Note: Descriptions are shown in the official language in which they were submitted.
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tN SITU TREATMENT FOR CONTAMINATED SURFACE WATERS AND
PRODUCTS THEREFOR
s
Field of the 'Invention
This invention relates to a novel non-toxic in situ method for the accelerated
to biological degradation of organic matter in the form of sewage sludge or
petroleum
hydrocarbons on the surface of aquatic objects submerged in bodies of
saltwater,
brackish, or freshwater. The invention includes novel non-toxic compositions
and novel
products that are particularly useful for practicing the novel methods.
is Description of the Prior Art
The delicate balance of our planets fragile aquatic ecosystems is being
disturbed at
an alarming rate. tndustrial, agricultural, and residential effluents enter
our waterways
polluting these systems with organic, metallic and inorganic compounds.
Current
methods of remediating aquatic sediments contaminated with organic pollutants
such as
2o sewage, oil, pesticides, herbicides and polychlorinated biphenyls involve
dredging up
the sediment and treating it elsewhere then returning it to the removal site.
These
existing methods are both expensive and damaging to benthic ecosystems by
killing
organisms. The need for an inexpensive, in situ and noninvasive method to
remediate
such situations has lead to the development of this novel method and
compositions.
2s Industrial, agricultural and residential effluents and storm water runoff
has
degraded the wa:er quality around the world. Larger and more frequent fish
kills are
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reported every year, such as the one occurring in the summer of y 996 in a
tributary of
the Chesapeake in which one billion fish of nineteen different genera were
reported
killed.
The over abundance of nutrients, as well as contaminants, in lakes and streams
s and estuaries has created~a crisis for aquatic organisms. The high
concentrations of
dissolved phosphorus, has resulted in a rapid increase in growth of aquatic
algae and
plants.
The problem of lake and stream eutrophication is increasing due to the
increase
in nutrients available to aquatic weeds from residential and agricultural
runoff. There
to has been speculation that agricultural runoff has a detrimental affect on
estuarine water
quality leading to the increase in HAB's (Harmful Algal Blooms) such as
Pfiesteria.
Larger and more frequent fish kills are reported every year, such as the one
occurring in the summer of 1996, in a tributary of the Chesapeake River, in
the United
States, in which one billion fish of nineteen different genera were reported
killed. The
is over abundance of nutrients, as well as contaminants, in lakes, streams and
estuaries
has created a crisis for aquatic organisms. The degradation of water quality
has
resulted from an increase in . nutrient concentrations (N03, P04), increased
oxygen
demand (BOD, COD), turbidity and raised bacterial counts (T-Coli, F-Coli).
This has
resulted in the closure of shellfish bed harvests, a reduction in number and
health of
zo commercial fish populations that spawn in estuarine waters. Aside from
accidentally
spills of pollutants, the run-off from agricultural operations has been the
targeted in
recent legislative restrictions on CLO's.
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Current methods of rernediating aquatic sediments contaminated with organic
pollutants, such as agricultural and residential sewage, fuel oil, PCB's and
other
industrial chemicals, involve dredging up the sediment, treating it elsewhere,
and then
returning it to the removal site. Surface water treatments, such as the
treatment of lakes
s for alga blooms, require the addition of poisonous chemical herbicides and
pesticides.
The need for inexpensive alternative treatments is clearly evident and has
encouraged
our research into this field.
Most conventional primary and secondary treatment facilities are inadequate in
terms of the complete removal of many inorganic and organic chemicals leading
to the
~o eutrophication in lakes, rivers, and bays. A typical sanitary analysis of
an
uncontaminated flowing river requires optimally:
pH 6.5-6.8 (and not < 8.5)
Dissolved oxygen 8.0-9.0 ppm (and not >4.00-5.00 ppm)
Color 5ppm
is Turbidity 5ppm
BOD (Biological Oxygen Demand at 20° C) l.2ppm
Total solids 500 ppm
Chloride 10 ppm as CI
By comparison analysis of the recent analysis of hog farm manure which is
Zo incorporated into farm soil showed very high values.
Supernatant Settled sludge portion
pH 7.53 pH 7. ~ 0
COD 14,000 mg/L COD 25,500 mg/L
z
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TDS 7,562 mg/L TDS 7,760 mg/L
TSS 1,880 mg/L TSS 4,560 mg/L
These values do not reflect what will be found in the streams containing
agricultural
runoff. These values will be diluted by rain and irrigation water and filtered
by the soil.
s The potential for environmental damage exists, if this type of waste is
accidentally
discharged into waterways undiluted.
The activated sludge method is the most commonly used secondary wastewater
treatment system for human waste. After primary treatment in which the
majority of
solids are settled out of the water column, these solids are diverted into an
activated
~o sludge reactor while the overlaying water is sent to an aerobic treatment
system before
discharge. In the aerobic treatment system, oxygen is supplied to the water by
aeration
incorporating either surface aerators or diffusers which utilize a mechanical
process
requiring energy input the amount of which is dependent upon the BOD
(Biological
Oxygen Demand) or COD (Chemical Oxygen Demand). However the activated sludge
is chamber, that treats the solids portion, is devoid of oxygen and anaerobic
degradation
is enhanced by and an increase in temperature and bacteria and nutrients.
A variation of this method is used in the treatment of concentrated livestock
waste such as at hog facilities. The raw waste at these facilities is stored
in what are
called anaerobic sludge lagoons or pits. They consist of large earthen or
cement lined
2o enclosures into which the raw slurry (manure and water) is pumped. The
slurry remains
in this enclosure, which is usually open to the air, for several weeks or
months before it
is removed and incorporated into the crop field soil. For the most part these
lagoons
remain anaerobic even though that are exposed to the air at the water surface.
In some
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cases aerators are used to diffuse oxygen into the lagoon to promote aerobic
degradation which reduces that amount of noxious gases created in the
anaerobic
breakdown of the manure.
Our time-release tablets disclosed and claimed in U.S. Patent No. 5,275,943
for
s biological degradation provides an efficient method for aerating wastewater
sufficiently
m cooperation or in place of secondary treatment systems. The incorporation of
advantageous microorganisms and various nutrients as well as dissolved oxygen
(by
the breakdown of hydrogen peroxide) can be added into almost any wastewater
environment through the use of time release tablets specifically designed for
that
io system to reduce BOD and noxious gases and establish a harmonious Eco-
balance.
The economy of treatment reties on the efficiency of the wastewater treatment
system to provide an environment, which supports the activity and growth of a
treatment
microflora along with factors such as the balance between oxygen and substrate
supply.
Our system designed under the U.S. Patent # 5,275,943 can incorporate
appropriately
is required nutrients, microorganisms and Oxygen via hydrogen peroxide to
balance the
organic and inorganic nature and control the biodegradability of the waste.
Similar studies have also been done by Higa (An Earth Saving Revolution,
Japan: Sunmark Publishing Inc. 1993, p. 154) in Japan, who combines
synthesizing
microorganisms with zymogenic microorganisms. He defines zymogenic
zo microorganisms as those that reduce organic matter to a soluble state while
creating
large quantities of antioxidants. Higa developed his own process of autolysis
where the
digestion of organisms takes place by enzymes naturally present and has used
it for
breaking down agricultural synthetic chemicals as well as harmful bacteria
such as
s
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E.coli. He has identified upwards of 80 different strains of microorganisms
known to
have the capacity to eradicate agricultural chemicals.
In both field and laboratory studies, Celiinite Technologies (U.S. patent No.
5,275,943) has now created controlled degradation systems. Successful use of
these
s systems involve ttie utilization of specific microorganisms, nutrients, and
oxygen
introduction through time-released aeration capsules for controlled
degradation of
manure and decaying detritus (plant matter). The changes in physicochemical
parameters in a static system and the passage of bacterial pathogens have also
been
analyzed demonstrating beneficial results.
to A recent study in Iowa (Stanley Buman,The Advanta4e of Manure Proceedings
from the Conference on Manure Management by the Soil and Water Conservation
Society, February 7 0-12, 1998) stated that a typical hog production facility
(CFO) of
2000 head generates 820,000 gallons of manure per year. Using industry
standard
calculations a producer could then land apply 3500 gallons per acre, therefore
235
is acres were needed to utilize the manure from this facility. Depending on
the crop, some
need only be fertilized every other year so that the land requirement could be
470 acres.
In 1996 Iowa produced 24,000,000 hogs or 9,840,000,000 gallons of manure
requiring
5,622,857 acres in order to land apply it. This data just covers hog manure,
not other
livestock. Combining all the types of livestock manure data together, then
looking at the
2o area needed to land apply it, one will find that the needed area far
exceeds the available
land for crops. These figures will only increase as the demand for U.S. pork
products
goes up worldwide.
h
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Storing it in open-air anaerobic sludge lagoons for a period of time, is the
typical
way in which a hog farm treats its manure. Periodically the surface liquid
fraction
(supernatant) is then pumped off and sprayed onto crop fields. The solids
(sludge) on
the bottom of these pits are later removed and tilled into the cropland. Large
corporate
s farms, which have concentrated huge amounts of manure into vast outdoor
sludge
lagoons, discharge a great deal of noxious gasses. These gases, byproducts of
anaerobic degradation of the manure, include compounds such as Hydrogen
Sulfide,
Methane, Ammonia, and Methyl Mercaptan, as well as Carbon Dioxide. These gases
cause a nuisance to local neighbors as well as having a detrimental effect on
the
io atmosphere, by contributing to global warming. New government restrictions
will force
farms to convert their treatment systems from anaerobic to aerobic treatment.
Typically
this would involve large capitol expenditure on the part of the farmer to
construct batch
reactors or place high-powered electric air pumping systems into their
lagoons, to insure
aerobic degradation.
is In lakes and ponds herbicides are commonly used to reduce the growth of
aquatic weeds. The most commonly used are the inorganic copper compounds such
as
Copper Sulfate. These compounds tend to block portions of the photosynthetic
process,
preventing the production of carbohydrates, thereby killing the weeds. Organic
herbicides, such as Diquat dibromide, also interfere with photosynthetic
processes to kill
zo the weeds, but are biologically persistent because they are difficult to
biodegrade and
may bioaccumufate in the tissues of other aquatic organisms.
Colorants have been used as herbicides with varying degrees of success.
Studies by Spencer have shown that their effectiveness is due to the blocking
of the
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light in the 610nm to 650nm range to the plants them selves. Visible light is
the portion
of the electromagnetic spectrum with wavelengths between 400 and 700
billionths of a
meter (400 to 700 nanometers). The colorants used are themselves non-toxic and
are
similar to food colorings. In principle the colorant defracts the light
preventing the wave-
s lengths necessary for photosynthesis from reaching the algae, causing its
decline in
growth.
All herbicides including the colorants cause the death and subsequent decay of
the algae and plants. As these dead plants start to decay they cause an
increase in the
waters demand on available dissolved oxygen. As dissolved oxygen levels in the
water
~o drop below 5.0 mg/L fish heath and fecundity are affected. !n some cases of
this
situation has resulted in fish kills. The need for method of preventing weed
production
without persistent herbicides and that does not cause fish kills is evident.
Oxygen depletion nuisances are caused by the release of excessive levels of
nutrients into waterways, which enhance eutrophication, and then finally,
oxygen
is depletion. Oxygen depletion can arise from the primary effect of direct
organic matter
inputs to the lake. In addition secondary effects of dying plankton and
decaying algae
can cause sudden death of fishes as well as he release of odors caused by CH4,
H2S,
and NH3 gases. The contemporary approach is to change the direct inputs of
organic
matter by anaerobic or mechanical waste treatment systems or by rerouting such
zo contaminated wastes to other locations such as flowing streams.
The BOD of a system is a function of the number and types of microorganisms
present as well as the rate of addition and type of substrates. Whether this
demand can
be satisfied or not depends on a balance existing between the fixed rate of 02
supply
s
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and the variable rate of demand unless methods of introducing oxygen can be
introduced. Thus, in aerobic biological growth, a sufficient amount of
available oxygen is
essential. Mechanical aeration processes are the contemporary solution to
satisfying
oxygen requirements of the system whereby a gas-liquid mass transfer process
takes
s place in which the driving force in the gas phase is the partial pressure of
the gas P9 in
accordance with Henry's law. !n the liquid phase, the concentration gradient
CS - C in
which CS is used as the saturation concentration at the gas-liquid interface
where C is
the concentration in the body of the liquid.
With a single timed-release layered tablet, several active steps will occur.
First,
o the outer layer will dissolve releasing a compound that liberates both
oxygen, in the
form of bubbles, and a combination of blue and yellow water-soluble dyes.
These
bubbles act to both disburse the dye into the water column, raise DO level in
the water,
and loosen particles at the sediment-water interface causing the tablet to
bury itself
deeper into the sediment.
is Next, the inner layers of the tablet disintegrate to release a combination
of
enzymes, buffers and aerobic and facultative anaerobic microorganisms. The dye
acts
to block the wavelength of light necessary for photosynthesis. This causes the
death of
the nuisance algae or plants, which sink to bottom as they decay. The
microorganisms
consume the detritus at a high rate, enhanced by the nutrients and enzymes and
2o dissolved oxygen. The high DO level also helps to prevent the fish kills
associated with
the increased demand created by the decaying plant matter. The source of the
oxygen
is a dry form of hydrogen peroxide which, in solution, quickly degrades to
molecular
oxygen and water, to oxygenate the water. Since micro-organisms receive 02
from DO
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in the liquid phase instead of the usual replacement of DO from the atmosphere
through
a process of stirring or agitation, we introduce it directly into the system
therefore
relocation or extensive mechanical processing systems are not required for the
gas/liquid interface. The oxygen transfer rate differs depending on the
characteristics of
s the water by such variables as dissolved solids, organics, surface-active
agents, the
amount needed can be determined by using the following standard equation:
dddt =K(CS - C~)
Where K=02 transfer rate; CS =concentration of dissolved 02 at saturation; C,
concentration of dissolved 02 at time t.
to Through inputting the time-release tablet intro the aquatic environment the
rate of
02 supply and the buffering capacity provided by a body of liquid containing
dissolved
02 is able to be in excess of the OZ required for microbial metabolism so that
the
development of anaerobic conditions is restrained. Thus, we have been able to
show
that in nonmechanical systems, for example, barrier ditches and lagoons, Oz
supply is
Is no longer limited to transfer at the liquid surface. Previous limitations
of treatment by
the low rate of OZ transfer can be compensated for either by an increase in
oxygen
introduced by time-release tablets created a reduction in the substrate load.
A way of analyzing the system is to examine the carbonaceous demand, which
can be estimated, using a basic approach whereby the oxygen requirement is
estimated
o as: 02 required per day = soluble BOD~ removed per day - BOD~ of solids
leaving the
system per day.
It should also be noted that alga multiplication usually has a beneficial
effect on
the oxygen balance in an aquatic environment since during photosynthesis most
algae
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produce more oxygen during daylight hours than they consume by respiration
during all
24 hours. For algae contained in the effluent of a aquatic system, Toms et aL
(Journal
Institute of Water Pollution Control, United Kingdom 1975 in Arceivala, p.
801) found
that the respiratory demand to be about 0.007 mg 02 per, mg as per hour, the
oxygen
s production to be about 0.1 mg 02 per mg per hour, that is, 15 times greater
than the
amount consumed. Thus, the role of algae in waste stabilization in aquatic
environments is beneficial to BOD for aerobic bacterial activity when the
algae provides
excess of oxygen required by bacteria, thus creating an aerobic environment.
The applicant is aware of prior art which makes the novel method possible. The
~o particles of the sodium carbonate peroxyhydrate mentioned as a part of the
novel
composition are created in a commonly used practice by spraying the pure
compound
with a solution containing sodium sulfate in a device know as a fluid bed
dryer. The
mixture then is heated to evaporate the solvent from solution. The size of the
resulting
particles is controlled by the length of time the resulting reaction is
allowed to proceed
i s before it is arrested by the drying process, the longer the reaction the
larger the
resulting particle size will become.
The aerobic bacteria, yeast and facultative anaerobic bacteria used in this
method
are placed into a dehydrated form by a commonly used method of thermal drying
in
which the incubator raised strain of bacteria are placed in a device which
quickly
'o evaporates the moisture from the culture without killing the bacteria or
yc=_ast. The
resulting organisms are in a suspended state and will become active upon
rehydration.
The enzymes used in the formulation of the novel composition are in dry
crystallized form and can be chosen from the entire range of available
enzymes. The
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_ i
enzymes) chosen will be particularly suited to help breakdown the contaminant
being
remediated, an example being protein kinases to breakdown proteins.
Lyophilized
enzymes are preferred.
The applicant is further aware of the following U.S. and Foreign Patents
listed
s below and whose contents are herein incorporated by reference. U.S. Patent
No.
1,057,281 teaches the use of all peroxy compounds in an oxygen bath for
medicinal
purposes with people. U.S. Pat. No. 1,917,489 discloses the use of a solvent
such as
trichloroethylene, sodium peroxide and potassium carbonate in a system used to
remove deposits from the inside walls of automotive radiators. U.S. Pat. No.
3,441,388
to describes the use of sodium perborate and salts of peroxyacids and their
use as oxygen
generating agents to decrease the dissolving time of solid materials in water
(i.e.
laundry detergents). U.S. Pat. No. 3,502,429 features the use of sodium
peroxide and
potassium superoxide in a system which removes excess carbon dioxide from the
atmosphere of a closed room, and replenished the oxygen taken up by
respiration. U.S.
is Pat. No. 4,248,642 relates to the use of microsites of effervescence of a
hypochlorite-
peroxide interaction to loosen micro-deposits of debris and organic matter
from reaction
cells in an automated analytical instrument. U.S. Pat. No. 4,293,426 discloses
the use
of calcium peroxide particles coated with an insoluble organic compound,
having a
melting point of at feast 50° C., used for water oxygenation. See in
particular Col. 5,
Zo lines 45-58. U.S. Pat. No. 4,395,344 describes the use of percarbonate to
mix the
caustic substances with the water above the clog, in a dry drain opener
preparation.
U.S. Pat. No. 4,156,039 teaches the use of sodium percarbonate particles
coated with
sodium perborate and their use as oxygen generating agents in water. U.~;.
Pat. No.
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4,025,453 relates to the activation of peroxide-based dry laundry bleaches in
an
aqueous medium with pH above 7.5 through the use of cyanamide. U.S. Pat. No.
4,026,798 describes the use of peroxygen compounds in a process for treatment
of dirty
dry cleaning bath solutions. U.S. Pat. No. 4,073,888 relates to the use of
peroxy
s compounds as stabilizers for use with chlorine dioxide and quaternary
ammonium salts
as sterilizing agents. U.S. Pat. No. 4,086,175 discloses the activation of
peroxide-based
dry laundry bleaches in a buffered aqueous medium through the use of cyanamide
and
magnesium. U.S. Pat. No. 4,120,650 features the use of dry peroxygen compounds
in
conjunction with chlorine releasing compounds in a laundry detergent
composition. U.S.
io Pat. NO. 4,197,198 teaches the use of peroxygen compounds as stabilizing
agents for
use with chlorine dioxide to degrade phenol compounds in a waste water stream.
U.S.
Pat. No. 4,251,486 features the use of sodium carbonate in a waste water
treatment
process for decomposing injurious substances. U.S. Pat. No. 4,253,971 teaches
the use
of peroxygen compounds as secondary algicide in the process of water treatment
is through the use of a linear polymeric biguanide. JP Patent 49-27799 relates
to the use
of calcium peroxide in fish culture to oxygenate breeding ponds. JP Patent 88-
156001
discloses the use of oxygen generating compounds packed in gas-permeable
nonwoven cloth bags for use in live fish transportation. JP Patent 89-51302
teaches the
use of oxygen generating compounds packed in gas-permeable nonwoven
2o polyethylene-coated cloth bags for use in live fish transportation.
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- F
SUMMARY OF THE INVENT10N
This invention combats several aspects of the pollution problem in the
environment. Al! involve treating the contamination at the site without
disturbing the
sediment and the animals and plants living there.
s The first aspect of the invention is the accelerated degradation of organic
matter on the
submerged sediment surfaces. In the environment there is an enormous problem
with
the accidental or intentional introduction of organic matter in the form of
raw or partially
treated sewage into waterways. Pipe damage, rain water overflow, and out dated
or
overburdened sewage treatment facilities are the causes. The sewage sludge
places a
io tremendous demand on the available dissolved oxygen levels resulting in a
hazardous
situation of low oxygen known as hypoxia. A typical hypoxic situation has
dissolved
oxygen levels of 2.0 milligrams per titer or less. This creates an environment
which is
toxic to many fish and aquatic invertebrates. As these fish and invertebrates
die and fall
to the bottom their decomposition adds to the oxygen depletion of the
surrounding
is water. In the past the only way to remediate such mishaps would be to
dredge up the
contaminated sediment, treat it, and return it to the environment. This
process is both
expensive and potentially damaging to the organisms which are crucial to the
balance of
the sediments ecosystem. The most common alternative chosen is to do nothing
which
would be viable if the spills were not chronic and frequent. If left alone
naturally
20 occurring anaerobic bacteria would breakdown these compounds over a long
period of
time. However the huge quantity and frequency of these spills overburdens the
sediment's ecosystem leading to oxygen deprivation and the death of many
organisms
necessary to the proper balance of the ecosystem. This type of damage can
destroy
IC
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ecosystems necessary to the propagation of commercially important species of
fish and
invertebrates. This invention proposes an in situ approach to help remediate
this
problem. Its approach is one in which the ability of naturally occurring
and/or seeded
microorganisms to breakdown these contaminants is enhanced by the timed-
release of
s oxygen gas, via chemical reaction, and chemical additives such as buffering
agents and
enzymes. This method proposes that situations, where aerobic bacteria no
longer exist
due to low oxygen levels, can be reseeded with timed-release tablets having an
inner-
core of dehydrated living bacteria. The choice of which additional additives
to enhance
the process, buffer the pH, and control the dissolving rate of the tablet,
will depend upon
~o each particular situation. The catabolic processes which could normally
take months
now occur in hours or days due to the accelerated growth of the aerobic
organisms.
Once the organic matter is completely broken down, the bacterial food source
is
depleted. Then the bacteria start to die off, eventually returning their
number to
precontamination balanced levels.
is The second aspect of the invention deals with the problem of pH balance in
aquatic systems. At present acid-contaminated lakes and streams have been
remediated by the introduction of large quantities of alkali such as lime
Ca(OH)2 in a
process known as liming. Liming produces a sharp rise in pH, causing a shock
to the
ecosystem resulting in the death of algae and invertebrates. These dead
organisms fall
zo to the bottom adding to the layer of decomposing organic matter created by
the death of
organisms already killed by the acid contamination itself. This layer decaying
organic
matter puts an increased demand on the available oxygen levels in the water
above the
sediment. This bottom water quickly becomes hypoxic, thereby causing the death
of
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additional animals and plants, starting a cycle of death. Eventually, over a
period of time
the lake will recover after liming to its proper pH level. This is the goal of
liming, but it is
short lived because of the chronic input of acid rain. The lake will have to
be retreated
periodically.
s The death cycle can be broken, however, by the use of the novel composition,
which will act to buffer and stabilize the pH in a slow, time-release manner
rather than a
sharp rise as in traditional liming methods. The novel composition also
simultaneously
raises available oxygen levels preventing hypoxia, and seeds aerobic bacterial
growth
in anaerobic sediments which are overburdened with decaying organic matter.
to In some freshwater lakes, the problem of pH balance is different then that
found
in saltwater lakes, because of a lack of buffering compounds in the water
matrix and
surrounding soils and sediment. This reduced buffering capacity of the lake
water
results in wide fluctuations of pH after acid rain events. These fluctuations
can prove to
be deadly to aquatic organisms. The optimum pH level is in the 6.8 to 7.8
range
~s depending upon the type of fish and invertebrates found in the lake. This
situation
requires the addition of a weak acid to the novel composition to achieve the
proper pH
in the final solution and a buffering ,agent to stabilize it. Other buffering
agents which
serve to control pH can be used. They include acetates such as calcium
magnesium
acetate, borates, and phosphate buffering agents.
zo A third aspect of the invention deals with the oxygenation and seeding of
hypoxic
bottom waters, referred to as hypolimnion, with aerobic and/or anaerobic
bacterial cysts
and/or yeast cysts. During prolonged, warm, calm weather, a thermocline
usually
develops separating cold, dense bottom water from the warm surface layer and
from
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atmospheric oxygen. Bacterial degradation of organic matter on the seabed is
likely to
reduce oxygen levels in bottom water or hypolimnion under these circumstances.
There
is also a difference in dissolved oxygen saturation points between fresh and
saltwater.
In freshwater the saturation IeveE of dissolved oxygen at 77° F. is
approximately 5.9
s milligrams per liter. This is much higher than that of saltwater at the same
temperature.
Because of this there can be a greater potential for hypoxia, low oxygen
levels, in
marine bottom water overburdened with decaying organic matter. Dangerously low
oxygen concentrations can result thereby damaging the ecosystem and the
environment. Low levels of oxygen in bottom waters can be raised by dispersing
on to
Io or below the surface of the water, above the zone in question, a quantity
of timed-
release tablets made of a dry particulate composition consisting essentially
of an outer-
coating of a water soluble substance such as hydroxypropyl methyicellulose or
polyethylene glycol, over an outer-layer of an oxidative alkali such as sodium
sulfate
coated sodium carbonate peroxyhydrate particles, additives including enzymes
such as
is protein kinases, buffering agents such as magnesium carbonate, acetates,
borates, and
phosphates and acids such as citric or sulfamic acid, sugars such as dextrose,
oxidation
catalysts such as manganese dioxide and, an inner-coating of a water soluble
substance such as hydroxypropyl methylcellulose or polyethylene glycol and an
inner-
core of dehydrated aerobic or facultative anaerobic and yeast bacterial cysts
in a
2o paraffin or gelatin binder and dextrose.
A fourth aspect of this invention deals with treating aquarium gravel or
aquaculture pond sediment, which is contaminated with an overload of decaying
organic
matter. This situation can be remediated using an approach similar to the one
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mentioned above. This approach is one in which the ability of naturally
occurring and/or
seeded aerobic microorganisms ability to breakdown these contaminants is
enhanced
by the timed-release of oxygen gas, via chemical reaction, and chemical
additives such
as buffering agents and enzymes. The choice of which additional additives to
enhance
s the process, buffer the pH, and control the dissolving rate of the tablet,
will depend upon
each particular situation. The rising bubbles of oxygen also act to
mechanically loosen
and resuspend the particles of organic matter around the tablet, allowing for
greater
exposed surface area of the particle accessible to bacteria and other
microorganisms
which can break it down at an accelerated pace.
to An object of the present invention is to provide an novel non-toxic in situ
method
for the accelerated biological degradation of organic matter in the form of
sewage
sludge on the surface of aquatic sediments in water by dispersing on to or
below the
surface of the water a quantity of timed-release tablets. Said tablets sink,
then dissolve
in layers, releasing oxygen bubbles which mechanically loosen and resuspend
the
is organic matter increasing the surface area available to bacteria. When the
inner-core of
the tablets dissolve aerobic bacteria are released. The bacteria then feed on
the
sewage sludge at an accelerated pace.
An additional object of this invention is to provide novel nontoxic in situ
method
for the accelerated biological degradation of organic matter in the form of
petroleum
2o hydrocarbons on the, surface of aquatic sediments in water by dispersing on
to or below
the surface of the water a quantity of timed-release tablets. Said tablets
sink, then
dissolve in layers, releasing oxygen bubbles which mechanically loosen and
resuspend
the organic matter increasing the surface area available to bacteria. When the
inner-
n
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core of the tablets dissolve aerobic bacteria are released. The bacteria then
feed on the
petroleum hydrocarbons at an accelerated pace.
Another object of this invention is to provide novel nontoxic compositions and
novel products that are particularly useful in practicing the novel methods.
s A further object of this invention is to provide novel nontoxic in situ
methods to
oxygenate and seed with aerobic bacteria the hypoxic bottom waters of lakes,
streams,
bays, and estuaries in a timed-release manner by dispersing on to or below the
surface
of the water a quantity of timed-release tablets. Said tablets sink then
dissolve in layers,
releasing oxygen bubbles which raise the dissolved oxygen in a controlled
manner and
~o reseed aerobic bacterial populations.
Still a further object of this invention is to treat acid-contaminated lakes
and
streams by buffering the pH and raising dissolved oxygen levels and seeding
aerobic
bacteria via the timed-release tablets of the novel composition.
Another object of this invention is to provide novel compositions and novel
~s products containing chemical ingredients for aiding in achieving the proper
pH and
dissolved oxygen and aerobic bacterial levels of surface and bottom water and
sediment in acid-contaminated lakes and streams:
A still further object of the present invention is the prevention of growth of
aquatic
algae by dissolving a water-soluble colorant that reflects light at the same
wavelength
zu used in photosynthesis by the algae and also to aid in the breakdown of
dead algae
which has settled at the sediment-water interface, by adding oxygen, nutrients
and
additives fist and then adding bacteria which breakdown the dead algae.
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DESCRIPTION OF THE PREFERRED EMBODIMENTS
Sodium carbonate peroxyhydrate particles coated with sodium sulfate, are dry
solids at room temperatures, are nontoxic to humans and to aquatic life, and
react with
water to release oxygen in such form that matter is loosened and removed from
s surfaces in the water, but does not remove the protective mucous coatings on
fish that
are in the water. The size of the particles chosen for use in the tablets is
decided
according to the rate of oxygen release that is desired. In addition, binding
agents such
as polyethylene glycol and coating agents such as methylcellulose can be added
to
achieve a time-released, tabletized version of the novel composition.
to Various dry-powder additives can be included in the novel composition,
which do
not interfere with the cleaning action of the oxidant, but provide beneficial
effects in the
aquatic environment. For example, magnesium carbonate may be included because
it
helps to maintain the proper balance of magnesium-to-calcium in the saltwater,
so that
magnesium is not leached from sensitive invertebrates such as anemones. Citric
acid
is can be included in the novel composition to adjust the pH of the water in a
safe range.
Other buffering agents which serve to control pH can be used. They include
acetates
such as calcium magnesium acetate, borates, and phosphate buffering agents.
The tablets themselves can be created by several methods including the
following example. The following is only one example and is not intended to
limit the
zo scope of the invention to the preferred embodiments mentioned. This example
involves
the use of several steps. In the first step is the creation of the inner core
of the tablet.
This is accomplished by dry mixing the heat-dried bacterial cysts with binding
agents
such as a paraffin or a gelatine, and/or a sugar such as dextrose. Any strain
of aerobic
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or facultative anaerobic bacteria or yeast that is capable of forming cysts,
endospores or
ascospores in adverse conditions can be used. The strain or strains chosen
will depend
upon their availability to breakdown the contaminant being remediated as well
as their
ability to survive in the particular aqueous environment. .These strains
include the
s bacterial genera Bacillus, Sporolactobacillus, Sporosarcina, Sphaerotilus,
Beggiatoa,
and Micrococcus. Also any yeast may be included, such as those within the
genera
Saccharomyces.
The formulation of the protective coat, cyst, endospore, and ascospore enable
the bacteria or yeast to survive long periods of time without food or
moisture. When
to placed in a hydrated environment, the organism breaks out of its protective
coating and
grows and reproduces. These types of organisms can be artificially induced to
form
cysts, endospores or ascospores by a commonly used method of dehydration known
as
heat drying. A common example of a product created by this method is the dry
powdered yeast used in baking and brewing.
is This mixture is then pressed into small tablets of approximately 50
milligrams by the
use of any known compactor such as a roller-type or rotary pelletizer. The
small tablets
can then be coated with a water soluble substance, such as hydroxypropyl
methylcellulose, in a device such as a drum dryer. In this process the tablets
are
sprayed while moving with a liquid solution containing the coating material.
The solvent
Zo is then heat evaporated in the dryer. The second step involves compressing
the core
tablet within the center of the larger final tablet. This is accomplished by a
device known
as rotary double tabletiZer such as the Korsch Pharmakontroll 2.03. This
device allows
for the core tablet to be positioned in the center while the outer-layer of
approximately
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600 milligrams of the oxidative alkaliladditive mixture is compressed around
it. The third
and final step involve coating the final tablet with a water soluble coating
such as
hydroxypropyl methylcelfulose in a drum dryer. In this process the tablets are
sprayed
white moving with a liquid soiutiort containing the coating material. The
solvent is then
s heat evaporated in the dryer.
The preferred embodiment of the instant invention is timed-release tablets of
a
dry particulate composition consisting essentially of an inner-core of
dehydrated
bacteria! cysts, an inner-coating of a water soluble substance such as
hydroxypropyl
methylcellulose, an outer-layer of an oxidative alkali such as sodium sulfate
coated
io sodium carbonate peroxyhydrate particles, and an outer-coating of a water
soluble
substance such as hydroxypropyl methylcellulose.
The timed-release tablets according to the instant invention may contain 10%
to
95% by weight of the inner-core additives such as a parrafin or a gelatin
bind, and/or
sugars such as dextrose.
The timed-release tablets according to the instant invention may also contain
from 0.1 % to 20% by weight of the outer layer additives including enzymes
such as
protein kinases, buffering agents such as magnesium carbonate, acetates,
borates and
phosphates and acids such as citric or sulfamic acid, sugars such as dextrose,
and
oxidation catalysts such as manganese dioxide.
2o The outer-coating timed-release tablets according to the instant invention
is a
water soluble compound comprising from 0.1 % to 5% by weight of the entire
tablet.
The inner-core coating of the timed-release tablets according to the instant
invention is
from 0.1 % to 5% by weight of the inner-core.
22
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The present invention is specifically designed to provide a better solution to
combat the problems associated with lake eutrofication. With a single timed-
release
layered tablet, several active steps wi(I occur. First, the outer layer will
dissolve
releasing a compound that liberates- both oxygen; in the form of bubbles, and
a
s combination of blue and yellow water-soluble dyes. The bubbles act to both
disburse
the dye into the water column, raise DO level in the water, and loosen
particles at the
sediment-water interface causing the tablet to bury itself deeper into the
sediment. Next,
the inner layers of the tablet disintegrate to release a combination of
enzymes, buffers
and aerobic and facultative anaerobic microorganisms. The dye acts to block
the
io wavelength of light necessary for photosynthesis. This causes the death of
the nuisance
algae or plants, which sink to bottom as they decay. The microorganisms
consume the
detritus at a high rate, enhanced by the nutrients and enzymes and dissolved
oxygen.
The high DO level also helps to prevent the fish kills associated with the
increased
demand created by the decaying plant matter. The source of the oxygen is a dry
form of
is hydrogen peroxide which as a solution quickly degrades to molecular oxygen
and water,
to oxygenate the water. Since micro-organisms receive ~02 from DO in the
liquid phase
instead of the usual replacement of DO from the atmosphere through a process
of
stirring or agitation, we introduce it directly into the system therefore
relocation or
extensive mechanical processing systems are not required for the gas/liquid
interface.
2o The oxygen transfer rate differs depending on the characteristics of the
water by such
variables as dissolved solids, organics, surface-active agents, the amount
needed can
be determined by using the following standard equation:
dcJdt=K(C~ - C,)
23
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Where K=02 transfer rate; Csub-s =concentration of dissolved 02 at saturation;
Csub-1
= concentration of dissolved 02 at time t.
Through inputting the time~release tablet intro the aciuatic environment the
rate of
s 02 supply and the buffering capacity provided by a body of liquid containing
dissolved
02 is able to be in excess of the OZ required for microbial metabolism so that
the
development of anaerobic conditions is restrained. Thus, we have been able to
show
that in nonmechanicai systems, for example, barrier ditches and lagoons, 02
supply is
no longer limited to transfer at the liquid surface. Previous limitations of
treatment by
io the low rate of 02 transfer can be compensated for either by an increase in
oxygen
introduced by time-release tablets created a reduction in the substrate load.
A way of analyzing the system is to examine the carbonaceous demand, which
can be estimated, using a basic approach whereby the oxygen requirement is
estimated
as: 02 required per day = soluble BODE removed per day - BOD" of solids
leaving the
is system per day.
1t should also be noted that alga multiplication usually has a beneficial
effect on
the oxygen balance in an aquatic environment since during photosynthesis most
algae
produce more oxygen during daylight hours than they consume by respiration
during all
24 hours. For algae contained in the effluent of a aquatic system, Toms et al
20 ("Observations on the performance of polishing lagoons" Journal Institute
of Water
Pollution Control, United Kingdom 1975 in Arceivala, p. 801 ) found that the
respiratory
demand to be about 0.007 mg O2 per mg as per hour, the oxygen production to be
about 0. ~ mg 02 per mg per hour, that is, 15 times greater than the amount
consumed.
24
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Thus, the role of algae in waste stabilization in aquatic environments is
beneficial to
BOD for aerobic bacterial activity when the algae provides excess of oxygen
required by
bacteria, thus creating an aerobic environment.
The tablets of ,the present invention release components over time that
s accomplish three tasks. The first task is the prevention of growth of
aquatic algae by
dissolving a water-soluble colorant that reflects light at the same wavelength
used in
photosynthesis by the algae. The second and third are to aid in the breakdown
of dead
algae which has settled at the sediment-water interface, by adding oxygen,
nutrients
and additives first and then adding bacteria which breakdown the dead algae.
This is
io accomplished by the addition of tablets to the surface water, which sink to
the bottom
releasing their components. The tablets quickly release a water-soluble
colorant, which
diffuses into the surface water, and acts to block the wavelength of ambient
light
necessary for photosynthesis to occur in growing algae. The colorant also
prevents the
necessary light from penetrating the surface water and to the existing algae
thereby
is killing it. Sinks dead alga sinks to the bottom where it decays. The
bacteria, nutrients
and additives help to breakdown the dead algae.
The following examples serve to provide a better understanding of the
invention,
without however limiting the scope of the invention to the embodiments
described.
Zo EXAMPLE 1
The following are the key steps required to carry out an environmental clean-
up operation:
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First the design of the initial sampling and testing program is customized to
fit
the situation and will include four general areas:
1. Sampling Grid Pattern--is the actual location of the sample sites and is
dependent upon the size shape- and, depth of the location as well as proximity
to
s possible sources or inputs of pollutants.
2. Diurnal Study--is the sampling of the chosen number of sampling points
over a period of 24 hours. The test parameters include temperature, pH,
dissolved
oxygen, specific conductivity, tidal flux, and weather conditions.
3. Depth Profile--this type of sampling involves the taking of samples at
io different depths and includes parameters such as biochemical oxygen demand
(BOD),
chemical oxygen demand (COD), total organic carbon (TOC), ammonia, nitrate,
nitrite,
total Kjeldahl nitrogen (TKN), hydrogen sulfide (H2S), total phosphate (T-
P04), ortho-
phosphate (O-P04), specific conductivity, temperature, total dissolved solids
(TDS),
total suspended solids (TSS), turbidity and chlorophyll A.
15 4. Sediment Analysis--the biological portion of this type involves the
identification of benthic organisms macroinvertebrates and bacteria, as well
as chemical
analysis including parameters as Total Organic Carbon (TOC), redox potential,
total
metals (As, Cd, Cr, Pb, Hg, Zn, Cu, Fe).
The initial testing will be carried out EPA guidelines and safe laboratory
2o practices. Sample will be taken using EPA guidelines and in properly
preserved
containers. A chain-of-custody will be maintained throughout the analysis.
Water
samples will be collected using non-contaminating hand dippers at the surface
or
Nanson or Niskin sampling devices at the surface depth. Sediment samples will
26
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obtained using a hand corer if the water is shallow and a Ekman or ponar grab
sampler
if the water is deep.
Results of the analysis are then plotted graphically in order to determine a
baseline and to see any indication of either over acidification due to acid
precipitation or
s oxygen demand overload due organic pollution such as sewage. If it is found
that the
treatment will reduce the BOD and or COD and breakdown the organic matter with
out
producing toxic residuals such as the oxidized form of mercury, than the
project will
move to the next phase if not aitematives will be discussed with the client.
The decision to proceed will depend on what effects adding oxygen gas would
to in compensating for the demand or in the acid situation what the buffering
capacity of
the product may due to the pH. If any of the heavy metals are found in high
concentration in solution and the solution is in the acid range (below 7.0)
than the
treatment would be beneficial in precipitating the metals out of solution. It
might be
advisable to add additional compounds (specific to the metal) to actively
chelate the
is metal into a complex which is biologically inactive. If the Biochemical
Oxygen Demand
(BOD) and Chemical Oxygen Demand (COD) in the contaminated zone are 50% higher
than that of a non-contaminated site in the area and the Dissolved Oxygen (DO)
level is
below 2.0 milligrams per liter, then the site is good candidate for treatment.
The custom design of the treatment will depend on the type and extent of
2o poiiution and the chemistry of the water. If for example, the problem is
acid rain
contamination, then the product must be buffered to achieve the proper pH. !f
the pH of
the water is lower than 6.3 than this particular method would not be
recommended
27
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especially is high metal concentrations such as mercury, are found because the
oxidation of metallic complexes can cause them to become even more toxic.
If the problem is untreated sewage sludge which has accumulated on the
sediment surface then the product should be pressed into tablets. There size
and shape
s will depend upon the conditions of the site and include; depth of
contaminant sludge
depth to the sediment surface, current strength and direction, water surface
conditions,
and weather. In order to predict where a tablet will land on the bottom once
dropped
from the surface. To determine this the currents at the site must be studied.
The faster
the current, the quicker the tablet will need to sink. This is accomplished by
pressing
io smaller rounder tablets. An example would be 500 milligram spherical
tablets. In slow,
calm water flat disk-like or elongated tablets can be used.
The actual treatment can take three forms. The first will involve spreading
the
granular product over the surface of the contaminated area. This will be
accomplished
using a boat with a hopper/spreader device as shown in my prior U.S. Patent
No.
is 5,275,943. The device has a hopper which is loaded with granular product or
tablets
and as the boat moves along its course the spreader shoots the product into
the water.
The rate at which the product is added to the water can be controlled by the
amount of
product being released from the hopper to the spreader and on the speed at
which the
boat travels. The course or pattern which the boat takes will depend upon the
site
2o conditions and the type and location of the contamination. 1f the water
column is being
treated, as is the case when granular product is required, a high boat speed
and loose
pattern can be used.
zs
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The second situation involves spreading tabletized product into the water
using the same device as above if the contamination is concentrated in the
sediment. In
that case tablets should be applied at a slow speed and tight overlapping
pattern is
required.
s The third situation involves spreading tabletized product into the water
using
the device also shown in my prior U.S. Patent No. 5,275,943 if the
contamination is
concentrated in the sediment. This device is used when the contamination is
concentrated in small specific area. It enables the crew to place tablet on to
a specific
spot on the sediment surface with great accuracy.
to Testing should be continue during the treatment process. This is done to
see if
the treatment is having a beneficial effect and to see if any adjustments need
to be
made. The parameters at least include dissolved oxygen, BOD, COD, pH,
temperature,
conductivity, TSS, TDS, Turbidity, and total metals. If dissolved metal
concentrations
are rising then the process should be stopped and reevaluated. A temporary
rise in
~s BOD, COD, TSS, and Turbidity should be followed by a drop and leveling off
at a value
which is within the acceptable range for the specific situation. If the pH is
raising to
quickly the process should be stopped and the concentrations being added
should be
reduced accordingly.
Follow-up testing should be continued until a steady baseline is achieved. It
2o should be noted that there are daily and seasonal variations which must be
accounted
in the evaluation of the steady baseline and the decision to terminate the
testing. The
parameters should include as many of the ones listed above.
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t
EXAMPLE 2
A4uatic Field Test
A small private pond in New York State was used for field trials from 4/21/98
to
5/2/98. The pond is approximately one foot-acre in size and has a viable
population of
s North American bass and freshwater sunfish. It also has had in past years a
chronic
problem with blooms of the filamentous. alga LYnabia sa. This algae is
considered a
nuisance because of it enormous growth rate and propagation capabilities and
its
tendency to completely overrun a ponds surface with thick mats of filamentous
growth.
Another nuisance plant in the study area is MYriophvllum sp., a non-indigenous
water
io milfoil.
A small area of the pond (6'x3'x2') was segregated using black plastic
material
waited on the bottom and with floats above. Within the area enclosed there is
a viable
mass of the filamentous alga Lynpbia sp,
Our Tests were conducted to determine the dye concentrations necessary to
~ s achieve a reduction in growth in this algae and the effect of dissolved
oxygen levels on
the growth of aerobic micro organisms in breaking down the settled detritus.
3200 mg layered tablets were produced containing a mixture of dyes (acid blue
#9 and acid yellow #23) and oxidative alkali enzymes (including cellulase) and
bacteria
cultivated for their ability to breakdown decaying plant matter.
2o YSI model 6920 remote monitoring probe sondes is being used to measure the
test parameters as well as separate tests for turbidity. Each probe is
designed to take
readings for Depth, temperature, Dissolved oxygen, conductivity, Total
Dissolved solids,
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Oxidation-Reduction Potential, and at set intervals. The weather conditions
are also
monitored over the duration of the test.
The results of the first field trial are displayed on Figure 1. That data
shows that
the tablets were able to raise DO levels above saturation. The dissolve time
ranged
s from 30 to 45 minutes. The water stayed saturated for 30minutes and it took
9 hours
and 45 minutes for the oxygen to be consumed. The growth of the algae was
reduced
as compared with the algae in the control area. As this particular algae grows
the mats
move closer to the surface. This distance was used as a measure growth rate.
The
control group grew at an average of 20mm per day as opposed to the treated
area
which a average rate of 6mm per day over 97 hour period. There were
fluctuations in
weather and temperature as well as rain during the test period. The rainfall
affected the
concentration of the dye. The long as the concentration of the dye remained
above
visually perceptible levels there seems to be a negative effect on the growth
rate of the
Lyn4iba sp. in the field. The effect of the tablets on the sediment surface
due to the
is bacterial breakdown of the detritus was noticeable. There areas surrounding
the where
that tablets {i Ocm radius) settled showed the most signs of change. The
larger bits of
detritus was reduced to fine particles giving the the impression of a clearer
area.
EXAMPLE 3
zo Manure Treatment Experimental Desiqn
Microbial treatment or "purification" may be regarded as a process by which
the
pollutants, in the raw waste: are converted to microbial cell biomass or
insoluble
substances. This biomass can then be separated from the final end produce
which is
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water containing a suitable BOD, resulting in the satisfactory achievement of
the
reduction of pollution associated with agricultural wastes.
The treatment we have developed however, does not rely on mechanical means
to aerate the manure. It uses the byproduct of a chemical reaction, hydrogen
peroxide,
s which in solution quickly degrades to molecular oxygen and water, to
oxygenate the
water. Based on Applicant's U.S. patented methodology (U.S. patent No.
5,275,943) it
uses a timed-release tablet to both oxygenate the water column slowly, and
introduce
aerobic bacteria, enzymes, buffers and additives. These components help to
speed up
the degradation of the manure and reduce gasses which would have otherwise
been
io created during anaerobic degradation. Because our process is aerobic, the
noxious
gases are not produced, thereby reducing the foul odors associated with these
pits. The
tablets are custom manufactured into layers to incorporate the chemical
requirements of
a particular situation such as the inclusion of a phosphate precipitant like
ferrous
chloride. The key to its success is providing a source of molecular oxygen on
a
~s continuous basis, gently disturbing the sludge particles at the bottom of
the lagoon with
oxygen bubbles. The raised particles of sludge create a greater surface area
on which
the aerobic bacteria can attach speeding up the degradation process.
In the aerobic environment the bacterial genera Nitrosomonas and Nitrobacter
convert Ammonium Nitrogen to Nitrite then Nitrite to Nitrate. Once the micro-
zo environment at the sediment-water interface is adjusted to promote aerobic
bacte~ ial
growth (Nitrification) the bacterial portion of the tablet dissolves. As these
bacteria
mature and reproduce they consume the sludge without producing the noxious
gases.
There are several odor-reducing steps occurring simultaneously, aside from the
aerobic
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- bacterial degradation of the manure. Physically the rising bubbles of oxygen
tend to
purge any dissolved gases out of solution there by removing them from manure.
Chemically the dissolution of the dry oxidative alkali raises the pH of the
manure
thereby preventing the volatilization ammonia nitrogen. Such biological
treatment
s degrades the polluting organic matter as a result of the activity of a
mixture of
microorganisms being cultivated and introduced by our patented methodology.
The
introduced bacteria, after moving from their suspended state to the growth
phase,
absorb and consume the existing organic matter as food provided they have the
proper
surrounding environment. Our method ensures that the environment is
sufficiently
to oxygenated to promote the growth of the aerobic and facultative anaerobes.
The fundamental principle is that wild microorganisms will multiply if they
are
provided with the organic matter in sewage and DO (dissolved oxygen). In the
process,
most of the biodegradable carbon compounds are converted to C02. In our
research
we introduce beneficial microorganisms, oxygen and nutrients sufficiently able
to repair
~s any imbalance created in a high BOD system.
EXAMPLE 4
2o Bench-scale test
An experimental design for the bench-scale testing based on one developed by
Dr. Bundy of Iowa State University (Lorimor, J., Bundy D.,Manure Odor
Reduction from
Pit Additives Iowa State University Department of Agricultural & Biosystems
Engineering May 1996) was utilized. These were completed to narrow down the
choices
25 between 12 variations of the prototype tablets, containing different
concentrations of
components, to be used in the field test onsite at the hog farm sludge lagoon.
Si>
3s
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reactors constructed of 4" diameter PVC 40" Tong with and end cap and treaded
top cap
and pressure relief hose to remove gas produced from the laboratory. The
reactors
were filled with 5 liters of Distilled water and sealed. Fresh hog manure was
acquired
from a local 1400 head facility that maintains a 125,000-gallon cement lined
anaerobic
s sludge lagoon. The percent moisture of the manure was determined to be 20%
using
AWWA standard method 2540b ("Method 2540 Solids" in Standard Methods for the
Examination of water and Wastewater. 17~" edition. APHA-AWWA-WPCF ed. By
Clesceri, L., Greenburg, A.E. and Trussell, R.R. 1989. Pgs. 2.71-79). Although
the
"Bundy method" suggests using manure that has been diluted to 4% solids with
water,
io we chose to adjust the test solution to 10% solids. This is because on
actual farms the
manure supernatant's test at between 10% and 20 % solids and our result would
be
closer to the field conditions. At the start of each test, a one-liter volume
of water and
manure was added to each container to bring the percent Solids up to 10%.
Total liquid
volume in each container was 6 liters. The mixture was then stirred with a
modified paint
is stirrer to ensure the homogenization of the sample. A YS1 model 6920 probe
sonde was
used to measure the test parameter. The probe is designed to take readings for
Depth,
temperature, pH, Dissolved oxygen, conductivity, Total Dissolved solids,
Oxidation-
Reduction Potential, and Ammonium-Nitrogen at set intervals. The initial
interval was
set at one minute, but later modified to every 15 minutes over a two-day
period. The
zo initial test determined that there was a lag time of 22 hours between the
saturation of
the water with dissolved oxygen and the consumption of the oxygen by the
bacteria
(Figure 2).
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This was followed by a sharp decline in the Dissolved Oxygen level down to a
hypoxic level below 2.Omg/I. The pH rose from 3.0 to 8.4 preventing the
volatilization of
ammonia, which does not volatilize at a pH over 5Ø After the initial burst
of off gasses
there was a noticeable reduction in odor between the control and the treated
samples. A
modification of the standard methods protocol will be used to quantify the
field test
results. Odor is very subjective and can vary from person to person so a panel
will be
used to standardize the results.
Robinson (Robinson, K. "Aerobic Treatment of Agricultural Wastes" in Microbial
Aspects of Pollution. led.) G. Sykes and F.A. Skinner, London: Academic Press,
1971,
to p. 94) also found the benefits of raising pH in a study. He found, in hog
waste, that an
alkaline pH value (8.5-9.0) could be maintained when the substrate has a high
N
content. He also found that the maintenance of such pH levels corresponds with
a high
rate of reduction of 02 demand of the substrate; lower rates of substrate
supply lead to
the production of acid conditions (pH 5.5-6.0).
is
EXAMPLE 5
Field Test
The field test of the tablets in the manure lagoon at the hog facility was
implemented from 419/98-4/1 fi/98. From the bench scale testing a quantity of
tablets
2o was added at intervals over a 7-day period. A preliminary sample was taken
at the start
of the test and one at the end. Test parameters include pH, Volatile Fatty
Acids, COD,
BOD, Total solids, Total Volatile Solids, Ammonia Nitrogen, Total Kjeldahl
Nitrogen, and
Total Phosphorus and Odor. The results are shown in Figure 3.
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EXAMPLE 6
Preparation of Tablets Containing Dyes
In order to produce a final tablet that has layer (delayed-release)
properties, a
s method of production involves a process called slug and grind which includes
several
steps.
The first requires the blending of ingredients below:
1 Dried bacteria or microorganisms (such as Nitrosomas sp., Nitrobacter sp.
and
Bacillus sp.) on a bran flake powder
0 2. Enzymes (such as amylase, cellulase)
3. Binders - Microcrystalline Cellulose (such as Avicil NT200/Lattice NT200)
4. Lactose (slows disintegration of Tablets)
5) Gums (such as Xanthan Fines)
6. Sodium Laural Sulfate (Surfactant)
is to create a premix slug.
The second step after blending for 5 minutes, tablets, such as 1.5" round, are
pressed
using a press such as a Rimic set at between 20-30 psi. These tablets are
added to
grinding machine with an #8 mesh screen. This produces preweight slug
granules.
The third step involves mixing the Dye powders below
20 1. Acid Blue #9
2. Acid Yellow #23
3 ti
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with a binder such as Microcrystalline Cellulose to make it more fiowable and
easier to
handle. This step helps to prevent the formation of dust , which makes the
handling of
these dye more difficult.
The fourth step in the manufacture process involves, the mixing of the final
ingredients
s below:
1. Sodium Carbonate Peroxyhydrate (Sodium Percarbonate)
2. Corn Starch
3. Binder (Microcrystalline Cellulose such as Avicil NT200/Lattice NT200)
with the resulting mixtures from steps two and three for 5 minutes.
~o The fifth step involves taking the the final mixture from step four and
pressing a tablet .
Tablets range from 0.5 to 10,000 grams can be produced using the standard
method for
a single station or rotary press. Prototypes were produced with the weight cam
on a
single station stokes press set to 59-62 grams and hardness adjusted to 90-1 i
0# Rimac
(1-1/2" rack). After pressing the tablets needed to relax 30 minutes in which
25-30 of
is their original hardness is lost. After that period the tablets hardness
remains stable.
The above tablets can be prepared in a similar way using other cellulose
derivatives as
blending ingredients and also as coatings to taylor made time release
profiles.
EXAMPLE 7
2o Tablets containing the components below can be manufactured as shown in
Example 6 above using conventional tableting methodology utilized in the
pharmaceutical industry which includes coatings so as to control the release a
spects of
the tablets.
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Coatings - com based sugar,or lactose, or water soluble synthetic polymers
Oxygen provider - sodium percarbonate
Nutrients or enzymes - cellulase, amylase, lactase,
Microbials- family Nitrosomas, _ and Nitrobactor and Bacillus,
Sporolactobacillus,
s micrococcus Arthrobacter, Flavobacterium, pseudomonas, Rhizomas, Rhizobium,
Rhizobacter, Azoarcus, Ralstonia, . Sporosarcina, Sphacrotilus, Beggiatoa,
Saccharomyces
Precipitants- Ferric Chloride, Alum, Lime
Buffers -magnesium carbonate
to Colorants - acid blue #9, acid yellow #23 other water soluble non-toxic
dyes
Binders and additives - microcrystaline cellulose, magnesium sterate
The foregoing description thereof is provided as illustrative of some of the
is preferred embodiments of the concepts of this invention. While these
embodiments
represent what is regarded as the best modes for practicing this invention,
they are not
intended as delineating the scope of the invention, which is set forth in the
following
claims. It will be understood that the above descriptions of the present
invention are
susceptible to various changes, modifications and adaptations, and the same
are
zo intended to be comprehended within the meaning and range of equivalents of
the
appended claims.
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