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
CROC C ee REESE THOR E HEHEHE MOOT EERO HEH ESOC ROTHER EET OEE OTOH ORT EREHEEO ORT EE SOE HEODEF EROS HOSE FOOES HOES
CROC POR See H CORE HEHEHE SEE HEHRTEEH DORE H OEE OHOTEG HEE OOH ETE SEHR H HOHE HEH DD ERE HHO HFELS
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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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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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Manganese Potential Diagram for Mn-O2-CO2-H29, 25°C, 10°M (from
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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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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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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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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
87
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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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106
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
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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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
137
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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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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 |
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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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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
100
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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
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7.00E-03 ;—---— ee
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0 20 40 60 80 100 120
Fe(III) Concentration
176
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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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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
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