WO2003068324A1 - Elimination de contaminant organique provenant de boue par catalyse ciblee - Google Patents

Elimination de contaminant organique provenant de boue par catalyse ciblee Download PDF

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WO2003068324A1
WO2003068324A1 PCT/US2002/003873 US0203873W WO03068324A1 WO 2003068324 A1 WO2003068324 A1 WO 2003068324A1 US 0203873 W US0203873 W US 0203873W WO 03068324 A1 WO03068324 A1 WO 03068324A1
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water
sludge
hydrophobic
iron
organic
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PCT/US2002/003873
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English (en)
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Marvin Motsenbocker
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Marvin Motsenbocker
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Priority to PCT/US2002/003873 priority Critical patent/WO2003068324A1/fr
Priority to AU2002243919A priority patent/AU2002243919A1/en
Publication of WO2003068324A1 publication Critical patent/WO2003068324A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/002—Sludge treatment using liquids immiscible with water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/06—Nutrients for stimulating the growth of microorganisms

Definitions

  • the invention relates to the field of environmental remediation and particularly to the destruction of organic chemical toxins in sludges such as contaminated soil, dredged sediments and oil spills.
  • Soil and groundwater pollution is a worldwide problem associated often with government and industrial sites where mishandling or improper disposal of chemicals has brought a variety of pollutants in contact with the soil.
  • Common pollutants include hydrocarbons including conjugated organic hydrocarbons and halogenated volatile organic solvents such as terra-, tri-, or di-chloroethylene, carbon tetrachloride, chloroform, methylene chloride and the like.
  • Many of these organic compounds are carcinogenic and damaging to specific organs such as the liver and kidneys (Price, P. S., Memo of the U.S. Environmental Protection Agency, Office of Water, Washington, D.C.(1985); Vogel, T. M., Environ. Sci. Technol. 21, 722, (1987)).
  • Sludges often contain such compounds which need to be broken down into smaller forms or otherwise altered in chemical structure or diluted to an acceptable low concentration.
  • the oceans, lakes and streams can acquire oil (crude oil or fractions of crude oil), gasoline or other hydrophobic material occasioned by accidents, offshore drilling operations, discharge of ballast water or spillage from oil tankers.
  • oil can form a continuous film or slick.
  • the oily film may block the transfer of air and light from the atmosphere, which are indispensable to marine life.
  • One way of dealing with this problem is to apply an oil collecting composition. That is, a composition is poured at the periphery of the oil slick and repels the oil, which is gathered into a narrower area and may be removed by mechanical means.
  • this oil-spill compression technique is only suitable on a relatively calm sea.
  • compositions are only efficient during a very short period of time, due to the solubility of the compositions in the oil.
  • Another method of controlling oil spills is to apply a surface-active agent to disintegrate the cohesive oily film into small droplets and disperse the droplets into the water column.
  • the surface active agent breaks the film, allowing transfer of air and light from the atmosphere.
  • surface-active agents typically are water-soluble and dissolve too quickly in water. Accordingly, they may penetrate the oil slick insufficiently or are effective for only a short time period.
  • the object of treating an oil spill is to physically remove the hydrophobic contaminant. Unfortunately there is no acceptable method of chemically destroying the organic hydrophobic molecules of these slicks in situ.
  • Undesirable organic contaminants within contaminated solid sludges and within thin sludges such as oil spills typically partition into a location outside of the bulk water phase.
  • the contaminants are found adsorbed onto surfaces of solid particles and/or form non-aqueous phase(s).
  • the contaminants form their own phase on top of the water and, to some extent, as dispersed droplets in the water. In both cases, the contaminant is not dispersed evenly through the volume of the sludge but is concentrated within a "target location" in the sludge.
  • DNAPLs dense non-aqueous phase liquids
  • U.S. Patent No. 5,789,649 which is herein incorporated by reference in its entirety.
  • the class of DNAPL contaminants in sludge presents a further problem to remediation because the high density and low water solubility of DNAPLs cause them to sink through the soil and water and follow topographic lows within an aquifer system, often accumulating atop the underlying clay stratum.
  • DNAPLs since most DNAPLs, like other organic contaminants, are sparingly soluble in water, the DNAPLs tend to adsorb to soil particles.
  • the DNAPLs may produce tenacious underground plumes of dissolved organic material which cannot readily and permanently be removed by standard pump and treat technology such as that described by Biswas, N., et al, Water Environ. Res. 64,170,10,1(992) and Hutter, G. M., et al., Water Environ. Res. 64, 69, (1992)).
  • hydrophobic because of their tendency to self-associate into target locations within the sludge based on their chemical characteristics of avoiding water.
  • U.S. Patent No. 5,679,574 refers to hydrophobic compounds or mixtures of such compounds such as crude oils, oils, refined and unrefined petroleum mixtures and other synthetic oils and greases in soil matrices.
  • U.S. Patent No. 5,567,324 mentions that PCBs and "other hydrophobic organic compounds typically have a high affinity for soil.” The affinity of these compounds for soil and sediment complicates attempts to remediate such sludges and is a serious problem that increases the cost of sludge remediation.
  • the inventor has reasoned that a major obstacle to the use of such chemistry is that the catalyst or other active agent(s) useful for destroying an organic compound decomposes rapidly. That is, the best active agents known to chemists for destroying organic contaminants unfortunately tend to be the most unstable. The reagent falls apart (reacts with water, water solute, or with itself) before it gets a chance to contact with and destroy the intended target molecule at the target location.
  • the hydroxyl radical is very desirable because it can destroy an organic molecule and can react with a wide variety of contaminants.
  • the hydroxyl radical cannot be prepared at one place and used at a second target location because the radical has a short half-life in water solution.
  • a hydroxyl radical primarily will react with and destroy molecule(s) that are closest to the radical when the radical is formed. This phenomenon is rarely mentioned and is not widely appreciated by those in the field of environmental remediation
  • Another obstacle to the efficient remediation of sludge by an active chemical agent is that the chemical agent (either the active form or a stable precursor form of it) becomes diluted upon contact with the sludge.
  • a target substance organic contaminant
  • a target substance organic contaminant
  • the chemical agent simply diffuses throughout the aqueous phase, then most of the agent would not be available at any moment to react with target organic molecules, which generally are at a lower concentration in the larger phase volume.
  • Another object of the invention is to provide a method for removing organic molecules from an oil spill or other thin sludge, the method comprising the steps of providing a fluid or solid mixture that contains at least one hydrophobic photoactive agent and then spreading the mixture from the first step onto the thin sludge such that the mixture receives light to activate the photoactive agent.
  • Another object of the invention is to provide an improved method for the in situ removal of volatile contaminants from the Vadose zone by use of a vacuum extraction well, the improvement comprising injecting at least one hydrophobic reagent that can destroy an organic molecule into the Vadose zone at or near the vacuum extraction well and applying a vacuum to the extraction well.
  • Another object of the invention is to provide a composition useful for remediating an oil spill comprising a hydrophobic photoactive thiazine dye derivative in a water immiscible solvent in a container that can be applied by spraying.
  • Yet another object of the invention is to provide a method for removing organic molecules from a sludge, the method comprising the steps of contacting the sludge with a first fluid that comprises a hydrophobic metal catalyst, the catalyst being able to partition into a target volume of the sludge, dewatering the sludge to remove at least some of the unbound hydrophobic catalyst, contacting the sludge with a second fluid that comprises at least one oxidant selected from the group consisting of hydrogen peroxide, organic peroxide, electrochemically activated water and a peroxyhydrate.
  • Yet another embodiment of the invention is to provide a method for destroying an organic contaminant in a sludge, the method comprising contacting the sludge with an aqueous composition that comprises soluble iron in the form of an iron salt, particularly iron fatty acid salt and an oxidant that reacts with the iron to produce a radical species that can destroy the organic contaminant.
  • the fatty acid is selected from the group consisting of a 3 carbon fatty acid (proprionic acid), 4 carbon fatty acid, 5 carbon fatty acid, 6 carbon fatty acid, 7 carbon fatty acid, and 8 carbon fatty acid.
  • the oxidant is hydrogen peroxide and is added to the sludge after addition of the iron fatty acid.
  • Another embodiment is a composition for destroying a contaminant of a sludge comprising a low molecular weight fatty acid iron salt wherein the fatty acid contains less than 9 carbons.
  • the fatty acid salt is in an aqueous composition that additionally comprises a water miscible organic solvent or other amphipathic compound to facilitate dissolution of the low molecular weight iron fatty acid salt.
  • Yet another embodiment is a method for producing a low molecular weight iron fatty acid salt suitable for eliminating a contaminant of a sludge, comprising adding iron chloride (Fe 2+ ,Fe 3+ or a mixture of Fe 2+ and Fe 3+ ) and adding the low molecular weight fatty acid to water to form a two phase system, and removing the iron-fatty acid phase from the system.
  • Yet another embodiment is a method for producing a low molecular weight iron fatty acid salt composition suitable for treating sludge, comprising taking the above-mentioned iron-fatty acid phase and dispersing it in water by adding at least 0.1% by weight co-detergent or organic solvent such as methanol or ethanol.
  • Yet another object of the invention is to provide a method for the chemical degradation and stabilization of chemical pollutants at a contamination source in a soil contaminated with pollutants comprising admixing with the soil at said contamination source an effective amount of a hydrophobic reactive reagent and a suitable stabilizing agent to form a stabilizing degradating reagent such that said admixing results in the reduction of permeability at the contamination source and the degradation of the pollutant by action of the reactive reagent.
  • the inventor has studied the destruction of organic molecules at solid phase surfaces with aqueous liquids, using methylene blue derivatives and porphine derivatives as active agents as described, for example, by Motsenbocker et al. Photochem. Photobiol. 58: 648-652 (1993), Motsenbocker et al. Anal. Chem. 65: 397-402 (1993), Motsenbocker et al. Anal. Chem. 65: 403- 408 (1993), Motsenbocker J. Biolum. Chemilum. 9: 15-20 (1994), and Motsenbocker et al, J. Biolum. Chemilum. 9: 7-13 (1994).
  • hydrophobic active agents such as those exemplified in the above-referenced publications can concentrate at a solid phase surface, within a hydrophobic phase in a solid sludge such as soil or marine sediment, or in a thin sludge such as an oil spill to more strongly react with and destroy organic contaminants that are found in a greater concentration there.
  • Embodiments of the invention provide more efficient destruction of organic contaminants from sludge with hydrophobic catalyst(s) and/or other active reagents that can concentrate at a target location of the organic contaminant.
  • the accumulation of and/or formation of chemical reactant at the target location itself alleviates the instability and dilution problems.
  • the hydrophobic catalytic agent is a low molecular weight iron-fatty acid salt wherein the fatty acid has fewer than 10 carbons, more preferably less than 9 carbons, and most preferably 5, 6 or 7 carbons and the salt is readily dispersible in water, or a water-organic solvent system.
  • hydrogen peroxide is used with the hydrophobic catalytic agent either by co-administration, or more preferably, by separate addition of hydrogen peroxide to the sludge.
  • Hydrophobic Agent(s) May be Used in a Variety of Formats
  • a theme of one embodiment of the invention is that at least one agent in an active form or activatable form is applied to the sludge and concentrates at a target location in the sludge.
  • a variety of chemicals are known which can become active agents directly or can cause formation of an active agent, which then destroys organic contaminants. These chemicals may be used individually or in combination with other chemicals to react with or generate an active agent that can destroy an organic contaminant in a target volume.
  • the active agents can be used in alternative formats, as reviewed below.
  • an aqueous fluid that contains or generates the active agent is applied to the sludge by, for example, gravity flow or by a vacuum as described in U.S. Patent No. 4,660,639.
  • the hydrophobic agent stays behind in a target location.
  • the target location may comprise, for example, bound water with solute at particle surfaces that does not elute by gravity separation and may comprise hydrophobic droplets in the sludge.
  • the hydrophobic agent thus progressively concentrates at the target location with time.
  • the hydrophobic agent may be in an active form ready to react with an organic contaminant, or may be in a more stable form and become activated from another compound that may contact the sludge at a different time.
  • the subsequent reaction between agent and organic molecule is greatly facilitated by the increased concentration of both reactants (active agent and the organic molecule contaminant) within the target volume.
  • reactants active agent and the organic molecule contaminant
  • increasing the concentration of a reactant will increase the reaction rate.
  • This increase is particularly favored by sludge dewatering. That is, when possible, it is particularly preferable that the sludge be dewatered after contacting with the active agent to remove bulk water and further concentrate the agent in the target zone volume, and thus increase the rate of organic contaminant destruction.
  • the inventor further has discovered methods for generating the active agent within the sludge itself, and preferably within the target location so that the activated agent more readily reacts with a contaminating organic molecule found there.
  • Such in situ generation is particularly important where the destructive agent (either the active agent or something made by it) decomposes rapidly.
  • a hydrophobic light activated dye catalyst concentrates within a target location such as at an oil droplet or scum of oil on water prior to light activation. Upon light irradiation the dye catalyst may (for example) generate destructive singlet oxygen within the target location.
  • a metal catalyst such as metal porphyrin that is sparingly soluble in water, or which is provided to the sludge within a water/organic solvent admixture becomes enriched at a target location, preferably at a high pH such as above pH 10, and more preferably above pH 11.
  • An oxidant such as hydrogen peroxide or a reagent that forms hydrogen peroxide optionally is added before or, (more preferably) after adding the metal.
  • hydrogen peroxide is converted to hydroxyl radical and/or other destructive agent at the target location.
  • the metal porphyrin is substituted with a low molecular weight iron anionic amphipathic salt such as an iron soap (preferably iron with an aliphatic carboxylic acid or other anionic surfactant).
  • a hydrophobic oxidant such as organic peroxide contacts the sludge and concentrates at the target location
  • a metal catalyst and a peroxide or peroxide generating molecule, that are sparingly soluble in water are added separately.
  • a preferred metal catalyst is an iron 3+ or 2+ salt with an anionic amphipathic compound such as an aliphatic sulfate or aliphatic carboxylate.
  • a phosphate salt is less preferred because the phosphate quenches the reaction with iron and may cause a pollution concern.
  • Most preferred is an iron fatty acid salt with a carboxylic acid between 3 and 8 carbons long. Both metal and oxidant concentrate at the target location.
  • the solution in which the active agent is administered to the sludge can be modified to enhance delivery of the active agent to the target site.
  • a water/alcohol mixture or a water/surfactant combination can be used to raise solubility of the hydrophobic active agent and increase the amount that is delivered.
  • the solubility of the hydrophobic agent drops and the agent more readily enters the target location by virtue of its affinity to a surface and/or affinity to hydrophobic regions (such as oil droplets and the like) within the sludge.
  • an active agent which reacts with organic contaminant achieves a concentration in the target location that exceeds its concentration in the bulk water phase of the sludge.
  • a precurser of an active agent such as an inactive porphine or preferably, low molecular weight iron fatty acid (or detergent) salt is targeted into a target location of the sludge and then is activated by a second reagent such as hydrogen peroxide, organic peroxide or a chemical that forms peroxide.
  • the activated agent reacts preferably with an organic chemical within the target location for greater efficiency of contaminant destruction in the sludge, hi such preferred embodiments, an activated reagent is made and used where it is needed, thus substantially bypassing the stability problem.
  • a hydrophobic reactant such as a catalyst becomes activated by contact of the sludge with elecfrochemically activated water.
  • the elecfrochemically activated water contains activated compounds that can give up or take one or more electrons from the reactant, thereby activating it.
  • Elecfrochemically activated water may be generated as for example, described in U.S. Patent Nos. 5,792,336; 5,445,722; 5,439,577 and 5,531,865.
  • a hydrophobic activated reactant is made elecfrochemically, by adding a hydrophobic molecule, or precursor to a hydrophobic molecule to water before activation of the water, or by adding the molecule to water that has been elecfrochemically activated.
  • a hydrophobic molecule, or precursor to a hydrophobic molecule to water before activation of the water, or by adding the molecule to water that has been elecfrochemically activated.
  • propanol or octanol may be added to water before electrochemical activation and can be transformed into a species that both partitions into the target volume and reacts with an organic contaminant there.
  • a lanthanide chelate is used either by adding it to water before electrochemical activation, or more preferably, by adding it to water immediately after electrochemical activation of the water.
  • an electrochemical activation device that adds a stream of dissolved or suspended lanthanide salt, or lanthanide chelate into the water immediately (less than 0.1 seconds) after activation.
  • the lanthanide becomes activated by undergoing a reaction with a short-lived active compound produced from the electrochemical activation.
  • the active lanthanide species has a much longer half life and is used to transfer electrochemical activation energy into the sludge.
  • Embodiments of the invention can remediate sludge such as contaminated soil or marine sediment in situ, as well as sludge that has been treated or moved into a container ex situ, such as feedlot waste or PCB contaminated material that has been removed from a contaminated site.
  • sludge such as contaminated soil or marine sediment in situ
  • sludge that has been treated or moved into a container ex situ, such as feedlot waste or PCB contaminated material that has been removed from a contaminated site.
  • Typical methods include jet grouting, permeation grouting, spraying, dropping, injection, and deep soil mixing. The preferred method will depend on the particular application. Where chemical grouting is needed to establish physical barriers or walls, and even floors, to contain hazardous waste, jet grouting is a useful method.
  • the hydrophobic catalyst or other hydrophobic reagent is supplied as a suspension in water and enters the target volume slowly over time after adding the suspension.
  • Embodiments of the invention can remediate a thin sludge such as an oil spill.
  • a hydrophobic dye catalyst such as a methylene blue derivative is applied to the thin sludge, optionally in a composition with other surface active compound(s) to assist dispersal into the oily phase.
  • the photoactive dye contributes to destruction and dissolution of the sludge by breaking down some of the organic contaminants.
  • the products of the reaction may contribute to further softening and dissolution of the oily phase. In this way, the dye contributes to dissolution in excess proportion to its mass because each smaller cleavage product created by the dye chemical reaction itself softens and helps disperse the oily phase.
  • a shorter alkane formed from a longer alkane or a fatty acid formed from a triglyceride may chemically act as a dispersant and help dissolve the oil spill.
  • Preferred formats for bringing one or more hydrophobic chemical reactants to a target location for destroying organic toxic molecules are presented below.
  • a wide range of chemical reactions are suitable for the invention.
  • a chemical known to destroy an organic molecule is selected based on its hydrophobicity or is made more hydrophobic in order to decrease its water solubility and increase its partition into a hydrophobic phase, hi other embodiments, the pH of the solution is adjusted to decrease hydrophilicity and facilitate adsorption of the chemical into the target volume.
  • the inventor has studied (1) porphine metal catalyzed destruction of an organic molecule at high pH, (2) destruction of that molecule by photoactivation of photoactive dyes, and (3) formation and use of low molecular weight iron soaps in water and water organic solvent mixtures and their use with hydrogen peroxide to destroy organic contaminants of sand particles, h particular, metal porphines were studied having varying solubility due to the presence or absence of ionized carboxyl and sulfonatyl groups. Photoactive dyes also were studied in this context, and derivatives of a preferred dye, methylene blue having different length alkyl residues (different solubilities) were made and evaluated for their ability to generate singlet oxygen.
  • iron soaps comprising Fe 2+ and/or Fe 3+ with low molecular weight aliphatic carboxylates, particularly between 3 and 9 carbons long, and more preferably between 4 and 7 carbons long.
  • controlling the amount and number of charged residues, as well as aliphatic chain length successfully adjusted the hydrophobicity of the reagent, to allow the reagent partition into the sludge target volume.
  • the preferred target volumes bind/and or concentrate organic contaminants, although the precise chemical mechanism(s) involved are not very well known.
  • the inventor theorizes that the preferred target volume of thin sludge comprises oil and binds/adsorbs hydrophobic reagents well due to the hydrophobic effect from mutual water avoidance of hydrophobic molecules.
  • the particle surfaces bind hydrophobic molecules, and particularly amphipathic molecules well because of the overall increase in entropy that results from orientation of the hydrophobic portion of a molecule to the surface of the particle.
  • Oily phases may exist in solid sludges as well, and such phases should absorb hydrophobic reactant(s). Accordingly, any amphipathic reagent, as well as hydrophobic reagent, may be useful for partitioning into the target volume.
  • Certain metal ions and metallo-conipounds such as copper, iron, and heme are known to react with peroxides to generate powerful oxidant species.
  • An example of this is the Fenton reaction in which the ferrous ion reduces H O 2 to generate the hydroxyl free radical, a known powerful oxidant which is known to destroy a wide range of organic molecules generally (Walling, C, Fenton's Reagent Revisited, Accnts of Chemical Research 8:125; 1975).
  • the hydroxyl free radical can react with hydrogen peroxide to generate the perhydroxyl free radical, which in turn can dissociate to generate the superoxide free radical, which goes on to make other active species.
  • Organic hydroperoxides also react with metal ions to generate organic oxy and peroxy free radical species.
  • Organic internal peroxides also generate free radical species from the reaction of the peroxide with metal-ions.
  • organic internal peroxide refers to molecules of the form ROOR', where R and R' are organic moieties which may be identical or different, and wherein both valences of the peroxy (peroxo) --0--0-- moiety are bonded directly to carbon. This definition is to be understood to include endoperoxides.
  • This "focusing" of the free radical is analogous to the magnified chain destruction that occurs in a cellular membrane, wherein organic molecule conjugated electron systems are adjacent each other, allowing the free radical to hop around and destroy a large number of organic molecules before the radical is extinguished.
  • metal-ion preferably Fe 2+ or Fe 3+ soap of a fatty acid
  • free radical generating reactions involve one- electron changes in oxidation state.
  • Metal-ions which undergo two-electron changes in oxidation state can also react with peroxides, but the direct reaction products generally are not free radicals and for this reason iron is preferred.
  • Singlet molecular oxygen another powerful oxidant, also may be produced from the reaction between a metal-ion containing compound and a peroxide compound.
  • Spectroscopic evidence for the generation of singlet molecular oxygen has been reported from the reaction of metal-ions with primary, secondary, and tertiary organic peroxides.
  • the mechanism for the generation of singlet oxygen has been elucidated in the case of secondary peroxides, via the Russell mechanism (J. Amer. Chem. Soc. 79:3872; 1957).
  • this consists of the combination of two secondary peroxy free radicals to form an unstable tetroxide, and then the concerted decomposition of the tetroxide to yield an alcohol, a ketone and singlet oxygen.
  • Singlet oxygen is a known oxidant of organic molecules but is more selective than the hydroxyl free radical.
  • Singlet oxygen for example, has been shown to oxidize conjugated aliphatic chains.
  • the specific mediators and mechanisms of the present invention may be extremely complex and may involve, for example, ferryl and perferryl ions as well as other chemical species. Therefore, the discussions presented herein of specific oxidant species and their mechanisms of generation, such as, for example, hydroxyl free radical and singlet oxygen, are understood to be for illustrative purposes only, and not meant to limit or constrained in any way the description of the invention to or by the presented mechanisms and species.
  • Porphyrins are capable of carrying out destructive reactions such as alkane and olefin oxidation by oxidation to alcohols or epoxides as described in Metalloporphyrins in Catalytic Oxidations, R. A. Sheldon, Ed., Marcel Dekker, New York (1994) and U.S. No. 5,914,013.
  • Many porphyrin systems require sacrificial reducing agents, but some can oxidize hydrocarbons without the need of a stoichiometric reductant. These include perhalo iron porphyrins (ibid.), UV light-assisted oxidation of alkanes in the presence of metalloporphyrins (J. Chem. Soc. Chem.
  • porphyrin It is preferred to limit the number of such negative charges to two, and if the porphyrin is applied to a sludge with a water-miscible solvent system such as 25% methanol or other organic solvent, the porphyrin should have fewer than two negative charges.
  • a preferred porphyrin contains manganese and has para electron withdrawing conjugated rings such as those described in Anal. Chem. although iron may be used due to cost constraints.
  • concentration of porphyrin to use preferably is between 0.0001 mg/gm and 1 mg per gm of sludge after mixing.
  • metal porphyrins have been discovered and which are useful as photoactive dyes.
  • hydrophobic porphyrins are desired for use with thin sludges such as oil spills that are illuminated by sunlight.
  • Metal porphines such as iron porphyrins having hydrophobic moieties such as benzene rings are particularly useful because such organic molecules adsorb to the surfaces of clay particles, other particles, and partition into oily phases of oil spills.
  • Hemoglobin and other protein porphyrins are less desirable because of their large protein portions, which cause precipitation, difficulty in handling and which dilute the effect of the heme porphyrin portion.
  • the inventor believes that as the hydrophobic compound in a water/organic compound solvent becomes diluted within the wet sludge, the compound may associate with a particle surface and/or a more hydrophobic phase in the sludge in order to maximize entropy.
  • the active agent compound typically is amphipathic, and this feature encourages the compound to associate with a surface, wherein the hydrophobic portion of the compound contacts the surface and a hydrophilic portion sticks out into the aqueous phase.
  • the preferred metal porphines are expected to behave this way.
  • the organic hydrophobic activatible compound is mixed with a detergent prior to contact with the sludge. The detergent helps the activatable compound remain soluble. As the activatable compound/detergent mixture becomes diluted within the wet sludge, the detergent concentration drops and the activatable compound more readily associates with surfaces and/or (if present) with an organic phase within the sludge.
  • a preferred concentration of po hyrin for a given sediment should be determined by a bench scale test. Bench scale tests customarily are performed for sediments to determine the hydrodynamic and chemical quality of the material to be treated.
  • a typical aqueous (water) remediation fluid is added at a 5% volume ratio to a sludge and may comprise for example between 0.1 mg and 10.0 gm of po ⁇ hyrin per liter volume and preferably between 1 and 100 mg of porphyrin per liter volume.
  • the porphyrin advantageously is diluted into a remedial fluid that contacts the sludge after first being dissolved in water or a small amount of organic solvent such as methanol, ethanol, or dimethylformamide.
  • an organic solvent if used, is further diluted at least ten fold and preferably at least 50 fold by addition to the remedial fluid.
  • a dilute sodium hydroxide solution such as ImM NaOH is preferred to solubilize a catalyst such as metal porphyrin.
  • one or more iron soaps made from low molecular weight anionic amphipathic compound(s) such as anionic detergent or fatty acid is dispersed in an aqueous fluid.
  • a metal which is more inexpensive and broadly reactive than a metal porphine, profitably may be used to form an active reagent such as a free radical or other active oxygen species at the target location site.
  • an active reagent such as a free radical or other active oxygen species at the target location site.
  • the iron as small molecular weight iron soap
  • an organic solvent such as methanol or ethanol
  • the iron as small molecular weight iron soap
  • ethanol or methanol can be added to between 0.01 and 10% vol/vol to water and more preferably between 0.5% and 5% to increase solubility of the iron soap prior to adding to sludge.
  • a surfactant such as an environmentally acceptable detergent may be added from, for example, 0.1% to 2% to increase the solubility.
  • the iron of the iron soap gradually binds to particle surfaces as the solution becomes diluted while diffusing through the sludge.
  • the inventor discovered that he could reversible bind such iron to a hydrophobic surface (plastic walls of a beaker) but not to a hydrophilic (glass beaker) surface by altering the proportion of alcohol in the iron soap solution.
  • control of a "solubility factor" such as organic solvent added to the water, pH, presence of surfactant, temperature and the like can be used by control of the iron soap solution itself , or can be carried out via control of a solubility factor of a subsequent wash fluid or of a fluid that contains hydrogen peroxide or other oxidant that will react with the iron.
  • metals such as of copper, iron, nickel, cobalt, vanadium, chromium, silver, rhodium, ruthenium, technetium, molybdenum, niobium, zirconium, platinum, tin, lead, hafnium, tantalum, tungsten, rhenium, titanium, osmium, mercury, cerium, samarium, europium, and ytterbium could be used as well.
  • the metal ion may be incorporated into a porphyrin, porphyrin derivative, porphyrin like compound, hematoporphyrin, etioporphyrin, protoporphyrin, uroporphyrin, mesoporphyrin, coproporphyrin, hematoporphyrin derivative, porphin, chlorin, phorbin, bacteriochlorin, porphyrinogen, phlorin, purpurin, rhodin, pheophorbide, erythrin, pheophyrin, pheophytin, phthalocyanine, phthalocyanine like compound, verdin, corrin, corrole, corphin, sapphyrin, and derivatives thereof.
  • the concentration of metal agent to use for a particular sludge should be optimized by a bench test as is routinely carried out in this art.
  • the concentration may, for example be between 0.01 gm/liter to 20 gm/liter and preferably between 0.1 gm/liter and 1 gm/liter (weight of metal plus ligand, if any).
  • an iron salt of an anionic soap or detergent is prepared and used as the hydrophobic catalyst.
  • hydrogen peroxide preferably is added during or, particularly after contact of the hydrophobic catalyst solution with the sludge and (optionally) washing to remove unbound catalyst and the Fenton's reaction may be used to create hydroxyl radicals.
  • “Soap” in this context includes carboxylic acid having shorter chain length than "fatty acids” that normally are thought of as being made and found in biological systems.
  • Preferred “soaps” are straight chain aliphatic carboxylic acids having between 3 and 8 carbons, and more preferably between 4 and 7 carbons.
  • anionic surfactants having amphipathic properties are useful and can be purchased or prepared in a small enough size to readily form iron salts that remain dissolved in or readily dispersed in an aqueous phase or aqueous phase having up to 10 % co- solvent such as ethanol or methanol without quickly precipitating.
  • Such surfactants useful for this embodiment include, for example water-soluble alkali metal alkylbenzenesulphonates, alkyl sulphates, alkylpolyethoxyether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alphasulphocarboxylates and their esters, alkylglycerylethersulphonates, fatty acid monoglyceridesulfates and sulfonates, alkylphenolpolyethoxy ethersulphates, 2- acyloxyalkane-1 -sulphonates, and betaalkyloxyalkanesulphonates.
  • Aliphatic saturated carboxylic acids can also be used as anionic surfactants and are preferred due to their low reactivity (no double bonds) and low cost.
  • alkylbenzenesulphonates with 4 to 8 carbon atoms in a linear or branched alkyl chain, more especially 4 to 6 carbon atoms
  • alkylsulphates with 3 to 8 carbon atoms in the alkyl chain, more especially from 3 to 5 carbon atoms
  • alkylpolyethoxy ethersulphates with 3 to 8 carbon atoms in the alkyl chain and an average of about 1 to about 3 -CH 2 CH 2 0 ⁇ groups per molecule
  • linear paraffin sulphonates with 3 to 10 carbon atoms, more especially from 3 to 7 carbon atoms and alpha-olefin sulphonates with 4 to 10 carbons atoms, more especially 4 to 6 carbon atoms.
  • the preferred soaps are "small chain" fatty acid having from 3 to 12, especially 4 to 8, and most
  • a small molecular weight iron salt of an amphipathic compound, and preferably an iron soap made from a "small chain" fatty acid is best prepared by adding iron chloride (either Fe 3+ or Fe 2+ ) and the anionic compound to water to make a two phase system with an oily phase (typically) above the water phase. At least some of the cationic iron partitions into the anionic oily phase and is removed from the water. In the inventor's experience, it is best to add an excess of iron. The excess iron remains in the water phase, and substantially all of the anionic charges in the oily phase become neutralized by iron that enters this phase.
  • This method is preferred in order to prepare an iron salt composition of a oily phase that has less influence on changing pH during use, particularly when a "small chain" fatty acid is used. That is, if an excess of fatty acid remains that is not paired up with iron, the iron soap material will act more strongly as an acid and decrease the pH of the sludge during use. In some cases, however, an excess of fatty acid or other acid is desired in the hydrophobic catalyst in order to decrease the effective pH at the particle surfaces for reaction with Fenton's reagent.
  • the particle surfaces where the contaminant exists slightly acidic, and preferably between pH 3.0 and pH 6.0, and more preferably between pH 3.7 and pH 5.0 to match the pH optimum of the Fenton's reaction.
  • one embodiment of the invention is to leave an excess of protonated acidic groups in the iron soap to control pH to a low pH value so that after contact with sludge, the pH of the sludge particle surfaces will drop.
  • acidic surfactants including for example, one or more small chain fatty acids to impart the desired acidic properties.
  • saturated aliphatics are preferred, it is acceptable for some embodiments to use an anionic surfactant (amphipathic molecule) having one or more double bonds.
  • mixtures of two or more anionic amphipathic molecules such as described here are used together.
  • iron complexes are used in a water solution of approximately 0.2 to 10% ethanol and preferably 1 to 5% ethanol or other lower hydrogen bonding water miscible solvent.
  • peroxide or peroxide compound is meant to be inclusive of hydrogen peroxide, inorganic peroxides such as such as sodium peroxyborate tefrahydrate (sodium perborate tefrahydrate) and calcium peroxide; peroxide complexes such as urea hydrogen peroxide, and superoxide salts such as sodium superoxide.
  • inorganic peroxides such as sodium peroxyborate tefrahydrate (sodium perborate tefrahydrate) and calcium peroxide
  • peroxide complexes such as urea hydrogen peroxide
  • superoxide salts such as sodium superoxide.
  • the superoxide free radical dismutates (via reaction with its conjugate acid, the perhydroxyl free radical) to form hydrogen peroxide.
  • peroxide or peroxide compound also is meant to include organic peroxides, other compounds containing the peroxy (peroxo) — O--O-- moiety, superoxides, and other peroxide precursor compounds which generate peroxide species in situ.
  • organic peroxides include hydroperoxides, internal peroxides, endoperoxides, diacyl peroxides, ketone peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, peroxyketals, and peroxyacids.
  • oxidants that are already in large scale commercial use, such as a peroxyhydrate or other agent which releases hydrogen peroxide in aqueous solution.
  • a peroxyhydrate is to be understood as to encompass hydrogen peroxide as well as any material or compound which in an aqueous composition yields hydrogen peroxide.
  • alkali metal peroxides including sodium peroxide and potassium peroxide, alkali perborate monohydrates, alkali metal perborate tetrahydrates, alkali metal persulfate, alkali metal percarbonates, alkali metal peroxyhydrate, alkali metal peroxydihydrates, and alkali metal carbonates especially where such alkali metals are sodium or potassium.
  • the oxidizing agent is hydrogen peroxide, which is easily obtained from many sources. Other oxidants such as sodium hypochlorite are contemplated and also are readily available.
  • Elf Atochem, Inc. is a source of many organic peroxide compounds.
  • 1- Hydroperoxycyclohexyl-1-hydroxy cyclohexyl peroxide and tert-Butyl hydroperoxide can be obtained from Pfaltz and Bauer.
  • fatty acid hydroperoxides such as, for example, linolenic acid hydroperoxide, arachidonic acid hydroperoxide, and docosahexaenoic acid hydroperoxide
  • other lipid hydroperoxides such as, for example, cholesterol hydroperoxide, cholesteryl linoleate hydroperoxide, trilinolein hydroperoxide, phosphatidylcholine hydroperoxide, and phosphatidylethanolamine hydroperoxide
  • peroxide compounds are available from commercial sources, and include 3- chloroperoxybenzoic acid, l,l-bis(tert-butylperoxy)cyclohexane, peracetic acid, monoperoxyphthalic acid, tert-butyl peroxide, 2,5,bis(tert-butylperoxy)-2,5-dimethyl-3- hexyne, cumene hydroperoxide, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, lauroyl peroxide, benzoyl peroxide, dicumyl peroxide, 2,5-dihydroperoxy-2,5-dimethylhexane, tert- butyl peracetate, tert-amyl hydroperoxide, diisononanoyl peroxide, decanoyl peroxide, succinic acid peroxide, 2,4-pentanedione peroxide, di-tert-butyl peroxide
  • stabilizers such as one or more organic phosphonates, stannates, pyrophosphates, as well as citric acid as well as citric acid salts may be included and when present considered as part of the oxidizing agent.
  • the inclusion of one or more such stabilizers aids in reducing the decomposition of the hydrogen peroxide due to the presence of metal ions and or adverse pH levels in the remedial fluid used to contact the oxidant with the sludge. These should represent only a minor proportion (less than about 10% wt.) relative to the weight of the oxidizing agent itself.
  • hydrogen peroxide optionally with a small amount of stabilizer is used.
  • a wash step is not included between addition of catalyst and the hydrogen peroxide, and simply adding more peroxide solution is used to wash out unbound iron catalyst.
  • a photoactive dye is a material that undergoes a chemical reaction when activated by light and is useful for embodiments of the invention where light, particularly sunlight, is available.
  • Typical photoactive agents include, but are not limited to at least one of porphyrins, and their derivatives; furocoumarins such as psoralens; phthaalocyanines, such as aluminum phthalocyanine; merocyanines such as MC540; and other photoactive dyes such as acridine; xanthene dyes, e.g., rose bengal and eosin Y, and thiazine dyes, such as phenothiazine dyes.
  • a dye or dye precursor during synthesis may be conjugated with another moiety.
  • Particularly preferred for this embodiment are long chain aliphatic chain hydrophobic derivatives of methylene blue prepared by adding one or more aliphatic chains by reactions described by Masuya et al. U.S. No. 5,344,928 and Motsenbocker U.S. No. 5,532,171.
  • the aliphatic chains are greater than 4 carbons, more preferably greater than 6 and most preferably greater than 8 carbons long.
  • the photoactive dye is a thiazine dye, such as, but not limited to, at least one of thionine, toluidine blue, neutral red, and even more preferably, methylene blue or an alkyl derivative of methylene blue.
  • the photoactive agent may be activated by visible light, sunlight, ultraviolet radiation, light emitting diodes and other forms of radiation.
  • a hydrophobic agent such as an iron soap or a porphyrin which is sparingly soluble in water is used in the presence of a surface active agent in order to improve solubility of the hydrophobic agent in water.
  • the surface active agent also improves hydrodynamic characteristics of the sludge that the hydrophobic agent is added to.
  • Such surface-active agent or surfactant generally may be present in an amount of from 0.01% to 5% by weight, and preferably from .05% to 1% by weight.
  • the surface-active agent can be anionic, nonionic, cationic or zwitterionic or a mixture of such agents.
  • Nonionic surfactants suitable for use in the present invention include water-soluble compounds produced by the condensation of ethylene oxide with a hydrophobic compound such as an alcohol, alkyl phenol, polypropoxy glycol, or polypropoxy ethylene diamine. Also suitable are alkyl amine oxides, alkyl polyglucosides and alkyl methylsulfoxides.
  • Preferred nonionic surfactants are polyethoxy alcohols formed as the condensation products of 1 to 30 moles of ethylene oxide with 1 mole of branched or straight chain, primary or secondary aliphatic alcohols having from about 8 to about 22 carbon atoms; more especially, 6 to 15 moles of ethylene oxide are condensed with 1 mole of straight or branched chain, primary or secondary aliphatic alcohol having from about 10 to about 16 carbon atoms.
  • Certain polyethoxy alcohols are commercially available under the trade-names "Neodol", “Synperonic", and "Tergitol”.
  • Anionic surfactants suitable for use in solubilizing a hydrophobic active agent of the invention include water-soluble alkali metal alkylbenzenesulphonates, alkyl sulphates, alkylpolyethoxyether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alphasulphocarboxylates and their esters, alkylglycerylethersulphonates, fatty acid monoglyceridesulfates and sulfonates, alkylphenolpolyethoxy ethersulphates, 2- acyloxyalkane-1 -sulphonates, and betaalkyloxyalkanesulphonates.
  • Soaps can also be used as anionic surfactants.
  • Preferred anionic surfactants are alkylbenzenesulphonates with about 9 to about 15 carbon atoms in a linear or branched alkyl chain, more especially about 11 to about 13 carbon atoms; alkylsulphates with about 8 to about 22 carbon atoms in the alkyl chain, more especially from about 12 to about 18 carbon atoms; alkylpolyethoxy ethersulphates with about 10 to about 18 carbon atoms in the alkyl chain and an average of about 1 to about 12 - CH 2 CH 2 O ⁇ groups per molecule; linear paraffin sulphonates with about 8 to about 24 carbon atoms, more especially from about 14 to about 18 carbon atoms and alpha-olefin sulphonates with about 10 to about 24 carbons atoms, more especially about 14 to about 16 carbon atoms; and soaps having from 8 to 24, especially 12 to 18, carbon atoms.
  • Cationic surface active agents suitable for use in the invention include the quaternary ammonium compounds, e.g. cetyltrimethylammonium bromide or chloride and distearyldimethylammonium bromide or chloride, and the fatty alkyl amines.
  • Zwitterionic surfactants that can be used in the present invention include water- soluble derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium cationic compounds in which the aliphatic moieties can be straight or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, especially alkyldimethylammoniopropane sulphonates and carboxylates (betaines) and alkyldimethylammoniohydroxypropane sulphonates and carboxylates wherein the alkyl group in both types contains from about 8 to 18 carbon atoms.
  • the energy for destroying the organic contaminant comes from a chemical oxidant such as hydrogen peroxide, peroxide precursor or ozone that is added to air or water that contacts the sludge.
  • the chemical oxidant then reacts with a catalyst (which maybe a hydrophobic catalyst) that is preferentially adsorbed at the target solid phase surface, and/or a separate hydrophobic phase that may exist within the sludge, such as oil droplets.
  • the target solid phase surface typically comprises clay particles but any hydrophobic or hydrophilic surface within the sludge may contain adsorbed organic contaminants and represent a target location as termed herein.
  • One embodiment in this context is to first contact the sludge with remedial fluid (typically an aqueous solution such as water, or water/ethanol mixture) that contains the metal catalyst.
  • remedial fluid typically an aqueous solution such as water, or water/ethanol mixture
  • the catalyst concentrates at the target location within the sludge.
  • the oxidant is added by contacting a second remedial fluid with the sludge.
  • the oxidant reacts with the metal catalyst and with the target contaminant.
  • the oxidant first reacts with metal catalyst to form a (typically very unstable) active intermediate which then attacks the contaminant.
  • hydrogen peroxide is converted at the target location into hydroxyl radical.
  • the radical then reacts with target compound in the immediate vicinity of the catalyst.
  • reaction mechanisms such as the formation of a ternary complex between catalyst, oxidant and target compound
  • the reaction occurs within the target location, which typically is a surface layer on particles and/or oily phase droplets, thereby overcoming or alleviating the chemical stability and dilution problem.
  • a catalyst such as iron is already present in the sludge, preferably in the sludge target phase and a hydrophobic oxidant is added to the sludge.
  • the hydrophobic oxidant concentrates at the surfaces of sludge particles and/or organic phase and destroys organic molecules found there.
  • a wash fluid may be added and/or a dewatering step may be included (by, for example, gravity or with a vacuum) to increase the concentration of active agent at the target location or decrease inhibition of the destruction reaction with water.
  • the solutions optionally may further comprise one or more water miscible solvents to facilitate solubility of the catalyst or oxidant, and/or may contain a detergent to improve solubility.
  • the metal is ferric or ferrous iron and is added to the sludge as a salt complex with a weakly amphipathic compound such as a small chain fatty acid. The metal adsorbs onto particles, particularly at hydrophobic regions. h most preferred embodiments hydrogen peroxide is added and the Fenton's reaction ensues. Washes, dewatering and the like also can be used for this embodiment as described elsewhere.
  • a high pH aqueous solution such as water or water/ethanol above pH 10, preferably above pH 11 and more preferably above pH 12, is used in combination with a metal catalyst such as porphine.
  • a metal catalyst such as porphine.
  • the inventor has studied porphines that can destroy an organic molecule in the presence of high pH and found that a poiphine having para-electron withdrawing residues is preferred to maximize the destruction rate. Further, dissolved oxygen, if required, is only needed at a very low concentrations, as described in Motsenbocker et al. Anal. Chem. 65: 397-402 (1993).
  • a surface active agent such as Tween-20 may be added with the active agent to help the agent remain suspended in water so that the active agent may enter the target location, hi this case, the detergent advantageously is in a molar excess of at least 10 and preferably of at least 50 with respect to the active agent.
  • the detergent in some embodiments may facilitate reaction between the active agent and the organic contaminant, in a manner suggested by Motsenbocker et al. J. Biolumin. Chemilumin. 9: 7-13 (1994).
  • the active agent is a metal po ⁇ hine catalyst wherein the metal is a manganese.
  • the high pH may be prepared by any of a number of procedures known to the skilled artisan, including for example, addition of sodium hydroxide to water, and use of anodic water prepared elecfrochemically.
  • the latter is particularly preferred because such water contains other active agents that can destroy organic molecules.
  • a photoactive dye is added to a thin sludge consisting of floating particles such as oil droplets or oily film from an oil spill and concentrates there. Sunlight activates the photoactive hydrophobic dye, leading to decomposition and dispersal of the organic contaminants.
  • This embodiment is particular useful at the water-air interface of a toxic spill wherein the organic toxin forms a scum or thin layer of material at or near a surface of water that is illuminated.
  • the dye derivative has a high association for the target phase such that at least 2% of the applied dye, and more preferably at least 10% of the applied dye remains there for at least a few hours and preferably for at least 3 days, and does not disperse readily into the water, hi one embodiment a methylene blue derivative is used having a single substitution of a long aliphatic chain of at least 8 carbons, preferably at least 12 carbons and more preferably at least 16 carbons.
  • the single aliphatic chain anchors the dye into (or on) an oil phase but allows the planer ring system of the dye to contact the water phase at the oil surface.
  • the dye preferably is mixed in a hydrophobic water immiscible solvent such as mineral oil, light vegetable oil, or more preferably, as an emulsion designed specifically for dispersing oil slicks.
  • a hydrophobic water immiscible solvent such as mineral oil, light vegetable oil, or more preferably, as an emulsion designed specifically for dispersing oil slicks.
  • emulsions are known, as for example, described in U.S. Nos. 3,959,134; 3,793,218; 4,382,873; 4,146,470; 5,567,324; 4,728,455 and 5,055,196, the contents of which are specifically incorporated by reference in their entireties.
  • the dye may be dissolved or suspended at a concentration of between 0.0001% to 5% weight/volume of the material that is to be applied to the slick.
  • the dye is between 0.01% to P/oweight/volume.
  • the final mixture or solution preferably is applied to a slick by spraying, h one embodiment, spraying is carried out from an aircraft. In a more preferred embodiment, spraying is carried out from a watercraft. Most preferably, the watercraft is an electric watercraft having superior stability characteristics to allow controlled spraying in rough seas, as described in co-pending application entitled "Advantageous Use of Battery Mass in Watercraft” filed February 19, 1999. Enhance Destruction by Stabilizing Agent
  • a suitable soil stabilizing reagent is mixed at an effective concentration with degradative agent and then applied to contaminated soil for the combined effect of reducing soil permeability and prolonged organic contaminant degradation.
  • the permeability (saturated hydraulic conductivity) of the soil is decreased, helping divert groundwater away from the contamination, and ensure destruction of a contaminated volume by entrapping and immobilizing both the contaminant source and the plume.
  • the concentration of clay in the soil may range from 1% to about 10% where a range of 5% to 10% is preferred. Further details of how to accomplish immobilization are known to the artisan and can be found in publications such as U.S. No. 5,789,649.
  • the admixing of the stabilized reductive reagent into the soil has the effect of reducing the permeability of the contamination source significantly. A permeability reduction of between one and 4 orders of magnitude are expected. Reduction of the soil permeability effectively excludes the groundwater from entering the contamination source and sequestering the organic contaminant.
  • the reduction in permeability combined with the oxidative action of the metallic couple serves to prevent the contaminant from entering the aquifer while, at the same time, degrading the toxic solvent.
  • the permeability has been so reduced as to divert ground water around the source and causes the dissipation of the contamination plume.
  • the presence of the degradative agent in the stabilized degradative reagent reduces the concentration of the stabilized contaminants and prevents further leaching into the environment.
  • a useful mechanical method of removing volatile contaminants from the subsurface medium in the vadose zone above the water table uses specially constructed wells that are drilled into the subsurface media in the contaminated area as described for example by Visser et al. U.S. No. 4,590,760, the contents of which are specifically incorporated by reference in its entirety.
  • the Visser disclosure describes constructing one or more wells so that fluids in the vadose zone but not substantially liquid in the saturated zone below the water table can flow into the well.
  • that invention can and normally will be used in combination with an additional system or systems for reclaiming contaminated groundwater because not all of the contaminant will be removed by the treatment according to the invention.
  • one or more additional pumps can be provided to remove groundwater from the aquifer, treat it and then recharge it into the aquifer after removing the contaminant therefrom.
  • the technique of removing water and placing it back is "well known in the art.”
  • a major limitation to the Visser process described by U.S. No. 4,590,760 is that it works best for removal of contaminants having vapor pressures of 100 mmHg at temperatures of 25 degrees celcius or less. Many organic contaminants have lower vapor pressures than this and are removed with greater difficulty (time and expense) if at all. Embodiments of the invention can alleviate this problem.
  • An active agent according to the invention can be injected near or into the same wells used for the Visser process. The agent can convert larger organic molecules having lower vapor pressures to smaller organic molecules having greater vapor pressures.
  • the chemical degradation process of the present invention with the vapor recovery process of Visser, a greater range of organic molecules can thus be removed more economically from a contaminated soil sludge, hi particular, the Visser process minimizes the amount of water that is needed to be physically moved and removes small organic molecules most efficiently.
  • hydrophobic active agents can be administered to a soil sludge within a small volume of remedial water and are most conveniently and efficiently administered in a water mixture with another solvent having a high vapor pressure.
  • an active agent of the invention such as manganese porphyrin may be dissolved in a 50% methanol-water solution and added to the soil.
  • a vacuum is applied according to the Visser process, which removes the methanol and causes the active agent to concentrate onto particles and within oily phase materials in the ground, effectively focusing the destructive energy of the active agent at the location where it is most needed.
  • the vacuum extraction well process of removing volatile organics can be operated so as to dry the surrounding clay so that it cracks and becomes more permeable, allowing contact of the applied active agent with dispersed contaminants.
  • Embodiments of the invention may be practiced in alternative formats as exemplified above to exploit the ability of a hydrophobic catalyst and/or other reactant to concentrate at a target volume that contains an organic contaminant. These and yet other formats can work with a large variety of catalysts and/or other active agents to degrade organic hydrophobic contaminants found in sludge as reviewed above.
  • at least one active agent or activatable agent is hydrophobic and partitions into the target volume.
  • Most preferred agents are peroxides, reagents that produce peroxides, metal catalysts, including hydrophobic complexes of metals such as po ⁇ hyrins and low molecular weight iron soaps, and photoactive dyes, although other chemistries not specifically named herein can be used, particularly if at least one reactant can be made suitably hydrophobic to partition into a hydrophobic (i.e. less hydrophilic than water) target phase.
  • Active as used herein means that the compound becomes altered to allow the compound directly, or indirectly through generation of a secondary compound such as a free radical or oxidant such as singlet oxygen, to react with and change the structure of an organic compound in a sludge.
  • a secondary compound such as a free radical or oxidant such as singlet oxygen
  • the phrase "react with and change the structure” means that at least one carbon covalent bond of the organic compound is destroyed. Destruction of at least one covalent bond results in the conversion of the compound into another compound, thereby "removing” it.
  • the new compound is more oxidized and . less toxic than the unaltered compound.
  • Hydrophobic means the propensity to avoid water and to dissolve more easily in a less hydrogen bonding solvent (compared to water) such as ethanol.
  • a hydrophobic molecule will tend to adhere to the surfaces of clay particles in sediment sludges and will more readily partition into a oil phase than into a water phase.
  • a hydrophobic molecule often is sparingly soluble in water. For example, some hydrophobic compounds dissolve to a maximum concentration of only between O.Olmg/liter to 100 mg liter in warm water.
  • hydrophobic active agent By adding a water miscible solvent such as methanol, ethanol, dimethyl formamide or the like to the water, a greater amount of the hydrophobic molecule may dissolve, hi practice, a "hydrophobic" active agent is sparingly soluble and is first dissolved in an organic solvent such as dimethyl formamide or ethanol, and then diluted from this solvent into water, hi such case, the active agent solution that contacts the sludge may have a small amount of other solvent in it.
  • the hydrophobic active agent is present in an aqueous solution (optionally with up to 50% of a co-solvent present) and will slowly precipitate over the course of several hours to several days, i this case, the agent preferably is dissolved immediately before use.
  • Hydrophobic activatable compound means a compound that is hydrophobic and that can be converted into a form that directly or indirectly destroys an organic compound, converting it into another chemical form.
  • hydrophobic in this context means that the compound has at least a portion that does not solvate in water well and prefers a less hydrogen bonding solvent such as ethanol, methanol, dimethylformamide, dimethyl sulfoxide, isoproanol or the like, or a water admixture with such solvent.
  • a hydrophobic compound does not dissolve well in water and may not dissolve at a high concentration.
  • Methylene blue which has a conjugated ring system but is charged may be dissolved at a high concentration in water but derivatives may be prepared that lower its solubity and increase its amphipathic characteristics by providing a long or bulky additional hydrophobic moiety that is particularly useful for partitioning into an oily phase such as an oil spill.
  • Many metal po ⁇ hyrins are known that are fairly soluble in water (some even above lOOmg/liter) but which still are useful because their amphipathic characteristics allow them to adhere well to particle surfaces and concentrate into a target volume.
  • Hydrophilic oxidant is a reagent that can oxidize an organic contaminant, either directly or in concert with a catalyst such as a po ⁇ hine or uncomplexed metal ion, and which partitions into the target location.
  • Iron soap is a salt of Fe+2 and/or Fe+3 with one or more anionic surfactants (amphipathic compounds).
  • a "low molecular weight iron soap” is a salt of an anionic surfactant having a weak hydrophobic portion (smaller aliphatic chain or other hydrophobic part) such that the iron salt does not readily precipitate. That is, the aliphatic chain is smaller than that normally used for a detergent or soap. In the context of a soap, the aliphatic chain preferably is less than 12 carbons and more preferably less than 10 carbons long. Most typical low molecular weight iron soaps are ferric and/or ferrous iron complexes with small chain length fatty acids.
  • Organic compound means a compound that comprises carbon atoms covalently bound to other atoms and that is at least partly soluble (partitions into) in organic phases and includes, for example, such compounds as Bis(2-chloroethoxy) ether; l,2-Bis(2-chloroethoxy) ethane; Bis(2-chloroethoxy) methane; Bis(2-chloroethoxy) phthalate; Bis(2-chloroethyl) ether; Bis(2- chloroisopropyl) ether; 4-Bromophenyl phenyl ether; 4-Chloroaniline; 2-Chloronaphthalene; 4-Chlorophenyl phenylether; 2-Chlorophenol; 1,2-Dichlorobenzene; 1,3-Dichlorobenzene; 1,4-Dichlorobenzene; 3,3-Dichlorobenzidine; 2,4
  • Nitrosodiphenylamine; n-Nitrosodi-n-propylamine; and Phenyl naphthalene Sites where sludges that contain such organic compounds may be found include burn pits, chemical manufacturing plants and disposal areas, contaminated marine sediments, disposal wells and leach fields, electroplating/metal finishing shops, firefighting training areas, hangars/aircraft maintenance areas, landfills and burial pits, leaking collection and system sanitary lines, oil spills, leaking storage tanks, radiologic/mixed waste disposal areas, oxidation ponds/lagoons, pesticide/herbicide mixing areas, solvent degreasing areas, surface impoundments, and vehicle maintenance areas and wood preserving locations.
  • Partition into a target volume means that a substance prefers to enter this volume instead of remaining in the aqueous phase outside the volume.
  • whether a substance partitions into a target volume can be determined experimentally by adding a trace amount of the substance (less than that needed to saturate the target volume) in an aqueous solution or mixture and contacting that solution or mixture with the target volume (clay particles, non-miscible oily phase) and allowing equilibration of the substance between the bulk water phase and the target volume.
  • the aqueous solution or mixture then is removed by, for example decanting or aspiratmg (if a liquid) or gravity sedimentation (if a soil or other sediment).
  • the concenfration of the substance in the bulk aqueous phase and in the target phase is determined. If the concentration of substance in the bulk aqueous phase is lower than the concentration of substance found in the target volume after equilibration then the substance has partitioned into the target volume.
  • Remedial water means an aqueous fluid that contains at least one catalyst or other agent (such as an oxidant) that can destroy an organic contaminant upon contact with a sludge, h some cases, the "water” is a solution of water and other solvent or additive such as detergent that increases solubility of the catalyst and/or other agent.
  • the inventor has used solutions of methanol, ethanol and/or dimethy formamide in water to facilitate solubilizing dye catalysts such as derivatized methylene blue and metal po ⁇ hines.
  • water is present in at least 50% volume and more preferably at least 80% by volume.
  • a 10% ethanol solution in water may be used to solubilize a metal po ⁇ hine catalyst and used administer the catalyst to a sludge, hi some embodiments a detergent may be added. More preferably an aliphatic detergent (lacking conjugated double bonds), that does not react readily with the activated dye is used to facilitate dissolving the reagent in remedial water.
  • Sludge means a material that contains at least 10% water by weight, and may comprise animal waste, dredged material, human waste, soil or sediment, wet byproduct from mining, or farming, such as tailing, feed lot waste, biomass production waste, or any combination of the foregoing.
  • Thin sludge refers to a variety of sludge that consists of hydrophobic organic molecules such as from gasoline or an oil spill that separates out from water and forms definable target volumes such as a scum on the water surface and oil droplets within the water.
  • Stabilizing agent means a material that can be added to a soil to reduce soil permeability.
  • stabilizing reagents are known and are contemplated to be useful in the instant invention.
  • Typical stabilizing agents may include but are not limited to Portland cement, soluble silicates-cement, pozzolan-lime, pozzolan-cement, clay cement, clays such as bentonite, iron chloride mixtures, and fly ash.
  • Bentonite clay for instance, is a high swelling, sodium montmorillonitic clay mineral, which, because of its mineralogical structure, has the capability of taking water between the structural sheets.
  • Sodium montmorillonite is ideally composed of two sheets of silica tetrahedron on either side of an octrahedral gibbsite sheet. Isomo ⁇ hous substitution within the layers of the sheet result in charge deficiencies. Cations may be present between the layers to balance the charge deficiencies. These interlayer bonds are therefore relatively weak and easily separated by imposed stresses such as the adso ⁇ tion of water or other polar liquids. Hence, montmorillonitic clays may swell to approximately 200 times their original volume. (Evans, et al, "Influence of Industrial Wastes on the Geotechnical Properties of Soils.” Proc. of the 15th Mid- Atlantic Ind. Waste Conf., Bucknell University, Bethlehem, PA. (1983)). This characteristic makes these materials useful in the embodiment of civil engineering-applications such as soil-bentonite slurry trench cutoff walls.
  • Target location means a portion of the sludge volume which is enriched with an undesirable organic molecule. For example, clay particles found within a contaminated coastal bay sediment would have undesirable organic molecules at their surfaces. When comparing the material in "bound" water on these surfaces (surface-bound water) with the bulk phase water existing between particles (that can be removed by gravity separation) it can be seen that the concenfration of a particular organic molecule in the bulk phase water is less than that in the bound phase.
  • the "target location” is the volume of liquid at the surface of the particles and which is not eluted by gravity. Target location also includes accumulations of organic (carbon containing solvent and/or solute) molecules such as hydrocarbon vented naturally in the earth or waste or other spill that results in an accumulation such as that seen sometimes accumulating atop an underlying clay stratum.
  • the iron complexes were made using short chain length aliphatic carboxylic acids from two to 12 carbons long. All carboxylic acids were protonated.
  • Iron sulfate (4.0 gm Fe2(SO4)3) was added to hexanoic acid (10.7 gm) and stirred for 10 minutes. No dissolution of the Fe2(SO4)3 was seen. Then 14.7 gm of water were added and stirred. Gradually a reddish color (indicating Fe+2) formed and deepened. The color gradually formed in the upper hydrophobic hexanoic acid phase, leaving the water phase.
  • Iron chloride (3.2 gm FeC13) was added to 10.3 gm hexanoic acid. Then 12.5 ml of water were added and stirred. The FeC13 dissolved and all of the color went into a hydrophobic hexanoic acid phase. The color stayed in the hydrophobic phase despite further additions of water. This result indicated that iron chloride is preferred over iron sulfate for this embodiment of the invention.
  • Iron chloride (2.4 gm) was added to 63 ml of a 5% acetic acid solution (vinegar) with stirring.
  • Canola oil (31.2 gm) was added to form a hydrophobic phase. Most of the color stayed in the water phase. This result indicated that acetic acid does not work as well as longer chain length carboxylic acids.
  • Iron chloride (8.2 gm) was added to 20.1 gm of proprionic acid with stirring. Then 75 ml of water were added and mixed by stirring. A small amount of red colored flocculant formed as a light layer on the top of the water.
  • Iron chloride (7.6 gm) was added to 36 ml of heptanoic acid. Then 60 gm of water were added. Red iron color stayed within the hydrophobic phase.
  • a bottle of decanoic acid was heated to between 32 and 45 degrees centigrade. Then 57.4 gm (1/3 mole) were removed and 16.2 gm iron chloride (1/10 mole) was added and stirred with moderate heating for 20 minutes. Then 63.5 gm of 95 degrees centigrade water were added and mixed further. Much color entered the bottom (clear) layer with some color forming as a cloudy suspension in the upper layer. Then 0.1 ml of the upper hydrophobic phase was taken and added to a beaker of hot water. The oily colored drops floated on the surface of the hot water and slowly released some color into the water. The two phase mixture was cooled and the water removed. The hydrophobic phase that contained iron was heated and washed with more water.
  • Example 2 h this example, iron short chain aliphatic carboxylic acids from Example 1 were used to target a hydrophobic surface.
  • Decanoic acid iron catalyst from Example 1 was added (0.05 ml) to 18 ml of hot water in a glass (hydrophilic surface) beaker and swirled.
  • the red oily catalyst did not adhere to the glass wall of the beaker. This was repeated with a plastic (hydrophobic surface) beaker.
  • the red oily catalyst adhered to the plastic surface upon contact.
  • Two mis of denatured alcohol were then added to each 18 ml mixture (10% final concentration) and swirled. The alcohol caused about half of the red color to desorb from the plastic. By repeated swirling it became evident that the red hydrophobic catalyst was coming off to form droplets, and then re- binding to the plastic surface.
  • Hexanoic acid iron catalyst from Example 1 was added (0.05 ml) to 22 ml of hot water in a plastic (hydrophobic surface) cup.
  • the colored hydrophobic catalyst coated out on the plastic surface.
  • Two ml of denatured alcohol (10% final concentration) were added and swirled. The color did not desorb from the plastic surface.
  • contaminated sediment was treated with a preferred iron short chain length aliphatic carboxylic acid prepared from Example 1, and Fenton's reaction was employed using H202 and the targeted catalyst.
  • Wl ite sand was heated to above 100 degrees centigrade for 15 minutes to remove water. Then 74 gm of the dried sand was mixed by stirring with 7.9 gm of used motor oil from a regular oil change.
  • the oil-coated sand (contaminated sediment) was then treated as follows. One gram portions of oily sand were placed into three 5 oz plastic dixie cups. The first cup was control and utilized treatment with iron sulfate. The second and third cups had the same amount of iron, but in a hydrophobic catalyst form. The contaminated sand in each cup was mixed, washed and then exposed to dilute hydrogen peroxide solution to destroy organic contaminants on the sand particle surfaces.
  • Iron sulfate (1.2 ml of 20mM) was added to the first (control) cup and mixed well. The water was decanted and the sediment was rinsed twice with 25 gm of water. Then water was added to a final amount of 2ml water.
  • iron-hexanoic acid hydrophobic catalyst (0.1 ml of iron-hexanoic acid) prepared in Example 1 was added with 1.1 ml water (final iron concenfration of 20mM in 1.2 ml) and mixed well. This was rinsed as for the control above and then water was added to 2ml total as above.
  • the third cup was treated the same as the second cup except that 0.1ml of the iron-incubation water was replaced with denatured alcohol. After washing, 2 ml of 0.03 % vol/vol hydrogen peroxide in water solution were added to each cup, briefly mixed and left at room temperature for one week.
  • Example 4 hi this Example a hydrophobic photoactive dye derivative is used to degrade and disperse an oil spill.
  • a mixture of mono and di-octyl methylene blue photoactive dyes (one and two 8 carbon chains, respectfully, on the non-conjugated nitrogens) is prepared according to procedures known in the organic chemistry field and as described in U.S. Nos. 5,344,928 and 5,532,171.
  • the dye mixture containing between 10% and 90% mono-octyl and between 10% and 90% di-octyl derivative, is mixed at 1% wgt/vol into mineral oil and is applied by spraying onto a section of a crude oil spill, to cover approximately 50% of the surface of the oil.
  • a similar area of the oil spill is similarly treated with mineral oil without the photoactive dye as a control. After one day, two days, and after one week both sections are examined. The concentration of polyaromatic hydrocarbons in the spill material is determined and found to be decreased by treatment with the photoactive dye derivative.
  • ethanol without po ⁇ hine is diluted 50 fold into the same NaOH solutions to prepare 1ml portions that are added to the other 15 8ml vials with soil-luminol.
  • the vials are shaken well and left to sit overnight.
  • the following day the amount of luminol in the soil is measured and the amount of metal po ⁇ hine in the supernatant is measured. It will be found that the samples which contain the metal po ⁇ hine catalyst have less luminol by the treatment and that much of the metal po ⁇ hine is attached to the soil particles.
  • Example 6 hi this experiment 6 luminol-soil samples are prepared as described in Example 2. A 1 ml solution of Hemin (iron po ⁇ hyrin) in water (lOOug/ml) is added to each soil sample and the sample is shaken for 1 minute. Then the soil is decanted and washed once with 1 ml of water. Then 1 ml of 5mM hydrogen peroxide with 0.1 mM EDTA chelator is added to three samples. As a control, just plain water with 0.1 mM EDTA chelator is added to the other three samples. All samples are shaken one minute and left to stand overnight. The following day the luminol is removed from the samples by ethanol washing and measured. The samples treated with Hemin catalyst will be seen to have less luminol compared to the control samples.
  • Hemin iron po ⁇ hyrin
  • Example 7 h this example soil contaminated with aromatic hydrocarbons is treated with hydrophobic catalyst and hyrophilic catalyst.
  • One gram portions of screened soil that is contaminated with aromatic hydrocarbons are weighed into ten 8ml vials. Each vial is sealed with a Teflon-lined cap.
  • a 10 mg portion of Fe meso-tetraphenylpo ⁇ hine is dissolved into 5 ml of ethanol and then diluted 50 fold into (5) one ml solutions of 0.1 mM EDTA.
  • a 10 mg portion of Fe meso-tefrakis(4-carboxyphenyl) po ⁇ hine is dissolved into 5 ml of ethanol and then diluted 50 fold into (5) one ml solutions of 0.1 mM EDTA.
  • Each prepared one ml solution is added to a separate 8 ml vial with lgm of hydrocarbon contaminated soil. The vials are shaken well, decanted, and rinsed with 1 ml of water that contains O.lmM EDTA. Then 1 ml of 20mM hydrogen peroxide 0.1 mM EDTA solution is added to each vial, shaken well, and left to sit for 3 days.
  • the amounts and types of aromatic hydrocarbons are determined and it is found that the meso-tetraphenylpo ⁇ hine treated soil has less aromatic hydrocarbon after the treatment compared with the more hydrophilic catalyst control.
  • the experiment is repeated with 0.1 M NaCl in all solutions and it is seen that treatment with the more hydrophobic catalyst yields a greater loss in organic contaminant compared with treatment with the more hydrophilic catalyst.

Abstract

L'invention concerne une amélioration de la dégradation de des contaminants tels que des HAPs dans de la boue par ciblage de la production d'espèces réactive tels qu'un radical hydroxy sur le site où cela est nécessaire. En créant des espèces réactives sur le site souhaité, lesdites espèces présentent une probabilité plus faible de pourrissement avant la réaction avec une molécule contaminante. L'invention concerne également des procédés et des matières conçues pour séparer un ou plusieurs catalyseurs hydrophobes, oxydants ou autre composé en phase hydrophobe ou à la surface de particules afin d'améliorer la destruction de contaminants hydrophobes. Dans des modes de réalisation de boues solides des savons de fer fabriqués à partir de carboxylates aliphatiques courts sont utilisés pour focaliser la puissance destructrice sur des micro-sites huileux dans la boue. Dans des modes de réalisation préférés pour des déversements de pétrole des colorants photoactifs et amphipatiques tels que des dérivés de bleu de méthylène qui adhèrent à la phase huile et qui focalisent les réactions de destructions dirigés par la lumière à l'intérieur de l'huile elle-même.
PCT/US2002/003873 2002-02-11 2002-02-11 Elimination de contaminant organique provenant de boue par catalyse ciblee WO2003068324A1 (fr)

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WO2011056508A3 (fr) * 2009-10-28 2011-08-04 The University Of Vermont And State Agricultural College Procédé et système de décarboxylation oxydative sélective d'acides gras
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CN112121841A (zh) * 2020-10-10 2020-12-25 西安建筑科技大学 一种利用膜生物反应器剩余污泥制备氮磷共掺杂碳催化剂的方法
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CN115819790A (zh) * 2022-12-12 2023-03-21 无锡市南京大学锡山应用生物技术研究所 肿瘤靶向的声动力锆基有机框架材料

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US7976241B2 (en) 2006-03-27 2011-07-12 Verutek Technologies, Inc. Soil remediation method and composition
FR2907694A1 (fr) * 2006-10-27 2008-05-02 Michel Mazon Procede de stabilisation des dechets menagers et assimiles
US9895730B2 (en) 2007-09-26 2018-02-20 Ethical Solutions, Llc Method for extraction and surfactant enhanced subsurface contaminant recovery
US8057682B2 (en) 2008-05-16 2011-11-15 Verutek Technologies, Inc. Green synthesis of nanometals using plant extracts and use thereof
WO2011056508A3 (fr) * 2009-10-28 2011-08-04 The University Of Vermont And State Agricultural College Procédé et système de décarboxylation oxydative sélective d'acides gras
EP2494007A4 (fr) * 2009-10-28 2013-09-25 Univ Vermont Procédé et système de décarboxylation oxydative sélective d'acides gras
EP2494007A2 (fr) * 2009-10-28 2012-09-05 The University Of Vermont And State Agricultural College Procédé et système de décarboxylation oxydative sélective d'acides gras
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CN102665944A (zh) * 2009-11-11 2012-09-12 拿波利菲德里柯二世大学环境和农业新材料核磁共振多学科研究中心 螯合土壤中的有机碳的方法
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CN109575036A (zh) * 2018-12-11 2019-04-05 怀化学院 金属血卟啉双醚二酯类化合物，催化剂及其制备方法以及环己烷催化氧化方法
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