Mn(II) Oxidation by HOCI in the Presence of Iron

Oxides: A Catalyzing Effect

by

William Scott Dewhirst II

Thesis submitted to the Faculty of the

Virginia Polytechnic and State University

in partial fulfillment of the requirements for the degree of

MASTER OF SCIENCE

in

ENVIRONMENTAL ENGINEERING

APPROVED: \ ere) 2. wD

William R. Knocke, Chairman

aul XA rhe 0,

Daniel L. Gallaghef

ohn C. Little

February, 1997

Blacksburg, Virginia

Keywords: Manganese, Iron, Oxides, Adsorption, Oxidation, Catalyzed

Mn(I) OXIDATION BY HOCL IN THE PRESENCE OF IRON OXIDES: A CATALYZING EFFECT

by

William Scott Dewhirst II

Dr. William R. Knocke, Chairman

Department of Environmental Engineering

(ABSTRACT)

The oxidation of soluble manganese (Mn(II)) to insoluble manganese dioxide

(MnO, (;)) is fairly well understood; however, the role of ferric hydroxide/oxides

(Fe(OH)3,;)) in catalyzing the oxidation of Mn(ID by oxidants such as free chlorine

(HOCI) is one specific aspect of manganese removal via oxidation that requires further

investigation. Data collected in this study indicate that the rate of Mn(II) oxidation may

be beneficially catalyzed by the presence of previously formed Fe(OH)s(5) particles. The

mechanistic means by which this enhanced oxidation is accomplished was the focal point

of this research. Specifically, the research objectives were as follows:

(1) To study all possible Mn(ID) removal mechanisms for a typical groundwater

system to determine the necessary experimental conditions required to isolate

the study of Mn(II) oxidation in the presence of ferric hydroxides/oxides

(Fe(OH); (9) (2) To investigate the means by which ferric hydroxides/oxides (Fe(OH); (s)) may

enhance the removal of Mn(II) during water treatment by interacting with

HOCI; and

(3) To develop an engineered system that captures the observed catalyzing effect

iron oxides have on Mn(II) oxidation by HOCI citing key system design

parameters.

To complete these objectives a combination of batch and continuous flow bench-scale

experiments were utilized. Batch study results indicated that the primary Mn(II) removal

mechanism was a combination of adsorption and oxidation, specifically, adsorption of

Mn(II) onto the iron oxide surface where Mn(II) is subsequently oxidized. A continuous

flow system was developed to utilize this removal mechanism under water treatment

plant conditions to improve the efficiency of iron and manganese removal. The results

from experimentation with the continuous flow system indicated the following:

e Sufficient free chlorine residual in effluent insures consistent system

performance,

e Initial iron oxide concentration within reactor system must have adequate

adsorption capacity for initial adsorption-oxidation step to occur,

e Removal efficiency and reactor stability increase with the accumulation of

manganese oxides, and

e Solution pH and reactor hydraulics affect system performance significantly.

The results suggest that this technology has the potential to change the look of

conventional groundwater treatment systems that practice iron and manganese removal.

iii

DEDICATION

This paper is dedicated to my wife, Dawn, without whose support I would not

have been able to complete this work. Her patience and prayers were a source of strength

during the writing of this paper. Also, this work is dedicated to my parents who have

always been a source of encouragement for me and offered continuous support and

motivation.

ACKNOWLEDGMENTS

The list of those to thank for their help in completing this work is immense. First,

thanks go out to Dr. Knocke, my advisor, who always made time to discuss the results

being observed in the laboratory and offered insight into the observations made. His

motivation to complete the task as well as his thought-provoking questions were truly a

stimulus. In addition, he provided a means to share the findings of this paper to the

engineering profession by assisting with the preparation of abstracts for professional

meetings presentations. Special thanks to Drs. Little and Gallagher for providing

guidance and assistance as committee members.

Thanks also to Julie Petruska whom I depended upon a great deal in setting up the

experimental apparatus, preparing chemical solutions, and with the determination of

acceptable experimental methods. She was always available to help with a question and

her knowledge of so many topics was a blessing.

Marilyn Grender, the laboratory technician, provided endless insight into the

operation of the atomic adsorption spectrophotometer and other laboratory equipment

used during data collection. Her assistance in this area improved the quality of results

immensely.

To the Charles E. Via, Jr. Department of Civil Engineering and specifically to

Mrs. Marion Via whose donation to the University provided scholarship and research

moneys to conduct the studies presented here. Having been a Via Scholar during my

undergraduate career, I owe practically my entire schooling to the Via Endowment.

Thanks also to the Edna Bailey Sussman Fund for providing almost $3000 of funding for

this research over a three month period. Without the financial support of these two

entities, the results presented here would not have been possible.

TABLE OF CONTENTS

ADSUraCt 2.0... eececeecceccccccecsesesessecccecssnssseesseccesceseceessssseessccessssaunensseseeceeessauaanesescesess

Dedication .........ccccccsesececccccsssscccessscescssecscescecseeesceceuesecsseueeeeececsuaaescescuauseeessauanerees

Acknowledgment.............ccsscccccccessesesecececeesensneceeceseessnsusecessosseceeeasecesseeeseneecreseeees

Table of Content 0.00.00... ccccsceesessscesceveeccceecevecceccecccccecceseeeceeeceseeseeeaeeescusanaeaoeeoaneea

T. INTRODUCTION... ceceeseceteceecsessesessssssesssserssstsessssseestessseearenseeeees A.

B.

Identification Of Problem ................ccceeeecccsecesseececcesusescesensusecceeeusessceeeeeaness

Research ODJectives..........c:scccccccsssssssscccessesssnseceevsesssnateecesesenseueecerseseneeees

TT. BACKGROUND... cccececesesensnsnenneneeeseeseceseseenssseseeseseeseseeseseseneeeneeseeea

QmMOAw> Occurrence of Iron and Manganese in Natural Waters ........... eee sence

Chemistry of Manganese in Natural Waters oo... eeeeceeeeeeeeeeneeeeeeees

Methods for Manganese Removal from Water Supplies.........00..0. cee

Chemistry of Iron in Natural Waters...............ccccsscccesssneccesesnceeeeesnnceeeeesees

Oxidation of Soluble Iron in Natural Waters ......... ees eeesseeeeereeeetreeeeeeneees

Tl. EXPERIMENTAL METHODS AND MATERIALS ooo cee eeeeesenees

Om MOO

wD Synthetic Water Makeup............:ceeeccsssecesseceseecsecesseeessneesecessnecereeseseesenees

Glassware Preparation...........:.cccscccsscscssscesseeeeneessaeecseeeseneecsseessteeeeeeessneeesaes

Preparation of Reaction Stock Solutions .......... ec ccccsccesseceseseeceseenseeseseeees

PH Adjustment 0.00.0... cee ccesscccesseccsesseesessecessecsssseecsseeceseeeeceneescseaseeeseaees

Experimental Apparatus...........csccecsscccseecesecessecesneceeseesnecenectenesessseseaeeess

Collection of Samples .............cccccccccsssscessccecsseecesseeeseseeecseaeesessneeeseneeeseeeeees

Measurement Techniques for Data Collection... ee eeeseeseeeseeseeeeeees

TV. RESULTS we ec sccceeecneecsneceacessesesecesessacessessseeseessssosecesaceseeesneseseesaeeens

D.

E.

Experimental Setup..........cccccsscsscssccsesssssssssscessessesseceseseecsseeseeessecseesseenees Studies of Possible Mn(II) Removal Mechanisms ................ccccscccseeeseeeee

Mn) Removal via Surface Catalyzed Oxidation of Mn(ID) with

Fe(IID) OxideS 0.0... ccccssecesssecsssseccesceecsseeeeseasecesesesseeeees cesesseeeeesseesesseeeens

Fe(III) Oxide Slurry Reactor System/Mn(I]) Adsorption onto

V. DISCUSSION o.oo. cece ceececssceesessnseeescseeeeseesaeeesessaeeesesssueesesessaeeseesaeeeessenaas

A.

B. Studies of Possible Mn(II) Removal MechanismS.............c..ccccssssssessseeees

Mn(iI) Removal via Surface Catalyzed Oxidation of Mn(II) with

Fe(IID) Oxides «00. cescccssnecesnccssceeessessseesseeseseseesasessescssascesassessseveaascesaseens

vi

C. Fe(III) Oxide Slurry Reactor System/Mn(II) Adsorption onto

RECO Oe DOR SPEEA EASE OH E EEE TEREST OEEEHEEH EHEC EO EOE HE HEEEM ED ET ESE OS EOE ESE HDD OCCT SEHOS

VI. SUMMARY & CONCLUSIONS

A. Summary of Results

B. Conclusions

VIL. REFERENCES 000... ccc ccccccsssecsseeesecessateecsceseenessseecsanecsacessneeceaeeeeaeeceeaesesnesesas

APPENDICES Appendix A: Tabulation of Experimental Results

Appendix B: Operation and Detection Limit Determination for

Atomic Adsorption-Spectrophotometry

Appendix C: Calculations

Appendix D: Model Formulation/Related Calculations

Vil

Table 1:

Table 2:

Figure 1:

Figure 2:

Figure 3:

Figure 4:

Figure 5:

Figure 6:

Figure 7:

Figure 8:

Figure 9:

Figure 10:

Figure 11:

Figure 12:

Figure 13:

Figure 14:

Figure 15:

Figure 16:

Figure 17:

Figure 18:

Figure 19: Figure 20:

Figure 21:

LIST OF TABLES AND FIGURES

Summary of Field Data Collected at Groundwater Treatment

Facility Treating for Iron and Manganese Removal ...............:ceee 3

Mn (II) Oxidation Reactions for Different Oxidants......... eee 12

Schematic of Conventional Groundwater Treatment Facility ........... 4

Typical Iron Breakthrough Pattern for Dual-Media Filter.........0....... 5

Manganese Potential Diagram for Mn-O2-CO2-H20), 25°C, 10° M (from Morgan”) .v.iccccessscsscssessesesssessssesesessssssssessssseeessesen 10 Solubility of Iron in Relation to pH and Eh at 25°C and 1 atm,

Total Dissolved Sulfur 10“ M; Bicarbonate Species 10°M

(from Hem!!), ooo. ccccccecesessssecsesessessssesecsessesessstssestseestssessssesesessesesasens 18

Schematic of Experimental Setup for Isotherm Studies...........00....... 32

Schematic of Experimental Setup for Catalyzed Mn(il)

Oxidation in the Presence of Iron Oxides (Batch System)................ 34

Schematic of Iron Oxide Slurry Reactor System............ cc eeceeeeeeeeeees 38

Preliminary Studies to Determine MnCOQ3,,) Formation

Potential and Mn(II) Removal via CaCO3,,) Adsorption...............0. 46

Preliminary Studies to Determine Role CaCO3,,) Formation has on Mn(II) Removal via AdSorption.............:ccccesssceeeeeeseceeetesneeees 47

Preliminary Studies to Determine MnCO3,,) Formation

Potential and Mn(II) Removal via CaCO3,,) Adsorption..............006 49

Solution Phase Oxidation via HOCLI..........ccccccessscesssseceeseeseseeeeesees 50

Cartesian Plot of Adsorption of Mn(ID) onto Fe(II) oxides.............. 52

Langmuir Isotherm Plot of Adsorption of Mn(II) onto Fe(III)

OXICGES.......cccecesscccesssnccecesseceesssensececestnsceeeneceeceseaseccessaneessceseacesetensaaeens 53

Cartesian Plot of Adsorption of Mn(II) onto Fe(IID) oxides

(purified 1rOn StOCK)..........cccsssssccsessseccesssscccesesesecesenseesessneeeeeesenseeesens 55

Surface Catalyzed Oxidation of Mn(II) onto Fe(III) Oxides;

Examination of Order of Addition of Metal Species....................00 56

Effects of Various Fe(II]) Oxide Levels on Mn(II) Oxidation

Kinetics; Batch System pH 7..........cccccesccesssccesceesseecescecsssecssesessesesses 58

Effects of Various Fe(III) Oxide Levels on Mn(II) Oxidation

Kinetics; Batch System pH 8.0.0... ccsccssccsesecsscecsseeeessecssssesseeeseaeeeenes 59

Actual versus Predicted HOC] Demand: Enhanced Mni(II)

Oxidation in the Presence of Fe(IID) Studies .0.........cccesccceessesceveees 61

Reaction Order and Rate Constant Determination ................ccccceeees 62

Mn(II) Oxidation Rate Constants as a Function of Fe(III)

CONCENrATION 0... eceeesscesssssccecsseseecesessneecsesnecesessesesessatesesesaeeceesas 63

Bench-Scale Continuous Flow System with Varying Fe(III)

Oxide Slurry Concentration; No Additional HOC] Dose............0.... 65

Viil

Figure 22:

Figure 23:

Figure 24:

Figure 25:

Figure 26:

Figure 27:

Figure 28:

Figure 29:

Figure 30:

Figure 31:

Figure 32:

Figure 33:

Figure 34:

Bench-Scale Continuous Flow System with Varying Fe(III)

Oxide Slurry Concentration; Effect of HOCI Dose... eee

Iron and Manganese Oxide Concentrations in Bench-Scale

Continuous Flow System.............cccsccccsesssecesecsnseesessaceceesesateeseeseeeeetens

Adsorption of Soluble Manganese (Mn(II)) onto Freshly

Precipitated Manganese Oxides (MnO x(5)) .....eeeeeceseseeceeeeseeeeseneeeeeeens

Langmuir Isotherm for Adsorption of Mn(II) onto Freshly

Precipitated Manganese Oxides (MnO) Bench-Scale Continuous Flow System; pH 7..............cceseseceesesneeeeees

Bench-Scale Continuous Flow System; pH 8............csseeessceeseneeeeees

Summary of Rate Constant Values for Batch System Model at

pH 8

Model Predicted and Observed Results for Batch Reactor

System at pH 8

Model Predicted and Observed Results for Slurry Reactor

System at PH 8.0.0.0... eeesscsesessesssseeesceesssceeeseecesetecececececeeeeessseeseeeeas

Comparison between Davies” Results to Observed Results..............

Extended Isotherm Studies to Determine Optimum

Equilibrium Time for Adsorption Isotherm Determination Experimentally Determined Rate Constants for Mn(II)

Removal During Batch Studies Normalized with Respect to

Coe e ranean aawesecnecenneseonenecnateenees

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POOH EDO HEHE ROTHER AEF EDD EHO SHEE SED EHEO MATTER EEEH EEE EH OTE De

CHAPTER I

INTRODUCTION

A. Identification of Problem

The occurrence of iron and manganese in surface and groundwater supplies poses

many challenges for the water treatment engineer and plant operator. These metals are

commonly found in small to moderate concentrations in most groundwater supplies and

may be prevalent in some surface water supplies, most notably reservoir impoundments

during “turnover.” The problems associated with these metals, although only aesthetic in

nature, can be rather severe and may deter the public from consuming otherwise safe

water. As consumers become more and more alarmed of the possible risks associated

with their water supplies, the aesthetic properties of the water will inevitably play a

significant role in their perception of an acceptable drinking water.

Various treatment techniques have been developed for removing these ions from

solution. These methods range from aeration to chemical oxidation to greensand

adsorption and most recently oxide-coated filter media. It is safe to say that the oxidation

of each metal by conventional oxidants has been thoroughly studied and is fairly well

understood. In most studies conducted to date, however, the two metals are studied

independently to determine the oxidation rate or other desired parameter for each metal

species. Thus, little research has been conducted that examines the interaction between

the two metals during oxidation despite the fact that they are normally found together in

natural waters.

The results of a field study at a groundwater treatment facility related to iron and

manganese removal suggested that some interaction between the two metals may occur

during conventional treatment. The field data collected indicated, as expected, that iron

was effectively oxidized by aeration alone whereas manganese appeared to be unaffected.

However, significant manganese removal was noted upon chlorination of the

groundwater. This contradicts literature reported observations that manganese oxidation

via chlorine (HOC)) is relatively unsuccessful in the pH 7-8 range.' However, one

significant difference between the observed conditions and those reported in the literature

is the presence of oxidized iron particles in solution. A summary of the field data is

provided in Table 1.

The oxidation of soluble manganese (Mn(II)) to insoluble manganese dioxide

(MnO,,s)) is fairly well understood; however, the role of ferric hydroxide/oxides

(Fe(OH); (5) in catalyzing the oxidation of Mn(II) by oxidants such as free chlorine

(HOCI) is one specific aspect of manganese removal that requires further investigation.

Previous researchers have noted catalyzed oxidation of Mn(IIJ) via molecular oxygen in

the presence of metal oxide surfaces including iron in natural water systems,” but the

possible advantages this phenomenon may offer under water treatment conditions have

yet to be fully investigated.

This treatment technology was pursued because of the problems associated with

conventional groundwater treatment facilities; a schematic of such a facility is shown in

Figure 1. One inherent problem associated with these groundwater treatment plants is the

use of strong oxidants, most commonly potassium permanganate (KMnO,). Although

this chemical is very effective at oxidizing any soluble manganese, several treatment

problems are associated with this method of treatment:

e the production of colloidal sized MnO, (;) particles which often pass through

the filtration process*>

e the sensitivity of the raw water to the dose of such a strong oxidant, resulting

in over or under-treatment as the raw water quality varies

e the cost of using stronger oxidants (e.g. KMnOxg, ClO2, 03) when compared to

the cost of weaker oxidants (eg. HOCI)

In addition, other problems have been noted with conventional systems employing

weaker oxidants such as chlorine. Figure 2 shows a typical breakthrough curve for a

dual-media filter used at such a facility to remove oxidized iron from solution. Initially,

the effluent quality of the filter increases during the “ripening” period, however, the iron

Table 1: Summary of Field Data Collected at Groundwater Treatment Facility

Treating for lLron and Manganese Removal

Speciation (mg/L)**

Oxidant Metal Total <8 um Soluble

Aeration Fe 1.3 1.1 <0.1

Mn 0.45 0.45 0.43

Aeration Fe 1.7 1.0 < 0.1

& HOC] Mn 0.42 0.38 0.25

**Data collected during full-scale pilot studies between pH 7.3-7.5. Treatment train:

aeration, chlorine addition (if applicable), two hour detention time (no mixing), and

filtration. Samples were collected, filtered, and tested following two hour detention time.

Total represents influent concentration (acid digested solids), < 8 um simulates the

effluent from a dual-media filter, and soluble represents particles passing a 0.2 um filter.

Wash

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level of 0.30 mg/L within 10 hours of startup.

The goal of this study is to propose the use of a newly engineered system

emphasizing chlorine for soluble Mn(II) removal. The system is geared toward

improving and economizing the treatment processes at conventional groundwater

treatment facilities for the removal of iron and manganese. It should be noted that the

proposed process should be considered in waters with low organic content because HOC]

will be used as the primary oxidant. It is well known that the interactions between

chlorine and organic compounds result in the formation of trihalomethanes and other by-

products regulated by the Safe Drinking Water Act.® In addition, previous research has

indicated that iron complexed by organic material is not effectively oxidized by HOCI.”®

B. Research Objectives

From the aforementioned observations several research objectives were

established:

(1) To study all possible Mn(II) removal mechanisms for a typical groundwater

system to determine the necessary experimental conditions required to isolate

the study of Mn(II) oxidation in the presence of ferric hydroxides/oxides

(Fe(OH) (sy);

(2) To investigate the means by which ferric hydroxides/oxides (Fe(OH); (s)) may

enhance the removal of Mn(IJ) during water treatment by interacting with

HOC]; and

(3) To develop an engineered system that captures the observed catalyzing effect

iron oxides have on Mn(II) oxidation by HOCI citing key system design

parameters.

In order to accomplish these objectives, several different types of experimental

systems were arranged as described in Chapter III. First, however, a thorough review of

previous research studying the chemistry of iron and manganese as well as treatment

techniques available for their removal (presented in Chapter IT) was conducted. Finally,

the results and discussion of the results obtained during these experiments will be

discussed in Chapters IV and V, respectively, followed by the listing of formulated

conclusions in Chapter VI.

CHAPTER II

BACKGROUND

A. Occurrence of Iron and Manganese in Natural Waters

The fact that iron and manganese are commonly found in most groundwaters and

a portion of surface water supplies is easily explained by their abundance in the earth’s

crust. Iron was reported by Sung and Morgan” as being the fourth most abundant element

by weight; Bowers and Huang!” cite iron as being “ the single most abundant

micronutrient in soil systems, occurring naturally as oxides.” Manganese is also widely

found in nature in various oxide and mineral forms in association with silicates,

carbonates, and sulfides.'’ Manganese represents approximately 0.1% of the earth’s crust,

making it the tenth most abundant element. Iron is more abundantly found than

manganese in water supplies because of the 50:1 geochemical ratio of iron to manganese

in the earth’s lithosphere.’

The presence of iron and manganese in natural waters is a result of the dissolution

of the minerals and oxides containing these metals. Often, the dissolution reactions take

place under anaerobic conditions, yielding the reduced metal species manganous (Mn(II))

and ferrous (Fe(II)) oxidation states. Such manganese release has even been noted in

water treatment plant sedimentation basins if insufficient oxidant is present.'? Stone and

Morgan’*!® have shown the reduction of Mn(III) and Mn(IV) oxides by organic materials

to the Mn(ID form. Significant release of iron and manganese is commonly observed in

the oxygen-deficient hypolimnetic waters of reservoirs as bacteria reduce the oxide as an

alternative energy source (electron acceptor). During reservoir overturn, the waters are

completely mixed, explaining the seasonal occurrence of these metals in reservoir

supplies. However, because of the continuous presence of iron and manganese minerals

in groundwater aquifers, the presence of these metals in groundwater supplies is much

. I more consistent. 7

B. Chemistry of Manganese in Natural Waters

In the absence of dissolved oxygen, chlorine or other oxidants, Mn(II) is the stable

form of manganese in most natural waters.'* However, as with most metals, manganese

has the capability of forming numerous compounds which can affect its solubility

significantly. Among the various chemical species that may form are pyrolusite (MnOx,,)),

manganite (6-MnO(OH),)), rhodonite (MnSiO3,.)), hausmannite, Mn304(5), pyrochroite

(Mn(OH),)), rhodochrosite (MnCO x), and alabandite (MnS,,)). In most cases, however,

manganese solubility is limited by the hydroxide (OH), carbonate (CO3”), or sulfide (S?)

composition of the water.'* It is important to note that despite being the most well known

oxidized form of Mn(II), MnOz,) is not the only higher oxidized form of Mn(It).'® The

main chemical equilibria controlling Mn(lII) solubility are summarized as follows, and a

stability plot is provided in Figure 3 (all solubility products (K,,.) and energies of

formation (AF°) are reported at 25°C by Morgan’):

(1) = MnCO3,) <> Mn(II) + CO3” Kyo = 4.68 x 107'' = AF° =-194.8 kcal

(2) MnS,) <> Mn(il) +S” Ky = 7x 10°'° AF® = -53.0 kcal

(3) Mn(OH)s «) <= Mn(Il) + 20H” Kyo = 9.1 x 10” AF° = -147.3 kcal

Any of these reactions can control solubility in the absence of oxidants, as it is not

unusual to find carbonate, hydroxide, and sulfide species in the hypolimnion of lakes or

in groundwaters. Other possible, but less common, complexes include those with cyanide

(CN’), phosphate (PO,”), and silicas.'? The complexation observed between manganese

and silica or phosphate compounds is often used to control manganese in water supplies

through a process known as sequesterization. '”7°

In waters containing organics, researchers observed that little or no complexation

occurs between the organics and Mn(II) even at high dissolved organic carbon (DOC)

levels.*' Data collected by Knocke et al.' showed that complexation of Mn(II) by DOC

increased with pH, however, the vast majority of Mn(II) remains uncomplexed by organic

Figure 3:

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10

matter regardless of solution pH.

C. Methods for Manganese Removal from Water Supplies

1. Chemical Oxidation

The notorious reputation of manganese and its detrimental effect on water quality

dates back to the late 19th century when Brown reported a case of black slime in an

English distribution system attributed to manganese oxides.” Since that time a great deal

of study has been devoted to alternative methods of manganese oxidation and removal

before it enters the distribution system. As time has passed, the recommended means of

controlling this metal have shifted from biological treatment to chemical oxidation to the

use of catalysts to surface adsorption/oxidation techniques.'**?* Each of these

treatment methods have individual limitations and drawbacks making it difficult to

prescribe one method to be effective on all water supplies. To better understand the

various means of removal, a keen understanding of the oxidation chemistry of manganese

must first be developed.

As previously discussed, the chemistry of manganese for higher oxidation states

of the metal beyond the soluble Mn(II) form is very complex in that many oxidized forms

can result. Table 2 summarizes chemical reduction-oxidation reactions which describe the

oxidation of Mn(II) in the presence of various chemical oxidants. '

Although dissolved organics do not complex significantly with Mn(II), they do

create an oxidant demand that must be accounted for when determining proper oxidant

dosing. Generally, weaker oxidants such as oxygen and chlorine are ineffective for

oxidation except at elevated pH levels or at excessive oxidant doses. However, stronger

oxidants such as chlorine dioxide, potassium permanganate, and ozone, have the ability to

satisfy competitive organic demands and oxidize Mn(II).”°> The oxidation of Mn) under

low DOC levels is discussed individually by oxidant.

11

Table 2: Mn(IJ) Oxidation Reactions for Different Oxidants

Oxidant Reaction Stoichiometry

Or(aq) Mn** + 0.5 Oo(aq) + HxO > MnO.) + 2H" 0.29 mg O>/ mg Mn

O3¢aq) > Oraq) | Mn?" + Os(aq) + HO > MnOx,s) + Oxaq) + 2H” 0.88 mg O3;/mg Mn

HOCI Mn” + HOCI + H,O > MnO,,) + Cl + 3H" 1.30 mg HOCI/ mg Mn

KMnO, Mn” + 2KMnO, + H,O > 5MnO,,) + 4H” 1.92 mg KMnO,/mg Mn

ClO, — | Mn** + 2CIO) + HO > MnOx,) + 2ClOx (ag) + 4H* | 2.45 mg C1O2/mg Mn

clo,

12

a. Mn(iI) Oxidation via O>2 (aq). In early studies of manganese oxidation in the

presence of molecular oxygen, Hem”° found that an increase in solution pH increased the

rate of Mn(II) oxidation and precipitation by aeration; further, the rate is significantly

reduced when HCO; and SO,” are present. Morgan’ used elevated initial Mn(II)

concentrations of 11 mg/L to investigate these findings further. The formation of

MnCO x) and the ion-pair of MnHCO3" were cited as reasons to explain the slowing of

oxidation kinetics in the presence of carbonate species; however, the presence of sulfate

did not affect the oxidation kinetics significantly. The reaction rate was found to be

directly proportional to temperature; as the temperature was halved the reaction rate was

approximately halved. Morgan also found the oxidation of manganese by Ox aq) 1S

autocatalytic in nature. However, Hem?’ reported that the catalytic effect is slowed to a

pseudo-first order reaction as the amount of precipitate surface becomes large in

comparison to soluble, unreacted manganese. The presence of surface catalysts or

manganese bacteria have been suggested to be required for Mn(II) oxidation in some

natural waters.”®

Using x-ray diffraction, the oxidation products of manganese and oxygen were

determined to be a mix of Mn(III) and Mn(IV) species.”’ The product of O2(aq) Oxidation

according to Morgan’ resembled Mn304;) rather that MnO). The overall products are

generally colloidal and variable in composition from MnO, 2 - MnO; s. Kessick and

Morgan” concluded that MnOOH,, is the primary product of autoxidation in aqueous

solution. In other studies, temperature was found to have a significant effect on the form

of precipitate; specifically as temperature was decreased the predominant precipitate was

B-MnOOH,,) especially at temperatures less than 10°C. Eventually, however, the final

form of the oxide will be MnO, (se

b. Mn(ID) Oxidation via O3qq.. Ozone is primarily tested as an oxidant for

treatment of waters with significant organic content, a condition which may limit the use

of other conventional oxidants. Despite the strength of ozone as an oxidizing agent,

13

Weng et al.’ found that regardless of the ozone dose, soluble manganese often remained

in the finished water following filtration at levels exceeding the SMCL of 0.05 mg/L.

The ozone dose utilized was sufficient to provide an ozone residual yet Mn(II) oxidation

remained incomplete. Wilczak et al.*° discovered that ozonating waters containing

Mn(II) resulted in the formation of mostly colloidal MnO2,). Their results also confirmed

those of Weng et al.’ in that regardless of the O3 dose, high levels of soluble Mn(II)

remained in the filtered water. For effective soluble Mn(II) removal, the authors of these

articles relied on further treatment involving oxide coated filter media and permanganate

addition, respectively. These methods will be discussed later.

c. Mn(iD) Oxidation via HOCI. Chlorine is commonly used as an attempt to

oxidize Mn(II) in water supplies. Such oxidation requires long periods of detention time

depending on the pH and chlorine concentration.*! Wong’ suggested that the pH be

maintained at pH 8.5 and that calcium be added to destabilize the net negative charge of

MnOx;) for improving filtration performance. Two other researchers reported the need

for calcium to destabilize the colloidal MnO; particle to improve filtration.°*"? Wong?

recommended a chlorination-filtration system over aeration-filtration and potassium

permanganate-manganese greensand filtration for both economic and operational reasons.

Mathews” noted that when chlorination is used, filter media need not be coated with

manganese oxides for acceptable effluent quality.

Hao et al.”* studied the kinetics of Mn(II) oxidation by chlorine to develop a

kinetic model and to study the effect various organic ligands (chelating agents) have on

the Mn(II) oxidation rate. These studies utilized a very large initial Mn(II) concentration

(5.5 mg/L) atypical of natural water systems. These studies concluded that the most

important parameter governing the rate of oxidation was the stoichiometric ratio of

chlorine to manganese. The kinetics increased as this ratio was increased as well as for

increases in solution pH.

The importance of adsorption in the autocatalytic oxidation of Mn(II) has been

well documented.!7?7?

d. Mn(iI) Oxidation via Potassium Permanganate (KMnO,. The use of

potassium permanganate as an oxidant for Mn(ID) has long been practiced.>”? The use of

KMn0O, is often favored over weaker oxidants because the rate of oxidation is much more

rapid,’ occurring almost instantaneously provided that sufficient oxidant for interaction

with Mn(II) is present.’ One problem cited with the use of KMnOz is the formation of

colloidal sized MnOx,s) particles which pose filtration concerns.** Van Benschoten et

al.“ developed a relatively accurate kinetic model for Mn(II) oxidation via KMnOy.

e. Mn(II) Oxidation via ClO, The use of chlorine dioxide as an oxidant for

Mn(I) has not been studied extensively as this oxidant is not as popular as those

previously discussed. Knocke et al.,' assuming only a one electron transfer product to

ClO,,, showed similar oxidation rates to those of KMnO, with some variation occurring

with the presence of organics. Also, the growing concern over residual chlorite

concentration (limit of 1 mg/L) in the upcoming D-DBP Rule may further limit the use

of ClO) as a primary oxidant for Mn(II) removal.*°

2. Other Treatment Techniques

a. Ion Exchange. The use of ion exchange systems for Mn(II) removal is

somewhat rare as treatment difficulties can easily arise if oxidation occurs in the resin bed

(particularly if reduced iron becomes oxygenated). As with other ion exchange

operations, the Mn(II) ions in solution are exchanged for sodium or hydrogen ions on the

resin.”’ If operated correctly, such a system can be very effective, yet brine disposal is an

issue.?°

15

b. Manganese Greensand Adsorption-Regeneration. This “filtration” process

employs filter media naturally or synthetically coated with manganese oxides. The

effective size of the media is generally quite small forcing pressure filtration in many

instances. Once the adsorptive capacity of the greensand has been expended, the bed is

regenerated with an oxidant, normally potassium permanganate.”” An alternative is to

provide continuous regeneration with permanganate.°’ One potential drawback of these

systems is the need for pump(s) to provide the pressure necessary to force the raw water

through the filters; this is not a concern if well head pressures are sufficient.

c. Oxide-Coated Filter Media. Several researchers dating back to the early 20th

century have noted a “natural greensand effect” occurring in filters treating manganese

4.22, 31, 34.38.39 The beneficial effect the manganese oxides have on water laden waters.

treatment are well noted; however, significant research on the mechanistic means of the

process was not conducted until recently by Knocke et al.**°? In removal studies using

ozone, regardless of the ozone dose, effective manganese removal was not seen until the

use of an oxide-coated filter media was used.* Knocke et al.*® noted that the removal of

Mn(II) by filtration through oxide coated media is at first an adsorption process.

Generally, the uptake is very rapid, as expected based on the data presented by Morgan

and Stumm”? for Mn(II) adsorption onto previously formed MnO, ;;. However, in the

absence of an oxidant, the removal efficiency approached zero as the available number of

adsorption sites was exhausted. Once oxidant was applied, the surface catalyzed the

oxidation of the adsorbed Mn(II), resulting in the regeneration and actual growth of the

manganese oxide surface around the filter media.*®

The application of free chlorine under neutral pH conditions was found to be

effective at oxidizing surface sorbed Mn(II). This mode of operation provided for

continuous regeneration of the oxide coating on the filter media; thus, backwashing with

a permanganate solution need not be necessary.””

16

D. Chemistry of Iron in Natural Waters

The oxidation state of iron that will be found in water is related to several

different variables. Primarily, the reduction-oxidation potential of the water as well as the

organic content are key factors, but alkalinity and other parameters may affect tron

speciation.® 41. 42,43.44,45 a mong the most common precipitates that can be formed by

interactions between iron and other species are Fe(OH)s(5) (hydrated ferric oxides),

FeCO3x,) (siderite), Fe(OH)a5), and FeS2s) (pyrite).”' The chemical equilibria for these

reactions are summarized as follows with a stability plot provided in Figure 4fl®

(4) Fe(OH) (s) <> Fe(II) + 3H20

(5) FeCO3 (5) <> Fe(II) + CO3”

(6) Fe(OH)2 (5) <> Fe(II) + 20H”

(7) FeS (s) > Fe(II) + 28 i +2e

In waters containing high levels of alkalinity, the carbonate concentration often controls

iron solubility as described by equation (5).*° Reduced Fe(II) can be removed from

solution due to hydroxide or sulfide concentrations.*' These compounds are likely to

dominate under low oxygen conditions along with other possible complexes formed with

cyanides, silicates, phosphates, and numerous other inorganic materials.“° However if

adequate oxygen is present in waters of neutral to alkaline pH these reactions will

compete with the oxidation of iron to iron hydroxide (equation (4)) if low levels of

. 47 organic material are present.

E. Oxidation of Soluble Iron in Natural Waters

Similar treatment techniques for Mn(II) oxidation/removal are available for

soluble iron removal (ion exchange, greensand adsorption, biological processes, chemical

oxidation using O03, KMnQO,, ClOz, etc.). These methods of treatment are discussed in

detail by others,® '% 7% 337-4849 but will not be covered in this paper as the use of such

17

vv | T t TT J T Ty Tt

; [Fe]—mole/}

Eh- volts

nS Ser os

LED “is C one LT ad No gO ty a pe pA Solel LE

he RNS

-O4

-~O6 “ © HFeO,

-0.8 4 0 2] 4 6 8 lO l2 I4

Figure 4: Solubility of Iron in Relation to pH and Eh at 25°C and 1 atm, Total Dissolved Sulfur 107 M; Bicarbonate Species 107M (from Hem*').

18

techniques was not the focus of this work. The limits of this discussion on iron oxidation

will include only oxidation via dissolved oxygen or free chlorine. These oxidants are

commonly used for iron removal and have been found to be very effective in low organic

waters.

Numerous researchers have noted the complexation effect that organic materials

have on soluble iron in water supplies.* 41, 42,43, 44, 45.47.59 This phenomenon significantly

reduces the ability of precipitates or oxidation products to form as the iron is relatively

unreactive.’ The effect organic interaction has on Fe(II) oxidation will be discussed in

the upcoming section.

1. Oxidation via Dissolved Oxygen. Ghosh et al.*” presented a study of Illinois

waters to investigate the factors governing the oxidation rate of iron in natural waters via

aeration. Their study indicated that in high alkalinity groundwaters, the majority of the

iron precipitated following aeration was in the form of ferrous carbonate, not the oxidized

form of ferric hydroxide. Several researchers refuted the results of the Ghosh et al.*’

study, citing discrepancies with the saturation levels with respect to iron and carbonate

reported as well as the fact that the alkalinity concentrations used in synthetic water

samples were not of the same magnitude as those found naturally.“* *°*' In response to

these studies, Morgan and Birkner”’ presented results from their studies indicating that

Fe(II) oxidation via oxygen follows a first-order rate and that FeCO3 species are less

rapidly oxidized than free Fe(II) ions.

Sung and Morgan’ demonstrated that lepidocrocite (‘y-FeOQOH),) was the primary

product of iron oxidation under average pH conditions. In addition, the authors noted that

the reaction is autocatalytic in the presence of previously formed iron oxides at pH values

greater than 7. The observed Fe(II) oxidation rate was slowed in the presence of

complexing ions such as SO,” and CI’, confirming the work of previous researchers.

The effects organics have on the oxygenation and oxidation of iron(II) has been

well documented.® 4! :47.5! This property constitutes a major difference in

19

comparison to soluble Mn(II) which is only slightly complexed by organics under normal

pH conditions.! Shapiro” presented a study aimed at understanding the interactions

between soluble iron and organic matter in waters. His study resulted in several key

conclusions:

1. the amount of iron bound by the organic matter increased with pH;

2. the metal was unaffected by exposure to air;

3. although visible by color, the metal complex could not be filtered from

solution; and,

4. iron was not held solely by the mechanism known as chelation.

Researchers have hypothesized that iron may indeed be oxidized, but that it serves as the

oxidant for organic material. Theis and Singer’” and Jobin and Ghosh*? suggested the

following cyclical arrangement to explain this hypothesis:

0, organics Fe(II) + organics ——> Fe(III) + complexed organics —————> Fe(II) + oxidized organics (8)

Generally speaking, oxygenation of waters containing reduced Fe(II) complexed with

organics is relatively ineffective at oxidizing the complexed iron in solution.

2. Oxidation with free chlorine. Mathews” performed studies to determine the

effectiveness of chlorination for the oxidation of soluble iron in solution. As expected,

these studies exhibited that iron oxidation with chlorination was very effective; however,

if organics are present oxidation is limited. Knocke et al.' reported that Fe(II) oxidation

by free chlorine was rapid (less than 10 seconds in most cases) in the pH range of 5.0 to

7.0 studied.

Knocke et al.° presented data for Fe(II) oxidation in the presence of organics

which indicated that the organic material provided enough of an oxidant demand to

reduce the amount of Fe(II) oxidation occurring. Only when a significant excess of

chlorine was added was this oxidant effective. It should be noted that this study reported

that the oxidized iron product was colloidal in size. Additional research studies indicated

20

that Fe(II) forms strong complexes with high molecular weight organics and weaker

complexes with lower molecular weight organics.’

F. Importance of Iron and Manganese Oxides

The previous sections discussed the formation of oxidized forms of iron and

manganese. The importance that these oxide surfaces exhibit in the natural environment

and under water treatment plant conditions has been the focus of many research

efforts.'°°*°8 The research to be presented by this paper focused on the importance of

the iron oxide surface in catalyzing oxidation of manganese via free chlorine. Thus, an

understanding of the properties and effect the iron oxide surface has in natural water

systems is of extreme importance in presenting this work. In addition, the adsorptive and

catalyzing properties the manganese surface exhibits must also be considered.

1. Iron Oxides. Bowers and Huang'® studied the adsorption of soluble metals onto

various forms of iron oxides, reporting that iron is capable of forming complexes with

numerous different materials. Other researchers” presented a study detailing the

adsorption of Cu(II) onto geothite (a-FeOQOH),) and reported such interactions to occur

very rapidly. The same study determined that divalent cations form a monodentate

innersphere surface complexes (such complexes are believed to be stronger than ionic

interactions) with geothite. This property can be assumed to exist between Mni(II), a

divalent cation, and geothite.*

Several scientists have studied the effect that the iron oxide surface has on Mn(II)

oxidation, which is of great importance to the work to be presented.”” °’ Wilson*”

investigated the effect that various surfaces play on the rate of Mn(II) oxidation; one

surface of particular interest was geothite. The results indicated that the geothite surface

played a role in catalyzing the oxidation of Mn(II) by oxygen. Wilson hypothesized that

the removal observed was most likely due to Mn(II) adsorption followed by oxidation on

the iron oxide surface. He likened the catalytic effect noted to that observed in Mn(II)

21

oxidation when MnO,xs) is present. However, Wilson stated that “it is doubtful whether

particulate matter would influence the oxidation process under natural loading

conditions,” perhaps suggesting the limited usefulness of his findings during water

treatment.”

Wilson’s study focused on geothite, an aged form of the freshly precipitated iron

oxide, lepidocrocite, resulting from oxygenation of Fe(II).°> Sung and Morgan”®

presented a similar study that focused on this “young” iron oxide form. These researchers

reported that manganese has a strong affinity for the lepidocrocite (y-FeOOH) surface,

particularly at pH levels above 6.9 which is the zero point of charge (ZPC) for the oxide.

Adsorption isotherms for Mn(II) onto the iron surface and data suggesting a catalyzed rate

of oxidation in the presence of the iron surface were presented. Of particular interest was

the kinetic model presented that found the surface rate constants for Mn(II) oxidation on

the iron surface and the MnOy,,) surface to be the same order of magnitude.”° It appears,

however, that the authors made a faulty assumption in stating that the iron surface is not

altered significantly with the surface oxidized species. One would expect that as Mn(II)

is adsorbed and oxidized a MnO,,) coating would develop with a high affinity for Mn(II)

and catalytic effect in its oxidation. This may explain why the “iron” surface appeared to

exhibit a similar surface rate constant to that of the MnO») surface.

Davies and Morgan’ studied the rate of Mn(II) oxidation on several different

metal oxide surfaces with Mn(II) affinity ranking in the following order: lepidocrocite >

geothite > silica > alumina. In this work it was assumed that a “bidentate complex” was

the chemical interaction between Mn(II) and the iron oxides. In this type model, the

Mn(I]) ion is shared by two oxide surface sites. Again, results indicating the accelerated

rate of Mn(ID) oxidation in the presence of iron oxides were presented as well as two

hypotheses as to why such a catalyzation effect is seen:

e A lower activation energy is required for electron transfer from Mn(II) to O2;

and

22

e Mn(II oxidized by Fe(III) resulting in an oxidized Mn(IID) and a reduced

Fe(II); the Fe(II) is then rapidly oxidized back to Fe(III) by available oxygen

Note, however, that these authors propose a bidentate complex whereas Grossel et al »

had proposed a monodentate complex between Cu(II), another divalent cation, and

geothite.

Another key point relating to surface chemistry was highlighted by Davies and

Morgan?’ who stated that it is difficult to ascertain whether the surface (iron) or the

modified surface (containing some MnOvy;)) is responsible for the catalyzing effect unless

the surface is in excess. This statement summarizes the difficulty in understanding the

mechanism under study. Finally, the authors reminded future researchers that it is

important to consider competition for surface sites brought about by ionic strength,

[MncI])], [CI], and specific surface areas of the oxides. A kinetic model of their findings

was presented as well.

Research conducted at a full scale water treatment plant in England employing

sludge blanket clarifiers indicated a similar phenomenon occurs under water treatment

conditions.” In this system, Mn(II) adsorption onto the iron oxide surface present in the

sludge blanket was observed to occur according to the Langmuir isotherm. The

adsorption was noted to be enhanced and less sensitive to differences in pH as the

concentration of the sorbent material (iron oxides) increased. The researchers observed

that the sludge blanket assumed a darker color with time, implying MnO,;.) formation by

oxidation with dissolved oxygen. They also noted that the sorbed Mn(ID) (resulting in

MnO,;,) formation) resulted in a surface that provided a greater sorptive capacity than the

original “iron-only” surface. The study recommended that the system be analyzed using

chlorine as the oxidant to provide more rapid oxidation of the Mn(II).

In other research conducted on these oxides under water treatment plant

conditions, Stenkamp and Benjamin® observed the superiority of iron oxide coated sand

media for filtration operations.

23

2. Manganese Oxides. Similar research has been conducted on the effect that

11, 40, 60, 61

manganese oxides may have on the scavenging of materials from natural waters.

It is important to consider the adsorptive properties of these oxides as they can result as a

product of Mn(ID adsorption onto iron oxides provided there is sufficient oxidant present.

As discussed previously, oftentimes the product of Mn(II) oxidation is a small,

colloidal sized MnO,;;) particle that is difficult to remove from the water column. Posselt

et al.,°° discussed the often difficult coagulation of such particles and the need for

stabilization by calcium or other divalent ions. However, of more importance for this

work is the adsorptive and catalytic properties of manganese oxides studied by several

researchers. | “°°! Probably the most well known work relating to properties of

manganese oxides was presented by Morgan and Stumm.” They noted that the oxide

surface served as an adsorption site for Mn(II) and served to catalyze the oxidation

reaction. The zero point of charge of the colloidal manganese oxides studied during their

work was 2.8 + 0.3 pH units. It was noted that the adsorption of additional amounts of

Mn(II) increased with increasing pH as the surface becomes more negatively charged.

They used a Langmuir isotherm to describe the adsorption of Mn(II) onto the MnOx)

surface. One key point made concerning the surface properties of the oxides was that

flocculation tends to slow Mn(ID adsorption as diffusion, a slower step, occurs within the

solid phase. Finally, at pH 7.5, the oxide had the capacity for 0.5 mol Mn(II) per mole of

MnO) with very rapid adsorption rates.“ Xyla etal.” reported that y-MnOOH,)

(manganite) had 1/ 7" the surface area of MnO ,).

The adsorption of two divalent cations (cadmium and zinc) onto manganese

oxides has also been studied.*’ However, researchers have reported that sorption of

Mn(II) onto manganese oxides exceeds that of these metals.''*“° Posselt et al.'! further

studied the adsorptive properties of manganese oxides and developed the following

conclusions:

e Adsorption decreased with increasing ionic strength as competitive adsorption

increased;

24

e Mn(ID adsorption onto the oxide is greater than for any other ion studied; and

e Neutral or negatively charged particles not readily adsorbed!!

These and other characteristics of the manganese oxide surface will be important in the

understanding of the work to be presented.

G. Summary

Iron and manganese are commonly found in drinking water supplies due to natural

processes. The chemistry of these metals is quite complex and can be controlled by any

number of ions, the presence of organics, or reduction-oxidation conditions. This

complexity can make it difficult to accurately predict the behavior of these metals

amongst various oxidants.

Generally speaking Fe(II) can be easily oxidized by weaker oxidants (O2 and

HOCI) provided the Fe(II) has not formed complexes with organics, significant oxidant is

present, and the pH is in the neutral to basic range. However, the same cannot be said for

Mni(II) where oxidation normally requires the use of stronger oxidants (KMnO,, ClOd,

O3) to complete oxidation in a reasonable time frame. Alternative technologies such as

oxide coated filter media have been developed; these technologies develop and utilize a

MnOxs) surface to catalyze Mn(II) oxidation. Having an oxidized surface present allows

the use of weaker oxidants such as HOC] to oxidize the Mn(II) adsorbed on the MnOx;s)

surface.

The ferric hydroxide/oxide surface has also been proven to have a catalyzing

effect on Mn(II) adsorption and/or oxidation using similar oxidants. It is this interaction

between the soluble Mn(II) and the oxidized Fe(III) surface that will be further

investigated by this research. In addition, the ability of the oxidized Mn(IV) surface to

overtake the Fe(III) surface in catalyzing Mn(II) adsorption and subsequent oxidation will

be examined.

25

CHAPTER III

EXPERIMENTAL METHODS AND MATERIALS

The purpose of this chapter is to provide a complete description of the

experimental setup and the laboratory methods used to collect the data to be presented. In

cases where the laboratory method is more completely described in Standard Methods,”

only a brief description is provided that highlights any alterations made to the original

method.

A, Synthetic Water Makeup

For each experimental situation a synthetic water sample was prepared containing

the following constituents (unless otherwise stated):

e 3 meq/L Catt (150 mg/L as CaCO3)

e 3 meq/L HCO, (150 mg/L as CaCO3)

e 0.5 mg/L Mn(Il)

The pH, HOC! dose, and ferrous iron (Fe(1I)) concentrations were varied for each

experiment to determine the role that each parameter may have in the adsorption/surface

oxidation of Mn(II) onto the iron oxide surface. Stumm and Singer” cite an important

difference between studies employing synthetic versus natural waters. Natural waters

will contain possible catalysts or inhibitors that will affect the rate of reactions and

phenomenon occurring. This fact should be considered when using the results of this

research in “real-world” applications.

B. Glassware Preparation

All glassware used during these experiments was thoroughly cleaned to insure that

the glassware would not be a source of metals being studied. Initially, each piece of

glassware was cleaned using the following procedure:

26

1. Rinsed with hydroxylamine sulfate (HAS); removes oxidized metals from the

surface of the glassware.

2. Rinsed with tap water, washed with soapy water, and thoroughly rinsed again

with tap water.

3. Placed in a 10% nitric acid bath for at least 12 hours to ensure adequate time

for 1on exchange to occur.

4. Removal from the acid bath followed by three rinses with tap water and one

rinse of distilled water.

5. Allowed to dry before use.

The glassware treated using this procedure included the reaction vessels (standard BOD

bottles), stock solution containers, sample collection tubes, pipettes, and volumetric

flasks used to prepare solutions. Following each experiment, the reaction vessels were

immediately rinsed with tap water and steps 3-5 listed previously were repeated.

Several experiments were conducted at the start of the research to insure that the

glassware preparation procedures were successful. Randomly selected reaction vessels

were filled with Milli-Q water and allowed to stand for 24 hours after which samples

were collected. The concentration of Mn(II) in the vessels tested was below the detection

limit for the AA-S (results summarized in Table A-1); therefore, the acid washing

procedures described were an effective means of ridding the system of unaccounted for

manganese.

Next, it was desired to measure the chlorine demand of the Milli-Q water in the

acid washed vessels for two reasons:

1. To ensure organic materials had been sufficiently cleaned from the glass

surface; and

2. To help explain chlorine demand variability in future experimentation.

The amount of chlorine demand measured for time periods up to 1 day of detention time

was found to be insignificant (see Table A-2). Thus, the chlorine demand of the Milli-Q

27

water and of the glass vessels should not be considered major sources of error during

experimentation.

C. Preparation of the Reaction Stock Solutions

All water used to prepare each solution was deionized/distilled water which was

further treated through the use of a Milli-Q water system (Millipore Corporation,

Norwalk, CT) to ensure ion-free water with limited organic material present. In each

case, a concentrated stock solution was prepared which was then diluted when the

synthetic water was prepared. Preacidification of the Milli-Q water for the iron and

manganese stock solutions was accomplished through the addition of reagent grade

concentrated nitric acid (HNO3). Such acidification minimized the potential for Mn(ID

and Fe(II) oxidation in these stock solutions.

1. Manganese(II) Stock Preparation. The manganese stock solution used

throughout these studies was prepared by adding reagent grade manganous sulfate

monohydrate crystals (MnSO,:H,0; Fisher Scientific; Pittsburgh, PA) to preacidified (~

pH 2) Milli-Q water to obtain a concentration of 1 mg as Mn(II) per mL of solution.

Because of the low pH conditions, manganese oxidation via molecular oxygen should

proceed very slowly. The solution was kept in an air tight container, and the visual

appearance and concentration of the solution was checked daily to insure no Mn(II)

oxidation had occurred.

2. Ferrous Iron Stock Preparation. A ferrous iron stock solution was prepared in a

similar fashion to the manganese solution. Ferrous iron sulfate heptahydrate crystals

(FeSO,-7H,O) were dissolved in preacidified (~ pH 2) Milli-Q water to obtain a stock

solution concentration of 1 mg as Fe(II) per mL of solution. This solution was prepared

weekly or bi-weekly to prevent loss of soluble iron via iron oxidation within the stock

28

solution. The concentration and visual appearance were checked daily so that iron oxide

formation could be accurately determined.

Reagent grade American Chemical Society certified ferrous iron sulfate

heptahydrate crystals with a 99%+ purity (Aldrich Chemical Company, Milwaukee, WI)

was used for all experiments except for selected isotherm determinations. The impurity

of the iron stock introduced background manganese (approximately 1.82 x 10“ mg Mn

per mg FeSO,-:7H,O added) into solution which became more and more evident as the

iron concentration was increased (see Table A-3). In cases where high concentrations of

iron were desired (i.e. isotherm determinations at 200, 400, and 600 mg/L Fe(II), a

purified grade of iron sulfate heptahydrate (Alfa Aesar, Ward Hill, MA) was used to

reduce the experimental error. In the development of isotherms, it is important to only

account for the “outer” adsorptive capacity of a particular species, not that which may

become entrapped within forming flocs during flocculation.

3. HOC] Stock Preparation. The chlorine stock solution was formed by diluting a

stock solution of 5.25% sodium hypochlorite to a concentration of 1 mg as HOC! per mL

of stock solution. This solution was stored in a sealed brown container under

refrigeration to slow the degradation of the chlorine solution. The concentration of the

stock solution was quantified by amperometric titration daily before use. The appropriate

volume to be added to solution was then calculated based upon the measured stock

concentration to insure proper chlorine dosing.

4. Hardness and Alkalinity Stock Preparation. The hardness and alkalinity stock

solutions were each prepared at concentrations of 1 meq or 50 mg/L as CaCQO3 per mL of

stock solution. The hardness solution was prepared using reagent grade calcium chloride

crystals (CaCl,) and sodium bicarbonate (NaHCO;) was used for the alkalinity of the

synthetic water. Again, Milli-Q water was used to dissolve these solids in separate

containers. These stock solutions were bottled separately to prevent the possible

29

formation of CaCO3,,. The accuracy of the hardness stock (CaCl) was checked by

measuring the [Ca’”] on a Perkin Elmer Atomic Adsorption Spectrophotometer Model

703 (AA-S).

D. pH Adjustment

The solution pH of the synthetic water samples was adjusted using nitric acid and

sodium hydroxide solutions (1N ), each prepared from concentrated reagent grade stock

solutions. For fine adjustment of pH, dilutions of these solutions were prepared;

however, care was taken to limit the amount of these solutions added to the synthetic

water sample prepared to less than 0.1% by volume to minimize dilution effects. In

addition, the pH was not allowed to increase more than 0.25 pH units above the target

pH. This was done to minimize the potential for unnecessary chemical oxidation or

precipitation. In all cases the initial pH of all test solutions was brought to within 0.10

pH units of the desired level.

E. Experimental Apparatus

1. Adsorption/Isotherm Studies. Sample solutions (500 mL each) under various

pH and iron concentrations were used to determine the quantity of soluble Mn(II) that

would adsorb onto iron oxide particles on a “mol Mn(II) sorbed per mol Fe(II) in

solution” basis. The solution, maintained at a temperature of 10 + 2°C using an ice water

bath, was first buffered and adjusted to the desired pH, after which the calcium and iron

were added to solution. The pH was again adjusted, and the solution aerated to complete

the oxidation of the iron in solution. After 10-15 minutes of reaction time (measured by a

stabilization in the solution pH since oxidation of Fe(II) produces acid), the aeration was

halted, and an initial sample was withdrawn from the reaction vessel and acidified to

provide an estimate of the Fe(III) concentration. Mn(II) was added to solution and

allowed to gently mix with the iron precipitate. After 5 minutes, samples were collected

to determine the amount of Mn(II) that had adsorbed to the iron particles. (The

30

determination of the 5 minute reaction time is discussed in the Results and Discussion

Chapters of the paper.) One sample was filtered to determine the instantaneous soluble

Mn(I]) concentration after 5 minutes while the second was acidified to measure the initial

Mn(I]) in solution. All of the samples obtained by this procedure were filtered using the

0.45 um syringe filters following the procedure outlined in Section F.1. Figure 5 shows a

diagram of this experimental design.

The soluble iron in solution was oxidized prior to Mn(II) addition so that no

Mn(II) ions would be incorporated within the forming iron flocs. The desire was to

measure only the amount of Mn(II) adsorption onto the iron oxide surface, not the

combined effects of flocculation. In addition, it was determined from several filtration

experiments that the use of 0.45 um syringe filters provided comparable results to the use

of 30k ultrafiltration cells as little or no colloidal particles (less than 0.45 pm in size)

were being produced. As stated earlier, it is important to account for the impurity of |

reagent grade iron sulfate heptahydrate and the levels of manganese its use can introduce

into solution.

2. Mn(II) Removal Batch Studies. One key aspect of this research effort was to

determine the kinetics of manganese adsorption/surface oxidation onto the freshly formed

iron oxides in solution. For this reason it was necessary to have several reaction vessels

available so that when a sample was taken at the desired time, it would not affect the

results of subsequent samples collected. Ifa larger vessel was used and samples were

withdrawn at set intervals, there is more of an opportunity to capture misrepresentative

data points if the system is not thoroughly mixed. Also, the reactor(s) used must be

sealed to prevent loss of CO, which could lead to an increase in solution pH.

For each experiment a 2L solution of synthetic water sample was prepared using

Milli-Q water and the stock solutions previously discussed. In each case, the alkalinity

and hardness solutions were added first followed by pH adjustment at or below the

desired pH. Then, the desired soluble iron concentration was added to solution. The pH

31

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32

of the solution was again adjusted to the desired level and was allowed to mix for

approximately five minutes to ensure complete iron oxidation via molecular oxygen

dissolved in the water. Mn(II) was then added to solution at a dose of 0.5 mg/L and

allowed to interact for five minutes with the iron solids present so that adsorption data

could be collected. Finally, the dose of HOC] was added which represented the start of

the reaction time "clock." The well mixed solution was carefully poured into six standard

BOD bottles with care to limit the aeration of the sample and thus stripping of CO,. A

Teflon stirbar was placed in each bottle, and magnetic stirrers slowly mixed the samples.

A schematic of this system is shown in Figure 6.

Samples were collected at the desired time by removing one of the six bottles

from the water bath and measuring the pH and temperature of the solution within the

vessel. Next, the sample was filtered using both a 0.45um syringe filter and a 30k

ultrafilter. The use of these size filters was an attempt to characterize the size of the

particles formed, and the importance of size in the removal of Mn(II) from solution. A

more detailed description of the filtration techniques is given in Section F. To simulate

groundwater conditions, all of the experimental tests were conducted at 10 + 2°C. To

maintain the temperatures at this level, the reaction vessels were submerged in a cold

water bath with a temperature of approximately 10°C. A refrigeration type unit was used

to circulate an antifreeze-water mixture through tubing placed within the Plexiglas tank to

maintain the bath at the desired temperature. In addition, the Milli-Q water used to

prepare the synthetic water sample being tested was refrigerated to assist in the initial

temperature adjustment of the solution.

Initially, the Mn(II) was added prior to the addition of the iron stock solution, but

this resulted in a Mn(II) “sink” due to the possible entrapment of ions within the iron floc.

Therefore, in later experiments, the Mn(II) was added after the iron was completely

oxidized. This not only allowed for a better measurement of the change in Mn(ID) in the

system due to interactions with the iron oxide surface, but also permitted adsorption

measurements for each of the various experimental conditions.

33

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3. MnO, Adsorption Batch Studies. This experiment was conducted in an

attempt to understand the mechanism by which the adsorptive/surface oxidation reactions

continue over long periods of time. Once the initial iron oxide surface has been utilized,

it was hypothesized that a manganese oxide surface may indeed serve as the main

mechanism in continuing the catalyzed oxidation of soluble manganese. Therefore, this

experiment was intended to serve two purposes:

1. To measure the adsorptive capacity of freshly precipitated MnOx().

2. To determine if the rate of Mn(II) removal from solution for an

equivalent amount of formed manganese oxides based upon Mn(I])

adsorption on the iron oxide surface from adsorption studies is similar

to that noted in batch studies.

Again, a 2L sample volume was prepared similar to that outlined in the batch

study procedure, but preformed manganese oxides were added instead of iron stock

solution. The MnO,) solids were formed by slowly adding HOCI into a Mn(II) solution

to prevent the formation of permanganate. The HOCI was added at 1.25 times the

stoichiometric dose requirements based upon the approximate Mn(II) solution

concentration to insure that all the Mn(ID in solution was indeed oxidized and not simply

adsorbed onto the MnO,.) surface. To further test the completeness of oxidation, a stock

sample was filtered through a 30k ultrafilter to measure the soluble manganese

concentration and the chlorine residual. The soluble manganese concentration was below

detection limits, and sufficient excess chlorine was present to complete the oxidation of

any sorbed Mn(II). A solid extraction using HAS was performed on the stock solution to

obtain an estimate for the stock concentration of MnO).

The adsorption data determined from the aforementioned adsorption studies

(Section E.1.) was used to estimate the amount of MnOx) to be added to solution. For

example, to compare the rate of removal via MnOx,.) versus a given iron concentration,

the quantity of Mn(II) adsorbed for that iron concentration was obtained from the

isotherm results. Based upon the reaction for Mn(II) oxidation to MnO,), the equivalent

35

amount of MnO,;;) surface was calculated and added to solution. In theory, this method is

a conservative estimate for the amount of MnOx;.) surface available for adsorption as the

preformed particles should have a greater surface area than those hypothesized to have

formed on the outside of the iron oxide particle.

Samples were collected similarly to the procedure described in the previous

section as one of the six bottles was removed from the water bath at the desired time and

the pH and temperature of the solution within the vessel were measured. The sample was

filtered using both a 0.45um syringe filter and a 30k ultrafilter; the use of the 30k

ultrafilters served to capture the possibly colloidal preformed MnO x) particles that may

still reside in solution. The experimental setup is identical to that depicted in Figure 5.

4. Iron Oxide Slurry Reactor System. Three bench-scale slurry-type reactors were

constructed to simulate a single-stage flocculation basin with a settling zone at a full-

scale water treatment facility. Each was designed with a baffling system to separate the

mixing and settling zones within the reactor to promote the flocculation and subsequent

settling of the particles formed. The reactors each had a volume of approximately 2.3 L

and were intended to have internal recycle of solids as they settled from solution. Each

basin was equipped with a stirring paddle (25 rpm) which mixed the incoming

constituents throughout the mixing zone of the reactor. The reactors were designed to

operate in parallel as each had an effluent line that drained to a sink. The effluent line

served as the sampling point for evaluating effluent quality and treatment efficiency.

It was desired to use the same synthetic water makeup for the operation of the

reactors as had been used for the batch studies. Because of the limited pumping

capabilities and the size of the reactors, large volumes of stock solutions were required to

attain the desired detention times. In addition, because of the possible interactions that

may occur between the constituents of the water makeup (i.e. Ca” and alkalinity stock),

the stock solutions were prepared individually to limit reactivity between ions. Therefore,

a mixing unit was required to mix the solution prior to dosing each reactor. Separate

36

stock solutions for Mn(II), HOCI, and alkalinity were combined in the mixer with chilled

tap water from a constant head tank. Three separate feed lines (one going to each reactor)

were used to add this portion of the solution makeup to each reactor. A separate stock

solution containing Ca’ (which could react with the alkalinity) and Fe(II) (which is

extremely reactive with chlorine) was added separately to each reactor for the reasons

cited. The iron and calcium stock solution as well as the Mn(ID stock solution were

slightly acidified to pH 2.5-3 to retard the oxidation of these reduced species prior to

dosing. The level of acidification was determined by titration using 0.02N sulfuric acid.

A schematic of the reactor set-up is shown in Figure 7.

The temperature for these experiments was adjusted by cooling the influent tap

water in the constant head tank prior to it being fed into the mixing unit. In addition, the

reactors were submerged in an ice water bath throughout the experiments. Unfortunately,

the temperature could not be maintained at the desired level used during other

experimental studies, 10 + 2°C. The actual temperatures of experimentation, 13-20°C

should speed the interactions between the experimental constituents and increase the rates

of reaction observed when compared to those of the batch studies conducted.

The stock solution concentrations for these constituents were adjusted as

necessary to account for changes in detention time. The tap water flow was also adjusted

as necessary for changes in detention time as the pumps used could only pump at a

constant rate. Therefore as the detention time changed, the tap water flow was increased

for shorter detention times or decreased for longer detention times to balance the volume

of liquid entering and leaving the mixer. Overall, the desired water makeup follows that

described in Section A with a soluble iron concentration of 2 mg/L. The chlorine dose

was varied throughout the experiments to determine its importance in the reactions.

Several different sampling schemes were used to study the state and effectiveness

of the continuous flow slurry systems. Effluent samples were collected periodically to

study the effluent quality with frequent sampling (once every thirty minutes for at least

two detention times) occurring whenever a system parameter was altered. The main

focus of this sampling was to note changes in the soluble effluent manganese

37

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38

concentration; therefore, these samples were all filtered using 0.45um filters. However,

the loss of solids in the effluent was a key parameter to consider; thus, some effluent

samples underwent acid digestion (no filtration) to measure the total iron and manganese

in the effluent.

Samples were collected from each reactor and digested with acid as well to

measure the total iron and manganese solids concentrations in the mixing zone of the

reactor. An additional means of measuring the solids concentration within each reactor

was the use of a standard suspended solids test. To insure that the reactors were being

properly dosed, samples were taken from both the mixer (see Figure 7) and the influent

lines and analyzed for Mn(II), Fe(II), and HOCI. Finally, chlorine samples were obtained

from the mixer to quantify the actual chlorine dose entering the reactors. Residual

chlorine from each reactor was also determined by filtering the effluent and measuring the

free chlorine in solution.

F. Collection of Samples

Samples were collected from each of the experimental setups as previously

described. Each sample was then filtered using one or both of the methods described

below. Immediately following the filtration of each sample, two drops of concentrated

nitric acid were added to the filtrate to prevent further reactions from occurring. The

samples were agitated using a vortex mixer to ensure consistent solution characteristics.

The procedures followed for each of these filter types are described in more detail below.

1. Syringe Filter Procedures (0.45um). A portion of the collected sample was

poured into a clean, dry 150 mL beaker. A 25mm diameter 0.45um filter (Gelman

Science, Ann Arbor, MI) was placed in the filter chamber and approximately 10 mL of

Milli-Q water were passed through the filter to rinse the membrane. The syringe was

filled and rinsed once with the sample to reduce likelihood of cross-contamination. A 12

mL sample was drawn into the syringe and was filtered to obtain the sample for this

39

reaction time. The first 2 mL of the filtrate were discarded as dilution was a concern

from the residual Milli-Q water which may reside on the membrane following the rinse

procedure.

2. 30k Ultrafiltration Procedures. The ultrafiltration equipment used was

manufactured by Amicon (Model # 8200), and all manufacturers' specifications were

followed during these experiments. The 30k filters (Amicon Diaflow Ultrafilters YM30

Membranes; Beverly, MA) were stored in the filtration chamber when not in use, soaking

in a slightly acidic distilled-deionized water solution. A portion of this solution was

passed through the membrane and the remainder discarded from the chamber when a

sample was to be filtered. The sample to be analyzed was added to the chamber, and the

solution was stirred by a magnetic stirrer and pressurized with nitrogen gas at 20 psig.

The initial 10 mL of filtrate was discarded as residual amounts of the previously filtered

solution occupied the filtrate effluent tube. Two 10 mL samples were then collected

immediately to prevent buildup of iron particles within the membrane prior to sample

collection. This could be a source of error as Mn(II) in solution that had not previously

sorbed to the iron surface might do so within the filter membrane. The membrane was

cleaned after each use by rinsing with pressurized distilled water to dislodge any particles

trapped within the filter membrane. Again, a slightly acidic distilled-deionized water

solution was added to the filtration chamber for membrane storage.

Manufacturer specifications recommend that the filters be operated at 55 psig for

filter operations so that the permeability of the membrane may be constantly monitored.

As previously stated the solutions were filtered at 20 psig; this lower pressure was

intended to insure that the particles greater than the pore size would be retained.

However, parallel tests were conducted at applied pressure of 20 and 55 psig to determine

if the pressure affected the results. From the data collected, it did not appear as though

the higher pressure produced results different from the 20 psig results. Also, neither

40

pressure condition resulted in Mn(II) concentrations different from the data collected

using the syringe filters (0.45 jm.).

G. Measurement Techniques for Data Collection

1. pH and Temperature. The pH of all solutions was measured using a Fisher

Accumet 710 pH meter (Fisher Scientific Co.; Pittsburgh, PA). The meter was calibrated

daily using standard pH 4 and pH 7 buffer solutions refrigerated to 10°C. All temperature

readings were taken using a standard alcohol thermometer (Fisher Scientific Co.;

Pittsburgh, PA).

2. HOCI Residual. Monitoring of the HOCI stock solution and the residual HOC!

in the test solutions was measured via amperometric titration with phenylarsine oxide

(PAO) as outlined in Standard Methods” (Method # 4500-Cl D). This titration

procedure requires a 200 mL sample volume; however, because of the limited amount of

sample remaining following filtration procedures, a 1:1 dilution was made using Milli-Q

water. To ensure the dilution would not affect the results a sample was tested using both

a dilute and a full strength sample, and comparable results were obtained. The 100 mL

sample volume was filtered using a 0.45um filter to remove any oxidized particles from

solution that may interfere with the titration results. To the 200 mL diluted sample,

approximately 1 mL of pH 7 phosphate buffer and one gram of potassium iodide (KI)

were added. The titration was then performed using a Fisher Scientific Titration

Controller Model # 450 (Fisher Scientific Co.; Pittsburgh, PA) by the addition of standard

0.0054N PAO.

3. Soluble Metals Concentration. Metals analyses were performed using a Perkin

Elmer Atomic Adsorption Spectrophotometer Model 703 (Perkin Elmer, Norwalk, CT).

All tests were performed using the recommended settings of the manufacturer for

wavelength, lamp current, etc. A detection limit test as outlined in the Perkin Elmer

4]

Instrument Manual” was conducted on several occasions to determine the accuracy,

reproducibility, and detection limit of the equipment used. A summary of the results

from this procedure is outlined in Appendix B as well as a summary of the operating

parameters used during analysis.

4, Suspended Solids Concentration. The determination of suspended solids

followed the procedure outlined in Standard Methods™ (Method # 2540 D.). Glass-fiber

filters were prepared by passing three 20 mL aliquots of distilled water through each

filter. The filters were then stored for at least one hour prior to use in a 105°C oven to

evaporate any water bound to the filter. Before use, the filters were stored in a desiccator

to bring them to room temperature, and subsequently weighed using a standard laboratory

scale. The sample for which solids data was desired was filtered using a vacuum pump

with approximately 10 pounds of applied pressure differential. Distilled water was used

to rinse the sides of the filtration cone to insure all solids were captured. The volume of

sample filtered was recorded, and the filter was again placed in the 105°C oven fora

minimum of one hour. Again the filter was brought to room temperature in a desiccator

prior to being weighed for analysis.

5. Acid Digestion of Oxidized Solids. For several experiments, the concentration

of iron in solution was desired to aid in the understanding of the phenomenon under

study. In most cases the iron in solution was in a solid, oxidized form which forced the

development of a digestion technique to solubilize the metal ions so that AA-S could be

used for concentration determination. For lower concentrations of oxidized iron, several

drops of concentrated nitric acid were used for digestion, and very little dilution was

noted. However, for higher concentrations of iron, concentrated hydrochloric acid was

used as iron can bind with the chloride introduced as well as be solubilized by the effects

of acidification. This phenomenon was unknown for earlier experiments, as its use can

reduce the necessary volume of acid required significantly (reducing the dilution effects).

42

In cases where large amounts of acid were required, the volume added was recorded, and

the dilution effects accounted for by calculation. A similar procedure was utilized to

measure the quantity of manganese solids in solution as well.

43

CHAPTER IV

RESULTS

The experimental data collected to satisfy the research objectives will be

summarized in this chapter. The order of presentation will generally follow the order the

data were collected as each experiment served as a “building block” for future

experiments. The intent of these studies was to explain the possible interaction that

occurred between the iron oxide solids and soluble manganese at the groundwater

treatment facility (field data summarized in Table 1). The experimentation was designed

to study each of the possible removal mechanisms in detail to explain the observed

phenomenon. Additional experimentation was conducted to develop a continuous flow

system, and to cite key system parameters for the design of such a system to provide a

means of more effective iron and manganese removal. All data presented in this chapter

are summarized in tabular format in Appendix A. A discussion of the data presented here

can be found in Chapter V.

One key note concerning the experiments conducted is the type of iron stock used.

As noted in Chapter III, when larger concentrations of Fe(II) were added to solution,

increasing quantities of Mn(II) were introduced into solution as well. This explains the

increased amount of Mn(II) noted at time zero of the experiment(s). A summary of the

impurity of the iron stock used is included in tabular format (Table A-3) in Appendix A.

By using this iron stock, it is impossible to decipher whether the initial Mn(II) measured

is removed by entrapment (co-precipitation) within forming flocs or by the other means to

be studied during the experimentation. This should be considered when reviewing the

results presented.

A. Experimental Setup

Initial experimentation was undertaken to define a set of controlled experimental

conditions under which the enhanced oxidation of soluble manganese in the presence of

44

iron oxides and HOCI could be observed without interference from other removal

mechanisms. Several experiments were first conducted to study other possible removal

mechanisms for Mn(II) that could be responsible for the observed results. These

mechanisms were hypothesized to include:

Formation of MnCO3 (s) Co-precipitation with/Adsorption onto CaCQs3 (s) Solution phase oxidation of Mn(II) by HOCI (no Fe(III solids present)

Adsorption onto iron oxides

These tests were used to determine appropriate lengths of experimentation at various pH

conditions. Also, as previously mentioned, the results were used to set future

experimental conditions such that any of these mechanisms would not be responsible for

manganese “sinks” from the system as the investigation of enhanced oxidation of soluble

manganese in the presence of iron oxides and HOC! was undertaken.

B. Studies of Possible Mn(II) Removal Mechanisms

1. Formation of MnCQ3(s) and Co-precipitation with/Adsorption onto CaCQ3 5). These

two mechanisms were analyzed simultaneously as they occur under similar pH and

solution conditions. For the experimental conditions outlined in Chapter III, the solution

makeup is saturated with respect to both MnCOs3 (,) and CaCO3 « at pH 9. (Solubility

product calculations confirming this are included in Appendix C.) In order to account for

the possible removal of Mn(ID) at this solution pH, the Mn(II) concentration in solution

was measured over time. The results shown in Figure 8 indicate that Mn(II) was indeed

removed by one or both of these phenomena. Thus, the white chemical precipitate

observed during experimentation could have been MnCO 3) or CaCO3,.) or a combination

of the two carbonate species.

Measurements of the Ca’ concentration were taken which indicated that at least a

portion of the precipitate was CaCQ3,;); however, it was desired to determine if MnCO3 ()

precipitation was occurring as well, as predicted by the solubility product of the solid.

Figure 9 compares the results from the previous experiments with data obtained by

45

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replacing CaCl, in the solution make-up with an ionic strength equivalent of NaCl, again

at pH 9. The reduction in Mn(II) is minor compared to that when Ca’* was in solution

indicating that the majority of the Mn(II) removed in the previous experiment was a result

of either adsorption onto CaCOx,) or some other form of co-precipitation with Ca” and

CO;°: however a small portion of the Mn(II) removed was due to the formation of

MnCO3 4s).

Similar experimentation was conducted at pH 8 to confirm the theoretical

calculations for species’ solubility which indicated that neither MnCO3 (;) or CaCQ3 (s) is

capable of forming at this solution pH. The results for this experiment, shown

graphically in Figure 10, confirmed that no significant formation of either solid species

occurred; thus negligible Mn(II) reductions were noted. The data for these studies is

summarized in Appendix A in Tables A4-A8.

2. Solution Phase Oxidation. Solution phase oxidation was defined for this study to

mean: “any oxidation that occurs in solution between a metal ion species not in contact

with any surface and an available oxidant in solution.” In most cases, this term will apply

to Mn(II) oxidation occurring with only HOCI and the background levels of alkalinity and

hardness in solution. Studies were undertaken to assess the rate and quantity of solution

phase oxidation of Mn(II) via HOC! at solution pH of 7 and 8; the results of these

experiments are shown in Figure 11. The amount of oxidation that occurs is negligible

over the time period studied indicating that this mechanism plays a minor role in Mn(II)

removal at these pH conditions. The slow oxidation kinetics for Mn(II) oxidation via

HOCI at this pH as well as the reduced temperatures used in these studies help explain

the depressed amount of observed oxidation.

3. Adsorption of Mn(Il) onto Freshly Precipitated Iron Oxides. At most groundwater

treatment facilities, any soluble iron is oxidized rapidly upon aeration resulting in the

formation of iron oxides in solution with the unreacted manganese. This provides yet

48

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another possible means of Mn(II) removal- adsorption of Mn(II) onto freshly precipitated

iron oxides. Before adsorption studies could be performed, the time required for such a

phenomenon to occur was determined. Previous research” had indicated that a 5-minute

contact time was sufficient for adsorption. For this experimentation, adsorption times of

5 minutes were used to allow for an equilibrium to develop between the iron oxides and

Mn (ID in solution.

Adsorption studies were conducted at pH 7 and 8 to develop isotherms for MndID

sorption onto newly formed iron oxides. These data are plotted on a Cartesian coordinate

system in Figure 12. The studies indicated that the adsorptive capacity of iron oxides for

Mn(II) is quite small, and thus the role this mechanism, like solution phase oxidation,

plays in Mn(II) removal is relatively minor and is certainly not the dominant mechanism.

This observation holds true only over the range of iron oxide concentrations studied to

develop the isotherm data. However, as expected, the adsorption capacity is greater at pH

8 as the iron oxide surface carries a more negative surface charge.

The data were also analyzed using Langmuirian isotherm theory as shown in

Figure 13. At an equilibrium Mn(II) concentration of 0.50 mg/L, which represents the

level of influent soluble manganese used throughout these studies, the maximum

adsorptive capacity determined at pH 8 was 0.005 mg Mn(II)/mg Fe(III). Due to the

spread of the data a best fit line could not be drawn for the data collected at pH 7

conditions for both Figures 12 and 13. Numerous attempts were made to collect more

accurate isotherm data at this pH condition, but all attempts were unsuccessful as the

sorbed quantities of manganese were quite small and difficult to measure.

Adsorption capacities would be expected to be even greater at higher pH

conditions, however, because it has been shown that other mechanisms may dominate

Mn(II) removal at higher pH values under the experimental conditions being utilized, it

would be difficult to determine the role adsorption alone may have in Mn(II) removal.

Therefore, the adsorption studies were only conducted to a maximum solution pH of 8

standard units.

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One issue noted during experimentation was the elevated levels of manganese

introduced into solution as higher concentrations of iron oxides were used. This was

explained by the impurity of the iron stock solution as the purity of the ferrous iron

sulfate heptahydrate crystals used during experimentation was only 99%. This

introduction of manganese made the adsorption studies more challenging and also

allowed for the enmeshment of soluble manganese into the iron oxide flocs as they

formed. For this reason, the adsorption studies presented previously may indicate greater

quantities of Mn(II) were sorbed than would normally be observed.

To investigate this issue further, a purified grade (99.999%) of ferrous iron sulfate

heptahydrate crystals (FeSO,- 7H2O) was obtained and adsorption studies were repeated.

The results of these studies are summarized in Figure 14 and indicate that the adsorption

is slightly lower than that observed using the standard iron stock solution. Adsorption

capacities were determined to be 0.0001 and 0.0016 mg Mn/mg Fe(III) for pH 7 and 8,

respectively for an equilibrium Mn(iI) concentration of 0.35 mg/L.

C. Mn(f1) Removal via Surface Catalyzed Oxidation of Manganese with Iron Oxides

In the previous adsorption experiments the reaction vessels were free of oxidants

with the exception of dissolved oxygen which has little effect on soluble manganese as

indicated by the field data previously presented'. Thus far in the experimentation, no

mechanism alone has proven to be capable of the magnitude of Mn(II) removal observed

in the field studies. The next set of experiments were performed to study the hypothesis

that the iron surface (Fe(III) catalyzed the reaction between Mn(II) and HOCI. This was

believed to be a pseudo-combination of two mechanisms: adsorption and solution phase

(chemical) oxidation.

Initially, these experiments were conducted under similar conditions to those seen

at typical groundwater treatment facilities where the iron is allowed to oxidize with

Mn(II) present in solution. However, as indicated in Figure 15, this resulted in greater

removal of Mn(II) from solution possibly due to entrapment of the Mn(II) ions within the

54

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56

iron hydroxide flocs as they were forming. It was desired to study the possible

adsorption-surface oxidation step, and the entrapment phenomenon that was observed

would complicate this study significantly, often making it impossible to predict the

magnitude of Mn(II) removal by each mechanism. Thus, future experimentation was

completed as described in Chapter III by first air oxidizing the soluble iron in solution

prior to adding soluble manganese to solution. In addition, this experimental setup allows

one to use the chlorine demand of the system to track the level of Mn(II) oxidation that

has occurred with each time step. This is the most direct means of quantifying that

portion of the Mn(II) removed from the system that has been oxidized versus that which

may have only been adsorbed.

Numerous experiments were conducted at pH 7 and 8 at various iron oxide

concentrations to study the surface catalyzed oxidation phenomenon. In addition to the

results of these experiments, other studies were conducted concurrently that lend insight

into particle sizes formed and the processes used in the collection of data. First, from the

data tables provided in Appendix A, it can be seen that the concentrations of soluble

manganese in the filtrate of the 0.45 ym filters and the 30k ultrafilters do not appear to be

different from one another. The is confirmed by statistical calculations provided in

Appendix C. For this reason, ultrafiltration was not used for these studies as it is more

costly and difficult to operate. This observation also indicated that the particles being

formed exceeded 0.45 jum in diameter.

The results of the surface catalyzed Mn(II) removal experiments are summarized

in tabular format in Appendix A. A portion of these results have been selected and

plotted in Figures 16 and 17, the results for pH 7 and 8 conditions, respectively. As

indicated, the reactions are highly pH and iron concentration dependent as more rapid

rates of Mn(II) removal were noted under higher pH and iron concentration conditions.

Further analysis of the data collected during these experiments, specifically HOC]

demand data, suggested that the enhanced Mn(II) removal observed was the product of an

adsorption step followed by surface oxidation of the sorbed Mn(II). A full summary of

57

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59

the comparison between observed and predicted HOCI demand for different experimental

conditions (Fe(III) and pH) is provided in Appendix A; however, the plot provided in

Figure 18 provides an example of typically observed results. If Mn(II) removal was a

result of oxidation via HOCI alone, one would expect the 1:1 line shown to be a “best-fit”

line through the data points shown. Because the data points are located below the 1:1

line, the chlorine demand of the system lags behind what would be expected if Mn(II)

removal was solely due to oxidation via HOCI. Therefore, the removal of Mn(II) from

solution is the result of oxidation and a different mechanism, most likely adsorption.

Additional information gathered from these experiments was the rate of the

reactions with respect to Mn(II) oxidation. Using the method outlined by Grady and

Lim,™ the rate of Mn(II) oxidation was analyzed and the order of reaction and a rate

constant “k” were calculated for the results presented at pH 7 and 8. In the determination

of reaction rate, the initial Mn(II) concentration was taken to be the concentration of

Mni(II) following the five minute adsorption/interaction period with Fe(III) oxides, not the

initial Mn(II) concentration. Otherwise, the Mn(II) removal rate would appear to be very

rapid initially (most of Mn(II) removal due to adsorption) and much slower as the

experiment continued (actual Mn(II) oxidation catalyzed by the Fe(III) oxides). The data

for each of the experiments conducted using different Fe(II) concentrations at pH 7 and 8

were analyzed individually by plotting the log of the equilibrium Mn(IJ) concentration

versus the log of instantaneous rate of reaction. The resulting best-fit-line provided the

order of reaction (slope) as well as the rate constant for a Mn(II) concentration of 1 mg/L

(y-intercept). The rate constants for a Mn(II) concentration of 0.50 mg/L were also

determined using the equation of the best-fit-line on the log-log plot. An example of the

determination of these parameters for a typical experiment is shown in Figure 19. The

rate constants determined for each individual experiment for a given pH were then plotted

versus the Fe(III) concentration to develop an equation of the rate constants with respect

to Fe(II). A plot of these equations is provided in Figure 20.

60

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The next step in the research effort was to attempt to utilize this new found technology to

develop a treatment system to enhance the removal of soluble iron and manganese from

water supplies.

D. Iron Oxide Slurry Reactor System and Mn(II) Adsorption onto MnO x

Three bench-scale systems (described in Chapter III, Section E.4) were

constructed and operated in parallel, each reactor containing a different concentration of

Fe(III) oxides. Data collected from these reactors indicated that this system setup could

meet the desired level of treatment for iron and manganese removal. However, caution

should be taken when considering the results because of the difficulties discussed in

Chapter III of maintaining the temperature during the studies at 10°C. The higher

temperatures used during experimentation most likely resulted in increased rates of

reaction and thus improved performance. Regardless, during the study, several key

observations were made that provide further insight into the mechanistic means by which

this phenomenon occurs.

Initial data collected emphasized the importance of HOCI in solution which

reiterates that manganese removal is not solely an adsorptive process onto Fe(III) oxides.

The reactor system failed if the stoichiometric requirements of HOC] for the influent iron

and manganese levels were not satisfied. This is exhibited in Figure 21 where the system

was operated with no additional HOC! dose at a detention time of 1 hour (There is a 1

mg/L residual in the tap water). For this experiment the effluent Mn(II) concentration

approaches the influent concentration of 0.50 mg/L with 64 hours. However, when the

same reactor setup was tested with a HOCI concentration of 4 mg/L, an immediate

reduction in Mn(II) is noted. Figure 22 shows the complete set of test results for this

reactor setup indicating the point at which the chlorine dose was increased from

approximately 1 mg/L (residual in tap water) to 4 mg/L. These results confirm the

importance the presence of HOCI has on the effectiveness of the system.

64

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Perhaps the most important operating phenomenon noted was the buildup of

MnO, js) in the slurry over time, provided there was sufficient chlorine to complete the

Mn(II) oxidation step. Figure 23 provides a graphical representation of the data leading to

this conclusion. In addition to the buildup of MnO, (s) in the slurry, another trend should

be noted from Figure 23: the initial iron concentration decreases to a steady-state

concentration over time. These results seem to indicate that the MnQ, ,,) in the slurry

may take a leading role in the removal of Mn(II) from the system, in essence replacing the

Fe(III) oxide as the primary Mn(II) adsorptive surface.

For these reasons, it was necessary to examine the adsorptive properties of

MnOxs) for Mn(II). The results of these studies are summarized in Figure 24. Again, a

five minute time period was used during the adsorption studies to allow for an

equilibrium relationship to develop between Mn(II) and of MnO,,). Langmuir isotherm

plots for the sorption of Mn(ID onto MnO, (s) are provided in Figure 25. At an

equilibrium Mn(II) concentration of 0.50 mg/L, the adsorptive capacity of MnOxys) for

Mn(I]) at pH 7 and 8 was 0.20 and 0.21 mg Mn(II)/mg MnO x), respectively. It should be

noted that the adsorptive capacity of MnO, (s, for Mn(II) far exceeds that of freshly

formed iron oxides (Fe(III)) as previously presented.

Several plots were prepared to exhibit slurry reactor performance under various

operating conditions. Figure 26 provides an indication of typical reactor performance at

pH 7 while Figure 27 represents pH 8 conditions. The system was found to be much

more stable at higher pH conditions (i.e. not as sensitive to changes in system parameters

such as initial Mn(II) concentration or HOC! dose). Generally, the success of the reactor

systems were independent of changes in solution pH between 7 and 8. (The slight

disruption noted around hour 60 for the pH 7 system was caused by an upset in the

experimental setup, specifically, the constant head tank supplying tap water to the system

froze overnight.) However, when the pH was reduced to 6, a level which does not

promote efficient adsorption of Mn(II) onto either iron or manganese oxide surfaces, the

effluent quality with respect to soluble manganese began to deteriorate rapidly despite

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sufficient HOC] and the large concentration of manganese oxides present in the slurry.

Figure 27 also shows the performance of the system over a range of different operating

conditions including the pH 6 condition.

E. Model Development and Results

These experimental observations were used to develop a mathematical model to

predict the effluent water quality from a slurry reactor system, using several

experimentally determined input variables. It should be noted that the laboratory

experiments were not designed with this modeling effort in mind; therefore the

experiments conducted do not allow for the calibration of the model or provide a means

of confirming its accuracy. Note that due to concern over the accuracy of the isotherm

determined for Mn(II) adsorption onto iron oxides at pH 7, the modeling exercise does

not include this pH condition.

The model describes Fe(OH)3;) catalyzed Mn(II) oxidation via HOC! using mass

balances for manganese and chlorine. It was assumed that the reduced iron entering the

slurry reactor would be immediately oxidized by the HOC! in solution as was noted in

Chapter II for the pH range under study. Other assumptions made in the development of

the equations are discussed in the following sections. A computer printout of the model

with model simulations is provided in Appendix D. The model input parameters

included:

e Influent and effluent soluble manganese concentrations

e HOCI concentration

e Initial iron and manganese oxide concentrations

e Volume of reactors and flow rate through system; sets hydraulic detention

time

e Isotherm data to estimate sorbed Mn(ID on Fe(IID oxides and MnO).

e Influent iron concentration

73

1. Modeling Approach. Generally, models are developed around a series of mass balance

equations for several parameters within the system. This too is the case for the model to

describe iron catalyzed manganese oxidation via chlorine where mass balances for

manganese and chlorine were developed. The fate of Mn(II) in solution is by far the most

complex of the two parameters in that its removal is made possible by several different

mechanisms. Below is the equation developed for the mass balance of total manganese in

the system.

dC dq dq a V+ a *M re + M 0 =@,, ‘Cy, — Qu Cy, —k,-q, -[HOCI]-M,, (9)

—k,-Qy ‘LHOCT]: M sino

where: C,, = Soluble Mn (Mn(II)) in reactor (mg Mn(ID/L)

V= Volume of Reactor (L)

dr= Amount of sorbed Mn(II) onto iron oxide surfaces as predicted by

Langmuir isotherm (mg Mn(II) sorbed/mg Fe oxide)

Mee = Mass of iron oxides in system (mg Fe oxide)

qm = Amount of sorbed Mn(II) onto iron oxide surfaces as predicted by

Langmuir isotherm (mg Mn(II) sorbed/mg Mn oxide)

Mmno= Mass of manganese oxides in system (mg Mn oxide)

Qin = Total flow into reactor (L/min)

Qout = Total flow out of reactor (L/min)

Coin = Influent concentration of soluble manganese (mg Mn(II)/L)

Cmour= Effluent concentration of soluble manganese (mg Mn(II)/L)

k; = Rate constant describing the surface catalyzed oxidation step

(L/min‘mg HOC])

[HOCI] = Concentration of free chlorine in solution (mg HOCI /L)

74

The original idea for the model was to predict the system performance under

startup conditions, however, the inclusion of the manganese oxide adsorption term and

the rate of sorbed Mn(ID) oxidation on the manganese oxide surface allows for the

prediction of effluent quality as these oxides accumulate over time as exhibited in Figure

23. Unfortunately no experimental data were collected for the determination of the rate

of Mn(II) oxidation on the manganese oxide surface. For the purposes of simulating

reactor performance, the rate of oxidation on the manganese oxide surface will be

assumed to be equal to that of the iron oxide surface.

Plots of the Langmuir isotherms for the determination of the “q” parameters have

been presented in Figures 13 and 25. The concentrations of soluble manganese (influent

and effluent), [HOCI], and oxide surface concentrations can be estimated from the data

collected. [NOTE: By CSTR theory Cy = Cmout.] The volume and flow rate through the

reactors will be used to set the hydraulic detention time for each model simulation.

Next, a relationship between the amount of free chlorine in solution was

developed to describe the decay or utilization of free chlorine within the system. The rate

constant used in this equation is stoichiometrically related to k; in the mass balance

relationship for manganese; both k), kz, and k3 describe the rate of surface catalyzed

oxidation. Note that the decay of HOC] in the presence of Fe(II) is assumed to follow the

stoichiometric requirement for oxidation of Fe(II) to Fe(III).

dC a VV =O, Croct, —Qou *Croci,, ~*2°Ir LHOCI:V —k;-qy -[HOCI]-V dt (10)

~ 0.64-[Fe(I1)]-V

where: Cyoci = HOCI in solution (mg HOCL/L)

Cuoctin = Influent concentration of HOC! (mg HOCI/L)

Cuyociout = Effluent concentration of HOC] (mg HOCI/L)

k) = Rate constant for surface catalyzed oxidation step (mg Fe(III)

oxide/mg Mn(II)-min)

75

k3 = Rate constant for surface catalyzed oxidation step (mg Mn

oxide/mg Mn(I])-min)

{HOC]] = Concentration of free chlorine in solution (mg HOCI/L)

[Fe(H)] = Concentration of influent Soluble Iron (mg Fe(II)/L)

A mass balance for Fe(IJ) could not be written for the experimental system due to

the lack of sufficient data for Fe(I])/Fe(II]) accumulation and loss from the system. As

noted previously, the iron oxide concentration decreased to a steady state value over time;

however, it should be stressed again that the model intends only to predict the startup

condition. In essence, an iron mass balance is not required based on this criteria, but

would be required for the development of a model to predict long term reactor

performance. The model could be extended to the long term performance, but it is

suggested that reactor hydraulics and settling characteristics of the particles first be

investigated to determine whether iron solids will accumulate over time or continue to

wash out of the system as was observed during these studies. Note that the HOC! demand

the influent iron exhibits was accounted for in the HOC] mass balance, as it was assumed

its conversion to Fe(III) was instantaneous at these pH conditions in the presence of

HOC] and that it would follow stoichiometric proportions.

A key assumption made in the writing of the mass balance equations was that the

concentration of iron and manganese oxide solids in solution remains constant. As

presented in Figure 23, this is unlikely. Consideration was given to including a solids

accumulation or loss term, but defining the value for such a term would be difficult with

the reactor setup utilized to conduct these experiments and the available data collected.

As noted by the data collected and summarized in Appendix A Tables A41-A43, solids

were consistently being lost from the system in the effluent. A more hydraulically stable

reactor with better short circuiting prevention devices would be more successful at

predicting the value of such a term.

76

2. Simplified Model for Batch System. Before attempting to implement the previous

system of equations to the continuous flow system, a more simplified model was

developed to fit the parameter k (rate constant) to existing batch study data. The

equations for this model are summarized here. The first equation represents the mass

balance for manganese in the system, and the second a mass balance for chlorine. It

should be noted that during the batch studies, all Fe(II) in the system was completely

oxidized via oxygen prior to the addition of HOC] and thus it poses little or no HOC!

demand. Note that the manganese oxide concentration was assumed to be zero

throughout the batch studies as these terms are not included in the following equations.

d[C

Pel v4 M,, =k {HOCI}-4p “My, (1)

d{HOCH |, _ a -k, [HOCI]-q,-V (12)

The resulting equations which must be solved simultaneously are:

where:

-b-C dc, Lebee (HOC Me. + .

Mn): "= m (13) dat V a-b

+7 M (1+5-C,)

d .b- a[HOC!] =—k, Hocn 22 Sn (14)

dt 1+6-C m

HOCLI:

a, b= empirical Langmuir Isotherm Constants

k> = k,/A; where A = V-MWuoci/Mee : MWnan

77

3. Model Estimation Technique. The Runge-Kutta differential equation estimation

technique for initial value problems was used to approximate the solution of the

differential equations developed. The solution of the differential equations is an average

of values of the equation taken at different points in the interval x, < x > x»+;. The

formula is presented below:

Ynei =n +2 (ku + 2k, +2k,,3 +Kii4)

where

Kii=f Xn¥n)s

Ki =f (x +h +2 nk ) n2 n 3 Yn 2 nls

1 1 k = +—h,y,_ +—hk.,), n3 f@, 9 Vn 2 2)

kg = f (x, +h,y, +hk,,).

For this model, the independent variable (x) is reaction time and the dependent variable

(y) is soluble manganese concentration and HOCI concentration. The choice of the step

size, h, is critical in obtaining the most accurate representation of the equation(s) being

approximated. For the purposes of this model, a step size of 0.05 minutes or 3 seconds

was used for approximating the mass balance equations for the batch studies and a time

interval of 1-5 minutes for the CSTR estimations. For more detail on the Runge-Kutta

method, please refer to the text by Boyce and DiPrima.”

4. Model Results for Batch Studies. The rate constant “k” used for the model calculations

could not be calculated by laboratory experimentation because of the combination of

mechanisms associated with this term. For this reason, a rate constant was fitted to the

data for each of the batch experiments performed studying iron catalyzed manganese

removal via the adsorption-oxidation process at pH 8. Figure 28 provides a summary of

78

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the rate constant values determined for each of the batch experiments at pH 8. The ideal

outcome of such an exercise is for the best fit “k” to be a constant value over the range of

experimental conditions, signifying that the model provides a good prediction of the

observed results. As noted in Figure 28, the model seemed to provide a relatively good

prediction of the results as all of the rate constants predicted are within the same order of

magnitude. The average ‘k” value determined was 3.43 x 10°.

Figure 29 exhibits the fit of the rate constant value to a portion of the batch data

collected at pH 8 conditions. The points represent experimental data collected and the

lines a best fit of the model calculations using the optimum rate constant value (based

upon the residual sums of squares) for those specific experimental conditions (i.e. Fe(III)

concentration, pH, etc.).

5. Model for Continuous Flow System. The original equations (Equations 9 and 10)

presented for the mass balances of Mn(II) and HOCI were modified and differentiated

resulting in the following equations that must be solved simultaneously for the continuous

flow system:

d Mn(IT): Cu

dt

bC 'D'C O° Cy, ~ Qa Cu, ~ ky We ‘[HOCT]- a My. — ky Ay -[HOCT]. . m M sno

" ou 1+5C, 1+b'C,, 1 ab a'b' ( 5)

V+—_—____- M,, +. -M,, (1+ bC,,) (1+5'C,,)

tHocy; LOC dt

bC i

Q-[HOCI, ]-Q-[HOCI]-k, -tHocn. “2—"—.v—x, Hocn. 22. 1+ dC, 1+5'C,, 7 (16)

where: a’, b> = Empirical Langmuir Isotherm Constants

k3 = k,/B; where B = V-MWuocl!Mnno . MWwn

80

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Again, the Runge-Kutta method of differential equation estimation was used to

develop a solution to these equations. The resulting solution is an estimate of the effluent

Mn(II) concentration for a continuous flow system for the system parameters used in the

equations. The “k” value used in the model equations for the continuous flow system

(slurry reactor system) is the average value determined by the batch system model under

pH 8 conditions, 3.43 x 10°.

Figure 30 shows the model predictions for effluent Mn(II) and HOC]

concentrations assuming that only iron oxides participate in the adsorption and

subsequent oxidation of Mn(II). This assumption would hold only for the initial startup of

the reactor system because, as shown in Figure 23, the manganese oxide concentration

increases with time. One would expect that these manganese oxides would also

participate in the adsorption/surface oxidation steps as previously described, resulting in

lower effluent Mn(II) concentrations.

The “dip” in Mn(II) concentration predicted by the model for the conditions noted

is attributed to the transition from the rapid, adsorption step to the slower, oxidation step

of the reaction. Initially, the iron oxides present adsorb solution Mn(II) until the

adsorptive capacity of the oxides is expended. The effluent Mn(II) concentration begins

to increase until the oxidation of Mn(II) on the iron oxide surface begins resulting in a

sustainable, consistent effluent quality. Additional model estimations under various

operating conditions are provided in Appendix D; the bolded parameter indicates that

input was changed from the previous simulation provided. Generally, the model provides

a good indication of the importance of each of the key system parameters, however,

because of the limited amounts of data available under this work, the quantitative

accuracy of the model cannot be assessed.

82

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83

CHAPTER V

DISCUSSION

This chapter is intended to provide a thorough discussion of the results presented

in the previous chapter and to provide a basis for the development of meaningful

conclusions that can be taken from these studies. From the results previously presented it

appears obvious that some interaction does indeed occur between Mn(II) and oxidized

iron (Fe(III)) particles in solution at pH values between 6 and 8. Some important

considerations brought about during these studies are presented in the following sections.

A. Studies of Possible Mn(I) Removal Mechanisms

1. Formation of MnCQ3,,) and Adsorption onto CaCQ3 5). Because of the solubility

relationships between Mn(II), Ca**, and CO3” ,which are affected by solution pH, it was

necessary to determine if either MnCOx) formation or CaCO3,,) formation could directly

affect the Mn(II) concentration. Previous researchers including Davies’ have noted the

interferences on Mn(II) oxidation studies at high pH levels due to MnCO3;,) formation

whereas others note that it is not a problem for up to 20 hours after saturation.””

Using the experimental parameters listed in Chapter III, a white precipitate was

observed in solution after a period of approximately 60 minutes. This observed

precipitate corresponded with a reduction in Mn(II) as noted in Figure 8. The Ca’? in the

solution makeup was replaced with an ionic strength equivalent of Na’ to eliminate the

formation potential of CaCO3). The Mn(II) removal observed as depicted in Figure 9,

was considerably less when compared to the previous experiment indicating that

MnCO;,,) formation plays a minor role Mn(II) removal; thus, CaCO3,,) formation and the

adsorption of Mn(II) onto its surface or co-precipitation was primarily responsible for the

observed Mn(II) reduction.

At pH 8, no precipitate was observed during testing and subsequently the Mn(II)

concentration was effectively unchanged as summarized in Figure 10. For this reason,

84

subsequent experimentation was conducted at solution pH less than 8 pH units so that

these solid formations could not interfere with the iron catalyzed Mn(II) removal studies.

(Recall that the field data shown in Table | was taken under solution pH ranging from

73-7.5.)

2. Solution Phase Oxidation. Several researchers have noted the ineffectiveness of HOCI

to oxidize Mn(II) in solution.''** Studies were conducted to confirm these findings to

ensure that the unique set of experimental conditions used during these studies would

produce similar results. Studies, the results of which are shown in Figure 11, conducted

at pH 7 and 8 confirmed the findings of previous researchers that Mn(I]) is not effectively

oxidized by HOC] at pH levels less than 8 pH units. The experiment at pH 8 was allowed

to continue for a period of 21 hours at which point a reduction of only 6% of the initial

Mn(II) was measured; this further indicates the slow kinetics of such oxidation. Once a

MnOx;) surface develops in solution, one would expect the oxidation kinetics to increase

substantially as the surface serves as a site for adsorption as noted by Morgan and

Stumm” and enhances the oxidation of the sorbed Mn(II) as observed by Hao”*. As noted

by Knocke et al.', however, the slower oxidation kinetics observed can be attributed to

the depressed temperature of 10° C used during experimentation. The formation of

MnO,xis) was subdued by the lower temperatures and the neutral pH conditions, both

factors that affect the release of H” from the Mn(II) surface in turn affecting the

. + . . . . +

reduction-oxidation reactions which occur via transfer of electrons (H').

3. Adsorption of Mn(II) onto Freshly Precipitated Iron Oxides. One hypothesis for the

reduction in Mn(II) in the field studies was the adsorption of Mn(II) onto the oxidized

Fe(III) surface. However, as summarized by Figures 12 and 13, the capacity for Mn(II)

by the Fe(III) surface ts relatively small. The observed Mn(II) adsorption was indeed

solely adsorption on the Fe(III) surface rather than entrapment of Mn(II) within forming

Fe(III) flocs as Mn(II) was added after Fe(II) oxidation during all adsorption studies. This

85

is one aspect of the experimental techniques that differs from that experienced under

water treatment plant conditions. Normally, the reduced metal species are part of the raw

water makeup and have the ability to interact at all phases of the treatment process. The

technique used during these studies allows one to quantify that Mn(I]) removal which can

be solely attributed to adsorption onto the Fe(III) surface and the Mn(ID) removal

occurring as a result of other processes. Also, it allows for the development of isotherms

for the adsorption of Mn(II) onto Fe(III).

The type of adsorption that was observed between the Mn(II) and the Fe(IID)

oxides and Mn(II) and MnO, (;) is hypothesized to be physical adsorption, not chemical

adsorption. The bonds between the constituents in physical adsorption are typically

weaker than those in chemical adsorption, and the adsorption is oftentimes reversible

because of this fact. This was exhibited in the work presented by Lloyd et al.” for Mn(II)

adsorption onto MnO,,). The amount of Mn(ID) that is adsorbed by the Fe(II) oxides is

dependent upon the amount of Mn(ID) in solution and the temperature.

Several different isotherm theories have been developed, the most well known

being those by Freundlich and Langmuir. Freundlich theory most often applies to carbon

adsorption where there is a linear response between the logarithm of the solute

concentration and the logarithm of the amount adsorbed per unit weight of adsorbent.

However, in cases where a maximum capacity is observed, Langmuirian theory applies.

(The data collected during these studies were tested using both Langmuir and Freundlich

theory with Langmuirian theory more closely predicted the data. These calculations are

included in Appendix C.) As noted in Figure 12, a maximum capacity was observed in

each of these adsorption studies. Therefore, the key assumption of Langmuirian theory is

satisfied, a fixed number of sites are available for adsorption on the surface of the

adsorbent.” Although it is difficult to conclude with the number of data points shown,

the same theory could be applied to Figure 14 for the adsorption of Mn(II) onto purified

Fe(III) oxides.

86

As previously reported the observed capacity of the Fe(III) surface for Mn(ID) at

pH 8 was 0.005 mg Mn(II)/mg Fe(IH]). When compared to the results of Davies* who

conducted similar experiments, the values appear to be significantly lower than those

Davies reported. Figure 31 shows a plot of data taken from Davies’ work with the data

point collected under these studies at pH 8 plotted. One would expect the point to lie

closer to the line indicated for lepidicrocite rather than geothite since the Fe(II) oxides

used in these studies were a “fresh” precipitate.

Naturally, when two studies are conducted using different methods by different

researchers, results will differ; however, some explanation must exist for this rather large

discrepancy. One key difference is in the preparation of the iron oxide particles used

during experimentation. The oxides used during these studies were formed in solution

immediately prior to the addition of the Mn(II). These solids were also exposed to the

ionic strength of the test solution for a period of time prior to Mn(ID addition. Davies

prepared his iron oxides in advance, washing them with distilled water and storing them

in a plastic container. Thus, when his solids were to be used they had not been exposed

to the ionic strength of the solution, instead the adsorption sites were free of sorbed

particles until added to the test solution.

A key experimental parameter when conducting these studies is the length of time

allowed for an equilibrium to occur between the Fe(III) surface and the Mn(II) in solution.

Several initial tests using relatively small Fe(III) concentrations were conducted

measuring the Mn(IJ) concentration over prolonged time periods. These results, plotted

in Figure 32, indicated that the equilibrium between Mn(II) and Fe(IID occurred within 5

minutes of interaction as the Mn(II) concentration did not change significantly over the

remainder of the reaction time. For this reason, the adsorption data collected as part of

this work were collected after 5 minutes of interaction between the Mn(II) and Fe(III).

An oversight in this decision was the lack of investigating the required equilibrium time

when higher concentrations of Fe(III) were studied. Perhaps, because of the increased

amount of surface present when higher Fe(III) concentrations are used, the time required

for adsorption equilibrium to be reached may be somewhat longer. In addition, the

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depressed temperatures used during these studies (10°C) compared to the 25°C used by

Davies’ could affect the rate of adsorption significantly. Metcalf and Eddy, Inc.®’

suggests that lower amounts of adsorption occur at lower temperatures; this was

seemingly confirmed by the results of this study. This may explain a portion of the

difference noted between the results of these studies and those of Davies’.

The results of this study could also be compared to those of Lloyd et. al.”’ who

presented Langmuir isotherms for Mn(II) adsorption onto hydrated iron oxides (Fe(II))

and MnO, at 10°C. Sung and Morgan” also present adsorption data for Mn(II) onto the

Fe(III) which is noted only for reference. Lloyd et al.°’ noted that adsorption equilibrium

was observed to occur after a period of only five minutes, the same time period used for

the studies presented by this paper. The authors reported that at a solution pH of 8.0, the

maximum adsorption ratio is 0.05 mg sorbed Mn(II) per mg of Fe(IID) compared with a

ratio of 0.005 mg Mn(II)/mg Fe(II) observed during the studies conducted for this paper.

One potential cause for this order of magnitude difference in adsorption ratios is the ionic

strength of the solution used during this research is approximately 2.5 times that used by

Lloyd et al.’ in the collection of their data. Therefore, numerous ions are competing for

the limited number of available adsorption sites on the oxide surface; this in turn may

reduce the amount of observed Mn(II) adsorption.

Obviously, a discrepancy exists between the data presented by these three studies.

Most likely, these differences can be attributed to the properties of the iron oxides used in

each study. The manner in which these solids were formed affects their chemical

characteristics significantly. To provide a true comparison of the results between these

three studies, an analysis of the surface areas of the iron oxides used would be required.

Unfortunately, this was beyond the scope of this research. Thus, it is recommended that

future researchers thoroughly investigate, accounting for temperature, surface area

variability and other factors, the required equilibrium time that should be used to study

the Mn(II) adsorption or other species adsorption onto a surface.

90

The noted adsorption of Mn(II) onto the Fe(III) surface obviously had some effect

on the removal of Mn(IJ) from solution; however, the next phase of the research focused

on the possible catalyzing effect the oxidized iron surface has on the sorbed Mn(II). The

primary question to be addressed was whether or not the iron oxide surface could assist

and serve as a catalyst in the oxidation of Mn(II), similar to the phenomenon observed

when MnOx,) is present in solution.

B. Mn(ID) Removal via Surface Catalyzed Oxidation of Mn(I]) with Fe(II) Oxides

Although the iron surface does not provide as much adsorptive capacity as an

MnO,;;) particle with respect to Mn(II) adsorption, it is much easier to oxidize Fe(II) than

Mn(II) using weaker, less expensive oxidants under normal water treatment and pH

conditions. While it is possible to develop an MnO,;,) particle in solution using stronger

oxidants, the resulting particle is often not of sufficient size nor electrostatically stable to

be settled or filtered from solution. Thus, the use of the iron oxide particle as an initial

adsorption surface upon which particle growth can occur is a possible Mn(II) removal

scheme that appeared to be worthwhile and was further investigated during these

experiments.

As noted in Figure 15, when Fe(II) is concurrently oxidized with Mn(II) in

solution, a true representation of the rate of Mn(II) oxidation via catalyzation of the

Fe(II) cannot be studied. Although this is the condition that would occur under water

treatment plant conditions, it was first necessary to determine how much of an effect the

Fe(III) surface had on Mn(II) oxidation. Thus, the remainder of the experiments

conducted were performed by first oxidizing the Fe(II) to Fe(III) via oxygenation and then

applying the desired concentration of Mn(II) into solution. This eliminated the potential

for Mn(1I) being trapped in the forming Fe(III) floc particles.

Figures 16 and 17 clearly indicate the catalyzing effect higher concentrations of

iron oxides have on the oxidation and removal of Mn(II) from solution. Regardless of the

solution pH, an increase in Fe(III) concentration corresponds to an increase in the rate of

9]

Mn(II) removal. Note that the results plotted in Figures 16 and 17 show the combined

effects of the removal of Mn(ID as a result of adsorption onto the Fe(III surface as well

as the surface catalyzed oxidation step. Time zero for these plots is the start of the

adsorption step; chlorine was added after a period of five minutes.

Another key observation in the analysis of the data presented is the comparison

between the expected versus actual HOC] demand with respect to the removal of Mn(iI)

from solution. Assuming that the Mn(II) is immediately oxidized once it has been

adsorbed by the Fe(III) surface would be an incorrect assumption according to Figure 18.

This suggests that the oxidation of Mn(II) once on the surface is slow when compared to

the adsorption step. This fact was utilized in the development of the model that was

presented in Chapter IV. However, the Mn(II) oxidation rate by HOC is still enhanced

by the presence of the surface in that it is much more rapid than solution phase oxidation.

Taking a closer look at the actual rate of Mn(II) removal due to the Fe(III surface

catalyzed oxidation step and adsorption, it would be expected for the reaction order to be

at least one as is normally the case under a catalyzed condition. However, as exhibited in

Figure 19 which provides an analysis of the surface catalyzed oxidation rate, this is not

true as the reaction order actually approaches zero.

This is initially puzzling until the combination of mechanisms responsible for the

observed outcome are considered. Essentially, three mechanisms are acting

simultaneously to remove Mn(II) from solution:

1. Mn(ID adsorption onto Fe(iID,

2. Mn(II) oxidation on Fe(III), and

3. Mn(D) adsorption onto MnO x,).

The data plotted in Figure 19 remove the first mechanism from consideration as the initial

data point at time zero follows the adsorption step of Mn(ID onto Fe(III). Thus, the plot

exhibits the reduction in Mn(ID due to its oxidation on the Fe(III) surface and its

adsorption onto the formed MnO,;,) surface on the Fe(III) particle. The combination of

92

these mechanisms may indeed result in an overall zero order reaction. Unfortunately,

these two mechanisms could not be separated for individual study to determine the role

each plays in Mn(II) removal. However, the development of an MnOx.) surface on the

Fe(III) oxide, as also noted by Lloyd et al.,°’ may provide an explanation for the constant

rate of Mn(II) removal observed. As the Mn(II) concentration decreases in solution (as it

is adsorbed and oxidized on the Fe(III) surface), the MnO,;;) surface that develops has a

greater affinity for Mn(ID than the Fe(III) surface. The result is what appears to be a

constant Mn(IJ) removal rate; actually the catalyzed Mn(II) oxidation rate has slowed, but

the MnO,,.) adsorption has counteracted this reduction in the rate of catalyzed Mn(II)

oxidation.

When analyzing the reaction rates for Mn(II) oxidation in the presence of Fe(III),

the rate is observed to increase with an increase in the Fe(III) concentration as exhibited

in Figure 20. (Note, however, that the rate over the Fe(III) concentrations studied does not

change a great deal based on the range of the y-axis values.) However, if the reaction rate

is normalized with respect to the iron oxide concentration, as shown in Figure 33, the

opposite is true as the reaction rate decreases with increase in Fe(III) concentration. This

outcome is not surprising based upon the nature of the oxidized iron product,

predominately Fe(OH)3;). The product is somewhat amorphous and flocculent, therefore

some agglomeration of iron oxide particles will occur. Assuming such interaction

between the iron particles, not all of the iron added to solution results in additional Fe(III

surface for catalyzing Mn(I]) oxidation.

The interaction noted during these experiments between the Fe(III) oxides and

Mn(II) have also been noted by other researchers as well.”°°°°°? Lloyd et al.°’ noted that

during the adsorption experiments for Mn(II) onto Fe(III), the adsorbent color changed

from the orange associated with iron to a chocolate brown indicating the possible

presence of MnO x) as well. Wilson” also noted that Mn(II) oxidation is indeed

catalyzed by the iron surface similarly to that observed in the presence of MnOy). Sung

and Morgan” reported that the oxidation rate of Mn(II) on freshly precipitated Fe(III) was

93

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approximately equal to that of Mn(II) onto MnO,)._. However, an assumption made

when analyzing the rate data appears to be unacceptable based upon the findings of this

work; it was assumed that “the surface is not altered significantly with the surface

2.99.58 used excessive concentrations of Mn(II) oxidized species.” Several researchers

(2.75-5.5 mg/L) to study the induced oxidation rates. The reaction rate would be

expected to slow as Mn(II) is reduced; therefore, the catalyzing effect is more evident

when higher Mn(II) concentrations are used. The studies presented under this work were

intended to study the catalyzed oxidation under more typically observed Mn(II)

concentrations for water treatment.

°2.55.56.59 results discussed conducted their Each of the previous researchers

experiments in the presence of oxygen whereas the testing conducted during this research

used a more powerful oxidant, chlorine. As noted by studying the results presented by

Wilson”? and Lloyd et al.,”’ elevated pH values are required for Mn(II) oxidation to occur

in a timely manner. Lloyd et al.”’ also noted that as a result of higher pH values being

used, as MnO,,) develops in solution, the suspension of particles becomes more difficult

to settle as the zero point of charge for MnO,;,) lies between 2.8 and 4.5 pH units.

Because of the elevated pH used by Lloyd et al.,°? Ca’, which could normally help to

stabilize the MnOxs),° > may instead be precipitated out of solution as CaCO3;). As noted

previously, the solution pH used during this research does not allow for the precipitation

of CaCOx,,), leaving Ca” available for stabilizing the MnO,;) that forms. Also, through

the use of a stronger oxidant such as chlorine, the reactions proceed much more rapidly,

allowing for treatment under typical water treatment conditions without requiring longer

detention times.

The next phase of the research simulated water treatment plant conditions, to test

a high solids reactor system that can be utilized to remove both iron and manganese from

solution using chlorine as an oxidant. The use of such system appears to be a more viable

option that the typical groundwater treatment system employed currently (Figure 1).

95

C. Fe(III) Oxide Slurry Reactor System and Mn( I) Adsorption onto MnO ys)

From the discussion presented thus far, it is apparent that Mn(II) oxidation can

indeed be enhanced by the presence of Fe(III) and the use of HOC] as an oxidant. This

portion of the research sought to develop an acceptable bench scale reactor system that

could be employed at a water treatment facility for the removal of Mn(II) and Fe(II) from

solution. The system presented here could also be used for surface water supplies

containing Fe(II) and Mn(II), but the water must have a low organic content as HOCI is

used as the oxidant which is known to form harmful by-products, trihalomethanes and

haloacetic acids.

One note when considering the results presented for the slurry reactor system is

that the experimental design was unable to maintain the temperature throughout the

experiments at 10°C, instead the temperatures within the reactors were maintained

between 13-20°C. This should improve performance as adsorption and oxidation rates

should increase with temperature.

The initial results presented in Figure 21, prove how vital the presence of an

oxidant is and that the observed phenomenon is not merely an adsorptive process. Ina

matter of hours the effluent Mn(II) concentration approaches that of the influent

concentration. This result occurs once the adsorptive capacity of the large concentration

of Fe(III) oxides has been expended. (Note that breakthrough occurred first in the reactor

that contained a smaller concentration of Fe(III) oxides.) The pH of the solution is

slightly less than 7 which is not conducive to adsorption processes which prefer higher

pH conditions (resulting in a more negatively charged particle as H” is expended from the

surface site). Also note that no additional HOCI was added to solution to assist with

Mn (I]) removal, but there was a 1 mg/L residual in the tap water fed through the system.

However, this amount of HOC] is inadequate to oxidize the Fe(II) being fed to the system

which would require a minimum of 1.28 mg/L HOC] as dictated by stoichiometry’. Thus,

little or no HOC] was available for Mn(II) oxidation.

96

Following the addition of supplemental HOCI to the system (Figure 22), the

effluent Mn(II) concentration rapidly decreased to levels well below the SMCL of 0.05

mg/L despite the pH being held less than 7 standard units. The use of chlorine in the

system provides several advantages over the conventional oxidants used for Mn(II)

removal:

e Stronger oxidant than oxygen allowing for more rapid reaction times at lower

pH values,

e Provides a disinfectant residual which will be required following the

implementation of the Groundwater Treatment Rule,

e Allows the Mn(II) to be adsorbed onto larger Fe(III) particles rather than

oxidizing the individual Mn(iI) particles (as potassium permanganate would

do) providing for the settling or filtration of the combined particles from

solution,

e HOCl is more flexible to changes in raw water quality; permanganate will turn

water pink if overdosed due to sudden decrease in Mn(II).

As alluded to previously, however, HOC! would not be an acceptable choice for waters

laden with organic materials. In general, the successful performance of the system

required that a residual of HOC] exist in the effluent. This indicated that the oxidant

demand of the system had been satisfied. Normally, a HOC! residual of 0.50 mg/L was

associated with superior reactor performance.

Part of the discussion in the previous section suggested that MnO,;,) developed on

the iron surface or was intermixed with the iron particles as the process continued over a

period of time. A portion of the work conducted on this new system was devoted to

understanding the effect that each of these oxide forms had on the removal of Mn(II)

from solution. Data were collected in all experiments on the influent, effluent, and in-

reactor concentrations of Mn(II) and Fe(ID/Fe(IID to study the possible “growth” of

97

MnO,;s) within the system. A portion of the data collected is plotted in Figure 23 which

provides some enlightening information to the processes occurring within the slurry

reactor system. Note the extended time period over which these results were taken as

well as the trends that are evident. While the concentration of Fe(III) in the reactor

decreased to a relatively constant value, the concentration of MnO,;,) within the system

increased.

This observation is important for several reasons; first, it is believed that during

the initial stages of operation only this steady-state concentration of iron particles

participates in catalyzing Mn(II) oxidation. These particles, encapsulated by a MnO)

coating, grow in size helping them to settle rather than “washing out” of the reactor.

Once a sufficient coating of MnO,;,) develops, this surface is believed to dominate the

adsorption and oxidation of Mn(II) in solution. The freshly precipitated iron particles

formed via oxidation and those remaining from the initial slurry do not participate and are

washed out of the system because of their smaller size. Thus the steady-state iron slurry

concentration most likely represents those particles initially encapsulated by MnOxs)

coatings.

Another point that should be noted from these observations and the data

summarized in Appendix A is the importance of reactor hydraulics and design. The

reactor system used in these experiments was not optimum as was evidenced by the loss

of solids from the system. Ideally, these solids should settle from solution, and the slurry

concentration would increase with time. Thus, a wasting of solids similar to the practices

of a wastewater treatment plant would be used to maintain system control. The use of a

settling aid polymer was not investigated, but is recommended during future studies if

similar problems persist.

Based upon the data collected, the lack of settling cannot be solely attributed to

the formation of particles (i.e. MnO) that are far from their zero point of charge. The

loss of solids was a problem continuously experienced by the system and periodically

small upsets due to reactor hydraulics would result in additional loss of solids. The

98

reactors used in these experiments were indeed “‘bench-scale”; because of this fact they

were unable to absorb minor system changes as well as a full scale reactor would.

However, improvement was noted in retention of solids when the hydraulic detention

time within the reactor was increased from 1 hour to 2 hours. The results presented were

all observed using a 2 hour hydraulic detention time with the exception of the data

presented in Figures 21 and 22.

The lack of defined mixing conditions is another deficiency of the conventional

groundwater treatment facility for iron and manganese removal. The use of gentle mixing

proved to be very beneficial to the success of the system. Without providing for

interaction between the particles, adsorption would be curbed as well as the exposure of

the adsorbed metal species to an oxidant source. However, mixing intensities should be

maintained at levels consistent with flocculation, not rapid mix. The floc particles that

were observed during these studies were very fragile in nature. As previously mentioned,

the inability to stabilize and rectify the negative surface charge of MnO x) particles can

lead to failure of the system.

The previous point provides insight into another benefit of the proposed system,

the increased opportunity for particle interaction and flocculation. Flocculation theory for

orthokinetic flocculation (equation shown) indicates the rate of flocculation is

proportional to the square of number of particles and to the cube of the particle diameter.

~2EGD° N* Rate of Orthokinetic Flocculation = (17)

where: € = collision efficiency factor

G = velocity gradient

D = particle diameter

N = particle concentration

Thus, the slurry reactor system (which resembles that of a solids contact unit)

provides a significant number of particles for interaction. Also, because the particles

grow via adsorption and subsequent oxidation, the diameter of the particles is

99

continuously growing. In this manner the flocculation of the particles is significantly

enhanced allowing for the formation of larger, more settleable particles. Based upon the

experimental methods used the particle sizes exceeded 0.45um as minimal difference was

noted between the filtrate of the 30k ultrafilters and the 0.45um filters.

Because of the seemingly dominant role MnO,,,) has in catalyzing Mn(II)

oxidation over time, its adsorptive properties for Mn(II) for use in this study were

investigated. The adsorptive capacity observed for Mn(II) by MnOx;s) was reported

earlier as 0.20 and 0.21 mg Mn(ID/mg MnOx,;) at solution pH of 7 and 8, respectively.

Lloyd et al.°’ conducted similar experimentation at 10°C and reported a maximum

adsorption ratio at pH 8 of 0.7 mg Mn(II)/mg MnOx,;)._ In the well known work of

Morgan and Stumm”®, the adsorptive capacities of MnO,;;) for Mn(II) were observed to

be 0.31 and 0.76 mol Mn(II)/mol MnO.) at pH 7 and 8, respectively (these values

translate to 0.20 and 0.48 mg Mn(II)/mg MnO,;,), respectively). Again, a wide range of

results is noted between the different results reported. Most likely this can be attributed

to the formation and the chemical properties of the MnOxs) particles formed by each

researcher. Again, without taking a measurement of the surface areas it is difficult to say

that the MnO.) particles formed by each are “equal.”

Regardless of which values are compared versus the results previously presented

for Mn(II) adsorption onto Fe(II), the capacity of the MnO,;,) surface far exceeds that of

the Fe(III) surface. This explains the outstanding performance of the slurry reactor

system once sufficient MnOx:s) surface had been developed within the reactor. As noted

in Figures 26 and 27, only when the system is starved of HOC] does it approach a failure

condition. Figure 27 provides a glimpse of the system performance under various

chlorine conditions. After approximately 20 hours of operation at a 1 mg/L dose of

HOCI, the HOC]! dose is increased to 2 mg/L, a minimal amount for the influent levels of

Fe(II) and Mn(ID) entering the system (stoichiometry dictates that just under a 2 mg/L

dose of HOC! will satisfy the requirements for the influent Mn(IJ) and Fe(II)). Reactor

performance is outstanding for this minimal dose of oxidant. The presence of the MnOxs)

100

particles in solution provide stability to the system as well as absorbing slight fluctuations

in influent Mn(II) and HOCI concentrations. The Fe(II)-oxide only system does not offer

the same abilities primarily due to its lack of Mn(II) adsorptive capacity.

However, as previously mentioned the Fe(III) particles do serve a vital purpose in

the system performance in that they are believed to be the initial site of Mn(II) adsorption

and subsequent MnO,x;,) formation. This provides for the formation of larger, more

settleable particles that can be removed via conventional solids-liquid separation

technologies. As has been stated previously, the oxidation of Fe(II) and Mn(II) can be

accomplished rather simply using stronger oxidants, however, the removal of the

oxidized particles from solution can be difficult. Treatment for the removal of iron and

manganese is a two step process:

(1) oxidize the metal species to an insoluble form and

(2) remove the oxidized particle(s) form the finished water.

The second item is often overlooked when devising an effective iron and manganese

removal strategy!

From the previous discussion and results presented it is apparent that the proposed

reactor system will provide acceptable levels of effluent Mn(II) provided sufficient HOC]

is provided. However, the same cannot be said of reactor performance at pH 6 as

depicted in Figure 27 toward the end of the experimentation. What was observed under

this scenario appeared to be desorption of Mn(II) and an upset in system performance.

At the lower pH conditions, adsorptive capacities decrease as the H” ions more effectively

compete for adsorptive sites on the surface of the oxide particles. This in turn reduces the

ability of the oxides to enhance Mn(II) oxidation.

D. Model Results

1. Batch System Model. The batch system model was primarily used as a means of

determining an appropriate rate constant value (k) to be used in the continuous flow

model to be discussed in the next section. The results of the batch system model

101

provided some insight into the mechanisms of Mn(II) removal that were observed during

experimentation.

The model does not appear to fully account for all of the Mn(II) removal

mechanisms that occur at the various Fe(II) concentrations as there was some variability

in the rate constant values determined. Under a perfect modeling condition, the model

would predict the observed data over the range of conditions under study with no

variability in the rate constant value. However, as observed in Figure 28, this was not the

case for the pH condition modeled by this work as there is minor variability in the model

predicted rate constants as the slope of the line indicates.

As the model was developed it was formulated using Freundlich isotherm theory

and also formulated using Langmuir isotherm theory. The two models were conducted in

a “side-by-side” comparison to determine which provided a better representation of the

observed data. The comparison showed that the Langmuirian model provided a better fit

of the predicted results to those observed in the laboratory as the residual sums of squares

was lower. (The results of this comparison are provided in Appendix D.) It should be

noted that other isotherm theory exists that was not considered under this work, therefore,

it should not be implied that the Langmuir isotherm used in this modeling exercise will

hold true in future research efforts. It is important to again note that the oxide particles

formed during experimentation are somewhat unique and can be site specific, and thus

future researchers should investigate all isotherm theories for the proper representation of

their data.

2. Slurry Reactor System Model. As shown in Figure 30, the model developed provided a

good representation of the importance of the key system parameters noted in previous

discussion of the slurry reactor system. As previously mentioned, the quantity of data

collected under these experiments was insufficient to conduct a full comparison on the

quantitative accuracy of the model presented. However, several model simulations have

been provided in Appendix D under various operating conditions, changes in detention

102

time, iron concentration, HOCI concentration, influent Mn(II), etc., to exhibit the

importance and effect each of these parameters have on system performance. The model

seems to be able to predict trends, similar to those observed during the laboratory studies.

One parameter that was included in the model equations that was not included in

the modeling exercise was the adsorption of Mn(II) onto the MnO, that is hypothesized

to form on the outside surface of the iron oxide particles. As exhibited in the results

presented, this surface has a much greater adsorptive capacity and has been observed to

serve as a catalyst for Mn(II) oxidation.”? Also, it was previously noted that this oxide

surface does indeed provide stability to the system under conditions where the system

would normally be stressed and approach failure. The inclusion of this term in the model

should be considered further in future research. This will require more data collection to

include the oxidation rate of Mn(II) in the presence of MnO,;,) and quite possibly a term

to describe the growth of MnO, ;s) in the system over time as was observed and noted in

Figure 23. Model simulations including this term and the surface oxidation term for

Mn(II) adsorbed onto the MnOx(s) surface are included in Appendix D.

The same type of solids accumulation term should be included for the iron oxides

within the reactor system. Although from the data collected during these studies the iron

oxide concentrations within the reactor system were observed to decrease to a steady state

concentration over time, this was believed due to the hydraulics of the system used.

Thus, 1t would be expected that the iron oxide concentration would also increase as the

influent Fe(II) is oxidized to a solid Fe(III) particle.

Overall, the model presented here offers insight into the mechanisms that were

observed to affect the removal of Mn(II) from the system. Generally speaking, it does

predict the response in the effluent quality that would be expected from the changes made

in the system parameters. Thus, this model provides a good baseline for the development

of future models describing this phenomenon. These future models may provide

additional input parameters, the ability to input a specific pH condition, or simply use a

larger data set for comparisons between the model predicted results and those observed

103

experimentally. It is vital that prior to using the model developed herein, that sufficient

data be collected for model calibration.

104

CHAPTER VI

SUMMARY & CONCLUSIONS

A. Summary of Results

An important consideration concerning the oxidation of Mn(II) is its subsequent

removal from solution by solid-liquid separation techniques (i.e. filtration, etc.). This

often poses more of a problem than actual oxidation as the species formed following

oxidation carry a significant negative particle charge which must be neutralized for

effective settling and/or filtration. Although the oxidation of Mn(II) can be

accomplished, it is important to understand that Mn(II) removal is a two-step process;

oxidation followed by removal of the insoluble manganese product from solution.

The results of these studies suggest that surface catalyzed oxidation by the iron

surface may be a valuable technology to utilize for both iron and manganese removal.

These data confirmed the field observations that soluble manganese interacts with iron

oxide solids. It was hypothesized that the manganese in solution initially adsorbs to the

iron surface after which the catalyzed oxidation occurs.

While this indicates that Fe(OH) (s) could enhance Mn(II) removal via HOC!

oxidation (catalyzed oxidation), the low concentrations of iron present in most waters

would not provide enough surface to significantly improve Mn(II) removal. Thus, an

engineered system was developed involving oxidized iron particles in a slurry reactor

similar to solids contact units. By increasing the number of iron particles within the

treatment basin, flocculation and removal of iron can be significantly improved. This in

turn will enhance manganese removal because of the adsorptive/oxidative interaction it

has with the iron surface.

The proposed system which is depicted in Figure 34, offers several advantages

over the conventional groundwater treatment system for iron and manganese removal.

These include:

e Increased number of particles (for flocculation)

105

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e More economical; HOC! relatively inexpensive oxidant for Mn(II) removal

e Groundwater Disinfection Rule will require disinfection

e Larger particles; increased sedimentation decreasing filter loading

e More flexible to changes in water quality (chemical dosing not as critical with

HOCI)

Additional information concerning the performance of the newly engineered reactor

system was also discovered under this research effort. The most critical observation was

the dominance that the MnO xq) that forms over time has on system performance.

Because of its high adsorptive capacity for Mn(II), MnO,(s) provides the system with

additional stability which allows for minor changes in HOCI dose or Mn(IJ) concentration

to be adsorbed by the system.

The success of the slurry reactor system as reported by these studies indicates that

it has potential for improving the conventional means of groundwater treatment for iron

and manganese removal. However, additional research is required to better define key

system parameters and to develop a more detailed model for such a system. Also, the

problems associated with the settling of the particles should be further assessed to

determine if it is solely due to reactor hydraulics, and if polymer addition can alleviate the

problem.

B. Conclusions

Several conclusions can be drawn from the results presented in this paper:

(1) The interaction noted between Mn(II) and Fe(III) at the groundwater

treatment facility under study is the result of a combined adsorption-

surface oxidation reaction that occurs on the surface of the iron oxide

particle.

107

(2) The rate of Mn(II) adsorption-surface oxidation increased with increasing

concentration of iron oxides.

(3) The proposed slurry reactor system offers an effective solution to the

Mn(I) removal problems encountered by existing groundwater treatment

systems by utilizing the interactions observed.

(4) The key system parameters for the slurry reactor system include iron oxide

concentration, pH, chlorine concentration, and detention time.

(5) Over long periods of operation, the manganese oxide surface dominates

the adsorption-surface oxidation of Mn(II) in the system resulting in

improved performance and greater system stability.

C. Areas of Future Research

The results of these studies indicated that the conventional treatment schemes

used currently can be done more efficiently and with higher levels of performance.

However, to fully grasp the potential that the system presented by these studies offers,

additional work should be performed. The system parameters that should be used in the

design of a full-scale system should be better defined. The results presented by this study

indicated that the following are key design parameters:

e hydraulic detention time

e oxidant dose

e relative concentrations of iron and manganese oxides within the system

e solution pH

However, additional research is required to better define the recommended limits of these

parameters and to develop a more detailed model for such a system.

The problems associated with the settling of the particles should be further

assessed to determine if it due to reactor hydraulics or other factors such as detention

time, clarifier overflow rates, or mixing intensity. The use of a polymer to assist in the

108

flocculation and settling of the particles should also be studied to determine if this could

alleviate the problem.

Finally, the model presented has several deficiencies that should be addressed in

the development of a new model that allows for more variation in system parameters. For

example, the model presented with this work only applied to the pH 8 conditions as

accurate isotherm and oxidation rates were only measured for this condition. A model

with a pH term included would add a great deal of flexibility to determining optimum

ranges of operation. Secondly, the model presented also assumes that the iron and

manganese oxide concentrations remain constant which as presented previously is not the

case. This was an assumption made to simplify the model that should be allowed to vary

in future modeling efforts on the system presented. These are two examples of model

deficiencies that currently exist with the model presented herein that should be addressed

in future work. Again, it is stressed that prior to using the model developed during these

studies further, it should be calibrated to insure its accuracy.

The results presented in this paper will hopefully stimulate future researchers to

further investigate this apparently useful phenomenon.

109

CHAPTER VII

REFERENCES

1. Knocke, William R. ef af; American Water Works Association Research Foundation

Report: Alternative Oxidants for the Removal of Soluble Iron and Manganese.

March 1990.

2. Davies, Simon H.R. Thesis, Mn(II) Oxidation in the Presence of Metal Oxides.

California Institute of Technology. 1985.

3. Adams, Reginald B. “Manganese Removal by Oxidation with Potassium

Permanganate.” Journal of the American Water Works Association, 52:2:219-228

(February 1960).

4. Weng, Cheng-nan et a/. “Ozonation: An Economic Choice for Water Treatment.”

Journal of the American Water Works Association, 78:11:83-89 (November

1986).

5. Wong, James M. “Chlorination-Filtration for Iron and Manganese Removal.” Journal

of the American Water Works Association, 76:1:76-79 (January 1984).

6. Ponitus, Frederick W. “Complying With the New Drinking Water Regulations.”

Journal of the American Water Works Association, 82:2:32 (February 1990).

7. Knocke et al. “Impact of Dissolved Organic Carbon on the Removal of Iron During

Surface Water Treatment.” Unpublished Article.

8. Knocke, William R. ET AL.“Examining the Reactions Between Soluble Iron, DOC, and

Alternative Oxidants During Conventional Treatment.” Journal of the American

Water Works Association, 86:1:117-127 (January 1994).

\©

. Sung, Windsor and Morgan, James J. “Kinetics and Product of Ferrous Iron

Oxygenation in Aqueous Systems.” Environmental Science & Technology.

14:5:561-568 (May 1980).

10. Bowers, A.R. and Huang, C.P. “Role of Fe(III) 1n Metal Complex Adsorption by

Hydrous Solids.” Water Research. 21:7:757-764 (1987).

11. Posselt, Hans S. ef al. “Cation Sorption on Colloidal Hydrous Manganese Dioxide.”

Environmental Science & Technology. 2:12:1087-1093 (December 1968).

110

12.

13.

14.

15.

16.

17.

18.

19.

20.

21.

22.

23.

Morgan, James J. Chemical Equilibria and Kinetic Properties of Manganese in

Natural Waters (1967). in: Principles and Applications of Water Chemistry,

Samuel D. Faust and Joseph V. Hunter. eds., John Wiley and Sons, New York,

561-624.

Hoehn, Robert C. ET AL. “Effects of Storage and Preoxidation on Sludge and Water

Quality.” Journal of the American Water Works Association. 79:6:62 (June 1987).

Stone, Alan T. and Morgan, James J. “Reduction and Dissolution of Manganese (III)

and Manganese (IV) by Organics: 1. Reaction with Hydroquinone.”

Environmental Science & Technology. 18:6:450-456 (June 1984).

Stone, Alan T. and Morgan, James J. “Reduction and Dissolution of Manganese (III)

and Manganese (IV) by Organics: 2. Survey of the Reactivity of Organics.”

Environmental Science & Technology. 18:8:617-624 (August 1984).

Stone, Alan T. “Reductive Dissolution of Manganese (III/IV) Oxides by Substituted

Phenols.” Environmental Science & Technology. 21:10:979-987 (October 1987).

Bourg, Alaln C.M. and Bertin, Clotilde. “Seasonal and Spatial Trends in Manganese

Solubility of an Alluvial Aquifer.” Environmental Science & Technology. 28:5:868-876 (May 1994).

Morgan, J.J. and Stumm, Werner. “Analytical Chemistry of Aqueous Manganese.”

Journal of the American Water Works Association, 57:1:107-119 (January 1965).

Robinson, R. Bruce ET AL. “Iron and Manganese: Sequestration Facilities Using

Sodium Silicate.” Journal of the American Water Works Association, 84:2: 77-82

(February 1992).

McFarland, Wayne E. “Groundwater Treatment Alternatives for Industry: Part I: Iron

and Manganese Removal.” Plant Engineering. 62-66. July 11, 1985.

LaZerte, Bruce D. and Burling, Kirsten. “Manganese Speciation in Dilute Waters of

the Precambrian Shield, Canada.” Water Research. 24:9:1097-1101 (1990).

Zapffe, Carl. “The History of Manganese in Water Supplies and Methods for its

Removal.” Journal of the American Water Works Association, 25:5:655-676 (May

1933).

Hao, Oliver J. ET AL. “Kinetics of Manganese(II) Oxidation with Chlorine.” ASCE

Journal of Environmental Engineering.” 117:3:359-374 (May/June 1991).

Lil

24.

25.

26.

27.

28.

29.

30.

31.

32.

33.

34.

35.

36.

Van Beschoten, John E. ET AL. “Kinetic Modeling of Manganese(II) Oxidation by

Chlorine Dioxide and Potassium Permanganate.” Environmental Science & Technology. 26:7:1327-1333 (July 1992).

Knocke, William R. ET AL. “Using Alternative Oxidants to Remove Dissolved

Manganese from Waters Laden with Organics.” Journal of the American Water

Works Association, 79:3:75-79 (March 1987).

Hem, J. D. U.S. Geological Survey Water Supply Paper 1667-A pp. 52-59 (1963).

Hem, John D. “Rates of Manganese Oxidation in Aqueous Systems.” Geochimica et

Cosmochimica. 45:1369-1374 (1981).

Diem, Dieter and Stumm, Werner. “Is dissolved Mn?* being oxidized in absence of

Mn-bacteria or surface catalysts?” Geochimica et Cosmochimica. 48:1571-1573

(1984).

Kessick, Michael A. and Morgan, James J. “Mechanism of Autoxidation of

Manganese in Aqueous Solution.” Environmental Science & Technology. 9:2:157-

159 (February 1975).

Wilczak, Andrzej et al. “Manganese Control During Ozonation of Water Containing

Organic Compounds.” Journal of the American Water Works Association,

85:10:98-104 (October 1993).

Griffin, Attmore E. “Manganese in Water Supplies.” Journal of the American Water

Works Association, 52:10:1326-1334 (October 1960).

Jenkins, Stephen R. and Engeset. “The Cost of Effective Manganese Removal from

Wyoming Waters.” Journal of the American Water Works Association, 83:11:631-

633 (November 1975).

Posselt, Hans S. et al. “Coagulation of Colloidal Hydrous Manganese Dioxide.”

Journal of the American Water Works Association, 60:1:48-68 (January 1968).

Mathews, Everett R. “Iron and Manganese Removal by Free Residual Chlorination.”

Journal of the American Water Works Association, 37:7:680-686 (July 1947).

Ponitus, Frederick W. “An Update of the Federal Regs.” Journal of the American

Water Works Association, 88:3:36-46 (March 1996).

Alsentzer, Harry A. “lon Exchange in Water Treatment.” Journal of the American

Water Works Association, 55:6:742-752 (June 1963).

112

37. Willey, Benjamin F. and Jennings, Harry. “Iron and Manganese Removal with

Potassium Permanganate.” Journal of the American Water Works Association,

55:6:729-734 (June 1963).

38. Knocke, William R. ET AL. “Soluble Manganese Removal on Oxide-Coated Filter

Media.” Journal of the American Water Works Association, 80:12:65-70

(December 1988).

39. Knocke, William R. ET AL. “Removal of Soluble Manganese by Oxide-Coated Filter

Media: Sorption Rate and Removal Issues.” Journal of the American Water Works

Association, 83:8:64-96 (August 1991).

40. Morgan, James J. and Stumm, Werner. “Colloid-Chemical Properties of Manganese

Dioxide.” Journal of Colloid Science. 19:347-359 (1964).

41. Hem, John D. Equilibrium Chemistry of Iron in Ground Water (1967). in: Principles

and Applications of Water Chemistry, Samuel D. Faust and Joseph V. Hunter.

eds., John Wiley and Sons, New York, 625-643.

42 Theis, Thomas L. and Singer, Philip C. “Complexation of Iron (II) by Organic Matter

and Its Effect on Iron (II) Oxygenation.” Environmental Science & Technology.

8:6:569-573 (June 1974).

43. Jobin, Robert and Ghosh, Mriganka. “Effect of Buffer Intensity and Organic Matter

on the Oxygenation of Ferrous Iron.” Journal of the American Water Works

Association, 64:9:590-595 (September 1972).

44. Shapiro, Joseph. “Effect of Yellow Organic Acids on Iron and Other Metals in Water.

Journal of the American Water Works Association, 56:8:1062-1081 (August

1964).

45. Olson, Larry L. and Twardowski Jr., Charles J. “FeCO3 vs. Fe(OH); Precipitation in

Water Treatment.” Journal of the American Water Works Association, 67:3:150-

153 (March 1975).

46. Winklehaus, Charles ET AL. Discussion on “Precipitation of Iron in Aerated Ground

Waters.” ASCE Journal of the Sanitary Engineering Division. 92:SA6:129-137

(December 1966).

47. Ghosh, Mriganka M. ET AL. “Precipitation of Iron in Aerated Ground Waters.” ASCE

Journal of the Sanitary Engineering Division. 92:SA1:199-213 (February 1966).

113

48.

49.

50.

51.

52.

53.

54.

55.

56.

57.

58.

Cromley, J. Timothy and O’Connor, John T. “Effect of Ozonation on the Removal of

Iron from a Ground Water.” Journal of the American Water Works Association,

68:6:315-319 (June 1976).

Mouchet, Pierre. “From Conventional to Biological Removal of Iron and Manganese

in France.” Journal of the American Water Works Association, 84:4:158-167

(April 1992).

Stumm, Werner and Singer, Philip C. Discussion on “Precipitation of Iron in Aerated

Ground Waters.” ASCE Journal of the Sanitary Engineering Division.

92:SA5:120-124 (October 1966).

Morgan, James J. and Birkner, Francis B. Discussion on “Precipitation of Iron in

Aerated Ground Waters.” ASCE Journal of the Sanitary Engineering Division.

92:SA6:137-143 (December 1966).

Grossl, Paul R. “Rapid Kinetics of Cu(II) Adsorption/Desorption on Geothite.”

Environmental Science & Technology. 28:8:1422-1429 (August 1994).

Stenkamp, V. Susie Benjamin, Mark M. “Effect of Iron Oxide Coating on Sand

Filtration.” Journal of the American Water Works Association, 86:8:37-50

(August 1994).

Edwards, Marc. “Chemistry of Arsenic: Removal During Coagulation and Fe-Mn

Oxidation.” Journal of the American Water Works Association, 86:9:64-78

(September 1994).

Wilson, Donald E. “Surface and Complexation Effects on the Rate of Mn(II) in

Natural Waters.” Geochimica et Cosmochimica. 44:1311-1317 (1980).

Sung, Windsor and Morgan, James J. “Oxidative Removal of MnII) from Solution

Catalyzed by the y-FeOQOH (lepidocrocite) Surface.” Geochimica et

Cosmochimica. 45:2377-2383 (1981).

Davies, Simon H.R. and Morgan, James J. “Manganese(II) Oxidation Kinetics on

Metal Oxide Surfaces.” Journal of Colloid and Interface Science. 129:1:63-77

(April 1989).

Jenne, E.A. “Controls on Mn, Fe, Co, Ni, Cu, and Zn Concentrations in Soils and

Water: the Significant Role of Hydrous Mn and Fe Oxides.” in Trace Inorganics

in Water. Robert A. Baker ed. American Chemical Society. Washington. 337-387. 1968.

114

59. Lloyd, A. et al. “The Removal of Manganese in Water Treatment Clarification

Processes.” Water Research. 17:11:1517-1523 (1983).

60. Xyla, Aglaia G. et al. “Reductive Dissolution of Manganese(III, IV) (Hydr)oxides by

Oxalate: The Effect of pH and Light.” Langmuir. 8:1:95-103 (1992).

61. Zasoski, R.J. and Burau, R.G. “Sorption and Sorptive Interaction of Cadmium and

Zinc on Hydrous Manganese Oxide.” Soil Sci. Soc. Am. J. 52:81-86 (1988).

62. American Water Works Association and Water Pollution Control Federation.

Greenberg, Arnold E., Clesceri, Lenore S., and Eaton, Andrew D. Editors for

Standard Methods for the Examination of Water and Wastewater. 18th edition.

1992.

63. Instructions for Perkin Elmer Atomic-Adsorption Spectrophotometer Model 703 Norwalk, CT. May 1978.

64. Grady, C.P.L. and Lim, H.C. Biological Wastewater Treatment. Marcel Dekker, Inc.

New York. 1980.

65. Boyce, William E. and DiPrima, Richard C. Elementary Differential Equations and

Boundary Value Problems. John Wiley & Sons. New York. 1986.

66. Reynolds, Tom D. Unit Operations and Processes in Environmental Engineering.

PWS-Kent Publishing Company. Boston. 1982.

67. Metcalf and Eddy, Inc. Wastewater Engineering: Treatment, Disposal, and Reuse:

2nd Edition. McGraw-Hill, Inc. New York. 1979.

OTHER SOURCES

Anderson, Dewy R. ET AL. “Iron and Manganese Studies of Nebraska Water Supplies.”

Journal of the American Water Works Association, 65:10:635-641 (October

1973).

Baadsgaard, Marinus and Pai, Punda. “Iron and Manganese Removal in Groundwater

Wells.” Public Works. 122:2:59 (February 1991).

Bourg, Alaln C.M. and Richard-Raymond, Francoise. “Spatial and temporal variability in the water redox chemistry of the Drac River calcareous alluvial aquifer (Grenoble,

France). Journal of Contaminant Hydrology. 15:93-105 (1994).

115

Chadik, Paul A. and Amy, Gary L. “Removing Trihalomethane Precursors from Various

Natural Waters by Metal Coagulants.” Journal of the American Water Works

Association. 75:10:532-536 (October 1983).

Cleasby, John L. “Iron and Manganese Removal- A Case Study.” Journal of the

American Water Works Association, 67:3:147-149 (March 1975).

“Committee Report: Research Needs for the Treatment of Iron and Manganese.” Journal

of the American Water Works Association, 79:9:119-121. (September 1987).

Knocke, William R. and Van Benschoten, John E. Discussion of “Kinetics of

Manganese(II) Oxidation with Chlorine.” (ASCE Journal of Environmental

Engineering.” 117:3:359-374). ASCE Journal of Environmental Engineering.”

119:2:390-399 (March/April 1993).

“Removing Iron and Manganese” Public Works. 122:5:C-19-C-20.

Welch, W. Arthur. “Potassium Permanganate in Water Treatment.” Journal of the

American Water Works Association, 55:6:735-741 (June 1963).

116

APPENDIX A:

TABULATION OF

EXPERIMENTAL RESULTS

117

Table A-1: 2 Blanks to Insure Proper Glassware Preparation (Mn(II) Removal)

3 meq/L Ca™’, 3 meq/L HCO3, No Fe(II), Mn(ID), or HOC!

BOD 0.45 um Filtered 30k Ultrafiltered # 1 30k Ultrafiltered # 2 Bottle # | Tube # | Mn(mg/L)| Tube# | Mn(mg/L)| Tube # Mn (mg/L)

61 1 0.012 2 0.016 5 0.02

231 3 0.017 4 0.019 6 0.021

Table A-2: Check HOC! Demand of Milli-Q Water

3 meq/L Ca**, 3 meq/L HCO3, 2 mg/L HOCI, No Fe(II) or Mn(il)

Time

(min)

0

135

1440

pH 7

HOCI (mg/L 2.04

1.94

1.86

118

pH 8

HOCI (mg/L 2.03

1.9

1.92

Table A-3: Introduction of Mn(II) by Addition of Reagent Grade A.C.S.

Certified Ferrous Sulfate Heptahydrate (>99%); Aldrich Chemical Co.

Date mg FeSO4*7H20O Added | Volume (L) Mn (mg/L) mg Mn/mg FeSO4*7H20

11/18/94 200 0.2 0.194 1.94E-04

11/18/94 400 0.2 0.368 1.84E-04

11/18/94 600 0.2 0.559 1.86E-04

Rerun 400 0.2 0.3595 1.80E-04

Rerun 600 0.2 0.541 1.80E-04

9/11/94 497.8 2 0.094 3.78E-04

9/11/94 4978.2 2 0.1725 6.93E-05

9/12/94 4978.2 2 0.22 8.84E-05

11/23/94 248.9 0.25 0.195 1.96E-04

11/23/94 497.8 0.25 0.375 1.88E-04

11/23/94 659.6 0.25 0.475 1.80E-04

AVERAGE VALUE: 1.84E-04

* Although the results are somewhat variable, the average value seems to be a good

estimate based upon specific tests conducted to determine this value.

Also there are inherent laboratory errors which render exact repetition impossible.

119

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Preliminary Research Studies

Mn (II) Removal via CaCO3 and MnCO3 Ppt.

Table A-6: CaCO3/MnCO3 Interference Tests 6/13/94; Check of Previous Test

pH = 9; 3 meq/L Ca*’, 3 meq/L HCO3,, 0.5 mg/L MniII), No Fe(II) or HOCI, 10°C

Time BOD Final Temp. 0.45 um Filtered

(min) Bottle # pH (C) Tube # Mn (mg/L)

0 Blank 9 ~10 A 0.49

120 ND ND ND B 0.047

120 ND ND ND Cc 0.067

120 ND ND ND D 0.05

Table A-7: CaCO3/MnCO3 Interference Tests 6/15/94

pH = 8; 3 meq/L Ca**, 3 meq/L HCO3, 0.5 mg/L Mn(ID, No Fe(II) or HOCI, 10°C

Time BOD Final Temp. 0.45 um Filtered

(min) Bottle # pH (C) Tube # | Mn (mg/L)

0 Blank 8.01 10.2 50 0.514

30 41 8 10.4 51 0.51

60 57 7.98 10.4 52 0.507

90 73 8 10.3 53 0.509

120 97 8.01 10.1 54 0.497

150 309 8.01 10.1 55 0.499

180 356 8.12 10.3 56 0.506

Table A-8: CaCO3/MnCO3 Interference Tests 6/15/94

pH = 9; 3 meq/L Na’, 3 meq/L HCO3, 0.5 mg/L Mn(ID, No Fe(II) or HOCI, 10°C

Replaced CaCl in solution with NaCl (same ionic strength)

Time BOD Final Temp. 0.45 um Filtered

(min) Bottle # pH (C) Tube # | Mn (mg/L)

0 Blank 9.01 10.2 57 0.488

60 ND 8.91 9.2 58 0.47

120 ND 8.92 10 59* 0.447

180 ND 8.8 10.5 61 0.421

* Filter was torn; not noted until sample had been discarded

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133

Predicted vs. Actual HOCI Requirements Results Summarized from Data Previously Presented

Table A-32: Predicted vs. Actual HOCI Requirements pH 8

Reaction Fe = 4 mg/L

Time Mn | AMn | HOC! | Est. Sorbed HOC! Required (mg/L}

(min) | (mg/L)| (mg/L)| (mg/L)| Mn (mg/L)| Predicted | Predict Mn Oxed} Actual

0 0.54 0 2.1 0.02 0 0 0.00

30 0.46 | 0.07 | 1.98 0.02 0.09 0.07 0.12 60 0.39 | 0.15 | 1.91 0.02 0.19 0.17 0.19

120 0.26 | 0.28 | 1.87 0.02 0.37 0.34 0.23

180 0.12 | 0.41 | 1.76 0.01 0.54 0.52 0.34

240 0.03 | 0.51 | 1.66 0.00 0.66 0.66 0.44

300 0 0.54 | 1.61 0.00 0.70 0.76 0.49

Reaction Fe = 8 mg/L

Time Mn | AMn| HOC} | Est. Sorbed HOC] Required (mg/L)

(min) _ | (mg/L)| (mg/L)| (mg/L)| Mn (mg/L)| Predicted | Predict Mn Oxed| Actual

0 0.52 0 1.97 0.04 0 0 0.00

30 0.40 | 0.12 | 1.84 0.04 0.15 0.10 0.13

60 0.32 | 0.20 | 1.75 0.04 0.26 0.22 0.22

135 0.08 | 0.44 | 1.61 0.02 0.57 0.55 0.36

180 0 0.52 | 1.45 0.00 0.68 0.68 0.52 240 0 0.52 | 1.39 0.G0 0.68 0.68 0.58 300 0 0.52 | 1.39 0.G0 0.68 0.68 0.58

Reaction Fe = 15 mg/L

Time Mn | AMn | HOC! JEst. Sorbed HOC! Required (mg/L)

(min) _| (mg/L)| (mg/L)| (mg/L)| Mn (mg/L)| Predicted | Predict Mn Oxed| Actual

0 0.49 0 1.73 0.08 0 0 ND

30 0.46 | 0.03 | ND 0.07 0.04 n/a ND

60 0.39 | 0.10 | 1.47 0.07 0.13 0.04 0.26

90 0.26 | 0.24 | ND 0.06 0.31 0.23 ND

120 0.12 } 0.37 | 1.23 0.04 0.48 0.42 0.50

150 0.03 | 047 | ND 0.01 0.60 0.59 ND 180 0 0.49 | 1.27 0.00 0.64 0.64 0.46

Reaction Fe = 20 mg/L

Time Mn | AMn | HOC! | Est. Sorbed HOC] Required (mg/L) (min) _ | (mg/L)| (mg/L)| (mg/L)| Mn (mg/L)| Predicted | Predict Mn Oxed} Actual

0 0.52 0 2.03 0.10 0 0 ND 30 0.32 | 0.21 | 1.75 0.09 0.27 0.16 0.28

60 0.14 | 0.38 | 156 0.06 0.49 0.41 0.47 135 0.00 | 0.52 | 1.38 -0.06 0.68 0.68 0.65

180 0 0.52 | 1.42 0.00 0.68 0.68 0.61

240 0 0.52 | 1.35 0.00 0.68 0.68 0.68 300 0 0.52 | 1.35 0.00 0.68 0.68 0.68

Reaction Fe = 50 mg/L

Time Mn | AMn | HOC! |Est. Sorbed HOC] Required (mg/L) (min) | (mg/L)| (mg/L)| (mg/L)| Mn (mg/L)| Predicted | Predict Mn Oxed| Actual

0 0.582 0 1.48 0.26 0 0 ND

20 0.13 | 0.46 | ND 0.15 0.59 0.40 ND 40 0.01 | 057 | ND -0.03 0.74 0.74 ND 60 0.01 | 0.58 | 1.33 -0.08 0.75 0.75 0.15

80 0.00 | 058 | ND -0.21 0.76 0.76 ND 100 0.00 | 058 | ND -0.16 0.75 0.75 ND 120 0 0.58 | 1.27 0.00 0.76 0.76 0.23

Reaction Fe = 100 mg/L

Time Mn | AMn | HOC! | Est. Sorbed HOC] Required (mg/L)

min) _|(mg/L)| (mg/L)| (mg/L)| Mn (mg/L)| Predicted | Predict Mn Oxed]| Actual

0 0.5 0 1.41 0.51 0 0 ND

10 0.22 | 0.28 | ND 0.38 0.36 -0.13 ND

20 0.17 | 0.33 | ND 0.34 0.43 -0.02 ND 30 0.10 | 0.40 | ND 0.26 0.52 0.18 ND 40 0.06 | 044 | ND 0.19 0.57 0.33 ND

50 0.03 | 0.47 | ND 0.08 0.61 0.50 ND 60 0.01 | 0.49 | 1.12 -0.08 0.64 0.64 0.29

* For each case inilial HOC! dose = 2 mg/L unless otherwise noted; 0.45 um results used;

HOC! Req'd calculated from "0" value.

134

Predicted vs. Actual HOC! Requirements Results Summarized from Data Previously Presented

Table A-33: Predicted vs. Actual HOC! Requirements pH 7

Reaction Fe = 2 mg/L

Time Mn | AMn |} HOC! | Est. Sorbed HOCI Required (mg/L)

(min) | (mg/L)} (mg/L)| (mg/L)} Mn (mg/L)| Predicted | Predict Mn Oxed| Actual

0 0.52 0 2 0.00 0 0 ND

30 0.48 | 0.04 | 1.85 0.00 0.06 0.05 0.15

60 0.47 | 0.05 | 1.85 0.00 0.07 0.06 0.15

120 0.43 | 0.09 | 1.82 0.00 0.12 0.12 0.18

180 0.40 | 0.12 | 1.76 0.00 0.15 0.15 0.24

240 0.36 | 0.16 | 1.67 0.00 0.21 0.21 0.33

300 0.308 | 0.21 | 1.63 0.00 0.27 0.27 0.37

Reaction Fe = 8 mg/L

Time Mn | AMn | HOC! | Est. Sorbed HOCI Required (mg/L) (min) mg/L) | (mg/L)| (mg/L)| Mn (mg/L)| Predicted | Predict Mn Oxed | Actual

0 0.52 0 1.66 0.01 0 0 ND

30 0.37 | 0.15 | 1.57 0.01 0.20 0.18 0.09

60 0.34 | 0.18 | 1.56 0.01 0.23 0.21 0.10

90 0.30 | 0.22 | 1.57 0.01 0.29 0.27 0.09

120 0.26 | 0.25 | 1.48 0.01 0.33 0.32 0.18

180 0.16 | 0.36 1.5 0.01 0.46 0.45 0.16

240 0.067 | 0.45 | 1.33 0.00 0.59 0.58 0.33

Reaction Fe = 10 mg/L

Time Mn | AMn | HOC! | Est. Sorbed HOC] Required (mg/L)

(min) __|(mg/L)| (mg/L) | (mg/L)| Mn (mg/L) | Predicted | Predict Mn Oxed| Actual

0 0.53 0 1.84 0.02 0 0 ND

30 0.40 | 0.13 | 1.54 0.01 0.17 0.15 0.30

60 0.33 | 0.20 | 1.58 0.01 0.26 0.25 0.26

90 0.27 | 0.26 | 1.56 0.01 0.34 0.32 0.28

120 0.20 | 0.34 | 1.48 0.01 0.44 0.43 0.36

150 0.15 | 0.39 | 1.47 0.01 0.50 0.49 0.37

180 0.083 | 0.45 | 1.33 0.01 0.59 0.58 0.51

Reaction Fe = 20 mg/L

Time Mn |; AMn | HOC! | Est. Sorbed HOCI Required (mg/L) (min) | (mg/L)| (mg/L) | (mg/L)| Mn (mg/L)| Predicted | Predict Mn Oxed| Actual

0 0.56 0 1.81 0.03 0 0 ND

15 0.45 | 0.11 | ND 0.03 0.14 0.10 ND

30 0.42 | 0.14 {| ND 0.03 0.18 0.14 ND

45 0.39 | 0.17 | ND 0.03 0.22 0.19 ND

60 0.33 | 0.23 1.5 0.03 0.30 0.27 0.31

75 0.28 | 0.28 | ND 0.03 0.36 0.33 ND

90 0.24 | 0.32 | 1.49 0.02 0.41 0.38 0.32

* For each case initial HOCI dose = 2 mg/L unless otherwise noted; 0.45 um results used;

HOC] Req'd calculated from "0" value.

135

Mna(ID Oxidation onto MnO,

Table A-34: 9/19/94: pH = 8; MnO, Target = 0.525 mg/L; 0.5 mg/L as Mn(ID); Ca** & HCO3 = 3 meq/L; HOCI = 2 mg/L; 10°C

Time Final Temp. 0.45 um Samples 30k Sample # 1 30k Sample # 2 Avg. HOC]

(min) pH {C)} Tube # Mn (mg/L) Tube # Mn (mg/L) Tube # Mn (mg/L) Ultra (mg/L)

0 Extracted- MnOx 1 0.294 2 0.307

0 Extracted- Both 3 0.793 4 0.852

5-adsorb 8.02 10.8 5 0.47 6 0.454 7 0.456 0.46 ND

20 ND ND 8 0.451 9 0.44 10 0.443 0.44 1.87 40 7.83 16 ti 0.439 12 0.436 13 0.438 0.44 1.93

60 7.83 10.2 14 0.439 15 0.433 16 0.431 0.43 1.90

80 7.86 10.2 17 0.434 18 0.428 19 0.422 0.43 1.91

100 7.84 10.2 20 0.426 21 0.416 22 0.416 0.42 1.91

120 7.84 9 23 0.416 24 0.409 25 0.417 0.41 1.91

* Note: MnOx concentration ~ 0.47 mg/L.

Table A-35: 9/20/94: pH = 8; MnO x Target = 1.77 mg/L; 0.5 mg/L as Mn(II); Ca** & HCO3 = 3 meq/L; HOCI = 2 mg/L; 10°C

Time Final Temp. 0.45 um Samples 30k Sample # 1 30k Sample # 2 Avg. HOCI

(min) pH (C) Tube # Mn (mg/L) Tube # Mn (mg/L) Tube # Mn (mg/L) Ultra (mg/L)

0 Extracted- MnOx 26 1.147 27 1.139

0 Extracted- Both 28 1.543 29 1.667

5-adsorb 8 10.8 30 0.448 31 0.428 32 0.42 0.42 ND

20 ND ND 33 0.362 34 0.356 35 0.351 0.35 2.31

40 7.89 10.5 36 0.336 37 0.339 38 0.336 0.34 2.31

60 7.91 11 39 0.316 40 0.304 41 0.305 0.30 2.34

80 7.89 9.8 42 0.294 43 0.285 44 0.287 0.29 2.31

100 7.9 9.8 45 0.274 46 0.269 47 0.265 0.27 ND

120 7.89 10 48 0.252 49 0.249 50 0.247 0.25 2.34

* Note: MnOx concentration ~ 1.81 mg/L.

Table A-36: 9/21/94: pH = 8; MnO, Target = 1.77 mg/L; 0.5 mg/L as Mn(1I); Ca** & HCO3 = 3 meq/L; HOCI = 2 mg/L; 10°C

Time Final Temp. 0.45 um Samples 30k Sample # 1 30k Sample # 2 Avg. HOCI

(min) pH (C) Tube # Mn (mg/L) Tube # Mn (mg/L) Tube # Mn (mg/L) Ultra (mg/L)

0 Extracted- Both 51 1.305 52 1.257

0 Filtered- Both 53 0.448 54 0.465

5-adsorb 8.01 10.5 55 0.444 56 0.412 57 0.407 0.41 ND

30 ND ND 58 0.377 59 0.36 60 0.35 0.36 2.22

60 7.78 9 61 0.329 62 0.326 63 0.333 0.33 2.15

120 7.97 9 64 0.292 65 0.285 66 0.284 0.28 2.16

180 7,89 9 67 0.244 68 0.238 69 0.24 0.24 2.10

240 ND 9.8 70 0.213 71 0.2 72 0.21 0.21 2.06

360 ND 8.5 73 0.135 74 0.125 75 0.128 0.13 2.01

* Note: MnOx concentration ~ 2.02 mg/L.

136

Table A-37: CSTR System: Before and After 4 mg/L HOC] Dose was Added

Influent = 0.5 mg/L as Mn(II), Fe(f1) = 2 mg/L, Ca** and HCO’ = 3 meq/L, pH = 6.85, 15°C, HOC! as indicated; 6}; = 1 hour

Total Mn Reactor 1; Mn Reactor 2; Mn Reactor 3;

Elapsed Fe(III) = 250 Fe(II) = 500 Fe Hl) = 750 Mn Mixer

Time of Sampling | Time (hr) mg/L mg/L mg/L (mg/L) Other/Comments

No HOCI Added; ~ 1 mg/L Residual in Tap Water

10/10/94 10:40 0 0.875

10/10/94 10:55 0:15 0.127 0.036 0.016

10/10/94 11:10 0:30 0.156 0.065 0.026

10/10/94 11:25 0:45 0.194 0.088 0.047

10/10/94 11:40 1:00 0.219 0.113 0.064

10/10/94 11:55 1:15 0.271 0.153 0.088

10/10/94 12:10 1:30 0.297 0.204 0.121

10/10/94 12:40 2:00 0.35 0.261 0.182

10/10/94 13:10 2:30 0.393 0.318 0.233

10/10/94 13:40 3:00 0.421 0.357 0.444

10/10/94 14:10 3:30 0.401 0.337 0.334

10/10/94 14:40 4:00 0,331 0.334 0.472

10/10/94 15:10 4:30 0.466 0.172 0.187

10/10/94 17:10 6:30 0.501 0.44 0.43

10/10/94 17:40 7:00 0.511 0.497 0.472

10/10/94 20:55 10:15 0.578 0.581 0.511

10/11/94 12:55 0.539 0.594 0.555

10/12/94 0:30 0 Began HOCI Feed = 4 mg/L

10/12/94 0:45 0:15 0.404 0.329 0.417

10/12/94 1:00 0:30 0.187 0.094 0.063

10/12/94 1:15 0:45 0.173 0.062 0.057

10/12/94 1:30 1:00 0.186 0.065 0.047

10/12/94 1:45 1:15 0.171 0.055 0.031

10/12/94 2:00 1:30 0.149 0.044 0.006

10/12/94 2:15 1:45 0.135 0.628 0.005

10/12/94 2:30 2:00 0.123 0.02 0

10/12/94 2:45 2115 0.098 0.01 0

10/12/94 3:00 2:30 0.085 0.01 0.001

10/12/94 3:15 2:45 0.071 0.008 0.004

10/12/94 3:30 3:00 0.057 0.007 0.002 0.512

10/12/94 12:40 12:10 0.007 0.001 0.001

10/13/94 13:40 13:10 0.009 0.005 0.001 0.69 pH(1): 6.85; (2): 6.81; (3) 6.86 10/15/94 19:00 18:30 HOCI(1): 1.61; (2):1.44; (3): 1.67

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APPENDIX B

OPERATION AND DETECTION LIMIT DETERMINATION FOR

ATOMIC ADSORPTION-SPECTROPHOTOMETER

Detection Limit Determination

a. Procedure. The detection limit of the AA-S used for analysis of all Fe(II) and

Mn(II) samples was determined only for manganese as this is the most critical parameter

under study. The test procedure used to determine the limit of detection was taken

directly from the operating manual for the AA-S (Instructions for Perkin Elmer Atomic-

Adsorption Spectrophotometer Model 703. Norwalk, CT. May 1978°). In general, two

low concentration standards are prepared, the first at 5 times the estimated detection limit

and the second at 10 times the estimated detection limit. The standards are analyzed

alternately (reading a blank in between the two standard readings) twenty or more times

once optimum operating conditions have been obtained. The absorbance means are

determined by this procedure and are used to calculate the detection limit of the

instrument for the element in question. This determination was conducted on two

different occasions; both results are given in the following sections.

b. Detection Limit Determination 8/8/94. The average detection limit was found

to be approximately 0.005 mg/L by this procedure. This value suggests that any value

between 0.005 and 10 x 0.005 mg/L should be reported as detect only as the

quantification limit is defined as 10 times the detection limit. Thus only values greater

than the SMCL of 0.05 mg/L can be reported as true numerical values. Because the

blank readings varied greatly form the beginning to the end of the test, the results were

somewhat questionable. This phenomenon should not affect the results because the

standard values are corrected by accounting for the discrepancy between the zero value

and the value “seen” by the AA-S. The test was rerun on 8/26/94 to confirm the findings

157

of this determination. Table B-1 summarizes the data collected for this test procedure as

well as providing a sample calculation for the detection limit value.

c. Detection Limit Determination 8/26/94. During the data collection for this

procedure, the AA-S appeared to malfunction after the 20th reading. Therefore, two

results will be reported; one for the first 20 readings which meets the minimum number

required for this determination and the second for all 25 readings. By ignoring the final 5

readings, the detection limit is approximately 0.006 mg/L which compares well to the

previously determined value. Also, the blank reading in this determination is less

variable than the previous test. However if all the readings are used in the determination,

the detection limit swells to 0.008 mg/L, and the blank readings appear very irregular for

the final 5 readings. Tables B-2 and B-3 provide a listing of both cases discussed with

Table B-2 being shaded after the 20th reading to indicate that these values were not used

in the detection limit determination.

Operation

Standard operating procedures as recommended by the manufacturer were used

during AA-S analysis.

158

Table B-1: Detection Limit Determination for Mn on AA-S 8/8/94

(25 of 25 Readings used for Calculation)

Reading Blank Standard 1 Blank Standard 2 Corrected Values

Number (Zero) | (0.075 mg/L)}| (Zero) | (0.150 mg/L) Sl $2

1 -0.001 0.072 -0.003 0.148 0.074 0.15

2 -0.001 0.073 -0.001 0.146 0.074 0.148

3 -0.003 0.068 -0.008 0.142 0.0735 0.147

4 -0.002 0.071 0 0.145 0.072 0.147

5 -0.004 0.071 -0.004 0.145 0.075 0.148

6 -0.002 0.072 -0.001 0.152 0.0735 0.1525

7 0 0.078 0 0.151 0.078 0.15

8 0.002 0.074 -0.005 0.143 0.0755 0.15

9 -0.009 0.069 -0.006 0.143 0.0765 0.1485

10 -0.005 0.066 -0.006 0.145 0.0715 0.1495

11 -0.003 0.07 -0.007 0.143 0.075 0.1485

12 -0.004 0.07 -0.002 0.146 0.073 0.1495

13 -0.005 0.071 -0.002 0.145 0.0745 0.149

14 -0.006 0.069 -0.005 0.143 0.0745 0.1485

15 -0.006 0.069 -0.006 0.143 0.075 0.148

16 -0.004 0.071 -0.005 0.145 0.0755 0.15

17 -0.005 0.07 -0.005 0.146 0.075 0.1505

18 -0.004 0.073 -0.005 0.143 0.0775 0.148

19 -0.005 0.067 -0.008 0.144 0.0735 0.153

20 -0.01 0.065 -0.008 0.141 0.074 0.1495

21 -0.009 0.064 -0.009 0.141 0.073 0.1505

22 -0.01 0.064 -0.01 0.137 0.074 0.1465

23 -0.009 0.063 -0.01 0.139 0.0725 0.1485

24 -0.009 0.065 -0.008 0.141 0.0735 0.151

25 -0.012 0.062 -0.011 0.138 0.0735 0.152

26 -0.017

STANDARD CONCENTRATION =| 0.075 0.15

MEAN =|} 0.0743 | 0.14934

Ratio = 2.01

STANDARD DEVIATION = || 0.001541 | 0.001669

Detection Limit =

Detection Lmit (0.075 Standard) =

Detection Lmit (0.15 Standard) =

S tan dard Concentration x 3 § tan dard Deviations|

Average Detection Limit =

Mean

0.0047 mg/L 0.0050 mg/L

159

0.0048 mg/L

Table B-2: Detection Limit Determination for Mn on AA-S 8/26/94

(20 of 25 Readings used for Calculation)

Reading Blank Standard 1 Blank Standard 2 Corrected Values

Number (Zero) (0.075 mg/L) (Zero) (0.150 mg/L) Sl $2

1 0.002 0.078 0.006 0.152 0.074 0.15

2 -0.002 0.078 0.001 0.15 0.0785 0.148

3 0.003 0.077 0) 0.149 0.0755 0.149

4 0 0.076 0 0.149 0.076 0.149

5 0 0.079 0.004 0.151 0.077 0.148

6 0.002 0.079 0.002 0.152 0.077 0.1495

7 0.003 0.078 0.002 0.154 0.0755 0.152

8 0.002 0.079 0.003 0.152 0.0765 0.15

9 0.001 0.077 0 0.154 0.0765 0.1535

10 0.001 0.079 0.001 0.155 0.078 0.153

11 0.003 0.082 0.001 0.157 0.08 0.154

12 0.005 0.081 0.004 0.156 0.0765 0.152

13 0.004 0.081 0.003 0.154 0.0775 0.15

14 0.005 0.081 0.004 0.152 0.0765 0.149

15 0.002 0.078 0.006 0.157 0.074 0.1525

16 0.003 0.081 -0.005 0.153 0.082 0.155

17 0.001 0.077 -0.001 0.15 0.077 0.1505

18 0 0.081 0.002 0.151 0.08 0.1515

19 -0.003 0.078 0.003 0.153 0.078 0.151

20 0.001 0.078 0.001 0.155 0.077 0.1535

21 0.002 0.084 0.003 0.158 0.0815 0.1535

22 0.006 0.083 0.006 0.159 0.077 0.1525

23 0.007 0.084 0.003 0.156 0.079 0.152

24 0.005 0.071 0.001 0.144 0.068 0.148

25 -0.009 0.069 -0.012 0.147 0.0795 0.161

26 -0.016

STANDARD CONCENTRATION =| 0.075 0.15

MEAN =| 0.07715 | 0.15105

Ratio = 1.96

STANDARD DEVIATION = | 0.001941 | 0.00207

Detection Limit =

S tan dard Concentration x3 S tan dard Deviations

Mean

Detection Lmit (0.075 Standard)= 0.0057 mg/L

Detection Lmit (0.15 Standard)= 0.0062 mg/L

Average Detection Limit =

160

0.0059 mg/L

Table B-3: Detection Limit Determination for Mn on AA-S 8/26/94

(25 of 25 Readings used for Calculation)

Reading Blank Standard 1 Blank Standard 2 Corrected Values

Number (Zero) | (0.075 mg/L)}| (Zero) | (0.150 mg/L) $1 $2

1 0.002 0.078 0.006 0.152 0.074 0.15

2 -0.002 0.078 0.001 0.15 0.0785 0.148

3 0.003 0.077 0 0.149 0.0755 0.149

4 0 0.076 0 0.149 0.076 0.149

5 0 0.079 0.004 0.151 0.077 0.148

6 0.002 0.079 0.002 0.152 0.077 0.1495

7 0.003 0.078 0.002 0.154 0.0755 0.152

8 0.002 0.079 0.003 0.152 0.0765 0.15

9 0.001 0.077 0 0.154 0.0765 0.1535

10 0.001 0.079 0.001 0.155 0.078 0.153

11 0.003 0.082 0.001 0.157 0.08 0.154

12 0.005 0.081 0.004 0.156 0.0765 0.152

13 0.004 0.081 0.003 0.154 0.0775 0.15

14 0.005 0.081 0.004 0.152 0.0765 0.149

15 0.002 0.078 0.006 0.157 0.074 0.1525

16 0.003 0.081 -0.005 0.153 0.082 0.155

17 0.001 0.077 -0.001 0.15 0.077 0.1505

18 0 0.081 0.002 0.151 0.08 0.1515

19 -0.003 0.078 0.003 0.153 0.078 0.151

20 0.001 0.078 0.001 0.155 0.077 0.1535

21 0.002 0.084 0.003 0.158 0.0815 0.1535

22 0.006 0.083 0.006 0.159 0.077 0.1525

23 0.007 0.084 0.003 0.156 0.079 0.152

24 0.005 0.071 0.001 0.144 0.068 0.148

25 -0.009 0.069 -0.012 0.147 0.0795 0.161

26 -0.016

STANDARD CONCENTRATION =|} 0.075 0.15

MEAN = || 0.07712 | 0.15152

Ratio = 1.96

STANDARD DEVIATION = |] 0.002762 | 0.002838

Detection Limit =

Detection Lmit (0.075 Standard) =

Detection Lmit (0.15 Standard) =

S tan dard Concentration x 3 S tan dard Deviations '

Mean —

0.0081 mg/L 0.0084 me/L

Average Detection Limit= 0.0082

16]

mg/L

1 4

Table B-5: Summary of Operating Parameters Used for AA-S Analysis

Element | Lamp Current | Wavelength (nm) | Relative Noise | Sensitivity | Linear Range

Fe 30 mA 248.3 1.0 0.10 mg/L 5 mg/L

Mn 20 mA 279.5 1.0 0.052 mg/L 2 mg/L

* Note: All analysis performed with Nominal Spectrum Band Width = 0.2 nm (UV

Range); Acetylene Flame (oxidizing) with air as oxidant.

162

Appendix C: Calculations

Stock Solution Calculations:

Mn Stock: 0.5 mg Mn™ per mL stock solution

0.5 mg Mn™ x 169.01mg MnSO,-H,O = 1.54 mg MnSO,-H,O per mL solution

mL solution 54.94 mg Mn™*

Fe Stock: 1mg Fe™ per mL stock solution

1mg Fe™ x 278.02 mg FeSO, .7H,O = 4.98 mg FeSO, +7H,O per mL solution

mL solution 55.847 mg Fe"

Ca Stock: 1 meg Ca™ per mL stock solution

1 meq Ca™* x 20.04 mg Ca™* x 110.99 mg CaCl, = 55.5 mg CaCl, per mL solution

mL solution meq asCa™ 40.08 mg Cae™

NaHCO, Stock: 1meq HCO; per mL stock solution

Lmegq HCO; , 61.02 mg HCO; , 84.01mg NaHCO; = 84.01 mg HCO, per mL solution

mL solution meq as HCO; 61.02 mg HCO,

HOCI Stock: 1mg HOCI per mL stock solution

Img HOCI 1mole HOCI 1mole OCI 1mole NaOCl 74.44 = 10°mg NaOCl — x - x x — x = 1.42 mg NaOCl per mL solution

mL solution 52.46x10'mg HOC] 1mole HOC! 1mole OCI 1 mole NaOCl

NaOCl Stock: 5.25% Solution = 52,500mg / L = 52.5mg /mL

52.5mg / mL Therefore

1.42mg / mL = 37; Dilute NaOCl Stock Solution 37:1

Chlorine Chemistry.

Cl, + HO<—> HOCI + H* + Cr

HOCI<—> H* + OCT (pK, = 7.5)

163

Relationship Between HOCI and Cl,

1mg HOCI 1 mole HOCI mole Cl, | 70.906 x 10° mg Cl, — x - x = 1.35 mg Cl, per mL solution

mL solution 52.46x10°mg HOCIL 1mole HOCI 1 mole Cl,

Amperometric Titration Calculation and Mn/Cl, Ratio Determination:

(mL titrant)(normality of PAO)(mg / meq of Cl,) | (mL titrant)(0.00564)(35450) Cl, (mg/L) = , =

Sample Volume in mL 200 mL

Example: 1.23mL of PAO added as titrantto 2:1 diluted sample

HOCI(mg | L) = (2 x 1.23mL )(0.00564)( 35450) x Img HOC! _ 1.82 mg asHOCI/ L

200 mL 1.35 mg Cl,

Mn”™ + HOCI + H,O— > MnO, + Cl + 3H* (1.30mg HOCI req'd permg Mn")

_ 0.5 mg Mn™ x 1mole Mn™

L 54.94 x 10° mg Mn**

2mg HOC! x 1 mole HOC!

L 52.453 x 10° mg HOCI

Mn** | =9.1x10°M

= 3.81x10°M HOCI] =[Cl,]=

[Cl] _ 3.81x10°M _ = 4.2

[Mn] 9.1x10°M

164

MnCoO, Interference

K,, =10°° =[Mn* |[CO;] < NOTTEMPERATURECORRECTED

Mn**])=9.1x10° M 1. [COs ]> = 5.51 10° M for ppt. to occur i x

Creo, = 3meq/L=3x10° M;

Carbonate System pK, values corrected for temperature (10°C):

pK,, =6.46 pK,, =10.49

pH =9; a, = 0.9694 a, =0.0306

[CO,] 0.0306 = ve [CO;]=9.2x10°M; .. ppt. will occur 3x10

pH =8; a, =0.9945 a, = 0.0055

[C9, ] 0.0055 = 3 3x10° M

3=> [CO;]=1.64x10°M; .. ppt. will not occur

165

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166

Ce/(

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Ce/(

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Mn(ID onto Fe(IH)

200

150 y = 140.53x + 37.091 ° o ¢

100 ¢ : * o

50 o¢ S

0 —

0 0.1 0.2 0.3 0.4 0.5 0.6

Mn Concentration (Ce), mg/L

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a= 0.007 yint.=l/ab= 37.091

b= 3.79

pH 7: Determination of Langmuir Isotherm Constants

Mnai(II) onto Fe(II)

6000 .

5000 .

4000 |

3000 = 1094, , 2000 y = 1094.5x + 739.05 o oe

1000

0 o | _¢| o*? % 6

0 0.1 0.2 0.3 0.4 0.5 0.6

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Slope = 1/a = 1094.5

a= 0.00091 yint.=1/ab= 739.05

b= 1.48

167

In(X

/M),

mg/mg

In(X/M), m

g/mg

pH 8: Determination of Freundlich Isotherm Constants

Mn (II) onto Fe(IID

pi

-4.9000 = =-3.5000 = -3.0000 = -2.5000 =-2.0000 3=— -1.5000 »=— -1.0000 = -0.5000 G0 D00

y = 0.5749x - 4.9044 4

2 —_t.—_ Sv -6 s ¢ d gz. ———y

-3.

In(Mn Concentration (Ce)), mg/L

Slope =I/n= 0.5749 n= 1.74

yint=Ink= -4.9044

k= 0.00741

pH 7: Determination of Freundlich Isotherm Constants

MniID onto Fe(IID)

000 -2.5000 -2.0000 -1.5000 -1.0000 -0.5000 4.0900

r -4 y = 0.2723x - 6.8594 6

o -

° 2 10

in(Mn Concentration (Ce)), mg/L

Slope = I/n = 0.2723

n= 3.67

yint=Ink= -6.8594

k= 0.00105

168

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Constant

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4.00E-02 |-

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1.00E-02 |-—

0.00E+00 --—-

Rate Constant k vs. Fe(III) Concentration pH 8

Fe(III) (mg/L) | Rate Constant (units)|Units = mg Mn/L-min

4.6 1.71E-03

8.3 2.29E-03

15.57 8.30E-03

19.85 2.51E-03

94 2.27E-02 (Pure)

96.3 5.39E-02 (Reg.)

50.48 Indeterm Data

Avg. 1.52E-02

171

Rate Constant vs. Fe(II) Concentration

pH 8

y = 0.0004x - 0.0013

R? = 0.768

Fe(III) Concentration

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Fe(III) (mg/L) | Rate Constant (units)|Units = mg Mn/L-min

1.9 1.75E-04

8 2.13E-03

9.88 3.57E-03

21 2.92E-03

53.67 5.62E-03

101 2.01E-03

112.77 6.50E-03 Avg. 3.28E-03

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0 20 40 60 80 100 120

Fe(III) Concentration

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APPENDIX D:

MODEL FORMULATION/

RELATED CALCULATIONS

18]

BATCH SYSTEM MODEL

CALCULATIONS AND

FORMULATION

182

pH 8 Batch Model! Results: Langmuir

pH 8; Fe = 4.6 mp/L; HOC! = 2 mg/L

Time, min Observed 1.50E-02 2.00E-02 2.50E-02 3.43E-02

0 0.493 0.493 0.493 0.493 0.493

30 0.464 0.435 0.417 0.400 0.368

a 0.391 0.383 0.350 0.319 0.267

120 0.256 0.291 0.239 0.195 0.130

180, 0.124 0.216 0.157 0.112 0.058

240 0.027 0.157 0.100 0.063 0.025

300 0 0.112 0.063 0.034 0.011

Sq. Residuals 0.040 0.015 0.016 0.045

Best Fit

pH 8; Fe = 8.3 mg/L; HOC! = 1.97 mg/L

Time, min Observed L.50E-02 2.00E-02 2.5UE-02 3.43E-02

0 0.488 0.488 0.488 0.488 0.488

30 0.402 0.393 0.365 0.338 0.293

a 0.317 0.313 0.267 0.227 0.166

120 0.078 0.192 0.137 0.096 0.050

180 0 O.LIS 0.068 0.040 0.015

240) 0 0.068 0.033 0.016 0.004

300 a 0.040 0.016 0.007 0.001

Sq. Residuals 0.0325 0.0132 0.0143 0.0357

Best Fit

pH 8; Fe = 19.85 mg/L; HOCI = 2.03 mg/L

Time, min Observed 1.00E-02 1.50E-02 2.00E-02 = 3.43£-02

0 0.438 0.438 0.438 0.438 0.438

30 0.315 0.316 0.268 0.227 0.142

oO 0.143 0.227 0.164 O19 0.050

135 0.002 0,102 0.052 0.028 0.005

180 0 0.065 0.028 0.012 0.001

240 0 0.037 0.012 0.004 0.000

300 0 0.021 0.006 0.002 0.000

Sq. Residuals 0.0230 0.0061 0.0092 0.0383

Best Fit

pH 8; Fe = 50.48 mg/L; HOCI = 1.48 mg/L

Time, min Observed 4.50E-02 5.00E-02 5.50E-02 6.00E-02 3.43E-02

0 0.344 0.344 0.344 0.344 0.344 0.344

20 0.127 OES 0.105 0.096 0.088 0.143

40 0.011 0.056 0.049 0.043 0.038 0.077

0) 0.006 0.032 0.027 0.023 0.019 0.047

80 0 0.019 0.016 0.013 0.011 0.031

100 0 0.012 0.010 0.008 0.006 0.021

120 0 0.008 0.006 0,005 0.004 0.015

Sq. Residuals 0.0034 0.0027 0.0025 9.0026 0.0078

Best Fit

pH 8; Fe = 94 mg/L; HOC] = 1.41 mg/L

Time, min Observed 3.50E-02 4.00E-02 4.50E-02 3.43E-02

0 0.353 0.353 0.353 0.353 0.353

10 0.225 0.203 G.191 0.180 0.205

20 0.169 0.140 0.129 0.119 0.142

30 0.1054 0.108 0.098 0.090 0.109

40 0.063 0.087 0.079 0.072 0.089

50 0.031 0.074 0.067 0.061 O.075

o~ 0.005 0.064 0.058 0.053 0.065

Sq. Residuals 0.0073 0.0072 0.0080 0.0074

Best Fit

pH 8; Fe = 15.57 mg/L; HOCI = 1.73 mg/L

Time, min Observed 2.50E-02 3.00E-02 3.50E-02 4.00E-02 3.43E-02

0 0.488 0.488 0.488 0.488 0.488 0.488

30 0.286 0.281 0.251 0.224 0.201 0.228

4) 0.113 0.160 0.129 0.104 0.084 0.107

90, 0.005 0.093 0.068 0.050 0.037 0.052

120 6.002 0.056 0.037 0.025 0.017 0.027

150 0.003 0.034 0.021 0.013 0.008 0.014

180 0 0.021 0.012 0.007 0.004 0.007

Sq. Residuals 0.0143 0.0072 0.0066 0.0095 0.0064

Best Fit

pH 8; Fe = 96.3 mg/L; HOC! = 1.95 mg/L

Time, min Observed 4.50E-02 5.00E-02 S.50E-02 6.00E-02 3.43E-02

0 0.354 0.354 0.354 0.354 0.354 0.354

10 0.142 O.141 0.131 0,122 0.114 0.168

20 0.085 0.080 0.073 0.066 0.060 0.102

30 0.028 0.053 0.047 0.042 0.038 0.07]

40 0.001 0.038 0.033 0.029 0.026 0.052

50 0 0.029 0.025 0.022 0.019 0.040

et 0 0,022 0.019 0.016 0.014 0.032

Sq. Residuals 0.0033 0.0027 0.0025 0.0027 0.0081

Best Fit

183

pH 8 Batch Model Results: Freundlich

pH 8; Fe = 4.6 mg/L; HOCI = 2 mg/L

Time, min Observed 8.00E-02 Y%.0Q0E-02 9.50E-02 1.53E-01

0 0.493 0.493 0.493 0.493 0.493

30) 0.464 0.381 0.371 0.366 0.315

o) 0.391 0.309 0.295 0.289 0.228

120 0.256 0.222 0.207 0.200 0.143

180 0.124 0.171 0.158 O.1S1 0.102

240 0.027 0.138 0.126 0.120 0.078

300 0 0.115 0.104 0.099 0.063

Sq. Residuals 0.0426 0.0420 0.043 0.069

Best Fit

pH 8; Fe = 8.3 mp/L; HOC = 1.97 mg/L

Time, min Observed 9.00E-02 9.50E-02 LOOE-01 1.53E-01

0 0.488 0.488 0.488 0.488 0.488

30 0.402 0.316 0.309 0.303 0.251

(ct) 0.317 0.230 0,223 0.216 0.163

120 0.078 0.145 0.139 0.133 0.092

180 0 0.103 0.098 0.094 0.062

240 0 0.079 0.075 0.071 0.045

300 0 0.063 0.059 0.056 0.035

Sq. Residuals 0.0402 0.03981 0.03983 0.05379

Best Fit

pH 8; Fe = 19.85 mp/L; HOC] = 2.03 mp/L Time, min Observed 8.00E-02 8.50E-02 9.00E-02 9¥.50E-02 1.53E-01

9 0.438 9.438 0.438 OA38 0.438 0.438

30 0.315 0,223 0.216 0.209 0,203 0.148

OO 0.143 0.143 0.136 0.130 0.124 0.081

{35 0.002 0.088 0.083 0.079 0.075 0.034

180 0 0.051 0.047 0.044 0.042 0.024

240 Q 0.037 0.034 0.032 0.030 0.017

300 a 0.028 0.026 0.024 0.023 0.012

Sq. Residuals 0.02054 0.02052 0.0208 0.0214 0.0339

Best Fit

pH 8; Fe = 50.48 mg/L; HOC! = 1.48 mg/L

Time. min Observed 2.50E-01 3.00E-01 3.50E-01 4.00E-01 = 1.53E-01

QO 0.344 0.344 0.344 0.344 0.344 0.344

20 0.127 0.096 0.081 0.070 0.062 0.139

40 0.011 0.049 0.040 0.033 0.028 0.080

A 0.006 0.030 0.024 0,020 0.017 0.053

80 0 0.021 0.017 0.014 0.012 0.039

100 0 0.016 0.013 0.010 0.009 0.030

120 0 0.013 0.010 0.008 0.007 0.024

Sq. Residuals 0.00385 0.00377 0.0043 0.0049 0.0101

Best Fit

pH 8; Fe = 94 mg/L; HOCI = 1.41 mg/L

Time, min Observed 9.50E-02 1.00E-01 1.50E-01 2.00E-01 1.53E-01

0 0.353 0.353 0.353 0.353 0.353 0.353

10 0.225 0.233 0.229 0.193 0.166 0.191

20 0.169 0.171 0.166 0.128 0.102 0.126

30 0.1054 0.132 0.128 0.092 0.070 0.091

40 0.063 0.106 0.102 0.070 0.052 0.069

50 0.031 0.088 0.084 0.056 0.040 a,0s5

60 0.005 0.074 0.070 0.046 0.032 0.045

Sq. Residuals 0.011 0.0091 0.0082 0.0101 0.0054

Best Fit

pH 8; Fe = 15.57 mg/L; HOCI = 1.73 mp/L

Time, min Observed 1.Q0E-Q1 1.50E-01 2.00E-Ol 2.50E-01 1.53E-01

0 0.488 0.488 0.488 0.4838 0.488 0.488

30 0.286 0.259 0.207 0.171 0.145 0.205

oe 0.113 0.171 0.125 0.097 0.079 0.123

nN 0.005 0.125 0.087 0.065 0.052 0.085

120 0.002 0.097 0.065 0.048 0.037 0.064

150 0,003 0.079 0.052 0.037 0.029 0.050

180 0 0.065 0.042 0.030 0.023 0.041

Sq. Residuals 0.038 9.0212 0.0213 0.0257 0.0210

Best Fit

pH 8; Fe = 96.3 mg/L; HOCI = 1.95 mg/L

Time, min Observed 1.50E-01 2.00E-01 2.S0E-01 1.53E-01

0 0.354 0.354 0.354 0.354 0.354

10 0.142 0.155 0.126 0.105 0.153

20 0.085 0.089 0.066 0.052 0.087

30 0.028 0.058 0.041 0.031 0.057

40 0.001 0.041 0.028 0.021 0.040

50 0 0.031 0.021 0.015 0.030

a 0 0.024 0.016 0.012 0.024

Sq. Residuals 0.0043 6.0022 0.0033 0.0040

Best Fil

184

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OF

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a (GONG e PSAS 4S OFGELS)o

[ZSAS-LSASe((6CASe H 1SAS+

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AS

a PISAG) a (BONS 4 PSAS ES OFSELG)«

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cy

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PSAS4S OF PEL).

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VITA

William Scott Dewhirst IJ was born in 1971 in Richmond, Virginia and

attended high school in Henrico County at Hermitage High School. Upon

completion of his high school career, he enrolled at Virginia Polytechnic

Institute and State University (Virginia Tech) to pursue an undergraduate

degree in civil engineering. Immediately following his undergraduate

work and receipt of a Bachelors of Science in Civil Engineering, he

continued on to receive a Masters of Science in Environmental

Engineering at Virginia Tech. At the time of this writing, he resides in “

Greenville, South Carolina where he is employed with Black & Veatch

DOS ced DLQLIE

Consulting Engineers.

208