Method for reducing environmental effectiveness of environmental contaminants

Abstract

The present invention provides methods for reducing the environmental effectiveness of one or more environmental contaminants in solids, liquids, and combinations of solids and liquids.

Description

Technical Field

[0001] The present invention relates to the remediation of environmental pollutants to reduce their environmental availability. Background Art

[0002] Many pollutants are known to be toxic to humans and the environment. One such known environmental pollutant, mercury, has been listed as a priority hazardous substance by the Agency for Toxic Substances and Disease Registry (ATSDR) of the U.S. Department of Health and Human Services. The U.S. National Priorities List (NPL) maintained by the U.S. Environmental Protection Agency (EPA) lists many mercury-contaminated sites, such sites containing various contaminant-containing materials, including solids (such as soil, debris, waste), liquids (such as groundwater, lakes, ponds), and combinations of solids and liquids (such as sludge, slurry, sediment). Most of these sites have not been decontaminated to remove mercury. Unacceptable levels of mercury or mercury compounds may also be present in sites not listed in the U.S. NPL. Similar concerns have been raised for environmental pollutants other than mercury.

[0003] Mercury contamination has a variety of different sources, such as mining and ore processing, metal smelting, chlor-alkali plants, production of mercury thermometers and thermostats, production of fluorescent lamps, and battery manufacturing. There are also many landfills contaminated with mercury-containing waste. In addition, mercury contaminants often exist in multiple forms at the same site, including elemental mercury, organic mercury compounds, and inorganic mercury compounds. Different mercury forms and / or different substances often require different treatment methods.

[0004] Mercury-contaminated materials may also contain a variety of other environmental pollutants. For example, some materials are also contaminated with organic matter and / or other heavy elements, and these other environmental pollutants pose similar challenges. Thus, reducing the environmental availability of environmental pollutants at any particular site is technically challenging and costly, depending on the contaminated material, the state of the material, the type of waste, the form of mercury, and the other pollutants or environmental contaminants present. Reducing the environmental availability of environmental pollutants, and thus reducing the bioavailability of the pollutants and therefore their bioaccumulation (especially in materials such as soil, groundwater, sediment, and slurry) is of particular interest.

[0005] Currently, commercial remediation methods applied to soils and other solids include stabilization / solidification, washing, thermal desorption, and vitrification. Methods applied to water and other liquids include precipitation / coprecipitation, adsorption, filtration, and bioremediation. Methods applied to sediments and other solid and liquid combinations include in situ capping, dredging / excavation, combinations of these approaches, and Monitored Natural Recovery (MNR) and enhanced Monitored Natural Recovery (EMNR). Monitored Natural Recovery relies on natural processes to protect the environment and receptors from unacceptable pollutant exposures, while enhanced MNR applies materials or amendments to enhance the natural recovery process (e.g., adding a thin layer cap or reactive amendments such as carbon). These remediation technologies all provide benefits for controlling the environmental impacts of environmental pollutants, including human health and ecological risks, but these remediation technologies also have limitations.

[0006] Another factor to consider for some remediation technologies is that environmental pollutants have a tendency to migrate (or leach) from their location after being isolated or stabilized. The U.S. EPA also regulates this and has developed the Toxicity Characteristic Leaching Procedure (TCLP), which is a test designed to determine the mobility of organic and inorganic analytes present in liquids, solids, and multiphase wastes.

[0007] Before a technology is selected for remediation of an actual contaminated site, complex laboratory-scale and pilot-scale studies and screening tests must be conducted to evaluate the technology to determine its suitability. Additionally, the variability of each site to be treated makes the remediation of mercury and other environmental pollutant contaminations very expensive and time-consuming. Therefore, new and more commercially attractive methods are needed to reduce the environmental and bioavailability of environmental pollutants in solids and liquids and their combinations. Summary of the Invention

[0008] The present invention provides methods for reducing the environmental availability of at least a portion of one or more environmental pollutants in a substance containing one or more environmental pollutants. The benefits provided by the methods of the present invention are to reduce the environmental availability of toxic environmental pollutants in the substance. Such toxic pollutants include mercury and methylmercury, as well as heavy elements and ecotoxic organic substances. Heavy elements are commonly referred to as heavy metals, and heavy elements whose environmental availability can be reduced through the practice of the present invention include mercury, chromium, arsenic, and selenium.

[0009] The advantages provided by the method of the present invention are that, by reducing the environmental availability of environmental pollutants in a substance, the bioavailability and bioaccumulation of such pollutants are also reduced. When the environmental pollutant is mercury, another advantage is that the method of the present invention does not require the presence of sulfide, so the reduction in environmental availability and thus the reduction in bioavailability are not negatively affected by acidic conditions that allow sulfide to form hydrogen sulfide, sulfuric acid or sulfate compounds; the lack of such sulfur-containing compositions further minimizes mercury methylation.

[0010] The method of the present invention can be used as the only method for reducing the environmental availability and / or presence of environmental pollutants (such as mercury) in a substance, or can be used to supplement and / or enhance the reduction in the environmental availability and / or amount of such environmental pollutants in a substance achievable by the prior art.

[0011] An embodiment of the present invention is a method for reducing the environmental availability of at least a portion of one or more environmental pollutants in a substance containing one or more environmental pollutants. The method includes adding and / or applying a halogen-containing adsorbent and an oxidant capable of oxidizing elemental mercury to the substance. In the halogen-containing adsorbent, the halogen includes one or more halogens selected from chlorine, bromine and / or iodine and one or more matrix materials. Adding and / or applying the halogen-containing adsorbent and the oxidant to the pollutant-containing substance reduces the environmental availability of at least a portion of one or more environmental pollutants in the substance.

[0012] These and other embodiments and features of the present invention will become more apparent from the following description and the appended claims. Detailed Description

[0013] The present invention provides a method for reducing the environmental availability of environmental pollutants. As used throughout this document, the term "reducing environmental availability" refers to stabilizing, immobilizing, fixing, encapsulating, separating, containing, destroying, detoxifying, decomposing and decaying at least one environmental pollutant, reducing the amount of at least one environmental pollutant, reducing the mobility of at least one environmental pollutant and / or reducing the migration ability of at least one environmental pollutant. Stabilization and / or immobilization can be carried out in a medium. Reducing the environmental availability of environmental pollutants will in turn reduce the bioavailability of the pollutants and thus reduce their bioaccumulation.

[0014] As used herein, the terms "an environmental pollutant" and "environmental pollutants" mean chemical elements or their compounds or mixtures known to be harmful to humans and / or to affect the environment (ecosystem). Environmental pollutants are typically regulated by one or more governmental agencies. Examples of environmental pollutants include various forms of mercury, e.g., elemental mercury (metallic mercury), organic mercury compounds, and inorganic mercury compounds; other organic substances (including, e.g., but not limited to, hydrophobic organic compounds, polycyclic aromatic hydrocarbons, polyfluoroalkyl substances, perfluoroalkyl substances, polychlorinated biphenyls, dioxins, furans, and / or chlorinated pesticides); harmful elements, organic heavy element compounds, and inorganic heavy element compounds (including, e.g., but not limited to, compounds containing As, Pb, Zn, Cu, Cr, Ni, and / or Cd); and other environmental pollutants known to those skilled in the art.

[0015] As used throughout this document, terms such as "treated", "contacted", and "remediated" indicate that the halogen-containing adsorbent interacts with a substance containing one or more environmental pollutants in a manner that reduces the environmental availability of one or more environmental pollutants.

[0016] The remediation agents in the practice of this invention are halogen-containing adsorbents and oxidants. The halogen-containing adsorbent is sometimes also referred to herein as "halo-adsorbent". The halogen-containing adsorbent is typically formed from one or more halogen-containing compounds and one or more matrix materials. Many matrix materials (especially activated carbon) can be used or obtained in a wide variety of particle sizes ranging from nanometers to centimeters.

[0017] The matrix materials include carbonaceous materials and inorganic materials. Suitable carbonaceous materials that can be used as adsorbents in the practice of this invention include, e.g., but not limited to, activated carbon, carbon black, charcoal, and coke. The preferred carbonaceous material is activated carbon, which can be used in many forms, including, e.g., but not limited to, powdered, granular, microspherical, pelletized, or extruded forms; and has a high specific surface area.

[0018] Suitable inorganic materials include inorganic oxides such as alumina (amorphous alumina and crystalline alumina), silica, magnesia, and titania; natural zeolites such as chabazite, clinoptilolite, and faujasite; synthetic zeolites such as synthetic chabazite, zeolites with a high Si:Al ratio (such as ZSM-5, beta zeolite), zeolites with a medium Si:Al ratio (such as Y zeolite, mordenite), zeolites with a low Si:Al ratio (such as A zeolite, X zeolite), silicoaluminophosphate (SAPO) zeolites, ion-exchanged zeolites, uncalcined zeolites with or without an organic structure-directing agent, aluminosilicates with an ordered pore structure (such as MCM-41, MCM-48, SBA-15, HMS, MSU-X); clay minerals such as kaolin, kaolinite, bentonite, and montmorillonite; synthetic clays such as synthetic hectorite, magadiite, zinc montmorillonite, magadiite, kaolinite, and lithium montmorillonite; organic clays such as montmorillonite treated with stearyltrimethylammonium salts, dimethyldialkyl(C 14 -C 18 ) ammonium salts, methyldihydroxyethylammonium salts, and hydrogenated tallow ammonium salts, as well as aminopropyltriethoxysilane and octadecylamine; bentonite, lithium montmorillonite, and palygorskite treated with quaternary ammonium salts; and zeolites treated with N,N,N-trimethyl-1-hexadecylammonium chloride; inorganic hydroxides such as iron hydroxide; mixed metal oxides such as hydrotalcite and metallated double-layer clays; diatomaceous earth; cement dust; hydrotreating catalysts, including catalysts on a matrix comprising alumina, silica, and / or titania, inorganic carbonates (such as alkali metal carbonates (e.g., sodium carbonate and potassium carbonate) and alkaline earth metal carbonates (e.g., calcium carbonate)); and mixtures of any two or more of the foregoing. Preferred inorganic materials include inorganic oxides (especially silica), natural zeolites (especially chabazite), and clay minerals (especially kaolinite and bentonite); CaCO3 is also a preferred matrix material.

[0019] The halogen element in the halogen adsorbent can be chlorine, bromine, iodine, or a mixture of any two or more of these halogens. Bromine and iodine are preferred halogens; bromine is a more preferred halogen. Suitable halogen-containing substances for forming the halogen adsorbent include, for example but not limited to, elemental iodine and / or iodine compounds, elemental bromine and / or bromine compounds, elemental chlorine and / or chlorine compounds, and other suitable halogen compounds, as known to those skilled in the art. Halogen-containing substances that can be used include elemental halogens, hydrohalic acids, alkali metal halides, alkaline earth metal halides, and ammonium halides. Mixtures of any two or more halogen-containing substances can be used; the mixture can contain the same or different halogens.

[0020] Hydrohalic acids include hydrogen chloride, hydrogen bromide, and hydrogen iodide. Bromides and iodides are preferred halides; more preferably, bromides. Alkali metal halides include lithium halide, sodium halide, potassium halide, rubidium halide, and cesium halide; sodium halide and potassium halide are preferred. Preferred alkali metal halides include sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, and potassium iodide; more preferably, sodium bromide, potassium bromide, and potassium iodide. Alkaline earth metal halides include magnesium halide, calcium halide, strontium halide, and barium halide, and magnesium halide and calcium halide are preferred. Preferred alkaline earth metal halides include magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, and calcium iodide; more preferably, magnesium bromide and calcium bromide. Ammonium halides include ammonium chloride, ammonium bromide, and ammonium iodide; the preferred ammonium halide is ammonium bromide. More preferred halogen-containing substances include elemental bromine, hydrogen bromide, sodium bromide, potassium bromide, and calcium bromide, especially sodium bromide.

[0021] The halogen-containing adsorbent can be made from a matrix material and one or more halogen-containing substances as described in, for example, U.S. Patent Nos. 6,953,494 and 9,101,907 and International Patent Publication No. WO2012 / 071206, especially for bromine-containing adsorbents. In some embodiments, the preferred halogen-containing adsorbent is a bromine-containing adsorbent. In some embodiments, the preferred halogen-containing adsorbent is a halogen-containing activated carbon. In other embodiments, the preferred halogen-containing activated carbon is chlorine-containing activated carbon, bromine-containing activated carbon, and iodine-containing activated carbon. In a preferred embodiment, the halogen-containing adsorbent is iodine-containing activated carbon and bromine-containing activated carbon. In a more preferred embodiment, the halogen-containing adsorbent is bromine-containing activated carbon. Bromine-containing activated carbon can be obtained from Albemarle Corporation.

[0022] In other embodiments, the preferred halogen-containing adsorbents are chlorine-containing activated carbon and iodine-containing activated carbon. In still other embodiments, the preferred halogen-containing adsorbents are halogen-containing chabazite, halogen-containing bentonite, halogen-containing kaolinite, and halogen-containing silica; more preferably, the halogen-containing adsorbents are iodine-containing chabazite, bromine-containing chabazite, iodine-containing bentonite, bromine-containing bentonite, iodine-containing kaolinite, bromine-containing kaolinite, iodine-containing silica, and bromine-containing silica; even more preferably, bromine-containing silica, bromine-containing kaolinite, and bromine-containing bentonite.

[0023] In another embodiment, the preferred halogen-containing adsorbents include bromine-containing silica, bromine-containing kaolinite, and bromine-containing bentonite.

[0024] Based on the total weight of the halogen-containing adsorbent, the amount of halogen (or halogen content) on the matrix material is typically equivalent to the total bromine content (or calculated as bromine) in the range of about 0.1 wt% to about 50 wt%, preferably equivalent to the range of about 0.25 wt% to about 40 wt%, more preferably in the range of about 0.5 wt% to about 35 wt%, even more preferably in the range of about 1 wt% to about 20 wt%, and still more preferably in the range of about 2 wt% to about 12 wt% of the total bromine content.

[0025] Unless otherwise specified, the phrases "calculated as bromine", "reported as bromine", "calculated on a bromine basis" and similar phrases for halogens as used throughout this document refer to the amount of halogen where the numerical value is calculated for bromine. For example, chlorine may be used, but the amount of halogen in the halogen-containing adsorbent is expressed as a value for bromine.

[0026] The halogen-containing activated carbon applicable to the method of the present invention may have a wide range of particle sizes and distributions from nanometers to centimeters; and may be formed in the form of activated carbon, including, for example, but not limited to, powder, granular, microspherical, pellet or extruded forms; high specific surface area, a variety of unique pore structures; and other characteristics familiar to those skilled in the art.

[0027] Halogen-containing adsorbents, especially halogen-containing carbonaceous adsorbents, especially iodine-containing adsorbents and bromine-containing adsorbents, more especially bromine-containing carbonaceous adsorbents, can reduce the environmental availability of pollutants in substances by including, for example, but not limited to, oxidation and / or adsorption. Adsorption can reduce the environmental availability of such pollutants by reducing the mobility of environmental pollutants. Other ways in which halogen-containing adsorbents can reduce the environmental availability of pollutants are by enhancing the degradation of such pollutants via surface reactions; and / or by inhibiting the formation of pollutants (such as methylmercury); and / or by other mechanisms. In the method of the present invention, regardless of whether applied to solids or liquids or combinations thereof, the environmental pollutants adsorbed by the halogen-containing adsorbent are stabilized, so that the amount desorbed into the environment is substantially minimized.

[0028] The oxidants applicable to the practice of the present invention are compounds capable of oxidizing elemental mercury. These oxidants are generally capable of oxidizing other heavy elements, including chromium, arsenic and selenium. In the practice of the present invention, these oxidants are inorganic oxidants and organic oxidants. Inorganic oxidants are generally salts. Organic oxidants are preferably organic peroxides and haloacetohydantoins.

[0029] In the practice of the present invention, inorganic salts suitable as oxidants include persulfates, permanganates, hypochlorites, hypobromites, chlorites, chlorates, bromates, and perchlorates; preferably permanganates, hypochlorites, and chlorates. Preferably, these salts are their alkali metal salts, alkaline earth metal salts, and / or ammonium salts; more preferably, the salts are alkali metal salts.

[0030] In the practice of the present invention, suitable inorganic salts used as oxidants include ammonium persulfate, sodium persulfate, potassium persulfate, sodium permanganate, potassium permanganate, ammonium hypochlorite, sodium hypochlorite, potassium hypochlorite, magnesium hypochlorite, calcium hypochlorite, ammonium hypobromite, sodium hypobromite, potassium hypobromite, calcium hypobromite, ammonium chlorite, sodium chlorite, potassium chlorite, calcium chlorite, ammonium chlorate, sodium chlorate, potassium chlorate, ammonium bromate, sodium bromate, potassium bromate, ammonium perchlorate, sodium perchlorate, and potassium perchlorate.

[0031] Preferred inorganic oxidants include alkali metal permanganates, alkali metal hypochlorites, and alkaline earth metal chlorates. More preferred inorganic oxidants are sodium permanganate, potassium permanganate, sodium hypochlorite, potassium hypochlorite, magnesium chlorate, and calcium chlorate. Even more preferred inorganic oxidants are potassium permanganate, sodium hypochlorite, and calcium chlorate.

[0032] Organic oxidants as organic peroxides have hydrocarbyl groups, each group of which contains four to about twelve carbon atoms, preferably four to about ten carbon atoms; the hydrocarbyl groups can be the same or different and can be alkyl (straight-chain, branched-chain, or cyclic), aryl, or aralkyl. Preferred hydrocarbyl groups are branched-chain alkyl groups and aralkyl groups. Suitable hydrocarbyl groups include tert-butyl, 1,1-dimethylpropyl, 1,1-dimethylbenzyl, and 1,1-dimethyl-4-methylphenyl; preferably tert-butyl and 1,1-dimethylpropyl. Suitable organic peroxides include di-tert-butyl peroxide, bis(1,1-dimethylpropyl) peroxide, tert-butyl 1,1-dimethylbenzyl peroxide, tert-butyl 1,1-dimethyl-4-methylphenyl peroxide, and bis(1,1-dimethylbenzyl) peroxide. Preferred organic peroxides include di-tert-butyl peroxide.

[0033] Organic oxidizing agents as haloalkylhydantoins are halo-5-hydroxyalkylhydantoins and halo-5,5-dihydroxyalkylhydantoins, which are 1,3-dibromo-derivatives, 1,3-dichloro-derivatives and / or N,N'-bromochloro-derivatives (or 1,3-bromochloro derivatives) of 5-hydroxyalkylhydantoins and 5,5-dihydroxyalkylhydantoins. Halo-5,5-dihydroxyalkylhydantoins are preferred. More preferred haloalkylhydantoins are halo-5-alkylhydantoins and halo-5,5-dialkylhydantoins, especially those in which each alkyl group contains up to about 6 carbon atoms. Even more preferred are halo-5,5-dialkylhydantoins in which each alkyl group independently contains up to 3 carbon atoms. Particularly preferred is halo-5,5-dimethylhydantoin.

[0034] Suitable hydantoins include 5-methylhydantoin, 5-ethylhydantoin, 5-(1-propyl)hydantoin, 5-(2-propyl)hydantoin, 5-(2-methylpropyl)hydantoin, 5-(2-butyl)hydantoin, 5-phenylhydantoin, 5-ethyl-5-methylhydantoin, 5-ethyl-5-methylhydantoin, 5-methyl-5-(2-methylpropyl)hydantoin, 5-ethyl-5-(2-methylpropyl)hydantoin, 5-methyl-5-phenylhydantoin, 5-ethyl-5-phenylhydantoin, 5-benzyl-5-methylhydantoin, 5,5-dimethylhydantoin and 5,5-diethylhydantoin; preferred are 5,5-dimethylhydantoin and 5,5-diethylhydantoin, especially 5,5-dimethylhydantoin.

[0035] Preferred haloalkylhydantoins are 1,3-chloro-5,5-dimethylhydantoin, 1,3-bromochloro-5,5-dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin; more preferred are 1,3-bromochloro-5,5-dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin, especially 1,3-dibromo-5,5-dimethylhydantoin.

[0036] Mixtures of any two or more oxidizing agents can be used, including mixtures containing two or more inorganic oxidizing agents, mixtures containing two or more organic oxidizing agents, and mixtures of one or more inorganic oxidizing agents and one or more organic oxidizing agents. Preferably, the oxidizing agent is one or an inorganic oxidizing agent.

[0037] The oxidizing agent and the halogen adsorbent are generally used in amounts of about 1:1 to about 1:25 by weight, preferably about 1:2 to about 1:20, more preferably about 1:3 to about 1:15, and even more preferably about 1:3 to about 1:10 oxidizing agent:halogen adsorbent. The preferred amount of the oxidizing agent can vary with the amount of elemental mercury present in the substance to be treated.

[0038] Mercury and other environmental pollutants are adsorbed onto or removed by halogen-containing adsorbents, especially halogen-containing activated carbons, more especially iodine-containing adsorbents and bromine-containing adsorbents, more especially bromine-containing carbonaceous adsorbents, and still more especially bromine-containing activated carbons. Different halogen (especially bromine) species can form on the halogen-containing adsorbents (especially bromine-containing adsorbents, especially bromine-containing activated carbons). For example, bromine (one bromine species) can oxidize elemental mercury and form mercury bromide, which can be adsorbed into the pores of activated carbon; in another form, bromide ions can chemically bond with ionic mercury and be adsorbed onto the surface of activated carbon; another component can catalyze mercury oxidation and enhance the stabilization or adsorption of the mercury oxide product.

[0039] The oxidizing agent used in accordance with the present invention can oxidize elemental mercury, causing the oxidized mercury to bond with halogen atoms on the adsorbent and / or be absorbed into the pores of the matrix material of the halogen-containing adsorbent.

[0040] Some halogen-containing adsorbents, especially halogen-containing activated carbons, especially iodine-containing adsorbents and bromine-containing adsorbents, more especially bromine-containing carbonaceous adsorbents, especially bromine-containing activated carbons, can physically and chemically adsorb mercury in different oxidation states, including elemental mercury, mercury oxide, and organic mercury. Mercury adsorbed on halogen-containing activated carbon, especially bromine-containing activated carbon, is stable over a wide range of pH values, where "stable" means that the mercury does not separate from the adsorbent in appreciable amounts after adsorption.

[0041] The halogen-containing adsorbent and oxidizing agent used in the method of the present invention can be combined with other optional components such as pH buffers (including, for example, but not limited to ammonium carbonate, metal carbonates, ammonium phosphate, and metal phosphates); carriers (including, for example, but not limited to sand and slurry); binders (including, for example, but not limited to slurry, clay, and polymers); and / or other additives (including, for example, but not limited to iron compounds and sulfur compounds).

[0042] In the practice of the present invention, the halogen-containing adsorbent and oxidizing agent can be used in various forms, including as a dry solid or in combination with a suitable fluid, for example, in the form of a slurry. As used herein, the term "suitable fluid" means a fluid such as water and other fluids. Given the teachings of the present disclosure, those skilled in the art have the knowledge to select a suitable fluid, as the selection depends on variables such as the composition of the substance, the composition of the environmental pollutants present in the substance, and the like.

[0043] A blend comprising a halogen-containing adsorbent and an oxidizing agent capable of oxidizing elemental mercury is a composition of the present invention and is formed by a method comprising combining a matrix material, a halogen-containing compound, and an oxidizing agent in any order. When the mixing is carried out sequentially, preferably the matrix material is combined with the halogen-containing compound to form the halogen-containing adsorbent, and then the halogen-containing adsorbent is combined with the oxidizing agent. Dry blending of the components is a convenient method for combining the components. In some embodiments in which the halogen-containing compound is a salt (such as an alkali metal halide), the halogen-containing compound can be combined with the adsorbent by an initial wetting technique; the halogen-containing adsorbent can be dried before contacting with the oxidizing agent. The matrix material, halogen, halogen-containing compound, oxidizing agent, their amounts, and their preferred options are as described above.

[0044] Some treatment of the substance can be carried out in-situ and ex-situ. Here, "in-situ" means treatment carried out without moving the substance from its location. Examples of in-situ treatment include injecting a halogen-containing adsorbent into soil (usually as a slurry) or mechanically mixing a halogen-containing adsorbent with soil. Similarly, "ex-situ" means treatment carried out during or after removing the substance from its location; after treatment, the substance may or may not return to the location.

[0045] Pyrolysis and dry distillation are two common ex-situ heat treatment methods for mercury remediation. This technique heats the contaminated medium to volatilize mercury, and then condenses the vapor into liquid elemental mercury. Halogen-containing adsorbents and oxidizing agents can be used to adsorb mercury as an alternative to a liquid mercury condenser or to remove mercury from the tail gas discharged from the condenser.

[0046] In some applications, the halogen-containing adsorbent and oxidizing agent will remain in or with the substance. In other applications, the adsorbent and any remaining oxidizing agent can be collected after use. When the halogen-containing adsorbent is collected after use, the adsorbent can be disposed of, or regenerated and reused.

[0047] A substance containing one or more environmental pollutants is a solid, a liquid, or a combination of a solid and a liquid, or a combination of one or more solids and one or more liquids. When the substance is a solid, it can contain more than one solid. When the substance is a liquid, it can contain more than one liquid.

[0048] In some methods of the present invention, the use of a halogen-containing adsorbent and an oxidizing agent can be an independent remediation approach or can supplement the use of other remediation methods, regardless of whether applied to a substance comprising one or more solids, one or more liquids, or a combination of at least one solid and at least one liquid. In other methods according to the present invention, in the same remediation procedure, a halogen-containing adsorbent and an oxidizing agent can be used in addition to one or more other remediation agents.

[0049] Adding a halogen-containing adsorbent and an oxidizing agent to contaminated waste will adsorb one or more contaminants. In some embodiments, the halogen-containing adsorbent and the oxidizing agent are retained in the material to stabilize and / or solidify the material. In other embodiments, the combined halogen-containing adsorbent, oxidizing agent, and material are often placed in a landfill together with a binder and other compounds.

[0050] As used herein, the term "one solid and / or more solids" includes, but is not limited to, soil, debris, waste, and other such materials known to those skilled in the art. Soil is a preferred solid to be treated in the practice of the present invention.

[0051] The method of the present invention is provided for reducing the environmental availability of at least a portion of one or more environmental contaminants in a solid containing one or more environmental contaminants. The material as a solid is sometimes referred to herein as a solid material.

[0052] Adding and / or applying a halogen-containing adsorbent and an oxidizing agent to a solid may include:

[0053] (a) injecting the halogen-containing adsorbent and the oxidizing agent into the solid, optionally through pores and / or wells and / or channels present in the material (whether already existing or artificially created, such as by drilling in the material); and / or

[0054] (b) applying the halogen-containing adsorbent and the oxidizing agent to the surface of the solid; and / or

[0055] (c) combining the halogen-containing adsorbent and the oxidizing agent with at least a portion of the surface of the solid; and / or

[0056] (d) placing the halogen-containing adsorbent and the oxidizing agent in a vacuum well for treating the solid; and / or

[0057] (e) adding the halogen-containing adsorbent and the oxidizing agent to the contained solid; and / or

[0058] (f) combining the halogen-containing adsorbent and the oxidizing agent with the solid; and / or

[0059] (g) adding the halogen-containing adsorbent and the oxidizing agent to a reaction barrier; and / or

[0060] (h) forming a reaction barrier containing the halogen-containing adsorbent and the oxidizing agent.

[0061] Combining the halogen-containing adsorbent and the oxidizing agent with the surface of the solid as in (c) above can be carried out by combining the halogen-containing adsorbent and the oxidizing agent with a portion of the solid and then applying the combination of the adsorbent, oxidizing agent, and solid to the surface of the solid, or by combining the halogen-containing adsorbent and the oxidizing agent with the surface of the solid.

[0062] Some preferred methods of adding and / or applying a halogen-containing adsorbent and an oxidizing agent to a solid are:

[0063] (a) injecting a halogen-containing adsorbent and an oxidizing agent into the solid;

[0064] (b) applying a halogen-containing adsorbent and an oxidizing agent to the surface of the solid; and / or

[0065] (c) combining a halogen-containing adsorbent and an oxidizing agent with at least a portion of the surface of the solid.

[0066] Embodiments of treating a solid to reduce the environmental availability of one or more environmental contaminants involve (i) drilling, boring, and / or channeling in the solid, (ii) covering the surface of the solid with a layer of a halogen-containing adsorbent and an oxidizing agent, and (iii) heating some portions of the solid to cause one or more environmental contaminants (such as mercury) to migrate to the surface having the halogen-containing adsorbent and the oxidizing agent.

[0067] Another embodiment of treating a solid to reduce the environmental availability of one or more environmental contaminants involves (i) drilling, boring, and / or channeling in the solid, (ii) filling some of the holes or channels with a halogen-containing adsorbent and an oxidizing agent, and (iii) blowing heated air into the holes or channels to cause one or more environmental contaminants (such as mercury) to migrate to the holes filled with the halogen-containing adsorbent and the oxidizing agent.

[0068] In some embodiments of the present invention, the solid is heated in a vacuum well to vaporize environmental contaminants (such as mercury); when a halogen-containing adsorbent and an oxidizing agent are present in the vacuum well as in (d) above, the halogen-containing adsorbent and the oxidizing agent can together adsorb one or more vaporized environmental contaminants. In these procedures, the halogen-containing adsorbent and the oxidizing agent are placed in the vacuum well such that they contact the vapor at one or more locations before the vapor generated in the vacuum well is discharged to the atmosphere. One application of such a procedure is soil vapor extraction (SVE) for mercury remediation, and a halogen-containing adsorbent (especially brominated activated carbon) can be placed in the vacuum well together with the oxidizing agent to adsorb mercury.

[0069] In certain types of solid matter soils, halogen-containing sorbents and oxidizing agents can be used to immobilize mercury before and / or during stabilization and solidification (S / S) of in-situ and / or ex-situ soil treatment. An ex-situ method adds a halogen-containing sorbent, an oxidizing agent, one or more binders, and other components to the contaminated material and mixes them together in a reactor. The mixture is then stabilized and cemented or placed in a landfill. In some embodiments, brominated powdered activated carbon can be used with an oxidizing agent during the S / S treatment process. Mercury adsorbed by brominated powdered activated carbon is stable during the manufacture and curing of concrete. This is advantageous because fly ash and cement are typical binders used in S / S technology.

[0070] In another embodiment of the present invention where a halogen-containing sorbent (especially brominated powdered activated carbon) and an oxidizing agent are used together as a remediation agent for mercury-contaminated soil, the halogen-containing sorbent and the oxidizing agent are spread on top of the contaminated soil. In this method, the soil is not disturbed, and the halogen-containing sorbent (especially brominated activated carbon) and the oxidizing agent are present in the top layer of the soil and prevent the migration of mercury from the soil.

[0071] The halogen-containing sorbent (especially brominated activated carbon) can be mixed with an oxidizing agent and another agent to produce a mixture that improves the penetration of the halogen-containing sorbent into solids (especially soil). The amount of the halogen-containing sorbent added can be less than 10% of the soil surface layer, the amount of the oxidizing agent can be up to 10% of the soil surface layer, and the thickness of the soil surface layer can be up to 10 cm. In some embodiments, a pH regulator is also applied, which can be applied alone or mixed with the halogen-containing sorbent and the oxidizing agent, optionally together with an agent that improves the penetration of the halogen-containing sorbent and the oxidizing agent into solids.

[0072] The method of the present invention is provided for reducing the environmental availability of at least a portion of one or more environmental contaminants in a liquid containing one or more environmental contaminants. As used herein, the term "one liquid and / or multiple liquids" includes, but is not limited to, groundwater, wastewater, surface water, brine, fresh water (such as lakes, ponds), and other such substances known to those skilled in the art. A substance that is a liquid is sometimes referred to herein as a liquid substance.

[0073] Adding and / or applying a halogen-containing sorbent and an oxidizing agent to a liquid can include:

[0074] (a) Injecting the halogen-containing sorbent and the oxidizing agent into the liquid; if desired, the sorbent and any remaining oxidizing agent used can be filtered; and / or

[0075] (b) Applying the halogen-containing sorbent and the oxidizing agent to the surface of the liquid; and / or

[0076] (c) Combining a halogen-containing adsorbent and an oxidizing agent with a liquid; and / or

[0077] (d) Passing the liquid through a fixed bed comprising a halogen-containing adsorbent and an oxidizing agent; and / or

[0078] (e) Passing the liquid through a filter comprising a halogen-containing adsorbent and an oxidizing agent; and / or

[0079] (f) Pumping the liquid through a fixed bed or column containing a halogen-containing adsorbent and an oxidizing agent; and / or

[0080] (g) Adding a halogen-containing adsorbent and an oxidizing agent to the volume of liquid contained.

[0081] Combining a halogen-containing adsorbent and an oxidizing agent with a liquid as in (c) above can be carried out by combining the halogen-containing adsorbent and an oxidizing agent with a bulk liquid, or by combining the halogen-containing adsorbent and an oxidizing agent with a portion of the liquid to form a slurry and then combining the slurry with the remaining liquid.

[0082] Some substances are combinations of at least one solid and at least one liquid and include sludge, slurry, sediment, pore water (such as soil pore water or sediment pore water) and other combinations of solids and liquids. Sediments, soil pore water and sediment pore water are preferred combination substances to be treated in the practice of the present invention. These combinations are sometimes referred to as multiphase substances. Methods of the present invention are provided for reducing the environmental availability of at least a portion of one or more environmental contaminants in a combination comprising one or more environmental contaminants. Substances as combinations are sometimes referred to herein as combination substances.

[0083] Adding and / or applying a halogen-containing adsorbent and an oxidizing agent to a combination can include adding and / or applying a halogen-containing adsorbent and an oxidizing agent to the combination. In such methods, adding and / or applying a halogen-containing adsorbent and an oxidizing agent to a combination can include:

[0084] (a) Injecting a halogen-containing adsorbent and an oxidizing agent into the combination, optionally through pores and / or wells and / or channels present in the substance (whether already existing or artificially created, such as by drilling in the combination); and / or

[0085] (b) Applying a halogen-containing adsorbent and an oxidizing agent to the surface of the combination; and / or

[0086] (c) Combining a halogen-containing adsorbent and an oxidizing agent with at least a portion of the surface of the combination as described above for solid and / or liquid substances; and / or

[0087] (d) Combining a halogen-containing adsorbent and an oxidizing agent with the combination; and / or

[0088] (e) Place the halogen-containing adsorbent and the oxidizing agent in a vacuum well for treating the combination in a manner similar to that described for solid substances; and / or

[0089] (f) Add the halogen-containing adsorbent and the oxidizing agent to the combination contained; and / or

[0090] (g) Cover the surface of the substance with a layer containing the halogen-containing adsorbent and the oxidizing agent; and / or

[0091] (h) Place the halogen-containing adsorbent and the oxidizing agent in a lid; and / or

[0092] (i) Add the halogen-containing adsorbent and the oxidizing agent to a reaction barrier; and / or

[0093] (j) Form a reaction barrier containing the halogen-containing adsorbent and the oxidizing agent; and / or

[0094] (k) Place the halogen-containing adsorbent and the oxidizing agent in a geotextile mat.

[0095] Combining the halogen-containing adsorbent and the oxidizing agent with the combination as in (d) above can be carried out by combining the halogen-containing adsorbent and the oxidizing agent with the combination, or by combining the halogen-containing adsorbent and the oxidizing agent with a part of the combination to form a mixture, and then combining the mixture with the surface of the combination. In these embodiments, the halogen-containing adsorbent can include, for example, but not limited to, halogen-containing activated carbon adsorbents, preferably bromine-containing carbon adsorbents, and more preferably bromine-containing activated carbon adsorbents.

[0096] Some preferred methods of adding and / or applying the halogen-containing adsorbent and the oxidizing agent to the combination are:

[0097] (a) Inject the halogen-containing adsorbent and the oxidizing agent into the combination;

[0098] (b) Apply the halogen-containing adsorbent and the oxidizing agent to the surface of the combination;

[0099] (c) Combine the halogen-containing adsorbent and the oxidizing agent with at least a part of the surface of the combination; and / or

[0100] (d) Combine the halogen-containing adsorbent and the oxidizing agent with the combination.

[0101] As will be appreciated by those skilled in the art, depending on the material being processed, many variables regarding the use of the present invention must be considered. In all methods of the present invention, whether applied to solids, liquids, or combinations thereof, in view of the teachings herein, those skilled in the art have the knowledge to determine: the amount of halogen adsorbent to be used; whether optional components are used in combination with the adsorbent, and if so, the specific optional components that will provide benefits and their amounts; the number of applications of the method of the present invention that will provide benefits and the time intervals between such applications; whether the method of the present invention is used in combination with known remediation methods, and if so, how to obtain beneficial results, and so on.

[0102] The following examples are presented for illustrative purposes and are not intended to impose limitations on the scope of the present invention.

[0103] Example 1

[0104] An adsorbent containing NaBr (NaBr-PAC) was formed by impregnating powdered activated carbon (PAC; 10.24 g NaBr / 100 g PAC) with NaBr dissolved in water using the incipient wetness impregnation method, and then the mixture was dried overnight in an oven at 105 °C to give a bromine loading of 8 wt% in the NaBr-PAC adsorbent. Blends of NaBr-PAC and oxidants were formed by dry mixing the NaBr-PAC adsorbent with different oxidants at a weight ratio of NaBr-PAC:oxidant of 5:1.

[0105] Chlor-alkali soil containing elemental mercury, organic mercury, and other contaminants was treated with various adsorbents by dry mixing each adsorbent with a portion of the soil. Each portion was mixed with water to extract water in the form of a soil leachate; samples of each soil leachate were taken for analysis. The amount of mercury present in the leachate of the treated soil was determined by cold vapor atomic absorption (CVAA; atomic absorption mercury spectrometer with Zeeman background correction, Ohio Lumex Co., model RA915+) in an atomic absorption spectrometer equipped with a mercury vapor analyzer. The results are summarized in Table 1.

[0106] Table 1

[0107]

[0108] 1 Comparative example.

[0109] 2 Relative to the weight of the soil treated.

[0110] 3 Average of two runs.

[0111] 4 Formed from elemental bromine and PAC.

[0112] 5 BD = below the detection limit (1 μg / kg).

[0113] The results summarized in Table 1 show that the blend of NaBr-PAC and the oxidizing agent provides performance equivalent to that of Br-PAC in reducing leachable mercury after treatment.

[0114] Other embodiments of the present invention include, but are not limited to:

[0115] A) A method for reducing the environmental availability of at least a portion of one or more environmental pollutants in a substance containing one or more environmental pollutants, the method comprising

[0116] adding and / or applying a halogen-containing adsorbent and an oxidizing agent capable of oxidizing elemental mercury to the substance, wherein the halogen-containing adsorbent comprises one or more halogens selected from chlorine, bromine, and / or iodine and one or more matrix materials,

[0117] thereby reducing the environmental availability of at least a portion of one or more environmental pollutants in the substance.

[0118] B) The method according to A), wherein the halogen-containing adsorbent comprises a matrix material selected from one or more carbonaceous materials, and / or wherein the halogen-containing adsorbent comprises a matrix material selected from one or more inorganic materials.

[0119] C) The method according to B), wherein the carbonaceous material is activated carbon, and / or wherein the inorganic material is selected from inorganic oxides, natural zeolites, inorganic carbonates, and clay minerals.

[0120] D) The method according to B) or C), wherein the inorganic material is selected from chabazite, silica, kaolinite, and bentonite.

[0121] E) The method according to any one of A) to D), wherein the halogen-containing adsorbent is a bromine-containing adsorbent.

[0122] F) The method according to A), wherein the halogen-containing adsorbent is a halogen-containing activated carbon adsorbent.

[0123] G) The method according to A), wherein the halogen-containing adsorbent is a bromine-containing activated carbon adsorbent.

[0124] H) The method according to any one of A) to G), wherein the halogen-containing adsorbent has a halogen content of about 0.1 wt% to about 50 wt% calculated as bromine and based on the total weight of the halogen-containing adsorbent.

[0125] I) The method according to any one of A) to G), wherein the oxidizing agent is an inorganic oxidizing agent, and / or wherein the oxidizing agent is an organic oxidizing agent.

[0126] J) The method according to that described in I), wherein

[0127] the inorganic oxidizing agent is a permanganate, hypochlorite and / or chlorate, and / or wherein the inorganic oxidizing agent is an alkali metal salt, alkaline earth metal salt and / or ammonium salt; and / or

[0128] wherein the organic oxidizing agent is an organic peroxide or a haloacetohydantoin.

[0129] K) The method according to that described in I), wherein

[0130] the inorganic oxidizing agent is an alkali metal permanganate, alkali metal hypochlorite and / or alkaline earth metal chlorate, and / or

[0131] when the oxidizing agent is an organic peroxide, the organic peroxide has a branched alkyl group and / or an aralkyl group, and wherein when the oxidizing agent is a haloacetohydantoin, the haloacetohydantoin is a halo-5,5-dialkylhydantoin.

[0132] L) The method according to that described in I), wherein

[0133] the inorganic oxidizing agent is potassium permanganate, sodium hypochlorite and / or calcium chlorate, and / or

[0134] the organic oxidizing agent is selected from tert-butyl peroxide, 1,3-bromo-chloro-5,5-dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin.

[0135] M) The method according to any one of A) to L), wherein the one or more environmental pollutants are mercury, chromium, arsenic and / or selenium.

[0136] N)) The method according to any one of A) to M), wherein the substance containing the environmental pollutant is a solid, and wherein adding and / or applying the halogen-containing adsorbent and the oxidizing agent to the solid includes:

[0137] (a) Injecting the halogen-containing adsorbent and the oxidizing agent into the solid;

[0138] (b) Applying the halogen-containing adsorbent and the oxidizing agent to the surface of the solid;

[0139] (c) Combining the halogen-containing adsorbent and the oxidizing agent with at least a part of the surface of the solid;

[0140] (d) Placing the halogen-containing adsorbent and the oxidizing agent in a vacuum well for treating the solid;

[0141] (e) Add a halogen-containing adsorbent and an oxidizing agent to the contained solid;

[0142] (f) Combine the halogen-containing adsorbent and the oxidizing agent with the solid;

[0143] (g) Add a halogen-containing adsorbent and an oxidizing agent to the reaction barrier; and / or

[0144] (h) Form a reaction barrier containing a halogen-containing adsorbent and an oxidizing agent;

[0145] Optionally, wherein the solid is soil.

[0146] O) The method according to any one of A) to M), wherein the substance containing the environmental pollutant is a liquid, and wherein adding and / or applying the halogen-containing adsorbent and the oxidizing agent to the liquid includes:

[0147] (a) Inject a halogen-containing adsorbent and an oxidizing agent into the liquid;

[0148] (b) Apply a halogen-containing adsorbent and an oxidizing agent to the surface of the liquid;

[0149] (c) Combine a halogen-containing adsorbent and an oxidizing agent with the liquid;

[0150] (d) Pass the liquid through a fixed bed containing a halogen-containing adsorbent and an oxidizing agent;

[0151] (e) Pass the liquid through a filter containing a halogen-containing adsorbent and an oxidizing agent;

[0152] (f) Pump the liquid through a fixed bed or column containing a halogen-containing adsorbent and an oxidizing agent; and / or

[0153] (g) Add a halogen-containing adsorbent and an oxidizing agent to the contained volume of liquid.

[0154] P) The method according to any one of A) to M), wherein the substance containing the environmental pollutant is a combination of at least one solid and at least one liquid, and wherein adding and / or applying the halogen-containing adsorbent and the oxidizing agent to the combination includes:

[0155] (a) Inject a halogen-containing adsorbent and an oxidizing agent into the combination;

[0156] (b) Apply a halogen-containing adsorbent and an oxidizing agent to the surface of the combination; (c) Combine a halogen-containing adsorbent and an oxidizing agent with at least a part of the surface of the combination;

[0157] (d) Combine the halogen-containing adsorbent and the oxidizing agent with the combination;

[0158] (e) Place the halogen adsorbent and the oxidizing agent in a vacuum well for treating the combination;

[0159] (f) Add the halogen adsorbent and the oxidizing agent to the combination contained;

[0160] (g) Cover the surface of the substance with a layer containing the halogen adsorbent and the oxidizing agent;

[0161] (h) Place the halogen adsorbent and the oxidizing agent in a lid;

[0162] (i) Add the halogen adsorbent and the oxidizing agent to a reaction barrier;

[0163] (j) Form a reaction barrier containing the halogen adsorbent and the oxidizing agent; and / or

[0164] (k) Place the halogen adsorbent and the oxidizing agent in a geotextile mat.

[0165] Q) According to the method described in P), wherein the addition and / or application includes:

[0166] (a) Inject the halogen adsorbent and the oxidizing agent into the combination;

[0167] (b) Apply the halogen adsorbent and the oxidizing agent to the surface of the combination;

[0168] (c) Combine the halogen adsorbent and the oxidizing agent with at least a part of the surface of the combination; and / or

[0169] (d) Combine the halogen adsorbent and the oxidizing agent with the combination;

[0170] Optionally, wherein the combination is sediment.

[0171] R) According to the method described in Q), wherein the halogen adsorbent comprises a matrix material, and the matrix material is activated carbon.

[0172] S) According to the method described in A), wherein the substance is soil or sediment, wherein the halogen adsorbent is a bromine-containing activated carbon adsorbent, and wherein the oxidizing agent is sodium hypochlorite, potassium bromate or calcium chlorate.

[0173] T) According to the method described in Q), wherein

[0174] the oxidizing agent is an inorganic oxidizing agent, and the inorganic oxidizing agent is an alkali metal permanganate, an alkali metal hypochlorite and / or an alkaline earth metal chlorate; and / or

[0175] The oxidizing agent is an organic oxidizing agent, and when the organic oxidizing agent is an organic peroxide, the organic peroxide has a branched alkyl group and / or an aralkyl group, and wherein when the oxidizing agent is a halo-hydantoin, the halo-hydantoin is a halo-5,5-dialkyl hydantoin.

[0176] (U) According to the method described in T, wherein

[0177] The inorganic oxidizing agent is potassium permanganate, sodium hypochlorite and / or calcium chlorate; and / or

[0178] wherein the organic oxidizing agent is selected from tert-butyl peroxide, 1,3-bromo-chloro-5,5-dimethyl hydantoin and 1,3-dibromo-5,5-dimethyl hydantoin.

[0179] V) A blend of a halogen adsorbent and an oxidizing agent capable of oxidizing elemental mercury, wherein the halogen adsorbent contains one or more halogens selected from chlorine, bromine and / or iodine.

[0180] W) According to the blend described in V, wherein the halogen of the halogen adsorbent is bromine and / or iodine, wherein the halogen adsorbent contains a matrix material selected from one or more carbonaceous materials, wherein when the oxidizing agent is an inorganic oxidizing agent, the oxidizing agent is a permanganate, a hypochlorite and / or a chlorate, and / or wherein the oxidizing agent is an alkali metal salt, an alkaline earth metal salt and / or an ammonium salt, and wherein when the oxidizing agent is an organic oxidizing agent, the oxidizing agent is an organic peroxide or a halo-hydantoin.

[0181] X) A method for forming a blend of a halogen adsorbent and an oxidizing agent capable of oxidizing elemental mercury, the method comprising:

[0182] a) i) Combining a halogen-containing compound and a matrix material to form a halogen adsorbent, and ii) combining the halogen adsorbent with an oxidizing agent; or

[0183] b) Combining a halogen adsorbent and an oxidizing agent.

[0184] Y) According to the method described in X), wherein when the halogen of the halogen adsorbent is bromine, the matrix material is a carbonaceous material, wherein when the oxidizing agent is an inorganic oxidizing agent, the inorganic oxidizing agent is a permanganate, a hypochlorite and / or a chlorate, and / or wherein the inorganic oxidizing agent is an alkali metal salt, an alkaline earth metal salt and / or an ammonium salt, and wherein when the oxidizing agent is an organic oxidizing agent, the organic oxidizing agent is an organic peroxide or a halo-hydantoin.

[0185] Z) According to the method described in Y), wherein

[0186] The inorganic oxidant is an alkali metal permanganate, an alkali metal hypochlorite and / or an alkaline earth metal chlorate; and / or

[0187] When the oxidant is an organic oxidant, when the organic oxidant is an organic peroxide, the organic peroxide has a branched alkyl group and / or an aralkyl group, and wherein when the organic oxidant is a halogenated hydantoin, the halogenated hydantoin is a halogenated 5,5-dialkylhydantoin.

[0188] AA) According to the method described in Z), wherein

[0189] The inorganic oxidant is potassium permanganate, sodium hypochlorite and / or calcium chlorate; and / or

[0190] The organic oxidants are selected from tert-butyl peroxide, 1,3-bromo-chloro-5,5-dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin.

[0191] AB) According to the method according to any one of Y) to AA), wherein the matrix material is activated carbon.

[0192] Any component mentioned by chemical name or chemical formula anywhere in this specification or its claims, whether mentioned in the singular or plural, is recognized as existing before it comes into contact with another substance (e.g., another component, solvent, etc.) mentioned by chemical name or chemical type. It does not matter what chemical changes, transformations and / or reactions (if any) occur in the resulting mixture or solution, because such changes, transformations and / or reactions are the natural result of bringing the specified components together under the conditions required by the present disclosure. Thus, these components are recognized as ingredients that are brought together to perform the desired operation or form the desired composition. Furthermore, although the following claims may refer to substances, components and / or ingredients in the present tense ("comprises", "is", etc.), the substances, components or ingredients referred to are meant to be present simultaneously just before they first come into contact, blend or mix with one or more other substances, components and / or ingredients according to the present disclosure. Thus, the fact that a substance, component or ingredient may lose its original properties through a chemical reaction or transformation during the contacting, blending or mixing operation, if carried out according to the present disclosure and the ordinary skill of a chemist, has no practical significance.

[0193] The present invention may include the materials and / or procedures described herein, consist of them or consist essentially of them.

[0194] As used herein, the term "about", when used to modify the amount of a component in a composition of the present invention or the amount of a component used in a method of the present invention, refers to, for example, variations in the numerical amount that may occur during the following processes: typical measurement and liquid handling procedures used in the real world for preparing concentrates or using solutions; errors that occur through inadvertence in these procedures; differences in the manufacture, source, or purity of the components used to prepare the composition or to carry out the method; and the like. The term about also encompasses amounts that differ due to different equilibrium conditions of the composition resulting from a particular initial mixture. Whether or not modified by the term "about", the claims include equivalent values of the amounts.

[0195] Unless otherwise expressly stated, the article "a / an" (if used in this text and as used herein) is not intended to limit the description or claim to a single element to which the article refers and should not be construed as limiting the description or claim to a single element to which the article refers. On the contrary, unless expressly indicated otherwise in the text, the article "a / an" (if used in this text and as used herein) is intended to cover one or more such elements.

[0196] The present invention is susceptible to considerable variation in its practice. Accordingly, the foregoing description is not intended to limit the present invention to the specific exemplifications presented above and should not be construed as limiting the present invention to the specific exemplifications presented above.

Claims

1. A method for reducing the environmental availability of at least a portion of one or more environmental pollutants in a substance containing one or more environmental pollutants, the method comprising adding and / or applying a halogen-containing adsorbent and an oxidizing agent capable of oxidizing elemental mercury to the substance, wherein the halogen-containing adsorbent comprises one or more halogens selected from chlorine, bromine, and / or iodine and one or more matrix materials, thereby reducing the environmental availability of at least a portion of one or more environmental pollutants in the substance.

2. The method according to claim 1, wherein the halogen-containing adsorbent comprises a matrix material selected from one or more carbonaceous materials, and / or wherein the halogen-containing adsorbent comprises a matrix material selected from one or more inorganic materials.

3. The method according to claim 2, wherein the carbonaceous material is activated carbon, and / or wherein the inorganic material is selected from inorganic oxides, natural zeolites, inorganic carbonates, and clay minerals.

4. The method according to any one of claims 2 to 3, wherein the inorganic material is selected from chabazite, silica, kaolinite, and bentonite.

5. The method according to any one of claims 1 to 4, wherein the halogen-containing adsorbent is a bromine-containing adsorbent.

6. The method according to claim 1, wherein the halogen-containing adsorbent is a halogen-containing activated carbon adsorbent.

7. The method according to claim 1, wherein the halogen-containing adsorbent is a bromine-containing activated carbon adsorbent.

8. The method according to any one of claims 1 to 7, wherein, calculated as bromine and based on the total weight of the halogen-containing adsorbent, the halogen-containing adsorbent has a halogen content of from about 0.1 wt% to about 50 wt%.

9. The method according to any one of claims 1 to 7, wherein the oxidizing agent is an inorganic oxidizing agent, and / or wherein the oxidizing agent is an organic oxidizing agent.

10. The method according to claim 9, wherein the inorganic oxidizing agent is a permanganate, a hypochlorite, and / or a chlorate, and / or wherein the inorganic oxidizing agent is an alkali metal salt, an alkaline earth metal salt, and / or an ammonium salt; and / or wherein the organic oxidizing agent is an organic peroxide or a haloacetohydantoin.

11. The method according to claim 9, wherein the inorganic oxidizing agent is an alkali metal permanganate, an alkali metal hypochlorite, and / or an alkaline earth metal chlorate, and / or when the oxidizing agent is an organic peroxide, the organic peroxide has a branched alkyl group and / or an aralkyl group, and wherein when the oxidizing agent is a haloacetohydantoin, the haloacetohydantoin is a halo-5,5-dialkylhydantoin.

12. The method according to claim 9, wherein the inorganic oxidizing agent is potassium permanganate, sodium hypochlorite, and / or calcium chlorate, and / or the organic oxidizing agent is selected from tert-butyl peroxide, 1,3-bromo-chloro-5,5-dimethylhydantoin, and 1,3-dibromo-5,5-dimethylhydantoin.

13. The method according to any one of claims 1 to 12, wherein the one or more environmental pollutants are mercury, chromium, arsenic, and / or selenium.

14. The method according to any one of claims 1 to 13, wherein the substance containing the environmental contaminant is a solid, and wherein adding and / or applying the halogen-containing adsorbent and the oxidant to the solid includes: (a) injecting the halogen-containing adsorbent and the oxidant into the solid; (b) applying the halogen-containing adsorbent and the oxidant to the surface of the solid; (c) combining the halogen-containing adsorbent and the oxidant with at least a part of the surface of the solid; (d) placing the halogen-containing adsorbent and the oxidant in a vacuum well for treating the solid; (e) adding the halogen-containing adsorbent and the oxidant to the contained solid; (f) combining the halogen-containing adsorbent and the oxidant with the solid; (g) adding the halogen-containing adsorbent and the oxidant to a reaction barrier; and / or (h) forming a reaction barrier containing the halogen-containing adsorbent and the oxidant; Optionally, wherein the solid is soil.

15. The method according to any one of claims 1 to 13, wherein the substance containing the environmental contaminant is a liquid, and wherein adding and / or applying the halogen-containing adsorbent and the oxidant to the liquid includes: (a) injecting the halogen-containing adsorbent and the oxidant into the liquid; (b) applying the halogen-containing adsorbent and the oxidant to the surface of the liquid; (c) combining the halogen-containing adsorbent and the oxidant with the liquid; (d) passing the liquid through a fixed bed containing the halogen-containing adsorbent and the oxidant; (e) passing the liquid through a filter containing the halogen-containing adsorbent and the oxidant; (f) pumping the liquid through a fixed bed or column containing the halogen-containing adsorbent and the oxidant; and / or (g) adding the halogen-containing adsorbent and the oxidant to the contained volume of the liquid.

16. The method according to any one of claims 1 to 13, wherein the substance containing the environmental contaminant is a combination of at least one solid and at least one liquid, and wherein adding and / or applying the halogen-containing adsorbent and the oxidant to the combination includes: (a) injecting the halogen-containing adsorbent and the oxidant into the combination; (b) applying the halogen-containing adsorbent and the oxidant to the surface of the combination; (c) combining the halogen-containing adsorbent and the oxidant with at least a part of the surface of the combination; (d) combining the halogen-containing adsorbent and the oxidant with the combination; (e) placing the halogen-containing adsorbent and the oxidant in a vacuum well for treating the combination; (f) adding the halogen-containing adsorbent and the oxidant to the contained combination; (g) covering the surface of the substance with a layer containing the halogen-containing adsorbent and the oxidant; (h) placing the halogen-containing adsorbent and the oxidant in a cover; (i) adding the halogen-containing adsorbent and the oxidant to a reaction barrier; (j) forming a reaction barrier containing the halogen-containing adsorbent and the oxidant; and / or (k) placing the halogen-containing adsorbent and the oxidant in a geotextile pad.

17. The method according to claim 16, wherein the adding and / or applying includes: (a) injecting the halogen-containing adsorbent and the oxidant into the combination; (b) Apply a halogen-containing adsorbent and an oxidizing agent to the surface of the combination; (c) Combine the halogen-containing adsorbent and the oxidizing agent with at least a portion of the surface of the combination; and / or (d) Combine the halogen-containing adsorbent and the oxidizing agent with the combination; Optionally, wherein the combination is a sediment.

18. The method according to claim 17, wherein the halogen-containing adsorbent comprises a matrix material, and the matrix material is activated carbon.

19. The method according to claim 1, wherein the substance is soil or sediment, wherein the halogen-containing adsorbent is a bromine-containing activated carbon adsorbent, and wherein the oxidizing agent is sodium hypochlorite, potassium bromate or calcium chlorate.

20. The method according to claim 17, wherein the oxidizing agent is an inorganic oxidizing agent, and the inorganic oxidizing agent is an alkali metal permanganate, an alkali metal hypochlorite and / or an alkaline earth metal chlorate; and / or the oxidizing agent is an organic oxidizing agent, and when the organic oxidizing agent is an organic peroxide, the organic peroxide has a branched alkyl group and / or an aralkyl group, and wherein when the oxidizing agent is a haloacetohydantoin, the haloacetohydantoin is a halo-5,5-dialkylhydantoin.

21. The method according to claim 20, wherein the inorganic oxidizing agent is potassium permanganate, sodium hypochlorite and / or calcium chlorate; and / or wherein the organic oxidizing agent is selected from tert-butyl peroxide, 1,3-bromo-chloro-5,5-dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin.

22. A blend of a halogen-containing adsorbent and an oxidizing agent capable of oxidizing elemental mercury, wherein the halogen-containing adsorbent comprises one or more halogens selected from chlorine, bromine and / or iodine.

23. The blend according to claim 22, wherein the halogen of the halogen-containing adsorbent is bromine and / or iodine, wherein the halogen-containing adsorbent comprises a matrix material selected from one or more carbonaceous materials, wherein when the oxidizing agent is an inorganic oxidizing agent, the oxidizing agent is a permanganate, a hypochlorite and / or a chlorate, and / or wherein the oxidizing agent is an alkali metal salt, an alkaline earth metal salt and / or an ammonium salt, and wherein when the oxidizing agent is an organic oxidizing agent, the oxidizing agent is an organic peroxide or a haloacetohydantoin.

24. A method for forming a blend of a halogen-containing adsorbent and an oxidizing agent capable of oxidizing elemental mercury, the method comprising: A) i) Combine a halogen-containing compound and a matrix material to form a halogen-containing adsorbent, and ii) Combine the halogen-containing adsorbent with an oxidizing agent; Or B) Combine a halogen-containing adsorbent and an oxidizing agent.

25. The method according to claim 24, wherein when the halogen of the halogen-containing adsorbent is bromine, the matrix material is a carbonaceous material, wherein when the oxidizing agent is an inorganic oxidizing agent, the inorganic oxidizing agent is a permanganate, a hypochlorite and / or a chlorate, and / or wherein the inorganic oxidizing agent is an alkali metal salt, an alkaline earth metal salt and / or an ammonium salt, and wherein when the oxidizing agent is an organic oxidizing agent, the organic oxidizing agent is an organic peroxide or a haloacetohydantoin.

26. The method according to claim 25, wherein the inorganic oxidant is an alkali metal permanganate, an alkali metal hypochlorite, and / or an alkaline earth metal chlorate; and / or when the oxidant is an organic oxidant, when the organic oxidant is an organic peroxide, the organic peroxide has a branched alkyl group and / or an aralkyl group, and wherein when the organic oxidant is a halogenated hydantoin, the halogenated hydantoin is a halogenated 5,5-dialkylhydantoin.

27. The method according to claim 26, wherein the inorganic oxidant is potassium permanganate, sodium hypochlorite, and / or calcium chlorate; and / or the organic oxidants are selected from tert-butyl peroxide, 1,3-bromo-chloro-5,5-dimethylhydantoin, and 1,3-dibromo-5,5-dimethylhydantoin.

28. The method according to any one of claims 25 to 27, wherein the matrix material is activated carbon.

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