WO1999026885A1 - Compositions and methods for adsorption and remediation of organic compounds - Google Patents

Compositions and methods for adsorption and remediation of organic compounds Download PDF

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Publication number
WO1999026885A1
WO1999026885A1 PCT/US1998/025131 US9825131W WO9926885A1 WO 1999026885 A1 WO1999026885 A1 WO 1999026885A1 US 9825131 W US9825131 W US 9825131W WO 9926885 A1 WO9926885 A1 WO 9926885A1
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WO
WIPO (PCT)
Prior art keywords
sop
composition
pesticide
leachate
soil
Prior art date
Application number
PCT/US1998/025131
Other languages
French (fr)
Inventor
George H. Snyder
Curtis Elliott
John L. Cisar
Mark C. Elizer
Original Assignee
University Of Florida
Calcium Silicate Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University Of Florida, Calcium Silicate Corporation filed Critical University Of Florida
Priority to AU16042/99A priority Critical patent/AU1604299A/en
Publication of WO1999026885A1 publication Critical patent/WO1999026885A1/en

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Classifications

    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation

Definitions

  • the present invention relates generally to the removal of organic compounds from soils, hazardous spills, and aqueous environments. More particularly, this invention pertains to a technology for reducing runoff and/or leaching of organic compounds such as pesticides present in an environmental or industrial setting.
  • compositions and methods are disclosed for stabilized organic polymer formulations capable of binding organic compounds, such as insecticides, herbicides, fungicides and nematicides. Also provided are methods of using such compounds in the remediation of environmental contamination, in the reduction of pesticide leaching from soil samples, and in the preparation of time-release organic fertilizer and pesticide formulations.
  • landfill leachate Other pollutants that comprise landfill leachate include pathogenic organisms, solvents, pesticides, hazardous wastes, and industrial and wastewater sludges (U.S. Patent 4,995,969, specifically incorporated herein by reference).
  • Off-site treatment may involve piping the leachate to a nearby sewer system, and combining it with the municipal sanitary sewage.
  • This off-site treatment methodology requires that the community have a municipal treatment facility capable of processing the leachate loadings; and that the concentration of leachate to wastewater be small to effectuate effective processing.
  • on-site treatment of leachate with package plants has been attempted; but with limited success.
  • Another type of leachate treating system includes one or more open oxidation ponds or lagoons. This type of system tends to be relatively slow and requires a relatively large land area. In addition, the open pond is unsightly, has an objectionable odor and is a breeding ground for mosquitoes.
  • LaVigne describes a method of on-site leachate treatment in which the leachate is forced to run through a plot containing leachate-tolerant plants and microorganisms that are capable of metabolizing organic carbon compounds and adsorbing heavy metals within the leachate.
  • adsorbents One method of removing organic compounds from aqueous solutions or the environment has been through adsorbents.
  • Many inorganic adsorbents are known in the art and have been used for some time. These adsorbents are defined as solid phase materials having very high surface area-to- weight ratios and exhibiting the ability to concentrate adsorbates on their surfaces (U. S. Patent 4,147,624, specifically incorporated herein by reference).
  • Inorganic adsorbents include activated carbon, silica, silicates, alumina, and clays.
  • Mineral substrates such as sepiolite, attapulgite (palygorskite) and smectities may be modified to obtain a more organophilic surface to be effective adsorbents for certain uses, however a relatively high surface area and a cationic exchange capacity above about 5 milliequivalents per 100 grams of adsorbent is required (U.S. Patent 4,444,665; specifically incorporated herein by reference).
  • these clay minerals aluminosilicates
  • swell or slake in aqueous systems resulting in gel formation or colloidal dispersions that are extremely difficult to separate from the liquid.
  • colloidal dispersions that are extremely difficult to separate from the liquid.
  • granular forms of these clays in naturally occurring state are useless since they simply fall apart in aqueous media.
  • Adsorptive minerals such as bauxite does not exhibit this deficiency, but such clays must be rendered substantially non-gelling or non-slaking by an expensive heat treatment.
  • attapulgite clay may be rendered non-gelling and non-slaking by calcining at temperatures in the range 200°C-550°C (McCarter et al., 1950).
  • Unmodified, heat-treated attapulgite has disclosed use in water treatment for removing certain metal cations, hormones, toxins, viral micro-organisms and pesticides. Reference is made to the following U.S. Patents to Sawyer: Nos.
  • a specially processed form of heat-treated attapulgite has disclosed use as a filter aid in Re. No. 25,464 (Oct. 15,
  • such compounds are not useful in soil strata such as golf course greens where a high degree of percolativity is required and where the addition of such products would compromise the percolation and drainage of these soils.
  • compositions and methods for adsorption of organic compounds the development of controlled-release formulations of organic fertilizers and pesticides, and methods for the removal of organic leachates (such as pesticides) from agricultural and commercial environs, as well as industrial sites and environmental contamination.
  • devices and apparatus for the remediation of organic wastes in situ and in solution using reactive barriers, flow through filtration systems, and organic waste containment facilities are provided.
  • compositions are provided for the reduction of pesticide leaching from athletic facilities, and in particular, golf course greens, and athletic turfs.
  • the invention disloses and claims a stabilized organic polymer comprising phenol-formaldehyde-polyethylene glycol.
  • the polyethylene glycol is crosslinked with the phenol-formaldehyde using a Williamson ether synthesis to produce the stabilized organic polymer.
  • This polymer may be utilized directly, or bound to a matrix or a substrate.
  • the polymer compound is capable of binding an organic compound, and in particular, organic contaminants, fertilizers, and pesticides.
  • the pesticide may be an insecticide, a herbicide, a fungicide, or a nematicide.
  • the composition may be comprised within an agricultural site, a reactive containment barrier, or a hazardous spill cleanup device or apparatus.
  • the composition may also be formulated into a filter or sedimentation take or other water treatment device.
  • the composition may be formulated into a soil amendment, additive, or hazardous spill barrier or containment means.
  • the composition may be formulated for use in a device or system for treating water, sewage, wastewater, or agricultural leachate, or for removomg organic pollutants from a solution.
  • the water treatment device will comprise at least a first inlet port from which the contaminated solution is introduced into the device, one or more chambers in which the composition is placed either alone or on one or more supports or matrices and in which the solution is contacted with the composition to adsorb the organic contaminant(s) from the solution, and then one or more oulet ports from which the purified water is released.
  • the SOP adsorbant compositions may be comprised with a system for removing pesticides from a leachate.
  • the system generally comprises at least one leachate supply source, a water impervious treatment basin with at least one inlet port into which the SOP composition is placed and into which the leachate supply source flows to contact the leachate with the SOP composition, and at least one outlet port, and flow ontrol means for draining the treated leachate from the treatment basin.
  • the system may also comprise a continuous flow system or a batch processing system.
  • the invention also discloses and claims a method of preparing a SOP composition that has the desired property of being able to adsorb one or more organic compounds onto the polymer.
  • the method generally involves coating, spraying, aerosolizing, or otherwise contacting a suitable matrix with the SOP compound under conditions effective to permit coating of the matrix with the compound.
  • a method of preparing a golf course to prevent leaching of a pesticide from the course is also provided by the invention.
  • This method generally involves amending one or more layers of soil underneath the golf course grass with one or more SOP compositions.
  • the composition may be applied to discreet layers under the athletic turf, or alternatively may be mixed throughout the soil underneath the grass.
  • the invention also discloses and claims a controlled-release pesticide and a controlled-release organic fertilizer composition that comprises the SOP compound described herein.
  • Such formulations permit the time-released or slow-release of the adsorbed pesticide or fertilizer, as it slowly desorbs from the SOP.
  • Organophosphates, fish emulsions, manure filtrates, and other organic fertilizers are all contemplated to be amenable to controlled-release using the SOP compositions, and their slow desorbtive properties.
  • the present invention concerns stabilized organic polymers (SOPs) that are capable of binding to organic compounds and preventing the leaching of such organic compositions from the area in which the SOPs are located.
  • SOPs stabilized organic polymers
  • the SOPs of the present invention may be prepared so that they bind either polar or non-polar organic compounds, or alternatively, may be designed such that a single SOP, or a combination of two or more distinct SOPs may bind both polar and non- polar compounds.
  • the ability of SOPs to bind more than one type of organic compound makes them useful for a variety of organic chemical remediation situations.
  • the SOP is a phenol-formaldehyde-polyethylene glycol polymer.
  • the inventors have shown that phenol-formaldehyde-polyethylene glycol compositions are highly desirable for their mechanical durability.
  • polyethylene glycol (PEG) of various molecular weights may be used in the production of the SOP, difunctional PEGs such as those with average molecular weights of about 5000 is preferred for adsorption of many pesticides.
  • PEGs having greater molecular weights including those having about 6000. about 7000, about 8000, about 9000, or even about 10,000 or greater average molecular weights may be employed in the formulation of the SOP of interest.
  • the inventors contemplate the use of smaller molecular weight PEGs may be beneficial for the remediation and adsorption of certain organic compounds.
  • SOP formulations employing PEGs having an average molecular weight of about 4000, about 3000, about 2000, about 1000, or even about 500 or so molecular weight may be useful in certain embodiments.
  • Exemplary PEG 5000 was obtained from Union Carbide
  • the phenol is at least a technical grade phenol, although any grade phenol may be used so long as the phenol used does not contain trace impurities that would alter or inhibit the proper polymerization of the compound.
  • the phenol component used in the preparation of the phenol formaldehyde compound may comprise one or more of the following phenol derivatives: 1-hydroxyphenol, 2- hydroxyphenol, 3-hydroxyphenol, 1 ,2-dihydroxyphenol 1,3-dihydroxyphenol, 1,4- dihydroxyphenol, and the like.
  • the phenol formaldehyde component of the SOP was a PF resole (Durite AL-5801 PF Resin, Bordon Chemical, Louisville, KY).
  • the adsorbant properties of the PF-PEG SOP compound permit their direct use in binding organic compounds, without the need of coating the compound onto a substrate.
  • the matrix may be a natural compound such as cachasa, a plant byproduct often referred to as filtercake.
  • This filtercake is the crude residue that remains following digestion and/or extraction of soluble components of plant materials.
  • Cachasa in particular, refers to the filtercake obtained following the processing of sugarcane to remove its soluble components for the preparation of refined sugar. After separation of the solid components from the filtrate, the solids are compressed and/or compacted, with the resulting undigested plant material solids being referred to as the filtercake.
  • the substrate upon which the SOP is coated is a sand, sea sand, or a mineral such as silicate.
  • Formulations of the PF-PEG SOP coated onto sand particles are particularly preferred for use in the preparation of athletic turfs, such as golf courses, and the like, where maintaining the percolativity of the soil is important.
  • These sand-SOP formulations (termed “biosand” by the inventors) are also desirable for amendment to agricultural soils, and to other environmental sites where location of the SOP for the purpose of adsorbing organic compounds is desirable.
  • the adsorbant may be desirable to apply to a substrate or matrix having a larger particle or mesh size than a granular substrate such as sand.
  • the inventors contemplate the SOP compositions may be formulated for application to rocks, gravel, pebbles, clay, expanded clay, silicates, silica gels, zeolites, or metals (including metal filings, shaving, pellets, beads, turnings, etc.).
  • the matrices may be a synthetic compounds such as plastics (e.g., polystyrenes, polypropylenes, polybutalenes, etc.), synthetic fibers (e.g., nylon, rayon, dacron, orlon, etc.) or other monomeric or polymeric resins and the like.
  • plastics e.g., polystyrenes, polypropylenes, polybutalenes, etc.
  • synthetic fibers e.g., nylon, rayon, dacron, orlon, etc.
  • the SOP composition may be desirable to apply to substrates such as beads, glass, glass fibers, fabrics, ceramics, fiber filters, spun fibers, and the like. Indeed, it may also be desirable to coat the adsorbant onto plant-derived materials other than cachasa or filtercake. Cellulose fibers, lignins, and other plant-extractable materials may form the substrate upon which the SOP is formulated. Virtually any solid or semi-solid support, matrix, or substrate is envisioned to be useful in the creation of SOP-formulations where it is desirable to impart the adsorptive capabilities of the polymer to a target surface.
  • the SOP compositions are used to adsorb organic compounds, they may also be used to form part of an apparatus or a device that is intended to remove or reduce the concentration of organic compounds from an environment or a contaminated site, solution, or water source.
  • a SOP composition may be added to the soil in or around a sports facility, agricultural, commercial or residential turf or field, or alternatively, in and around an industrial facility or hazardous materials site.
  • the SOP composition may be added to the soil, or may be formulated onto sand for application to a subsurface layer of a golf course green.
  • the SOP composition may comprise part of a water filter, a water treatment facility, a sediment filter, or a reactive barrier.
  • the compositions may be used to adsorb organic contaminants from a groundwater source, or a municipal water supply, or may be placed in the ground as a barrier to prevent leaching or seepage of contaminated water into a given area, or to prevent or reduce the amount of contaminant moving through the ground from one site to another.
  • organic compounds such as herbicides, rodenticides, insecticides, fungicides, microbicides, and nematicides are widely applied in agricultural and residential areas.
  • SOP compositions disclosed herein.
  • SOP-sand compositions were used to reduce or contain the leaching of 2, 4-dichlorophenoxyacetic acid (2.
  • Organic compounds including pesticides, may also be used in large industrial processes or may be used by an individual in or around the home. Because of the widespread use of organic compounds, spills are a common occurrence. In such instances, the application or introduction of one or more SOP compositions to the affected area may be used to adsorb or contain such an organic spill.
  • the SOP composition may conveniently be formulated as a particulate or "cat litter-like" substrate and applied to the contaminated site. After application to the spill, the SOP composition containing the adsorbed contaminant(s) may conveniently be collected and subsequently destroyed (e.g., incineration) or disposed of. Alternatively, the contaminant may be desorbed from the polymer and disposed of thereafter in convenient fashion, and under suitable guidelines and procedures for the handling and disposal of the particular waste material contained by the adsorptive polymer.
  • a SOP composition may be used to form a barrier at a perimeter around the spill.
  • the barrier does not need to encircle the spill, but rather may be placed at a location in the general direction of migration of the spill so that it may be contained by the adsorbant.
  • the SOP composition may be applied to a location below the spill to adsorb the runoff.
  • a SOP composition may be placed as a barrier at a location as preventive measure. That is, a barrier may be placed next to a water source, for example, so that, in an event of an organic contaminant spill, the water source is protected by the intervening reactive barrier.
  • the water source may be surface water such as a puddle, creek, river, reservoir, pond, lake, sea, ocean, or pool, or it may be subterranean water such as an aquifer, groundwater, well head, well casing, or well water.
  • a barrier may be used to prevent the dispersal into the environment of organic compounds following their use and is not restricted to accidental spills of organic compounds.
  • a common use of pesticides is in the maintenance of sports facilities.
  • Sports facilities include, but are not limited to, those of golf, tennis, croquet, polo, horse racing, football, baseball, soccer, or cricket.
  • a SOP composition may be added to the soil of the facility or may be a component of a drainage treatment system that collects wastewater, runoff, or leachate from the sports facility. Alternatively, the composition may be formulated into a layer underneath the sod layer.
  • Preferred embodiments comprise an SOP compound as an amendment to the soil of a sports facility.
  • an SOP composition may serve as an amendment to the soil of a golf course green, in such a manner as to prevent pesticide leaching.
  • an SOP composition As a component of a golf course, it is important that the SOP composition maintain the high rate of percolativity or conductivity that is desired of a golf course, be placed in a location so to efficiently bind the pesticides applied to the course, and prematurely adsorb or inactivate the pesticide before its role is accomplished in the soil. Therefore, it is preferred that a SOP composition is used as an amendment to the subterranean layers of the golf course and particularly a green.
  • an SOP composition comprises the gravel drainage blanket, intermediate layers, or the lower levels of the root zone.
  • a SOP composition may amend the upper layer of the root zone provided that the binding of pesticides in this layer is not undesirable.
  • the SOP compound may inactivate the pesticide upon binding, one may not wish to amend the soil in direct contact with the roots when pesticides that target the root or pests that reside in this area are applied, but instead provide a sublayer of SOP-treated soil (For example, see FIG. 7B).
  • the SOP composition is added as a discreet layer beneath the sod layer in one or more of the subsurface, or subterranean, layers.
  • an SOP composition When mixed throughout the soil, an SOP composition may be effective at a range of ratios. In preferred embodiments, the ratio of SOP composition to non-SOP compositions is about 15% by volume.
  • a SOP composition may be blended throughout the soil during construct of a golf green, or other facility, or may be added to the soil at a later date by , for example, tilling.
  • a SOP may be added to form one or more discrete layers within the soil. In preferred embodiments, the percentage of SOP composition comprising a discrete layer is such that it binds nearly all of the applied organic and maintains the conductivity of the soil.
  • the addition of an SOP to a soil may be by way of injecting the compound into the ground throughout a given layer of the soil or at a discrete layer beneath the surface (FIG.
  • injecting it is meant application of a substance via pressure through a spike or nozzle-like structure.
  • Devices for injecting the substance are described in U.S. Patents 5,461,992 and 5,671,887. It is contemplated that the accumulation of the organic compound within the
  • SOP-comprising layer or composition may serve to enhance microbial degradation of the organic compound.
  • the formulation of the invention may be used to enhance microbial colonization of an area where SOP is present.
  • an SOP composition may improve the overall nature or character of the soil, as well as provide organic leachate adsorption.
  • a SOP composition may be added to the soil to the adsorb organic compounds in the soil, to alter the percolativity of the soil, consistency or integrity of the soil. It is common practice to add compounds to soils, particularly soils high in clay, to improve the ability of these soils to support plant growth.
  • the SOP compositions may not only provide organic adsorption, but may in fact improve the overall quality of the soil to which it is added.
  • an SOP composition may comprise a filter that is operatively connected to the drainage system of a golf green (FIG. 6).
  • operatively connected it is meant that the filter is attached to the drainage system such that water or other aqueous solutions that flow through the drainage system enter the filter by a input port, contact a chamber comprising an SOP composition, and exit the outlet port.
  • the filter is able to be removed and replaced.
  • Another important aspect of the present invention is its use in the removal of organic compounds from aqueous solutions.
  • the aqueous solutions may be water, wastewater, sewage, leachate, groundwater, or industrial runoff.
  • the aqueous solution is leachate.
  • One method of removing organic compounds from an aqueous solution is by use of a water treatment system.
  • a water treatment system may be a simple column filter or a part of a complex municipal water treatment facility.
  • U.S. Patent 4,995,969 describes a treatment system for landfill leachate.
  • the invention is a biological living filter system.
  • the invention comprises a treatment basin which is lined with a water impervious material and filled with an organically enriched treatment medium which is conductive to maintaining a population of micro-organism and plants.
  • This system may be modified to comprise one or more SOP compositions.
  • a SOP may be added to the treatment medium or may be a component to a filter placed either prior to the application of the leachate to the treatment medium or after the leachate has transgressed the treatment medium or both.
  • an SOP may be used in the landfill leachate treatment system similar to that taught by U.S. Patent 4,995,969 in lieu of the biological material, obviating the need to establish and maintain a living ecosystem.
  • Filters generally have an intake port, a chamber, and an outlet port.
  • the chamber comprises an SOP composition such that organic compounds within aqueous solutions are bound by the SOP composition and prevented from flowing through the outlet port thereby purifying the aqueous solution.
  • the composition may be supported by a matrix such as sand, beads, fiber, etc., comprised within a filter cartridge, or, alternatively, coated on the chamber walls itself.
  • the water systems commonly used by municipal water treatment facilities include sequence batch biological reactor, continuous activated sludge, trickling filter, aerated lagoon, and anaerobic filter.
  • the aqueous solution may be treated by flowing through a column comprising an SOP composition or by contacting the aqueous solution with particles comprising an SOP composition in a batch method.
  • particles comprising an SOP composition are added to a water sample suspected of containing one or more organic compounds, mixed to provide sufficient contact between the particles and the organic compounds to allow binding, and then separated from the newly purified aqueous solution.
  • Separation may be by means of gravity, centrifugation, magnetism (in the case of coating the SOP onto a magnetic substrate such as iron filings), or filtration through a size-selective porous membrane, or a mesh filter, or other size-exclusionary grating, grid, etc.
  • FIG. 1 Shown is the effect of SOP on retention of fenamiphos metabolite applied at 1.125 g AI m " .
  • FIG. 2. Shown is the effect of zeolite and diatomaceous earth on fenamiphos leaching (up to five successive 6.5cm irrigations).
  • FIG. 3. Shown is the effect of zeolite and diatomaceous earth on metabolite leaching (up to five successive 6.5cm irrigations).
  • FIG. 4. Shown is the effect of zeolite and diatomaceous earth on saturated hydraulic conductivity.
  • FIG. 5A. Shown is a diagram depicting a SOP comprising barrier for the prevention of surface water contamination by organic compounds. Movement or leaching of the organic compound is shown as dashed lines with arrows. 2 represents a SOP comprising barrier. 4 represents water. 5 represents an organic compound spill or application.
  • FIG. 5B Shown is a diagram depicting a SOP comprising barrier for the prevention of subterranean water contamination by organic compounds. Movement or leaching of the organic compound is shown as dashed lines with arrows.
  • FIG. 6 Shown is a diagram depicting an underground drainage system operatively connected to a filtering device comprising an SOP composition. Movement or leaching of the organic compound is shown as dashed lines with arrows. 5 represents an organic compound spill or application. 6 represents an underground drainage pipe. 7 represents the inlet means to the filtering device. 8 represents the filtering device comprising an SOP composition. 9 represents an outlet device.
  • FIG. 7A Depicted is a spike injecting an SOP composition into the soil at a discrete layer. 10 indicates the injecting spike. 12 indicates the root zone. 13 indicates the intermediate layer.
  • FIG. 7B Depicted is the soil after application by injection of an SOP composition into a discrete layer as demonstrated in FIG. 7A.
  • the SOP is a discrete layer within the lower root zone.
  • 11 represent the SOP composition layer in the lower root zone.
  • FIG. 8. Shown is a schematic diagram of a plant layout for the large-scale production of the compositions of the present invention. Depicted is 14 feeder; 15, conveyor; 16, pin mixer; 17, pump; 18, polymer feed tank; 19, agitator; 20, PEG mix tank; 21, fuel; 22, F.D. fan; 23, combustion system; 24, cyclones; 25, fluid bed dryer; 26, cooler; 27, screen/mill; 28, screen; 29, mill; 30, acid tank; 31, in line mixer; 32, product storage; 33, control room.
  • FIG. 9 Shown is a process flow diagram for the large-scale production of
  • compositions and methods of the present invention provide for the containment of pesticides or other organic compounds at the source of the spill or their application, as opposed to a common collection site. This allows an individual to apply compositions of the present invention to a spill before it has an opportunity to enter a water system. Upon entering a water system the organic compound is diluted and may be more difficult to remove because of the high volume of water that may need to be treated.
  • the SOP compounds of the present invention and compositions comprising them are able to bind organic compounds with a wide range of polarities, they can be manufactured cheaply, and do not require sophisticated training in their implementation. Therefore, the compositions of the present invention are effective, economical, and easy to implement.
  • SOP-sand compositions of present invention do not affect the conductivity or percolativity of the soil to which it is applied. This attribute is ideal for the use in soils that require efficient draining of water such as an athletic turf, and in particular, a golf green.
  • the ease of coating a substrate with one or more of the SOP formulations disclosed herein provides a facile means to develop apparatus and devices for the purification and remediation of aqueous solutions, including sludge, sewage, groundwater, surface water, municipal water supplies, and the like.
  • aqueous solutions including sludge, sewage, groundwater, surface water, municipal water supplies, and the like.
  • the simplicity and cost-effectiveness of the present invention in preparing barriers, flow- through filtration apparatus, and the preparation of devices for contacting the SOP- substrate compositions with an organically-contaminated aqueous source make these devices desirable for use in conjunction with many existing water treatment devices or apparatus to adsorb organic contaminants from solution.
  • the ability of the SOP compositions to slowly leach or desorb the bound organic compounds make them useful as controlled-release formulations for delivering organic compounds (such as fertilizers or pesticides) to a target area at a controlled rate.
  • organic compounds such as fertilizers or pesticides
  • the slow- or delayed-release capability of the formulation to desorb organics from it make it idea as an adjuvant or a delivery vehicle for the controlled- release of organic herbicides, organic pesticides (including nematicides, insecticides, fungicides, and microbicides) to a target area.
  • the ability of the SOP to be coated onto a biofriendly inert substrate such as a mineral, silicate, or sand particle, provide a biocompatible matrix for the delivery of slow-release fertilizers or pesticides to a target area without introducing incompatible or unsuitable adjuvants or substrates into the environment.
  • the stabilized organic polymers of the present invention have been shown to bind organic compounds with a wide range of polarities and are capable of both being manufactured cheaply, and also coated onto a variety of substrates for use in particular embodiments. While the inventors have demonstrated the facility and utility of SOP- matrix formulations comprising phenol-formaldehyde PEG in adsorbing organic pesticides, they also contemplate that a variety of additional stabilized organic polymers may be developed by varying either the concentration of one or more of the substrates during formulation, or by substituting other derivatives of these compounds in the development of modified SOPs that also function as effective organic adsorbants. As such, the inventors contemplate that each of these modified SOP formulations may be useful in the methods of the present invention, and are therefore these components or the processes used for making them are within the scope of the invention.
  • the SOP of the present invention comprises polyethylene glycol (PEG).
  • PEG is made up of chains of repeating ethylene glycol subunits that may be of variable lengths. Because of the variable nature of PEG, it may be produced or is commercially available in a variety of different molecular weight formulations. Commercially, PEG is generally identified and sold by the average molecular weight of the subunit PEGs in the formulation. For example, molecular weights of PEG commercially available include, but are not limited to, 200, 300, 400, 550, 600, 900, 1000, 1,450, 1,500, 2,000, 3,350, 3,400, 4.600, 8,000, and
  • Higher molecular weight PEG compounds may also be synthesized by condensing two or more molecules of lower- weight PEGs (e.g., condensation of a
  • PEG of molecular weight about 7,000 with a PEG of molecular wight about 9,000 may yield a PEG compound of an approximate molecular weight of about 15,000 to
  • PEG polyethylene glycol and derivatives
  • PEG derivatives including methoxypolyethylene glycol and derivatives, polyoxyethylene (functionalized derivatives), and ether derivatives (polyethylene ethers; surfactants).
  • PEG materials with functional end groups There are many known commercial PEG materials with functional end groups. These should be considered as possible improvements over halogen functionalized PEG.
  • crown ethers and related compounds is contemplated, owing to their chemical similarity to PEG, albeit in a cyclic form.
  • PEG and polyethleneimines and copolymers of each have the potential to complex a wide range of organic materials.
  • the inventors contemplate of utilizing SOP compositions that comprise a PF-PEG compound that is not completely polymerized.
  • Free -OH groups on the PF-PEG polymer may be desirable in certain circumstances, and may improve soil conditioning properties.
  • the SOP of the present invention comprises phenol- formaldehyde (PF).
  • PF phenol- formaldehyde
  • the inventors have determined that commercially available phenol-formaldehyde resin (Bordon Chemical, Louisville, KY) are quite effective for production of an inexpensive, effective adsorbent.
  • commercially available phenol-formaldehyde resin (Bordon Chemical, Louisville, KY) are quite effective for production of an inexpensive, effective adsorbent.
  • the inventors contemplate that slight variations may be made concerning the type of PF or use of compounds chemically similar to PF and still remain within the scope of the present invention.
  • a resole grade formulation with excess formaldehyde was employed, however, other grades of PF having less formaldehyde may be useful in optimizing the large-scale manufacturing of PF-PEG formulations.
  • Mixes of resole with novalac grades of PF have been used in industry for many years because of improved properties along with less excess formaldehyde.
  • epoxy groups may react directly with the PEG, thus eliminating the need to functionalize the PEG with bromine.
  • the inventors developed a method for creating a PF/PEG resin utilizing the commercially-produced PF resole.
  • the first step was to optimize the production of the PEG halide. It was determined that the halide PEG-Br (formed with an excess of H 2 SO 4 and NaBr) could be created more efficiently than the PEG-C1. Reaction conditions of about 70°C for about 1 hour were found to be most useful for preparation of the PEG-Br component, although the temperature of the reaction could vary from ambient temperature to about 100°C or so without serious adverse affects to the PEG-Br. Likewise, the time of reaction may be on the order of from about 30 min to about 10 hr or so depending upon the reaction temperature.
  • the PEG-Br may be formed directly by the addition of HBr to the PEG or be addition of NaBr with an excess of H 2 SO 4 .
  • the second step was to optimize conditions for reacting the PEG-Br with the commercial PF.
  • a series of formulations varying in a number of parameters (PEG:PF:Br, pH, curing time and temperature) were created and tested visually and mechanically.
  • the SOP compounds have utility based on their chemical properties
  • the SOP is bound to a matrix, support, or substrate to form a SOP composition. Binding of the SOP to a support in such a way as to maintain the chemical properties of the compound while gaining one or more physical properties of the support increases the utility of the compounds.
  • the SOP compounds of the present invention may have utility without being bound to a substrate, in preferred embodiments the SOP compounds of the present invention are bound to a matrix or substrate.
  • the binding of the compound to a matrix may provide the compound with a property of the matrix. This property may be weight, size, stability, shape, pliability, or magnetism.
  • porous substrates may be used, the inventors contemplate that porous substrates are not preferred because much of the SOP fills the pores and, therefore, is not on the surface of the SOP composition. Because the inventors contemplate that only surface
  • the porous substrates may not be an efficient use of the SOP compound.
  • the matrix is filtercake, rocks, gravel, pebbles, sand, clay, silicate, silica gel, zeolite, or metal (including iron filings).
  • the matrix is sand.
  • the compounds of the present invention also may be bound to synthetic compounds such as plastics (polystyrene or polypropylene), resins, beads, glass, ceramics, fiber filter, fiberglass and the like.
  • the SOP is typically sprayed, coated, aerosolized, or otherwise applied to the particular substrate and then cured at a temperature of from about 100°C to about 180°C for a period of time from about 5 min to about 5 hr.
  • the curing temperature is about 180°C for about 10 min.
  • the SOP must be returned to a neutral or slightly acidic pH before use.
  • a suitable acid such as H 2 SO 4 or HCI
  • SOP compositions with a pH of as low as about pH 5.0 have been quite effective as organic adsorbants. Neutralization of the SOP produces a striking color change in the SOP composition from a dark bluish-black color to a bright reddish- orange material.
  • the SOP has been shown to be stable and active for a period of time of at least 1 to 2 years, with excellent activity remaining after 6, 12, or even 18 or more months.
  • the SOP composition once cured and neutralized is shelf-stable at room or outdoor ambient temperatures, and does not appear to be reduced in capacity by either moisture or dessication.
  • FC filtercake
  • the SOP compositions are used in the adsorption of organic compounds.
  • the compositions comprise an apparatus that is able to remove organic compounds from the environment or contaminated aqueous solutions. These embodiments include sport fields, agricultural fields, filters, water treatment facilities, barriers, etc.
  • the apparatus is a golf course green.
  • the SOP compositions need not be a component of an apparatus and may be applied directly to an organic compound for purposes of adsorbing the compound.
  • prefened embodiments of the present invention include apparatuses comprising one or more SOP compositions of the present invention.
  • apparatuses include, but are not limited to, sports fields (golf greens, football fields, etc.), agricultural fields (vineyards, crops, etc.), lawns, filters, water treatment systems, and barriers.
  • the apparatus is a golf green comprising one or more SOP compositions.
  • any apparatus comprising an SOP compound or composition able to bind organic compounds is believed to be within the scope of this invention.
  • the present invention may be used to bind herbicidal compounds and prevent the dispersal of these compounds in the environment.
  • Many herbicidal compounds are well known and may be placed into groups based on their chemical structure.
  • Such structural groups include the triazines, the phenylureas, the carbamates, the phenoxyalkanoic acids, the aryloxyphenoxypropanoic acids, the sulphonylureus, the bipyridylium cations, the uracils, the pyridazines, the amides, the dinitroanilines, the benzonitriles, triazinone, the cyclohexanediones, and others (Tekel and Kovacicova, 1993; Tadeo et al., 1996; Gronwald, 1994).
  • herbicidal compounds commonly used on USGA golf greens and their properties are listed at the internet address http://www.usga.org/green.
  • Triazines have been used in non-cropped land and in a variety of crops to control many grass and broad-leaf weeds. Triazines have the general formula as shown:
  • triazines and triazinones include, but are not limited to, Ametryn, Atrazine, Cyanazine, Desmetryn, Metamitron, Metoprotryn, Metribuzine, Prometryn, Propazine, Simazine, Terbuthylazine, and Terbutryn (Tekel and Kovacicova, 1993).
  • Phenylureas represent another large class of organic compounds which often provide environmental hazards where they are applied. Phenylureas have the general formula:
  • phenylureas Although employed since the early fifties, use of phenylureas has increased recently to replace the more persistent triazine compounds.
  • phenylureas include, but are not limited to, Buturon, Chlorbromuron, Chloroxuron, Chlorotoluron,
  • Carbamate pesticides include herbicides, insecticides, acaracides, and fungicides.
  • Thiocarbamates are used as herbicides in maize and wheat and are often used in conjunction with an antidote (Tadeo et al., 1996).
  • the general structure of the thiocarbamates are:
  • Phenoxyalkanoic acids also known as phenoxyacids, are the oldest group of synthetic herbicides and are still used today in the control of weeds in cereal crops. Although use of these compounds has dwindled recently, the low cost of these compounds insures their continued use. Phenoxyacids have the general formula of:
  • Phenoxyacids examples include, but are not limited to, 2,4,5-T,
  • Aryloxyphenoxypropanoic acids often termed phenoxyphenoxys, are more recently developed pesticides that decompose rapidly leaving the conesponding free acids as the main metabolites (Tekel and Kovacicova, 1993).
  • aryloxyphenoxypropanoic acids include, but are not limited to, Fluazifop-butyl, Haloxyfop-ethoxyethyl, and Quazalofop-ethyl (Tekel and Kovacicova, 1993).
  • sulphonylureas are generally used for weed control of cereal crops. They are highly effective and, therefore, require a low application dose. An excellent review of their properties, mode of action, degradation
  • sulphonylureas include, but are not limited to, Bensulphuron- methyl, Chlorimuron-ethyl, Chlorsulfuron, Metsulfuron, Metsulphuron-methyl, Sulphometuron-methyl, Triasulfuron, and Tribenuron (Tekel and Kovacicova, 1993).
  • Bipyridinium cations are membrane destroyers and are widely used weed killers that are highly toxic to mammals. Examples of bipyridinium cations include, but are not limited to, Diquat and Paraquat (Tekel and Kovacicova, 1993).
  • uracils are photosynthetic inhibitors.
  • examples of uracils include, but are not limited to, Bromacil, Lenacil, and Terbacil (Tekel and Kovacicova, 1993).
  • Bromacil is commonly used for general vegetation control.
  • Terbacil is often applied to established mint and alfalfa. 4.5.1.9 PYRIDAZINE
  • pyridazine includes, but is not limited to, Chloridazone (Tekel and Kovacicova, 1993).
  • Anilides are amides which are often used for the pre-emergence control of annual grass and certain broad-leaf weeds and are often applied in mixtures with atrizine in maize (Tadeo et al., 1996). Amides have the general chemical formula:
  • anilides include, but are not limited to, Acetochlor. Propachlor, Dimethenamid, Chloroacetamides, Alachlor, and Metolachlor (Tadeo et al., 1996).
  • dinitroanilines examples include, but are not limited to, Butralin, Ethalfluralin, Pendimethalin, and Trifluralin (Tadeo et al., 1996).
  • Benzonitriles have the general formula:
  • benzonitriles include, but are not limited to, Bromoxynil and Ioxynil (Tadeo et al, 1996).
  • Cyclohexanediones are used for post-emergence control of grass weeds in certain broadleaf crops and are frequently refened to as graminicides.
  • Examples of cyclohexanediones include, but are not limited to, Sethoxydim, Clethodim, and
  • herbicides that are not included in the above structural groups are, but are not limited to, Bentazone and 3-(2,4-dichloro-phenyl)-perhydroindolizine-
  • LD 50 means the amount of material that will generally kill 50% of the animals in a study (rats, mice or rabbits, usually). LD 50 values given here are for rats, unless otherwise specified. Sex of the animal was not specified unless indicated. Values preceded by "greater than” (>) mean the LD 50 is higher than the quoted figures, which were the highest amounts tested.
  • Banvel D dicamba 1040 — barban, Carbyne 1300 N
  • Diama, octyl ammonium methyl 600-794 arsonate, Crab-E-Rad diallate, Avadex 395 M TABLE 1 (CONTINUED) dicamba, Banvel D 1040 — dichlobenil, Casoron 3060 500 (rabbits) dichloral urea, Crag DCU > 31,600 — dichlorprop, 2-(2,4-DP) acid 400 (mice) 1400 dicryl 1800-3160 10,000 (rabbits) diphenamid, Dymid, Enide 1048-1798 > 6320 diquat 400-440 > 500 (rabbits) disodium methanearsonate, Ansar 184, 2800 N
  • Eptam 1630 males
  • 3160 2641 rabbits
  • maleic hydrazide sodium salt 6950 4000 (rabbits) TABLE 1 - (CONTINUED) molinate, Ordram 501 (males) 660 > 2000 (rabbits) (females) monosodium acid methanearsonate, 700-1800 —
  • MSMA Ansar 170 monuron
  • Telvar 3500-3600 N monuron Telvar 3500-3600 N monuron
  • TCA Telvar 3500-3600 N monuron
  • MSMA monosodium acid 700-1800 — methanearsonate, Ansar 170
  • NPA nitraline Planavin 2000 2000 (rabbits) norea
  • NPA Alanap, N-l -naphthyl 2000-8500 N phthalamic acid octyl ammonium methyl arsonate, 600-794 —
  • Penta sodium salt Dowicide G 78-218 257 phenyl mercuric acetate, PMA, Scutl 30 S
  • Betasan 770 males
  • 3950 rabbits
  • Pramitol 2980 N prometryne Caparol 80W 3750 N propanil
  • Stam F-34 Rogue 560-1384 7080 (rabbits) propazine > 5000 N prophan IPC 9000 N pyrazon
  • Pyramin 4200 males 2500 M
  • the present invention may be used to bind insecticidal compounds and prevent the dispersal of these compounds in the environment.
  • compounds have been formulated and their use in the grants a possible need for remediation. Aldicarb, Allethrin, Ambush, Aminocarb, APM, Basudin, Bioallethrin, Bioremethrin, Biphenthrin, Bufencarb, Butacarb, butoxide, Carbanolate,
  • Carbaryl Carbofuran, Cinerin I, Cinerin II, Counter, Cyfluthrin, Cygon, Cyhalothrin, Cymbush, Cypermethrin, Cythion, Dasanit, Decis, Deltamethrin, Diazinon, Dibrom, Dimethoate 480, Dioxacarb, Dipel, Dyfonate, Dylox, Endosulfan, Ethidimuron, Fenpropathrin, Fenvalerate, Flucyrintae, Fluvalinate, Furadan, Guthion, Hopper Stopper, Imidan, Jasmolin I, Jasmolin II, Lagon, Lannate, Lorsban, Malathion,
  • Metasystox-R Methomyl, Methoxychlor, Mexacarbate, Monitor, Ortho, Oxamyl, Parathion, Permethrin, Piperonyl, Pirimor, Pounce, Promecarb, Pyrethrin I, Pyrethrin II, Pyrinex, Resmethrin, Ripcord, Sevimol, Sevin, Sniper, Supracide, Tetramethrin, Thimet, Thiodan, and Tralomethrin are among the compounds that have been utilized recently for insect control (Chen and Wang, 1996; Yang et al, 1996, Saskatchewan
  • Fungicidal compound use and the dispersal of these compounds in the environment represent a potential biological hazard.
  • Fungicides such as Benomyl, Captan, Chlorothalonil, Copper Sulfate, Cyproconazole, Dodine, Flusilazole, Fosetyl- Al, Gallex, Mancozeb, Metalaxyl, Prochloraz, Propiconazole, Tebuconazole,
  • the present invention may be used to bind nematicidal compounds and prevent the dispersal of these compounds in the environment.
  • Many nematicidal compounds are well known.
  • Fenamiphos an anticholinesterase compound, (Nemacur®, Bayer Crop
  • Temik® 15G (aldicarb) and Mocap® 10G and Mocap® EC (ethoprop) (Rhone-Poulenc Ag Products) are non-fumigant granular nematicides that are often recommended for agricultural application.
  • the liquid fumigant, Telone II® (1,3-dichloropropene, Dow AgroSciences, Indianapolis, IN) is also used as a nematicide in many areas.
  • nematicidal compounds include Scotts' Pro-Turf Nematicide/Insecticide 5G, fensulfothion, Dasanit 15G, chitin and other organic nitrogen sources, Clandosan 618 25G, methyl bromide 68.6% + chloropicrin 1.4%, Brom-O-Sol 70, methyl bromide 67% + chloropicrin 33%, Ten-O-Gas 67, dichloropropene + methyl isocynate, Vorlex, metam-sodium, Vapam, dischlopropene + chloropicrin, Telone C- 17, Ten-O-Cide 30D, dazomet, Basamid 99G, (Hagan, http://www.acesag.aubum.edu department ipm/Nematode.htm, incorporated herein by reference).
  • nematicidal compounds including trade and common names, may be found in Table 2 (http://www.missouri.edu/ ⁇ extbsc/turf/fundesc.htm, incorporated herein by reference). Many of the nematicidal compounds that are commonly used on USGA golf greens and their properties are listed at the internet address http://www.usga.org/green.
  • the chemical nature of the present invention provides for its ability to bind a large variety of organic compounds. Therefore, the inventors contemplate that the present invention may be used to bind organic compounds to prevent their dispersal in the environment or to facilitate the "cleanup" of such compounds in the event of a spill. Furthermore, the inventors contemplate that the present invention may be used to remove an organic compound from a solution.
  • Patent 4,147,624 discloses a list of organic compounds that are removable from a water stream by adsorption on polymeric adsorbents and is incorporated herein by reference. This list is provided by Table 3. The inventors contemplate that the compounds, compositions, and methods of the present invention may be used to remove one or more compounds of Table 3 from an aqueous solution.
  • the present invention provides for a simple, economical method for cleaning up spills at the source.
  • the inventors contemplate that the present invention may be applied to the spill as an adsorbent compound.
  • This compound applied as a particulate, such as sand, clay, "cat litter-like" substance, etc., may be used by individuals in the household or to adsorb more substantial industrial spills. After application, the adsorbent may be collected and disposed of without the worry of the compound being dispersed into the environment following disposal.
  • the particulate may be applied directly to the spill or used to form a physical barrier at a perimeter around the spill.
  • This barrier would essentially function as a containment or "fire" wall, preventing the spread of the spill.
  • the cunent invention may be used as part of a barrier to prevent one or more organic compounds or pesticides from entering surface water.
  • the barrier may be a fence- or wall-like structure that is placed between the spill, or area of application, of one or more organic compounds or pesticides and surface water (FIG. 5A).
  • the surface water may be a puddle, creek, river, reservoir, pond, lake, sea, or ocean.
  • the present invention may be used to prevent one or more organic compounds or pesticides from entering subtenanean water such as aquifers, groundwater, well heads, well casing, or well water (FIG. 5B).
  • subtenanean water such as aquifers, groundwater, well heads, well casing, or well water (FIG. 5B).
  • the inventors contemplate that the source of the spill may be from nearly any individual or commercial facility that uses, transports, stores, manufactures, or unearths organic compounds.
  • the compositions of the present invention may be used in the petroleum industry from drilling of the wells, to the continued pumping of oil from the ground, to oil refineries, to storage of the processed petroleum products, to transportation of the product, to the distribution of the product to the individual user, to the use of the product by the individual user.
  • compositions of the present invention may be used as an amendment to the soil sunounding an underground gasoline storage tank to reduce the impact of leakage on the environment.
  • the compound stored underground may be other organic compounds and need not be gasoline.
  • the inventors contemplate the use of the present invention in strip mining and ore processing.
  • the compounds of the present invention may be applied to the organic compounds used in these processes to prevent their further dispersal into the environment.
  • a golf course may be designed comprising one or more sops or SOP compositions of the present invention to decrease the level of pesticides or their metabolites from entering ground and surface water.
  • the sops or SOP compositions of the present invention may be added as an amendment to one or more layers of the soil of a golf course or may be a component of a water treatment system or filter through which the water of a golf course flows.
  • a critical problem with the design of a golf course is maintaining high percolativity or high rate of conductivity. It is desirable that water applied to a course readily pass through the soil. Prior attempts have been made to add clays, thatch, etc. to subtenanean layers of a golf green, but these materials were shown to decrease the conductivity of the green and, therefore, were undesirable. When used as a soil amendment, the inventors contemplate that one or more sops or SOP compositions of the present invention may be added to any of the subtenanean layers.
  • the subtenanean layers of a golf course and their construction are well known to those of skill in the art.
  • one or more sops or SOP compositions of the present invention comprise the subtenanean layers of a golf green.
  • the subtenanean layers of a USGA golf green include, starting at the surface and increasing in depth: the root zone, the intermediate layer, and the gravel drainage blanket.
  • one or more sops or SOP compositions of the present invention comprise the gravel drainage blanket, intermediate layers of a golf green, or the lower level of the root zone.
  • one or more sops or SOP compositions of the present invention may comprise the upper level of the root zone without affecting the pesticidal activity.
  • the inventors contemplate a number of methods by which the subtenanean layers of a golf green may be amended by the compounds and compositions of the present invention.
  • one or more SOP compounds may be added to the material (sand, gravel, clay, silt, etc.) that makes up a subtenanean layer of a golf green.
  • one or more SOP compositions may be added to the material that makes up a subtenanean layer or a golf green.
  • the SOP composition comprises sand.
  • One or more subtenanean layers of a golf green may consist of one or more SOP compositions or may comprise of a ratio of one or more SOP compositions to "unamended" material. In prefened embodiments, the ratio of SOP composition to "unamended" material is 15% by volume.
  • prefened embodiments are golf greens comprising the compounds and compositions of the present invention
  • the inventors contemplate that the compounds and compositions of the present invention may be amendments to the soils of other sections of the golf course including, but not limited to, fairways, greens, tee boxes, rough, traps, ponds, range, etc.
  • the properties of the SOP compositions of the present invention may make the compositions desirable as amendments to soils besides those of a golf course. Because other sports facilities may demand similar properties of the soil as golf courses, the inventors contemplate that the compounds and compositions of the present invention may be useful as amendments to the soil other sport fields. Such other sports include, but are not limited to, tennis, croquet, polo, horse racing, football, baseball, soccer, cricket, etc.
  • agricultural field i.e., garden, vineyard, pasture, crop, fruit or vegetable orchard, etc.
  • pesticides or other organic compounds i.e., industrial facilities, waste storage or treatment facilities, job sites, construction sites, chemical factories, weapon facilities, etc.
  • compositions of the present invention may be used as an amendment to the soil in any instance when one desires to improve the nature of the soil.
  • the compositions of the present invention may be added to the soil to increase the adsorption of organic compounds by the soil, to alter the percolativity of the soil, or to alter the consistency of the soil. It is common practice to add compounds to soils, particularly soils high in clay, to improve the ability of these soils to support plant growth.
  • the inventors contemplate that the compositions of the present invention may improve upon the existing technology by providing additional benefits (i.e., pesticide adsorption).
  • the prefened embodiment of the present invention is as a supplement to a golf green capable of binding pesticides applied to the green, the inventors appreciate that such a use requires implementation during building or rebuilding of the golf green. Therefore, the inventors contemplate alternative methods of preventing the leaching of pesticides in water supplies.
  • the inventors contemplate the use of an underground pipe system that collects water at a centralized location. This may be one or more French drains.
  • a French drain is comprised of a sloping trench lined with soil-filter fabric and filled with gravel.
  • a perforated pipe with the perforations facing the bottom of the trench and connected to a solid drain line provides more efficient draining.
  • the SOP of the present invention may me added to the soil-filter fabric in another it may be added to the gravel.
  • the SOP of the present invention may be a component of a filter that the water flows through at a centralized location (FIG. 6). This filter may be constructed so that it can easily be replaced periodically. Besides under a golf green, the underground pipe-filter system may be used in other places.
  • this system may be placed underground at any section of a golf course (i.e., the fairways, greens, tee boxes, rough, traps, ponds, range, etc.), sports fields (i.e., tennis, croquet, polo, horse racing, football, baseball, soccer, cricket, etc.), lawns, agricultural field (i.e., gardens, vineyards, pasture grasses, crops, fruit and vegetable orchards, etc.), or in any location that pesticides or other organic compounds are applied such as industrial facilities, waste storage and treatment facilities, job sites, construction sites, chemical factories, and weapon facilities.
  • a golf course i.e., the fairways, greens, tee boxes, rough, traps, ponds, range, etc.
  • sports fields i.e., tennis, croquet, polo, horse racing, football, baseball, soccer, cricket, etc.
  • lawns i.e., gardens, vineyards, pasture grasses, crops, fruit and vegetable orchards, etc.
  • the inventors contemplate that the present invention may be utilized as part of a treatment facility for any aqueous solution suspected to contain organic compounds.
  • the source of the aqueous solution may be sewage, groundwater, wastewater, leachate, or industrial runoff.
  • Water collected at a common facility may be contacted with the compound of the present invention to reduce the levels of organic compounds or pesticides in the water.
  • Water treatment systems are well known to those of skill in the art and include, but are not limited to, Sequencing Batch Biological Reactor (SBA), continuous activated sludge, trickling filter, aerated lagoon, and anaerobic filter. These systems, and others, may be adapted to more efficiently treat organic compounds by the processes and compositions of this invention.
  • the water may be treated by flowing through a column comprising the compound of the present invention or by contacting the water with particles comprising the present invention in a batch method.
  • the batch method comprises adding particles comprising the compound of the present invention to a water sample suspected of containing one or more organic compounds, mixing to allow sufficient contact between the particles and the organic compounds to allow binding, and separating the particles bound to the organic compounds from the newly purified water. Separation may be the product of natural gravity, centrifugation, or filtration through a size selective porous membrane.
  • the compound of the present invention may be physically associated with a matrix susceptible to magnet forces, such as iron filings.
  • the iron filings coated with the compound of the present invention may be utilized in the batch method thereby allowing separation of the coated filings bound to organic compounds from the water by magnetism. Separation by magnetism is faster than gravitational settling and does not require the sophisticated machinery nor volume limitation of centrifugation.
  • U.S. Patent 4,511,657 teaches a method of treating chemical wastes using an SBA system and is incorporated herein by reference.
  • the patent describes one or more tanks comprising activated sludges.
  • the activated sludges are comprised of a variety of organisms capable of metabolizing various organic compounds.
  • the compositions of the present invention may be added to the biological organism- containing activated sludge or may be utilized in one or more separate tanks from the tank or tanks comprising activated sludge, or may be used in lieu of the biological material. The latter obviates the need to maintain the viability of living organisms.
  • filters or other apparatuses comprising the compositions of the present invention may be used in combination with treatment systems known in the art.
  • FILTERS The inventors contemplate that the compounds of the present invention may be utilized as part of a filter.
  • Filters generally have an intake port, a chamber, and an outlet port.
  • compounds such as activated carbon are part of the chamber and are used in filters to bind compounds in solution.
  • Activated carbons are available in different grades with different binding activities. However, not all grades perform well in all purposes and effective grades tend to be expensive.
  • the present invention may be used in the place of or in addition to activated carbon in the chamber of a filter system.
  • a filter comprising one or more SOP compounds or compositions would increase the range of organic compounds capable of filtration from an aqueous solution. 4.9.3 LANDFILL LEACHATE FILTRATION
  • United States Patent No. 4,995,969 describes a treatment system for landfill leachate and is incorporated herein by reference.
  • the invention is a biological living-filter system for the treatment of sanitary landfill leachate which comprises a treatment basin which is lined with a water impervious material and filled with an organically enriched treatment medium which is conductive to maintaining a population of micro-organisms.
  • the system also includes leachate tolerant plants growing in the treatment medium.
  • This system modified to include one or more SOPs of the present invention, provides a greater range of adsorbence when compared to the system minus an SOP of the present invention.
  • the SOP may be added to the treatment medium at concentrations disclosed herein, or it may be a component of a filter placed either prior to the application of the leachate to the treatment medium or after the leachate has transgressed the treatment medium.
  • one or more SOPs of the present invention may be used in a landfill leachate treatment system similar to that taught by U.S. Patent No. 4,995,969 in lieu of the biological material. This obviates the need to establish and maintain a living ecosystem.
  • compositions of the invention also find utility as a means of providing controlled-release ("slow- release" "timed-release", etc.) pesticide formulations.
  • the preparation of the controlled-release product begins with the cured SOP composition described above.
  • the polymer is contacted with the fertilizer(s) or pesticide(s) by spraying, coating, soaking, or depositing the organic compound(s) onto the polymer and then allowing the product to dry.
  • the pesticide or fertilizer may be formulated in a solvent having a low boiling point, and then contacted with the polymer under conditions such that the solvent is evaporated and the organic pesticide or organic fertilizer component is deposited onto the adsorbant.
  • the resulting material may then be used as a controlled-release delivery vehicle for the adsorbed organics and delivered to the particular agricultural, commercial, or residential site where introduction of the fertilizer or pesticide is desired.
  • the filter may be comprised of glass tubes 6 x 30 cm packed 10 cm deep with medium-size silica sand amended 15% (vol./vol.) with candidate adsorbent.
  • an adsorbent material within the green might prove useful for reducing or preventing groundwater contamination by fenamiphos and its metabolites. To be useful in greens, the adsorbent should not seriously impact the hydraulic conductivity of the root zone mix.
  • Several adsorbents were evaluated in laboratory-column studies for reducing fenamiphos and fenamiphos metabolite leaching.
  • a stabilized organic polymer was made from sugarcane filter-cake (FC) stabilized with a phenol-formaldehyde polymer and polyvinyl chloride (PVC). The resulting material was crushed and graded into batches of particles conesponding to very coarse sand (VCS; 1.0-2.0 mm), coarse sand (CS; 0.5-1.0 mm), and medium sand (MS; 0.25-0.50 mm).
  • fenamiphos metabolite sulfone
  • Fenamiphos was oxidized with aqueous potassium permanganate and the resultant sulfone was extracted into methylene chloride. After evaporation of the solvent, the crude sulfone was solubilized in ethanohwater (65:35). This solution was extracted with hexane:ether (50:50) to remove coextractants, the sulfone remaining in the ethano water phase. Pure (92%) sulfone crystals created by enrichment of the ethanol:water with water were isolated by filtration.
  • the sand was either unamended, or amended 15% by weight with granular zeolite, or two grades of Stabilized Organic Polymer (SOP) having particle sizes approximating that of the sand.
  • SOP Stabilized Organic Polymer
  • a stabilized organic polymer was made from sugarcane filter-cake (FC) stabilized with a phenol-formaldehyde polymer and polyvinyl chloride (PVC). The resulting material was crushed and graded into batches of particles conesponding to very coarse sand (VCS; 1.0-2.0 mm), coarse sand (CS; 0.5-1.0 mm), and medium sand (MS; 0.25-0.50 mm).
  • the adsorption capacity of various size grades of SOP for fenamiphos and fenamiphos metabolite was determined in 1.25 cm diameter glass columns containing 10 cm sections of 15% (vol./vol.) SOP mixed in a USGA-sand. An excess of fenamiphos (11 mg) and metabolite (12 mg) was applied at the top of separate columns (4 replications for each organophosphate) and leached into the profile with small increments of water. Then the columns were flushed with two 50 ml portions of water. Each resultant leachate was analyzed for fenamiphos or metabolite by placing 200 ⁇ l of leachate into 10 ml methylene chloride.
  • the nematicide fenamiphos was applied as a liquid to the lysimeter area at the label rate of 1.12 g A.I. m " .
  • the area was inigated following application, and maintained as a golf green.
  • Percolate was collected from the lysimeters four times during the ensuing 28 days, and analyzed for both fenamiphos and fenamiphos metabolite (sulfoxide + sulfone).
  • SOP significantly (p ⁇ 0.05) reduced metabolite leaching 66%.
  • the inventors have some concern that the lysimeters were not fully drained before the start of the study, resulting in at least a portion of the soil profile being saturated with water. This may have contributed to the very high pesticide leaching that was observed.
  • Adso ⁇ tion was greatest for fenamiphos, which is the least polar of the pesticides tested. Less adso ⁇ tion was found for the fenamiphos metabolites, which are more polar than the parent compound, and the most polar pesticides, dicamba and 2,4-D, were not adsorbed by the SOP. It should be noted that fenamiphos, dicamba, and 2,4- D were chosen for study because a) in previous studies they have been observed to leach in a USGA green, b) they represent a range of polarities, and c) the inventors are experienced in their analysis. Other pesticides that may be of interest in turfgrass management have polarity characteristics similar to or comparable with one of the pesticides used in the inventors' studies.
  • FC pesticide based SOP.
  • Two methods were used for determining the effect of various treatments on pesticide adso ⁇ tion: batch and column.
  • batch method 10 g of candidate adsorbent along with 40 ml water and pesticide was placed in a 50 ml glass tube. After shaking for 1 h, the filtrate was collected. Pesticide in the extract of the filtrate was analyzed by gas chromatography (GC).
  • GC gas chromatography
  • Pesticide 6 x 30 cm were packed 10 cm deep with medium-size silica sand amended 15% (vol./vol.) with candidate adsorbent. Pesticide was placed on the surface, followed by 10 ml water. After 1 h, six 50-ml aliquots of water were added to the tubes to leach pesticide. Pesticide in the combined leachate was extracted and analyzed by GC. The SOP used in the field was formulated with polymers synthesized in-house.
  • Phenol was detected in the percolate. In the lab it was determined that there was 93% less leaching of phenol when the commercial PFR was used to treat FC than when PFR was polymerized in-house, as was done when making up the SOP used in the field trials. Polymer treatments of FC or of quartz sand that did not improve dicamba and
  • 2,4-D adso ⁇ tion included polyurethanes, polyethylene, styrene-butadiene latex, nitrated phenol-formaldehyde, and amino phenol-formaldehyde, a nitroso phenol- furfuraldehyde, DMSO phenol-formaldehyde derivative, and a urea phosphate formaldehyde.
  • Treatments equivalent to PFR included urea formaldehyde, furfural urea, and furfural phenol.
  • Treatments with improved adso ⁇ tion of dicamba and 2,4-D were various metal adducts of urea formaldehyde, including iron, copper, and aluminum. A calcium metal adduct produced variable results.
  • polyethylene glycol stood out as the most promising candidate for adsorbing polar pesticides.
  • the PEG was attached to the PF by creating a PEG halide with HCI and reacting it with the PF
  • PEG represents a class of compounds
  • the next step was to find the best PEG. This was done by studying a series of PEGs of widely different characteristics in combination with PF. Mechanical properties (durability, hardness) of the resulting compound were noted as well, both for the PF/PEG polymer alone, and when mixed with FC. Difunctional PEG with molecular weight of 5000 was selected as being optimal both for adso ⁇ tion of a polar pesticide, fenamiphos sulfone (Table 7), and for mechanical durability.
  • the sulfone application rate was 1 mg per 10 cc of adsorbent for the batch method, and 4.2 mg per column for the column method, which approximately conespond to the recommended field application rate of fenamiphos.
  • FC/resin combination was found to adsorb the polar fenamiphos sulfone well in both batch and column studies (Table 7). The product thus created appears to be a useable SOP.
  • the resin is added to a dry substrate. More time and energy is required to dry FC than is needed for sand. An adjustment of pH is required for proper curing of the resin. Far more reagent is required to shift the pH of the highly buffered FC than is required for sand. When made with sand, the final product does not require milling to achieve proper grain size.
  • Resin candidate # 6 in Table 8 has been used to coat sand. At a 10% by weight concentration, this material adsorbed 96 and 90% of applied (2X normal application rate) fenamiphos and fenamiphos metabolite, respectively, in a column study. 5.7 EXAMPLE 7 - FIELD EVALUATION OF SOP-COATED SAND 5.7.1 LYSIMETER RECONSTRUCTION
  • Silica sand was coated with SOP at the rate of 10% by weight.
  • the prepared material had a particle size range well within United States Golf Association (USGA) specifications (Table 9), which requires sand must be at least 60% medium+coarse, and less than 20% fine+very fine sand.
  • USGA United States Golf Association
  • freshly-obtained rooting mix sand was used to completely refill the excavated hole, and this sand also was used over the coarse sand layer in the six lysimeters that did not receive the SOP-sand composition treatment.
  • SOP-sand treated and untreated lysimeters were ananged in blocked pairs.
  • the cv. Tifdwarf bermudagrass sod cut from over the lysimeter was trimmed to a soil depth of approximately 4 cm and replaced over the lysimeter. The green was maintained using standard practices thereafter.
  • FIG. 3 Virtually no fenamiphos was leached in lysimeters containing SOP-sand (FIG. 3). Two weeks after application, total metabolite leaching was reduced 90% by the SOP- sand composition (FIG. 4). The comparative reduction declined with time. Seven weeks after application total metabolite leaching was reduced 76% (FIG. 5). This apparently occuned because after the initial great adso ⁇ tion of metabolite by SOP sand, there was a slow deso ⁇ tion of the material, as evidenced by a gradual increase in accumulative metabolite leaching in the SOP-sand lysimeters over time (FIG. 6).
  • the initial high concentration of metabolite in percolate was prevented by the SOP-sand.
  • This gradual deso ⁇ tion characteristic of the SOP-sand composition provided evidence that the composition may also be used as a "slow-release" carrier for pesticides and/or other organic compounds.
  • the area containing the lysimeters was maintained continuously as a golf green since the previous study, and periodically, lysimeter water was evacuated and discarded. Eight and a half months after the initial fenamiphos was sprayed over the lysimeter area, the green was hollow-core aerified and topdressed, which are standard greens maintenance practices used to improve soil aeration and water penetration. In the afternoon, fenamiphos (Nemacur® 3E) was mixed with 3 to 4 liters of water and applied with a sprinkling can over 1 m areas centered over the lysimeters to provide an application rate of 1.125 g A.I. m " .
  • the plot area was irrigated to provide 0.8 cm water, and maintained as a golf green thereafter. Lysimeter water sampling began again three days following the second application of pesticide, and continued weekly or more often for at least six weeks following the application. The samples were analyzed for both fenamiphos and metabolite.
  • EXAMPLE 8 - LARGE-SCALE PRODUCTION OF PF-PEG SOP A 700 gallon final polymer feed tank and a 150 gallon PEG mixing tank was utilized. This generates a batching feed capacity of five (5) hours operation and production of forty (40) tons of finished SOP-Sand (Biosand) product. The following quantities of materials and conditions were utilized in preparation of a polymer batch.
  • FIG. 8 and FIG. 9 An exemplary plant layout and process steps for large-scale production of the SOP compositions of the present invention are shown in FIG. 8 and FIG. 9.
  • the inventors utilized the following scheme for large-scale production of SOP-coated sand compositions.
  • Pin Mixer (30" diameter) operated at 300 RPM, resulting in tip speed of about 75 to about 125 ft/sec, with a tip speed of about 100 ft/sec being shown by the inventors to be highly desirable for large-scale preparation of the SOP-sand compositions disclosed herein.
  • Two (2) "flat 60° angled spray nozzles" each dedicated separately to a metering pump, utilized for spray / atomizing the polymer feed into the Pin Mixer.
  • the nozzles are located on top of the Pin Mixer approximately 12" apart and in the first 25%) zone of the mixer.
  • Vibrating frequency of dryer regulated to maintain retention time of about ten (10) minutes for Biosand material in Fluid Bed Dryer.
  • Outlet flue gas is water quench to maintain temperature of about
  • a Fluid Bed Cooler may be operated in the following manner:
  • Inlet air was adjusted to 8,000 CFM (180 CFM per FT 2 of cooler deck area). Higher air velocities would cause air entrainment from cooler air discharge.
  • Biosand product temperature was maintained below 150° F. In existing cooler.
  • Recycle Mill was operated at the following status to eliminate clustering of Biosand material and prevent unnecessary damage / fracturing of the polymer coating on the sand.
  • Biosand with sulfuric acid in mixer were as follows: 1. All mixer components were treated with brushable ceramic surface coating.
  • Screw mixer was operated at 250 RPM.
  • Sulfuric spray nozzle was positioned 12" above screw portion of mixer and utilized at 60° flat spray nozzle.
  • Sand (dried and sized to -30 + 60 mesh) was fed to Pin Mixer at 14,000 LBS./Hour.
  • Biosand polymer was supplied to the Pin Mixer by two (2) independent metering pumps at a rate of 1.0 GPM each. This equates to a rate of 1200 LBS. / hour of material and approximately 900 LBS. / hour of Biosand resin once H 2 O is removed by the Fluid Bed Dryer.
  • compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of prefened embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

Abstract

Disclosed are methods, compounds, and apparatus for the adsorption of organic compounds and the remediation of such compounds from water, wastewater, surficial and groundwater, and other aqueous and environmental sources. Also disclosed are methods for the containment, reduction, and prevention of organic leaching from soils, agricultural, industrial, and commercial environments, and in particular, sports and athletic turf facilities where pesticides are frequently applied. Methods are disclosed for the containment of organic leachate from golf courses, tennis facilities, football, baseball fields and the like, as well as methods and compositions for the preparation of controlled-release pesticides and fertilizers.

Description

DESCRIPTION
COMPOSITIONS AND METHODS FOR ADSORPTION AND REMEDIATION OF ORGANIC
COMPOUNDS
1.0 BACKGROUND OF THE INVENTION
The present application is a continuation-in-part of U. S. Patent Provisional Application Serial Number 60/066,692, filed November 24, 1997, the entire content of which is specifically incorporated herein by reference.
1.1 FIELD OF THE INVENTION
The present invention relates generally to the removal of organic compounds from soils, hazardous spills, and aqueous environments. More particularly, this invention pertains to a technology for reducing runoff and/or leaching of organic compounds such as pesticides present in an environmental or industrial setting. In preferred embodiments, compositions and methods are disclosed for stabilized organic polymer formulations capable of binding organic compounds, such as insecticides, herbicides, fungicides and nematicides. Also provided are methods of using such compounds in the remediation of environmental contamination, in the reduction of pesticide leaching from soil samples, and in the preparation of time-release organic fertilizer and pesticide formulations.
1.2 DESCRIPTION OF RELATED ART
Despite a considerable number of substances and techniques to prevent or to alleviate the contamination of water sources, pollution of water sources remains a major concern. Because groundwater contamination can, and often does, come from a variety of sources, better containment of potential pollutants at their source is a viable solution to this problem.
In conventional methods of water treatment, wastewater of several sources are collected in a central treatment plant to be processed. This processing requires constant monitoring and maintenance by experts. In U.S. Patent 4,971,698, (specifically incorporated herein by reference), Weber et al. provide a decentralized method of removing biodegradable contaminants from wastewater. This method allows for the treatment of the wastewater by the individual producer and/or the source. This process is dependent on the biodegradation of the contaminants by microorganisms or products thereof. Although this method may be an economical method of containing compounds at the source, it usefulness is limited to specific biodegradable compounds. Furthermore, the method is dependent on the maintained viability of the microorganisms or products thereof and, therefore, may require constant reapplication.
1.2.1 LANDFILL LEACHATE TREATMENT
Because of the anaerobic nature of landfills, microbes within a landfill tend to produce a large amount of organic acids as their metabolites. This is due to common biochemical pathways for first stage anaerobic metabolism. Due to the strong reducing nature of these organic acids, heavy metals and other compositions become cationic and readily mobile. This association of organic acids and inorganic materials is referred to as landfill leachate. Other pollutants that comprise landfill leachate include pathogenic organisms, solvents, pesticides, hazardous wastes, and industrial and wastewater sludges (U.S. Patent 4,995,969, specifically incorporated herein by reference).
The extent to which leachate is able to leave a landfill location by groundwater or surface water transport has been a point of interest for many years. Studies suggest that in an arid or semiarid climate site, the water transport rates are slow, and, consequently, pollution problems are limited. Conversely, in temperate climate sites, water transport rates are fast and, consequently, leachate pollution presents a serious environmental problem. To prevent aquifer and groundwater contamination by landfill leachate, design criteria for landfills strongly encourage or require construction in soils rich in clay, located above the water table and situated at assumed safe distances from drinking and surface water resources. In spite of these precautions, leachate problems pervade many landfill locations resulting in contamination of water resources. More recently, attention has been focused on the concept of lining landfills with impermeable membranes, then collecting and treating leachate either off-site or on-site. Off-site treatment may involve piping the leachate to a nearby sewer system, and combining it with the municipal sanitary sewage. This off-site treatment methodology requires that the community have a municipal treatment facility capable of processing the leachate loadings; and that the concentration of leachate to wastewater be small to effectuate effective processing. For large landfill operations, on-site treatment of leachate with package plants has been attempted; but with limited success. Another type of leachate treating system includes one or more open oxidation ponds or lagoons. This type of system tends to be relatively slow and requires a relatively large land area. In addition, the open pond is unsightly, has an objectionable odor and is a breeding ground for mosquitoes.
In U. S. Patent 4,995,969 (specifically incorporated herein by reference), LaVigne describes a method of on-site leachate treatment in which the leachate is forced to run through a plot containing leachate-tolerant plants and microorganisms that are capable of metabolizing organic carbon compounds and adsorbing heavy metals within the leachate.
Although the method described in U. S. Patent 4,995,969 may be effective and economical, it is dependent on the establishment of a biological "ecosystem" within the landfill. Because of variations between individual landfills, a considerable amount of time and experimentation may be needed to establish the "ecosystem" in a given landfill. Furthermore, if the materials in a landfill should change over time, this would require that adjustments be made to the makeup of the "ecosystem" to account for the changes. This adjustment time may lead to an inordinate amount of leachate escaping into the environment. Finally, it is plausible that some landfills will not be able to support the growth of the organisms disclosed in U. S. Patent 4,995,969. 1.2.2 LEACHING OF PESTICIDES AND METABOLITES FOLLOWING APPLICATION TO SOILS
Modern landscaping and agricultural production depends heavily on the application of pesticides. Similarly, outdoor sports venues require extensive and repeated pesticide applications for maintenance. Unfortunately, this leads to the contamination of the environment, particularly soil and groundwater. Although most herbicides are only mildly toxic to man, some can accumulate and kill when a critical concentration is reached. Generally, insecticides, rodenticides, and nematicides are more toxic to man than herbicides.
1.2.3 ADSORBENTS
One method of removing organic compounds from aqueous solutions or the environment has been through adsorbents. Many inorganic adsorbents are known in the art and have been used for some time. These adsorbents are defined as solid phase materials having very high surface area-to- weight ratios and exhibiting the ability to concentrate adsorbates on their surfaces (U. S. Patent 4,147,624, specifically incorporated herein by reference). Inorganic adsorbents include activated carbon, silica, silicates, alumina, and clays.
In treating aqueous systems for removal of contaminants, various grades of activated carbon or bone char impregnated with activated carbon have been widely used. Not all grades perform well in all uses, and the more effective grades tend to be rather expensive. Likewise, mineral-based adsorbents have not performed well in aqueous systems.
Mineral substrates such as sepiolite, attapulgite (palygorskite) and smectities may be modified to obtain a more organophilic surface to be effective adsorbents for certain uses, however a relatively high surface area and a cationic exchange capacity above about 5 milliequivalents per 100 grams of adsorbent is required (U.S. Patent 4,444,665; specifically incorporated herein by reference). Unfortunately, in their naturally occurring state, many of these clay minerals (aluminosilicates) swell or slake in aqueous systems resulting in gel formation or colloidal dispersions that are extremely difficult to separate from the liquid. Likewise, granular forms of these clays in naturally occurring state are useless since they simply fall apart in aqueous media.
Adsorptive minerals such as bauxite does not exhibit this deficiency, but such clays must be rendered substantially non-gelling or non-slaking by an expensive heat treatment. For example, attapulgite clay may be rendered non-gelling and non-slaking by calcining at temperatures in the range 200°C-550°C (McCarter et al., 1950).
Unfortunately, this treatment alone is not sufficient for the mineral to effectively remove contaminants from many contaminated aqueous liquids.
Surface modification of minerals has been demonstrated, but the majority of these compositions require swelling or gelling-grade clays, e.g., montmorillonite, bentonite, hectorite and other smectities including attapulgite and sepiolite in order to be useful for adsorption of organic compounds (Cowan et al., 1960). Difficulties in handling these materials, however, have precluded their use in large-scale treatment of organic compounds. U.S. Patent 4,167,481 to Cremers et al. (specifically incorporated herein by reference) discloses effective removal of metal cations from wastewater but the process requires addition of polyamines and the presence of a cation exchanger such as natural bentonites, montmorillonites and zeolites.
Unmodified, heat-treated attapulgite has disclosed use in water treatment for removing certain metal cations, hormones, toxins, viral micro-organisms and pesticides. Reference is made to the following U.S. Patents to Sawyer: Nos.
4,054,515, 4,116,825; 4,116,826; 4,1 16,827; 4,1 16,828. A specially processed form of heat-treated attapulgite has disclosed use as a filter aid in Re. No. 25,464 (Oct. 15,
1963) of U.S. Patent No. 3,080,214. a method of preparing heat-treated, so-called "activated" attapulgite which is substantially non-gelling and non-slaking is disclosed in U.S. Patent No. 3,041,238 to Allegrini.
These compounds, however, are unsuitable for the removal of compounds from agricultural and industrial applications which are exposed to aqueous solutions, and in applications where such clays and formulations are either prohibitively expensive, or produce undesirable by products such as slaking or gelling endproducts.
For example, such compounds are not useful in soil strata such as golf course greens where a high degree of percolativity is required and where the addition of such products would compromise the percolation and drainage of these soils.
1.3 DEFICIENCIES IN THE PRIOR ART Although a number of compositions and methods have been developed to remove or reduce the concentration of organic compounds from the environment, each has one or more shortcomings that render them unsuitable for use in certain agricultural and industrial processes. In particular, they all suffer from an inability to maintain particle size and integrity when contacted with aqueous environments. Likewise, the present methods and compositions of organic adsorption are either prohibitively expensive or unsuitable for application in areas where such particle size maintenance and percolation factors are critical. Finally, improvements in the formulations of timed-release, or controlled-release agricultural products are needed, particularly in the area of slow-release pesticide and herbicide formulations. The availability of a stable formulation that would permit the controlled release of organic fertilizers and pesticides would represent a breakthrough in the field of agriculture, and provide biofriendly compositions for controlled release of insecticides, herbicides, pesticides, and the like for both the commercial farmer, and the home gardener.
2.0 SUMMARY OF THE INVENTION
The present invention overcomes these and other shortcomings in the prior art by providing compositions and methods for adsorption of organic compounds, the development of controlled-release formulations of organic fertilizers and pesticides, and methods for the removal of organic leachates (such as pesticides) from agricultural and commercial environs, as well as industrial sites and environmental contamination. Also provided are devices and apparatus for the remediation of organic wastes in situ and in solution using reactive barriers, flow through filtration systems, and organic waste containment facilities. In certain embodiments, compositions are provided for the reduction of pesticide leaching from athletic facilities, and in particular, golf course greens, and athletic turfs. The invention disloses and claims a stabilized organic polymer comprising phenol-formaldehyde-polyethylene glycol. Preferably the polyethylene glycol is crosslinked with the phenol-formaldehyde using a Williamson ether synthesis to produce the stabilized organic polymer. This polymer may be utilized directly, or bound to a matrix or a substrate. Preferably, the polymer compound is capable of binding an organic compound, and in particular, organic contaminants, fertilizers, and pesticides. The pesticide may be an insecticide, a herbicide, a fungicide, or a nematicide. The composition may be comprised within an agricultural site, a reactive containment barrier, or a hazardous spill cleanup device or apparatus. The composition may also be formulated into a filter or sedimentation take or other water treatment device. Likewise, the composition may be formulated into a soil amendment, additive, or hazardous spill barrier or containment means. The composition may be formulated for use in a device or system for treating water, sewage, wastewater, or agricultural leachate, or for removomg organic pollutants from a solution. Typically, the water treatment device will comprise at least a first inlet port from which the contaminated solution is introduced into the device, one or more chambers in which the composition is placed either alone or on one or more supports or matrices and in which the solution is contacted with the composition to adsorb the organic contaminant(s) from the solution, and then one or more oulet ports from which the purified water is released.
Alternatively, the SOP adsorbant compositions may be comprised with a system for removing pesticides from a leachate. The system generally comprises at least one leachate supply source, a water impervious treatment basin with at least one inlet port into which the SOP composition is placed and into which the leachate supply source flows to contact the leachate with the SOP composition, and at least one outlet port, and flow ontrol means for draining the treated leachate from the treatment basin. The system may also comprise a continuous flow system or a batch processing system.
The invention also discloses and claims a method of preparing a SOP composition that has the desired property of being able to adsorb one or more organic compounds onto the polymer. The method generally involves coating, spraying, aerosolizing, or otherwise contacting a suitable matrix with the SOP compound under conditions effective to permit coating of the matrix with the compound.
A method of preparing a golf course to prevent leaching of a pesticide from the course is also provided by the invention. This method generally involves amending one or more layers of soil underneath the golf course grass with one or more SOP compositions. The composition may be applied to discreet layers under the athletic turf, or alternatively may be mixed throughout the soil underneath the grass.
The invention also discloses and claims a controlled-release pesticide and a controlled-release organic fertilizer composition that comprises the SOP compound described herein. Such formulations permit the time-released or slow-release of the adsorbed pesticide or fertilizer, as it slowly desorbs from the SOP. Organophosphates, fish emulsions, manure filtrates, and other organic fertilizers are all contemplated to be amenable to controlled-release using the SOP compositions, and their slow desorbtive properties. These and other features of the invention will be apparent to those of skill in the art having benefit of the teachings of the present disclosure:
In a first embodiment, the present invention concerns stabilized organic polymers (SOPs) that are capable of binding to organic compounds and preventing the leaching of such organic compositions from the area in which the SOPs are located.
The SOPs of the present invention may be prepared so that they bind either polar or non-polar organic compounds, or alternatively, may be designed such that a single SOP, or a combination of two or more distinct SOPs may bind both polar and non- polar compounds. The ability of SOPs to bind more than one type of organic compound makes them useful for a variety of organic chemical remediation situations.
In a preferred embodiment, the SOP is a phenol-formaldehyde-polyethylene glycol polymer. The inventors have shown that phenol-formaldehyde-polyethylene glycol compositions are highly desirable for their mechanical durability. Although polyethylene glycol (PEG) of various molecular weights may be used in the production of the SOP, difunctional PEGs such as those with average molecular weights of about 5000 is preferred for adsorption of many pesticides. Alternatively, PEGs having greater molecular weights (including those having about 6000. about 7000, about 8000, about 9000, or even about 10,000 or greater average molecular weights may be employed in the formulation of the SOP of interest. In certain embodiments, the inventors contemplate the use of smaller molecular weight PEGs may be beneficial for the remediation and adsorption of certain organic compounds.
As such, SOP formulations employing PEGs having an average molecular weight of about 4000, about 3000, about 2000, about 1000, or even about 500 or so molecular weight may be useful in certain embodiments. Likewise, when preparing SOP compositions for the adsorption of multiple types of organic compounds, it may be desirable to prepare the SOP using two or more different-sized PEGs as starting materials. Indeed, the skilled artisan will be able to vary both the concentration and the average molecular weight of the PEG to prepare modifications to the basic SOP described herein as needed to provide compositions having slightly different, or more advantageous formulations for the remediation or adsorption of particular target organic compounds. Exemplary PEG 5000 was obtained from Union Carbide
Chemicals (Dallas, TX).
Although formaldehyde was used in an illustraive embodiment, the inventors also contemplate that other low-molecular weight aldehydes such as acetaldehyde, propionaldehyde, or butaraldehyde, and the like may be substituted in the general polymer formulation to provide certain SOP derivative formulations that may be desirable for certain applications of the polymer composition.
Preferably the phenol is at least a technical grade phenol, although any grade phenol may be used so long as the phenol used does not contain trace impurities that would alter or inhibit the proper polymerization of the compound. Alternatively, the phenol component used in the preparation of the phenol formaldehyde compound may comprise one or more of the following phenol derivatives: 1-hydroxyphenol, 2- hydroxyphenol, 3-hydroxyphenol, 1 ,2-dihydroxyphenol 1,3-dihydroxyphenol, 1,4- dihydroxyphenol, and the like. In an illustrative embodiment, the phenol formaldehyde component of the SOP was a PF resole (Durite AL-5801 PF Resin, Bordon Chemical, Louisville, KY). The adsorbant properties of the PF-PEG SOP compound permit their direct use in binding organic compounds, without the need of coating the compound onto a substrate. However, in an illustrative embodiment, the inventorshave shown that the SOP compound is readily formulated for coating, crosslinking, absorbing, or binding to a solid substrate or a matrix. This matrix, or substrate, may provide support or impart other physical properties to the SOP compound that facilitate its use in a variety of practical applications.
For example, in one embodiment, the matrix may be a natural compound such as cachasa, a plant byproduct often referred to as filtercake. This filtercake is the crude residue that remains following digestion and/or extraction of soluble components of plant materials. Cachasa, in particular, refers to the filtercake obtained following the processing of sugarcane to remove its soluble components for the preparation of refined sugar. After separation of the solid components from the filtrate, the solids are compressed and/or compacted, with the resulting undigested plant material solids being referred to as the filtercake.
In another embodiment, the substrate upon which the SOP is coated is a sand, sea sand, or a mineral such as silicate. Formulations of the PF-PEG SOP coated onto sand particles are particularly preferred for use in the preparation of athletic turfs, such as golf courses, and the like, where maintaining the percolativity of the soil is important. These sand-SOP formulations (termed "biosand" by the inventors) are also desirable for amendment to agricultural soils, and to other environmental sites where location of the SOP for the purpose of adsorbing organic compounds is desirable.
In further embodiments, it may be desirable to apply the adsorbant to a substrate or matrix having a larger particle or mesh size than a granular substrate such as sand. In these instances, the inventors contemplate the SOP compositions may be formulated for application to rocks, gravel, pebbles, clay, expanded clay, silicates, silica gels, zeolites, or metals (including metal filings, shaving, pellets, beads, turnings, etc.). Alternatively, the matrices may be a synthetic compounds such as plastics (e.g., polystyrenes, polypropylenes, polybutalenes, etc.), synthetic fibers (e.g., nylon, rayon, dacron, orlon, etc.) or other monomeric or polymeric resins and the like.
Likewise, it may be desirable to apply the SOP composition to substrates such as beads, glass, glass fibers, fabrics, ceramics, fiber filters, spun fibers, and the like. Indeed, it may also be desirable to coat the adsorbant onto plant-derived materials other than cachasa or filtercake. Cellulose fibers, lignins, and other plant-extractable materials may form the substrate upon which the SOP is formulated. Virtually any solid or semi-solid support, matrix, or substrate is envisioned to be useful in the creation of SOP-formulations where it is desirable to impart the adsorptive capabilities of the polymer to a target surface.
Because the SOP compositions, in the broadest sense, are used to adsorb organic compounds, they may also be used to form part of an apparatus or a device that is intended to remove or reduce the concentration of organic compounds from an environment or a contaminated site, solution, or water source. For example, in one preferred embodiment, a SOP composition may be added to the soil in or around a sports facility, agricultural, commercial or residential turf or field, or alternatively, in and around an industrial facility or hazardous materials site. In a preferred embodiment, the SOP composition may be added to the soil, or may be formulated onto sand for application to a subsurface layer of a golf course green.
In another embodiment, the SOP composition may comprise part of a water filter, a water treatment facility, a sediment filter, or a reactive barrier. As such, the compositions may be used to adsorb organic contaminants from a groundwater source, or a municipal water supply, or may be placed in the ground as a barrier to prevent leaching or seepage of contaminated water into a given area, or to prevent or reduce the amount of contaminant moving through the ground from one site to another.
Because of the widespread environmental use of organic compounds (and particularly organic pesticides and the like), the entrance and contamination of environmental soils, sites, and particularly water sources, is nearly inevitable. The types of organic compounds that may be introduced into an environmental site are many. For example, organic pesticides such as herbicides, rodenticides, insecticides, fungicides, microbicides, and nematicides are widely applied in agricultural and residential areas. The inventors have demonstrated, however, that the application of pesticides to a target area may be contained through the use of the SOP compositions disclosed herein. For example, in one embodiment SOP-sand compositions were used to reduce or contain the leaching of 2, 4-dichlorophenoxyacetic acid (2. 4-D) and 3,6- dichloro-o-anisic acid (Dicamba) in a soil sample. Likewise, migration of the nematicide fenamiphos, and its metabolites, through the soil layers under a golf course green was shown to be affected by the presence of a SOP-sand adsorbant amendment in the soil.
Organic compounds, including pesticides, may also be used in large industrial processes or may be used by an individual in or around the home. Because of the widespread use of organic compounds, spills are a common occurrence. In such instances, the application or introduction of one or more SOP compositions to the affected area may be used to adsorb or contain such an organic spill. For such non- agricultural uses, the SOP composition may conveniently be formulated as a particulate or "cat litter-like" substrate and applied to the contaminated site. After application to the spill, the SOP composition containing the adsorbed contaminant(s) may conveniently be collected and subsequently destroyed (e.g., incineration) or disposed of. Alternatively, the contaminant may be desorbed from the polymer and disposed of thereafter in convenient fashion, and under suitable guidelines and procedures for the handling and disposal of the particular waste material contained by the adsorptive polymer.
Alternatively, a SOP composition may be used to form a barrier at a perimeter around the spill. Of course, the barrier does not need to encircle the spill, but rather may be placed at a location in the general direction of migration of the spill so that it may be contained by the adsorbant. For example, if the spill was to occur on an inclined surface, the SOP composition may be applied to a location below the spill to adsorb the runoff. Furthermore, a SOP composition may be placed as a barrier at a location as preventive measure. That is, a barrier may be placed next to a water source, for example, so that, in an event of an organic contaminant spill, the water source is protected by the intervening reactive barrier. The water source may be surface water such as a puddle, creek, river, reservoir, pond, lake, sea, ocean, or pool, or it may be subterranean water such as an aquifer, groundwater, well head, well casing, or well water. Of course, a barrier may be used to prevent the dispersal into the environment of organic compounds following their use and is not restricted to accidental spills of organic compounds.
A common use of pesticides is in the maintenance of sports facilities. Sports facilities include, but are not limited to, those of golf, tennis, croquet, polo, horse racing, football, baseball, soccer, or cricket. A SOP composition may be added to the soil of the facility or may be a component of a drainage treatment system that collects wastewater, runoff, or leachate from the sports facility. Alternatively, the composition may be formulated into a layer underneath the sod layer. Preferred embodiments comprise an SOP compound as an amendment to the soil of a sports facility. In a preferred embodiment, an SOP composition may serve as an amendment to the soil of a golf course green, in such a manner as to prevent pesticide leaching.
As a component of a golf course, it is important that the SOP composition maintain the high rate of percolativity or conductivity that is desired of a golf course, be placed in a location so to efficiently bind the pesticides applied to the course, and prematurely adsorb or inactivate the pesticide before its role is accomplished in the soil. Therefore, it is preferred that a SOP composition is used as an amendment to the subterranean layers of the golf course and particularly a green. In preferred embodiments, an SOP composition comprises the gravel drainage blanket, intermediate layers, or the lower levels of the root zone. A SOP composition may amend the upper layer of the root zone provided that the binding of pesticides in this layer is not undesirable. In other words, because the SOP compound may inactivate the pesticide upon binding, one may not wish to amend the soil in direct contact with the roots when pesticides that target the root or pests that reside in this area are applied, but instead provide a sublayer of SOP-treated soil (For example, see FIG. 7B). In this schematic, the SOP composition is added as a discreet layer beneath the sod layer in one or more of the subsurface, or subterranean, layers.
When mixed throughout the soil, an SOP composition may be effective at a range of ratios. In preferred embodiments, the ratio of SOP composition to non-SOP compositions is about 15% by volume. A SOP composition may be blended throughout the soil during construct of a golf green, or other facility, or may be added to the soil at a later date by , for example, tilling. A SOP may be added to form one or more discrete layers within the soil. In preferred embodiments, the percentage of SOP composition comprising a discrete layer is such that it binds nearly all of the applied organic and maintains the conductivity of the soil. The addition of an SOP to a soil may be by way of injecting the compound into the ground throughout a given layer of the soil or at a discrete layer beneath the surface (FIG. 7 A and FIG. 7B). By the term injecting, it is meant application of a substance via pressure through a spike or nozzle-like structure. Devices for injecting the substance are described in U.S. Patents 5,461,992 and 5,671,887. It is contemplated that the accumulation of the organic compound within the
SOP-comprising layer or composition may serve to enhance microbial degradation of the organic compound. As such, the formulation of the invention may be used to enhance microbial colonization of an area where SOP is present.
Because the SOP compounds may be affixed substrates of different particle sizes and compositions, an SOP composition may improve the overall nature or character of the soil, as well as provide organic leachate adsorption. A SOP composition may be added to the soil to the adsorb organic compounds in the soil, to alter the percolativity of the soil, consistency or integrity of the soil. It is common practice to add compounds to soils, particularly soils high in clay, to improve the ability of these soils to support plant growth. The SOP compositions may not only provide organic adsorption, but may in fact improve the overall quality of the soil to which it is added.
As an alternative to or in addition to soil amendments, an SOP composition may comprise a filter that is operatively connected to the drainage system of a golf green (FIG. 6). By operatively connected it is meant that the filter is attached to the drainage system such that water or other aqueous solutions that flow through the drainage system enter the filter by a input port, contact a chamber comprising an SOP composition, and exit the outlet port. In preferred embodiments, the filter is able to be removed and replaced. Another important aspect of the present invention is its use in the removal of organic compounds from aqueous solutions. The aqueous solutions may be water, wastewater, sewage, leachate, groundwater, or industrial runoff. In preferred embodiments, the aqueous solution is leachate. One method of removing organic compounds from an aqueous solution is by use of a water treatment system. A water treatment system may be a simple column filter or a part of a complex municipal water treatment facility.
U.S. Patent 4,995,969 describes a treatment system for landfill leachate. Briefly, the invention is a biological living filter system. The invention comprises a treatment basin which is lined with a water impervious material and filled with an organically enriched treatment medium which is conductive to maintaining a population of micro-organism and plants. This system may be modified to comprise one or more SOP compositions. A SOP may be added to the treatment medium or may be a component to a filter placed either prior to the application of the leachate to the treatment medium or after the leachate has transgressed the treatment medium or both. Alternatively, an SOP may be used in the landfill leachate treatment system similar to that taught by U.S. Patent 4,995,969 in lieu of the biological material, obviating the need to establish and maintain a living ecosystem.
A simple filter system in taught in U.S. Patent 5,685,981. Filters generally have an intake port, a chamber, and an outlet port. In preferred embodiments, the chamber comprises an SOP composition such that organic compounds within aqueous solutions are bound by the SOP composition and prevented from flowing through the outlet port thereby purifying the aqueous solution. The composition may be supported by a matrix such as sand, beads, fiber, etc., comprised within a filter cartridge, or, alternatively, coated on the chamber walls itself.
The water systems commonly used by municipal water treatment facilities include sequence batch biological reactor, continuous activated sludge, trickling filter, aerated lagoon, and anaerobic filter. The aqueous solution may be treated by flowing through a column comprising an SOP composition or by contacting the aqueous solution with particles comprising an SOP composition in a batch method. In the batch method, particles comprising an SOP composition are added to a water sample suspected of containing one or more organic compounds, mixed to provide sufficient contact between the particles and the organic compounds to allow binding, and then separated from the newly purified aqueous solution. Separation may be by means of gravity, centrifugation, magnetism (in the case of coating the SOP onto a magnetic substrate such as iron filings), or filtration through a size-selective porous membrane, or a mesh filter, or other size-exclusionary grating, grid, etc.
3.0 BRIEF DESCRIPTION OF THE DRAWINGS
The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.
FIG. 1. Shown is the effect of SOP on retention of fenamiphos metabolite applied at 1.125 g AI m" . FIG. 2. Shown is the effect of zeolite and diatomaceous earth on fenamiphos leaching (up to five successive 6.5cm irrigations).
FIG. 3. Shown is the effect of zeolite and diatomaceous earth on metabolite leaching (up to five successive 6.5cm irrigations). FIG. 4. Shown is the effect of zeolite and diatomaceous earth on saturated hydraulic conductivity. FIG. 5A. Shown is a diagram depicting a SOP comprising barrier for the prevention of surface water contamination by organic compounds. Movement or leaching of the organic compound is shown as dashed lines with arrows. 2 represents a SOP comprising barrier. 4 represents water. 5 represents an organic compound spill or application. FIG. 5B. Shown is a diagram depicting a SOP comprising barrier for the prevention of subterranean water contamination by organic compounds. Movement or leaching of the organic compound is shown as dashed lines with arrows. 1 represents soil. 2 represents a SOP comprising barrier. 3 represents bedrock. 4 represents water. 5 represents an organic compound spill or application. FIG. 6. Shown is a diagram depicting an underground drainage system operatively connected to a filtering device comprising an SOP composition. Movement or leaching of the organic compound is shown as dashed lines with arrows. 5 represents an organic compound spill or application. 6 represents an underground drainage pipe. 7 represents the inlet means to the filtering device. 8 represents the filtering device comprising an SOP composition. 9 represents an outlet device. FIG. 7A. Depicted is a spike injecting an SOP composition into the soil at a discrete layer. 10 indicates the injecting spike. 12 indicates the root zone. 13 indicates the intermediate layer.
FIG. 7B. Depicted is the soil after application by injection of an SOP composition into a discrete layer as demonstrated in FIG. 7A. In this particular example, the SOP is a discrete layer within the lower root zone. 11 represent the SOP composition layer in the lower root zone. FIG. 8. Shown is a schematic diagram of a plant layout for the large-scale production of the compositions of the present invention. Depicted is 14 feeder; 15, conveyor; 16, pin mixer; 17, pump; 18, polymer feed tank; 19, agitator; 20, PEG mix tank; 21, fuel; 22, F.D. fan; 23, combustion system; 24, cyclones; 25, fluid bed dryer; 26, cooler; 27, screen/mill; 28, screen; 29, mill; 30, acid tank; 31, in line mixer; 32, product storage; 33, control room.
FIG. 9. Shown is a process flow diagram for the large-scale production of
SOP-sand compositions. Depicted is 15, conveyor; 16, pin mixer; 17, pump; 18, polymer feed tank; 19, agitator; 20, PEG mix tank; 22, F.D. fan; 23, combustion system; 24, cyclones; 25, fluid bed dryer; 26, cooler; 28, screen; 29, mill; 30, acid tank; 32, product storage; 33, control room; 34, L.D. fan; 35, stack. 4.0 DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
4.1 IMPORTANT ASPECTS OF THE INVENTION
The compositions and methods of the present invention provide for the containment of pesticides or other organic compounds at the source of the spill or their application, as opposed to a common collection site. This allows an individual to apply compositions of the present invention to a spill before it has an opportunity to enter a water system. Upon entering a water system the organic compound is diluted and may be more difficult to remove because of the high volume of water that may need to be treated. The SOP compounds of the present invention and compositions comprising them are able to bind organic compounds with a wide range of polarities, they can be manufactured cheaply, and do not require sophisticated training in their implementation. Therefore, the compositions of the present invention are effective, economical, and easy to implement. One important aspect of the SOP-sand compositions of present invention is that they do not affect the conductivity or percolativity of the soil to which it is applied. This attribute is ideal for the use in soils that require efficient draining of water such as an athletic turf, and in particular, a golf green.
Furthermore, the ease of coating a substrate with one or more of the SOP formulations disclosed herein provides a facile means to develop apparatus and devices for the purification and remediation of aqueous solutions, including sludge, sewage, groundwater, surface water, municipal water supplies, and the like. The simplicity and cost-effectiveness of the present invention in preparing barriers, flow- through filtration apparatus, and the preparation of devices for contacting the SOP- substrate compositions with an organically-contaminated aqueous source make these devices desirable for use in conjunction with many existing water treatment devices or apparatus to adsorb organic contaminants from solution.
Finally, the ability of the SOP compositions to slowly leach or desorb the bound organic compounds make them useful as controlled-release formulations for delivering organic compounds (such as fertilizers or pesticides) to a target area at a controlled rate. The slow- or delayed-release capability of the formulation to desorb organics from it, make it idea as an adjuvant or a delivery vehicle for the controlled- release of organic herbicides, organic pesticides (including nematicides, insecticides, fungicides, and microbicides) to a target area. Moreover, the ability of the SOP to be coated onto a biofriendly inert substrate, such as a mineral, silicate, or sand particle, provide a biocompatible matrix for the delivery of slow-release fertilizers or pesticides to a target area without introducing incompatible or unsuitable adjuvants or substrates into the environment.
4.2 SOP COMPOUNDS The stabilized organic polymers of the present invention have been shown to bind organic compounds with a wide range of polarities and are capable of both being manufactured cheaply, and also coated onto a variety of substrates for use in particular embodiments. While the inventors have demonstrated the facility and utility of SOP- matrix formulations comprising phenol-formaldehyde PEG in adsorbing organic pesticides, they also contemplate that a variety of additional stabilized organic polymers may be developed by varying either the concentration of one or more of the substrates during formulation, or by substituting other derivatives of these compounds in the development of modified SOPs that also function as effective organic adsorbants. As such, the inventors contemplate that each of these modified SOP formulations may be useful in the methods of the present invention, and are therefore these components or the processes used for making them are within the scope of the invention.
4.2.1 POLYETHYLENE GLYCOL In a preferred embodiment, the SOP of the present invention comprises polyethylene glycol (PEG). PEG is made up of chains of repeating ethylene glycol subunits that may be of variable lengths. Because of the variable nature of PEG, it may be produced or is commercially available in a variety of different molecular weight formulations. Commercially, PEG is generally identified and sold by the average molecular weight of the subunit PEGs in the formulation. For example, molecular weights of PEG commercially available include, but are not limited to, 200, 300, 400, 550, 600, 900, 1000, 1,450, 1,500, 2,000, 3,350, 3,400, 4.600, 8,000, and
10,000. Higher molecular weight PEG compounds may also be synthesized by condensing two or more molecules of lower- weight PEGs (e.g., condensation of a
PEG of molecular weight about 7,000 with a PEG of molecular wight about 9,000 may yield a PEG compound of an approximate molecular weight of about 15,000 to
18,000.
Also available commercially are different grades of PEG based on the percentage of impurities and PEG derivatives including methoxypolyethylene glycol and derivatives, polyoxyethylene (functionalized derivatives), and ether derivatives (polyethylene ethers; surfactants). There are many known commercial PEG materials with functional end groups. These should be considered as possible improvements over halogen functionalized PEG.
Alternatively, the use of crown ethers and related compounds is contemplated, owing to their chemical similarity to PEG, albeit in a cyclic form. Both PEG and polyethleneimines and copolymers of each have the potential to complex a wide range of organic materials.
In certain embodiments, the inventors contemplate of utilizing SOP compositions that comprise a PF-PEG compound that is not completely polymerized.
Free -OH groups on the PF-PEG polymer may be desirable in certain circumstances, and may improve soil conditioning properties.
4.2.2 PHENOL-FORMALDEHYDE COMPONENT
In preferred embodiments, the SOP of the present invention comprises phenol- formaldehyde (PF). Although phenol-formaldehyde may be formulated for use in the SOP, the inventors have determined that commercially available phenol-formaldehyde resin (Bordon Chemical, Louisville, KY) are quite effective for production of an inexpensive, effective adsorbent. However, the inventors contemplate that slight variations may be made concerning the type of PF or use of compounds chemically similar to PF and still remain within the scope of the present invention. There are many different commercial grades of phenol formaldehyde resins.
In an exemplary embodiment, a resole grade formulation with excess formaldehyde was employed, however, other grades of PF having less formaldehyde may be useful in optimizing the large-scale manufacturing of PF-PEG formulations. Mixes of resole with novalac grades of PF have been used in industry for many years because of improved properties along with less excess formaldehyde. However, owing to the functional nature of resole, it may not be desirable to replace all of the resole PF with a novalac grade of the resin.
Likewise, some grades of PF are availble with epoxy groups. These epoxy groups may react directly with the PEG, thus eliminating the need to functionalize the PEG with bromine.
4.2.3 METHODS OF SOP PRODUCTION
The inventors developed a method for creating a PF/PEG resin utilizing the commercially-produced PF resole. The first step was to optimize the production of the PEG halide. It was determined that the halide PEG-Br (formed with an excess of H2SO4 and NaBr) could be created more efficiently than the PEG-C1. Reaction conditions of about 70°C for about 1 hour were found to be most useful for preparation of the PEG-Br component, although the temperature of the reaction could vary from ambient temperature to about 100°C or so without serious adverse affects to the PEG-Br. Likewise, the time of reaction may be on the order of from about 30 min to about 10 hr or so depending upon the reaction temperature. At higher temperatures, less time is required for reaction, while at lower temperatures, longer reaction times are contemplated. Regardless of the reaction conditions, the desirable product is a viscous flowable solution. The PEG-Br may be formed directly by the addition of HBr to the PEG or be addition of NaBr with an excess of H2SO4. The second step was to optimize conditions for reacting the PEG-Br with the commercial PF. A series of formulations varying in a number of parameters (PEG:PF:Br, pH, curing time and temperature) were created and tested visually and mechanically. In small scale, approximately 45 g of the PF resole is reacted with 5 g of the PEG-Br component in the presence of about 8 g of NaOH and sufficient water to thorougly mix the components and control the overall exothermic nature of the reaction. Typically agitating the mixture thoroughly for a period of from about 1 to about 3 hrs is most desirable with the temperature of the reaction being controlled to less than about 100°C. The resulting SOP (the PF-PEG product) changes color to a somewhat milky appearance, but nevertheless remains a viscous flowable solution.
4.2.4 USES OF SOP
Although the SOP compounds have utility based on their chemical properties, in preferred embodiments, the SOP is bound to a matrix, support, or substrate to form a SOP composition. Binding of the SOP to a support in such a way as to maintain the chemical properties of the compound while gaining one or more physical properties of the support increases the utility of the compounds.
4.3 SOP COMPOSITIONS
Although the SOP compounds of the present invention may have utility without being bound to a substrate, in preferred embodiments the SOP compounds of the present invention are bound to a matrix or substrate. The binding of the compound to a matrix may provide the compound with a property of the matrix. This property may be weight, size, stability, shape, pliability, or magnetism. Although porous substrates may be used, the inventors contemplate that porous substrates are not preferred because much of the SOP fills the pores and, therefore, is not on the surface of the SOP composition. Because the inventors contemplate that only surface
SOP is functional in the present invention, the porous substrates may not be an efficient use of the SOP compound.
In preferred embodiments, the matrix is filtercake, rocks, gravel, pebbles, sand, clay, silicate, silica gel, zeolite, or metal (including iron filings).. In the most preferred embodiment, the matrix is sand. However, the inventors contemplate that the compounds of the present invention also may be bound to synthetic compounds such as plastics (polystyrene or polypropylene), resins, beads, glass, ceramics, fiber filter, fiberglass and the like. The SOP is typically sprayed, coated, aerosolized, or otherwise applied to the particular substrate and then cured at a temperature of from about 100°C to about 180°C for a period of time from about 5 min to about 5 hr. In a preferred embodiment, the curing temperature is about 180°C for about 10 min. Following curing, the SOP must be returned to a neutral or slightly acidic pH before use. Typically, after application to the substrate, the SOP is contacted with a suitable acid (such as H2SO4 or HCI) to reduce the pH to about 7.0, although in some embodiments, SOP compositions with a pH of as low as about pH 5.0 have been quite effective as organic adsorbants. Neutralization of the SOP produces a striking color change in the SOP composition from a dark bluish-black color to a bright reddish- orange material. The SOP has been shown to be stable and active for a period of time of at least 1 to 2 years, with excellent activity remaining after 6, 12, or even 18 or more months. The SOP composition once cured and neutralized is shelf-stable at room or outdoor ambient temperatures, and does not appear to be reduced in capacity by either moisture or dessication.
4.3.1 METHODS OF MAKING SOP FILTERCAKE COMPOSITIONS
Because it was determined that the creation of a stable and effective filtercake (FC) pellet requires that the final product be 30% resin by weight, the potentially less expensive alternative of coating sand grains with resin was determined. By using sand, only 5% (by weight) of the final product is resin. Other advantages of using sand as the base media rather than FC include not worrying that the FC will catch fire at the curing temperature of the resin. Because it is preferable to add the resin to a dry substrate, more time and energy is required to dry FC than is needed for sand. An adjustment of pH is required for proper curing of the resin. Far more reagent is required to shift the pH of the highly buffered FC than is required for sand. Finally, when made with sand, the final product does not require milling to achieve proper grain size.
4.3.2 USES OF SOP COMPOSITIONS
In the broadest sense, the SOP compositions are used in the adsorption of organic compounds. In preferred embodiments the compositions comprise an apparatus that is able to remove organic compounds from the environment or contaminated aqueous solutions. These embodiments include sport fields, agricultural fields, filters, water treatment facilities, barriers, etc. In the most prefened embodiment, the apparatus is a golf course green. The inventors further contemplate that the SOP compositions need not be a component of an apparatus and may be applied directly to an organic compound for purposes of adsorbing the compound.
4.4 SOP COMPRISING APPARATUS
As mentioned above, prefened embodiments of the present invention include apparatuses comprising one or more SOP compositions of the present invention. Such apparatuses include, but are not limited to, sports fields (golf greens, football fields, etc.), agricultural fields (vineyards, crops, etc.), lawns, filters, water treatment systems, and barriers. In the most prefened embodiment, the apparatus is a golf green comprising one or more SOP compositions. Essentially any apparatus comprising an SOP compound or composition able to bind organic compounds is believed to be within the scope of this invention.
4.5 REMOVAL OF ORGANIC COMPOUNDS BY SOP COMPOSITIONS
Following is a brief discussion of various organic compounds which represent potential sources for environmental pollution and, therefore, represent targets for SOP-based remediation.
Because of the worldwide use of pesticides for a variety purposes including the control of agricultural, household, forestry, industrial, stored product, and veterinary pests, the eventual emergence of these compounds in environmentally sensitive areas is nearly inevitable. The presence of these compounds in water sources leads to contact by wildlife and man. Although, as a general rule, herbicides are not as toxic to man as insecticides, rodenticides and nematicides, each can accumulate in the body and kill when certain concentrations are reached. The inventors contemplate that the present invention in all of its embodiments will greatly decrease the level of organic pesticides in the environment.
4.5.1 HERBICIDAL COMPOUNDS In an important embodiment, the present invention may be used to bind herbicidal compounds and prevent the dispersal of these compounds in the environment. Many herbicidal compounds are well known and may be placed into groups based on their chemical structure. Such structural groups, as noted by Tekel and Kovacicova (1993) and included herein by reference, include the triazines, the phenylureas, the carbamates, the phenoxyalkanoic acids, the aryloxyphenoxypropanoic acids, the sulphonylureus, the bipyridylium cations, the uracils, the pyridazines, the amides, the dinitroanilines, the benzonitriles, triazinone, the cyclohexanediones, and others (Tekel and Kovacicova, 1993; Tadeo et al., 1996; Gronwald, 1994). For example, herbicidal compounds commonly used on USGA golf greens and their properties are listed at the internet address http://www.usga.org/green.
4.5.1.1 TRIAZINES AND TRIAZINONES
Herbicides belonging to the triazine class make up nearly 30% of all herbicides applied in agriculture (Tekel and Kovacicova, 1993). Because of their wide use and their stability, they tend to be the herbicides most frequently found in environmental samples. Triazines have been used in non-cropped land and in a variety of crops to control many grass and broad-leaf weeds. Triazines have the general formula as shown:
Figure imgf000027_0001
Triazines
Figure imgf000028_0001
Examples of triazines and triazinones include, but are not limited to, Ametryn, Atrazine, Cyanazine, Desmetryn, Metamitron, Metoprotryn, Metribuzine, Prometryn, Propazine, Simazine, Terbuthylazine, and Terbutryn (Tekel and Kovacicova, 1993).
4.5.1.2 PHENYLUREAS
Phenylureas represent another large class of organic compounds which often provide environmental hazards where they are applied. Phenylureas have the general formula:
Figure imgf000028_0002
Although employed since the early fifties, use of phenylureas has increased recently to replace the more persistent triazine compounds. Examples of phenylureas include, but are not limited to, Buturon, Chlorbromuron, Chloroxuron, Chlorotoluron,
Diphenoxuron, Diuron, Fenuron, Fluometuron, Isoproturon, Linuron, Metabenzthiazuron (Methabenzthiazuron), Metobromuron, Metoxuron, Mono linuron,
Monuron, Neburon, Siduron, and Thiazafluron (Tekel and Kovacicova, 1993).
4.5.1.3 CARBAMATES
Carbamate pesticides include herbicides, insecticides, acaracides, and fungicides. Thiocarbamates are used as herbicides in maize and wheat and are often used in conjunction with an antidote (Tadeo et al., 1996). The general structure of the thiocarbamates are:
Figure imgf000029_0001
Thiocarbamates Examples of carbamates include, but are not limited to, Chlorpropham,
Desmedipham, EPTC, Phenmedipham, Propham, and Triallate (Tekel and Kovacicova, 1993).
4.5.1.4 PHENOXYLKANOIC ACIDS Phenoxyalkanoic acids, also known as phenoxyacids, are the oldest group of synthetic herbicides and are still used today in the control of weeds in cereal crops. Although use of these compounds has dwindled recently, the low cost of these compounds insures their continued use. Phenoxyacids have the general formula of:
Figure imgf000029_0002
Phenoxyacids Examples of phenoxylkanoic acids include, but are not limited to, 2,4,5-T,
2,4,5-TB, 2,4-D, 2,4-DB, 2,4-DP, Dichlorprop, Diclofop, Fenoprop (2,4,5-TP), Fenoxaprop, Haloxyfop, MCPA, MCPB, Mecoprop (MCPP), and Quazalofop(Tekel and Kovacicova, 1993).
4.5.1.5 ARYLOXYPHENOXYPROPANOIC ACIDS
Aryloxyphenoxypropanoic acids, often termed phenoxyphenoxys, are more recently developed pesticides that decompose rapidly leaving the conesponding free acids as the main metabolites (Tekel and Kovacicova, 1993). Examples of aryloxyphenoxypropanoic acids include, but are not limited to, Fluazifop-butyl, Haloxyfop-ethoxyethyl, and Quazalofop-ethyl (Tekel and Kovacicova, 1993).
4.5.1.6 SULPHONYLUREAS
Developed in the 1970s by DuPont, sulphonylureas are generally used for weed control of cereal crops. They are highly effective and, therefore, require a low application dose. An excellent review of their properties, mode of action, degradation
, and persistence in soil is provided by Blair and Martin (1988). Sulphonylureas have the general formula:
Figure imgf000030_0001
Sulphonylureas
Examples of sulphonylureas include, but are not limited to, Bensulphuron- methyl, Chlorimuron-ethyl, Chlorsulfuron, Metsulfuron, Metsulphuron-methyl, Sulphometuron-methyl, Triasulfuron, and Tribenuron (Tekel and Kovacicova, 1993).
4.5.1.7 BIPYRIDINIUM CATIONS
Bipyridinium cations are membrane destroyers and are widely used weed killers that are highly toxic to mammals. Examples of bipyridinium cations include, but are not limited to, Diquat and Paraquat (Tekel and Kovacicova, 1993).
4.5.1.8 URACILS
Along with the triazines and phenylureas, uracils are photosynthetic inhibitors. Examples of uracils include, but are not limited to, Bromacil, Lenacil, and Terbacil (Tekel and Kovacicova, 1993). Bromacil is commonly used for general vegetation control. Terbacil is often applied to established mint and alfalfa. 4.5.1.9 PYRIDAZINE
An example of a pyridazine includes, but is not limited to, Chloridazone (Tekel and Kovacicova, 1993).
4.5.1.10 ANILIDES
Anilides are amides which are often used for the pre-emergence control of annual grass and certain broad-leaf weeds and are often applied in mixtures with atrizine in maize (Tadeo et al., 1996). Amides have the general chemical formula:
Figure imgf000031_0001
Amides
Examples of anilides include, but are not limited to, Acetochlor. Propachlor, Dimethenamid, Chloroacetamides, Alachlor, and Metolachlor (Tadeo et al., 1996).
4.5.1.11 DlNITRO ANILINES Dinitroanalines are used on a wide variety of crops, but particularly in winter and spring cereals (Tadeo et al., 1996). They are scarcely found in surface or underground water because of their low water solubility and high lipophilicity (Tadeo et al., 1996). These compounds have the general formula:
Figure imgf000031_0002
Dinitroanilines Examples of dinitroanilines include, but are not limited to, Butralin, Ethalfluralin, Pendimethalin, and Trifluralin (Tadeo et al., 1996).
4.5.1.12 BENZONITRILES
These compounds are frequently applied in combination with phenoxyacids to broaden the range of weeds controlled. Benzonitriles have the general formula:
Figure imgf000032_0001
Examples of benzonitriles include, but are not limited to, Bromoxynil and Ioxynil (Tadeo et al, 1996).
4.5.1.13 CYCLOHEXANEDIONES
Cyclohexanediones are used for post-emergence control of grass weeds in certain broadleaf crops and are frequently refened to as graminicides. Examples of cyclohexanediones include, but are not limited to, Sethoxydim, Clethodim, and
Tralkoxydim (Gronwald, 1994).
4.5.1.14 OTHER HERBICIDES
Examples of herbicides that are not included in the above structural groups are, but are not limited to, Bentazone and 3-(2,4-dichloro-phenyl)-perhydroindolizine-
2,4-dione.
4.5.2 HERBICIDE TOXICITY
As mentioned above, the wide-spread use of herbicidal compounds may likely lead to the eventual emergence of these compounds in environmentally sensitive areas and contact with wildlife or man. These chemicals can be toxic through contact with the skin (dermal), by ingestion (oral) and by breathing (inhalation). Table 1 lists some common herbicides and gives the oral and dermal toxicity rating for each (Florida Agricultural Information Retrieval System, http://hammock.ifas.ufl.edu/txt/fairs/40158). LD50 means the amount of material that will generally kill 50% of the animals in a study (rats, mice or rabbits, usually). LD50 values given here are for rats, unless otherwise specified. Sex of the animal was not specified unless indicated. Values preceded by "greater than" (>) mean the LD50 is higher than the quoted figures, which were the highest amounts tested.
TABLE 1
HERBICIDE TOXICITY
Chemical Oral (mg/kg) Dermal (mg/kg)
Acrolein, Aqualin 46 S
Aero Cyanate, potassium cyanate, 841-850 —
KOCN
Aero Cyanamide, calcium cyanamide 1400 (rabbits) —
Alanap, NPA, N-l -naphthyl 2000-8500 N phthalamic acid
Alipur-O, cycluron 1500 — allyl alcohol 64 89 (rabbits)
Amiben 3500-5620 3136 (rabbits)
Amitrole, Amizol 5000-14,700 > 10,000 (rabbits)
Amitrole and ammonium thiocyanate, 5000 —
Cytrol
Ammonium sulfamate, AMS, Animate 1600-3900 N
Ansar 184, disodium methanearsonate, 2800 N
Sodar
Ansar 157, MSMA 750 N TABLE 1 - (CONTINUED)
Ansar 170, MSMA, monosodium acid 700-1800 — methanearsonate
Aqualin, acrolein 46 S
Arsan, cacodylic acid, Phytar 138 1350 N
Atlacide, sodium chlorate 1350-1940 (fatal to cats) M
Atlas A, sodium arsenite 10-50 M
Atratone 2400 —
Atrazine 3080 N
Avadex, diallate 395 M
Avadex BW, triallate 1675-2161 2225-4050 (rabbits)
Balan, benefin > 10,000 N
Bandane 575 > 12,000
Banvel D, dicamba 1040 — barban, Carbyne 1300 N
Baron, erbon 1120 M benefin, Balan > 10000 N bensulide, Betasan, Prefar 770 (males) > 3950 (rabbits)
Benzac, 1281, 2,3,6-TBA acids and 750-1644 1000 salts, Trysben
Betasan, bensulide, Prefar 770 (males) > 3950 (rabbits)
Bluestone, copper sulfate est. 15,000 (lethal to S humans)
Bromocil, Hyvar-X 5200 M
Bromoxynil, Buctril 270 —
Butyrac l l8, 2,4-DB 400 (mice) —
Cacodylic acid, Arsan, Phytar 138 1350 N
Calcium arsenate, Kalo 35-100 M
Calcium chlorate 4500 —
Calcium cyanamide, Aero Cyanamide 1400 (rabbits) — TABLE 1 - (CONTINUED)
Can-Trol, MCPB, sodium salt 700 1000
Caparol 80W, prometryne 3750 N
Carbyne, barban 1300 N
Casoron, dichlobenil > 3160 500 (rabbits)
CDAA, Randox 700 M
CDEC, Vegadex 850 M
Chlordane 335 (males) 430 840 (males) 690
(females) (females)
Chloro IPC, CIPC 5000-8000 N
Copper sulfate, Bluestone est. 15,000 (lethal to S humans)
4-CPA, parachlorophenoxyacetic acid 300-700 —
Crab-E-Rad, ocytl ammonium methyl 600-794 — arsonate, Diama
Crag DCU, dichloral urea > 31,600 —
Cycluron, Alipur-O 1500 —
Cytrol, amitrole and ammonium 5000 — thiocyanate
Dalapon, Dowpon, Radapon 3860-9000 M
Dacthal > 3000 > 10,000 (rabbits)
2,4-D acid, Weedone 638 375 1500
2,4-DB, Butyrac l l8 400 (mice) —
2,4-D butyl ester, Esteron 76 BE 620 500
2,4-DEP, Falone 44E 850 M
2,4-DES, sesone 1000 —
Des-I-Cate, endothal 38-206 750
Diama, octyl ammonium methyl 600-794 — arsonate, Crab-E-Rad diallate, Avadex 395 M TABLE 1 (CONTINUED) dicamba, Banvel D 1040 — dichlobenil, Casoron 3060 500 (rabbits) dichloral urea, Crag DCU > 31,600 — dichlorprop, 2-(2,4-DP) acid 400 (mice) 1400 dicryl 1800-3160 10,000 (rabbits) diphenamid, Dymid, Enide 1048-1798 > 6320 diquat 400-440 > 500 (rabbits) disodium methanearsonate, Ansar 184, 2800 N
Sodar
2,4-D isopropyl ester, Esteron 76-E 700 — diuron, Karmex 3400 M
DMTT, Mylone 500-650 M
DN-289, dinitrobutylphenol, dinoseb, 37-60 500 (guinea pigs)
Elgetol 318
Dowicide 7, Penta PCP 125-210 150-350
Dowicide G, Penta sodium salt 78-218 257
Dowpon, dalapon, Radapon 3860-9000 M
2-(2,4-DP) acid, dichlorprop 400 (mice) 1400
2,4-D sodium salt 666-805 —
Dybar, fenuron 6400 M
Dymid, diphenamid, Enide 1048-1798 > 6320 endothall, Des-I-Cate 38-206 750
Enide, diphenamid, Dymid 1048-1798 > 6320
Eptam 1630 (males) 3160 2641 (rabbits)
(females) erbon, Baron 1120 M
Esteron 76 BE, 2,4-D butyl ester 620 800 Esteron 76 E, 2,4-D isopropyl ester 700 — Falone 44E, 2,4-DEP 850 M TABLE 1 - (CONTINUED) fenac 1780-3000 > 3160 (rabbits) fenuron Dybar 6400 M fenuron TCA, Urab 5700 (males) 4000 M (females)
Herban, norea 1470 23,000 hexachloracetone, HCA Weed Killer 1290-1550 M
Hyvar, isocil 3250 M
Hyvar-X, bromacil 5200 M
IPC, propham 9000 N imazethapyr, Pursuit >5000 mg/kg (rats) >2000 mg/kg (rabbits) isocil, Hyvar 3250 M
Kalo, calcium arsenate 35-100 M
Karmex, diuron 3400 M
Kloben, neburon > 11,000 M
KOCN, potassium cyanate, Aero 841-850 —
Cyanate
Kuron, silver, 2-(2,4,5-TP) ester 650 — linuron, Lorex 1500 M maleic hydrazide amine, MH-30 2340 4000 (rabbits) maleic hydrazide sodium salt, MH-40 6950 4000 (rabbits)
MAMA, Ansar 157 750 N
MCPA acid 700 > 1000
MCPA amine 1200 > 1000
MCPB sodium salt, Can-Trol 700 1000
MCPP sodium salt, Mecoprop 650 —
MH-30, maleic hydrazide amine 2340 4000 (rabbits)
MH-40, maleic hydrazide sodium salt 6950 4000 (rabbits) TABLE 1 - (CONTINUED) molinate, Ordram 501 (males) 660 > 2000 (rabbits) (females) monosodium acid methanearsonate, 700-1800 —
MSMA, Ansar 170 monuron, Telvar 3500-3600 N monuron, TCA, Urox 3700 (males) 2300 > 1000
(females)
MSMA, monosodium acid 700-1800 — methanearsonate, Ansar 170
Mylone, DMTT 500-650 M neburon, Kloben > 11,000 M
N-l -naphthyl phthalamic acid, Alanap, 2000-8500 N
NPA nitraline, Planavin 2000 2000 (rabbits) norea, Herban 1470 23,000
NPA, Alanap, N-l -naphthyl 2000-8500 N phthalamic acid octyl ammonium methyl arsonate, 600-794 —
Diama, Crab-E-Rad
Ordram, molinate 501 (males) 660 > 2000 (rabbits)
(females) parachlorophenoxyacetic acid, 4-CPA 300-700 paraquat 157 M
PCP, Penta, Dowicide 7 125-210 150-350 pebulate, Tillam 1120 (males) > 2936 (rabbits)
Penta, Dowicide 7, PCP 125-210 150-350
Penta sodium salt, Dowicide G 78-218 257 phenyl mercuric acetate, PMA, Scutl 30 S
Phytar 138, cacodylic acid, Arsan 1350 N TABLE 1 (CONTINUED) picloram, Tordon 8200 (females) > 4000 (rabbits) piperalin, Pipron 2500 > 2500 (rabbits)
Planavin, nitralin 2000 2000 (rabbits) polychlorobenzoic acid, Zobar 960-1140 M potassium cyanate, KOCN, Aero 841-850 —
Cyanate
PMA, Scutl, phenyl mercuric acetate 30 S
Pramitol, prometone 2980 N
Prefar, bensulide, Betasan 770 (males) 3950 (rabbits) prometone, Pramitol 2980 N prometryne, Caparol 80W 3750 N propanil, Stam F-34, Rogue 560-1384 7080 (rabbits) propazine > 5000 N prophan IPC 9000 N pyrazon, Pyramin 4200 (males) 2500 M
(females) pyridate, Tough 2000 mg/kg (rats) 3400 (rabbits) quizalofop, Assure 1670 mg/kg (male rats)
1480 mg/kg (female rats)
Radapon, dalapon, Dowpon 3860-9000 M
Randox, CDAA 700 M
Rogue, propanil, Stam, F-34 560-1384 7080 (rabbits)
Scutl, PMA, phenyl mercuric acetate 30 S sesone, 2,4-DES 1000 — siduron, Tupersan > 7500 > 5500 silvex, 2-(2,4,5-TP) ester, Kuron 650 — simazine > 5000 N TABLE 1 - (CONTINUED)
SMDC, Vapam, VPM 820 800 (rabbits)
Sodar, disodium methanearsonate, 2800 N
Ansar 184 sodium arsenite, Atlas A 10-50 M sodium chlorate, Atlacide 1350-1940 (fatal to cats) M sodium TCA 3370-5000 M
Stam F-34, propanil, Rogue, 560-1384 7080 (rabbits) sulfuric acid 1 oz. lethal to humans S
2,4,5-T acids and esters 481-500 —
2,3,6-TBA acids and salts, Trysban, 750-1644 1000
Benzac 1281
Telvar, monuron 3500-3600 N
Tillam, pebulate 1120 (males) > 2936 (rabbits)
Tordon, picloram 8200 (females) 4000 (rabbits)
2-(2,4,5-TP) ester, silvex, Kuron 650 —
Treflan, trifluralin 3700- > 10,000 > 5000 triallate, Avadex BW 1675-2161 2225-4050 (rabbits)
Trysben, Benzac 1281, 2,3 ,6-TBA 750-1644 1000 acids and salts
Tupersan, siduron > 7500 > 5500
Urab, fenuron TCA 5700 (males) 4000 M (females)
Urox, monuron TCA 3700 (males) 2300 > 1000 (females)
Vapam, VPM, SMDC 820 800 (rabbits)
Vegadex, CDEC 850 M
VPM, Vapam, SMDC 820 800 (rabbits)
Weedone 638, 2,4-D acid 375 1500
Zobar, polychlorobenzoic ; acid 960-1140 M aAcute LD50 values for rates in mg of substance per kg of body weight of test animal. (S = severe skin irritation; N = little or no skin irritation; M = mild skin initation).
4.5.3 INSECTICIDES
As described, the present invention may be used to bind insecticidal compounds and prevent the dispersal of these compounds in the environment. In recent years compounds have been formulated and their use in the grants a possible need for remediation. Aldicarb, Allethrin, Ambush, Aminocarb, APM, Basudin, Bioallethrin, Bioremethrin, Biphenthrin, Bufencarb, Butacarb, butoxide, Carbanolate,
Carbaryl, Carbofuran, Cinerin I, Cinerin II, Counter, Cyfluthrin, Cygon, Cyhalothrin, Cymbush, Cypermethrin, Cythion, Dasanit, Decis, Deltamethrin, Diazinon, Dibrom, Dimethoate 480, Dioxacarb, Dipel, Dyfonate, Dylox, Endosulfan, Ethidimuron, Fenpropathrin, Fenvalerate, Flucyrintae, Fluvalinate, Furadan, Guthion, Hopper Stopper, Imidan, Jasmolin I, Jasmolin II, Lagon, Lannate, Lorsban, Malathion,
Metasystox-R, Methomyl, Methoxychlor, Mexacarbate, Monitor, Ortho, Oxamyl, Parathion, Permethrin, Piperonyl, Pirimor, Pounce, Promecarb, Pyrethrin I, Pyrethrin II, Pyrinex, Resmethrin, Ripcord, Sevimol, Sevin, Sniper, Supracide, Tetramethrin, Thimet, Thiodan, and Tralomethrin are among the compounds that have been utilized recently for insect control (Chen and Wang, 1996; Yang et al, 1996, Saskatchewan
Agriculture and Food Crop Protection Guide 1997, http://www.gov.sk.ca/agfood/cpg/iccont.htm). Insecticidal compounds commonly used on USGA golf greens and their properties are listed at the internet address http://www.usga.org/green/table3.html.
4.5.4 FUNGICIDES
Fungicidal compound use and the dispersal of these compounds in the environment represent a potential biological hazard. Fungicides such as Benomyl, Captan, Chlorothalonil, Copper Sulfate, Cyproconazole, Dodine, Flusilazole, Fosetyl- Al, Gallex, Mancozeb, Metalaxyl, Prochloraz, Propiconazole, Tebuconazole,
Thiophanate Methyl, Triadimenol, Tridimefon, Triphenyltin hydroxide, and Ziram have been utilized (Shishkoff, http://www.bonsaiweb.com/forurn/articles/arts/fungicide.html; http://cygnus.tamu.edu/Texlab Nuts/Pecan/pecanf.html; Hollomon, 1993) Additional, fungicidal compounds, including trade and common names, may be found in Table 2 (http://www.missouri.edu/~extbsc/turf/fundesc.htm, incorporated herein by reference). Areas such as agricultural, turf, and sport fields (golf course, tennis lawns, etc.) frequently are treated with substantial amounts of organic fungicides. Fungicidal compounds commonly used on USGA golf greens and their properties are listed at the internet address http://www.usga.org/green/table3.html.
4.5.5 NEMATICIDES
In another important embodiment, the present invention may be used to bind nematicidal compounds and prevent the dispersal of these compounds in the environment. Many nematicidal compounds are well known. Fenamiphos, an anticholinesterase compound, (Nemacur®, Bayer Crop
Protection, Kansas City, MO) is widely used for nematode control on soils, and in particular golf course greens and fairways. There are few labeled alternatives to this pesticide. Snyder and Cisar (1993) observed considerable leaching of fenamiphos metabolites (sulfoxides and sulfones) following fenamiphos application to a USGA green. Leaching of the metabolites, and to a lesser extent the parent compound, greatly exceeded that of all other organophosphates examined (Snyder and Cisar, 1995). Because fenamiphos has been observed in waters in or adjacent to golf courses (Swancar, 1996), and because of a highly-publicized fish kill (Zaneski, 1994), regulations have been issued for limiting fenamiphos use on golf courses. In related studies, considerable leaching of pesticides such as dicamba and 2,4-D have been observed in agricultural and commercial turf grasses (Snyder and Cisar, 1997).
Temik® 15G (aldicarb) and Mocap® 10G and Mocap® EC (ethoprop) (Rhone-Poulenc Ag Products) are non-fumigant granular nematicides that are often recommended for agricultural application. Likewise, the liquid fumigant, Telone II® (1,3-dichloropropene, Dow AgroSciences, Indianapolis, IN) is also used as a nematicide in many areas. Other nematicidal compounds include Scotts' Pro-Turf Nematicide/Insecticide 5G, fensulfothion, Dasanit 15G, chitin and other organic nitrogen sources, Clandosan 618 25G, methyl bromide 68.6% + chloropicrin 1.4%, Brom-O-Sol 70, methyl bromide 67% + chloropicrin 33%, Ten-O-Gas 67, dichloropropene + methyl isocynate, Vorlex, metam-sodium, Vapam, dischlopropene + chloropicrin, Telone C- 17, Ten-O-Cide 30D, dazomet, Basamid 99G, (Hagan, http://www.acesag.aubum.edu department ipm/Nematode.htm, incorporated herein by reference). Additional, nematicidal compounds, including trade and common names, may be found in Table 2 (http://www.missouri.edu/~extbsc/turf/fundesc.htm, incorporated herein by reference). Many of the nematicidal compounds that are commonly used on USGA golf greens and their properties are listed at the internet address http://www.usga.org/green.
TABLE 2 TURFGRASS FUNGICIDES AND NEMATICIDES
Trade Name Common Name
Aliette fosetyl-Al
Apron 25W metalaxyl
Banol propamocarb hydrochloride
Banner propiconazole
Bayleton 25W triadimefon
Benomyl WP benomyl
Calo-clor inorganic mercuries
Calo-gran inorganic mercuries
Captan captan
Chipco 26019 iprodione
Curalan DF vinclozolin
Daconil 2787 chlorothaloni
Dithane M-45, F-45 and DF mancozeb
Duosan 75WP thiophanate methyl plus mancozeb
Fore 80WP mancozeb Trade Name Common Name
Formec 80WP mancozeb
Fungo 50WP and FL thiophanate methyl
Granular Turf Fungicide triadimefon
Koban etridiazole
Mancozeb DG mancozeb
Manzate 200DF mancozeb
Nemacur® fenamiphos
Pace metalazyl plus mancozeb
PCNB 10% Granular PCNB
Penncozeb mancozeb
Prostar flutolanil
Rubigan fenarimol
Scotts Fluid Fungicide II triadimefon plus metalaxy
Scotts Fluid Fungicide III triadimefon plus thiram
Scotts Fluid Fungicide V chloroneb
Scotts Fluid Fungicide V iprodione
Scotts Fungicide VII triadimefon
Scotts Pythium Control metalaxyl
Scotts Systemic Fungicide thiophanate methyl
Spotrete-F and 75WDG thiram
Subdue G metalaxyl
Teremec SP chloroneb
Tenaclor 75WP and 4.5FL PCNB
Tenaneb SP chloroneb
Tenazole etridiazole
Tersan 199 IDF benomyl
Thiramad 75WP thiram
Topsin M, 70WP and 4.5FL thiophanate methyl
Touche vinclozolin
Turfcide PCNB Trade Name Common Name
Twosome chlorothalonil plus fenarimol
Vorlan 50WP and FL vinclozolin
3336WP thiophanate methyl
4 Flowable mancozeb
4.6 INDUSTRIAL REMEDIATION
Besides pesticides, the chemical nature of the present invention provides for its ability to bind a large variety of organic compounds. Therefore, the inventors contemplate that the present invention may be used to bind organic compounds to prevent their dispersal in the environment or to facilitate the "cleanup" of such compounds in the event of a spill. Furthermore, the inventors contemplate that the present invention may be used to remove an organic compound from a solution.
Patent 4,147,624 discloses a list of organic compounds that are removable from a water stream by adsorption on polymeric adsorbents and is incorporated herein by reference. This list is provided by Table 3. The inventors contemplate that the compounds, compositions, and methods of the present invention may be used to remove one or more compounds of Table 3 from an aqueous solution.
TABLE 3
EXEMPLARY CLASSES OF ORGANIC COMPOUNDS REMOVABLE FROM AQUEOUS SOURCES BY ADSORPTION ON SOP COMPOSITIONS
Alcohols
Hexyl 2-Ethylhexanol
2-Octanol
Decyl
Dodecyl
Benzyl Cinnamyl
2-Phenoxyethanol Aldehydes and Ketones
2,6-Dimethyl-4-heptanone
2-Undecanone
Acetophenone Benzophenone
Benzil
Benzaldehyde Esters
Benzyl acetate Dimethoxyethyl phthalate
Dimethyl phthalate
Diethyl phthalate
Dibutyl phthalate
Di-2-ethylhexyl phthalate Diethyl fumarate
Dibutyl fumarate
Di-2-ethylhexyl fumarate
Diethyl malonate
Methyl benzoate Methyl decanoate
Methyl octanoate
Methyl palmitate
Methyl salicylate
Methyl methacrylate Polynuclear aromatics
Naphthalene
2-Methylnaphthalene
1 -Methylnaphthalene
Biphenyl Fluorene
Anthracene Acenaphthene
Tetrahydronaphthalene Alkyl benzenes
Ethylbenzene Cumene p-Cymene Acids (acidified)
Octanoic
Decanoic Palmitic
Oleic
Benzoic Phenols
Phenol o-Cresol
3,5-Xylenol o-Chlorophenol p-Chlorophenol
2,4,6-Trichlorophenol 1-Naphthol
Ethers
Hexyl
Benzyl
Anisole 2-Methoxynaphthalene
Phenyl Halogen compounds
Benzyl chloride
Chlorobenzene Iodobenzene o-Dichlorobenzene m-Dichlorobenzene 1 ,2,4,5-Tetrachlorobenzene o-Dichlorotoluene m-Chlorotoluene 2,4-Dichlorotoluene
1 ,2,4-Trichlorobenzene Nitrogene compounds Hexadecylamine Nitrobenzene Indole o-Nitrotoluene N-Methylaniline
Benzothiazole Quinoline Isoquinoline
Benzonitrile Benzoxazole
4.7 SPILL CLEANUP Due to the widespread use of pesticides and other organic compounds, accidental spills of such compounds are a common occurrence. The present invention provides for a simple, economical method for cleaning up spills at the source. In the event of a spill, the inventors contemplate that the present invention may be applied to the spill as an adsorbent compound. This compound, applied as a particulate, such as sand, clay, "cat litter-like" substance, etc., may be used by individuals in the household or to adsorb more substantial industrial spills. After application, the adsorbent may be collected and disposed of without the worry of the compound being dispersed into the environment following disposal.
The particulate may be applied directly to the spill or used to form a physical barrier at a perimeter around the spill. This barrier would essentially function as a containment or "fire" wall, preventing the spread of the spill. In another embodiment, the cunent invention may be used as part of a barrier to prevent one or more organic compounds or pesticides from entering surface water. In this embodiment, the barrier may be a fence- or wall-like structure that is placed between the spill, or area of application, of one or more organic compounds or pesticides and surface water (FIG. 5A). The surface water may be a puddle, creek, river, reservoir, pond, lake, sea, or ocean. The present invention may be used to prevent one or more organic compounds or pesticides from entering subtenanean water such as aquifers, groundwater, well heads, well casing, or well water (FIG. 5B). The inventors contemplate that the source of the spill may be from nearly any individual or commercial facility that uses, transports, stores, manufactures, or unearths organic compounds. For example, the compositions of the present invention may be used in the petroleum industry from drilling of the wells, to the continued pumping of oil from the ground, to oil refineries, to storage of the processed petroleum products, to transportation of the product, to the distribution of the product to the individual user, to the use of the product by the individual user. In an exemplary embodiment, the inventors contemplate that the compositions of the present invention may be used as an amendment to the soil sunounding an underground gasoline storage tank to reduce the impact of leakage on the environment. Of course, the compound stored underground may be other organic compounds and need not be gasoline.
In yet another embodiment, the inventors contemplate the use of the present invention in strip mining and ore processing. The compounds of the present invention may be applied to the organic compounds used in these processes to prevent their further dispersal into the environment.
4.8 PESTICIDE MANAGEMENT FOR SPORTS FACILITIES AND TURF GRASSES 4.8.1 SPORTS FACILITIES
Although the nature and design of golf courses prevent much of the pesticides from reaching ground and surface water, occasionally contamination of these waters occurs. Furthermore, even residual contamination may accumulate over time. Therefore, any measures that may be taken to reduce the environmental impact of the application of pesticides to golf courses should be considered.
A golf course may be designed comprising one or more sops or SOP compositions of the present invention to decrease the level of pesticides or their metabolites from entering ground and surface water. The sops or SOP compositions of the present invention may be added as an amendment to one or more layers of the soil of a golf course or may be a component of a water treatment system or filter through which the water of a golf course flows.
A critical problem with the design of a golf course is maintaining high percolativity or high rate of conductivity. It is desirable that water applied to a course readily pass through the soil. Prior attempts have been made to add clays, thatch, etc. to subtenanean layers of a golf green, but these materials were shown to decrease the conductivity of the green and, therefore, were undesirable. When used as a soil amendment, the inventors contemplate that one or more sops or SOP compositions of the present invention may be added to any of the subtenanean layers. The subtenanean layers of a golf course and their construction are well known to those of skill in the art. In prefened embodiments, one or more sops or SOP compositions of the present invention comprise the subtenanean layers of a golf green. The subtenanean layers of a USGA golf green include, starting at the surface and increasing in depth: the root zone, the intermediate layer, and the gravel drainage blanket. In prefened embodiments, one or more sops or SOP compositions of the present invention comprise the gravel drainage blanket, intermediate layers of a golf green, or the lower level of the root zone. The inventors contemplate that, although one or more sops or SOP compositions of the present invention may comprise the entire root zone, the presence of an SOP or SOP composition in the upper level may adsorb and prevent a pesticide that targets the roots or pests that reside in this area from functioning. However, in instances where the applied pesticide is not required to function in the root zone, one or more sops or SOP compositions of the present invention may comprise the upper level of the root zone without affecting the pesticidal activity. The inventors contemplate a number of methods by which the subtenanean layers of a golf green may be amended by the compounds and compositions of the present invention. In one embodiment, one or more SOP compounds may be added to the material (sand, gravel, clay, silt, etc.) that makes up a subtenanean layer of a golf green. In prefened embodiments, one or more SOP compositions may be added to the material that makes up a subtenanean layer or a golf green. In the most prefened embodiment, the SOP composition comprises sand. One or more subtenanean layers of a golf green may consist of one or more SOP compositions or may comprise of a ratio of one or more SOP compositions to "unamended" material. In prefened embodiments, the ratio of SOP composition to "unamended" material is 15% by volume.
Although prefened embodiments are golf greens comprising the compounds and compositions of the present invention, the inventors contemplate that the compounds and compositions of the present invention may be amendments to the soils of other sections of the golf course including, but not limited to, fairways, greens, tee boxes, rough, traps, ponds, range, etc.
4.8.2 SOIL AMENDMENTS
The properties of the SOP compositions of the present invention, high conductivity, inexpensive, able to bind a wide variety of organic compounds, easy to apply, uniform and adjustable size, etc., may make the compositions desirable as amendments to soils besides those of a golf course. Because other sports facilities may demand similar properties of the soil as golf courses, the inventors contemplate that the compounds and compositions of the present invention may be useful as amendments to the soil other sport fields. Such other sports include, but are not limited to, tennis, croquet, polo, horse racing, football, baseball, soccer, cricket, etc.
Furthermore, the inventors contemplate that the soil comprising the compounds and compositions of the present invention need not be that of a sports field but, rather, may be a lawn, agricultural field (i.e., garden, vineyard, pasture, crop, fruit or vegetable orchard, etc.), or any location that pesticides or other organic compounds are applied (i.e., industrial facilities, waste storage or treatment facilities, job sites, construction sites, chemical factories, weapon facilities, etc.).
Because the compounds of the present invention may be affixed to a number of substrates of different sizes and materials, the inventors contemplate that the compositions of the present invention may be used as an amendment to the soil in any instance when one desires to improve the nature of the soil. The compositions of the present invention may be added to the soil to increase the adsorption of organic compounds by the soil, to alter the percolativity of the soil, or to alter the consistency of the soil. It is common practice to add compounds to soils, particularly soils high in clay, to improve the ability of these soils to support plant growth. The inventors contemplate that the compositions of the present invention may improve upon the existing technology by providing additional benefits (i.e., pesticide adsorption).
4.8.3 DRAINAGE FILTRATION Although the prefened embodiment of the present invention is as a supplement to a golf green capable of binding pesticides applied to the green, the inventors appreciate that such a use requires implementation during building or rebuilding of the golf green. Therefore, the inventors contemplate alternative methods of preventing the leaching of pesticides in water supplies. In one such embodiment, the inventors contemplate the use of an underground pipe system that collects water at a centralized location. This may be one or more French drains. A French drain is comprised of a sloping trench lined with soil-filter fabric and filled with gravel. A perforated pipe with the perforations facing the bottom of the trench and connected to a solid drain line provides more efficient draining. Of course, other subtenanean drainage systems may be used and embodiments are not limited to French drains. In one embodiment, the SOP of the present invention may me added to the soil-filter fabric in another it may be added to the gravel. In yet another embodiment, the SOP of the present invention may be a component of a filter that the water flows through at a centralized location (FIG. 6). This filter may be constructed so that it can easily be replaced periodically. Besides under a golf green, the underground pipe-filter system may be used in other places. For example, this system may be placed underground at any section of a golf course (i.e., the fairways, greens, tee boxes, rough, traps, ponds, range, etc.), sports fields (i.e., tennis, croquet, polo, horse racing, football, baseball, soccer, cricket, etc.), lawns, agricultural field (i.e., gardens, vineyards, pasture grasses, crops, fruit and vegetable orchards, etc.), or in any location that pesticides or other organic compounds are applied such as industrial facilities, waste storage and treatment facilities, job sites, construction sites, chemical factories, and weapon facilities.
4.9 WATER, WASTEWATER, AND LEACHATE REMEDIATION 4.9.1 TREATMENT FACILITIES
The inventors contemplate that the present invention may be utilized as part of a treatment facility for any aqueous solution suspected to contain organic compounds. The source of the aqueous solution may be sewage, groundwater, wastewater, leachate, or industrial runoff. Water collected at a common facility may be contacted with the compound of the present invention to reduce the levels of organic compounds or pesticides in the water. Water treatment systems are well known to those of skill in the art and include, but are not limited to, Sequencing Batch Biological Reactor (SBA), continuous activated sludge, trickling filter, aerated lagoon, and anaerobic filter. These systems, and others, may be adapted to more efficiently treat organic compounds by the processes and compositions of this invention.
The water may be treated by flowing through a column comprising the compound of the present invention or by contacting the water with particles comprising the present invention in a batch method. The batch method comprises adding particles comprising the compound of the present invention to a water sample suspected of containing one or more organic compounds, mixing to allow sufficient contact between the particles and the organic compounds to allow binding, and separating the particles bound to the organic compounds from the newly purified water. Separation may be the product of natural gravity, centrifugation, or filtration through a size selective porous membrane. In one embodiment, the inventors contemplate that the compound of the present invention may be physically associated with a matrix susceptible to magnet forces, such as iron filings. The iron filings coated with the compound of the present invention may be utilized in the batch method thereby allowing separation of the coated filings bound to organic compounds from the water by magnetism. Separation by magnetism is faster than gravitational settling and does not require the sophisticated machinery nor volume limitation of centrifugation.
U.S. Patent 4,511,657 teaches a method of treating chemical wastes using an SBA system and is incorporated herein by reference. The patent describes one or more tanks comprising activated sludges. The activated sludges are comprised of a variety of organisms capable of metabolizing various organic compounds. The compositions of the present invention may be added to the biological organism- containing activated sludge or may be utilized in one or more separate tanks from the tank or tanks comprising activated sludge, or may be used in lieu of the biological material. The latter obviates the need to maintain the viability of living organisms. Of course, filters or other apparatuses comprising the compositions of the present invention may be used in combination with treatment systems known in the art.
4.9.2 FILTERS The inventors contemplate that the compounds of the present invention may be utilized as part of a filter. One such filter system is taught in U.S. Patent 5,685,981 (incorporated herein by reference). Filters generally have an intake port, a chamber, and an outlet port. Commonly, compounds such as activated carbon are part of the chamber and are used in filters to bind compounds in solution. Activated carbons are available in different grades with different binding activities. However, not all grades perform well in all purposes and effective grades tend to be expensive. The present invention may be used in the place of or in addition to activated carbon in the chamber of a filter system. A filter comprising one or more SOP compounds or compositions would increase the range of organic compounds capable of filtration from an aqueous solution. 4.9.3 LANDFILL LEACHATE FILTRATION
United States Patent No. 4,995,969 describes a treatment system for landfill leachate and is incorporated herein by reference. Briefly, the invention is a biological living-filter system for the treatment of sanitary landfill leachate which comprises a treatment basin which is lined with a water impervious material and filled with an organically enriched treatment medium which is conductive to maintaining a population of micro-organisms. The system also includes leachate tolerant plants growing in the treatment medium.
This system, modified to include one or more SOPs of the present invention, provides a greater range of adsorbence when compared to the system minus an SOP of the present invention. The SOP may be added to the treatment medium at concentrations disclosed herein, or it may be a component of a filter placed either prior to the application of the leachate to the treatment medium or after the leachate has transgressed the treatment medium. Alternatively, one or more SOPs of the present invention may be used in a landfill leachate treatment system similar to that taught by U.S. Patent No. 4,995,969 in lieu of the biological material. This obviates the need to establish and maintain a living ecosystem.
4.10 TIMED-RELEASE PESTICIDE COMPOSITIONS Results obtained by the inventors on the slow leaching of pesticides when bound to the SOP-sand compositions in a golf course green lysimeter suggested that in addition to use of the disclosed compositions to reduce leaching of pesticides, and in the remediation of pesticide-contaminated environmental sites, the compositions of the invention also find utility as a means of providing controlled-release ("slow- release" "timed-release", etc.) pesticide formulations. The preparation of the controlled-release product begins with the cured SOP composition described above. The polymer is contacted with the fertilizer(s) or pesticide(s) by spraying, coating, soaking, or depositing the organic compound(s) onto the polymer and then allowing the product to dry. In an exemplary embodiment, the pesticide or fertilizer may be formulated in a solvent having a low boiling point, and then contacted with the polymer under conditions such that the solvent is evaporated and the organic pesticide or organic fertilizer component is deposited onto the adsorbant. The resulting material may then be used as a controlled-release delivery vehicle for the adsorbed organics and delivered to the particular agricultural, commercial, or residential site where introduction of the fertilizer or pesticide is desired.
5.0 EXAMPLES
The following examples are included to demonstrate prefened embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute prefened modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.
5.1 EXAMPLE 1 - SOP COMPOSITIONS FOR GOLF COURSE GREENS
It is not proposed that SOP be mixed into the lower portion of the root zone mix, below the probable location of target organisms. It is statistically improbable that percolation water carrying pesticide would encounter two SOP granules when mixed at the rate of 1 liter m" (1% by volume in a 10 cm layer).
A column study was conducted to determine the effect of SOP concentration in a 10 cm layer of USGA-sand on the adsorption of fenamiphos metabolite (sulfone). It appeared that SOP should be incorporated at a rate of 15% (vol./vol.) to adsorb an amount of sulfone nearly equal to the normal application rate of fenamiphos (FIG. 1). The indication that this higher rate is required to assure contact between the SOP and the percolate, and is not due to poor adsorption of the metabolite by the SOP, was confirmed when an amount of SOP equivalent to a 1% rate was placed directly on the top of a soil column and treated directly with a solution of metabolite at the 1.125 g AI m" rate. During subsequent percolation events, no metabolite was recovered in the percolate. 5.2 EXAMPLE 2 - FILTERS
Glass columns 1.25 cm diameter by 40 cm long were filled approximately 30 cm deep with quartz sand (0.25 - 0.75 mm), after organic matter in the sand had been removed by heating in a muffle furnace at 550°C for at least two hours, and residue removed by washing with demineralized water. The sand was either unamended, or amended 15% by weight with granular zeolite, or two grades of Stabilized Organic Polymer (SOP) having particle sizes approximating that of the sand. Alternatively, the filter may be comprised of glass tubes 6 x 30 cm packed 10 cm deep with medium-size silica sand amended 15% (vol./vol.) with candidate adsorbent.
5.3 EXAMPLE 3 - PESTICIDE ADSORPTION BY SOP COMPOSITIONS
Because of the extent to which fenamiphos, and particularly fenamiphos metabolite, has been observed to leach in a USGA green, an adsorbent material within the green might prove useful for reducing or preventing groundwater contamination by fenamiphos and its metabolites. To be useful in greens, the adsorbent should not seriously impact the hydraulic conductivity of the root zone mix. Several adsorbents were evaluated in laboratory-column studies for reducing fenamiphos and fenamiphos metabolite leaching.
5.3.1 SOP
A stabilized organic polymer (SOP) was made from sugarcane filter-cake (FC) stabilized with a phenol-formaldehyde polymer and polyvinyl chloride (PVC). The resulting material was crushed and graded into batches of particles conesponding to very coarse sand (VCS; 1.0-2.0 mm), coarse sand (CS; 0.5-1.0 mm), and medium sand (MS; 0.25-0.50 mm).
5.3.2 SULFONE
Due to the unavailability of fenamiphos metabolite (sulfone), a protocol was developed for synthesizing sulfone in a pure crystalline form from fenamiphos. Fenamiphos was oxidized with aqueous potassium permanganate and the resultant sulfone was extracted into methylene chloride. After evaporation of the solvent, the crude sulfone was solubilized in ethanohwater (65:35). This solution was extracted with hexane:ether (50:50) to remove coextractants, the sulfone remaining in the ethano water phase. Pure (92%) sulfone crystals created by enrichment of the ethanol:water with water were isolated by filtration.
5.3.3 COLUMNS
Glass columns 1.25 cm diameter by 40 cm long were filled approximately 30 cm deep with quartz sand (0.25 - 0.75 mm) used for topdressing a USGA green, after organic matter in the sand had been removed by heating in a muffle furnace at 550°C for at least two hours, and residue removed by washing with demineralized water.
The sand was either unamended, or amended 15% by weight with granular zeolite, or two grades of Stabilized Organic Polymer (SOP) having particle sizes approximating that of the sand.
The columns were wetted and allowed to drip dry. A solution containing 125 and 141 μg fenamiphos and/or fenamiphos metabolite, respectively, in 140 μL was placed on the soil surface in each tube, and followed by 2 ml water. After 30 min, three 8 ml aliquots of water were applied to the soil columns, thereby simulating three precipitation events of 6.5 cm each. Leachate was collected from each precipitation event and analyzed for fenamiphos and/or metabolite by gas chromatography (GC) methods.
To determine conductivity, five hundred-ml bottles of water fitted with stoppers and glass tubes were inverted and suspended over each column to provide a constant water head of approximately 1 cm over each soil surface. Saturated hydraulic conductivity was measured over a 2-h period by collecting percolate over three or more measured time periods during the 2-h interval. Conductivity was calculated as cm hr .
5.3.4 RESULTS
Fenamiphos and metabolites were readily leached from sand. Of the amendments examined, the two grades of SOP greatly reduced fenamiphos and metabolite leaching, whereas 42 and 75% of the fenamiphos and metabolite, respectively, were leached by the third inigation (FIG. 2 and FIG. 3). Neither grade of SOP substantially reduced the saturated hydraulic conductivity of the sand, whereas zeolite reduced conductivity by 94% (FIG. 4).
5.4 EXAMPLE 4 - SOP VERSUS ACTIVATED CHARCOAL AND PROFILE™
A stabilized organic polymer (SOP) was made from sugarcane filter-cake (FC) stabilized with a phenol-formaldehyde polymer and polyvinyl chloride (PVC). The resulting material was crushed and graded into batches of particles conesponding to very coarse sand (VCS; 1.0-2.0 mm), coarse sand (CS; 0.5-1.0 mm), and medium sand (MS; 0.25-0.50 mm).
The adsorption capacity of various size grades of SOP for fenamiphos and fenamiphos metabolite was determined in 1.25 cm diameter glass columns containing 10 cm sections of 15% (vol./vol.) SOP mixed in a USGA-sand. An excess of fenamiphos (11 mg) and metabolite (12 mg) was applied at the top of separate columns (4 replications for each organophosphate) and leached into the profile with small increments of water. Then the columns were flushed with two 50 ml portions of water. Each resultant leachate was analyzed for fenamiphos or metabolite by placing 200 μl of leachate into 10 ml methylene chloride. After adding anhydrous sodium sulfate and shaking, the methylene chloride:organophosphate mixes were decanted into vials for analysis by gas chromatography. Adsorption was calculated as the difference between organophosphate applied minus that obtained in the total leachate. A similar adsorption capacity study was conducted for coarse-sand size activated charcoal and for the inorganic soil amendment "Profile™".
The charcoal and inorganic amendment displayed little pesticide-retention capacity (Table 4). The finer sizes of SOP retained appreciable quantities of fenamiphos and sulfone. If a layer of 0.5 mm diameter SOP particles two particles deep were contained within the profile, the total volume of the SOP would be approximately 1 liter m" . Since the recommended rate of fenamiphos is 1125 mg m" , it appears that the 2-particle layer could adsorb an entire application rate of fenamiphos or metabolite (Table 4). However, in previous studies, less than 1% of the applied fenamiphos and no more than 18% of the metabolite leached (Snyder and Cisar, 1995), which indicates that even a small amount of SOP could adsorb leachate from numerous applications of fenamiphos.
TABLE 4 ADSORPTION CAPACITY OF VARIOUS SOP GRADES, CHARCOAL, AND PROFILE FOR
PESTICIDES
Material* Fenamiphos Sulfone Fenamiphos Sulfone
-1
∞g g mg L
SOP-VCS 2.39 0.69 1434 414
SOP-CS 2.30 1.97 1380 1182
SOP -MS 2.39 2.27 1434 1362
S - Charcoal 0 0 0 0
Profile™ 0 0 0 0
*VCS=l-2mm, CS=0.5-1.0mm, and MS=0.25-0.50mm.
5.5 EXAMPLE 5 - PESTICIDE ADSORPTION BY SOP COMPOSITIONS IN A GOLF GREEN A stabilized organic polymer (SOP) was made from sugarcane filter-cake (FC) stabilized with a phenol-formaldehyde polymer and polyvinyl chloride (PVC). The resulting material was crushed and graded into batches of particles conesponding to very coarse sand (VCS; 1.0-2.0 mm), coarse sand (CS; 0.5-1.0 mm), and medium sand (MS; 0.25-0.50 mm). From these batches, a mix was made to conespond to the particle size distribution found in the USGA green at the Ft. Lauderdale Research and
Education Center.
Gravel, coarse (choker) sand, and rooting mix were added to six of the twelve lysimeters on the green to reproduce the soil profile in the vicinity of each lysimeter. Soil profiles in the other six lysimeters were similarly constructed, except that the graded SOP was mixed 15% by volume in the lower 10 cm of the rooting mix. Lysimeters were ananged in random fashion to provide six blocks of paired profile treatments (± SOP).
After the sod was established over the lysimeters, the herbicides dicamba and 2,4-D were sprayed on the lysimeter area two times, one week apart, at the label rates of 6 and 58 mg A.I. m" , respectively. The plots were first inigated one day after application, and were maintained as a golf green thereafter. Percolate water in the lysimeters was collected five times over a 37-day period and analyzed for dicamba and 2,4-D. The SOP had no effect on the amount of percolation (Table 5). In agreement with the inventors' previous studies (Snyder and Cisar, 1997), although the application rate of dicamba was only one tenth that of 2,4-D, nearly as much dicamba as 2,4-D was found in the percolate (Table 5). SOP did not reduce leaching of either pesticide.
TABLE 5
EFFECT OF SOP ON PERCOLATION AND LEACHING OF DICAMBA AND 2,4-D
Percolate Dicamba 2,4-D cm μg M" % of applied μg M~ % of applied
+ 22.6 2301 19.2 5427 4.7
24.8 2409 20.1 3006 2.6
Following the study involving 2,4-D and dicamba, the nematicide fenamiphos was applied as a liquid to the lysimeter area at the label rate of 1.12 g A.I. m" . The area was inigated following application, and maintained as a golf green. Percolate was collected from the lysimeters four times during the ensuing 28 days, and analyzed for both fenamiphos and fenamiphos metabolite (sulfoxide + sulfone).
As with the previous study, SOP had no effect on the amount of percolate collected during the study (Table 6). The percolation results from the two studies are consistent with the expectation that if the SOP were sized to match the sand sizes in the rooting mix, it would not alter the hydrological characteristics of the green. In agreement with previous observations (Snyder and Cisar, 1993), considerably more metabolite than parent fenamiphos was found in the percolate (Table 6). Only 11% as much fenamiphos leached in the SOP treatment as leached in the unamended soil profile. Considerably more metabolite leached in the unamended soil than was observed in previous studies (Snyder and Cisar, 1993). Nevertheless, SOP significantly (p < 0.05) reduced metabolite leaching 66%. The inventors have some concern that the lysimeters were not fully drained before the start of the study, resulting in at least a portion of the soil profile being saturated with water. This may have contributed to the very high pesticide leaching that was observed.
TABLE 6 EFFECT OF SOP ON PERCOLATION AND LEACHING OF PESTICIDES
SOP Percolate Fenamiphos Metabolite cm μg M" % of applied μg M"z % of applied
+ 35.3 5,900 0.49 167,300 13.9
- 34.6 52,500 4.37 495,400 41.3
The data from the two studies clearly illustrate that pesticide retention by the SOP, as constituted, varied with the polarity of the pesticides (polar molecules are more soluble in water, which is a polar molecule itself, than are non-polar molecules).
Adsoφtion was greatest for fenamiphos, which is the least polar of the pesticides tested. Less adsoφtion was found for the fenamiphos metabolites, which are more polar than the parent compound, and the most polar pesticides, dicamba and 2,4-D, were not adsorbed by the SOP. It should be noted that fenamiphos, dicamba, and 2,4- D were chosen for study because a) in previous studies they have been observed to leach in a USGA green, b) they represent a range of polarities, and c) the inventors are experienced in their analysis. Other pesticides that may be of interest in turfgrass management have polarity characteristics similar to or comparable with one of the pesticides used in the inventors' studies.
5.6 EXAMPLE 6 - SOP ADSORPTION OF HIGHER-POLARITY PESTICIDES
A series of adsorbent-formulation studies were conducted with dicamba, 2,4- D, and fenamiphos sulfone (FS). In order to simplify the chemistry of adsoφtion to better understand the underlying mechanisms, studies were conducted with silica sand coated with various polymers in addition to modifications of the sugarcane filter-cake
(FC) based SOP. Two methods were used for determining the effect of various treatments on pesticide adsoφtion: batch and column. By the batch method, 10 g of candidate adsorbent along with 40 ml water and pesticide was placed in a 50 ml glass tube. After shaking for 1 h, the filtrate was collected. Pesticide in the extract of the filtrate was analyzed by gas chromatography (GC). For the column method, glass tubes
6 x 30 cm were packed 10 cm deep with medium-size silica sand amended 15% (vol./vol.) with candidate adsorbent. Pesticide was placed on the surface, followed by 10 ml water. After 1 h, six 50-ml aliquots of water were added to the tubes to leach pesticide. Pesticide in the combined leachate was extracted and analyzed by GC. The SOP used in the field was formulated with polymers synthesized in-house.
In contrast, one set of lab studies was conducted with SOP formulated with commercially-available polymers. Both polymer type and polymer concentration were investigated. It was determined that the PVC added to increase the mechanical strength of the SOP used in the field was unnecessary when using commercially- available phenol-formaldehyde resin (PFR), and actually decreased adsoφtion. By the batch method in the lab, SOP formulated with commercially-available PFR adsorbed dicamba and 2,4-D, and significantly more so in the absence of added PVC. The optimal PFR concentration, maximum FC moisture content, maximum pH, and proper curing temperature were determined. Furthermore, in the field, it was noted that for some time after SOP was incoφorated into the lysimeter soil, percolate water was brownish in appearance. Phenol was detected in the percolate. In the lab it was determined that there was 93% less leaching of phenol when the commercial PFR was used to treat FC than when PFR was polymerized in-house, as was done when making up the SOP used in the field trials. Polymer treatments of FC or of quartz sand that did not improve dicamba and
2,4-D adsoφtion included polyurethanes, polyethylene, styrene-butadiene latex, nitrated phenol-formaldehyde, and amino phenol-formaldehyde, a nitroso phenol- furfuraldehyde, DMSO phenol-formaldehyde derivative, and a urea phosphate formaldehyde. Treatments equivalent to PFR included urea formaldehyde, furfural urea, and furfural phenol. Treatments with improved adsoφtion of dicamba and 2,4-D were various metal adducts of urea formaldehyde, including iron, copper, and aluminum. A calcium metal adduct produced variable results.
Following further screening of potential adducts, polyethylene glycol (PEG) stood out as the most promising candidate for adsorbing polar pesticides. The PEG was attached to the PF by creating a PEG halide with HCI and reacting it with the PF
(using a Williamson ether synthesis). Since PEG represents a class of compounds, the next step was to find the best PEG. This was done by studying a series of PEGs of widely different characteristics in combination with PF. Mechanical properties (durability, hardness) of the resulting compound were noted as well, both for the PF/PEG polymer alone, and when mixed with FC. Difunctional PEG with molecular weight of 5000 was selected as being optimal both for adsoφtion of a polar pesticide, fenamiphos sulfone (Table 7), and for mechanical durability.
TABLE 7 ADSORPTION OF FENAMIPHOS SULFONE BY VARIOUS SOP FORMULATIONS,
EXPRESSED AS A PERCENT OF APPLIED, AS DETERMINED BY TWO ADSORPTION
EVALUATION METHODS
Adsoφtion Evaluation Method*
Formulation Batch Column
(% of applied) Sand 6 0
PF/PEG resin > 99 > 99
PF/PEG on FC > 99 > 99
*The sulfone application rate was 1 mg per 10 cc of adsorbent for the batch method, and 4.2 mg per column for the column method, which approximately conespond to the recommended field application rate of fenamiphos.
After determining the formulation of the adsorbing resin, its use in combination with FC was investigated. The best granules in terms of mechanical stability required a minimum of 30% resin by weight. The FC/resin combination was found to adsorb the polar fenamiphos sulfone well in both batch and column studies (Table 7). The product thus created appears to be a useable SOP.
Further work was done to facilitate manufacture of this SOP. In order to avoid working with the dangerous and attention grabbing compounds formaldehyde and phenol, work was continued on developing a method for creating a PF/PEG resin utilizing commercially produced PF (Borden Chemical). The first step was to optimize the production of the PEG halide. It was determined that the halide PEG-Br (formed with H2SO4 and NaBr) could be created more efficiently than the PEG-C1. The second step was to optimize conditions for reacting the PEG-Br with the commercial PF. A series of formulations varying in a number of parameters
(PEG:PF:Br, pH, curing time and temperature) were created and tested visually and mechanically. Five appeared promising for pesticide adsoφtion studies.
The five more promising PFRs created with the commercial formaldehyde- phenol product and PEG were examined in a batch test along with the PFR + PEG formulated from formaldehyde and phenols separate reagents for their ability to adsorb fenamiphos and fenamiphos sulfone. The resins were exposed to 2.5 times the amount of fenamiphos and sulfone that would be expected from a labeled application. One of the formulations using the commercial formaldehyde-phenol adsorbed both fenamiphos and sulfone to the same, high, degree that was obtained with the product made from the formaldehyde and phenol as separate reactants (Table 8).
TABLE 8 EFFECT OF RESIN FORMULATION ON ADSORPTION OF PESTICIDES
Adsoφtion
Formulation Description fenamiphos sulfone
(% of applied)
1) Using phenol and formaldehyde as separate 95.5 84.0 reagents
Using commercially obtained phenol-formaldehyde
2) Added more PF resin to small amounts of PF 0 0 resin with PEG
3) Used stoichiometric amount of NaOH 45.3 2.9
4) Shorter reaction time and increased heat 62.8 25.7
5) Used PEG 400 57.9 25.2
6) Used 50%) stoichiometric amount of NaOH 96.5 90.68
Because it was deteπnined that the creation of a stable and effective FC pellet requires that the final product be 30% resin by weight, the potentially less expensive alternative of coating sand grains with resin was investigated. By using sand, only 5% (by weight) of the final product is resin. Other advantages of using sand as the base media rather than FC include not worrying that the FC will catch fire at the curing temperature of the resin. Preferably the resin is added to a dry substrate. More time and energy is required to dry FC than is needed for sand. An adjustment of pH is required for proper curing of the resin. Far more reagent is required to shift the pH of the highly buffered FC than is required for sand. When made with sand, the final product does not require milling to achieve proper grain size.
Resin candidate # 6 in Table 8 has been used to coat sand. At a 10% by weight concentration, this material adsorbed 96 and 90% of applied (2X normal application rate) fenamiphos and fenamiphos metabolite, respectively, in a column study. 5.7 EXAMPLE 7 - FIELD EVALUATION OF SOP-COATED SAND 5.7.1 LYSIMETER RECONSTRUCTION
Silica sand was coated with SOP at the rate of 10% by weight. The prepared material had a particle size range well within United States Golf Association (USGA) specifications (Table 9), which requires sand must be at least 60% medium+coarse, and less than 20% fine+very fine sand.
One month later (in early November) the twelve lysimeters in the USGA green at the Ft. Lauderdale Research and Education Center (Ft. Lauderdale, FL) were excavated to the gravel layer. Five cm of coarse sand, conesponding in size to that used in the original green's construction (Cisar and Snyder, 1993), was placed over the gravel layer. The SOP-sand composition was mixed at a rate of 20% by volume with freshly-obtained USGA rooting mix sand that conesponded in particle size to that used in the original green's construction (Cisar and Snyder, 1993) to provide a 10 cm deep layer over the coarse sand in six of the twelve lysimeters. Additionally, freshly-obtained rooting mix sand was used to completely refill the excavated hole, and this sand also was used over the coarse sand layer in the six lysimeters that did not receive the SOP-sand composition treatment. SOP-sand treated and untreated lysimeters were ananged in blocked pairs. The cv. Tifdwarf bermudagrass sod cut from over the lysimeter was trimmed to a soil depth of approximately 4 cm and replaced over the lysimeter. The green was maintained using standard practices thereafter.
TABLE 9 PARTICLE SIZE RANGE (MM) OF SOP-COATED SILICA SAND
Very coarse Coarse Medium Fine Very fine Silt + Clay
> 2.00 2.00 - 1.00 1.00 - 0.05 0.05 - 0.25 0.25 - 0.10 0.10 - 0.05 < 0.05
%
0.1 1.2 28.5 56.2 12.9 0.8 0.2
Five days later, the water collected in all lysimeters was evacuated and discarded. Fenamiphos, as Nemacur® 3E, was sprayed over the lysimeter area at the rate of 1.125 g A.I. m" , which is the rate recommended by the manufacturer's label. Immediately after application, 1.7 cm of irrigation was applied to the area. Thereafter, irrigation was applied as needed to maintain the turfgrass. The first rainfall was recorded five days later (3.00 cm). Lysimeter was evacuated on Day 2, Day 5, and Day 8 of the study. Pesticide in the lysimeter water was extracted with methyle chloride and analyzed by gas chromatography (Snyder and Cisar, 1993). A determination of both fenamiphos, and fenamiphos metabolite was performed.
5.7.2 DISCUSSION
Considerably more water was collected in the lysimeters than could be accounted for on the basis of rainfall, probably inigation, and expected evapotranspiration. While the reason for this finding was not determined, it is possible that soil in the recently reconstructed lysimeter profile may have had a much greater hydraulic conductivity than that of the long-established suπounding green, and the surface of the soil over the lysimeters may have been somewhat lower than in the suπounding area. Both of these factors could have resulted in movement of surface water, possibly containing pesticide, from areas suπounding the lysimeters to the lysimeters, with subsequent percolation through the lysimeters. For lysimeter water collected over the period from Day 2 to Day 8 of the study, there was a 72% reduction in fenamiphos leached in the SOP-sand lysimeters as compared to the unamended lysimeters (FIG. 1). For the more water soluble metabolite, the reduction in leaching was 54% (FIG. 2).
There was no significant (P<0.05) effect of SOP-sand on percolation, which averaged 57.7 cm during the seven weeks following fenamiphos application.
Virtually no fenamiphos was leached in lysimeters containing SOP-sand (FIG. 3). Two weeks after application, total metabolite leaching was reduced 90% by the SOP- sand composition (FIG. 4). The comparative reduction declined with time. Seven weeks after application total metabolite leaching was reduced 76% (FIG. 5). This apparently occuned because after the initial great adsoφtion of metabolite by SOP sand, there was a slow desoφtion of the material, as evidenced by a gradual increase in accumulative metabolite leaching in the SOP-sand lysimeters over time (FIG. 6). Nevertheless, the initial high concentration of metabolite in percolate was prevented by the SOP-sand. This gradual desoφtion characteristic of the SOP-sand composition provided evidence that the composition may also be used as a "slow-release" carrier for pesticides and/or other organic compounds.
The area containing the lysimeters was maintained continuously as a golf green since the previous study, and periodically, lysimeter water was evacuated and discarded. Eight and a half months after the initial fenamiphos was sprayed over the lysimeter area, the green was hollow-core aerified and topdressed, which are standard greens maintenance practices used to improve soil aeration and water penetration. In the afternoon, fenamiphos (Nemacur® 3E) was mixed with 3 to 4 liters of water and applied with a sprinkling can over 1 m areas centered over the lysimeters to provide an application rate of 1.125 g A.I. m" . The plot area was irrigated to provide 0.8 cm water, and maintained as a golf green thereafter. Lysimeter water sampling began again three days following the second application of pesticide, and continued weekly or more often for at least six weeks following the application. The samples were analyzed for both fenamiphos and metabolite.
5.8 EXAMPLE 8 - LARGE-SCALE PRODUCTION OF PF-PEG SOP A 700 gallon final polymer feed tank and a 150 gallon PEG mixing tank was utilized. This generates a batching feed capacity of five (5) hours operation and production of forty (40) tons of finished SOP-Sand (Biosand) product. The following quantities of materials and conditions were utilized in preparation of a polymer batch.
PEG Preparation
334 LBS. PEG 5800 Material is continuously mixed and
3.7 LBS. 1.1 H2SO4 indirectly heated to a temperature of
12 LBS. NaBr 70° C for a period of one (1) hour 53 Gals. H2O Final Polymer Preparation
3000 LBS. Resin "5801 " Materials are all added together in
Add PEG solution final Mix Tank in the order listed.
96 Gals. H2O The final polymer is continuously
1066 LBS. NaOH mixed and indirectly heated to maintain 70° C for pumping in Pin
Mixer.
An exemplary plant layout and process steps for large-scale production of the SOP compositions of the present invention are shown in FIG. 8 and FIG. 9. In particular embodiments, the inventors utilized the following scheme for large-scale production of SOP-coated sand compositions.
5.8.1 PIN MIXER
Best coating results of polymer to silica sand particles was obtained during the following conditions: 1. Paddle in mixer adjusted to minimum side wall clearance to pin mixer.
2. Paddle adjusted to 30° offset (downstream) from vertical position with respect to side wall.
3. Pin Mixer (30" diameter) operated at 300 RPM, resulting in tip speed of about 75 to about 125 ft/sec, with a tip speed of about 100 ft/sec being shown by the inventors to be highly desirable for large-scale preparation of the SOP-sand compositions disclosed herein.
4. Two (2) "flat 60° angled spray nozzles" each dedicated separately to a metering pump, utilized for spray / atomizing the polymer feed into the Pin Mixer. The nozzles are located on top of the Pin Mixer approximately 12" apart and in the first 25%) zone of the mixer.
5.8.2 DRYER
Best thermal setting results of resin were obtained by Fluid Bed Dryer under the following conditions: 1. Inlet air temperature to dryer set at about 500° F. 2. Inlet air velocity set at about 22,800 CFM (approximately 150 CFM per ft ) of dryer deck area.
3. Vibrating frequency of dryer regulated to maintain retention time of about ten (10) minutes for Biosand material in Fluid Bed Dryer. 4. Outlet flue gas is water quench to maintain temperature of about
200°F.
5.8.3 COOLER
In order to maximize cooling of the SOP-sand formulation (which the inventors have termed "Biosand"), and thus reduce or eliminate the adhesion of the particles to one another, a Fluid Bed Cooler may be operated in the following manner:
1. Inlet air was adjusted to 8,000 CFM (180 CFM per FT2 of cooler deck area). Higher air velocities would cause air entrainment from cooler air discharge.
2. Biosand product temperature was maintained below 150° F. In existing cooler.
5.8.4 RECYCLE MILL
Recycle Mill was operated at the following status to eliminate clustering of Biosand material and prevent unnecessary damage / fracturing of the polymer coating on the sand.
1.. Hammer Mill was utilized for application, mill was adjusted for 3/16" clearance between hammer tips and mill side wall.
2. Hammer Mill speed was operated at 800 RPM on a 32" diameter mill. Resulting tip speed of hammer was about 75 to about 125 ft/sec, with a tip speed of about 100 ft/sec being shown by the inventors to be highly desirable for large-scale preparation of the SOP-sand compositions disclosed herein.
5.8.5 PRODUCT MIXER
In line product Screw Mixer was employed to mix sulfuric acid with the Biosand product discharged from final product screening. Best results for coating
Biosand with sulfuric acid in mixer were as follows: 1. All mixer components were treated with brushable ceramic surface coating.
2. Screw mixer was operated at 250 RPM.
3. Sulfuric spray nozzle was positioned 12" above screw portion of mixer and utilized at 60° flat spray nozzle.
5.8.6 FEED RATES
Best results for Biosand functionality in field application (and processability to manufacture product) resulted in particle containing 6.5% by weight polymers coating of sand. Cunent manufacturing / process capabilities resulted in the following feed rates:
1. Sand (dried and sized to -30 + 60 mesh) was fed to Pin Mixer at 14,000 LBS./Hour.
2. Biosand polymer was supplied to the Pin Mixer by two (2) independent metering pumps at a rate of 1.0 GPM each. This equates to a rate of 1200 LBS. / hour of material and approximately 900 LBS. / hour of Biosand resin once H2O is removed by the Fluid Bed Dryer.
3. Sulfuric acid (50% solution) was pumped to product Screw Mixer at a rate of .25 GPM for the puφoses of providing a harder cured polymer coating of the sand.
6.0 REFERENCES
The following references, to the extent that they provide exemplary procedural or other details supplementary to those set forth herein, are specifically incoφorated herein by reference.
U.S. Patent No. 2,797,196. U.S. Patent No. 2,885,360. U.S. Patent No. 3,024,164. U.S. Patent No. 3,041,238.
U.S. Patent No. 3,080,214. U.S. Patent No. 3,234,003. U.S. Patent No. 4,054,515. U.S. Patent No. 4,116,825. U.S. Patent No. 4,116,826. U.S. Patent No. 4,116,827.
U.S. Patent No. 4,116,828. U.S. Patent No. 4,147,624. U.S. Patent No. 4,167,481. U.S. Patent No. 4,444,665. U.S. Patent No. 4,511,657.
U.S. Patent No. 4,971,698. U.S. Patent No. 4,995,969. U.S. Patent No. 5,461,992. U.S. Patent No. 5,671,887. U.S. Patent No. 5,685,981.
Blair and Martin, Pestic. Sci., 22:195-219, 1988.
Chen and Wang, "Chromatographic methods for the determination of pyrethrin and pyrethroid pesticides residues in crops, foods, and environmental samples,"
Journal of Chromatography A, 754(l-2):367-95, 1996. Cowan et al, "Adsoφtion by organoclay complexes," Clays and Clay Minerals,
9:459-467, 1960.
Gronwald, "Herbicides inhibiting acetyl-CoA carboxylase," Biochemistry Society
Transactions, 22(3):616-21, 1994. Hollomon, "Resistance to azole fungicides in the field," ," Biochemistry Society Transactions, 21 (4): 1047-51 , 1993.
McCarter et al. , "Thermal activation of attapulgus clay," Industrial and Engineering
Chemistry, 42:529-533, 1950. Shishkoff, "A Primer on Fungicide Use," http://www.bonsaiweb.com/forum/articles/arts/fungicide.html. Snyder and Cisar, "Mobility and persistence of pesticides applied to a USGA green.
IV. Dicamba and 2,4-D," Int. Turfgrass Soc. Res. J, 8:xx, 1997. Snyder and Cisar, "Mobility and persistence of pesticides in a USGA-type green. II.
Fenamiphos and Fonofos," Int. Turfgrass Soc. Res. J, 7:987-983, 1993. Snyder and Cisar, "Pesticide mobility and persistence in a high-sand-content green," USGA Green Section Record, 33(1):15-18, 1995. Swancar, "Water quality, pesticide occuπence, and effects of inigation with reclaimed water at golf courses in Florida. U.S. Geological Survey Water-Resources Investigations Report 95-4250," U.S. Department of the Interior, U.S. Geological Survey, Tallahassee, Florida, USA., 86, 1996. Tadeo, Sanchez-Brunete, Valcarcel, Martinez, Perez, J. Of Chromatography A, 754:347-365, 1996.
Tekel and Kovacicova, J. Chromatogr., 643:291-303, 1993.
Yang et al. "Recent advances in the residue analysis of N-methylcarbamate pesticides," Journal of Chromatography A, 754:3-16, 1996. Zaneski, "Wildlife pays the price for green fairways," 77ze Miami Herald, July 1 1, 1A, Miami, Florida, USA, 1994. http://cygnus.tamu.edu/Texlab/Nuts/Pecan/pecanf.html. http://www.acesag.auburn.edu/department/ipm/Nematode.htm. http://www.gov.sk.ca/agfood/cpg/iccont.htm. http://www.missouri.edu/~extbsc/turf/fundesc.htm. http://www.usga.org/green/.
All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of prefened embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

Claims

CLAIMS:
1. A stabilized organic polymer comprising phenol-formaldehyde-polyethylene glycol.
2. The method of claim 1, wherein said polyethylene glycol is crosslinked with said phenol-formaldehyde to produce said polymer.
3. A composition comprising the polymer of claim 1, wherein said polymer is bound to a matrix.
4. The composition of claim 3, wherein said polymer is capable of binding a pesticidal compound.
5. The composition of claim 4, wherein said pesticidal compound is an insecticide.
6. The composition of claim 4, wherein said pesticidal compound is a herbicide.
7. The composition of claim 6, wherein said herbicide is 2,4- dichlorophenoxyacetic acid or Dicamba.
8. The composition of claim 4, wherein said pesticidal compound is a fungicide.
The composition of claim 4, wherein said pesticidal compound is a nematicide.
10. The composition of claim 9, wherein said nematicide is fenamiphos.
11. The composition of claim 4, wherein said composition is comprised within a water treatment device, or a baπier.
12. The composition of claim 3, wherein said matrix comprises a silicate, sand, sea sand, rock, gravel, clay, expanded clay, silica gel, zeolite, metal, filtercake, plastic, or glass.
13. The composition of claim 12, wherein said matrix is sand.
14. The composition of claim 12, wherein said matrix comprises filtercake.
15. The composition of claim 14, wherein said filtercake is obtained from processed sugarcane.
16. A soil amendment comprising a composition according to claim 3.
17. A turf grass or agricultural field comprising a composition according to claim
3.
18. A system for treating water to remove organic pollutants, comprising
(a) an inlet port;
(b) one or more chambers comprising a composition according to claim 3 in an amount effective to remove said pollutants from said water; and
(c) an oulet port.
19. A filtration device for reducing the concentration of a pesticidal compound in an aqueous solution comprising an inlet port, a chamber comprising a composition according to claim 3, in an amount effective to remove said pesticidal compound from said aqueous solution, and an outlet port.
20. A system for removing a pesticidal compound from a leachate comprising:
a) a leachate supply source,
b) a water impervious treatment basin which slopes from a high end to a low end,
c) a treatment medium comprising a composition according to claim 3, in an amount effective to remove said pesticidal compound from said leachate, d) an inlet flow control means operatively connected to said leachate supply source and said high end of said treatment basin which allows the leachate to penetrate and flow vertically and horizontally through said treatment medium, and
e) an outlet flow control means for draining the treated leachate from the treatment medium at said low end of said treatment basin and for collecting the drained treated leachate at a point below said treatment medium, said outlet flow control comprising a drainage means for draining the leachate, whereby the leachate is first treated by said treatment medium after which said treated leachate flows through said drainage means.
21. A method of preparing a composition according to claim 3, comprising, coating a matrix with the compound of claim 1 under conditions effective to permit coating of said matrix with said compound.
22. A method of reducing the concentration of a pesticide in an aqueous solution comprising contacting an aqueous solution suspected of containing a pesticide with an amount of a composition according to claim 3 effective to reduce the concentration of said pesticide in said solution.
23. The method of claim 22, wherein said pesticide comprises at least a first insecticide, herbicide, fungicide, or nematicide.
24. The method of claim 23, wherein said pesticide is an insecticide.
25. The method of claim 23, wherein said pesticide is a herbicide.
26. The method of claim 25, wherein said herbicide comprises 2,4- dichlorophenoxyacetic acid or Dicamba.
27. The method of claim 23, wherein said pesticide is a fungicide.
28. The method of claim 22, wherein said pesticide is a nematicide.
29. The method of claim 28, wherein said nematicide is fenamiphos.
30. The method of claim 22, wherein said aqueous solution is a agricultural leachate, wastewater, water, sewage, groundwater, or industrial runoff.
31. The method of claim 30, wherein said aqueous solution is agricultural leachate.
32. A method of preparing a golf course to prevent leaching of a pesticide from said course, the method comprising amending the soil under said golf course with a composition according to claim 3.
33. A method of adsorbing a pesticide from an aqueous solution comprising contacting said solution with a composition according to claim 3 under conditions effective to adsorb said pesticide from said solution.
34. A system for removing a pesticide from a water source comprising;
a) an inlet means,
b) one or more chambers comprising an amount of a composition according to claim 3, effective to reduce the level of said pesticide in said water source,
c) means for contacting said water source with said composition,
d) an outlet means.
35. The system of claim 34, wherein said system comprises a continuous flow system or a batch processing system.
36. A method for preventing leaching of a pesticide from a soil said method comprising amending a soil with a composition according to claim 3, wherein said composition is present in said soil in an amount effective to prevent leaching of said pesticide.
37. The method of claim 36, wherein said composition comprises of from about 5% to about 95% of said soil.
38. The method of claim 37, wherein said composition comprises of from about 15% to about 50% of said soil.
39. The method of claim 36, wherein said composition is added throughout said soil.
40. The method of claim 36, wherein said composition is added to said soil in one or more discreet layers.
41. A controlled-release pesticide comprising the compound of claim 1.
42. A controlled-release organic fertilizer comprising the compound of claim 1.
43. The fertilizer of claim 42, comprising an organophosphate.
PCT/US1998/025131 1997-11-24 1998-11-24 Compositions and methods for adsorption and remediation of organic compounds WO1999026885A1 (en)

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CN109622594A (en) * 2018-12-07 2019-04-16 重庆玖正环境科技有限公司 A method of improving heavy metal pollution of soil using polymer absorption process
CN110255656A (en) * 2019-07-27 2019-09-20 安达兰泽科技有限公司 The processing method of triazinone industrial production wastewater
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009123699A3 (en) * 2008-03-31 2010-01-07 Rhodia Inc. Self-situating stimuli-responsive polymer compositions in soil additives and methods for use
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CN114452951B (en) * 2021-12-15 2023-12-01 淮阴工学院 Phenol formaldehyde aerogel rubidium/cesium specific adsorbent and preparation method and application thereof

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