simultaneous nitrification denitrification to meet low

12
Simultaneous NitrificationDenitrification to Meet Low Effluent Nitrogen Limits Jose Jimenez 1* , Derya Dursun 1 1 Brown and Caldwell, USA (Email: [email protected]) Abstract Simultaneous nitrificationdenitrification (SND) has been referred to as a biological process for nitrogen removal where nitrification and denitrification occur concurrently in the same aerobic reactor. SND facilities, investigated in this study, have been shown to remove 80 to 96 percent nitrogen without additional carbon and alkalinity. Carbon availability and bulk dissolved oxygen (DO) concentrations were found to be important process parameters for SND activity. Data suggest that a chemical oxygen demandtonitrogen (COD:N) ratio of at least 10.0 is required to achieve significant denitrification; and an optimum bulk DO concentration ranging from approximately 0.3 milligrams per liter (mg/L) to 0.7 mg/L appears to maximize SND activity. However, this low DO condition required for SND provides an environment more susceptible to sludge bulking as observed by the SVI data from the selected SND facilities in this study. Keywords Nutrient removal, nitrogen removal, simultaneous nitrificationdenitrification, low DO bulking, carbon INTRODUCTION Biological reduction of nitrogen in the activated sludge process relies primarily on two mechanisms: aerobic nitrification and anoxic denitrification. Generally, in conventional biological nutrient removal (BNR) facilities, the two processes are carried out in physically separated aerobic and anoxic zones with internal recycles (Barnard, 1975; Ju et al., 1995). However, nitrogen losses in excess of that required for biomass synthesis from aerated facilities have been observed frequently when the right environmental conditions are in place (Applegate et al., 1980; Rittmann and Langeland, 1985; von Münch et al., 1996; Pochana and Keller, 1999a; Daigger and Littleton, 2000, Trivedi and Heinen, 2000; Strom et al., 2004). This phenomenon has been referred to as simultaneous nitrificationdenitrification (SND) because both biological reactions occur concurrently in the same reactor. SND is a wellknown phenomenon in BNR activated sludge systems. It largely depends on the bioreactor configuration (macro environment that is related to mixing), bulk oxygen concentration, and floc size (micro environment that affects oxygen diffusivity on flocs) (Pochana and Keller, 1999a; Daigger and Littleton, 2000; Kaempfer et al., 2000; Stensel, 2001; Littleton et al., 2002; Littleton et al., 2003a; Littleton et al., 2003b Satoh et al., 2003; Ju et al., 2007). In addition to the environmental factors affecting SND, some studies have also indicated that the organic carbon available for denitrification plays a major role in SND activity (Barnard, 1992, Isaac and Henze, 1994; Pochana and Keller, 1999a; and Peng and Qi, 2007). Even thought the mechanisms responsible for SND are well understood; SND is difficult to control since it depends on limited controlled aspects of the process such as floc sizes, internal storage of COD and DO profile within the flocs (Pochana and Keller, 1999a; and Daigger et al., 2007). Therefore, SND process is not a simple matter to design and operate such systems. However, if the operating mechanisms could be better characterized, SND could be used in a wider range of applications thereby reducing the cost of using BNR and making it possible to use it more easily and reliably at existing facilities.

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Page 1: Simultaneous Nitrification Denitrification to Meet Low

Simultaneous Nitrification�Denitrification to Meet Low

Effluent Nitrogen Limits

Jose Jimenez1*

, Derya Dursun1

1Brown and Caldwell, USA (E�mail: [email protected])

Abstract

Simultaneous nitrification�denitrification (SND) has been referred to as a biological process for nitrogen

removal where nitrification and denitrification occur concurrently in the same aerobic reactor. SND facilities,

investigated in this study, have been shown to remove 80 to 96 percent nitrogen without additional carbon and

alkalinity. Carbon availability and bulk dissolved oxygen (DO) concentrations were found to be important

process parameters for SND activity. Data suggest that a chemical oxygen demand�to�nitrogen (COD:N) ratio

of at least 10.0 is required to achieve significant denitrification; and an optimum bulk DO concentration

ranging from approximately 0.3 milligrams per liter (mg/L) to 0.7 mg/L appears to maximize SND activity.

However, this low DO condition required for SND provides an environment more susceptible to sludge

bulking as observed by the SVI data from the selected SND facilities in this study.

Keywords

Nutrient removal, nitrogen removal, simultaneous nitrification�denitrification, low DO bulking, carbon

INTRODUCTION

Biological reduction of nitrogen in the activated sludge process relies primarily on two

mechanisms: aerobic nitrification and anoxic denitrification. Generally, in conventional

biological nutrient removal (BNR) facilities, the two processes are carried out in physically

separated aerobic and anoxic zones with internal recycles (Barnard, 1975; Ju et al., 1995).

However, nitrogen losses in excess of that required for biomass synthesis from aerated facilities

have been observed frequently when the right environmental conditions are in place (Applegate

et al., 1980; Rittmann and Langeland, 1985; von Münch et al., 1996; Pochana and Keller, 1999a;

Daigger and Littleton, 2000, Trivedi and Heinen, 2000; Strom et al., 2004). This phenomenon

has been referred to as simultaneous nitrification�denitrification (SND) because both biological

reactions occur concurrently in the same reactor.

SND is a well�known phenomenon in BNR activated sludge systems. It largely depends on the

bioreactor configuration (macro environment that is related to mixing), bulk oxygen

concentration, and floc size (micro environment that affects oxygen diffusivity on flocs)

(Pochana and Keller, 1999a; Daigger and Littleton, 2000; Kaempfer et al., 2000; Stensel, 2001;

Littleton et al., 2002; Littleton et al., 2003a; Littleton et al., 2003b Satoh et al., 2003; Ju et al.,

2007). In addition to the environmental factors affecting SND, some studies have also indicated

that the organic carbon available for denitrification plays a major role in SND activity (Barnard,

1992, Isaac and Henze, 1994; Pochana and Keller, 1999a; and Peng and Qi, 2007).

Even thought the mechanisms responsible for SND are well understood; SND is difficult to

control since it depends on limited controlled aspects of the process such as floc sizes, internal

storage of COD and DO profile within the flocs (Pochana and Keller, 1999a; and Daigger et al.,

2007). Therefore, SND process is not a simple matter to design and operate such systems.

However, if the operating mechanisms could be better characterized, SND could be used in a

wider range of applications thereby reducing the cost of using BNR and making it possible to use

it more easily and reliably at existing facilities.

Page 2: Simultaneous Nitrification Denitrification to Meet Low

A key to understanding SND activity in aerated facilities is to understand how process design

and operating parameters affect the performance of SND. The objective of this study is to

evaluate the treatment performance of SND facilities including an aerobic activated sludge pilot

plant treating synthetic wastewater. Operating data from selected treatment facilities using SND

were also evaluated to understand the factors affecting its performance.

METHODOLOGY

Evaluation of SND Plants Performance at Selected Treatment Facilities

Historical data collected from selected wastewater treatment plant facilities performing SND

were analyzed to understand how process design and operating parameters affect the SND

performance. Table 1 summarizes the facilities evaluated during this study. The plants are

mainly located on the southeast region of the United States, and they serve principally municipal

areas and receive domestic and commercial wastewater. The design capacities for these facilities

range in size from 50 cubic meters per hour (m3/hr) to 630 m

3/hr.

Table 1. Summary of selected treatment plants performing SND

Plant1 Location

Capacity

(m3/hr)

Process SRT

(days)

Effluent

TN (mg/L)

N Removal

(%)

SVI

(mL/g)2

Iron Bridge3 Orlando, FL 6,420 Bardenpho 15 2.0 96 115/165

Eastern

Reg.3

Orange Co., FL 4,010 Bardenpho 12 2.6 89 120/160

Snapfinger3 DeKalb Co., GA 2,410 Single�Stage 20 3.8 80 200/300

Central3 Ft. Myers, FL 1,765 Single�Stage NA 5.5 84 140/180

Winter

Haven3

Winter Haven, FL 1,205 Bardenpho 25 2.4 93 130/190

Mandarin5 Jacksonville, FL 1,205 MLE 18 4.0 90 150/180

Marlay

Taylor3

St. Mary’s Co., MD 965 Single�Stage 25 4.5 86 170/280

Northwest

Reg.3

Hillsborough Co.,

FL 805 Bardenpho 12 2.7 93 NA

Tarpon

Springs3

Tarpon Springs, FL 645 Bardenpho NA 2.2 92 NA

Stuart6 Stuart, FL 645 Single�Stage 18 5.5 86 212/350

Smith

Creek7

Raleigh, NC 545 A2O 25 4.5 90 200/245

1 Plants do not have supplemental carbon for denitrification

2Average and 90�percentile values

3 Average based on 2007�2008 data

4 Average data based on 2005�2006 data

5 Average data based on 2001�2003 data

6 Average data based on 2004�2005 data

7 Average data based on 2003�2005 data NA – Data not available

RESULTS AND DISCUSSION

Performance of SND Facilities

There are several plants that achieve higher SND performance and do not require additional

carbon and alkalinity to meet low effluent total nitrogen (TN) concentrations. One example is the

Iron Bridge Wastewater Treatment Plant (WWTP) (City of Orlando, Florida). This facility uses a

five�stage Bardenpho configuration as presented in Figure 1, with the main aerobic zone being

an oxidation ditch operating in SND mode. Figure 2 presents long�term effluent nitrogen

Page 3: Simultaneous Nitrification Denitrification to Meet Low

concentrations from this facility in the form of 30�day moving average concentrations. As

depicted heretofore, the Iron Bridge WWTP is able to meet very low effluent TN concentrations.

It should be noted this facility, as well as the other facilities presented in Table 1, do not have

supplemental carbon for denitrification. Dissolved oxygen, ammonia and nitrate profiles were

developed at the Iron Bridge WWTP and the average results are presented in Figure 3. During

this period, the average influent BOD5 and ammonia concentrations were 203 mg/L and 25

mg/L, respectively. The average DO concentration in the oxidation ditch was 0.3 mg/L. As

indicated in Figure 3, nitrification was essentially complete in the oxidation ditch at very low DO

concentrations with values typically less than 0.2 mg/L. Despite the complete nitrification

occurring in the oxidation ditch, the nitrate levels in the oxidation ditch averaged only 0.95

mg/L. Yearly average effluent nitrate values, leaving the oxidation ditch, as low as 1 mg/L have

been recorded at most of the facilities listed in Table 1, which is surprisingly low. Historical TN

removal for the Iron Bridge WWTP has been in the 92 to 98 percent range, with an average

value of 96 percent. Data for other SND facilities presented in Table 1 indicate that significant

total nitrogen removal was occurring at each facility with average removal efficiencies ranging

from 80 to 96 percent. Facilities with BNR configurations such as Iron Bridge, Eastern Regional,

Northwest Regional, Tarpon Springs, Winter Haven, Mandarin and Smith Creek exhibited TN

removal efficiencies of 89 to 96 percent; whereas, facilities using a single�reactor configurations

(without explicitly defined anoxic zones) for nitrogen removal such as Snapfinger, Central,

Marlay Taylor, and City of Stuart realized removal efficiencies in the order of 80 to 86 percent.

Anaerobic Anoxic Oxidation Ditch operated in SND

Influent and

RAS

Post

Anoxic

Post

Aerobic

Mixed Liquor Recycle

To FST

Figure 1. Schematic configuration for the Iron Bridge WWTP, City of Orlando, Florida

Page 4: Simultaneous Nitrification Denitrification to Meet Low

0

1

2

3

4

1/1/2005 7/1/2005 1/1/2006 7/1/2006 1/1/2007 7/1/2007 1/1/2008 7/1/2008

Eff

luen

t (m

g/L

)

Date

30�d TN 30�d TKN 30�d NOx�N

Figure 2. Effluent nitrogen concentrations at the Iron Bridge WWTP, Orlando, Florida

0 00.3

0

1

15.5

7.1

0.20.5

0.140 0

0.95

0.35 0.4

0

2

4

6

8

10

12

14

16

18

Anaerobic Anoxic Oxidation Ditch Post�Anoxic Post�Aerobic

Con

cen

trati

on

(m

g/L

)

DO NH3�N NO3�N

Figure 3. Dissolved oxygen, ammonia and nitrate profiles at the Iron Bridge WWTP,

Orlando, Florida

Page 5: Simultaneous Nitrification Denitrification to Meet Low

Factors Affecting SND

From previous studies, it has been found that two principal factors predominately influence

SND. These are the available carbon and the bulk DO concentration.

To accomplish denitrification in any process, the availability of readily biodegradable organic

carbon has been found to be the most essential factor (Barnard, 1992). Long term operation data

from the Winter Haven WWTP show the effect of the influent BOD5:TKN ratio on the effluent

nitrate concentrations from an activated sludge process operating in SND mode (Figure 4�A).

Data presented in Figure 4�B show the effect of the influent COD:N ratio on denitrification at the

pilot plant facility treating synthetic wastewater. Data from the full�scale facility show that

complete denitrification can be achieved consistently when the influent BOD5:TKN ratio is at

least 6.0; however, when this ratio falls below 2.0, limited denitrification was achieved at the

facility. Similar observations were obtained at the pilot plant where denitrification performance

increased as the influent sCOD:N ratio increased. Very limited denitrification was observed at

the pilot plant at sCOD:N ratios of 6.0 or lower; however, optimum denitrification occurred at

sCOD:N ratios in the 12�15 range. However, it should be noted that in the case of the pilot plant,

the sCOD also corresponded to the total COD available; therefore, in reality somewhat lower

sCOD:N ratios could be expected to work as well since other COD fractions will also be partly

used in the process via hydrolysis or fermentation. In addition, it should be noted here that the

higher sCOD:N ratio needed for denitrification in the pilot plant could be the result of the low

operating HRT of the process. These results indicate that the soluble carbon for denitrification

strongly influence the SND performance. This confirms results by others (Isaacs and Henze,

1994; Pochana and Keller, 1999a; Insel et al., 2003).

0

2

4

6

8

10

12

14

16

0 2 4 6 8 10 12

Eff

luen

t N

O3�N

(m

g/L

)

Influent BOD:TKN Ratio (mg BOD5/mg TKN as N)

(A) Winter Haven WWTP, City of Winter Haven, Florida

Page 6: Simultaneous Nitrification Denitrification to Meet Low

0

5

10

15

20

25

30

35

40

45

0 5 10 15 20

Eff

luen

t N

O3�N

(m

g/L

)

Influent rbCOD:N Ratio (mg COD/mg N)

(B) Pilot Plant, Marrero, Louisiana

Figure 4. Effect of available organic carbon on the effluent nitrate during SND activity

The control of bulk DO concentration in the system is an essential part of achieving a higher

degree of SND. It is well known that denitrification rates are the highest when the DO in bulk

liquid is close to zero (Lie and Welander, 1994). On the other hand, several studies have shown

that DO concentrations for nitrification should be higher than 1.0 mg/L with 2.0 mg/L often

recommended to achieve higher nitrification rates. Therefore, the success of the SND process

relies on the balance of the bulk DO concentration so both kinetic reactions, nitrification and

denitrification, can occur simultaneously in the same reactor. von Münch et al. (1996) found in

batch reactor experiments operated at 15 days SRT and approximately 20oC, that a bulk liquid

DO concentration of 0.5 mg/L was suitable to achieve a nitrification rate equal to the

denitrification rate, which would therefore lead to complete SND. Bliss and Barnes (1986) found

that a DO concentration of at least 0.2 mg/L was critical for nitrification. The graph presented in

Figure 5 shows the effect of bulk DO concentration on the overall SND activity at the Stuart

facility operating in SND mode. During the full�scale experiment, the bulk DO concentration in

the aerobic tank was manually modified to understand the impact of the DO concentration on the

overall SND process. During this experiment, the facility was operated at a constant SRT of 15

days and the influent total COD:N ratio ranged from 12 to 20. Based on the data collected at this

facility, an optimum bulk DO concentration ranging from approximately 0.3 mg/L to 0.7 mg/L

appears to maximize SND activity in the aerobic reactor. When the bulk DO concentration drops

below 0.3 mg/L, the SND performance is limited by nitrification; whereas, higher bulk DO

concentrations of 0.7 mg/L affect denitrification. However, it should be noted that these bulk DO

levels are dependent on the floc size in the system; therefore, it is difficult to draw a general

conclusion with these data. Larger floc size might require higher bulk DO levels than smaller

flocs due to the mass�transfer limitations within activated sludge flocs.

Page 7: Simultaneous Nitrification Denitrification to Meet Low

0

5

10

15

20

0 0.2 0.4 0.6 0.8 1 1.2 1.4

Eff

luen

t Q

uali

ty (

mg

/L)

Bulk DO Concentration (mg/L)

NH3�N NO3�N

Figure 5. Effect of bulk dissolved oxygen concentration on SND activity at the City of

Stuart WWTP, Florida

Low DO environments required for SND processes are conventionally considered more

susceptible to sludge bulking, primarily because of the excessive growth of filamentous bacteria

(Jenkins et al., 2003; Martin et al., 2004). This has been considered one of the main

disadvantages for SND processes. Many facilities being operated in SND mode produce mixed

liquor with marginal settling characteristics as presented in Table 1. Conventional BNR facilities

equipped with anaerobic or anoxic selectors often produce SVI values (90 percentile) of less than

120 and 150 mL/g (Parker et al., 2004). However, in the case of the selected SND facilities listed

in Table 1, SVI values (90 percentile) ranging from 160 to 245 mL/g (with selectors) and 180 to

300 mL/g (without selectors) have been recorded.

In many instances, severe low DO bulking conditions in many SND facilities have limited the

applicability of these processes due to their negative effects on the overall secondary clarification

capacity of the plants. This has driven many SND plants to convert to more conventional BNR

processes with high DO levels in the aeration tanks. Table 3 presents effluent TN and SVI data

from three facilities converted from SND to conventional BNR facilities. The main process

upgrade to the facilities listed in Table 3 included additional aeration capacity in the main

aerobic reactor to increase the bulk DO concentration to limit the growth of filamentous bacteria.

Based on 2008�2009 data, the conventional BNR mode of operation at the Mandarin and Smith

Creek facilities has led to a slightly decrease in the overall effluent TN removal. In the case of

the Winter Haven facility, higher TN removal efficiencies were achieved as a result of adding

external supplemental carbon to increase the post denitrification in the Bardenpho process.

Despite the slightly lower TN removal efficiencies at the Mandarin and Smith Creek plants, the

sludge settling characteristics improved tremendously, which allowed rerating of the facilities

without additional tankage requirements.

SND limited by

denitrification

SND limited by

nitrification Optimum SND

DO Regime

Page 8: Simultaneous Nitrification Denitrification to Meet Low

Table 3. Total nitrogen and SVI data comparison for SND plants upgraded to conventional

BNR facilities

Treatment Plant SND Operation Conventional Operation

1

TN Removal (%) SVI (mL/g) TN Removal (%) SVI (mL/g)

Mandarin 90 180 86 100

Smith Creek 90 245 82 110

Winter Haven 93 190 952 120

1 Average data based on 2008�2009 data

2 Upgrades included supplemental carbon addition for denitrification

Figure 6 presents long term SVI data from the City of Stuart facility. SVI data from January

2004 through December 2006 include operating SVI data when the facility was operating in

SND mode with average and 90�percentile SVI values of 212 and 350 mL/g, respectively due to

excessive growth of filamentous bacteria. As a result of the extremely high SVI data produced at

the Stuart SND facility, the treatment plant was upgraded in 2007 to incorporate anaerobic

selectors and to increase the aeration capacity of the process with the goal of improving the

settling characteristics of the mixed liquor to restore plant capacity. Figure 6 presents the SVI

data after the plant’s upgrade with average and 90�percentile SVI values of 90 and 110 mL/g,

respectively.

0

50

100

150

200

250

300

350

400

450

1/1/2004 1/1/2005 1/1/2006 1/1/2007 1/1/2008 1/1/2009

SV

I (m

L/g

)

Date

Construction

Period

A/O Process � Anaerobic Selector

and New Fine�bubble aeration

SND Process � Extended Aeration with

Mechanical Aerators

Figure 6. Long term SVI data at the City of Stuart WWTP, Florida

Data provided by the Winter Haven WWTP (City of Winter Haven, Florida) was used to explore

the effect of DO concentration on the settling conditions of the mixed liquor. Long term

operating data from this facility was reviewed and is presented in Figure 7. To characterize the

settling conditions of the mixed liquor, SVI measurements were collected three times per day in

a 2�liter settlelometer. During the full�scale trial, two identical trains were operated in parallel

under similar operating conditions (influent flows and loads, SRT of 8.5 days and MLSS of

Page 9: Simultaneous Nitrification Denitrification to Meet Low

3,300 mg/L); however, Train 1 was operated at DO concentrations slightly higher (0.6 mg/L to

0.95 mg/L) than Train 2 (0.25 mg/L to 0.5 mg/L). Figure 7 presents the SVI data collected at the

facility and compares the settling characteristics from both trains. Overall, Train 1 produced

considerably higher SVI values than Train 2, despite both treatment trains experiencing SND

activity. Based on the difference on the quality of the settling conditions between both trains,

plant personnel selected to implement DO control in both treatment trains, resulting in lowering

the SVI conditions in Train 1. These results seem to indicate that DO values ranging from 0.25 to

0.5 mg/L appear to reduce the propensity for low DO bulking due to excessive growth of

filamentous bacteria. However, it is important to mention these results are inconsistent with the

other data presented in Table 1 and Figure 6. One possibility could be that the lower DO

environment in the SND reactor is acting as an anoxic selector improving the settling conditions

of the sludge. Another possibility could be the growth of phosphorus accumulating organisms

(PAOs) at the low DO environment which have been demonstrated to significantly improve

mixed liquor settling rates (Schuler and Jang, 2007). However, this needs to be confirmed

further with additional research and microscopic analysis of the biomass samples since these

results are unique and different than the other SND facilities included in this study.

0

50

100

150

200

250

300

3/16/07 4/16/07 5/16/07 6/16/07 7/16/07 8/16/07 9/16/07

Slu

dg

e V

olu

me

Ind

ex (

mL

/g)

Date

Figure 7. Effect of bulk dissolved oxygen concentration on SND activity at the Winter

Haven WWTP, Florida

CONCLUSIONS

SND is a well�known phenomenon in BNR activated sludge systems and is a point of interest for

designers and operators of wastewater treatment plants as it may have potential advantages over

conventional nitrogen removal systems. SND facilities have been shown to meet very low

effluent total nitrogen levels without additional carbon and alkalinity. Data from SND facilities

indicate that 80 to 96 percent total nitrogen removal can be realized. This paper addressed the

impact of two main factors on the performance of SND plants, organic carbon and dissolved

Train 1 – Operating DO

from 0.6 to 0.95 mg/L

Train 2 – Operating DO from

0.25 to 0.5 mg/L

Train 1 – DO Control

Implemented. Operating

DO from 0.25 to 0.5 mg/L

Train 2 – Operating DO from

0.25 to 0.5 mg/L

Page 10: Simultaneous Nitrification Denitrification to Meet Low

oxygen. Data presented herein suggest that a COD:N ratio of at least 10.0 is required to

maximize denitrification; and an optimum bulk DO concentration ranging from approximately

0.3 mg/L to 0.7 mg/L appears to maximize SND activity in the aerobic reactor. However, this

low DO condition required for SND provides an environment more susceptible to sludge bulking

as observed by the SVI data from the selected SND facilities.

SVI data presented in this study suggest that excessive growth of filamentous bacteria, resulting

in bulking sludge, is the main disadvantage on SND processes. This has created capacity issues

in many SND facilities and as a result, some of them have upgraded to conventional BNR

configuration without sacrificing performance as it is the case for the Mandarin and Smith Creek

WWTPs.

SND activity was evaluated in a continuous�flow aerobic activated sludge pilot plant treating

synthetic wastewater. The pilot plant revealed BNR in excess of that required for biomass

synthesis, including biological phosphorus removal with acetate addition, which has been rarely

documented in single stage aerated reactors.

Even though SND processes have some advantages over conventional BNR facilities, the

application of such processes may be limited by several factors, including:

• Relatively high influent COD:N ratio required for SND.

• SND processes may require larger reactors for nitrification than conventional BNR

processes because of the low DO and its impact on nitrification rates.

• Sludge bulking issues due to the excessive growth of filamentous bacteria. This would

limit it applicability in plants with limited secondary clarification capacity.

• The operator has limited control over important parameters impacting SND in the plant,

such as floc size, internal storage of COD and the DO profile within the flocs.

ACKNOWLEDGEMENTS

The authors thank the owners and operators of the wastewater treatment facilities that provided

the data included during this study. Special thanks are extended to Mr. Brian Smith (City of

Orlando, Florida), Mr. Tim Madanagopal (Orange County, Florida), Mr. Dwayne Phillips (City

of Stuart, Florida), Mr. Terry Carver (City of Winter Haven, Florida) and Mr. DuWayne Potter

(St. Mary’s County, Maryland). Pilot plant data used during this study was collected in

connection with graduate studies by Jose Jimenez and supervised by Dr. Enrique La Motta at the

University of New Orleans, New Orleans, Louisiana.

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