Roughened surfaces (such as those sanded with 120- grit sandpaper) are known to enhance settlement for a variety of species, particularly oyster larvae and kelp spores. By creating micro-grooves, larvae and spores are more likely to attach and settle. Textured surfaces have been shown to improve settlement rates over smooth surfaces.
• Biofilm Growth: Encouraging the growth of biofilms on the coupler surface can serve as an attractant for larvae and spores. Biofilms often produce chemical signals that promote larval attachment.
• Chemical Settlement Cues: Some species respond to chemical cues such as L-dopa, a compound found in mussel byssal threads, or hydrogen peroxide, which can stimulate larval settlement. Incorporating these cues into the couplers could attract invertebrates like oysters.
• Hydrophobicity vs. Hydrophilicity: Different species prefer substrates that either repel or attract water. By manipulating the hydrophobicity or hydrophilicity of a surface (using coatings or surface treatments), the coupler can be tailored to different species’ preferences.
• pH Buffers: Some calcifying invertebrates require a stable, slightly basic environment to calcify properly. Incorporating pH-buffering materials (such as calcium carbonate or bioactive ceramics) can help create favorable conditions for these species.
• Bioactive Ceramics: These materials can slowly release calcium and other trace minerals, providing essential nutrients for calcification. Incorporating bioactive ceramics into the coupler design could enhance long-term settlement and growth.
3, Nutrient and Growth Enhancers
Calcium Carbonate (CaCCh), Phosphate (PO43 ), Ammonia (NHA), Nitrate (NCh ), Carbonate Ions (CO32 ), Bicarbonate Ions (HCO3 ), Carbon Dioxide (CO2), Magnesium (Mg2+), Iron (Fe), Silicon (Si), Manganese (Mn), Copper (Cu), Zinc (Zn), Cobalt (Co), Molybdenum (Mo), Strontium (Sr), Sulfate (SO42 ), Potassium (K+), Boron (B), Organic Carbon Sources, Microbial Symbiosis, Bioactive Compounds.
4, Geometric Designs for Enhanced Settlement
In addition to the materials used, the geometric design of the couplers can significantly influence the success of co-settlement. Designs can be tailored to provide sheltered spaces, increase surface area, or encourage water flow. Some potential designs include:
Honeycomb structures, lattice structures, curved surfaces, concave surfaces, hollow chambers, grooved patterns, ridged patterns, 3D-printed designs, spiral designs, mesh grids, dome-shaped structures, porous blocks, stepped surfaces, interlocking tiles, multi-layered plates, modular cubes, staggered stacking systems, slotted panels, textured spheres, wave patterns, undulating surfaces, hexagonal cells, perforated sheets, coral-like skeletons, cylinder tubes, funnel shapes, baffles for water circulation, concave and convex alternating surfaces, fluted columns.
Exemplary Species used in products of manufacture as provided herein:
1. Additional Floater Species (Brown Algae with Pneumatocysts)
• Sargassum natans and Sargassum fluitans, Turbinaria ornata, Dictyota spp, Padina spp.
2. Addition of Urchins as Exemplary Sinkers
Examplary sinkers are: Diadema antillarum ,Echinometra viridis, Lytechinus variegatus, Arbacia punctulate, Strongylocentrotus purpuratus, Tripneustes ventricosus, Tripneusteus gratilla
3. Inclusion of Marine Viruses as Sinkers
In alternative embodiments, exemplary FloCS systems incorporate engineered, non-pathogenic marine viruses as an enhancement mechanism for algal degradation. These viruses would be selectively designed to infect and degrade specific types of algae and their associated microbial communities, thereby accelerating biomass breakdown in the exemplary FloCS unit. Rather than acting as a traditional sinker that adds weight and sinks the exemplary FloCS, these viruses would facilitate the release of dissolved organic carbon (DOC) and particulate organic carbon (POC) from the algae, which can be transported more readily into deep-sea layers through natural carbon cycling processes. This targeted viral approach could enhance the overall efficiency of exemplary FloCS in sequestering carbon by expediting algal degradation and reducing potential microbialization near the surface.
Conclusion
Density and Modeling Data:
• Added GOLDSIM™ modeling for buoyancy dynamics, using density data and growth rates from the Metabolic Theory of Ecology (MTE).
• Results show that FloCS systems as provided herein remain buoyant for 250-300 days before transitioning to a sinking phase as algae growth ceases.
• Simulations identify optimal combinations of floaters (macroalgae) and sinkers (calcifying organisms) tailored to specific environmental conditions, maximizing carbon sequestration.
Microbialization Prevention and Algal-Induced Acidification:
• Developed methods to assess the prevention of microbial degradation and buffering of acidification in deep-sea environments using pressure chambers.
• Included equations to explain how the FloCS system buffers algal- induced acidification by absorbing CO2 through macroalgae and forming calcium carbonate via the sinker.
• Results demonstrate that FloCS effectively buffers against acidification and reduces microbial degradation, ensuring long-term stability of deep-sea ecosystems.
Nutrient and Growth Enhancers:
• Added essential nutrients for macroalgae and calcifying invertebrates, including calcium carbonate, phosphate, ammonia, nitrate, dissolved inorganic carbon (DIC), magnesium, iron, and other trace elements.
• FloCS couplers designed to release these nutrients gradually, supporting sustained settlement and growth over time.
Exemplary FloCS Settlement Trials:
• Conducted settlement trials using Macrocystis pyrifera kelp spores and oyster larvae on various surfaces (smooth, rough, untreated).
• Roughened surfaces significantly enhanced the settlement of both species, demonstrating the effectiveness of different textures in promoting cosettlement.
• Pre-settled oyster larvae successfully coupled with kelp spores, demonstrating the potential of FloCS systems as provided herein to facilitate cosettlement of macroalgae and calcifying organisms.
Potential Coupler Materials and Designs:
• Evaluated various materials for FloCS couplers, including plastics, ropes, calcium carbonate plugs, and natural materials like wood and basalt.
• Tested multiple geometric designs (e.g., honeycomb structures, lattice designs, grooved patterns) to maximize surface area, improve water flow, and provide ideal settlement conditions for both macroalgae and invertebrates.
FloCS Deployment in the Field:
• FloCS systems as provided herein are adaptable for specific geographic and environmental conditions, allowing customization of floaters and sinkers based on local water temperature, nutrient availability, and ocean currents.
• FloCS systems as provided herein enhance carbon sequestration by sinking organic material beyond the thermocline, with its effectiveness validated through modeling and experimental trials.
FIG. 17A-C illustrates linear regression analysis showing the relationship between algal biomass and:
FIG. 17A Virus-to-Microbe Ratio (VMR);
FIG. 17B Viral -Like Particles (VLPs), and
FIG. 17C microbial counts across pressurized and unpressurized treatments, where VMR and VLPs remained higher under pressure, while microbial counts increased significantly with algal biomass, particularly in unpressurized conditions.
Table 4 shows P-values from regression analysis assessing the effects of algal biomass and pressure on viral and microbial metrics. Significant p-values are indicated with asterisks: * for p < 0.05, ** for p < 0.01 :
FIG. 18A-D illustrates linear regression analysis showing the relationship between microbial biomass and algal biomass across pressurized and unpressurized treatments:
FIG. 18 A: Average microbial biomass per cell;
FIG. 18B: Mean microbial volume,
FIG. 18C: Total microbial biomass subset,
FIG. 18D: Total microbial biomass over time; treatments are standardized by algal biomass to account for variable amounts of algae across experiments.
Table 5 shows P-values showing the significance of the effects of algal biomass and pressure on different microbial metrics. Significant values are indicated with asterisks
FIG. 19A-D illustrates images comparing VMR samples with 20 grams algae:
FIG. 19 A: Normal Virus-to-Microbe Ratio (VMR),
FIG. 19B: exemplary FloCS unpressurized after 2 weeks, showing an overload of microbial growth,
FIG. 19C: exemplary FloCS unpressurized after 4 weeks, exhibiting a higher density of smaller microbes, and
FIG. 19D: exemplary FloCS pressurized after 2 weeks, demonstrating a significantly reduced microbial population due to pressure constraints.
References Example 1
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5) Baltar, Federico, et al. What Is Refractory Organic Matter in the Ocean? Frontiers in Marine Science , Vol 8 , 2021 https://www.frontiersin.org/articles/10.3389/fmars.2021.642637;
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A number of embodiments of the invention have been described.
Nevertheless, it can be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.
Claims
1. A product of manufacture for exporting or sequestering atmospheric carbon dioxide (CO2), methane, an inorganic or an organic nutrient, a pollutant, a metal, a plastic, or a combination thereof, from an aquatic or an ocean environment to an aqueous storage reservoir, wherein the carbon dioxide (CO2), methane, the inorganic or the organic nutrient, pollutant, metal, plastic, or combination thereof is degraded, modified or digested by an organism and exported or sequestered into or adherent to or attached to an aqueous storage reservoir, optionally a long-term aqueous storage reservoir, the product of manufacture comprising:
(a) an aqueous storage reservoir operatively connected to, or attached to, a floater component;
(b) a floater component attached to or operatively attached to the aqueous storage reservoir, wherein the floater comprises at least one organism, optionally at least one plant, macroalgae or algae, and the floater is capable of or fabricated for:
(i) sequestering, degrading or digesting atmospheric carbon dioxide (CO2), methane, an inorganic or an organic nutrient, a pollutant, a metal, a plastic, or a combination thereof, and
(ii) exporting the sequestered, degraded or digested atmospheric carbon dioxide (CO2), methane, the inorganic or organic nutrient, the pollutant, the metal, the plastic or the combination thereof to the aqueous storage reservoir, wherein the floater component comprises or has contained therein an organism, and the atmospheric carbon dioxide (CO2), methane, the inorganic or organic nutrient, the pollutant, the metal, the plastic or the combination thereof is degraded, modified or digested by the organism, wherein the floater component is sufficiently buoyant to keep or maintain the aqueous storage reservoir in the photic or euphotic, or epipelagic or sunlit, zone of an aquatic or ocean environment, or at least keep or maintain the aqueous storage reservoir above the mesopelagic zone of the aquatic or ocean environment,
wherein optionally the aqueous storage reservoir, optionally a long-term aqueous storage reservoir, is adapted or fabricated to be in an aquatic or ocean environment, wherein optionally the aquatic or ocean environment is a lake (optionally a deep lake with low oxygen bottom waters); a peat-land; a swamp; a man-made dump; a man-made reservoir; a flooded quarry; or a volcanic crater or a caldera; and
(c) a sinker component attached or adherent to the aqueous storage reservoir and/or the floater component, wherein the sinker comprises or has contained therein any organism or man-made material that is denser than water, and when in an aqueous environment is able to grow or expand such that over time it becomes sufficiently negatively buoyant to the degree that the product of manufacture sinks, and optionally the sinker component comprises a polymer material that undergoes an increase in density when immersed in seawater, and this increase in density can be achieved by the polymer selectively absorbing divalent cations, optionally calcium (Ca2+) and magnesium (Mg2+) ions, and optionally the polymer matrix comprises: polyacrylate or polyacrylic acid, poly(methacrylic acid) (PMAA), divinylbenzene (DVB), PMAA-DVB, styrene-divinylbenzene (S-DVB), styrene, polydopamine, polyvinyl alcohol, chitosan, activated carbon, a polyelectrolyte complex and/or a mixture thereof, and optionally the polymer composition is modified with one or more functional groups (and optionally the functional groups selectively bind to one or more divalent cations, optionally calcium (Ca2+) and/or magnesium (Mg2+) ions) to promote targeted ion absorption, and optionally this selective absorption induces localized crosslinking or structural contraction within the polymer resulting in a higher-density material without significant expansion in volume, and optionally the one or more functional groups comprise barium hydroxide, strontium hydroxide, calcium hydroxide or a combination thereof.
2. The product of manufacture of claim 1, wherein the floater component comprises or has contained therein:
- an organism of the genus Sargassum, or Sargassum natans, Sargassum fluitans, an organism of the genus Turbinaria, , or T. ornata, Dictyota spp, and/or a Padina spp.;
- as an organism of the division Rhodophyta (red algae), a plant of the genus Porphyra (optionally Porphyra umbilicalis or Porphyra purpurea), Gelidium, Audouinella or I.emanea:
- an organism of the division Phaeophyta (brown algae) or family Phaeophyceae , optionally a plant of the genus Ascophyllum optionally an Ascophyllum nodosum, a plant of the genus Macrocystis optionally a Macrocystis pomifera or a giant kelp (Macrocystis pyrifera ,' a plant of the genus Laminariales optionally kelp, for example, Laminaria setchellii, Laminaria hyperborean, Saccharina japonica or Nereocystis lueteana, or, a plant of the genus Sargassum optionally Sargassum muticunr,
- an organism of the phylum Chlorophyta (green algae), optionally a plant of the clades Chlorophyta, Streptophyta, Mesostigmatophyceae Chlorokybophyceae or Viridiplantae , or a plant of the genus Halimeda optionally Halimeda tuna,
- a halophyte, optionally, a plant of the family Poaceae or the genus Spartina optionally Spartina alterniflora, or plant of the genus Salicornia optionally a Salicornia bigelovir, a mangrove, optionally, a plant of the genus Rhizophora, optionally, a Rhizophora mangle, R racemosa or R. mucronate, a plant of the genus Atriplex, a plant of the genus Panicum, or Anemopsis californica,' or, seagrass, optionally any marine flowering plant or angiosperm optionally a plant of order Alismatales, or of the family Posidoniaceae, Zosteraceae, Hydrocharitaceae or Cymodoceaceae,' or a non-plant composition, optionally, a buoyant non-plant material, for example, the floater can comprise a man-made floater optionally, a degradable floater optionally a foam; or a non-degradable floater optionally a glass; or a low density, buoyant material.
3. The product of manufacture of claim 1 or claim 2, wherein the sinker component comprises or has contained therein, or is fabricated to contain:
- any organism that is denser than water;
- a sponge, a bryozoan (an invertebrate animal of the phylum Bryozoa, optionally an animal of the class Gymnolaemata or order Cheilostomata), an ascidian (an animal of the class Ascidiacea, optionally a sea squirt), a coral (or an animal of the class Anthozoa, optionally sea anemones, stony corals, soft corals and gorgonians), an animal of the phylum Mollusca, for example, a bivalve mollusk optionally a clam (for example, of the family Veneridcte. or of the genus Spisula, optionally a Spisula solidissima; or a Ruditapes decussatus or Venerupis decussatus) or a mussel, for example, and animal of the subclass Pteriomorphia, optionally Arcida, Ostreida, Pectinida, Limida, Mytilida and Pleriidci). or optionally animals of the family Pectinoidea (scallops), or animals of the subclass Palaeohelerodonla. including Unionida (freshwater mussels) and Trigoniida an animal of the genus Haliolis. optionally abalone, optionally, Haliotis asinina: and, animals of the genus Dreissena. optionally zebra mussel or Dreissena polymorpha:
- a bio-mineralizating organism, optionally comprising a coral, a mollusk or mollusk-like snail, an abalone, a bryozoan, a macroalgae (optionally Hahmeda spp.) and a coralline crustose algae (CCA) or microalgae-like coccolithophores; or
- a man-made or an inorganic component, optionally comprising concrete, metal, wood, an organic polymer (optionally plastic) or rock, or any material that can gain density through a chemical process.
4. The product of manufacture of any of the preceding claims, wherein the sinker is attached or adherent to the floater by a natural or a man-made process or material.
5. The product of manufacture of any of the preceding claims, wherein any part or all of the product of manufacture is fabricated with (or comprises):
- PEEK Plastic, PFA Plastic, Polyimide Plastic, Tori on PAI Plastic, Ultem PEI Plastic, Fiberglass (GP03), Garolite (CE, G-3, G-7, G-9, G-10, G-ll, LE, XX, XXX), Carbon Fiber, Various types of wood, Basalt, Volcanic Rock, Stainless Steel, Titanium, Aluminum, Bioactive Glass, Concrete, Marine-Grade Cement, Geopolymer Concrete, Biofilm-Encouraging Materials, Calcium Carbonate-Based Materials, Zeolite, Geotextiles, Bone-Based Materials, Rubber (Vulcanized), Clay, Quartz Sand Coated Materials, Marine Epoxy, Graphene-Coated Materials, Copper Alloys,
Magnesium Alloys, Natural Fibers (Hemp, Coconut Coir), Bioplastics, Silicone, Stainless Steel, Titanium and/or Aramid Fiber (Kevlar);
- a natural fiber, optionally Hemp, Coconut Coir, Jute, Flax and/or Cotton;
- a bio-based or a biodegradable material, optionally a bioplastic (PLA, PHB), Algal Biomass, Chitin and/or chitosan, and/or activated carbon;
- a wood-Based Material, optionally Balsa Wood, Bamboo, Cork, Oak, Cedar and/or Teak;
- a natural Stone, optionally Limestone, Marble, Granite, Slate, Sandstone, Basalt and/or Volcanic Rock;
- a clay or Earthen Material, optionally Terracotta, Natural Clay, Kaolinite, Bentonite, Ceramic Tiles and/or Zeolite;
- a marine-based substrate optionally Coral Skeletons, Oyster Shells, Mussel Shells and/or Coral Rubble;
- a Seaweed Matting, Peat Moss, Biochar, Soil Aggregates, Kelp-Based Mats and/or Bark;
- a Mineral-Based Material, optionally Pumice, Diatomaceous Earth, Shale, Quartz Sand and/or Silica-Based Substrates; and/or
- Cork, Reclaimed Timber, Coconut Shells, Sawdust Composite and/or Recycled Paper.
6. The product of manufacture of any of the preceding claims, wherein a surface of the product of manufacture is configured or shaped as a: Honeycomb structure, a lattice structure, a curved surface, a concave surface, a hollow chamber, a grooved pattern, a ridged pattern, a 3D-printed design, a spiral design, a mesh grid, a dome-shaped structure, a porous block, a stepped surface, an interlocking tile, a multilayered plate, a modular cube, staggered stacking system, a slotted panel, a textured sphere, a wave pattern, an undulating surface, a hexagonal cell, a perforated sheet, a coral-like skeleton, a cylinder tube, a funnel shape, a baffle for water circulation, a concave and/or a convex alternating surface and/or a fluted column.
7. The product of manufacture of any of the preceding claims, further comprising: Calcium Carbonate (CaCOs), Phosphate (PO43 ), Ammonia (NHA), Nitrate (NCh ), Carbonate Ions (CO32 ), Bicarbonate Ions (HCO3 ), Carbon Dioxide (CO2), Magnesium (Mg2+), Iron (Fe), Silicon (Si), Manganese (Mn), Copper (Cu), Zinc (Zn), Cobalt (Co), Molybdenum (Mo), Strontium (Sr), Sulfate (SO42 ), Potassium (K+), Boron (B), an Organic Carbon Source, a Microbial Symbiosis, a Bioactive Compound.
8. The product of manufacture of any of the preceding claims, further comprising:
(a) a surface texture, optionally a roughened surface (optionally sanded with 120-grit sandpaper) to enhance settlement for a variety of species, optionally oyster larvae and kelp spores;
(b) a biofilm growth enhancer;
(c) a chemical settlement cues, optionally L-dopa, mussel byssal threads, and/or hydrogen peroxide;
(d) a hydrophobic surface or a hydrophilic surface;
(e) a pH buffer, optionally calcium carbonate and/or a bioactive ceramic; and/or
(f) a bioactive ceramic.
9. A method for exporting or sequestering or degrading or digesting atmospheric carbon dioxide (CO2) into a long-term aqueous storage reservoir, comprising:
(a) providing a product of manufacture as set forth in any of the preceding claims;
(b) and placing the product of manufacture in an aquatic or ocean environment, and optionally the aquatic or ocean environment is a lake (optionally a deep lake with low oxygen bottom waters); a peat-land; a swamp; a man-made dump; a man-made reservoir; a flooded quarry; or a volcanic crater or a caldera.
10. The method of claim 9, wherein the product of manufacture or the sequestered, degraded or digested atmospheric carbon dioxide (CO2), methane, the inorganic or organic nutrient, the pollutant, the metal, the plastic or the combination thereof is periodically collected or harvested, or the product of manufacture or the sequestered, degraded or digested atmospheric carbon dioxide (CO2), methane, the inorganic or organic nutrient, the pollutant, the metal, the plastic or the combination thereof is collected or harvested about every week, about every month or about every year, or between about one week to one year or more.
11. Use of a product of manufacture as set forth in any of the preceding claims for exporting or sequestering or degrading or digesting atmospheric carbon dioxide (CO2) into a long-term aqueous storage reservoir.
12. A polymer material that increases in density upon immersion in seawater, wherein the increase in density results from or through selective absorption of divalent cations, wherein the polymer material comprises polyacrylate or polyacrylic acid, poly(methacrylic acid) (PMAA), divinylbenzene (DVB), PMAA- DVB, styrene-divinylbenzene (S-DVB), styrene, polydopamine, polyvinyl alcohol, chitosan, activated carbon, or a polyelectrolyte complex or a combination thereof, wherein the density increase occurs without substantial volumetric expansion, thus enhancing stability and functionality in marine environments.
13. The polymer material of claim 12, further comprising one or more or a plurality of functional groups that selectively bind to one or more divalent cations, optionally calcium (Ca2+) and/or magnesium (Mg2+) ions, thus promoting crosslinking or structural contraction that results in an increase in density, and optionally the one or more functional groups comprise barium hydroxide, strontium hydroxide, calcium hydroxide or a combination thereof.
14. A product of manufacture comprising or having contained therein a polymer material of claim 12 or claim 13.
15. The product of manufacture of any of the preceding claims, further comprising or having contained therein a polymer material of claim 12 or claim 13.
Applications Claiming Priority (2)
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| US202363547920P | 2023-11-09 | 2023-11-09 | |
| US63/547,920 | 2023-11-09 |
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| WO2025101950A1 true WO2025101950A1 (en) | 2025-05-15 |
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| PCT/US2024/055195 Pending WO2025101950A1 (en) | 2023-11-09 | 2024-11-08 | Products of manufacture for exporting atmospheric carbon dioxide into long-term water storage reservoirs |
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| WO (1) | WO2025101950A1 (en) |
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