U.S. patent application number 10/266467 was filed with the patent office on 2003-09-04 for method of using pulsed ozone to treat soils containing organic contaminants.
Invention is credited to Brown, Richard A., Lute, James, Nelson, Christopher, Robinson, Dave, Skladany, George.
Application Number | 20030165358 10/266467 |
Document ID | / |
Family ID | 27807195 |
Filed Date | 2003-09-04 |
United States Patent
Application |
20030165358 |
Kind Code |
A1 |
Brown, Richard A. ; et
al. |
September 4, 2003 |
Method of using pulsed ozone to treat soils containing organic
contaminants
Abstract
A method of treating a solid matrix containing organic
contaminants is provided. The method comprises the steps of a)
injecting ozone into the solid matrix for a period of time known as
the pulse duration; b) interrupting the injection of ozone into the
solid matrix for a period of time known as the gap duration; and c)
repeating step a) at least one additional time. Gap durations of
from about 2 hours to about 48 hours are disclosed. Pulse durations
of from about 0.25 hours to about 8 hours are also disclosed.
Recalcitrant organic contaminants are treated.
Inventors: |
Brown, Richard A.;
(Lawrenceville, NJ) ; Lute, James; (Cranbury,
NJ) ; Robinson, Dave; (Mt. Laurel, NJ) ;
Skladany, George; (Newtown, PA) ; Nelson,
Christopher; (Castle Rock, CO) |
Correspondence
Address: |
LUEDEKA, NEELY & GRAHAM, P.C.
P O BOX 1871
KNOXVILLE
TN
37901
US
|
Family ID: |
27807195 |
Appl. No.: |
10/266467 |
Filed: |
October 8, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10266467 |
Oct 8, 2002 |
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09300500 |
Apr 28, 1999 |
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60083327 |
Apr 28, 1998 |
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Current U.S.
Class: |
405/128.5 ;
435/262.5; 588/316; 588/320; 588/402; 588/406; 588/408;
588/409 |
Current CPC
Class: |
B09C 1/10 20130101; C02F
1/78 20130101; B09C 1/08 20130101 |
Class at
Publication: |
405/128.5 ;
588/208; 588/200; 435/262.5 |
International
Class: |
A62D 003/00 |
Claims
We claim:
1. A method of treating a solid matrix containing organic
contaminants comprising the steps of a) injecting ozone into the
solid matrix for a period of time known as the pulse duration; b)
interrupting the injection of the ozone into the solid matrix for a
period of time known as the gap duration; and repeating step a) at
least one additional time.
2. The method of claim 1 wherein the gap duration is from about 2
hours to about 48 hours.
3. The method of claim 1 wherein the gap duration is from about 24
hours to about 36 hours.
4. The method of claim 1 wherein the organic contaminant is
recalcitrant and the gap duration is from about 36 hours to about
48 hours.
5. The method of claim 1 wherein the pulse duration is from about
0.25 hours to about 8 hours.
6. The method of claim 1 wherein the pulse duration is about 0.25
hours.
7. The method of claim 1 wherein the pulse duration is from about 2
hours to about 3 hours.
8. The method of claim 1 wherein the gap duration is from about 24
hours to about 36 hours and the pulse duration is about 0.25
hours.
9. The method of claim 1 wherein the gap duration is from about 24
hours to about 36 hours and the pulse duration is from about 2
hours to about 3 hours.
10. The method of claim 1 wherein the gap duration is from about 36
hours to about 72 hors and the pulse duration is less than about 1
hour.
11. The method of claim 10 wherein oxygen or air is injected into
the solid matrix during the gap duration step b).
12. The method of claim 1 wherein the organic contaminants are
PAHs, chlorophenols, substituted aromatics, greater than C-8
hydrocarbons, pesticides, phthlates, explosives, surfactants or
wood related wastes.
13. The method of claim 1 wherein steps a) and b) are sequentially
repeated multiple times until a substantial amount of the organic
contaminants has been destroyed.
14. The method of claim 1 wherein the solid matrix is an
unsaturated soil.
15. The method of claim 1 wherein the solid matrix is saturated
with water.
16. The method of claim 1 wherein the solid matrix is a sludge.
17. The method of claim 14 wherein the solid matrix is treated in
situ.
18. The method of claim 15 wherein the solid matrix is treated in
situ.
19. The method of claim 1 wherein the organic contaminants are
PAHs.
20. The method of claim 1 wherein the organic contaminants are coal
tars.
21. The method of claim 1 wherein the organic contaminants are
creosote.
22. An in situ method of treating soil containing recalcitrant
organic contaminants comprising the steps of a) injecting ozone
into the soil, in situ, for a period of time known as the pulse
duration; b) interrupting the injection of the ozone into the soil
for a period of time known as the gap duration; and sequentially
repeating steps a) and b) until a substantial amount of the organic
contaminants has been destroyed.
23. The method of claim 22 wherein the gap duration is from about
24 hours to about 36 hours and the pulse duration is about 0.25
hours.
24. The method of claim 23 wherein the pulse duration is from about
2 hours to about 3 hours.
25. The method of claim 22 wherein the organic contaminants are
PAHs, chlorophenols, substituted aromatics, greater than C-8
hydrocarbons, pesticides, phthlates, explosives, surfactants or
wood related wastes.
26. A method of treating a solid matrix containing organic
contaminants and bacteria capable of biodegrading the organic
contaminant, comprising the steps of a) injecting ozone into the
solid matrix for a period of time known as the pulse duration, the
amount of ozone injected being insufficient to completely destroy
the bacteria, b) interrupting the injection of ozone into the solid
matrix for a period of time known as the gap duration, the gap
duration being sufficiently long so as to allow the regeneration of
the bacteria and the biodegradation of the organic contaminants; c)
injecting air or oxygen into the solid matrix during the gap
duration; and d) repeating steps a), b) and c) multiple times.
27. The method of claim 26 wherein the gap duration is from about
36 hours to about 72 hours and the pulse duration is less than
about 1 hour.
28. The method of claim 27 wherein the pulse duration is about 0.25
hours.
29. The method of claim 26 wherein additional bacteria capable of
biodegrading the organic contaminant is added to the solid matrix
during the gap duration.
Description
BACKGROUND OF THE INVENTION
[0001] Ozone is a gas with strong oxidizing properties. It is
commonly generated by forcing oxygen or air through narrowly spaced
electrodes under a high voltage, known as the corona discharge
method. The first commercial uses of ozone occurred in Europe in
the late 1890's for the treatment of drinking water. Since then,
ozone has been widely used for both the treatment of drinking water
and wastewater.
[0002] Ozone can react with organic contaminants via two general
pathways: a) direct oxidation; and b) oxidation through the
formation of free radical intermediaries. The most common radical
pathway utilizes hydroxyl radicals. Contaminants most amenable to
direct oxidation include polynuclear aromatic hydrocarbons,
chlorinated ethenes such as trichlorethylene, and chlorinated
phenols such as pentachlorophenol (PCP). A wider range of organic
contaminants, including halogenated solvents, pesticides and
aliphatic hydrocarbons, can be oxidized slowly by direct oxidation
or more rapidly oxidized by the hydroxyl radical mechanism.
Following only fluorine, which has an oxidation potential of 3
volts, hydroxyl radicals (oxidation potential of 2.96 volts) and
ozone (oxidation potential 2.07 volts) are the second and third
strongest oxidants known.
[0003] At many industrial and commercial facilities throughout the
United States, soil and groundwater have become contaminated with
organic pollutants. Accidental spills have occurred at other sites
contaminating both soil and groundwater. A variety of techniques
have been developed for the removal of these contaminants. One
common technique is soil excavation and off-site treatment of the
soil, which is often very expensive. Another treatment involves air
sparging technology using the controlled injection of air to strip
organic compounds from the water or to supply oxygen for
bioremediation of the contaminants. However, chlorinated olefins
and complex aromatics are often resistant to sparging and
bioremediation, thereby requiring more complex and expensive
treatments.
[0004] Ozone has been shown to be an effective oxidant in the
treatment of organic contaminants in solid matrices such as soils
(both saturated and unsaturated) and sludges. Previously, the
successful treatment of contaminated solid matrices has involved
the continuous application of ozone. Experience with this approach
has demonstrated that persistent, continuous ozonation of a
contaminated solid matrix can be an effective way of treating a
wide range of organic contaminants contained within the solid
matrix. Because ozonation is a direct chemical reaction, the rate
and effectiveness is expected to be proportional to the mass of
ozone added (weight percent, flow and time). The higher the ozone
mass, the more effective the reaction with the contaminants is
expected to be.
[0005] While continuous ozonation of solid matrices containing
organic contaminants is effective, it is also very expensive. Ozone
generators are costly not only to purchase but also to operate.
Ozone generators require a lot of power. As a result of the high
cost of using continuous ozonation to treat solid matrices
containing organic contaminants, ozonation is not often a
reasonable choice when evaluating the options available for
cleaning up a particular contaminated site.
[0006] It has been known that a single application of ozone could
improve the biodegradability of contaminants. This approach
involved using a single stage of ozone treatment followed by
biological treatment of the contaminants. Since ozone is a
microbial sterilant, there has always been the concern that the
ozone pretreatment would negatively impact or even completely
destroy the biodegradation phase by destroying the microbes upon
which biodegradation relies.
[0007] It is an object of the present invention to provide a method
of treating a solid matrix containing organic contaminants by using
ozone. It is a further object of this invention to provide a cost
effective method of treating a solid matrix containing organic
contaminants by using ozone in an efficient manner. Other objects
of the present invention will appear from the disclosure presented
herein.
SUMMARY OF THE INVENTION
[0008] This invention provides a method for the treatment of a
solid matrix containing organic contaminants. The method includes
the steps of a) injecting ozone into the solid matrix for a period
of time known as the pulse duration; b) interrupting the injection
of the ozone into the solid matrix for a period of time known as
the gap duration; and repeating step a) at least one additional
time.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIGS. 1 through 6 are graphs showing the effect of three
variables (pulse duration, gap duration, and total ozonation time)
on the destruction of several classes of organic compounds
(TPH/PAH, PCP and HCB) using ozone.
[0010] FIGS. 1 and 2 are graphs showing the percent reduction of
TPH/PAH as a function of the pulse duration and the gap duration.
FIG. 1 is for a short total ozonation time. FIG. 2 is for a long
ozonation time.
[0011] FIGS. 3 and 4 are graphs showing the percent reduction of
PCP as a function of the pulse duration and the gap duration. FIG.
3 is for a short total ozonation time. FIG. 4 is for a long
ozonation time.
[0012] FIGS. 5 and 6 are graphs showing the percent reduction of
HCB as a function of the pulse duration and the gap duration. FIG.
5 is for a short total ozonation time. FIG. 6 is for a long
ozonation time.
[0013] FIG. 7 is a schematic drawing of a vadose zone system.
[0014] FIG. 8 is a schematic drawing of a saturated zone
system.
[0015] FIG. 9 is a schematic drawing of a parallel ozone pulsing
system.
[0016] FIG. 10 is a schematic drawing of a co-axial ozone pulsing
system.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENT
[0017] The invention disclosed herein was discovered while
searching for a way to reduce the high cost of using ozone as a
treatment technology for solid matrices containing organic
contaminants. Previous ozonation development had been based on the
sustained, continuous application of ozone. Earlier work had shown
that many organic contaminants thus could be oxidized with ozone.
However, such treatment required high mass loadings of ozone
relative to the organic contaminant present to effect the
oxidation. The result of this initial development was the view that
ozone treatment was an expensive, niche technology, being able to
destroy many organic contaminants but at a high cost. As a
consequence, the use of continuous ozonation has not been widely
practiced.
[0018] Since ozone reaction with organic compounds is a chemical
oxidation, the rate and the extent of oxidation are a function of
the mass and the concentration of ozone added. Ozonation was
thought to require a mass loading of greater than stoichiometry
(.about.3 Kg ozone/Kg organic). To supply these levels of ozone, it
was generally expected that achieving acceptable reactions would
require a sustained, continuous application of ozone to the solid
matrix containing the organic contaminant. Such continuous
application of ozone would require a multiplicity of ozone
generators for sites with multiple injection points thereby raising
both the capital and the operating costs for the site being
remediated. Because of the high cost associated with continuous
ozonation, alternatives were explored.
[0019] The first alternative was to consider combining ozonation
and bioremediation. By using bioremediation to destroy at least
some of the contaminant mass, less ozone overall would be required,
thereby lowering the cost of the operation. Bioremediation is a
relatively inexpensive process, often requiring simple aeration of
the contaminant mass. Bioremediation is, however, a slower process
than ozonation and is limited to treating more soluble and reactive
organic contaminants. Biodegradation, by itself, is unable to
effectively degrade many insoluble recalcitrant organics. The
combination of ozonation and bioremediation could minimize the
amount of ozone used by using biological treatment to effect much
of the contaminant removal. Pre-oxidation with ozone, i.e.,
oxidation with ozone prior to bioremediation, could also make the
organic contaminants present in the solid matrix more amenable to
biodegradation. Thus, the combination of these two technologies
could provide a cost effective method for destroying organic
contaminants contained in the solid matrix.
[0020] Because ozone is ultimately toxic to bacteria, adding too
much ozone to a system would destroy the bacteria thereby making
bioremediation an impossibility without adding or regenerating an
adequate microbial population. It was decided that one way to
combine ozonation with bioremediation was to intermittently pulse
ozone into the solid matrix containing the organic contaminants,
i.e., turning the ozone on for a period of time, turning the ozone
off for a period of time, turning the ozone back on for a period of
time, and so forth. While the ozone was turned on and was injected
into the solid matrix for a period of time known as the pulse
duration, the ozone would attack the organic contaminants and
degrade them to more biodegradable compounds. When the ozone was
turned off, thus interrupting the flow of ozone to the contaminated
matrix for a period of time known as the gap duration,
bioremediation would be the main degradation mechanism for the
organic contaminants. Using a short ozone pulse duration would
minimize the toxic effect of the ozone on the microbial population,
while using a long gap duration would allow the microbial
population to regenerate and degrade the partially oxidized
contaminants in the solid matrix.
[0021] With this thinking a Creosote Lab Study was conducted.
Creosote Lab Study--Phase I
[0022] The work scope planned to compare the effectiveness of
bioremediation, ozonation and combined ozonation-bioremediation on
the treatment of creosote contaminated soils. There were three
criteria that would be used to evaluate the success of the
treatment: removal of PAHs (polyaromatic hydrocarbons), removal of
TPH (total petroleum hydrocarbons), and removal of NAPLs
(non-aqueous phase liquids). It was expected that: 1) Ozone would
destroy PAHs, but would not be effective on TPH or NAPLs. 2)
Bioremediation would reduce TPH but would not be effective on PAHs
or NAPLs. 3) The combination of ozonation and bioremediation would
treat all contaminants and remove NAPLs. The original protocol used
8 soil columns: 3 columns relying upon bioremediation with oxygen
injection; 3 columns having pulsed ozone, with oxygen being
supplied between each ozone pulse, i.e., during the gap duration;
an ozone only column as a control; and a nitrogen only column as a
control. The experimental design attempted to maintain the resident
microbial population using a short ozone pulse duration. The
results of this experimentation showed that ozonation caused a
significant reduction in the microbial population by at least three
orders of magnitude. The resulting low microbial population density
was insufficient to significantly contribute to contaminant
reduction by biologically oxidative mechanisms. This reduction in
overall population density appeared to be unrelated to the ozone
because the micro-organisms in the oxygen only columns also showed
a die-off. It appeared from follow-up work that the die-off was due
to the inability of the micro-organisms to tolerate levels of
ammonia-nitrogen and orthophosphate-phosphorus that spiked into the
soils at the level of contamination. This was an unusual and
totally unexpected result. Nutrient toxicity at the spiked
concentration levels had not been observed in any previous
treatability work.
[0023] A second surprising result was observed from this initial
work in the Creosote Lab Study. Although the microbial population
had been reduced to a level that would be ineffective in
contaminant removal, the periodic pulsing of ozone was effective in
reducing the target PAHs and TPH. The ozone pulsing applied an
amount of ozone equivalent to only 7.7 hours of continuous
ozonation (determined by adding together all of the pulse duration
times). This resulted in an average PAH reduction of almost 70% and
a TPH reduction of 60%. The pulsed oxygen control column showed
essentially no change in either TPH or PAHs. By way of comparison,
the continuous ozonation column only showed a PAH and TPH reduction
of only 42%. The nitrogen control column, which was exposed to 41
hours of continuous nitrogen gas, achieved a 4.5% reduction in PAH
levels and no reduction in TPH concentrations. These tests
demonstrated that ozone can effectively reduce PAH and TPH levels
and that pulsing ozone into the soil has a substantial efficiency
benefit in PAH/TPH removal. Based on the results of this study,
modifications were made to the experimental plan for Phase II of
the Creosote Lab Study.
Creosote Lab Study--Phase II
[0024] The goal of Phase II of the Creosote Lab Study was the
destruction of the total target contaminants (PAH and TPH) to below
clean-up levels. The soil columns from Phase I of the study were
modified in Phase II as follows:
[0025] Continuation of Pulsed Ozonation: During Phase I of the
Creosote Lab Study, this column had originally received 1 hour of
ozonation (pulse duration) every four days (gap duration) of
operation. During the gap duration time period, i.e., when the
ozone was turned off, this column had received room air on a
continuous basis. During Phase II, this column continued to receive
pulsed ozonation until the study was completed. This column
examined the effects of pulsed ozonation alone on the target
contaminants for an extended testing period.
[0026] Pulsed Ozonation with Reinoculation, Original TPH/PAH
Levels: During Phase I, this column had received one hour (pulse
duration) of oxygen gas every four days of operation (gap
duration). During the gap duration period, i.e., when the oxygen
was turned off, the column received room air on a continuous basis.
At the end of Phase I, there was no degradation of TPH or PAHs.
During Phase II, this column was re-inoculated with a commercial
hydrocarbon-degrading culture and received pulsed ozone for the
remainder of the study.
[0027] Pulsed Ozonation with Reinoculation, Reduced TPH/PAH Levels:
During Phase I, this column received one hour (pulse duration) of
ozone every four days of operation (gap duration). During the gap
duration period, i.e., when the ozone was turned off, the column
received room air on a continuous basis. During Phase II, this
column was reinoculated with a commercial hydrocarbon-degrading
culture and received pulsed ozone for the remainder of the
study.
[0028] Pulsed Oxygen Control: During Phase I, this column received
one hour (pulse duration) of oxygen every four days of operation
(gap duration). During the gap duration period, i.e., when the
oxygen was turned off, the column received room air on a continuous
basis. During Phase II, this column was reinoculated with a
commercial hydrocarbon-degrading culture and received pulsed oxygen
for the remainder of the study.
[0029] Continuous Ozonation: During Phase I, this column had
received only air on a continuous basis. During Phase II of this
study, this column was exposed to continuous ozonation (Monday
through Friday) over a two-week period.
[0030] As shown in the following table, the target PAH levels (PAH
<473 ppm) were finally achieved after 38 hours of total
ozonation in a pulsed mode (the 38 hours is the cumulative total of
all of the ozone pulse duration times):
1 Description Results, PPM Original Soil Total PAHs 1745; TPH 6600
Pulsed Ozone - no reinoculation Total PAHs 110; TPH 390 38 Hours
Total Ozonation Time Pulsed Ozone - Total PAHs 182; TPH 490
Reinoculation 28 Hours Total Ozonation Time Pulsed Ozone - Total
PAHs 240; TPH 700 reinoculation 25 Hours Total Ozonation Time
Pulsed oxygen - Total PAHs 2008; TPH 6200 Reinoculation 19 hours
Total oxygen Time
[0031] The purpose of this Creosote Lab Study was to examine the
relative performance of ozonation, biodegradation, and combined
ozonation and biodegradation in being able to treat LNAPL (light
non-aqueous phase liquids) and creosote contaminated soils. The
assumption going into the study was that biodegradation was a low
cost technology that would address TPH well and PAHs to a moderate
extent. Biodegradation was felt to be a potentially efficient means
of removing fuel components in the soil but could take a long time
to deal with LNAPLs or attain the target levels for PAHs.
Ozonation, a potentially more expensive technology, was expected to
address the PAHs well and TPH to a moderate extent. Ozone was not
expected to be an effective technology to treat LNAPLs. However,
giving the strengths of each technology, it was hoped that the
combination of ozonation and biodegradation would provide a cost
effective approach that would address both the PAHs and TPH
(LNAPL).
[0032] Continuous ozonation was found to be effective in attaining
the target PAH levels. A primary result of the study was the
observation that ozone would address the fuel components (LNAPL
residual). In the continuous ozonation and the pulsed ozonation
studies, TPH was degraded by .about.95-99%. A second key
observation was that pulsing ozone, in and of itself, provided a
significant improvement in the use of ozone without any biological
component. The process of using short pulses of ozone to allow
biodegradation to occur as well was found to not be necessary.
Simply pulsing ozone alone yielded the results that were
anticipated for the combined ozonation and biodegradation.
Biodegradation, when present, was found to give only an incremental
improvement (.about.10%) over the effect of pulsing alone.
Statistically Designed Study
[0033] As a follow-up to the Creosote Lab study, a series of column
studies were conducted. The columns contained 500 grams of
sterilized, washed and sieved sand. A mixture of creosote,
pentachlorophenol (PCP) and hexachlorobenzene (HCB) were added to
the columns. Original concentrations were approximately 17,000 ppm
creosote, 800 ppm pentachlorophenol and 800 ppm hexachlorobenzene.
Three factors were varied:
[0034] Pulse Duration--0.25, 1, 2, 3, and 4 hours
[0035] Gap Duration--2, 12, 24, 36, and 48 hours
[0036] Total Ozonation Time--4, 6, 8, 9, and 12 hours
[0037] The pulse duration is the time during which the ozone was
turned on for a single pulse of ozone. The gap duration is the time
during which the ozone was turned off between two separate pulses
of ozone. The total ozonation time is the cumulative total of the
pulse duration times.
[0038] Performance was evaluated based on two factors: ozone
efficiency--weight of ozone per weight of contaminant oxidized; and
percent destruction. The following table shows the results for
ozone efficiency based on the three variables studied.
2 Ozone Efficiency (wt. Ozone/wt. Contaminant) Gap Pulse Total
Duration, Average Duration, Average Ozonation Average Hrs Eff. Hrs
Eff. Time Eff. 2 1.56 0.25 1.30 4 1.01 12 2.41 1 2.01 6 1.40 24
1.49 2 1.45 8 1.50 36 1.39 3 1.56 9 1.78 48 1.26 4 1.78 12 1.90 30
Hours 4.10 30 Hours 4.10 30 Hours 4.10 Continuous Continuous
Continuous 68 Hours 8.4 68 Hours 8.4 68 Hours 8.4 Continuous
Continuous Continuous 129 Hours 18.0 129 Hours 18.0 129 Hours 18.0
Continuous Continuous Continuous
[0039] As can be seen from this table there is a big difference in
the ozone efficiency between continuous ozonation and pulsed
ozonation. Pulsed ozonation is more efficient. For pulsed
ozonation, the gap duration time has the greatest effect on ozone
efficiency. The shortest gap (2 Hours) shows a moderate efficiency.
As the gap increases to 12 hours, the efficiency drops. For the gap
duration time, there is a significant improvement in ozone
efficiency between 12 and 24 hours. After a gap of 24 hours, there
is a slight but continued improvement in efficiency for longer
gaps. The pulse duration time shows two results: a good efficiency
at an extremely short pulse duration (0.25 Hours) and a second
optimal efficiency at 2-3 hours. After a pulse of 3 hours,
generally the efficiency decreases with increasing time. This is to
be expected as the initial ozonation will react with the more
available, mobile contaminants. Once these are reacted it takes
proportionately more ozone to oxidize the remaining material. This
is especially true of the continuous ozonation. The total ozonation
time also affects the efficiency. A big difference between pulsed
and continuous ozonation is that the efficiency is greater for the
pulsed ozone and does not decrease (greater wt ozone per weight of
contaminant) as rapidly with increasing total ozonation time as
does that for continuous ozonation. The greater efficiency of
pulsing compared to continuous ozonation may be a result of
contaminants diffusing out of the solid matrix during the gap time
to the surfaces of the matrix where they are then reacted.
[0040] The percent reduction achieved for the different types of
contaminants was also examined as a function of the three
variables--gap duration, pulse duration, and total ozonation time.
The following table shows the results for TPH/PAH.
3 Percent Reduction TPH/PAH Gap Pulse Duration, Average % Duration,
Average % Total Average % Hrs Reduced Hrs Reduced Ozonation Time
Reduced 2 70.6 0.25 88.9 4 50.7 12 59.8 1 67.5 6 53.8 24 72.9 2
75.2 8 75.8 36 82.9 3 71.5 9 81.6 48 84.4 4 71 12 81.7 30 Hours
93.4 30 Hours 93.4 30 Hours 93.4 Continuous Continuous Continuous
68 Hours 97.4 68 Hours 97.4 68 Hours 97.4 Continuous Continuous
Continuous 129 Hours 98.4 129 Hours 98.4 129 Hours 98.4 Continuous
Continuous Continuous
[0041] The percent reduction in TPH/PAH is most strongly affected
by the total ozonation time. It increases with increasing time up
to 9 hours. This is to be expected as longer times allow more
reaction. The gap duration time has the second largest effect. The
percent reduction shows that a very short gap duration (2 hours)
achieves a moderate percent reduction. This decreases as the gap
duration increases to 12 hours. Between 12 and 24 hours for gap
duration there is a significant increase in the percent reduction.
The optimum gap duration time for the percent reduction is at a gap
of 24 to 36 hours, based on the improvement in performance. Finally
the pulse duration has some impact with the either at a very short
pulse (0.25 hours) or at about 2-3 hours.
[0042] The following table shows the results for PCP.
4 Percent Reduction PCP Gap Pulse Duration, Average % Duration,
Average % Total Average % Hrs Reduced Hrs Reduced Ozonation Time
Reduced 2 62.3 0.25 88 4 50.7 12 57.4 1 67.8 6 49.5 24 78.4 2 76 8
80.2 36 84.7 3 63.8 9 82 48 90.5 4 81 12 88.5 30 Hours 86.3 30
Hours 86.3 30 Hours 86.3 Continuous Continuous Continuous 68 Hours
93.5 68 Hours 93.5 68 Hours 93.5 Continuous Continuous Continuous
129 Hours 95.3 129 Hours 95.3 129 Hours 95.3 Continuous Continuous
Continuous
[0043] PCP is a more recalcitrant (more difficult to react) organic
than TPH/PAHs. The reduction of PCP follows the same patterns as
that for TPH/PAH, with some exceptions. First, as would be expected
the total ozonation time has the greatest effect on the percent
reduction. The amount of PCP reacted increases with increasing
total ozonation time. The gap duration is also important. In this
case PCP reduction increases with increasing gap duration times.
The biggest improvement is for gap durations between 12 and 24
hours. The pulse duration has an unusual behavior. Best results are
seen at short and long pulse durations. The short pulse duration is
surprising.
[0044] It takes at least 68 hours of continuous ozonation to equal
the performance of the pulsed ozonation. To achieve approximately
90% reduction in PCP pulsed ozonation required approximately
{fraction (1/7)}th the amount of ozone as compared to that required
for continuous ozonation.
[0045] The following table shows the results for HCB.
5 Percent Reduction HCB Gap Pulse Duration, Average % Duration,
Average % Total Average % Hrs Reduced Hrs Reduced Ozonation Time
Reduced 2 0 0.25 27 4 12.8 12 12.7 1 17.3 6 16.3 24 9.2 2 5.2 8 8.5
36 22.4 3 21.7 9 18.1 48 20.0 4 10.5 12 2.6 30 Hours 24.1 30 Hours
24.1 30 Hours 24.1 Continuous Continuous Continuous 68 Hours 30 68
Hours 30 68 Hours 30 Continuous Continuous Continuous 129 Hours
42.5 129 Hours 42.5 129 Hours 42.5 Continuous Continuous
Continuous
[0046] Hexachlorobenzene is an extremely recalcitrant compound. Its
behavior under pulsing conditions is very unusual. The total amount
of ozonation does not appear to show any definitive relationship.
One would expect that increasing the amount of ozonation would
increase the percent reduction, as is seen with the continuous
study. The factor that has the greatest and most identified affect
is the gap duration. The longer the gap duration, the greater the
reduction. The pulse duration shows a second order behavior. The
best performance is at either short pulses (about 0.25 hours) or
long pulses (about 3 hours).
[0047] The following table shows the conditions which gave the
highest and lowest percent reduction for the different
contaminants. As can be seen, the gap duration is extremely
important. The best results are with a 24-48 hour gap duration and
the worst results are with the short gap durations of approximately
12 hours. The pulse duration for best performance is 0.25 to 3
hours.
6 Conditions for Maximum Removal (Top 3) Contaminant Gap-Pulse-Time
% Gap-Pulse-Time % Gap-Pulse-Time % TPH/PAH 24-0.25-8 88.9 36-3-9
84.7 48-2-8 84.4 (creosote) Pentachlorophenol 48-2-8 90.5 24-2-12
88.5 24-0.25-8 88.0 Hexachlorobenzene 36-1-6 37.8 36-3-9 36.6
24-0.25-8 27. Conditions for Minimal Removal (% Reduction) TPH/PAH
Gap-Pulse-Time, Hours (creosote) Pentachlorophenol
Hexachlorobenzene 12-1-6 24.2 15.3 0.0
[0048] FIGS. 1-6 depict the effect of the three variables, pulse
duration, gap duration and total ozonation time on the destruction
of TPH/PAH, PCP, and HCB. The HCB was used as a surrogate for non
reactive and highly chlorinated compounds such as PCBs. The results
for each compound are shown in two figures; one at low total
ozonation time and the second at long total ozonation time. As
shown in the figures, the behavior of the three types of compounds
under pulsed ozonation is different, reflecting the differences in
reactivity. However, there are also some important generalizations
that can be made.
[0049] FIGS. 1 and 2 depict the contours for TPH/PAH. FIG. 1
depicts the percent reduction of TPH/PAH as a function of the gap
duration and the pulse duration at a low level of ozonation. As
shown, the best performance occurs using a moderate to long gap
duration with a short to medium pulse duration. At a short gap
duration, performance is enhanced by increasing the length of the
pulse duration. When the total ozonation time is increased (FIG. 2)
the behavior is similar. The best performance is again at long gap
durations and short pulse durations, or at short gap durations and
long pulse durations. These figures illustrate that the reaction
with TPH/PAH can be optimized.
[0050] FIGS. 3 and 4 depict the contours for PCP. FIG. 3 depicts
the percent reduction of PCP as a function of the gap duration and
the pulse duration at a low level of ozonation. The best
performance is with a short pulse and a long gap. Moderate
performance can be seen at short gaps and long pulses. As seen in
FIG. 4, increasing the total amount of ozonation does not
significantly alter the response other than generally increasing
the percent reduction. Optimal response is still at long gaps-short
pulses, or short gaps-long pulses.
[0051] FIGS. 5 and 6 depict the contours for HCB. FIG. 5 depicts
the percent reduction of PCP as a function of the gap duration and
the pulse duration at a low level of ozonation. The reaction of HCB
is very different compared to the other contaminants studied. The
best performance is attained with long gaps, almost irrespective of
the duration of the pulse. As the total amount of ozone is
increased, the best performance shifts to long pulses and long
gaps.
[0052] Several general conclusions can be drawn from this
study.
[0053] First, the gap duration used in pulsed ozonation is
important. Generally at least a 24 hour gap is most preferred. As
the reactivity of the contaminant decreases, the importance of the
gap duration increases. Generally the less reactive a contaminant
the longer the gap duration.
[0054] Second, the pulse duration is important with reactive or
moderately reactive contaminants. Short pulses are best, when
coupled with long gaps. As the reactivity drops, the importance of
the pulse duration drops. If long pulses are used, short gaps are
best.
[0055] Third, the conditions for best performance are a function of
the reactivity of the contaminant. Generally the less reactive the
contaminant the longer the gap duration.
Field Study With Coal Tars
[0056] A field pilot study of pulsed ozonation was conducted at a
former manufactured gas site. The site was contaminated with a
mixture of TPH and PAHs. Ozone (5% in oxygen) was injected, in
situ, in pulses into a confined aquifer. In between pulses nothing
was added. The main concern was the presence of DNAPL (dense non
aqueous phase liquids) in the test area. Ozone was sparged into the
aquifer at a varying rate. At the beginning of the study, the ozone
was pulsed for 1 hour a day for five days. At the end of the study
the ozone was pulsed for 8 hours a day for 4 days a week. At the
end of twelve weeks DNAPL levels were reduced from as great as
about 2 feet to less than 1 inch.
[0057] During the study it was thought that biological activity was
a key component of the performance. An examination of the data
would suggest that at the short pulse durations (1-2 hours/day),
biodegradation occurred. Oxygen uptake, a sign of aerobic
biodegradation, was observed. For the long pulse durations, there
doesn't appear to be much biological activity as the oxygen uptake
ceased.
[0058] This study illustrates the benefits of pulsing ozone. It
also shows that biodegradation is beneficial but is not necessary
for contaminant removal. The study was not run to optimize
conditions. The gap duration chosen, based on assumed conditions to
maintain biological reactivity, varied from about 24 hours during
the week to about 48-72 hours over the weekend. These values are,
from the other studies, in the proper range.
Coal Tar Lab Study
[0059] Two soil and two groundwater samples from a former
manufactured gas plant were used in the study. One soil contained
high contaminant levels (5,860 mg/Kg total PAHs; 369 mg/Kg
carcinogenic PAHs; 18,000 mg/Kg TPH; and 1,151 mg/Kg total BTEX),
and represented chemical hot spots at the site. The second soil
type ("bulk") was representative of more typical site conditions,
and as calculated contained significantly lower target contaminant
concentration levels (667 mg/Kg total PAHs; no carcinogenic PAHs;
2,295 mg/Kg TPH; and no total BTEX). The highly contaminated
("hot") soils alone were used in the continuous ozone test, while
an approximate 3:1 "mixture" of bulk and hot soil was used in the
remaining experiments.
[0060] The treatability tests performed indicate that indigenous
microorganisms could degrade at least portions of the BTEX, PAH,
and TPH contaminants under aerobic conditions and without the
addition of supplemental inorganic nutrients. Air stripping was
also a potential removal mechanism for the BTEX fraction and
certain PAH/TPH compounds. Ozone is an effective chemical oxidant
in the treatment of PAH and TPH, and was also expected to
successfully treat the BTEX fraction. Ozone could effectively
reduce target contaminant concentration levels by greater than 99%.
Ozone could be effectively used as a stand alone technology, or in
combination with air stripping and biological treatment. The use of
combined technologies may provide the most cost-effective option
for successfully remediating the target contaminants.
[0061] The slurry ozone breakthrough test, using a 20% solids
slurry of "sleeved" soil and groundwater, received a total of 78
hours of continuous ozonation, and was used to determine the
effects of ozonation on the target contaminants as a function of
treatment time. The ozone slurry breakthrough test determines the
consumption of ozone by easily oxidized materials, especially
non-contaminant ozone consumers. Breakthrough is defined as the
point at which the influent and effluent concentrations are
approximately equal or the point at which the difference between
the influent and effluent concentrations is essentially constant. A
similar control flask, receiving a continuous flow of nitrogen gas
for 73 hours, was used to correct for any volatile and/or
adsorptive contaminant losses. While reductions of greater than 99%
were observed for Total PAHs, Total Carcinogenic PAHs, and Total
Benzo[a]pyrene Equivalent PAHs in the slurry soil fractions during
the 78 hours of treatment, significant contaminant reductions were
obtained in as little as 22.6 hours: 96% for Total PAHs, 99% for
Total Carcinogenic PAHs, and 99% for Total Benzo[a]pyrene
Equivalent PAHs. TPH levels were reduced by 85% after 22.6 hours,
95% after 43.3 hours, and 99% after 55.8 hours. BTEX levels were
reduced by greater than 99% during the 22.6 hour period,
presumptively due to both chemical oxidation and air stripping. In
contrast, the nitrogen control flask showed Total PAH levels
reduced by 15%, Total Carcinogenic PAH levels reduced by 19%, and
Total Benzo[a]pyrene Equivalent PAH levels reduced by 12% over the
72 hour period, verifying that ozonation was the primary removal
mechanism for the PAHs present. TPH levels were reduced by 36%, and
Total BTEX concentrations decreased by 99%. BTEX compounds are
susceptible to air stripping, as are a limited number of the TPH
and PAH compounds present.
[0062] Four other conditions, all using 20% slurries, were run. The
control study was an aerated sample only to look at volatile
removal and biodegradation. The pulsed ozone received 15 minutes of
ozone every Monday, Wednesday and Friday for a total of 7.3 hours
of ozonation. The gap was 48 hours for the first two pulses and 72
hours for the third pulse. The Bio/Ozone study received just air
for .about.9 weeks followed by 24 hours of continuous ozone. The
Ozone/Bio study received 24 hours of ozone, was reinoculated and
then received 9 weeks of aeration. All three of these studies
showed elevated bacterial levels. The results of this study are
presented below.
7 Degradation Results, % Removed @ Nine Weeks Total PAHs Carcn PAH
TPH BTEX Air Only 49 0 47 100 Continuous 99 99 100 100 Ozone (78
hrs) Pulsed Ozone 89 33 100 100 (0.25 hrs pulses on Mon, Weds, Fri)
(7.3 hrs total O.sub.3 time) Ozone/Bio 77 56 100 100 (Sequential 24
hrs Ozone with 9 weeks Bio) Bio/Ozone 98 81 100 100 (Sequential 9
weeks Bio with 24 hrs Ozone)
[0063] Four classes of compounds were tracked--Total PAHs,
Carcinogenic PAHs, TPH, and BTEX. As can be seen from the results,
the pulsed ozone did achieve significant removal of contaminants at
a much shorter ozonation time than the other studies. This
illustrates that short pulses and long gaps are beneficial to
achieving contaminant reduction.
[0064] A second observation of this study is that biological
activity can be maintained when short pulses and long gaps are
used.
[0065] A third observation is that the sequential use of
biodegradation followed by ozonation does increase performance.
This is evidenced by the results of the Bio/Ozone study.
[0066] Pulsed ozonation greatly improves the efficiency of
ozonation. Because less ozone is used on a unit time basis both the
capital and operating cost can be reduced. This is illustrated for
a test case as shown below. The site is a 100'.times.200' area with
6-8 feet of soil needing treatment. The contaminant is
creosote.
[0067] Continuous Ozonation Assumptions
[0068] 10 wells injecting 10 SCFM of 3% O.sub.3
[0069] Total flow --100 SCFM
[0070] Ozone Requirement .about.150 lb/day of ozone at 3%
O.sub.3
[0071] Generator Requirement--3.times.50#/day units $100K each
[0072] Pulsed Ozone Assumptions
[0073] 10 wells injecting 10 SCFM of 3% ozone @ 2hr/day/well
[0074] Total flow: 10 SCFM of 3% O.sub.3 and 100 SCFM total air
flow
[0075] Ozone Requirement--14 lb/day
[0076] Generator Required: Single 25#/day unit @ $50K
[0077] The typical total cost for these systems might compare as
follows:
Comparison of Continuous and Pulsed Ozone System
[0078]
8 Continuous Ozonation Pulsed Ozonation Capital 250,000 100,000
(Generator, Wells and Piping) Installation 120,000 150,000
Utilities/yr Ozone 50,000 20,000 Labor/yr 80,000 80,000 Treatment
Time, Site 2 years 3 years Total Treatment Cost 630,000 540,000
[0079] In its most basic form, the present invention is a method of
treating a solid matrix containing organic contaminants comprising
the steps of a) injecting ozone into the solid matrix for a period
of time known as the pulse duration; b) interrupting the injection
of the ozone into the solid matrix for a period of time known as
the gap duration; and c) repeating step a) at least one additional
time. In practice, it is expected that steps a) and b) will be
sequentially repeated multiple times so as to achieve a greater
efficiency in the use of ozone. The preferred gap duration is from
about 2 to about 48 hours, while the most preferred gap duration is
from about 24 to about 36 hours. The preferred pulse duration is
from about 0.25 hours to about 8 hours, while the most preferred
pulse duration is either about 0.25 hours or from about 2 hours to
about 3 hours.
[0080] Pulsing ozone into a solid matrix containing organic
contaminants increases the efficiency of ozone usage, as compared
to a continuous ozonation system, from several fold to an order of
magnitude. Less ozone is used to obtain an equivalent, reduction in
the contaminants. The pulse duration and the gap duration are the
two key control parameters in ozone pulsing. While the total amount
of ozone added is also important, it is largely a function of the
amount of contaminant present in the solid matrix. The gap duration
has the largest effect on ozone efficiency. The pulse duration also
effects ozone efficiency but not as dramatically as does the gap
duration.
[0081] Ozone can be supplied by any of the commercially available
ozone generation systems. While these systems can generally supply
ozone at concentrations of up to about 15% ozone, the optimal
concentration range is from about 3% to about 7% ozone. The feed to
the ozone generator is usually either air or oxygen. When air is
used as the generator feed, a 2-3% ozone stream is usually
generated. When oxygen is used as the feed gas, 5-7% ozone is
typically generated. With either feedstock, the ozone concentration
can be increased by increasing the residence time of the feed gas
in the generator. This is done by decreasing the feed rate into the
ozone generator. It may be presupposed that higher ozone
concentrations would increase the speed of the reaction. However,
higher concentrations are generally more costly to generate.
[0082] The total ozonation time, i.e., the cumulative total of the
pulse duration times, has only a moderate effect on the ozone
efficiency. Pulsed ozonation is most efficient at the beginning of
the ozonation process. The efficiency drops off slightly with
increasing time. This is probably due to the more accessible and/or
reactive organics being oxidized first and the more strongly
absorbed organics requiring more exposure to ozone. Compared to
continuous ozonation, the decrease in efficiency for pulsed
ozonation is much less.
[0083] As would be expected, the total ozonation time has a
substantial effect on the percent destruction of the organic
contaminants. The total ozonation time exhibited the best
destruction at from about 9 to about 12 hours. Percent destruction
increased dramatically in going from 4 hours to 8 hours and much
slower in going from 8 hours to 12 hours. In general, the more
ozone to which an organic contaminant is exposed, the greater its
resulting destruction. This was evident in the high percent
reductions obtained with continuous ozonation.
[0084] By monitoring the ever decreasing concentrations of the
target contaminants, one skilled in the art can easily determine
when to terminate either a pulsed ozonation process or a continuous
ozonation process. The desired clean-up level is usually determined
by the site owner in conjunction with the regulatory agency having
jurisdiction over the cleanup. Preferably, the pulsed ozonation
process of the present invention would be operated until a
substantial amount of the organic contaminant has been
destroyed.
[0085] During the gap duration period, when the injection of ozone
into the solid matrix is interrupted, one can optionally choose to
inject either air or oxygen into the solid matrix to promote
biodegradation therewithin. However, the advantages of doing so may
not be very significant and is not a necessary component of the
pulsed ozone approach. To maximize the potential for
biodegradation, pulse durations of about less than an hour should
be used along with gap durations of from about 36 to about 72
hours.
[0086] Pulsed ozonation can generally be used in treating any
organic contaminants that may be contained within a solid matrix.
Pulsed ozonation is most beneficial in the treatment of solid
matrices containing recalcitrant organic compounds having one or
more of the following properties: non-volatile (volatility limit
less than about 1 mm Hg,); insoluble (solubility limit less than
about 1000 ppm); non-biodegradable (BOD.sub.5 less than about 0.1
mg/L oxygen.) (The solubility can be higher if the compound is both
non-volatile and non-biodegradable.) Specific compounds and classes
of compounds which can be treated using the present invention
include the following:
[0087] PAHs (Poly Aromatic Hydrocarbons):
[0088] Specifically carcinogenic PAHs--benzo(a)anthracene,
benzo(a)pyrene, benzo(b)fluoranthene, chrysene, dibenzo(a,h)
anthracene, indeno(1,2,3-c,d)pyrene; and coal tars, creosote,
combustion residues.
[0089] Chlorophenols:
[0090] such as PCP (pentachlorophenol), dinoseb.
[0091] Substituted Aromatics:
[0092] such as chlorobenzene and di-, tri-, and tetra
chlorobenzenes.
[0093] Hydrocarbons>C8 (number of carbon atoms in molecule):
[0094] such as weathered fuels (gas, jet, diesel); No. 2, No. 4,
and No. 6 fuel oils; API separator sludge; coal tars; oily wastes;
crude oil; residual oils; resid;, Bunker C; cutting oils;
lubricating oils.
[0095] Pesticides:
[0096] DDT, DDX, Chlorinated aryloxyalkanoic Acids such as 2,4-D;
or s-Triazenes such as atazine, simazine; or urea herbicides such
as monuron, chloroxuron; or Amide herbicides such as alachlor and
propachlor; pyretherin, rotenone, chlordane, heptachlor, diazinon,
parathion, malathion, carbofuran, propoxur, aldicarb, permethrin,
lindane, epichlorhydrin, toxaphene or those listed in EPA Method
8018.
[0097] Phthlates:
[0098] such as BEHP, Bis-2ethylhexyl phthlate, dioctylphthlate.
[0099] Explosives:
[0100] such as RDX, TNT, dinitrotoluene.
[0101] Surfactants:
[0102] such as Alkylarylsulfonates, lignosulfonates.
[0103] Wood related wastes:
[0104] such as paper making wastes, humates, lignins, kraft pulp
wastes, terpenes, turpentine.
[0105] The phrase "solid matrix" as used herein is intended to
include solid, permeable and semi-permeable materials such as
soils, either saturated or unsaturated with water, and sludges.
[0106] The present invention can be successfully applied either in
situ or ex situ.
[0107] A number of treatment configurations may be used in
practicing this invention. Some of the basic systems include a
vadose zone system as shown in FIG. 7. While only a single
injection well and a single extraction well are shown in this
drawing (and in FIG. 8), it is understood that multiple injection
wells and multiple extraction wells can readily be used at any
given site. One of the advantages of pulsing ozone as compared to a
continuous ozonation process is the ability to service multiple
injection points using fewer ozonation generators.
[0108] Another treatment system is a saturated zone system with
sparge points and vent well as shown in FIG. 8. Other treatment
systems include a slurry reactor for excavated soils, a constructed
pile with alternating levels of perforated pipe, and a container
equipped with ozone injection piping.
[0109] FIGS. 9 and 10 depict different configurations of an ozone
pulsing system. FIG. 9 depicts a parallel system with separate
ozone and air/O.sub.2 manifolds, whereby an injection well receives
either ozone or air/O.sub.2. The addition of ozone or air/O2 is
controlled by a valve--either a solenoid valve or a manual valve.
FIG. 10 depicts a coaxial system wherein the ozone is piped
directly into the air/O.sub.2 stream. The application of ozone is
controlled by a valve--either a solenoid valve or a manual
valve.
[0110] Operationally, pulsed ozonation can be used alone or
combined with other technologies such as bioremediation, product
recovery, thermally enhanced product recovery, soil vapor
extraction, and air sparging.
[0111] While the forms of the invention herein disclosed constitute
present embodiments of the invention, many others are possible. It
is not intended to mention all of the possible equivalent forms or
ramifications of the invention. It is to be understood that the
terms used herein are merely descriptive rather than limiting, and
that various changes may be made to the invention without departing
from the spirit or the scope of the invention.
* * * * *