text:
|Publication number
|Publication type
|Application number
|PCT number
|Publication date
|Aug 23, 1994
|Filing date
|Jun 6, 1991
|Priority date
|Jun 8, 1990
|Fee status
|Also published as
|Publication number
|John Cunningham
|Original Assignee
|The Sierra Horticultural Products Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (25), Non-Patent Citations (3), Referenced by (129), Classifications (24), Legal Events (7)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a continuation-in-part of U.S. Ser. No. 535,393, filed Jun. 8, 1990 and abandoned on Jan. 9, 1992.
This invention relates to improvements in biological remediation (bioremediation) efficiencies and improvements to the environmental soundness of the bioremediation approach to contamination cleanup. More particularly, it relates to improved nutrient delivery systems which reduce nutrient losses in open systems such as the ones found in most bioremediation operations. These nutrient delivery systems are amenable to both soil and water applications and are particularly helpful in reducing labor costs associated with nutrient application and also in reducing the potential for environmental damage due to nutrient run-off.
Bioremediation refers to the conversion of toxic environment contaminating compounds into innocuous substances by way of microbial digestion. Bioremediation has been successfully used to treat contaminated soil in above-ground treatment systems, above-ground slurry bioreactors, slurry pits, above-ground soil heaps, composting material, and in situ. A good example of in situ soil treatment came following the Exxon Valdez oil spill in Prince William Sound, Alaska. This oil contaminated miles of Alaskan shoreline and an approximately 70 mile section of shoreline was treated using bioremediation. This remediation process as it was employed focused on enhancing the indigenous microorganisms' growth and oil degrading activities through the application of nutrients.
Representative disclosures of bioremediation process include U.S. Pat. No. 4,035,289, to Michel Guillerme et al., which discloses a method for removing hydrocarbon residues from the effluents from oil well drilling. This method involves culturing microorganisms in a portion of the effluent and then adding the portion back to the remainder to degrade the hydrocarbons. Genetic Engineering News, vol. 9, No. 10 (Nov.-Dec. 1989) at page 3 presents a good example of the in situ bioremediation processes used to assist the clean-up of the Exxon Valdez oil spill in Prince William Sound, Alaska.
It is known that speeding the bioremediation process, by promoting the growth and activity of the waste-degrading microorganisms is desirable. In most situations the microorganisms naturally present in the soil and groundwater are capable of degrading the contaminating compounds. For a successful remediation, the bioremediator must enhance the growth and activity of these naturally occurring microorganisms. To that end, it is understood that supplying the microorganisms with nutrients and advantageous environmental conditions is beneficial. Just noted U.S. Pat. No. 4,035,289 teaches the addition of nitrogen and phosphorus sources to its culturing medium. U.S. Pat. No. 4,727,031 to Richard A. Brown et al., describes a composition of nutrients and a method of using the composition to stimulate the growth of aerobic bacteria, and particularly bacteria capable of hazardous waste degradation. This patent makes reference to Busch, Aerobic Biological Treatment of Waste Waters, Oligodynamics Press, Houston (1971), at page 107, for teaching that phosphorus and nitrogen are critical growth-limiting nutrients and when not present must be added to aerobic bacteria, such as those found naturally occurring in soil and water environments. Other similar disclosures of bioremediation include U.S. Pat. No. 3,846,290 to Richard Raymond, which discloses the advantageous injection of nutrients into subsurface water supplies to reduce contaminating hydrocarbons; U.S. Pat. No. 4,401,569 to Vidyut Jhaveri et al., which similarly shows injecting nutrients into the ground to enhance microbial action on contaminants; U.S. Pat. No. 4,925,802 to Michael Nelson et al., which shows adding an amino acid to bioremediation systems; U.S. Pat. No. 4,849,360 to Edward Azarowicz, which shows a multitank digestion process for degrading oily wastes; and U.S. Pat. No. 4,493,895 to Joseph F. Colaruotolo et al., which shows particular microorganisms which are capable of dissimilating halogenated compounds into the natural carbon cycle.
In general, therefore, bioremediations are speeded by adding nutrients, pH adjusters, and if aerobic microorganisms are used, oxygen to the soil and/or water of interest. By adjusting these parameters the indigenous microorganisms will multiply and become more active resulting in faster waste degradation. It only becomes necessary to add "foreign" microorganisms to the contaminated environment if the indigenous microorganisms do not posses the genes needed to create the enzymes necessary to degrade the contaminant, if the contaminant is at such a high concentration as to be toxic to the natural microorganisms, or if the contaminant concentration is so low the natural level of microorganisms cannot further degrade it to an acceptable level.
In most cases, bioremediations are performed in environments such as on site locations which can be classified as open systems. In the case of biodegradation in a closed environment, such as a batch bioreactor, it is sufficient to use an aqueous culture medium which completely and immediately supplies the microorganisms with the various nutrients required to increase degradation rates. These various nutrient elements are discussed in U.S. Pat. Nos. 4,035,289 and 4,727,031 which were noted above. Nutrient needs in open systems cannot be efficiently filled using the teachings of U.S. Pat. No. 4,035,289. This is because this patent shows the application of nutrient compounds which have virtually no ability to remain in the microorganisms' environment for extended periods in an open system. In this situation, it is necessary to apply these nutrients repeatedly to the open system throughout the remediation's duration.
The resulting depletion-reapplication cycle puts the microorganisms in a stressed state, and the microbes degradative efficiency is reduced. In addition, the washing away of the nutrients, from the point of application, is wasteful and may actually add to the environmental problem. One example of a nutrient runoff problem is blue baby syndrome which is caused by nitrates contaminating "potable" water supplies. This nutrient loss may be avoided to some extent by supplying nutrients in a form which can be associated or bound with the contaminant, such as a hydrocarbon waste, to provide a localized growth medium for the microorganisms.
U.S. Pat. No. 3,943,066, to Pierre Fusey, discloses a method for nutrient-waste mass association using an aqueous biodegradable emulsion of nitrogen- and phosphorus-containing substances with the hydrocarbon waste. In U.S. Pat. No. 4,460,692, to Jacques Tellier et al., a lipophilic microemulsion of an aqueous nutrient solution is applied in a layer upon the waste mass. These methods provide a way to associate essential nutrients onto the surface of the organic waste, but do not provide a controlled rate of nutrient release to the microorganisms' environment. In another, related disclosure, U.S. Pat. No. 4,401,762, also to Jacques Tellier et al., describes a process of culturing microorganisms using a microemulsion of nutrients and the use of this process in biodegradation settings.
The present invention addresses the problem of nutrient delivery to bioremediation environments by using controlled-release nutrient delivery systems engineered specifically for microorganisms. Controlled-release compositions have been used heretofore to provide nutrients to growing organisms, such as plants. See, for example, U.S. Pat. No. 4,657,576 to Johannes Lambie, which discloses a fertilizer composition for releasing nutrients to plants throughout the growing season; U.S. Pat. Nos. 3,300,293 and 3,252,786 to Andrew Bozzelli et al., which each relate to a slow-release fertilizer composition comprising a dispersion of urea-wax adduct in wax and its use fertilizing crops; U.S. Pat. No. 3,259,482 to Louis Hansen, which describes a slow-release fertilizer having a plurality of epoxy-polyester resin coatings and its use with plants; U.S. Pat. No. 3,232,739 to Steven Belak, which describes a polyurethane foam extended with free urea and the ability of the foams to supply urea fertilization to a plant throughout a long period of time; U.S. Pat. No. 3,252,786 to Andrew Bozzelli et al., which involves slow-release fertilizer compositions containing urea, wax, rosin, and optionally asphalt, and their use in fertilization processes; U.S. Pat. No. 3,475,154 to Haruhiro Kato et al., which describes resin-coated fertilizer particles and their use in garden settings; U.S. Pat. No. 4,120,685 to Silvio Vargiu et al., which describes fertilizers capable of achieving slow-release of nitrogen from urea-formaldehyde mixtures; U.S. Pat. No. 4,563,208 to Peter Backlund, which shows that fertilizer particles can be covered with a reaction product of urea and metal oxides; U.S. Pat. No. 4,210,437 to Robert Windgassen et al., which shows liquid fertilizer compositions which provide sulfur, nitrogen and micronutrient metals; and U.S. Pat. No. 4,756,738 to William J. Detroit, which shows a copolymer matrix which is capable of gradually releasing fertilizer.
Additional patents of note are U.S. Pat. No. 4,111,201, to Felix Theeuwes, and U.S. Pat. No. 3,952,741, to Richard Baker, which discloses devices capable of osmotically delivering beneficial agents. While for the most part, these patents are directed to delivering pharmaceutical agents to patients, they do generally include the delivery of any "active agent", including in the case of U.S. Pat. No. 4,111,201 microorganism attenuators, fermentation agents, nutrients and other agents that "benefit the environment of use" and in the case of U.S. Pat. No. 3,952,741, any agent in any way affecting any biological entity.
The current invention improves the efficiency of bioremediations in soil and/or aqueous environments by providing controlled-release compositions which supply nutrients to the microorganisms in a regulated, environmentally sound, and cost effective manner.
An improvement in bioremediation processes has now been found. Such bioremediation processes are those in which an organic chemical-contaminated soil or aqueous environment is remediated by the digestive action of microorganisms, on the chemical contaminant, within the environment. This digestive action typically takes two or more months before acceptable levels of degradation have taken place and the contaminated environment is no longer considered a threat. The improvement provided by the present invention involves applying to said environment, and thus the degrading microorganisms present therein, a controlled-release source of microorganism nutrients at a low level and optionally vitamins and/or nutrients which double as buffering agents (to keep the environment surrounding the product at a pH which is compatible with the growth and activity of the desired microorganisms). This controlled-release source is capable of continuously supplying an effective level of microorganism-promoting nutrients, some of which may double as buffering agents, to the contaminated environment during the prolonged period of digestive action. These prolonged periods of bioremediation action are those typically associated with this process in the art, such as at least about 1 week and more commonly from 1 to 100 weeks, especially from 10 to 40 weeks. The controlled-release source of nutrients typically releases nitrogen and/or phosphorus and/or sulfur to the microorganisms. This invention can find application in bioremediations performed in soils and/or aqueous environments which have become contaminated with aliphatic hydrocarbons. It can also find use in soils and/or aqueous environments which have been contaminated with aromatic hydrocarbons, including halogenated aromatic, polynuclear aromatic, polychlorinated biphenyls (PCB), trichloroethylene (TCE), percholorethylene, various pesticides, various herbicides, and with any chemical deemed to be bioremediable.
The invention can be used in soil environments and in aqueous environments. These environments can be open or closed. The soil environments include soil in above-ground treatment systems, above-ground slurry bioreactors, slurry pits, above-ground soil heaps, composting material, in situ, and the like. The aqueous environments include lakes, ponds, rivers, slurry pits, above-ground slurry bioreactors, bioreactors, ground water, and the like.
In addition to the macronutrients (nitrogen, phosphorus, and sulfur), the invention can serve to deliver essential micronutrients such as micronutrient metals to the microorganisms as well. In another embodiment additional growth promoters, a vitamin source, for example yeast extract, can be incorporated into the controlled-release composition or administered concomitantly to additionally promote the vitality and growth of the microorganisms. Thus, in additional aspects, this invention can deliver in a controlled-sustained manner macronutrients, micronutrients, buffers, vitamins and the like or any combination thereof, to the bioremediation microorganisms.
In a preferred embodiment, this invention provides significantly enhanced levels of bioremediation by the unexpected feature of using lower levels of nutrients--that is, lower use levels of nutrients at sustained levels give higher activity than is achieved at higher nutrient levels.
As will be apparent, the present invention is highly advantageous when applied to environments requiring bioremediation activities in that it provides a way to efficiently deliver essential nutrients, in an environmentally sound way, to the waste-degrading microorganisms throughout the entire remediation without the expensive, wasteful, labor intensive multiple reapplications called for in methods of the prior art. Surprisingly, in order to obtain the most efficient bioremediation, the concentration of the nutrients in the soil is maintained at a lower level than suggested by the prior art.
This invention will be described with reference being made to the accompanying drawings in which:
FIG. 1 is a graph showing bacterial levels in soil over time at various levels and types of nutrient addition in accord and not in accord with this invention;
FIG. 2 is a three line graph showing diesel fuel contamination levels at various nutrient release rates in accord and not in accord with this invention over a 100-day trial period of bioremediation; and
FIGS. 3-6 are a series of bar graphs comparing the levels of various hydrocarbon contaminants in an oil-fouled environment at a starting point (FIG. 3), after one month (FIG. 4), after about two months (FIG. 5), and after about three months (FIG. 6), when the present invention is practiced and when control conditions are imposed.
The materials employed in the present invention deliver nitrogen, phosphorus, and/or sulfur as macronutrients to the bioremediation microorganisms. Nitrogen can be delivered as nitrate, ammonium, urea or cyanamide. Phosphorus is typically delivered as phosphate. Sulfur is generally delivered as sulfate. Potassium, a usual component of plant nutrient material, may be present but generally is not required. The macronutrients employed to make up the controlled-release product are normally standard fertilizer materials and can include urea, ammonium nitrate, ammonium phosphates, ammonium sulfate, calcium nitrate, calcium cyanamide, sodium nitrate, calcium phosphates, single superphosphate, triple superphosphate, potassium nitrate, and potassium sulfate. These materials are highly water soluble with the exception of calcium cyanamide and calcium phosphates, and if employed without a controlled-release coating, would rapidly dissolve in and be dissipated in an open environment. The amounts of nitrogen, phosphorus, and sulfur can be varied in the product to give compositions having from 0 to 40 percent nitrogen, from 0 to 40 percent phosphorus, and from 0 to 20 percent sulfur by weight based on the overall micronutrient composition. Preferred ranges are from 10 to 40 percent nitrogen and 2 to 20 percent phosphorous and 0 to 10 percent by weight sulphur. In one preferred embodiment, the total nitrogen is approximately 28 percent nitrogen, and the phosphorous level is 3.5 percent or 8 percent in P2 O5 form. This type of product would be referred to as a 28-8-0 (0 being potassium in K2 O form) product in typical fertilizer nomenclature. At this time, it is accepted in the bioremediation industry that the product should release 1 to 10 parts nitrogen per part by weight phosphorus.
The materials employed in the present invention may also contain micronutrients to promote the growth and activity of the microorganisms. These micronutrients can include all those materials known by those in the art to be essential to the microorganisms. These can include metals, for example, magnesium, iron, manganese, calcium, and the like. The micronutrients are optional, and if present, are present in very low levels of typically less than 1 percent and more likely less than 0.1 percent by weight, such as from 1 to about 500 ppm by weight. These materials can be made to release at the same rate as the macronutrients or faster than the macronutrients depending upon the needs of the microorganisms. A faster release can be attained by coating these materials on the outside of particles so that they are released at the first part of the release cycle.
Since the microorganisms also utilize vitamins such as thiamine, folic acid, biotin, nicotinic acid, and the like, these can also be included into the controlled-release products. It has been shown that part per million concentrations, and in some cases a fraction of a part per million, of vitamins can drastically increase activities of the microorganisms and thereby increase speed of waste degradation. For this reason, from 0.01 to 100 ppm by weight of such vitamins may be included in the product.
Microorganisms also thrive best in particular pH ranges, such as from about 6.5 to 8, so a buffering system may also be added to the product to maintain the environment around the controlled-release particle at these desirable pHs. This buffering system can be made up of compounds which double as a nutrient source making the system even more desirable. For example, the phosphate phosphorous sources can provide buffering capacity into these desired pH ranges. Representative buffers are a 1:1 mixture of KOH and KH2 PO4 and a 2:1 disodium phosphate and monopotassium phosphate mixture.
The controlled-release compositions of this invention are particulate solid materials which comprise a water soluble core of the nitrogen and/or phosphorus and/or sulfur micronutrient source and optionally micronutrients and/or vitamins and/or buffers surrounded by a release rate-controlling coating. While any of the release rate-controlling membrane materials of the art, such as those included in the above-referenced Theeuwes or Baker patents can be used (these patents are incorporated herein by reference), it has been found in our work to be advantageous to use a resin formed from linseed oil and dicyclopentadiene (DCPD) copolymerized and bodied. Such a composition is employed commercially under the trademark "Osmocote", a trademark of Grace-Sierra Horticultural Products Company. This material is described in U.S. Pat. No. 3,223,518 and Dutch Patent No. 132,686, both of which are incorporated herein by reference. This "Osmocote" coating is advantageous due to its low cost and high effectiveness when used to create controlled-release products capable of lasting from one week to 100 weeks. A typical remediation will last from 10 to 40 weeks.
Variation on the linseed oil/dicyclopentadiene system replaces part of the linseed oil with soybean oil plus maleic anhydride and pentaerythritol. These materials all function equivalently. More specific examples of these materials include soybean oil at 60 to 65 percent and DCPD at 35 to 40 percent by weight; soybean oil at 35 to 40 percent by weight, linseed oil at 20 to 26 percent by weight and DCPD at 35 to 40 percent by weight; and soybean oil at 55 to 60 percent by weight, maleic anhydride at 2 to 5 percent by weight, pentaerythritol at 2 to 5 percent by weight and DCPD at 35 to 40 percent by weight.
Other types of controlled-release coatings which can achieve the desired controlled nutrient release to bioremediation environments include polyethylene, polypropylene, ethylene, propylene copolymer, ethylene-vinyl acetate copolymer, vinylidene chloride, vinyl chloride, vinylidene chloride-vinyl chloride copolymer, and polystyrene. These materials are discussed in more detail in U.S. Pat. No. 4,369,055 which is incorporated by reference.
The macronutrients employed in the present process are typically granular materials having grain sizes from about 0.1 to about 5 mm. These granules will be composed of any macronutrient, micronutrient, vitamin, and/or buffer previously mentioned or amenable to being granulated and will be coated with a resin layer. This coating will most likely be the linseed oil/DCPD copolymerized resin and will be applied to the granules and then heat cured onto the granules' surface creating a controlled-release film. The amount of this resin applied to the granules will range from 1 to 20 percent by weight (based on the weight of macronutrients) depending on the granules' shape and the required longevity of the product. The typical percent of resin used will be between 5 and 15 percent.
In accord with the process of this invention, the precise amount used will depend on the level of contamination being treated, the concentration of background nutrients, the percentages of nutrients in the controlled-release product of interest, and other conditions affecting the nutrient release.
Typical use levels for soil treatment will run from about 0.50 to about 50 pounds of controlled-release nutrients per cubic yard of contaminated soil. We have found, quite unexpectedly, that even though the release of nutrient is controlled and delayed, we get best results at lower overall use levels than we observed for non-controlled release (i.e., wholly soluble) materials. More specifically, while soluble materials give best results at about 5 or 10 pounds per cubic yard, so as to obtain a contaminant carbon:nitrogen:phosphorus atomic ratio of 100:20:1, we have obtained far better results using as little as 1 pound of controlled-release material per cubic yard of soil. On this basis we prefer to use 0.25 to 5 pounds per cubic yard and especially 0.5 to 3 pounds per cubic yard.
In soil environments, moisture must be present to allow the microorganisms to flourish. Moisture may be added if desired. The controlled-release product may be spread on the contamination and/or tilled into the contaminated soil. In the case of contaminated aqueous environments, use levels of from about 0.0005 to about 0.5 pounds per gallon are advantageous, again this is dependant upon the environmental conditions.
The environment being remediated can be the naturally occurring soil or aqueous environment. Alternatively it can be a modified environment wherein the modifications improve the rate or extent of bioremediation. In the case of soil environments, this can include turning over the soil, composting the soil, adding surfactant, or slurrying the soil in a water medium.
In the case of an aqueous environment, the natural environment can be groundwater, effluent from an industrial process or any other waste water source. The improvement can include holding the water in basins or ponds to assure adequate remediation time as well as other improvements known to the art of water treatment processing.
The bioremediation processes of this invention may rely upon the microflora present in situ at the contamination site and this is typically preferred. Alternatively microorganisms may be seeded into the contamination site and these added materials can include any of the organisms known in the art to affect contaminant degradation such as the Pseudonomids, Methylotrophic bacteria, Acinetobacter as well as a variety of anaerobic bacteria. It is not intended that his invention be limited to any particular type or family of organisms, including genetically engineered microorganisms.
The invention will be further illustrated with reference to the following examples. These examples are provided solely to illustrate ways of practicing the invention, and are not to be construed as limitations on the invention's scope, which is instead defined by the claims hereinafter appended.
A nitrogen and phosphorus nutrient granule in controlled-release form was prepared as follows. Granules each containing ammonium nitrate, 80%; ammonium phosphates, 12%; calcium phosphates, 5%; and inerts, 3% were screened to a Tyler mesh range of -6 to +12. This material was then coated with 7.4% by weight (basis finished product) of a linseed oil/DCPD copolymerized resin (6% w linseed oil/38% w DCPD). The coating was accomplished by heating the screened nutrient granules to approximately 70� C., then applying the resin at a flow rate which gives a uniform coating. This controlled-release material had a nitrogen content of approximately 28% and a phosphorus content of approximately 3.5%. The release characteristics of this product, as found in the laboratory, showed that the nutrients were released over a three month period at 70� F. The lab test consisted of statistically splitting 8 grams of the controlled-release product out of the bulk and placing it in a funnel containing approximately 200 ml of washed sand. The funnels were leached every seven days with water and the leachate analyzed for nutrients.
This material was applied to soil contaminated with diesel oil. It was predicted, using the old methodology of applying soluble nutrients, that the bioremediation would take four months. The contaminated soil was remediated in slightly over two months using this controlled-release product. This material was also applied to the beaches in Prince William Sound, Alaska, contaminated with oil from the Exxon Valdez, and supplied nutrients continuously to the indigenous microorganisms for approximately three months.
The preparation of Example 1 was repeated with the following changes. After applying the controlled-release resin, a dispersion containing micronutrients, vitamins, and a buffer was applied to the granules and cured. The cured dispersion consisted of 20% resin by weight with the remaining 80% consisting of phosphate buffer, magnesium, iron, potassium, manganese, molybdenum, thiamine, riboflavin, nicotinic acid, pantothenic acid, folic acid, biotin, choline, inositol, and protein. This dispersion was then overcoated with 0.5% (by weight of finished product) linseed oil/DCPD resin. Also coated with this dispersion and then overcoated was a urea substrate consisting of 25% urea granules coated with 11.1% resin and the remaining 75% urea coated with 13.8% resin. This added urea was then mixed with the micronutrient containing particles to comprise 20% by weight of total product and created a product containing approximately 29% nitrogen, and 3% phosphorus as well as micronutrients.
This product was tested in a laboratory microcosm competing against a dry soluble nutrient of comparable composition. At four weeks, the bacteria population in the controlled-release nutrient treated microcosm was an order of magnitude higher than the soluble nutrient treated microcosm and two orders of magnitude higher than the microcosm having no nutrient treatment.
The experiment of Example 1 is repeated with the following change. The linseed oil/DCPD resin is replaced, using, instead, a resin made from soybean oil, 57 percent; maleic anhydride, 2.5 percent; pentaerythritol, 2.5 percent; and dicyclopentadiene, 38 percent.
The experiment of Example 2 is repeated with the following change. The linseed oil/DCPD resin is replaced, using, instead, a soybean oil based resin as described in Example 3.
Nitrogen and phosphorus nutrient granules, in controlled-release form, are prepared as follows. Granules containing urea are screened to a Tyler mesh range of -6 to +12. Granules containing calcium phosphate, monobasic are also screened to a Tyler mesh range of -6 to +12. 22.6 pounds of the urea granules are heated to approximately 65 C. and 3.4 percent linseed oil/DCPD resin is applied. Then 7.8 more pounds of screened, uncoated urea is mixed into the 22.6 pounds of partially coated urea and the mix is brought up to approximately 65� C. After achieving this temperature, 6.1 percent linseed oil/DCPD resin is added by weight of substrate and resin. To conclude the coat 14.2 pounds of calcium phosphate, monobasic acid is added to the partially coated urea fractions and the temperature is brought up to approximately 70� C. Resin is applied at 5.7 percent on the total weight of the coated product. The final product contains 52.5 percent urea coated with 13.8 percent resin, 17.5 percent urea coated with 11.1 percent resin, and 30.0 percent calcium phosphate, monobasic coated with 5.7 percent resin. This product will supply nitrogen and phosphorus continuously, in a ration of 5 to 1 respectively, for three months in a moist environment kept at 20� C.
A bioremediation field trial was conducted to determine if controlled-release nutrients would enhance the degradation of diesel when compared to the standard practice of applying dry soluble nutrients. The results of the trial are presented in FIGS. 1-6.
The two controlled-release products were added at concentrations of 1, 5, and 20 lb/cu yard of soil. The first controlled-release product used is referred to as Customblen™ 24-89 and contains 27.5% nitrogen and 8% phosphorus in P2 O5 form. The second controlled-release product used is referred to as Max Bac™ 2 and contains 26% nitrogen, 10.5% phosphorus in P2 O5 format, and 0.65% potassium in K2 O form. The controlled-release products were prepared as described in Example 1 and Example 2 with the modification that the dispersion was coated onto the substrate before the controlled-release membrane was applied.
Two controls were present, one having no nutrient addition and one having 3.5 lb/cu yard of a 30-9-0 soluble fertilizer with an analysis of 16% ammonium, 14% nitrate, 3.27% water-soluble phosphate P, and 3.93% citrate-soluble phosphate P.
The eight experimental conditions were identified as follows:
______________________________________No nutrients A-seriesSoluble farm at B-series3.5 lb/cu yardCustomblen ™ 24-89 at C-series1 lb/cu yardCustomblen ™ 24-89 at D-series5 lb/cu yardCustomblen ™ 24-89 at E-series20 lb/cu yardMax Bac ™ 2 at F-series1 lb/cu yardMax Bac ™ 2 at G-series5 lb/cu yardMax Bac ™ 2 at H-series20 lb/cu yard______________________________________
Each of the eight samples (one for each set of experimental conditions) was run in triplicate 3'�3' plots. The pH of the test plots was held at 6.5-8.0 by adding calcium carbonate. Moisture was maintained uniform in that all the plots were treated identically and allowed to vary uniformly between 20-60% moisture during the tests. In each case, the initial concentration of contaminants in the soil was approximately 2500 mg diesel per Kg dry virgin soil. The test plots were troweled once per week to add oxygen.
Samples were taken at 0 elapsed time, 1 month later and 2 months later and analyzed for total bacteria, colony-forming units, phenanthrene degraders (known hydrocarbon degraders), and fluorescent Pseudonomids. The samples were also tested for levels of total hydrocarbon and individual hydrocarbon fractions by carbon number. Conductivity, as a measure of available nutrient concentrations, was also measured on each sample.
As shown in FIG. 1, it was observed that the total bacteria present in the samples remained relatively constant among all of the samples with the exception that the high use levels (20 lb/cu yard--series E and H) of controlled release products gave lower bacterial levels than the 1 lb/cu yard or 5 lb/cu yard series (series C, D and F, G). Similarly only modest differences were noted in colony-forming unit concentration but with better performance being seen with low controlled release nutrient levels than at high levels. There were major differences in levels of phenanthrene degrading bacteria among the 8 tests. The control with no added nutrient was as much as two orders of magnitude lower than the tests with nutrient. At high use levels (20 lb/cu yard--series E and H), the added fertilizer first boosted and then depressed the number of organisms observed. At low levels (1 and 5 lb/cu yard--series C, D, G and H) the number of such organisms elevated over time by as much as 21/2 orders of magnitudes and in several samples as much as one order of magnitude greater than the standard practice addition of soluble fertilizer. In virtually all cases where nutrient was added, including the control, the level of fluorescent Pseudonomids went up dramatically in the first month and then fell in the second month.
The actual bioremediation performance observed with these eight systems showed clearer advantages achieved by the present invention. In FIG. 2 the measured levels of total diesel contamination are plotted as a function of elapsed time.
The standard practice of adding dry soluble fertilizer reduced the contamination to about 750 ppm in 100 days. Interestingly, high loadings (20 lb/cu yard) of controlled release material gave poor results. At this condition, over 1000 ppm of contamination remained after 100 days. At a rate of 5 lb/cu yard, controlled release material reduced contamination to about 250 ppm in about 100 days. Best results were observed at the lowest rate of controlled release material addition--1 lb/cu yard. At this condition, the contamination was consumed the fastest and to the lowest level, 250 ppm.
Dirt samples initially containing added diesel contamination as noted above were bioremediated under 3 comparative conditions--condition A--no fertilizer, condition B--3.5 lb/cu yard of dry soluble fertilizer and condition F controlled release fertilizer at 1 lb/cu yard. Samples were taken at day 1, day 31, day 53, and day 95 and analyzed by gas chromatography. The results were digitized to give relative levels of each carbon number fraction. FIGS. 3, 4, 5 and 6 show the results of these analysis and illustrate a regular and striking advantage to the controlled release material which allowed the clean up to achieve a reduction in contamination to 16 units while the control was at 55 units and the soluble fertilizer test gave 41 units.
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|U.S. Classification
|71/6, 71/64.11, 435/262, 71/903, 210/610
|International Classification
|Cooperative Classification
|European Classification
|Jan 8, 1992
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text:
Update on the Ducks players at Worlds
Ducks defenseman Cam Fowler had an assist and will move on with the United States to the quarterfinals but teammate Luca Sbisa helped Switzerland to a 5-3 victory over the Americans on Monday at the IIHF World Champsionship in Kosice, Slovakia.
Fowler got the primary assist on James van Riemsdyk's third-period goal as he finished at even strength in playing 21 minutes, 42 seconds for the U.S., who will face the Czech Republic in the quarterfinals.
It was Sbisa's final game of the tournament as the Swiss finished in ninth place. The young Ducks rearguard was a plus-1 in 21:06 of action and wound up with one assist and eight shots on goal in six games overall as he logged the fourth-most ice time on the squad.
Meanwhile, Lubomir Visnovsky didn't play for Slovakia in its 4-1 victory over Denmark on Monday in the host country's finale and that might be a blessing for the Ducks as the defenseman can now focus on resting his aching shoulders.
Visnovsky logged nearly 24 minutes of ice time in Slovakia's 2-1 loss to Finland on Saturday, a loss that eliminated any possibility from reaching the quarterfinals. He played in three games and finished with two assists and a plus-1 rating.
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subset: commoncrawl


text:
FORT COLLINS, Colo. -- Four players on the Colorado State
University women's basketball team have been suspended for setting
off a chemical bomb outside the apartment of teammate Kelly Rae
Finley, athletic spokesman Gary Ozello said Saturday. There were no injuries and no structural damage.
"There's nothing we can do about it right now. This will be a
great experience for the rest of the players. It means that we will
have to play a lot harder. Sarah Hunter, the only remaining
starter, has to play nearly 40 minutes and have an MVP
performance," coach Jen Warden told The Associated Press.
Police detective David Grant identified the suspended players as
starting guards Emily Neal, 19, and Kelly Jo Mullaney, 18, both of
Minneapolis, and reserve forward Raysha Ritter, 18, of Grand
Junction, Colo., and reserve Brittney Stirling, 19, of Tucson,
Ariz., all freshmen.
Warden said the suspended players will not be allowed
to practice or sit on the bench when the Rams host New Mexico on
"This is a case where four teammates were trying to play a
prank on a teammate, and it went bad," Grant said. "They thought
the device would just make a loud bang, and that it would not be a
big deal. It was not meant in a malicious way by any means. I know
that Mullaney and Finley are very good friends."
He added, "No one was hurt, and there was no property damage;
but if someone had opened the door at the time the device exploded
there could have been serious injuries." The bomb was made of
chemicals that create an explosive acid.
Police spokeswoman Rita Davis said the four players all knew
that two other team members were staying at the victim's apartment
and thought it would be funny to scare them. She said they would be
charged with one count of reckless endangerment, a misdemeanor.
The Fort Collins Coloradoan said Mullaney, Neal and Finley, 21,
all played at the same Minnesota high school and have been friends
for several years. The four suspended players apparently drove to
Finley's apartment in Mullaney's car.
A witness reported their car after the Monday night incident.
"Once confronted, all four players confessed," Grant said.
Warden refused to say how long the suspensions would last. They
leave the Rams with just eight available players. Mullaney was the
team's leading scorer.
"This is an internal matter related to the team," Warden said.
"This is a challenge that will help everyone involved grow."
The suspensions came on the day following the Rams' 73-57 loss
Thursday night to Utah.
"Obviously, any time a student-athlete is involved in anything
like this, our Office of Student Affairs will work closely with
athletic department to determine the next step, if any, that will
be taken," said Ozzello.


text:
YSU Men's Basketball @YSUMensHoops
Three Men's Basketball Players Named to @NABC1927 Honors Court bit.ly/2arYjd7 pic.twitter.com/vwdo1O5mLi
Three Men's Basketball Players Named to @NABC1927 Honors Court bit.ly/2arYjd7 pic.twitter.com/vwdo1O5mLi
Carlton Brundidge scored 28 points and grabbed nine rebounds to lead No. 6 seed Detroit past No. 7 seed Youngstown State 92-79 in the first round of the Horizon League tournament on Saturday nigh
Cameron Morse scored 25 points to lead five players in double figures as Youngstown State ended the regular season with a 94-75 defeat of Northern Kentucky on Saturday night, avenging an earlier
Michael Karena, who came in averaging 9.0 points, scored 26 points with eight rebounds and Wright State beat Youngstown State 87-81 on Thursday night.
Jordan Johnson had a triple-double -- the fourth in Milwaukee men's basketball history -- to help the Panthers beat Youngstown State 87-51 Monday night.
Carrington Love scored 25 of his career-high 39 points in the second half, and Green Bay topped 100 points for the third time this season in a 107-90 win over Youngstown State on Saturday.
Jorden Kaufman scored all six of Youngstown State's points in the first overtime and Matt Donlan tipped in the winning shot with 1.2 seconds left in the second OT as Youngstown State beat Illinoi
Demonte Flannigan scored a career-high 30 points and Cleveland State beat Youngstown State 64-59 on Saturday night to snap a five-game skid.
Paris Bass scored 20 points on 7-of-14 shooting and Josh McFolley sank the go-ahead jumper to lift Detroit to a 94-92 win over Youngstown State on Saturday night.
Kahlil Felder led six players in double figures with 17 points and Oakland outran Youngstown State 107-85 on Thursday night.
Alec Peters scored 18 points, and Vashil Fernandez added 11 points and 13 rebounds as Valparaiso overwhelmed Youngstown State 97-68 Saturday night.
Cameron Morse had 22 points and Francisco Santiago made a key pair of late free throws to help Youngstown State beat Illinois-Chicago 82-78 on Thursday night.
Matt Donlan scored 16 points and Youngstown State topped Cleveland State 70-55 on Sunday.
Alec Peters and Darien Walker scored 18 points apiece to help lead Valparaiso to a dominating 96-65 win over Youngstown State on Monday night.
Michael Karena, Mark Alstork and Grant Benzinger each scored 13 points as Wright State routed Youngstown State, 81-45 on Saturday night.
Tyler White had 20 points, nine rebounds and six assists on Thursday night and Northern Kentucky beat Youngstown State 84-64 for its first Horizon League win of the season.
Cameron Morse scored a career-high 44 points on 72.2-percent shooting from the field as Youngstown State overwhelmed Green Bay 103-93.
Akeem Springs made 14 of 18 from the field, including 4 of 6 from 3-point range, and finished with a career-high 33 points to help Milwaukee beat Youngstown State 81-65 Thursday night.
Jorden Kaufman made a tip-in with one second left and finished with 18 points and 13 rebounds as Youngstown State beat Oakland 100-98 Monday night for the Penguins' second road win of the season.
Anton Wilson notched career highs with 34 points and nine rebounds, and Detroit erupted for 59 second-half points to beat Youngstown State 96-87 in each team's Horizon League opener on Saturday.
Demetrius Jackson scored 17 points Monday night and Notre Dame had to hold on late to beat Youngstown State 87-78.
Notre Dame's Zach Auguste catches the alley-oop pass from Matt Farrell and throws it down for an easy two points against Youngstown State (Live on ESPN3).
|Final Fours
|Tournament Record
|Championship Seasons
|Tournament Appearances


text:
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text:
By most measures, the rate remains the same
From 2000 to 2008, we averaged "about five mass shootings a year. We're now averaging 15. So that's a three-fold increase."
— PunditFact
on Wednesday, May 28th, 2014
The numbers are right, but trendline isn't clear
"Saturday's shootings reflect a disturbing trend. Mass shootings have become commonplace since the Virginia Tech massacre in 2007. There have been dozens of incidents where three or more people have been fatally wounded. Hundreds have died."
— PolitiFact National
on Tuesday, January 11th, 2011
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The Story: Loss: Great Short Stories for Women by Women (Paperback)Victoria Hislop
Paperback Published: 19/06/2014
- 10+ in stock
Click & Collect From your local shop
'I think few of the stories in Loss will leave readers cold...' Victoria Hislop, bestselling author and champion of the short story, has chosen her favourite short stories by women writers. Here are prizewinners, famous wits, well-known feminists, national treasures and rising stars. All the stories in this volume are about loss: lost lives, lost loves, lost innocence, even a lost leopard. The many ways in which loss touches our lives are shown in these varied stories. CONTRIBUTORS: Katherine Mansfield, Elizabeth Bowen, Dorothy Parker, Shirley Jackson, Flannery O'Connor, Elizabeth Taylor, Jean Rhys, Anna Kavan, Muriel Spark, Ellen Gilchrist, Penelope Fitzgerald, Lorrie Moore, Hilary Mantel, Susan Hill, Colette Paul, Yiyun Li, Helen Simpson, Edna O'Brien, Edith Pearlman, Emma Donoghue, Carrie Tiffany and Lucy Wood.
Publisher: Head of Zeus
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"A treasury of meaningful stories"
An unforgettable collection of short stories by talented female writers, and it looks beautiful on the shelf. A great gift or a treat for yourself - together with 'Life' and 'Loss', Hislop has... More
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So I had to get up at the buttcrack of dawn (i.e. 4am) to make some delicious Liege Belgian Waffles. Those suckers were so freaking good. The sugar pearls were melted in my mouth. I added a little whipped cream, strawberries, blueberries and chocolate shavings. Absolutely fabulous. I have enough batter to make one tonight so there will breakfast for dinner.
Anyhoo, I have been running on empty these last few days. Sleep is not my friend, as they have been missing. Tuesday I was exhausted and didn't have the opportunity to sleep till my normal sleep time. Wednesday was a hell of a night that kept me tossing and turning for hours. Today I decided to let the chef in me awaken. At this point in the day this is the first true moment I have sat down. Between drop offs, doctor appointments and putting on front brakes (yes, I helped to put them on after all I am a jack of all trades), I have yet to relax for a moment. Now time ticks for me to make dinner and pick up one child. Yeah, can't you feel the joy coming up my throat. I know that I am not working and I really shouldn't complain but sometimes I really want to get into my car and just drive somewhere quiet. Where I can eat, sleep and be happy on my own time. I love my family and they do make me hapy but there are moments I would like to locked then in a soundproof room for a week. Oh well I will treat my bedroom like an oasis and try to shut out the world tonight.
Peace, Love and Chocolate,


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Kelly Thevenot's Reviews > There's No Such Thing as Monsters
There's No Such Thing as Monsters
by Steve Smallman, Caroline Pedler
by Steve Smallman, Caroline Pedler
Kelly Thevenot's review
bookshelves: moods, picture-books
Dec 14, 2011
bookshelves: moods, picture-books
This a a good book about a child who is so excited about his new room and when it is time to go to bed he gets uneasy. His parents are there for him and there is nothing to be scared about. It would be a good story to read during down time.
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iHerb Customer Reviews
Savings of: $8.50 (25% off)
Sorry, this product is no longer in stock.
Great stuff
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This is one of those products that you can't get in stores. Iherb has the best price and fastest delivery. I once bought it from another company when Iherb was out of stock, but never again!
Vision Improve somehow
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Brite Eyes
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I've just started using this one day ago so I don't know how it will be long-term, but the drops felt gentle going in and no problem afterwards. If you keep a bottle in the fridge I suggest you warm the bottle in your hands a little before use.
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"Dry Eye" in cats
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My cat, Felix, had 2 eye surgeries for dry eye performed when Hurricane Frances was here in Florida. My Vet wanted to put him on Cyclosporin eyedrops every couple of days for life. I did a little reasearch and for several years now, he gets his eye drops (which I order from you) about once a week and he's happy and not had a problem since.
Great for the eyes
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I have used this for several months now after being told I had the beginnings of cataracts. Within a couple of weeks glare problems I had been having were considerably reduced.
Clear eyes
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The only eyedrops I've found that keeps my dry eyes moisturized; they are expensive but worth the price. Note that the drops are used by taking off the cap and removing the little collar then puncturing a hole by closing the bottle top; then replace the collar and bottle top.


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The epic struggle for control of planet Earth continues in this sequel to the 2001 comedy that confirmed everyone's worst suspicions about our furry four-legged companions. A former top spy for the clandestine feline espionage bureau MEOWS, Kitty Galore is determined to rule the world and finally gain the upper paw over her canine rivals. But when an unforeseen threat appears, cats and dogs must band together to defeat a common foe. Chris O'Donnell and 30 Rock's Jack McBrayer head up the cast of the production, with scripting duties being handled by Brother Bear's Ron J. Friedman and Steve Bencich. ~ Jason Buchanan, Rovi


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Dallas cop fired for shooting unarmed carjacking suspect
The officer's lawyer argued that she truly feared for her life when she fired at him, despite reports that his hands were raised and empyty
By Tanya Eiserer
Dallas News
DALLAS — A Dallas police officer was fired today after an internal investigation concluded that she violated the department's deadly force policy when she shot a 19-year-old carjacking suspect.
Senior Cpl. Amy Wilburn was among several other police officers facing disciplinary hearings before Police Chief David Brown. She lost her job in connection with the Dec. 9 shooting of Kelvion Walker.
An independent witness has said the officer shot Walker even though he had both hands in the air and showed no signs of having a weapon.
Wilburn's attorney, Robert Rogers, has previously said that the shooting was justified.
"Without getting into the specifics of an ongoing investigation, I can promise you that the officer involved was in fear for her life at that exact moment," Rogers said.
But an internal investigation determined that Wilburn fired her weapon "upon an unarmed person without fear or justification." Police have said no weapon was found in the car.
As with all the officers terminated today, Wilburn can appeal her firing under civil service rules.
McClatchy-Tribune News Service
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WELLINGTON, Fla. — A private senior transportation service, Senior Transportation and Rides (STAR), established in 2009 following a village-wide survey in which senior travel needs presented as one of the biggest hurdles those residents faced every day, was recently tweaked to be able to serve more seniors efficiently, The Palm Beach Post reported.
Now, Wellington residents aged 62 and older receive up to eight trips a month to and from their home to anywhere they desire (within a specified footprint) free of charge, according to the report.
For the full story, click here.
The American Occupational Therapy Association's plan helps families identify signs that older drivers may become unsafe and makes suggestions to help seniors maintain mobility, such as using paratransit services and reduced transit fare programs.
Metro plans to issue an RFP to take over the service in September, with the intent to have the system in place by spring 2017. The pilot program will be for users in the Maryland suburbs, where two-thirds of MetroAccess customers live.
The city's Access-A-Ride, which already has nearly 400 MV-1s in service, is a shared-ride, door-to-door service for people unable to use public buses and subways.
Thanks to the agreement, a tap of the Uber app will help remove the employment barrier of getting to job interviews for blind and visually impaired BIT candidates in Colorado.
That same audit also criticized the agency for a lack of oversight over the nonprofit, which failed to supply data supporting its ridership figures during the first audit ever conducted of its $20 million annual contract.
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Rocky is a very nice mover and is ridden both English and Western. He has great transitions and is cute over fences. Sound and Healthy. No vices. PERFECT…SOLD
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Just before the Republican convention, our attention shifted from police brutality—and the brutalization of policemen—back to terror. Glued to our TV sets, we watch as bombs blast and trucks slam viciously into strolling French families. 926 altre parole
Tag » Le Pen
Normal service will be resumed...maybe
This weekend my university is doing essential upgrading work and so my access to the database of newspapers I use to create this blog is disrupted. 515 altre parole
The French football team and immigration
This election year, immigration has been one of the most discussed issues. From Donald Trump's wall to Nigel Farage's Brexit, we've heard a lot about immigration. 832 altre parole
So what does Angela Merkel think?
In our post-Brexit world, there are some key figures that will strongly influence the outcome of the negotiations. One of them is Jean-Claude Juncker, the head of the EU Commission, a seasoned EU-politician who made us laugh earlier this week when he asked… 884 altre parole
Brexit and left wing politics
I am rather sick of reading the Guardian newspaper. Almost on a daily basis , the newspaper keeps dragging up the same old arguments to the surface regarding the issue of Brexit. 720 altre parole
123 altre parole
(Emmanuel) Macron proposed a solution that sounded revelatory in the context of the myopia of the political class: a conversation. "That's what politics is," he said.
On the same side as Matteo Salvini now.
I am not very good at voting these days. All I can say is thank goodness John Finnie is an MSP or my track record would be very poor indeed. 408 altre parole


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viscous and hard to measure
Posted by Kyriaki on Apr 06, 2013
the solution is so viscous and lumpy that it's impossible to measure. Although pleasant tasting enough (even in water)I found that I had flank pain after 2 days of dosing twice a day. I stopped immediately. I might try it again when I have reduced other herbs, in the case that it was the combination or just plain overload on my kidneys.
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Editor's note: Defensive back Drayton Florence, taken in the second round of this year's NFL draft by the San Diego Chargers, will chronicle his rookie experiences in a weekly diary for ESPN.com.
After knocking on the door a few times this season, we finally kicked it down this past Sunday against Cleveland.
We put together strong performances in all three phases of the game -- offense, defense and special teams -- and as a result, we got a win. There were several standout performances by some of my teammates that I'm glad we rewarded with a victory.
LaDainian Tomlinson was awesome again. He had 200 yards and an electrifying 70-yard touchdown run. L.T. once again showed he's one of the premier running backs in the league. Kwamie Lassiter ran back a pick for a score and we got four field goals from Steve Christie to help us get the win.
I made a couple of tackles, deflected a pass and helped out with a tackle on special teams. But individual statistics don't matter to me because we got a win. The main thing is winning.
The plane ride back to San Diego could've been fueled by the positive energy we all had after the game. When you play football for a living, winning games is what we live for. Since it was the first game my team won, I'll never forget the feeling. I finally feel like a real NFL player. There are a few milestones you have to reach before a rookie feels like he belongs and the first time your team gets a win ranks right up there with suiting up and playing in your first game.
Food tastes better after you get a win. When you've been on a losing streak, a win re-energizes the players. If you've worked as hard as we have, a win reinforces that the hard work we've put in isn't for nothing. Finally the guys on SportsCenter will quit referring to us as the lone winless team in the NFL or a team that doesn't deserve to be without a victory.
Now that we have our first win, it is time for us to string a few together. We've got a big game this week against Miami. Not only is the game against a good team in our conference, but it is on Monday night. I remember growing up watching Monday Night Football on television and dreaming that one day I'd be playing on Monday nights. Now I have the time to fulfill that dream.
While it will be a thrill, I'm looking at it like it's just another game. I know all of America will be watching, but to me there's no difference because the game will be played on a field 100 yards long and the game will still be 60 minutes long. Don't get me wrong, it will be fun to be playing under the lights, but I'm preparing like it is just another game. I guess you could say, I'm ready for some football.


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- FreelanceGraphic Design, 2007 - presentGraphic design; logos, banners, motion graphics. Instructional design; distance learning materials, ebooks, digital content, interactive lessons.
- Ministry of Education, KuwaitPhysical Education Teacher, 2006 - presentTeaching Primary and Intermediate school students. Preparing and Coaching students for different sport events and competitions.
- Screens International Company SIC, KuwaitMultimedia Specialist, 2007 - 2008Designing motion graphics and static graphics for clients. Carrying out unfinished tasks and aiding to finish projects before targeted date.
- Arabian Gulf University, Bahrain.Distance Teaching and Training, M.Ed., 2011 - 2014Graduated with honors; studied open and distance learning (ODL) including developing open and distance learning materials such as ebooks, educational websites, virtual learning environments (VLE), digital content writing and conversion as well as instructional design, coordinating with subject matter experts (SME), strategic planning and research in the field of education. Technological Excellence in Education award, university students category: ebook design, 1st place winner. (Bahrain, 2012).
- Technology Domain Institute, Kuwait.Graphics and Web Design, Diploma, 2006 - 2007Practiced Adobe CS bundle applications including Photoshop, Illustrator, InDesign, Flash, DreamWeaver, and After Effects. Performed several projects including magazines, websites, logos and branding. Finished ICDL certification.
- Public Authority for Applied Education & Training, Kuwait.Physical Education, Bachelors, 2001 - 2005Major in Sports Management.
The Most Common iOS 8/8.2/8.3 Upgrade Problems and Solutions
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