December 14, 2001
To the Graduate School:
This thesis entitled “The Characteristics of Potassium Permanganate Encapsulated
in Polymer” and written by Chapman Ross is presented to the Graduate School of
Clemson University. I recommend that it be accepted in partial fulfillment of the
requirements for the degree of Master of Science with a major in Environmental
Engineering and Science.
Dr. Lawrence C. Murdoch, Thesis Advisor
We have reviewed this thesis
and recommend its acceptance:
Dr. Lawrence C. Murdoch, Thesis Advisor
Dr. David L. Freedman, Committee Chairman
Dr. Cindy M. Lee, Committee Member
Accepted for the Graduate School:
THE CHARACTERISTICS OF POTASSIUM
PERMANGANATE ENCAPSULATED IN POLYMER
A Thesis
Presented to
the Graduate School of
Clemson University
In Partial Fulfillment
of the Requirements for the Degree
Master of Science
Environmental Engineering and Science
by
Chapman M. Ross
December 2001
Advisor: Dr. Lawrence C. Murdoch
ABSTRACT
Permanganate is a strong oxidant that has been used to remediate VOCs and
SVOCs in soil and groundwater. In this research, KMnO4 was encapsulated in a polymer
to create small particles, or microspheres, of a compound that slowly releases
permanganate. The KMnO4 microspheres could be used to create a reactive barrier in the
subsurface, or to create a fixed-bed reactor for above-ground treatment.
Two types of microspheres were evaluated and they consist of a total of 18
different formulations. One type contains a core of a single grain of permanganate
encapsulated in a shell of polymer (SGC), whereas the second consists of cores of
multiple grains (MGC).
Batch tests were conducted to show how rapidly the microspheres release
KMnO4, or how rapidly they degrade TCE.
The release tests consist of placing
microspheres and DDI water in a container and measuring the concentration of KMnO4
in the water as a function of time. The concentration change, or release rate, with time
and the total time of release was determined for each set of samples. Another set of tests
was conducted where TCE dissolved in water was placed in a container with
microspheres and the concentration of the TCE was measured as a function of time.
These tests yielded TCE degradation rates, and the time to remove 0.99 of the initial mass
of TCE (t0.99).
Chloride concentrations were measured to determine the extent of
dechlorination of the TCE.
The initial release rates of permanganate and the total time to complete release
vary by an order of magnitude among the different samples. The average early release
iii
rate, ko, is 2.70 [(g KMnO4 released/g KMnO4 initial)/day] and it ranges from 0.22 to
9.41 [(g KMnO4 released/g KMnO4 initial)/day]. The average time to reach maximum
concentration, tmax, for all microspheres is 27 days and it ranges from 3 to 80 days. Data
from batch release tests with SGC samples show higher ko values and shorter tmax values
than those of MGC tests. A simple empirical model was found to be a good fit (average
R2 = 0.929) for most of the release curves, and the parameters from this model serve as a
reasonable characterization of the release behavior.
TCE was degraded to below detectable amounts in the presence of the KMnO4
microspheres. In batch TCE tests, the average initial degradation rate is 1.8 [(mol
TCE/day)/ mg KMnO4] and it ranges from 0.07 to 3.8 [(mol TCE/day)/ mg KMnO4].
The average t0.99 value for all MGC microspheres is 15.5 days and it ranges from 1.3 to
30.9 days. Chloride measured during the test amounts to 2.56 mol of chloride per mol of
TCE, whereas 3 mol Cl- per mol TCE is expected based on the stoichiometry of the
degradation reaction. This suggests that 0.44 mol of chloride per mol of TCE, or 0.15 of
the expected chloride is missing.
The rate of TCE degradation was predicted using the observed rate of release of
KMnO4 and assuming an ideal reaction stoichiometry.
The actual rates of TCE
degradation were 3 to 4 times faster than the predicted rates during the first few days of
the tests. TCE was completely removed in some tests after a few days. However, where
TCE was present for longer than a few days, the degradation reaction rate decreased and
was less than predicted based on the release rate.
A conceptual model was developed to explain the results of the TCE degradation
tests. This model suggests that the reaction between TCE and KMnO4 takes place both in
iv
solution and inside the microspheres. TCE is degraded faster than predicted based on
release data alone, possibly due to a strong concentration gradient increasing the rate of
release of KMnO4 out of the microspheres. It is also possible that TCE diffused into, and
was degraded within the microspheres, as KMnO4 was diffusing out of the microspheres.
Incomplete recovery of chloride could occur if daughter products of the reaction were
being trapped in the microspheres.
Two characteristics of microsphere composition were correlated to release and
TCE degradation behavior. Chlorez 700, a chlorinated wax, seems to extend the time of
release. A higher mass fraction of KMnO4 in microspheres tends to increase the initial
degradation rate.
ACKNOWLEDGEMENTS
I would like to thank Dr. Larry Murdoch for his support and guidance in both research
and field work.
I would also like to thank Dr. Freedman for sparking my interest in environmental
engineering and in situ remediation.
Special thanks go to my parents and brother for their love and support throughout my
years at Clemson.
Unending thanks and love go to my many friends at Clemson who made my stay here
better than I could have ever hoped.
TABLE OF CONTENTS
Page
TITLE PAGE ................................................................................................................
i
ABSTRACT ..................................................................................................................
ii
ACKNOWLEDGEMENTS ..........................................................................................
v
LIST OF TABLES ........................................................................................................ viii
LIST OF FIGURES ......................................................................................................
xi
LIST OF SYMBOLS AND ABBREVIATIONS ......................................................... xvii
CHAPTER
1
INTRODUCTION ......................................................................................... 1
2
BACKGROUND ........................................................................................... 4
TCE Oxidation using KMnO4 - Laboratory Experiments ......................... 4
Field Experiments - TCE Oxidation using KMnO4 .................................. 6
KMnO4 Oxidation in Water Treatment ..................................................... 8
Controlled Release Theory ........................................................................ 9
Encapsulation Method ............................................................................... 11
Encapsulated KMnO4 ................................................................................ 13
3
RESEARCH OBJECTIVES .......................................................................... 14
4
MATERIALS AND METHODS ................................................................... 16
Materials .................................................................................................... 16
Experimental Methods............................................................................... 17
Batch Release Tests .............................................................................. 17
Drain-daily Release Tests ..................................................................... 19
TCE Degradation Tests ......................................................................... 20
TCE/Wax Adsorption Testing .............................................................. 26
Experimental Design ............................................................................. 27
5
RESULTS ...................................................................................................... 29
vii
Table of Contents (Continued)
Page
Release Tests ............................................................................................. 29
Release Plots ......................................................................................... 29
Model Selection .................................................................................... 32
Fitting Methodology ............................................................................. 35
Batch Release Parameters ..................................................................... 39
SGC Batch Release Tests...................................................................... 40
MGC Batch Release Tests .................................................................... 45
Batch Release Summary ....................................................................... 51
Drain-daily Release Tests ..................................................................... 57
Stoichiometry of TCE and KMnO4 ........................................................... 66
Adsorption to Shell Materials .................................................................... 66
Batch TCE Degradation Tests ................................................................... 69
Observed TCE Degradation .................................................................. 70
Observed and Predicted TCE Degradation ........................................... 73
Addition of Polymaleic Acid ................................................................ 91
6
DISCUSSION ................................................................................................ 95
7
CONCLUSIONS............................................................................................ 100
APPENDICES .............................................................................................................. 103
A
B
C
D
E
F
G
Response Factors ........................................................................................... 104
1-D Diffusion Model Derivation .................................................................. 112
Batch Release Data ........................................................................................ 117
Drain-Daily Release Data .............................................................................. 133
Adsorption Data for Freundlich Isotherms .................................................... 140
TCE Degradation Data ................................................................................... 144
Polymaleic Acid Addition.............................................................................. 166
REFERENCES ............................................................................................................. 171
LIST OF TABLES
Table
Page
Table 4.1
Encapsulated sample data. ......................................................................... 18
Table 4.2
Experimental matrix showing the tests that were performed on each
sample. ....................................................................................................... 28
Table 5.1
Model summary. ........................................................................................ 39
Table 5.2
Summary of batch test results. .................................................................. 52
Table 5.3
Model A parameter estimation .................................................................. 55
Table 5.4
Model B parameter estimation. ................................................................. 56
Table 5.5
Table Title ................................................................................................. 57
Table 5.6
Summary of drain-daily results. ................................................................ 65
Table 5.7
Summary of Freundlich parameters. ......................................................... 69
Table 5.8
Initial ratio of KMnO4 to TCE in degradation tests. ................................. 70
Table 5.9
Observed and predicted TCE degradation parameters. ............................. 84
Table A.1 Hach DR 2010 spectrophotometer standards for potassium
permanganate............................................................................................. 105
Table A.2 GC standards for 72 ml bottles .................................................................. 106
Table A.3 GC standards for 160 ml bottles ................................................................ 107
Table A.4 Chloride probe standards ........................................................................... 108
Table A.5 IC standards for potassium ........................................................................ 109
Table A.6 Beckman spectrophotometer standards for potassium permanganate ....... 110
Table C.1 SGC batch release data sample 19-230 ..................................................... 118
Table C.2 SGC batch release data sample 19-231 ..................................................... 118
Table C.3 SGC batch release data sample 19-232 ..................................................... 119
ix
List of Tables (Continued)
Table
Page
Table C.4 SGC batch release data sample 19-233 ..................................................... 119
Table C.5 SGC batch release data sample 19-234 ..................................................... 120
Table C.6 SGC batch release data sample 19-235 ..................................................... 120
Table C.7 SGC batch release data sample 19-236 ..................................................... 121
Table C.8 MGC batch release data sample 19-306 .................................................... 122
Table C.9 MGC batch release data sample 19-307 .................................................... 123
Table C.10 MGC batch release data sample 19-308 .................................................... 124
Table C.11 MGC batch release data sample 19-546 .................................................... 125
Table C.12 MGC batch release data sample 19-547 .................................................... 126
Table C.13 MGC batch release data sample 19-548 .................................................... 127
Table C.14 MGC batch release data sample 19-549 .................................................... 128
Table C.15 MGC batch release data sample 19-550 .................................................... 129
Table C.16 MGC batch release data sample 19-551 .................................................... 130
Table C.17 MGC batch release data sample 19-552 .................................................... 131
Table C.18 MGC batch release data sample 19-553 .................................................... 132
Table D.1 Drain-daily release data for low volume test with sample 19-306 ............ 134
Table D.2 Drain-daily release data for low volume test with sample 19-307 ............ 135
Table D.3 Drain-daily release data for low volume test with sample 19-308 ............ 136
Table D.4 Drain-daily release data for high volume test with sample 19-547 ........... 137
Table D.5 Drain-daily release data for high volume test with sample 19-551 ........... 138
Table D.6 Drain-daily release data for high volume test with sample 19-552 ........... 139
Table E.1
Boler wax batch adsorption data. .............................................................. 141
Table E.2
Boler wax calculations for isotherm fit ..................................................... 141
x
List of Tables (Continued)
Table
Table E.3
Page
Sample 19-363 batch adsorption data. ...................................................... 142
Table E.4 Sample 19-363 calculations for isotherm fit ............................................. 142
Table E.5
Chlorez 700 batch adsorption data. ........................................................... 143
Table E.6
Chlorez 700 calculations for isotherm fit. ................................................. 143
Table F.1
TCE degradation data for sample 19-307.................................................. 145
Table F.2
TCE degradation data for sample 19-308.................................................. 146
Table F.3
TCE degradation data for water controls (corresponds to Table F.1
and F.2) ...................................................................................................... 147
Table F.4
TCE degradation data for sample 19-363.................................................. 148
Table F.5
TCE degradation data for sample 19-546.................................................. 149
Table F.6
TCE degradation data for sample 19-547.................................................. 150
Table F.7
TCE degradation data for sample 19-548.................................................. 151
Table F.8
TCE degradation data for sample 19-549.................................................. 152
Table F.9
TCE degradation data for sample 19-550.................................................. 153
Table F.10 TCE degradation data for sample 19-551.................................................. 154
Table F.11 TCE degradation data for sample 19-552.................................................. 155
Table F.12 TCE degradation data for sample 19-553.................................................. 156
Table F.13 TCE degradation data for water controls (corresponds to Table F.4
and F.12) .................................................................................................... 157
Table F.14 Chloride stoichiometry data from TCE degradation tests. ........................ 158
Table F.15 Potassium data from TCE degradation tests.............................................. 159
Table F.16 Permanganate data from TCE degradation tests. ...................................... 163
Table G.1 Preliminary data for PMA experiment. ..................................................... 167
Table G.2 TCE and PMA degradation experiment data. ........................................... 168
LIST OF FIGURES
Figure
Page
Figure 2.1 Pathway for TCE oxidation by KMnO4 (adapted with permission
from Yan and Schwartz, 1999).................................................................. 5
Figure 2.2 Single grain core system............................................................................ 10
Figure 2.3 Multi-grain core system............................................................................. 11
Figure 2.4 Rotating disk device (courtesy of SWRI).................................................. 12
Figure 2.5 Schematic of spinning disk/microsphere formation (courtesy of
SWRI) ........................................................................................................ 13
Figure 4.1 Grain size distribution of technical grade KMnO4 (provided by Carus
Chemical Company). ................................................................................. 16
Figure 5.1 Example release plot showing key parameters, Cr,max, ko, t0.5, and tmax. .... 31
Figure 5.2 Model fits for sample 19-234 batch release data. Inset shows initial
data and model fits. ................................................................................... 36
Figure 5.3 Model fits for sample 19-551 batch release data. Inset shows initial
data and model fits. ................................................................................... 37
Figure 5.4 Batch release for sample 19-230. ko = 9.4 g KMnO4 released/g
KMnO4 initial/day, t0.5=0.020 days, tmax=6.3 days, Cr,max = 0.80 g
KMnO4 released/g KMnO4 initial, and R2=0.894. .................................... 41
Figure 5.5 Batch Release – Sample 19-231. ko = 7.6 g KMnO4 released/g
KMnO4 initial/day, t0.5=0.055 days, tmax=6.3 days, Cr,max = 0.91 g
KMnO4 released/g KMnO4 initial, and R2=0.819. .................................... 41
Figure 5.6 Batch Release – Sample 19-232. ko = 7.6 g KMnO4 released/g
KMnO4 initial/day, t0.5=0.060 days, tmax=6.3 days, Cr,max = 1.05 g
KMnO4 released/g KMnO4 initial, and R2=0.866. .................................... 42
Figure 5.7 Batch Release – Sample 19-233. ko = 8.8 g KMnO4 released/g
KMnO4 initial/day, t0.5=0.042 days, tmax=5.4 days, Cr,max = 1.02 g
KMnO4 released/g KMnO4 initial, and R2=0.794. .................................... 42
xii
List of Figures (Continued)
Figure
Page
Figure 5.8 Batch Release – Sample 19-234. ko = 7.7 g KMnO4 released/g
KMnO4 initial/day, t0.5=0.044 days, tmax=6.3 days, Cr,max = 0.81 g
KMnO4 released/g KMnO4 initial, and R2=0.866. .................................... 43
Figure 5.9 Batch Release – Sample 19-235. ko = 3.1 g KMnO4 released/g
KMnO4 initial/day, t0.5=0.178 days, tmax=3.0 days, Cr,max = 0.83 g
KMnO4 released/g KMnO4 initial, and R2=0.972. .................................... 43
Figure 5.10 Batch Release – Sample 19-236. ko = 2.2 g KMnO4 released/g
KMnO4 initial/day, t0.5=0.339 days, tmax=6.3 days, Cr,max = 0.86 g
KMnO4 released/g KMnO4 initial, and R2=0.986. .................................... 44
Figure 5.11 Batch Release - Sample 19-306. Average of triplicate bottles shown.
Error bars represent one standard deviation. ko = 0.15 g KMnO4
released/g KMnO4 initial/day, t0.5=1.69 days, tmax=6.8 days, Cr,max =
0.88 g KMnO4 released/g KMnO4 initial, and R2=0.907. ......................... 46
Figure 5.12 Batch Release - Sample 19-307. Average of triplicate bottles shown.
Error bars represent one standard deviation. ko = 0.034 g KMnO4
released/g KMnO4 initial/day, t0.5=7.931 days, tmax=26 days, Cr,max =
0.86 g KMnO4 released/g KMnO4 initial, and R2=0.886. ......................... 46
Figure 5.13 Batch Release - Sample 19-308. Average of triplicate bottles shown.
Error bars represent one standard deviation. ko = 0.104 g KMnO4
released/g KMnO4 initial/day, t0.5=12.75 days, tmax=36(est.) days,
Cr,max = 0.95(est.) g KMnO4 released/g KMnO4 initial, and R2=0.955. .... 47
Figure 5.14 Batch release test for 19-546. Average of duplicate bottles shown.
Error bars represent one standard deviation. ko = 0.19 g KMnO4
released/g KMnO4 initial/day, t0.5=5.26 days, tmax=36 days, Cr,max =
0.95 g KMnO4 released/g KMnO4 initial, and R2=0.969. ......................... 47
Figure 5.15 Batch release test for 19-547. Average of triplicate bottles shown.
Error bars represent one standard deviation. ko = 0.20 g KMnO4
released/g KMnO4 initial/day, t0.5=3.29 days, tmax=42 days, Cr,max =
0.80 g KMnO4 released/g KMnO4 initial, and R2=0.982. ......................... 48
Figure 5.16 Batch release test for 19-548. ko = 0.29 g KMnO4 released/g KMnO4
initial/day, t0.5=2.40 days, tmax=36 days, Cr,max = 0.94 g KMnO4
released/g KMnO4 initial, and R2=0.987. .................................................. 48
xiii
List of Figures (Continued)
Figure
Page
Figure 5.17 Batch release test for 19-549. Average of triplicate bottles shown.
Error bars represent one standard deviation. ko = 0.21 g KMnO4
released/g KMnO4 initial/day, t0.5=6.73 days, tmax=80 days, Cr,max =
0.88 g KMnO4 released/g KMnO4 initial, and R2=0.979. ......................... 49
Figure 5.18 Batch release test for 19-550. Average of triplicate bottles shown.
Error bars represent one standard deviation. ko = 0.22 g KMnO4
released/g KMnO4 initial/day, t0.5=4.38 days, tmax=46 days, Cr,max =
0.93 g KMnO4 released/g KMnO4 initial, and R2=0.975. ......................... 49
Figure 5.19 Batch release test for 19-551. Average of triplicate bottles shown.
Error bars represent one standard deviation. ko = 0.38 g KMnO4
released/g KMnO4 initial/day, t0.5=1.84 days, tmax=42 days, Cr,max =
0.92 g KMnO4 released/g KMnO4 initial, and R2=0.961. ......................... 50
Figure 5.20 Batch release test for 19-552. Average of triplicate bottles shown.
Error bars represent one standard deviation. ko = 0.21 g KMnO4
released/g KMnO4 initial/day, t0.5=3.01 days, tmax=18 days, Cr,max =
0.94 g KMnO4 released/g KMnO4 initial, and R2=0.953. ......................... 50
Figure 5.21 Batch release test for 19-553. Average of triplicate bottles shown.
Error bars represent one standard deviation. ko = 0.22 g KMnO4
released/g KMnO4 initial/day, t0.5=6.36 days, tmax=66 days, Cr,max =
0.94 g KMnO4 released/g KMnO4 initial, and R2=0.970. ......................... 51
Figure 5.22 Summary of batch test results. Listed in order of increasing t0.5. ............. 53
Figure 5.23 Drain-daily low volume - sample 19-306. Batch release data are
average of triplicate bottles. Error bars represent one standard
deviation. Cr,max(drain-daily)=0.72 and Cr,max(batch)=0.88. ..................... 58
Figure 5.24 Drain-daily low volume - sample 19-307. Batch release data are
average of triplicate bottles. Error bars represent one standard
deviation. Cr_max(drain-daily)=0.82 and Cr_max(batch)=0.86. ................... 59
Figure 5.25 Drain-daily low volume - sample 19-308. Batch release data are
average of triplicate bottles. Error bars represent one standard
deviation. Cr,max(drain-daily)=0.59 and Cr,max(batch)=0.95. ..................... 60
Figure 5.26 Drain-daily high volume - sample 19-547. Batch release data are
average of triplicate bottles. Error bars represent one standard
deviation. Drain-daily data are average of duplicate bottles.
Cr,max(drain-daily)=0.71 and Cr,max(batch)=0.80........................................ 62
xiv
List of Figures (Continued)
Figure
Page
Figure 5.27 Drain-daily high volume - sample 19-551. Batch release data are
average of triplicate bottles. Error bars represent one standard
deviation. Drain-daily data are average of duplicate bottles.
Cr,max(drain-daily)=0.86 and Cr,max(batch)=0.92........................................ 63
Figure 5.28 Drain-daily high volume - sample 19-552. Batch release data are
average of triplicate bottles. Error bars represent one standard
deviation. Drain-daily data are average of duplicate bottles.
Cr,max(drain-daily)=0.90 and Cr,max(batch)=0.94........................................ 64
Figure 5.29 Equilibrium concentration for sample 19-363 and TCE.
Representative data from one of four bottles per sample. ......................... 67
Figure 5.30 Equilibrium concentration for boler wax and TCE. Representative
data from one of four bottles per sample. .................................................. 67
Figure 5.31 Equilibrium concentration for Chlorez 700 and TCE. Representative
data from one of four bottles per sample. .................................................. 67
Figure 5.32 Freundlich isotherm for sample 19-363 and TCE. .................................... 68
Figure 5.33 Freundlich isotherm for boler wax and TCE. ............................................ 68
Figure 5.34 Freundlich isotherm for Chlorez 700 and TCE ......................................... 68
Figure 5.35 Batch TCE degradation test for 19-307. Symbols represent average
of quadruplicate bottles for observed TCE and duplicate bottles for
water controls. The error bars represent one standard deviation. ............. 71
Figure 5.36 Batch TCE degradation test for 19-308. Symbols represent average
of quadruplicate bottles for observed TCE and duplicate bottles for
water controls. The error bars represent one standard deviation. The
inset shows initial TCE activity................................................................. 72
Figure 5.37 Batch TCE degradation test for 19-546. Symbols represent average
of triplicate bottles for observed TCE and water controls. The error
bars represent one standard deviation. The inset shows initial TCE
activity. ...................................................................................................... 74
Figure 5.38 Batch TCE degradation test for 19-547. Symbols represent average
of triplicate bottles for observed TCE and water controls. The error
bars represent one standard deviation. ...................................................... 75
xv
List of Figures (Continued)
Figure
Page
Figure 5.39 Batch TCE degradation test for 19-548. Symbols represent average
of triplicate bottles for observed TCE and water controls. The error
bars represent one standard deviation. The inset shows initial TCE
activity. ...................................................................................................... 76
Figure 5.40 Batch TCE degradation test for 19-549. Symbols represent average
of triplicate bottles for observed TCE and water controls. The error
bars represent one standard deviation. ...................................................... 77
Figure 5.41 Batch TCE degradation test for 19-550. Symbols represent average
of triplicate bottles for observed TCE and water controls. The error
bars represent one standard deviation. The inset shows initial TCE
activity. ...................................................................................................... 78
Figure 5.42 Batch TCE degradation test for 19-551. Symbols represent average
of triplicate bottles for observed TCE and water controls. The error
bars represent one standard deviation. The inset shows initial TCE
activity. ...................................................................................................... 79
Figure 5.43 Batch TCE degradation test for 19-552. Symbols represent average
of triplicate bottles for observed TCE and water controls. The error
bars represent one standard deviation. The inset shows initial TCE
activity. ...................................................................................................... 80
Figure 5.44 Batch TCE degradation test for 19-553. Symbols represent average
of triplicate bottles for observed TCE and water controls. The error
bars represent one standard deviation. The inset shows initial TCE
activity. ...................................................................................................... 81
Figure 5.45 Observed and predicted initial TCE degradation rates. Observed rates
are average values calculated from triplicate batch TCE degradation
data. Predicted values are average values calculated from triplicate
batch release data. Error bars represent one standard deviation.
Samples are ordered by increasing observed rate. .................................... 85
Figure 5.46 Observed and predicted 0.99 mass removal times. Observed times
are average values calculated from triplicate batch TCE degradation
data. Predicted values are average values calculated from triplicate
batch release data. Error bars represent one standard deviation.
Samples are ordered as in Figure 5.42. ..................................................... 86
Figure 5.47 Batch TCE degradation test for 19-363. Symbols represent average
of triplicate bottles. The error bars represent one standard deviation. ..... 89
xvi
List of Figures (Continued)
Figure
Page
Figure 5.48 Chloride recovery in batch TCE degradation test. Values shown are
averages of triplicates. Error bars represent one standard deviation. ....... 92
Figure 5.49 PMA concentration analysis. ..................................................................... 93
Figure 5.50 TCE degradation test with PMA present. Symbols represent average
of triplicate bottles. The error bars represent one standard deviation. ..... 94
Figure 6.1 Conceptual model step 1. .......................................................................... 97
Figure 6.2 Conceptual model step 2. .......................................................................... 98
Figure A.1 Hach DR 2010 spectrophotometer response factor for potassium
permanganate............................................................................................. 105
Figure A.2 GC response factor for 72 ml bottles......................................................... 106
Figure A.3 GC response factor for 160 ml bottles....................................................... 107
Figure A.4 Chloride probe response factor.................................................................. 108
Figure A.5 IC response factor for potassium ............................................................... 109
Figure A.6 Beckman spectrophotometer response factor for filtered potassium
permanganate solutions ............................................................................. 110
Figure A.7 Beckman spectrophotometer response factor for unfiltered potassium
permanganate solutions ............................................................................. 111
LIST OF SYMBOLS AND ABBREVIATIONS
Arabic Symbols
Greek Symbols
Abbreviations
ATSDR
Agency for Toxic Substances and Disease Registry
DDI
Distilled Deionized Water
DOC
Dissolved Organic Carbon
GC
Gas Chromatograph
MGC
Multi-Grain Core
ORNL
Oak Ridge National Labs
PCE
Perchloroethylene or Tetrachloroethylene
SGC
Single Grain Core
SVOC
Semi-Volatile Organic Compounds
SWRI
Southwest Research Institute
TCE
Trichloroethylene
U.S. EPA
United States Environmental Protection Agency
VC
Vinyl Chloride
VOC
Volatile Organic Compounds
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CHAPTER 1
INTRODUCTION
Potassium Permanganate (KMnO4) is a versatile chemical oxidant used for a
variety of engineering applications. The predominant environmental engineering use for
KMnO4 is to oxidize volatile organic compounds (VOCs) and semi volatile organic
compounds (SVOCs) in soil and groundwater (e.g. Gates et al., 2001; Schnarr et al.,
1998; Siegrist et al., 1999). As the field of in situ remediation advances, oxidation using
KMnO4 steadily gains attention due to its ability to rapidly destroy VOCs such as
trichloroethylene (TCE) and perchloroethylene (PCE) and vinyl chloride (VC) (Vella and
Veronda, 1992; Walton et al., 1991).
Oxidation of TCE and PCE is particularly
significant because they are among the most common compounds polluting groundwater
in the U. S. (Westrick et al., 1984). In addition, TCE has been detected at more than 50%
of the Superfund sites (ATSDR, 1995; Plumb, 1987).
The oxidation of TCE by KMnO4 has been evaluated in both laboratory and field
tests. Lab tests indicate the reaction is second order, has three sequential steps, is
independent of pH in the range of 4 to 8, and is relatively quick with half-lives on the
order of 17 min (Yan and Schwartz, 1999; 2000). Field tests of oxidation of TCE by
KMnO4 as a remediation technology have brought to light several drawbacks. One
problem encountered is difficulty controlling distribution of oxidant in the subsurface
(Schnarr et al., 1998; ORNL, 1997). Nonuniform distribution of oxidant may result in
zones of incomplete contaminant degradation. In addition, this problem could prevent
delivery of oxidant to contaminant source zones. Another factor is insufficient oxidant
2
loading resulting from high soil oxidant demand (e.g. Cline et al., 1997; McKay et al.,
1998). Additionally, formation of MnO2 (a product of the reaction between KMnO4 and
TCE) can cause further remediation difficulties by lowering the hydraulic conductivity of
the soil in the treatment zone, thus limiting fluid movement through the area (Drescher et
al., 1998; Schroth et al., 2001). This has the potential to further isolate the contaminants
of concern.
In addition to soil and groundwater remediation, KMnO4 is commonly used in
wastewater and drinking water treatment. It has been used to oxidize trihalomethane
(THM) precursors (Colthurst and Singer, 1982), and Mn2+ (Carlson and Knocke, 1999) in
drinking water treatment, and to treat low-level phenols (g/L) (Vella et al., 1990). Other
uses include removal of TOC, COD, and color from a variety of industrial and domestic
wastewaters, (Walton et al., 1991), as well as taste and odor removal for drinking water
treatment (Cherry, 1962).
In this work, KMnO4 will be encapsulated in a polymer to create a compound that
is intended to slowly release permanganate. These KMnO4 microspheres are intended to
degrade TCE in situ. The rates that KMnO4 is released and the rate that TCE is degraded
in batch tests will be evaluated. The microspheres consist of KMnO4 coated in various
wax-like polymer shells varying in diameter from 60 to 2000 microns. Some of the
microspheres consist of single grains of KMnO4 (single grain core) enveloped in polymer
shells, whereas others consist of many grains of KMnO4 (multi-grain core) suspended in
a polymer matrix. The method used to create the microspheres is known as the rotating
disk technique (Pothakamury and Barbosa-Cánovas, 1995).
3
The microspheres have the potential to address some of the problems encountered
with current KMnO4 remediation methods. One potential advantage of the microspheres
is ease of delivery. Placement options of the microspheres, including use with hydraulic
fracturing, could distribute the oxidant within the treatment zone, specifically targeting
source zones of contamination. The amount of KMnO4 wasted oxidizing organic carbon
in soil and groundwater could be reduced by designing microspheres that allow TCE to
diffuse in and react with KMnO4. This would allow application of less oxidant, and it
follows that when less oxidant is used, less MnO2 is formed, helping to minimize flow
disruptions.
KMnO4 microspheres could also be used in a variety of other engineering
applications. Industrial wastewater, domestic wastewater, and drinking water treatment
could benefit from the controlled release properties of the microspheres. As an example,
microspheres that release KMnO4 over a period of two months could be applied to a
batch or flow-through reactor six times a year. This decreased application frequency
could lower equipment and labor costs by eliminating the need for a continuous feed of
KMnO4.
KMnO4 microspheres could also have potential in fixed-bed reactors for
treatment of any waste stream containing KMnO4 oxidizable contaminants. In addition
to improvements to processes, the coated microspheres could be safer to handle than raw
KMnO4.
CHAPTER 2
BACKGROUND
The use of KMnO4 in water and wastewater treatment systems is documented
back to the 1960’s. More recently, people have started using KMnO4 for remediation of
contaminants in the soil and groundwater. This work includes laboratory and field tests.
In the following section, the wastewater applications and the lab and field studies will be
discussed.
TCE Oxidation using KMnO4 - Laboratory Experiments
Oxidation and reduction reactions are described as pairs of half reactions. In
chemical oxidation for hazardous waste treatment, the waste component serves as the
reducing agent, and the oxidizing agent is added to complete the reaction (LaGrega et al.,
1994). Both laboratory and field studies have shown that TCE can be oxidized using
KMnO4 (ORNL, 1997; Yan and Schwartz, 1998; Siegrist et al., 1999).
The reaction cleaves the double carbon (C) bond to yield CO2, manganese dioxide
(MnO2), potassium chloride (KCl), and hydrochloric acid (HCl) (Yan and Schwartz,
1998), according to
C2Cl3H + 2KMnO4 ==> 2CO2 (aq) + 2MnO2 (s) + 2KCl + HCl
(1)
The complete reaction entails three sequential steps (Figure 2.1). First, a cyclic
hypomanganate ester is formed from TCE via an activated organometallic complex.
5
Cl
H
C
TCE
C
Cl
Cl
slow MnO 4- (VII)
O-
O
Step 1
(V)
OMnO 32-
Mn (V)
O
O
H
Cl
C
MnO 4+H +
Cl-
H2O
OH
Cl
H
C
C
Cl
Cl
Cl
Cl
Cyc lic Es te r
H
O
O
C
C
H
H
O
OH
C
Cl
C
O
C
C
H
OH
OH
C
C
Cl
Cl
Cl
Cl
HCl
(IV)
HMnO 3+HCl
(IV)
HMnO 3-
O
C
Cl
Cl
2H 2O
2H 2O
2HCl
2HCl
O
H
OH
Cl
(IV)
HMnO 3-
C
O
H
Cl
H
Mn
O
H
Cl
Step 2
Cl-
O
Mn (VI)
OHMn(VII)
+Mn(IV)
MnO 4+H 2O
OO
C
O
O
C
C
Cl
H
H2 O
2H 2O
HCl
HCl
OH
O
O
O
O
O
C
C
C
C
C
C
H
OH
H
Formic Ac id
OH
H
Glyoxylic Ac id
OH
Glyc olic Ac id
OH
HO
Oxalic Ac id
MnO 4-
Step 3
MnO 4-
slow
slow
slow
O
C
MnO 4-
O
Carbon Dioxide
Figure 2.1
Pathway for TCE oxidation by KMnO4 (adapted with permission from Yan
and Schwartz, 1999)
6
Next, the rapid decomposition of this cyclic ester with complete chlorine liberation
proceeds via various reaction pathways to form four carboxylic acids: formic acid,
glycolic acid, glyoxylic acid, and oxalic acid (Yan and Schwartz, 2000; Huang et al.,
1999). The stoichiometric amount of each acid formed is pH dependent. The final step in
the reaction is the oxidation of all the carboxylic acids to CO2 by permanganate (Yan and
Schwartz, 2000).
The first step of the reaction is rate limiting, second order, and independent of pH
in the range of pH = 4-8. The rate constant for the first step ranges from 0.66±0.02 to
0.89±0.03 M-1 s-1 according to Huang et al. (1999). Oxidation of TCE by MnO2 is
slower than by oxidation of TCE by KMnO4 (Seol and Schwartz, 2000).
Field Experiments - TCE Oxidation using KMnO4
In situ TCE oxidation using KMnO4 has been demonstrated in multiple field
experiments using a variety of application methods. Siegrist et al. (1999) accomplished
rapid TCE degradation in a field study using granules of KMnO4 injected into hydraulic
fractures. Treatment of the TCE was achieved by KMnO4 in the soil. This experiment
showed 90% removal at up to 12 cm above and below the fractures. In addition, even
after 10 months, the soil around the fracture still contained significant oxidizing potential.
Two field studies report difficulty uniformly distributing oxidant in the treatment
zone. In one study, Schnarr et al. (1998) performed two controlled field experiments
using TCE and PCE sources that were placed in soil saturated with water. Sites were
treated by flushing the saturated zone with a 10 g/L KMnO4 solution. In one experiment,
oxidant was injected into one set of wells, and effluent was extracted out of another set.
7
In the second experiment, a recycle loop was added connecting the injection and
extraction wells. Unconsumed KMnO4 from the extraction well was utilized, thereby
decreasing the amount of oxidant needed. PCE concentrations decreased by 90 to 100%
in the first experiment and by only 60% in the second. This relatively low fraction of
treatment was attributed to zones of soil that were highly saturated with the contaminants
and proved difficult to treat (Schnarr et al., 1998).
Another study by Oak Ridge National Labs used injection of a KMnO4 solution
into one horizontal well and extraction out of another (1997). Extracted water was mixed
with a KMnO4 solution and reinjected. Average TCE concentrations decreased from 164
mg/L to 28 mg/L in the field test site after two weeks. The results of the study showed
remediation of TCE to non-detectable levels in some areas, and incomplete removal in
others. These differences in contaminant removal were attributed to heterogeneities that
prevented uniform delivery of oxidant.
Other field studies have insufficient oxidant loading issues resulting from high
soil and groundwater oxidant demand. McKay et al. (1998) tested an in situ TCE
treatment technique using direct-push wells to inject KMnO4 solution at multiple depths.
Post-injection analysis of the site indicated some TCE was destroyed, but more oxidant
was needed to reduce the TCE to acceptable levels. Another remediation technique
tested for delivery of KMnO4 to a contaminated zone is called deep soil mixing (Cline et
al., 1997). This method involves mixing soil using eight-foot-diameter cutting blades.
The mixer is used during injection of KMnO4 to uniformly distribute the oxidant. The
mixer successfully blended the oxidant and soil during on field test of this technique by
Cline et al. (1997). However, clean-up suffered from insufficient oxidant loading so that
8
TCE mass removals were only 65% during this test. These results highlight the need to
deliver KMnO4 both uniformly and in adequate amounts.
In addition to uniform delivery and insufficient oxidant loading issues,
researchers have observed several possible drawbacks during remediation with KMnO4.
Formation of manganese dioxide (MnO2) solid can affect flow through the contaminated
area (Drescher et al., 1998). Also, manganese (Mn2+) has a secondary drinking water
standard of 50 g/L, so introducing high concentrations of manganese into the subsurface
is a concern (Drescher et al., 1998).
KMnO4 Oxidation in Water Treatment
KMnO4 is used for a wide variety of water and wastewater treatment applications.
Taste and odor removal are the most common uses during drinking water treatment
(Cherry, 1962). Another drinking water treatment application for KMnO4 is oxidizing
manganese (Mn2+) to MnO2. Mn2+ causes aesthetic problems, such as coloring of the
water and fouling or scaling of fixtures (Carlson and Knocke, 1999). KMnO4 has also
been used in the treatment of trihalomethane (THM) precursors. This process uses two
mechanisms to remove these chemicals: KMnO4 oxidizes them and forms MnO2 which
can in turn adsorb the precursors (Colthurst and Singer, 1982).
Industrial and textile wastewater treatment have seen extensive use of KMnO4. It
has been used in the textile industry for removal of many types of dyes, and for color
removal in food, chemical, wood products, and textile wastewaters.
KMnO4 is
commonly applied for total organic carbon (TOC) removal in industrial waste streams
9
(Walton et al., 1991). Multiple studies have shown that phenols can be removed from
industrial wastewaters by reaction with KMnO4 (Vella et al., 1990; Walton et al., 1991).
Controlled Release Theory
Controlled release compounds were developed in the pharmaceutical industry, but
their use is now common in agrochemicals, fertilizers, veterinary drugs, and food
industries. Controlled release is a method by which an active agent or agents are made
available
at
a
specific
rate
(Pothakamury
and
Barbosa-Cánovas,
1995).
Microencapsulation is the packaging of solid, liquid or gaseous materials in miniature
sealed capsules that release their contents at a controlled rate under certain environmental
conditions (Pothakamury and Barbosa-Cánovas, 1995).
The microspheres used for this work consist of cores of KMnO4 enveloped in
relatively inert material. Two geometries of core and shell material were evaluated. One
consists of cores of single grains of KMnO4 with shells of inert material and will be
called the single grain core (SGC) material (Figure 2.2). The other encapsulated material
consists of multiple grains of KMnO4 in a matrix of inert material (Figure 2.3). This will
be termed multi-grain core (MGC) material. Release of KMnO4 from microspheres will
be dictated by diffusion through the shell or matrix. The principal steps of release from
SGC material are (Pothakamury and Barbosa-Cánovas, 1995):
1. Diffusion of fluid into the microsphere.
2. Diffusion of the active agent (KMnO4) within the reservoir.
3. Dissolution or partitioning of the active agent (KMnO4) between the infiltrating
fluid and the shell material.
10
4. Diffusion of the active agent through the shell material and partitioning between
the shell and the surrounding medium.
5. Transport away from the shell surface into the surrounding medium.
Release from the SGC material is slightly different than from the MGC.
principal steps of release from MGC material are:
1. Diffusion of fluid into the matrix.
2. Dissolution of the active agent into the matrix.
3. Diffusion of the active agent to the surface of the matrix.
4. Transport away from the surface.
Figure 2.2
Single grain core system
The
11
Figure 2.3
Multi-grain core system
Encapsulation Method
The method used to encapsulate KMnO4 is known as the rotational suspension
separation system, or the rotating disk process (Pothakamury and Barbosa-Cánovas,
1995).
This process has been utilized in the chemical, food, pharmaceutical, and
biochemical industries (Dziezak, 1988). Microsphere preparation by the disk process
consists of three stages: 1) dispersion stabilization, 2) droplet formation, and 3) drying,
and/or post curing (Figure 2.4). The first stage is to prepare a dispersed slurry of the core
(in this case KMnO4) and liquid phase shell solution.
In the second stage, the slurry is introduced to a high-speed rotating disk. The
slurry is fed to the center of the rotating disk. It flows over the surface and is shed as
small droplets off the edge of the spinning disk. The droplets cool and harden into
microspheres before they reach the ground (Figure 2.5). The microspheres are collected
at the bottom of a cooling chamber. The feed rate, disk speed, and slurry viscosity
12
control the size of the microspheres. For this work, a four-inch-diameter disk was used
with disk speeds ranging from 500 to 1250 rpm. The feed rate was approximately 100
g/min. Encapsulation was performed at Southwest Research Institute (SWRI) in San
Antonio, Texas.
Figure 2.4
Rotating disk device (courtesy of SWRI)
13
Figure 2.5
Schematic of spinning disk/microsphere formation (courtesy of SWRI)
Encapsulated KMnO4
An encapsulated compound combining the oxidizing capabilities of KMnO4 with
the flexibility of controlled release technology could have applications in many
engineering processes.
Such a compound has the potential to address some of the
problems encountered during remediation of VOCs and SVOCs with KMnO4, and it
would also have a variety of uses in water and wastewater treatment. The first step in
applying such a technology is to understand the behavior of the microspheres in simple
systems approximating potential applications.
The purpose of this thesis is to
characterize the behavior of encapsulated KMnO4 samples in aqueous systems, and to
assess the ability of those samples to degrade TCE.
CHAPTER 3
RESEARCH OBJECTIVES
The objective of this project is to quantify the release characteristics of
encapsulated KMnO4 samples including initial rate of release and overall release time,
and to evaluate the capacity of these samples to degrade TCE.
The project consists of the following:
1. To determine distribution of KMnO4 grains within the microspheres for each batch
of samples using microscopic observations.
2. To determine the KMnO4 release rate over time, and the total time of release for
each set of samples using batch release tests.
3. To determine an effective method for release prediction during batch release tests.
4. To simulate flow-through release conditions using a specialized batch release test,
which will be termed a drain-daily release test.
5. To characterize adsorption of TCE to encapsulation materials using batch
TCE/polymer tests, including development of Freundlich isotherms.
6. To demonstrate degradation of TCE over time in the presence of different samples
of encapsulated KMnO4 in batch tests.
a)
Determine the concentration of MnO4- during the degradation of
TCE.
b)
Determine the concentration of daughter products of the
degradation reaction including chloride and potassium.
15
7. To develop a conceptual model of the degradation of TCE in batch tests with
microspheres.
CHAPTER 4
MATERIALS AND METHODS
Materials
The core reactive material consists of granular, technical-grade KMnO4
manufactured by Carus Chemical Company (Peru, IL). Sixty percent of the material has
a grain size between 177 and 420 microns and less than two percent is finer than 74
microns (Figure 4.1). TCE used is ACS reagent grade (Fisher Scientific, Fairlwan, NJ).
Polymaleic acid (PMA) used is made up of 37% dissolved organic carbon (DOC) with
23.0% aromaticity, and phenolic and carboxylic acidities of 3.2 and 13 meq/g DOC,
respectively (Karanfil, 1995).
Cumulative % Retained
100%
Specific Gravity = 2.7 g/cm3
Bulk Density = 1440 kg/m3
Mean Particle Size = 200 m
80%
60%
40%
20%
0%
0
100
200
300
400
500
Size (m)
Figure 4.1
Grain size distribution of technical grade KMnO4 (provided by Carus
Chemical Company).
17
All of the shell materials used in the microspheres consist of some type of waxblend polymer. Polymers include Polywax 1000, Fumed Silica, Paraffin Wax 1426,
Elvax 210, Ultem 1000, Boler Wax, Piccolyte S115 Resin, Piccolyte S125 Resin,
Epolene C-10, Epolene C-16, Cab-o-sil, and Chlorez 700. Variations in the blend of
polymers and manufacturing parameters resulted in two basic shell types (Table 4.1).
SGC microspheres consist of seven formulations, ranging in grain size from 60 to 1000
m. MGC microspheres consist of eleven formulations ranging in size from 600 to 2000
m. Chlorez 700, a chlorinated wax, was used in four of the MGC microspheres with the
intent of increasing adsorption of TCE onto the shell. In addition, the initial mass
fraction of KMnO4 was increased in three of the MGC microspheres from 0.4 to 0.5.
Table 4.1 details composition of each set of microspheres by mass fraction and grain size.
Experimental Methods
Batch Release Tests
Batch release tests were conducted by placing 0.2 g of microspheres in 250 ml
glass amber bottles containing 150 ml of distilled deionized (DDI) water, capped with
Teflon-lined lids. The bottles were agitated on an orbital shaker, and the concentration of
KMnO4 in the water was determined as a function of time. The bottles were sampled
once per hour for the first three hours and at least once every two days thereafter.
Measurements continued until the KMnO4 concentration changed by less than 5.0 mg/l
over ten days.
Table 4.1
Encapsulated sample data.
Wax Composition (mass fraction)
KMnO4 Grain Size
Core/
Total KMnO Filtered
(m)
Shell Sample Polywax Fumed Paraffin Elvax Ultem Boler Piccolyte Piccolyte Epolene Epolene
4
Chlorez
(80 Mesh)
Wax
S115
S125
Cab-o-sil
(mass
Type
1000 Silica
210 1000 Wax
C-10
C-16
700
(Y/N)
1426
Resin
Resin
fraction)
min max
SGC
19-230
SGC
19-231
SGC
0.745
0.015
0.76
0.24
N
90
250
0.400 0.100
0.50
0.50
N
60
500
19-232
0.400 0.100
0.50
0.50
N
60
350
SGC
19-233
0.560 0.140
0.70
0.30
N
60
500
SGC
19-234
0.60
0.40
N
120 500
SGC
19-235
0.315
0.315
0.070
0.70
0.30
N
90
500
SGC
0.080
0.80
0.20
N
90
700
0.054
0.60
0.40
N
800 2000
0.60
0.40
N
1000 2000
0.600
19-236
0.360
0.360
MGC 19-306
0.246
0.246
MGC 19-307
0.246
0.246
0.054
MGC 19-308
0.246
0.300
0.054
0.60
0.40
N
1000 2000
None 19-363
0.410
0.500
0.090
1.00
0.00
NA
1000 2000
MGC 19-546
0.246
0.300
0.054
0.60
0.40
N
600 2000
MGC 19-547
0.246
0.300
0.054
0.60
0.40
Y
600 2000
MGC 19-548
0.205
0.250
0.045
0.50
0.50
N
600 2000
MGC 19-549
0.224
0.327
0.050
0.60
0.40
N
800 2000
MGC 19-550
0.186
0.273
0.041
0.50
0.50
Y
800 2000
MGC 19-551
0.186
0.273
0.041
0.50
0.50
N
600 2000
MGC 19-552
0.246
0.300
0.60
0.40
N
800 2000
MGC 19-553
0.246
0.300
0.60
0.40
N
800 2000
0.054
0.054
0.054
0.054
18
Sampling was performed by pipetting 0.1 to 1.0 ml from each bottle and diluting
it with DDI water. The dilution amount was chosen based on KMnO4 concentrations
estimated by observing the color of the water. After dilution, aliquots were added to 10
ml or 25 ml spectrophotometer sample vials. KMnO4 concentration was measured using
absorbance (ABS) with a Hach DR/2010 portable datalogging spectrophotometer
operating at a wavelength of 525 nm. A response factor [(mg KMnO4/l)/ABS] was
developed for an appropriate range of KMnO4 concentrations using the same technical
grade KMnO4 present in the microspheres (App. A).
approximately 1.0 mg KMnO4/l.
The detection limit was
The spectrophotometer was zeroed before each
measurement, and the sample vials were rinsed five times with DDI water after each use.
Drain-daily Release Tests
Another type of test was performed to determine how a low concentration of
KMnO4 in the receiving water might affect the release of KMnO4from microspheres. In
these tests, the water was replaced daily to approximate release to an infinitely dilute
sink, or to flowing water. Low volume drain-daily tests were performed on type 2
samples in 50 ml glass vials. In order to increase the volume of the sink, high volume
drain-daily tests were performed on type 3 samples in 1 liter bottles.
Low Volume
Low volume drain-daily release tests were conducted by placing 0.02 g of
microspheres in 35 ml of DDI water and agitating on an orbital shaker. Once per day, the
DDI water was removed from the sample vials and filtered through medium porosity (6
m particle retention) filter paper (Whatman, cat. # 1003-110). The container was rinsed
20
with DDI water and the filtered solids (microspheres) were washed back into the
container with clean DDI water. The concentration of KMnO4 in the drained water was
measured, and the mass released for that volume of water was calculated. Dilution was
unnecessary when checking KMnO4 concentrations because the levels were significantly
lower than in the batch release tests. KMnO4 losses to the filter paper were ignored.
High Volume
High volume drain-daily release tests were conducted by placing 0.3 g of
microspheres in 900 ml of DDI water and agitating on an orbital shaker. Once per day, a
25 ml sample was removed with a pipette and tested for the KMnO4 concentration.
Based on the concentration observed, a volume of solution was drained from the
container and replaced with an equivalent volume of DDI water.
Initially, the
microspheres were allowed to settle, and drained water was decanted from the top.
Losses of microspheres were seen, and a week after the test began the draining procedure
was amended to include filtering through a fretted stone.
The volume of solution
removed was chosen such that the concentration in the container stayed between 3.0 and
10 mg KMnO4/l. Dilution was unnecessary when checking the KMnO4 concentrations,
because they were significantly less than in the batch release tests.
TCE Degradation Tests
TCE degradation tests were conducted by adding 0.03 to 0.2 g of microspheres
and 1.0 to 7.0 l of neat (pure) TCE in a serum bottle with 20 to 100 ml of DDI water,
and then agitating the bottle and measuring the concentration of TCE as a function of
21
time. Chloride ion, potassium ion, and KMnO4 concentrations were monitored in some
experiments.
TCE Analysis
TCE measurements were made using a Hewlett Packard 5890 Series II gas
chromatograph (GC) equipped with a flame ionization detector and a 2.44-m by 3.175mm column packed with 1% SP-1000 on 60/80 Carbopak B (Supelco). The carrier gas
was nitrogen (30 ml/min). The mass of TCE present in a bottle was determined by gas
chromatographic analysis of 0.1 ml headspace samples, taken with a 1.0 ml gastight
syringe (Precision Scientific, Baton Rouge). A response factor was created to relate the
total mass of the TCE in a bottle to the GC peak area. The detection limit was found to
be 0.02 mol TCE per bottle.
Assuming that the headspace and aqueous phases are in equilibrium, the total
mass present was converted to an aqueous phase concentration using:
Cl 
M
Vl  Hc Vg
(2)
where Cl is the aqueous phase concentration (µM), M is the total mass present
(µmol/bottle), Vl is volume of the liquid in the bottle (l), Vg is volume of the headspace in
the bottle (l), and Hc is Henry's constant (dimensionless) at 23°C (0.347, from Gossett
(1987)). The validity of assuming equilibrium between headspace and aqueous phases
was based on vigorous agitation of the aqueous phase (bottles incubated on a gyratory
shaker table) and the duration of the experiments.
22
The GC column was held at 180oC and each run took 6.0 min, with TCE having a
retention time of approximately 4.0 min. TCE standards were created using neat TCE
and two methanol stock solutions (2.8 and 36 mg TCE/g stock solution, respectively).
Stock solution A was prepared gravimetrically (to 0.1 mg) by pipetting methanol (10 ml)
and injecting TCE (200 l with a 200 l syringe) into one 30 ml serum bottle. Stock
solution B was prepared similarly, with methanol (50 ml) and TCE (75 l) in a 70 ml
serum bottle.
The bottles were sealed with Teflon-faced septa (20 mm diameter;
Supelco) and aluminum crimp caps prior to injection of TCE.
For standards, DDI water was added to four to six serum bottles, and the serum
bottles were sealed. Standards were run in both 72 ml (Vl = 20 ml) and 160 ml (Vl = 100
ml) serum bottles (Wheaton), because experiments were run in both size bottles.
For a representative set of standards, the following amounts were added to sealed
160 ml serum bottles: 10 l neat TCE, 250, 100, and 50 l of stock solution A
(containing 36 mg TCE/g stock) and 150 and 50 l of stock solution B (containing 2.8
mg TCE/g stock). The amount added was determined gravimetrically (to 0.1 mg) by
weighing the bottles before and after injection of the stock solutions. The bottles were
agitated in an inverted position (liquid in contact with the septum) for approximately one
hour to allow for equilibrium. Duplicate headspace samples were then injected onto the
GC. The peak areas were recorded and plotted versus mass of TCE in each bottle, and a
response factor was obtained from these data (Appendix A).
The TCE degradation tests were run in triplicate in 70 ml (Vl = 20 ml) and 160 ml
(Vl = 100 ml) bottles. After adding a certain mass of microspheres (see below), all bottles
were capped and 1.0 to 7.0 l of neat TCE was added using a 1.0 or 10 l syringe. The
23
first GC analyses were made after equilibrating the bottles for 20 to 30 min. Subsequent
measurements were made at least once every two days, until the GC peak area fell below
detection.
The above set-up yielded aqueous phase TCE concentrations of 290 to 700 M
(38 to 92 mg/l) based on equation 2. These concentrations were chosen to accommodate
a mass of microspheres that was large enough to be representative of a sample. In
addition, TCE concentrations of this order of magnitude have been documented in the
field (e.g., 21 mg/l at the Savannah River Site; Aiken, SC; Jerome et al., 1998). The mass
of microspheres added was determined in a preliminary experiment, with the goal of
finding an amount that would consume the TCE in no more than 14 days. Water controls
(no microspheres present) were used to evaluate TCE losses due to adsorption to the glass
and adsorption and diffusion through the septa.
KMnO4 Analysis
KMnO4 measurements were performed by removing a 0.1 ml sample from the
serum bottle, transferring it to a 5 ml glass vial, and diluting with up to 3.0 ml DDI water.
The ratio of sample to diluent was determined gravimetrically. Diluted samples were
homogenized with a vortex mixer and filtered through 0.1 m nylon syringe filters
(Whatman) to remove MnO2 solids. Absorbance was measured with a Beckman DU-640
spectrophotometer in a 100 l cuvette. Standards were performed with and without
filtering to demonstrate minimal losses to the filter (Appendix A). Response factors for
the filtered and unfiltered standards were equivalent. The detection limit for this method
was found to be 0.5 mg KMnO4 /l
24
Chloride Analysis
At the beginning and end of several of the TCE experiments, chloride ion
concentrations were measured with a combination chloride electrode (Orion, model
9617BN) attached to a pH-millivolt meter (Corning). These data were used to evaluate
the stoichiometry of TCE oxidation.
A response curve was constructed using KCl
standards ranging from 0.2 mM to 10 mM (Appendix A). An ionic strength adjustor (0.2
ml of 5 M NaNO3) was added to each 10 ml sample. The detection limit was found to be
0.2 mM Cl-.
After recording the millivolt value of each sample, a standard addition was
performed by adding 100 l of 150 mM KCl. This addition approximately doubled the
concentration of all the samples. Standard additions were performed to assess matrix
effects on chloride ion measurements. The percent recovery of the standard addition was
calculated using:
%re cov ery  100 *
Cb  Va  Vstd.add   Ca  Va 
Cstd.add  Vstd.add
(3)
where Cb is the concentration of the sample after the standard addition (M), Va is volume
of the sample (ml), Vstd.add is the volume of the standard addition (ml), Ca is the
concentration of the sample prior to the standard addition (M), and Cstd.add is the
concentration of the standard addition (M).
25
Potassium Analysis
Potassium (K+) was measured using an Ion Chromatograph (IC) (Waters 717)
plus autosampler with HPLC pump (Waters 515) and conductivity detector (Waters 432).
An IC-Pak Cation M/D column (Waters) was used with a 3 mM HNO3 and 0.1 mM
[ethylenedinitrilo]-tetraacetic acid (EDTA) eluent. An injection volume of 100 l and a
flow rate of 1 ml/min were used. A 1000 mg/l stock solution was prepared using
potassium nitrate (KNO3), and standards of 0, 0.3, 0.6, 1.5, 3.0, and 10 mg/l K+ were
made by dilution. A six-point calibration curve was generated from these solutions at the
beginning and end of each IC run (Appendix A). The detection limit for this analysis
method was found to be 0.2 mg K+/l.
Sampling for K+ analysis was performed by removing a 0.1 ml sample from the
serum bottle and diluting with as much as 3.0 ml DDI water. The ratio of sample to
diluent was determined gravimetrically. After dilution, the samples were homogenized
with a vortex mixer, then filtered through 0.1 m nylon syringe filters (Whatman) into
1.0 ml autosampler vials (Waters). Polypropylene glassware was used in all IC work to
minimize contamination by ions leaching from glass.
Evaluating the Effect of Polymaleic Acid on KMnO4 Oxidation of TCE
In order to assess the effect of humic acid on the degradation of TCE using
microspheres, an experiment was performed with a humic acid surrogate, polymaleic acid
(PMA). A preliminary experiment was performed in 160 ml serum bottles with 7.0 l
TCE, 100 ml DDI water, 820 mg/l KMnO4, and PMA concentrations ranging from 0 to
26
2700 mg/l. This test was designed to determine the lowest concentration of PMA needed
to decrease TCE oxidation by at least 0.5 (compared to no PMA present).
After the target PMA concentration was determined, testing with microspheres
was performed using triplicate 160 ml (Vl = 100 ml) serum bottles. One set of triplicate
bottles contained 2.05 g/l of microspheres (sample 19-547), another set contained
microspheres plus 1.9 g/l PMA, and a third set contained 1.9 g/l PMA with no
microspheres.
Triplicate water controls were used to evaluate TCE losses due to
adsorption to the glass and diffusion through septa. All bottles were sealed with Teflonfaced septa and crimp caps, and 7.0 l of neat TCE was added with a 10 l syringe. This
resulted in approximately 85 mol of TCE per bottle, or an aqueous phase concentration
of 700 M (93 mg/l).
TCE/Wax Adsorption Testing
TCE adsorption onto several wax compositions was evaluated in the absence of
KMnO4. This was done to quantify the relationship between TCE and the various waxes
used for encapsulation of the KMnO4 microspheres. Samples of wax (0.5 to 1.0 g) were
placed in 70 ml serum bottles with 45 ml of DDI water and sealed with Teflon-faced
rubber septa and aluminum crimp caps. Water controls (no wax present) were used to
evaluate losses due to adsorption to the glass and diffusion through septa. Varying
amounts of TCE were added (1.0, 5.0, and 20 l TCE (neat), and 250 ml TCE saturated
DDI). The actual amount delivered was determined gravimetrically, and this value was
used as the total initial mass of TCE present. After addition of TCE, bottles were allowed
to equilibrate for 20 to 30 min and 0.1 ml headspace samples were then injected onto the
27
GC. The bottles were monitored for three weeks or until the mass of TCE present
changed by less than 0.15 of the mass seen in the previous sampling event. This mass
was the total remaining in the bottle in equilibrium with the shell material (Me). The
equilibrium TCE concentration (Ce) was then calculated based on this mass using
equation 2. After determining Me and Ce, the following equation was used to produce a
Freundlich isotherm for adsorption of TCE onto each sample:
qe 
1
Mo  Me
 KCe n
m
(4)
where qe is the mass of TCE adsorbed per mass adsorbent at equilibrium (mg TCE/g
shell), Mo is the total initial mass of TCE in the bottle (mg), Me is the total mass
remaining in the bottle in equilibrium with the shell material (mg), m is the mass of shell
material present, K is a constant ((l/mg)*(mg/g)), Ce is the calculated equilibrium
concentration of TCE based on Me (mg/l), n is a constant (dimensionless).
Experimental Design
Batch release experiments were performed on all samples whereas drain-daily
release and TCE degradation tests used only a limited number of samples. Adsorption of
TCE to shell materials was tested and Freundlich isotherms were developed for each
material available. The experimental design is shown in Table 4.2.
Table 4.2
Experimental matrix showing the tests that were performed on each sample.
Tests
Release
Samples
19-230
19-231
19-232
19-233
19-234
19-235
19-236
19-306
19-307
19-308
19-546
19-547
19-548
19-549
19-550
19-551
19-552
19-553
TCE Batch Degradation
Potassium and
Batch Drain Daily TCE
Permanganate
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Chloride
X
X
X
X
X
X
X
X
Adsorption of TCE to
Shell Material
X
X
X
X
28
CHAPTER 5
RESULTS
Results from the batch tests show that KMnO4 was released from the
microspheres for periods ranging from 3 to 80 days, and initial rates of release vary over
two orders of magnitude depending on the type of microsphere. TCE was degraded to
less than detectable concentrations in all tests, but the rate of degradation varies over an
order of magnitude among the different formulations.
Results of the release and
degradation tests, along with models to explain the results, are presented in detail in the
following pages.
Release Tests
Initial release rates calculated from SGC batch tests are an order of magnitude
faster than the rates from MGC tests.
Release times for batch tests with MGC
microspheres are an order of magnitude longer than times for the SGC tests. The draindaily tests provide further data on the release behavior of the MGC particles.
Release Plots
Batch release data were plotted as Cr versus time (t) where
Cr 
concentrat ion of KMnO 4
 initial mass of KMnO 4 


volume of water


(5)
30
For drain-daily tests, the mass released was calculated after each drain-daily event and
divided by the initial mass present. This mass ratio was plotted versus time as cumulative
mass released per initial mass present.
The slope of these plots is used as the release rate. The concentration ratio
reached steady values of slightly less than 1.0 at the end of most tests. As a result, the
concentration ratio at the end of each test was assumed to be the maximum concentration
ratio that can be achieved by that material, and it was designated Cr,max (Figure 5.1).
The majority of the release data has similar characteristics. The concentration
generally increases as a linear function of time early in each test. The slope decreases
with time, however, and it approaches zero as t approaches the end of the test.
Based on these observations, the batch release data was divided into three periods
of release:
1. Early Period: Constant release rate at early times when microspheres are fully
active (zero-order behavior)
2. Transition Period: Diminishing release rate that occurs after microspheres
have released the majority of their payload
3. Final Period: Release rate approaches zero as the payload of microspheres
becomes exhausted.
1
C r,max
0.8
ko
Cr
0.6
0.5
0.4
0.2
0
0
t 0.5 5
10
15
20
25
30
35
40
45 t max 50
Time (days)
Figure 5.1
Example release plot showing key parameters, Cr,max, ko, t0.5, and tmax.
31
Model Selection
Three models were evaluated to explain the batch release data. Two models were
found in the literature that theoretically matched the behavior of the release. One model
(Model A) was developed by Kyodonieus (1980) specifically for MGC microspheres, and
another (Model B) is based on one-dimensional diffusion from a microsphere. The third
model (Model C) was chosen, because it approximated the three periods of release
commonly seen in these data. Model performance was evaluated based on a number of
objectives. It had to
1. Predict the release data with reasonable accuracy (determined by analysis
of coefficients of determination (R2 values) and plots of residuals).
2. Satisfy conditions associated with the end of release tests (i.e. at the end of
the test, Cr=Cr,max).
Model A - Release from a Spherical Wax Matrix with Dispersed
Particles
One model examined was developed to describe diffusion from spheres of
uniformly distributed solute dispersed in a wax matrix (Desai, 1965; Kydonieus, 1980).
The model assumes that 1) a pseudo-steady state exists, 2) the KMnO4 particles are small
compared to the average distance of diffusion, 3) the diffusion coefficient of the matrix is
constant, and 4) a perfect sink condition exists in the external media (i.e. concentration
equals zero). The concentration as a function of time is given by
2
2
1  1  Cr 3  Cr
3
 k' t
2
(6)
33
where
k'
SD
Ar 2
(7)
and S is the solubility of the solute in the matrix (g/cm3), D is the diffusivity (cm2/s), A is
the initial concentration of the solute in the matrix (g/cm3), and r is the radius of the
microspheres (cm). k’ is a fitting parameter that combines the effects of a variety of real
parameters.
Equation 6 was modified for this work to account for varying Cr,max values using
the following:

Cr
1  1 
 C
r , max

2
 3 2  Cr
  

3  Cr , max

2



  k 't
(8)
This model is designed to predict release up to Cr=Cr,max, therefore the model is
not valid after this point.
Model B - One-dimensional Release Approximation
The release of KMnO4 was assumed to occur by diffusion across the shell for the
mechanistic model developed for this work. It was assumed that one-dimensional (1-D)
diffusion occurred from a core containing a saturated solution of KMnO4 though the shell
with diffusivity, D, and into water with concentration, Cw. The analysis in App. B shows
that
34
DH 3 w

t


Cw  Csat 1  e TrVw 




(9)
while the concentration in the core = Csat. Cw is the concentration of KMnO4 in the water,
Csat = 63.8 g/l (CRC, 1987), D is diffusivity (cm2/s), H is a partitioning coefficient for
KMnO4 between the shell and the water (dimensionless), w is the initial mass of KMnO4
present in the solid phase (g), t is time (s), T is the thickness of the shell (cm), r is the
radius of the particle (cm),  is the unit weight of the particles (g/cm3), and Vw is the
volume of water (ml).
Substituting
a
DH 3w
TrV w
(10)
yields

C w  C sat 1  e  at

(11)
Where a is a fitting parameter that combines the effects of a variety of real
parameters.
The assumptions used to derive this model make it appropriate for early time, but
not for the whole release. As a result, this model is useful for characterizing the initial
release but is unable to predict when the release of KMnO4 will end.
35
Model C
The following model, Model C, was selected because it displays the three periods
of release seen in batch release experiments. Data were fit to the following equation:
Cr 
Cr , max t
t0.5  t
(12)
where t0.5 is the time when Cr = 0.5. Cr max was found experimentally for each sample,
and t0.5 was the fitted parameter.
Fitting Methodology
Two representative data sets for batch release (19-234 and 19-551) were fit with
all three models to select which one of the three to use with the remaining data (Figures
5.2 and 5.3). Fitting was performed by minimizing the sum of squared errors using
Microsoft Excel. Model A was fit to a reduced data set to account for known model
behavior near the end of the release. This data set was truncated just before Cr reached
Cr,max. Model B was fit to the first three data points of the release. Model C was fit to the
entire data set for each sample.
Two criteria, coefficients of determination (R2 values) and the distribution of the
residuals, were used to determine the goodness of fit of the models for each data set. The
residuals are equal to the difference between observed and predicted Cr values (McClave
and Dietrich, 1991). For each data set, the plots of the residuals versus time were
analyzed for patterns. Patterns in residual plots generally indicate systematic errors in the
0.9
3.6596E+01
0.0053
0.6267
0.8660
0.2312
0.75
0.9
0.6
Cr
0.75
0.6
0.45
Observed Release
0.45
Model A - Matrix
0.3
0.3
Model B - 1-D Diffusion
0.15
Model C
0.15
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0
0
2
4
6
8
10
12
14
Time (days)
Figure 5.2
Model fits for sample 19-234 batch release data. Inset shows initial data and model fits.
36
1.0
0.8
0.8
0.6
Cr
0.6
Observed Release
0.4
0.4
Model A - Matrix Model
Model B - 1-D Diffusion
0.2
0.2
Model C
0.0
0
2
4
6
8
0.0
0
10
20
30
40
50
60
Time (days)
Figure 5.3
Model fits for sample 19-551 batch release data. Inset shows initial data and model fits.
37
fit. Plots with randomly distributed residuals along the x-axis are desirable, and will be
termed uniformly distributed. Plots with grouped positive or negative residuals over the
domain are undesirable and will be termed non-uniformly distributed (McClave and
Dietrich, 1991)..
Values of R2 for fits of 19-234 release data vary from 0.34 to 0.87 (Table 5.1) for
Model B and Model C, respectively. The distribution of residuals is uniform for all fits.
Initial release data is best characterized by Model B (as seen in the inset of Figure 5.2).
Model A was fit to 70% of the data, and it performs satisfactorily over the truncated data
set. Model C had the highest R2 value of the three models.
Values of R2 for fits of 19-551 data are 0.76 for Model B and 0.96 for Models A
and C. Model C has the most uniformly distributed residuals over the domain. Model A
has non-uniformly distributed residuals with negative values before 15 days and positive
values after 15 days. Initial release data is best characterized by Model B (as seen in the
inset of Figure 5.3). Model A was fit to 80% of the data, and it performs satisfactorily
over the truncated data set. Model C has the highest R2 value of the three models.
Model C fits both data sets better than the other models. Fits with model A has
the highest R2 value for 19-234 (0.87) and ties for the highest for 19-551 (0.96). Model C
also produces uniformly distributed residuals for both 19-234 and 19-551 data. Model C
accurately predicts end conditions of release, whereas both Model A and B are not valid
at these end conditions.
Based on the fits of these two representative data sets, Model C was chosen for
predicting batch release data. While they do not provide the best fits, Models A and B
39
contain useful parameters for the design of microspheres. Therefore, these models will
be fit to MGC batch release data to estimate these parameters.
Table 5.1
Sample
19-234
19-551
Model summary.
Model
R2
Percentage
of Data Fit
Fit
Parameters
Model A - Matrix
0.63
70
k’=0.094
Model B - 1-D Diffusion
0.34
30
a=0.083
Model C
0.87
100
t0.5=0.044
Model A - Matrix
0.96
80
k’=0.0068
Model B - 1-D Diffusion
0.76
15
a=0.0041
Model C
0.96
100
t0.5=1.84
Batch Release Parameters
Four parameters were used to characterize the batch release data. In addition to
Cr,max and t0.5, an initial rate of release:
ko 
mass released
initial mass  day
(13)
was calculated by performing a linear regression on the first three data points. The
maximum release time, tmax, is the time taken to reach Cr,max.(Figure 5.1).
40
SGC Batch Release Tests
The initial rate of release from SGC microspheres is faster than that from MGC
microspheres, and this is reflected in the values for ko and t0.5. Data from SGC release
tests show consistently faster ko and shorter t0.5 values than tests with MGC samples. The
average ko value is 6.6 (±2.8) [g KMnO4 released/g KMnO4 initial)/day] with a minimum
of 2.2 [g KMnO4 released/g KMnO4 initial)/day] (sample 19-236) and a maximum of 9.4
[g KMnO4 released/g KMnO4 initial)/day] (sample 19-230). The average t0.5 value is 0.11
(±0.11) days, with a minimum of 0.020 days (19-230) and a maximum of 0.339 days (19236) (Figures 5.4-5.10). SGC release data show tmax values averaging 6.6 (±2.8) days
with a minimum of 3.0 days (19-235) and a maximum of 12.3 days (19-236).
All SGC data was fit with Model C. The average R2 value for SGC samples
(0.885±0.072) is lower than the average for all samples (0.929±0.0593) but is still within
an acceptable range. The residuals for all SGC fits are uniformly distributed.
41
1.0
0.8
Cr
0.6
Observed Release
0.4
Model C
0.2
0.0
0
2
4
6
8
10
12
14
Time (days)
Figure 5.4
Batch release for sample 19-230. ko = 9.4 g KMnO4 released/g KMnO4
initial/day, t0.5=0.020 days, tmax=6.3 days, Cr,max = 0.80 g KMnO4 released/g
KMnO4 initial, and R2=0.894.
1.0
0.8
Cr
0.6
Observed Release
0.4
Model C
0.2
0.0
0
2
4
6
8
10
12
14
Time (days)
Figure 5.5
Batch Release – Sample 19-231. ko = 7.6 g KMnO4 released/g KMnO4
initial/day, t0.5=0.055 days, tmax=6.3 days, Cr,max = 0.91 g KMnO4 released/g
KMnO4 initial, and R2=0.819.
42
1.0
Cr
0.8
0.6
Observed Release
0.4
Model C
0.2
0.0
0
2
4
6
8
10
12
14
Time (days)
Figure 5.6
Batch Release – Sample 19-232. ko = 7.6 g KMnO4 released/g KMnO4
initial/day, t0.5=0.060 days, tmax=6.3 days, Cr,max = 1.05 g KMnO4 released/g
KMnO4 initial, and R2=0.866.
1.0
Cr
0.8
0.6
Observed Release
0.4
Model C
0.2
0.0
0
2
4
6
8
10
12
14
Time (days)
Figure 5.7
Batch Release – Sample 19-233. ko = 8.8 g KMnO4 released/g KMnO4
initial/day, t0.5=0.042 days, tmax=5.4 days, Cr,max = 1.02 g KMnO4 released/g
KMnO4 initial, and R2=0.794.
43
1.0
0.8
Cr
0.6
Observed Release
0.4
Model C
0.2
0.0
0
2
4
6
8
10
12
14
Time (days)
Figure 5.8
Batch Release – Sample 19-234. ko = 7.7 g KMnO4 released/g KMnO4
initial/day, t0.5=0.044 days, tmax=6.3 days, Cr,max = 0.81 g KMnO4 released/g
KMnO4 initial, and R2=0.866.
1.0
Cr
0.8
0.6
Observed Release
0.4
Model C
0.2
0.0
0
2
4
6
8
10
12
14
Time (days)
Figure 5.9
Batch Release – Sample 19-235. ko = 3.1 g KMnO4 released/g KMnO4
initial/day, t0.5=0.178 days, tmax=3.0 days, Cr,max = 0.83 g KMnO4 released/g
KMnO4 initial, and R2=0.972.
44
1.0
0.8
Cr
0.6
Observed Release
0.4
Model C
0.2
0.0
0
2
4
6
8
10
12
14
Time (days)
Figure 5.10 Batch Release – Sample 19-236. ko = 2.2 g KMnO4 released/g KMnO4
initial/day, t0.5=0.339 days, tmax=6.3 days, Cr,max = 0.86 g KMnO4 released/g
KMnO4 initial, and R2=0.986.
Grab samples of approximately 40 particles were taken from each batch of the
SGC material and examined using a 15X optical microscope. The particles are nearly
spherical and consist of single grains of KMnO4 enveloped in shells of polymer.
Interestingly, the KMnO4 grain is skewed off-center for a majority of samples. One side
of the grain appeared to be in contact with the edge of the particle, whereas the other side
was enveloped by a relatively thick shell. Some of the microspheres (5 to 15%) lacked a
KMnO4 grain and were spheres of solid polymer.
The particles were placed in a drop of water and observed under the microscope.
A purple cloud of dissolved KMnO4 was produced was soon as a particle contacted
water. The source of the dissolved KMnO4 was always from a small region where the
KMnO4 grain was closest to the edge of the particle. The immediate dissolution of core
45
material suggests that shell material was either completely, or nearly, absent from that
point. This test was performed for all of the SGC samples, with the same result.
MGC Batch Release Tests
Values of ko for the MGC batch tests vary over an order of magnitude, but they
are consistently slower than the rates for the SGC samples. The average ko value is 0.2
(±0.09) [(g KMnO4 released/g KMnO4 initial)/day], with a minimum of 0.034 (sample
19-307) and a maximum of 0.38 (sample 19-551). The average t0.5 value is 5.1 (±3.3)
days, with a minimum of 1.69 (19-306) and a maximum of 12.75 (19-308) (Figures 5.115.21). The tmax values vary over an order of magnitude, averaging 39.5 (±20.4) days, with
a minimum of 6.8 (19-306) and a maximum of 80.1 (19-549).
Model C was fit to all MGC data. The average R2 value for all MGC fits is 0.957
(±0.032), and all values were greater than 0.9 except sample 19-307 (R2=0.885).
Residuals for samples 19-306 (Figure 5.11), 19-307 (Figure 5.12), and 19-552 (Figure
5.20) are non-uniformly distributed with grouped negative values before t0.5 and grouped
positive values after.. The remaining samples have uniformly distributed residuals across
the domain.
Microscopic observations of grab samples showed fewer exposed grains of
KMnO4 than with SGC particles. All of the microspheres examined contained between
10 and 20 grains of KMnO4.
46
1.0
0.8
Cr
0.6
0.4
Observed Release
Model CFitFit
Monod
0.2
0.0
0
2
4
6
8
10
12
14
Time (days)
Figure 5.11 Batch Release - Sample 19-306. Average of triplicate bottles shown. Error
bars represent one standard deviation. ko = 0.15 g KMnO4 released/g
KMnO4 initial/day, t0.5=1.69 days, tmax=6.8 days, Cr,max = 0.88 g KMnO4
released/g KMnO4 initial, and R2=0.907.
1.0
0.8
Cr
0.6
0.4
Observed Release
Model C Fit
Monod Fit
0.2
0.0
0
5
10
15
20
25
Time (days)
Figure 5.12 Batch Release - Sample 19-307. Average of triplicate bottles shown. Error
bars represent one standard deviation. ko = 0.034 g KMnO4 released/g
KMnO4 initial/day, t0.5=7.931 days, tmax=26 days, Cr,max = 0.86 g KMnO4
released/g KMnO4 initial, and R2=0.886.
30
47
1.0
0.8
Cr
0.6
0.4
Observed Release
Model
C Fit
Monod
Fit
0.2
0.0
0
5
10
15
20
25
30
35
Time (days)
Figure 5.13 Batch Release - Sample 19-308. Average of triplicate bottles shown. Error
bars represent one standard deviation. ko = 0.104 g KMnO4 released/g
KMnO4 initial/day, t0.5=12.75 days, tmax=36(est.) days, Cr,max = 0.95(est.) g
KMnO4 released/g KMnO4 initial, and R2=0.955.
1.0
0.8
Cr
0.6
0.4
Observed Release
Model C
Monod
FitFit
0.2
0.0
0
10
20
30
40
50
Time (days)
Figure 5.14 Batch release test for 19-546. Average of duplicate bottles shown. Error
bars represent one standard deviation. ko = 0.19 g KMnO4 released/g
KMnO4 initial/day, t0.5=5.26 days, tmax=36 days, Cr,max = 0.95 g KMnO4
released/g KMnO4 initial, and R2=0.969.
60
48
1.0
0.8
Cr
0.6
0.4
Observed Release
Monod Fit
0.2
0.0
0
10
20
30
40
50
60
Time (days)
Figure 5.15 Batch release test for 19-547. Average of triplicate bottles shown. Error
bars represent one standard deviation. ko = 0.20 g KMnO4 released/g
KMnO4 initial/day, t0.5=3.29 days, tmax=42 days, Cr,max = 0.80 g KMnO4
released/g KMnO4 initial, and R2=0.982.
1.0
0.8
Cr
0.6
0.4
Observed Release
Model CFitFit
Monod
0.2
0.0
0
10
20
30
40
Time (days)
Figure 5.16 Batch release test for 19-548. ko = 0.29 g KMnO4 released/g KMnO4
initial/day, t0.5=2.40 days, tmax=36 days, Cr,max = 0.94 g KMnO4 released/g
KMnO4 initial, and R2=0.987.
50
49
1.0
0.8
Cr
0.6
0.4
Observed Release
Model C
Monod
FitFit
0.2
0.0
0
20
40
60
80
100
Time (days)
Figure 5.17 Batch release test for 19-549. Average of triplicate bottles shown. Error
bars represent one standard deviation. ko = 0.21 g KMnO4 released/g
KMnO4 initial/day, t0.5=6.73 days, tmax=80 days, Cr,max = 0.88 g KMnO4
released/g KMnO4 initial, and R2=0.979.
1.0
0.8
Cr
0.6
0.4
Observed Release
Model C
Monod
FitFit
0.2
0.0
0
10
20
30
40
50
60
Time (days)
Figure 5.18 Batch release test for 19-550. Average of triplicate bottles shown. Error
bars represent one standard deviation. ko = 0.22 g KMnO4 released/g
KMnO4 initial/day, t0.5=4.38 days, tmax=46 days, Cr,max = 0.93 g KMnO4
released/g KMnO4 initial, and R2=0.975.
70
50
1.0
0.8
Cr
0.6
0.4
Observed Release
Model C
Monod
FitFit
0.2
0.0
0
10
20
30
40
50
Time (days)
Figure 5.19 Batch release test for 19-551. Average of triplicate bottles shown. Error
bars represent one standard deviation. ko = 0.38 g KMnO4 released/g
KMnO4 initial/day, t0.5=1.84 days, tmax=42 days, Cr,max = 0.92 g KMnO4
released/g KMnO4 initial, and R2=0.961.
1.0
0.8
Cr
0.6
0.4
Observed Release
Monod
FitFit
Model C
0.2
0.0
0
10
20
30
40
Time (days)
Figure 5.20 Batch release test for 19-552. Average of triplicate bottles shown. Error
bars represent one standard deviation. ko = 0.21 g KMnO4 released/g
KMnO4 initial/day, t0.5=3.01 days, tmax=18 days, Cr,max = 0.94 g KMnO4
released/g KMnO4 initial, and R2=0.953.
50
51
1.0
0.8
Cr
0.6
0.4
Observed Release
Model CFitFit
Monod
0.2
0.0
0
10
20
30
40
50
60
70
Time (days)
Figure 5.21 Batch release test for 19-553. Average of triplicate bottles shown. Error
bars represent one standard deviation. ko = 0.22 g KMnO4 released/g
KMnO4 initial/day, t0.5=6.36 days, tmax=66 days, Cr,max = 0.94 g KMnO4
released/g KMnO4 initial, and R2=0.970.
Batch Release Summary
The time to completely release KMnO4 from SGC microspheres was much
shorter than MGC microspheres. Maximum release times for the SGC particles ranged
from 3 to 12 days, whereas it ranged from 6 to 80 days for the MGC particles. In
addition, SGC samples released KMnO4 at a faster initial rate than MGC samples. As a
result, data from batch release tests with SGC samples show higher ko, and shorter t0.5
values than those of MGC tests (Table 5.2 and Figure 5.22). As t0.5 values increase in
both SGC and MGC tests, the initial rate of release, ko consistently decreases. The
average final concentration ratio, Cr,max, is 0.88 (±0.095) g KMnO4 released/g KMnO4
initial for all samples, and Cr,max ranges from 0.80 (19-230 and 19-547), to 1.05 (19-232)
(Table 5.2).
80
Table 5.2
Summary of batch test results.
Sample
Shell/
Core
Type
19-230
19-231
19-232
19-233
19-234
19-235
19-236
Average
Std. Dev.
19-306
19-307
19-308
19-546
19-547
19-548
19-549
19-550
19-551
19-552
19-553
Average
Std. Dev.
Average
Std. Dev.
SGC
SGC
SGC
SGC
SGC
SGC
SGC
SGC
SGC
MGC
MGC
MGC
MGC
MGC
MGC
MGC
MGC
MGC
MGC
MGC
MGC
MGC
total
total
t0.5
tmax
ko
R2 for
g
KMnO
released/
4
Cr,max
Model C
days
days
initial g KMnO4/
Fit
day
0.020
6.3
0.80
9.41
0.894
0.055
6.3
0.60
7.63
0.819
0.060
6.3
1.00
7.61
0.866
0.042
5.4
1.00
8.81
0.794
0.044
6.3
0.81
7.68
0.866
0.178
3.0
0.83
3.07
0.972
0.339
12.3
0.86
2.19
0.986
0.105
6.6
0.84
6.63
0.885
0.115
2.8
0.14
2.83
0.072
1.691
6.8
0.88
0.15
0.907
7.931
26.0
0.86
0.03
0.886
12.745
36.0
0.95
0.10
0.955
5.261
36.0
0.95
0.19
0.969
3.293
42.0
0.80
0.20
0.982
2.400
36.0
0.94
0.29
0.987
6.731
80.1
0.88
0.21
0.979
4.375
46.0
0.93
0.22
0.975
1.838
42.0
0.92
0.38
0.961
3.013
17.9
0.94
0.21
0.953
6.360
66.0
0.94
0.22
0.970
5.058
39.5
0.91
0.20
0.957
3.293
20.4
0.05
0.09
0.032
3.132
26.7
0.88
2.70
0.929
3.543
22.8
0.09
3.64
0.061
* indicates estimated value
Release Rate (g KMnO4 released/g KMnO4 initial/day)
Sample
0
1
2
3
4
5
19-230
19-233
19-234
19-231
19-232
19-235
19-236
19-306
19-551
19-548
19-552
19-547
19-550
19-546
19-553
19-549
19-307
19-308
6
7
8
9
10
80
90
SGC Samples
MGC Samples
t max
t 0.5
ko
0
10
20
30
40
50
60
70
Time (days)
Figure 5.22 Summary of batch test results. Listed in order of increasing t0.5.
53
The eccentric location of the core and the resulting exposure of grains of KMnO4
explain the fast release from the SGC microspheres. Final concentration ratios were
expected to be 1.0, but most were less than 1.0 (0.88 is the average). Several possible
explanations for Cr,max values below from 1.0 are
1. Some KMnO4 remains in the microspheres after release is complete.
2. Amount of KMnO4 in microspheres was overestimated by 10 percent.
3. Analytical error
Model C fits most of the data sets with R2 values greater than 0.90 (Table 5.2),
and the residuals are typically uniformly distributed about zero throughout the domain of
the data. The R2 values for the for all the fits average 0.929 (±0.0593).
MGC batch release data was also fit with Models A and B, and the fit parameters
are shown in Tables 5.3 and 5.4. After determining the k’ and a values for each data set,
several parameters were determined by experiment or estimation and used to solve for SD
(solubility of KMnO4 in the shell times diffusivity) in Model A and DH (diffusivity times
partitioning coefficient of KMnO4 between the shell and the water) in Model B. The
parameters used to calculated SD and DH are A, r, w, T, , and Vw (Model Selection).
Values for A, w, , and Vw were found experimentally, and values for r and T were
estimated (Table 5.5). After solving for SD and DH, approximate D values were used to
calculate a range for S and H.
Independent measurements of the diffusivity were
unavailable for this work. However, a range of values for D (2E-9 to 9E-9 cm2/s) was
estimated by the fabricators of the encapsulated material for the shell material used in this
work. The resulting range of S values is 2.33E-3 to 10.5E-3 g/cm3, and the range for H is
5.22E-3 to 23.5E-3. The H values are consistent with values reported by Cussler (1997).
Table 5.3
Model A parameter estimation
Model A - Matrix
Sample
k'
S*D
S*D
Smax ( when D=2E-7cm2/s)
Smin ( when D=9E-7cm2/s)
19-306
19-307
19-308
19-546
19-547
19-548
19-549
19-550
19-551
19-552
19-553
Average
Std. Dev.
1/d
1.13E-02
3.04E-03
3.03E-03
2.66E-03
4.99E-03
6.81E-03
2.91E-03
3.61E-03
6.75E-03
4.61E-03
2.67E-03
4.76E-03
2.66E-03
g/(cm*d)
4.31E-04
1.16E-04
1.15E-04
1.01E-04
1.90E-04
2.59E-04
1.11E-04
1.37E-04
2.57E-04
1.76E-04
1.02E-04
1.81E-04
1.01E-04
g/(cm*s)
4.99E-09
1.34E-09
1.33E-09
1.17E-09
2.20E-09
3.00E-09
1.28E-09
1.59E-09
2.98E-09
2.03E-09
1.18E-09
2.10E-09
1.17E-09
g/cm3
2.50E-02
6.71E-03
6.67E-03
5.86E-03
1.10E-02
1.50E-02
6.41E-03
7.95E-03
1.49E-02
1.02E-02
5.89E-03
1.05E-02
5.87E-03
g/cm3
5.55E-03
1.49E-03
1.48E-03
1.30E-03
2.45E-03
3.33E-03
1.43E-03
1.77E-03
3.31E-03
2.26E-03
1.31E-03
2.33E-03
1.30E-03
55
Table 5.4
Model B parameter estimation.
Model B - 1-D Diffusion
Sample
a
19-306
19-307
19-308
19-546
19-547
19-548
19-549
19-550
19-551
19-552
19-553
Average
Std. Dev.
1/d
1.49E-03
3.36E-04
1.04E-03
1.93E-03
1.95E-03
2.92E-03
2.07E-03
2.18E-03
4.14E-03
2.09E-03
2.16E-03
2.00E-03
9.09E-04
DH
cm2/s
DH
cm2/s
Hmax ( when D=2E-7cm2/s)
Hmin ( when D=9E-7cm2/s)
6.64E-04
1.50E-04
4.65E-04
8.64E-04
8.72E-04
1.30E-03
9.24E-04
9.71E-04
1.85E-03
9.33E-04
9.64E-04
8.93E-04
4.06E-04
7.68E-09
1.74E-09
5.38E-09
9.99E-09
1.01E-08
1.51E-08
1.07E-08
1.12E-08
2.14E-08
1.08E-08
1.12E-08
1.03E-08
4.70E-09
3.84E-02
8.68E-03
2.69E-02
5.00E-02
5.05E-02
7.54E-02
5.35E-02
5.62E-02
1.07E-01
5.40E-02
5.58E-02
5.17E-02
2.35E-02
8.54E-03
1.93E-03
5.98E-03
1.11E-02
1.12E-02
1.68E-02
1.19E-02
1.25E-02
2.38E-02
1.20E-02
1.24E-02
1.15E-02
5.22E-03
56
Table 5.5
Table Title
Parameter
Value
Units

0.51
0.075
0.080
0.0075
1.27
3
g/cm
cm
g
cm
g/cm3
Experimental
Estimation
Experimental
Estimation
Experimental
Vw
150
ml
Experimental
A
r
w
T
Method of Determination
Drain-daily Release Tests
All low and high volume drain-daily tests yielded lower Cr,max values than for the
batch release tests. The majority of drain-daily release tests show faster initial release
rates than seen in batch tests.
Low Volume
Low volume drain-daily results are reported below, but are not considered
representative due to experimental design flaws. Tests with samples 19-306, 19-307, and
19-308 yielded lower Cr,max values (0.72, 0.82, and 0.52, respectively) than the
corresponding batch tests (0.88, 0.86, and 0.95) (Figures 5.23, 5.24, 5.25). Initial release
rates are higher and lower than those from batch release data, and t0.5 values also vary
(Table 5.6).
Significant losses of KMnO4 occurred during the low volume tests, most likely
due to significant loss of KMnO4 to the filter membrane during filtering.
1.0
0.8
Cr
0.6
Batch
0.4
ModelC
- Batch
Model
Model
CABatch
Drain-Daily
0.2
Model
Model
CADrain-Daily
ModelC
- Drain-Daily
0.0
0
5
10
15
20
25
Time (days)
Figure 5.23 Drain-daily low volume - sample 19-306. Batch release data are average of triplicate bottles. Error bars represent one
standard deviation. Cr,max(drain-daily)=0.72 and Cr,max(batch)=0.88.
58
1.0
0.8
Cr
0.6
0.4
Batch
Model
Model
CA Batch
ModelC
- Batch
0.2
Drain-Daily
Model C
Model
ModelCA Drain-Daily
- Drain-Daily
0.0
0
5
10
15
20
25
30
Time (days)
Figure 5.24 Drain-daily low volume - sample 19-307. Batch release data are average of triplicate bottles. Error bars represent one
standard deviation. Cr_max(drain-daily)=0.82 and Cr_max(batch)=0.86.
59
1.0
Batch
Model C Batch
Model A - Batch
0.8
Drain-Daily
Model
Model
ModelCC
A Drain-Daily
- Drain-Daily
Cr
0.6
0.4
0.2
0.0
0
5
10
15
20
25
30
35
Time (days)
Figure 5.25 Drain-daily low volume - sample 19-308. Batch release data are average of triplicate bottles. Error bars represent one
standard deviation. Cr,max(drain-daily)=0.59 and Cr,max(batch)=0.95.
60
High Volume
Tests with samples 19-547, 19-551, and 19-552 yielded lower Cr,max values (0.71,
0.86, and 0.90, respectively) than the corresponding batch tests (0.80, 0.92, and 0.95)
(Figures 5.26, 5.27, and 5.28). The initial release rates for tests with all three samples are
2 times faster than batch release rates, and t0.5 values are all lower (Table 5.6).
Lower Cr,max values than seen in batch release tests are most likely the result of
small losses of microspheres from bottles during the removal of water that was replaced
with fresh DDI. These losses can be attributed to the incomplete settling of microspheres
prior to decanting. This experimental flaw was corrected after the first few sampling
events (by using a fretted stone to filter decant water), but a significant mass was
removed.
While losses of microspheres occurred during the beginning of the experiment,
these losses would have a negligible affect on the initial rate of release. Therefore, based
on these results, it was concluded that keeping a low concentration in the receiving water
does increase the rate of release.
1.0
0.8
0.6
Cr
Batch
Model C Batch
Model A - Batch
Drain-Daily
0.4
Model C
A Drain-Daily
- Drain-Daily
Model
0.2
0.0
0
5
10
15
20
25
30
35
40
45
50
Time (days)
Figure 5.26 Drain-daily high volume - sample 19-547. Batch release data are average of triplicate bottles. Error bars represent one
standard deviation. Drain-daily data are average of duplicate bottles. Cr,max(drain-daily)=0.71 and Cr,max(batch)=0.80.
62
1.0
0.8
Cr
0.6
Batch
0.4
Model
Batch
ModelAC- Batch
Drain-Daily
Model A
C Drain-Daily
Model
- Drain-Daily
0.2
0.0
0
10
20
30
40
50
60
70
80
Time (days)
Figure 5.27 Drain-daily high volume - sample 19-551. Batch release data are average of triplicate bottles. Error bars represent one
standard deviation. Drain-daily data are average of duplicate bottles. Cr,max(drain-daily)=0.86 and Cr,max(batch)=0.92.
63
1.0
0.8
Cr
0.6
Batch
0.4
Model
Batch
Model
AC
- Batch
Drain-Daily
0.2
Model
Drain-Daily
ModelAC-Drain-Daily
0.0
0
5
10
15
20
25
30
35
40
45
50
Time (days)
Figure 5.28 Drain-daily high volume - sample 19-552. Batch release data are average of triplicate bottles. Error bars represent one
standard deviation. Drain-daily data are average of duplicate bottles. Cr,max(drain-daily)=0.90 and Cr,max(batch)=0.94.
64
Table 5.6
Summary of drain-daily results.
Sample
19-306
19-306
19-307
19-307
19-308
19-308
19-547
19-547
19-551
19-551
19-552
19-552
Test
Drain-Daily,
low volume
Batch
Drain-Daily
low volume
Batch
Drain-Daily
low volume
Batch
Drain-Daily
high volume
Batch
Drain-Daily
high volume
Batch
Drain-Daily
high volume
Batch
t0.5
tmax
days
days
2
2.16
8.7
0.72
0.10
2
1.691
6.8
0.88
0.15
2
6.010
26.0
0.82
0.07
2
7.931
26.0
0.86
0.03
2
8.440
29.7
0.59
0.07
2
12.745
36.0
0.95
0.10
3
1.260
35.0
0.71
0.41
3
3.293
42.0
0.80
0.20
3
1.600
70.0
0.86
0.79
3
1.838
42.0
0.92
0.38
3
1.990
15.0
0.89
0.42
3
3.013
17.9
0.94
0.21
Type
ko
Cr,max
Ratio:
R2 for
ko DrainModel A
g KMnO4 released/initial g
daily/
Fit
KMnO4/day
ko Batch
0.904
0.67
0.907
0.937
2.3
0.886
0.905
0.7
0.955
0.978
2.1
0.982
0.923
2.1
0.961
0.953
2.0
0.953
65
Stoichiometry of TCE and KMnO4
An experiment was run to verify the stoichiometry of TCE oxidation by KMnO4.
Initial TCE concentrations were measured and KMnO4 was added to achieve the
stoichiometric amount for oxidation (i.e., 2 mol KMnO4/mol TCE). TCE was degraded
to below the detectable concentration. The reaction behaved as expected, but residual
KMnO4 was not measured. Therefore, less KMnO4 could have degraded the same mass
of TCE.
Adsorption to Shell Materials
Known masses of sample 19-363, boler wax, and Chlorez 700 (see Materials)
were placed in vials with four different concentrations of TCE in DDI water. TCE
concentrations were monitored until equilibration was achieved by day 30 (Figures 5.29
through 5.31). Minimal loss of TCE was seen in water controls.
After equilibrium was reached, the mass of TCE adsorbed per mass of shell, qe
was calculated based on equation 4. The equilibrium concentration of TCE, Ce was
calculated from the total mass remaining in the bottle, Me. Values of Ce and qe were
plotted on log axes and fitted using log(qe) = (1/n)*Log(Ce) + log(K). These parameters
(1/n and K) are used to define Freundlich isotherms for each material (Equation 4). The
average 1/n value is 1.055 (±0.058), and the average K value is 0.743 (±1.13)
[(l/mg)*(mg/g)] (Table 5.7). The K value for Chlorez 700 (2.05 (l/mg)*(mg/g)) is an
order of magnitude higher than the K for the other two samples tested.
The K values calculated for the Freundlich isotherms are lower than typical values
for TCE adsorption to granular activated carbon (K=28 (l/mg)*(mg/g)) while the 1/n
values were of the same order of magnitude (1/n=0.62) (Snoeyink, 1990). For
67
20
 M TCE
15
10
5
Water Controls
Adsorption Test
0
0
5
10
15
Time (days)
20
25
30
Figure 5.29 Equilibrium concentration for sample 19-363 and TCE. Representative data
from one of four bottles per sample.
20
 M TCE
15
10
Water Control
5
Adsorption Test
0
0
5
10
15
Time (days)
20
25
30
Figure 5.30 Equilibrium concentration for boler wax and TCE. Representative data
from one of four bottles per sample.
1000
 M TCE
800
Water Controls
600
Adsorption Test
400
200
0
0
5
10
15
Time (days)
20
25
30
Figure 5.31 Equilibrium concentration for Chlorez 700 and TCE. Representative data
from one of four bottles per sample.
68
2.0
1.5
y = 1.0293E+00x - 8.7517E-01
R2 = 9.9871E-01
LOG (Qe)
1.0
0.5
0.0
0.0
0.5
1.0
1.5
2.0
2.5
-0.5
-1.0
LOG (Ce)
Figure 5.32 Freundlich isotherm for sample 19-363 and TCE.
1.5
1.0
y = 1.0138E+00x - 1.3489E+00
R2 = 9.9724E-01
LOG (Qe)
0.5
0.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
-0.5
-1.0
-1.5
LOG (Ce)
Figure 5.33 Freundlich isotherm for boler wax and TCE.
1.5
1.0
y = 1.1212E+00x + 3.1250E-01
R2 = 9.9685E-01
LOG (Qe)
0.5
0.0
-1.5
-0.5
-1.0
-0.5
0.0
-1.0
-1.5
LOG (Ce)
Figure 5.34
Freundlich isotherm for Chlorez 700 and TCE
0.5
1.0
69
comparison, using average values for 1/n and K, qe would be four times higher for
activated carbon at Ce=92 mg/l. However, using 1/n and K values for Chlorez 700, qe
would only be 1.4 times higher for activated carbon at Ce=92 mg/l. These results show
that Chlorez 700 adsorbs TCE more than sample 19-363 and boler wax. The results also
indicate that at the starting concentration of the TCE degradation experiments, Chlorez
700 would adsorb approximately the same mass of TCE as an equivalent mass of
granular activated carbon.
Table 5.7
Summary of Freundlich parameters.
Sample
1/n
K
19-363
Boler Wax
Chlorez 700
Average
Std. Dev.
Activated Carbon
dimensionless
1.029
1.014
1.121
1.055
0.058
0.62
(l/mg)*(mg/g)
0.133
0.0448
2.05
0.743
1.13
28
R2 for linear
regression
0.999
0.997
0.997
0.998
Batch TCE Degradation Tests
Batch tests were performed to evaluate the degradation of TCE in the presence of
MGC microspheres. The ratio of KMnO4 to TCE was determined to account for KMnO4
release behavior (Table 5.8). In each case, the chosen mass of microspheres provided an
excess of KMnO4 needed for stoichiometric for the oxidation of the TCE. Batch release
data were used to predict the degradation of TCE, and adsorption of TCE to the shell
material was examined as a possible sink.
70
Table 5.8
Initial ratio of KMnO4 to TCE in degradation tests.
Sample
19-307
19-308
19-546
19-547
19-548
19-549
19-550
19-551
19-552
19-553
Stoichiometric.
amount required
mol KMnO4/mol TCE
6.8
6.8
5.0
6.7
3.6
6.7
4.4
3.3
5.7
4.4
2.0
TCE was degraded to below detectable concentrations in all tests. For tests with
type 2 microspheres the initial rate of TCE degradation is approximately equal to that
predicted based on the rate of release of KMnO4 during batch release tests. Observed
initial rates for type 3 microspheres are greater than predicted. In both sets of tests, the
actual time taken to achieve complete removal of TCE was longer than predicted based
on release data alone.
Observed TCE Degradation
TCE batch degradation tests lasted from 4 to 38. For tests with microspheres 19307 and 19-308, an initial mass of 11 mol TCE (38 mg/l aqueous concentration) was
present in each bottle. The mass of TCE decreased to below detection in the presence of
both samples (Figures 5.35 and 5.36).
14
mole TCE/Bottle
12
10
8
6
Observed TCE
4
Expected (Batch)
Water Control
2
0
0
Figure 5.35
5
10
15
20
Time (days)
25
30
35
40
Batch TCE degradation test for 19-307. Symbols represent average of quadruplicate bottles for observed TCE and
duplicate bottles for water controls. The error bars represent one standard deviation.
71
14
12
10
12
8
6
mole TCE/Bottle
4
10
2
0
0
1
2
3
4
8
6
4
Observed TCE
Expected TCE (Batch)
2
Control
0
0
5
10
15
20
25
Time (days)
30
35
40
45
Figure 5.36 Batch TCE degradation test for 19-308. Symbols represent average of quadruplicate bottles for observed TCE and
duplicate bottles for water controls. The error bars represent one standard deviation. The inset shows initial TCE
activity.
72
Initially, minimal losses were seen in water controls, but after 22 days, the mass of TCE
in these bottles began to decrease with time. For tests with microspheres 19-546, 19-547,
19-548, 19-549, 19-550, 19-551, 19-552, and 19-553, an initial mass of 85 mol TCE (92
mg/l aqueous concentration) was degraded to below detection (Figures 5.37 through
5.44).
For the tests with microspheres 19-307 and 19-308, losses in water controls were
most likely due deterioration of the septa resulting from repeated punctures with a
syringe needle. When the experiment was run with microspheres 19-546, 19-547, 19548, 19-549, 19-550, 19-551, 19-552, and 19-553 septa were changed every five to ten
injections to minimize diffusive. The old septa and crimp cap were removed and a fresh
septa and crimp cap were placed on the bottle and crimped. This process was performed
in less than 2.0 sec, and as a result negligible TCE losses were seen during this change.
As a result of this procedure, minimal losses of TCE in water controls were seen over the
entire duration of the experiment.
Observed and Predicted TCE Degradation
Observed TCE amounts were compared to TCE amounts predicted from batch
and high volume drain-daily release data.
Predicted amounts were determined by
assuming KMnO4 was released by the microspheres into water containing dissolved TCE
at the same rate as it was released into DDI water during batch release tests. Similar
concentrations of microspheres were used in the batch TCE degradation and KMnO4
release tests (1.2 to 1.3 g microspheres/l in batch release tests, compared to 0.6 to 2.0 g
100
mol TCE/Bottle
80
100
60
Control
80
Expected TCE
Expected TCE w/ ADS
Expected TCE (K+)
60
Observed
40
40
20
20
0
0
1
2
3
4
0
0
5
10
15
Time (days)
20
25
30
Figure 5.37 Batch TCE degradation test for 19-546. Symbols represent average of triplicate bottles for observed TCE and water
controls. The error bars represent one standard deviation. The inset shows initial TCE activity.
74
100
mole TCE/Bottle
80
Control
60
Expected TCE (batch)
Expected TCE (batch w/ ads)
Expected TCE (dd)
40
Expected TCE (dd w/ ads)
Observed
20
0
0
1
2
Time (days)
3
4
Figure 5.38 Batch TCE degradation test for 19-547. Symbols represent average of triplicate bottles for observed TCE and water
controls. The error bars represent one standard deviation.
75
100
mole TCE/Bottle
80
100
60
80
Observed TCE
Expected TCE (batch w/ ads)
60
Expected TCE (batch)
40
Expected TCE (K+)
40
Control
20
0
0
1
2
3
4
20
0
0
5
10
15
Time (days)
20
25
30
Figure 5.39 Batch TCE degradation test for 19-548. Symbols represent average of triplicate bottles for observed TCE and water
controls. The error bars represent one standard deviation. The inset shows initial TCE activity.
76
100
mole TCE/Bottle
80
60
Observed TCE
Expected TCE
40
Control
20
0
0
2
4
6
8
Time (days)
10
12
14
Figure 5.40 Batch TCE degradation test for 19-549. Symbols represent average of triplicate bottles for observed TCE and water
controls. The error bars represent one standard deviation.
77
100
mole TCE/Bottle
80
100
Observed TCE
60
Expected TCE (batch)
Expected TCE (K+)
80
60
Control
40
40
20
0
20
0
1
2
3
4
0
0
5
10
15
Time (days)
20
25
30
Figure 5.41 Batch TCE degradation test for 19-550. Symbols represent average of triplicate bottles for observed TCE and water
controls. The error bars represent one standard deviation. The inset shows initial TCE activity.
78
mole TCE/Bottle
100
80
60
Control
Expected TCE (batch)
Expected TCE (dd)
Observed TCE
40
100
80
60
40
20
20
0
0
1
2
3
4
0
0
4
8
Time (days)
12
16
Figure 5.42 Batch TCE degradation test for 19-551. Symbols represent average of triplicate bottles for observed TCE and water
controls. The error bars represent one standard deviation. The inset shows initial TCE activity.
79
100
mole TCE/Bottle
80
Control
60
Expected TCE (Batch)
100
Expected TCE (DD)
80
Observed TCE
40
60
40
20
20
0
0
1
2
3
4
0
0
3
6
Time (days)
9
12
Figure 5.43 Batch TCE degradation test for 19-552. Symbols represent average of triplicate bottles for observed TCE and water
controls. The error bars represent one standard deviation. The inset shows initial TCE activity.
80
100
mole TCE/Bottle
80
100
60
80
Observed TCE
Expected TCE (batch)
Expected TCE (K+)
40
60
40
20
Control
0
0
1
2
3
4
20
0
0
5
10
15
Time (days)
20
25
30
Figure 5.44 Batch TCE degradation test for 19-553. Symbols represent average of triplicate bottles for observed TCE and water
controls. The error bars represent one standard deviation. The inset shows initial TCE activity.
81
microspheres/l in TCE degradation tests).
It was also assumed that TCE was
stoichiometrically oxidized by KMnO4. The potential effect of adsorption was calculated
for samples with shell materials matching the 19-363 blank (i.e., samples 19-546, 19-547,
and 19-548). Assuming equilibrium, the mass of TCE adsorbed to the polymer shell was
calculated (using equation 4) for each predicted TCE value. The mass adsorbed was then
subtracted from the predicted TCE degradation value based on batch release.
Determination of predicted parameters
The observed and predicted rates of TCE degradation were compared based on
normalized initial rates and the time to remove 0.99 of the initial mass of TCE. The
initial rate of degradation was calculated by performing a linear regression on the first
few observed and predicted data points. Enough data points were included in each
regression to make the R2 value less than 0.95. The mass of microspheres varied among
the batch test, so the initial degradation rate was normalized by the initial mass of
KMnO4 present.
This normalized degradation rate is in units of (mol TCE/mg
KMnO4)/day. The other parameter used for comparison of observed and predicted rates
was the time to achieve removal of 0.99 of the initial mass of TCE (t0.99). The t0.99 values
were calculated by interpolation.
Comparison with observed values
A small-sample Student’s t-test was used to determine if observed and predicted
values were drawn from different populations (McClave and Dietrich, 1991).
confidence interval was calculated based on:
A
83
1
2 1
( x1  x2 )  t / 2 s p   
 n1 n2 
(14)
where
sp
2
2
2

n1  1s1  n2  1s2

n1  n2  2
(15)
and x1 and x2 are the means of sample sets 1 and 2, respectively, n1 and n2 are the number
of observations in sample sets 1 and 2, s1 and s2 are the standard deviations of sample sets
1 and 2, and t/2 is based on (n1+n2-2) degrees of freedom. A t/2 value of t0.025=2.776
was used for a 95% confidence interval with 4 degrees of freedom.
Statistical comparisons indicated observed t0.99 values are much larger than
predicted for tests with samples 19-307 and 19-308, and observed initial TCE
degradation rates for tests with samples 19-546 through 19-553 are faster than predicted.
In tests with samples 19-307 and 19-308, the average observed initial rates of
TCE degradation (0.068 and 0.188 (mol TCE/mg KMnO4)/day, respectively) are slower
than predicted rates (0.124 and 0.283 (mol TCE/mg KMnO4)/day). However, these
rates are variable, and the differences between observed and predicted values are not
statistically significant using a 95% confidence interval (Table 5.9 and Figure 5.45). The
observed values for t0.99 (30.9±4.4 and 23.0±3.9 days) are approximately four times
greater than predicted times (7.6±0.34 and 5.5±1.9 days) (Table 5.9 and Figure 5.46).
Paired observed and predicted t0.99 values are different with 95% confidence. These data
Table 5.9
Sample
Observed and predicted TCE degradation parameters.
Time to .99 removal, t0.99
(observed)
Time to .99 removal, t0.99
(predicted)
Initial Degradation Rate
(observed)
Initial Degradation Rate
(predicted)
Average
Average
Average
Average
Stand Dev.
(days)
Stand Dev.
(days)
Stand Dev.
(mol/day/mg KMnO4)
Ratio:
Initial Rate
(observed)/
Initial rate
(predicted)
Stand Dev.
(mol/day/mg KMnO4)
19-307
30.85
4.44
7.57
0.34
0.068
0.037
0.124
0.011
0.55
19-308
23.04
3.88
5.48
1.89
0.188
0.047
0.283
0.044
0.66
19-546
18.54
13.13
2.74
0.25
2.116
0.272
0.655
0.150
3.2
19-547
1.29
0.35
2.28
0.30
1.969
0.119
0.527
0.058
3.7
19-548
24.18
9.10
4.87
1.34(est.)
2.767
0.111
0.816
0.000
3.4
19-549
5.96
3.34
2.57
0.33
1.674
0.310
0.435
0.019
3.8
19-550
20.27
3.58
5.85
0.65
1.775
0.158
0.491
0.061
3.6
19-551
6.05
4.99
5.69
1.35
3.776
0.237
0.923
0.083
4.1
19-552
5.51
1.90
3.41
1.35
1.709
0.050
0.438
0.054
3.9
19-553
19.31
7.15
8.34
1.07
2.001
0.193
0.493
0.111
4.1
84
19-307
19-308
19-549
Expected Rate
Sample
19-552
Observed Rate
19-550
19-547
19-553
19-546
19-548
19-551
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
Initial TCE Degradation Rate (mol TCE/day/mg KMnO4)
Figure 5.45 Observed and predicted initial TCE degradation rates. Observed rates are average values calculated from triplicate batch
TCE degradation data. Predicted values are average values calculated from triplicate batch release data. Error bars
represent one standard deviation. Samples are ordered by increasing observed rate.
19-307
19-308
19-549
Expected Time
Sample
19-552
Observed Time
19-550
19-547
19-553
19-546
19-548
19-551
0
5
10
15
20
25
30
35
40
Time (days)
Figure 5.46 Observed and predicted 0.99 mass removal times. Observed times are average values calculated from triplicate batch
TCE degradation data. Predicted values are average values calculated from triplicate batch release data. Error bars
represent one standard deviation. Samples are ordered as in Figure 5.42.
suggest that the initial rate of TCE degradation is less than or equal to the predicted rate,
and the t0.99 values indicated degradation was slower than predicted late in the tests.
Average initial TCE degradation rates for tests using samples 19-546 through 19553, are three to five times greater than the predicted rates (Table 5.9 and Figure 5.45).
All of these pairs of values are drawn from separate populations with 95% confidence.
Average observed values of t0.99 are all greater than or equal to predicted values with the
exception of sample 19-547 which produced a shorter t0.99 than that predicted (Table 5.9
and Figure 5.46). Despite the trend in the averages, these pairs of values fail to show
they are different with 95% confidence.
The only sample that shows a significant
statistical difference between observed and predicted t0.99 values is 19-550. Adsorption
had a minor effect on predicted TCE degradation for samples 19-546, 19-547, and 19548, according to results in Figures 5.37, 5.38, and 5.39. The small effect of adsorption
during batch degradation tests is further exemplified by observed losses of TCE in a
batch test with sample 19-363, which consisted of only shell material (Figure 5.47). The
bottles contained TCE and a mass of 19-363 (0.06 g) equal to the mass of shell material
present in the corresponding degradation tests with samples 19-546, 19-547, and 19-548.
The test was terminated after 30 days, and the results indicate that an average of 0.17 of
the initial mass was adsorbed. The effect of this amount of adsorption on the results of
the TCE degradation tests is negligible. The contribution of adsorption to mass loss of
TCE during the batch degradation tests is insufficient to explain the disparity between
observed and predicted rates.
Drain-daily data provided a better prediction of TCE degradation than batch
release tests for samples 19-547 and 19-552 (Figures 5.38 and 5.43), but not for 19-551
88
(Figure 5.42). Drain-daily prediction for the test with sample 19-552 fit observed TCE
data well during the first day of treatment, but overestimated TCE degradation at later
times. Drain-daily data predict initial degradation better than batch data.
These results suggest that the diffusive release of KMnO4 and the stoichiometric
degradation of TCE are unable to account for observed loss of TCE. It appears that some
processes other than simple release occur during TCE degradation. TCE is typically
degraded faster than predicted during the first few days.
In some cases, TCE is
completely degraded during this early stage. In cases when TCE remains after a few
days, however, the observed rate of TCE degradation is slower than predicted by release.
Permanganate analysis
Measurements of MnO4- were made during TCE degradation tests for samples 19546, 19-548, 19-550, and 19-553 (from day 13 until TCE concentrations fell below the
detection limit). In addition, permanganate (MnO4-) concentrations were measured for all
tests on day 85.
MnO4- concentrations were negligible during TCE degradation, and at t = 85 days.
Concentrations of MnO4- at 85 days were expected to average 230 (ranging from 113 to
395) mol/bottle. These expected concentrations are based on the difference between
Cr,max and the stoichiometric amount of KMnO4 needed to oxidize the initial mass of TCE
present. Tests with samples 19-547 and 19-548 showed MnO4- amounts of 0.46 (±0.73)
and 0.23 (±0.40) mol/bottle, respectively. Amounts of MnO4-were below detection for
all other tests.
100
mole TCE/Bottle
80
60
Water Control
40
Observed TCE
20
0
0
5
10
15
Time (days)
20
25
30
Figure 5.47 Batch TCE degradation test for 19-363. Symbols represent average of triplicate bottles. The error bars represent one
standard deviation.
The lack of significant MnO4- concentrations in all tests indicates either
retardation of the release of the remaining MnO4-, or existence of a sink for the unused
MnO4-.
Manganese dioxide observations
The color of the water was observed during TCE degradation and after complete
removal of TCE. Color was consistent from bottle to bottle.
Initial color of the water was purple in most cases. Purple was only visible during
the first 2 to 4 hours of the test. Later, the water took on a brown cloudy appearance.
This color and turbid condition increased in intensity until TCE degradation was
complete.
Purple indicates release of KMnO4, and brown indicates the presence of MnO2.
The turbidity is caused by precipitation of solid MnO2. These observations indicate that
some TCE and KMnO4 reacted in solution.
TCE degradation based on Potassium
The concentration of potassium ion (K+) in solution was measured during tests
conducted with samples 19-546, 19-550, and 19-553.
It was assumed that K+ was
released from the microspheres into the bulk water at the same rate as MnO4-. Results
were plotted as predicted TCE remaining based on an amount of permanganate
corresponding to the K+ concentration, for comparison with observed TCE values.
Average potassium concentrations over the duration of the experiment are 60.8
(±9.84) mg/l. The data show (Figures 5.37, 5.41, and 5.44) that the predicted TCE based
on K+ is higher (up to 5 times) than TCE observed. A higher predicted amount of TCE
91
than observed means that the concentration of potassium is lower than expected when
assuming K+ is released at the same rate as MnO4- is used to degrade TCE. This finding
suggests that either K+ is not being released at the same rate as MnO4-, or that
permanganate is not being utilized at the predicted rate based on the stoichiometry of the
reaction with TCE.
Extent of TCE Degradation Based on Chloride Release
The extent of TCE dechlorination in batch tests was estimated by measuring the
concentration of chloride (Cl-) and comparing this to the expected stoichiometry, i.e. 3
mol Cl-/mol TCE consumed. Cl- measurements were made on samples taken on day 85.
The amount of chloride released was consistent for all of the samples, with an average
stoichiometric recovery of 2.56 (±0.05) mol of chloride per mol of TCE (Figure 5.48).
Standard additions indicated minimal matrix effects on the samples, yielding an average
recovery of 0.967 (±0.0359). These results indicate that 0.44 mol of chloride per mol of
TCE or 15 percent of the expected chloride cannot be detected. This suggests the
presence of an undetermined sink for either TCE or chloride ions.
Addition of Polymaleic Acid
A preliminary experiment with TCE, KMnO4, and PMA (a humic acid surrogate)
was performed to determine the minimum concentration of PMA necessary to inhibit
TCE degradation.
A concentration of 1.9 g/l PMA almost completely prevented
oxidation of TCE by KMnO4 (Figure 5.49).
92
moles Cl -:moles TCE
Recovered Stoichiometrically
3.0
2.5
2.0
1.5
1.0
0.5
0.0
19-546
19-547
19-549
19-550
19-551
19-552
19-553
Sample Number
Figure 5.48 Chloride recovery in batch TCE degradation test. Values shown are
averages of triplicates. Error bars represent one standard deviation.
A second test was performed with microspheres (19-547) and TCE in the
presence of 1.9 g/l PMA. Only 0.1 of the initial mass of TCE was consumed compared to
water controls (Figure 5.50). The bottles with TCE and microspheres but no PMA
showed complete removal of TCE in less than two days.
Results indicate that
microspheres did not prevent interference with TCE oxidation by KMnO4, but a very
high concentration was needed to cause interference.
The lowest level that caused
significant interference in the preliminary experiment was 497 mg/l PMA. At 37% DOC,
this concentration is 10 to 100 times typical reported values in groundwater (Vilks and
Bachinski, 1996; Dia et al., 2000).
90
 mol TCE / Bottle
75
60
45
0 mg/L PMA, 0 mg/L KMnO4
30
2671 mg/L PMA, 820 mg/L KMnO4
1870 mg/L PMA, 820 mg/L KMnO4
7 L TCE
100 mL DDI
1179 mg/L PMA, 820 mg/L KMnO4
497 mg/L PMA, 820 mg/L KMnO4
15
112 mg/L PMA, 820 mg/L KMnO4
0 mg/L PMA, 820 mg/L KMnO4
0
0
2
4
6
8
10
12
14
16
18
Time (hours)
Figure 5.49 PMA concentration analysis.
93
90
mole TCE/Bottle
75
60
90
TCE (WC)
TCE + PMA
45
TCE + Microspheres
75
TCE + PMA + Microspheres
30
60
15
45
0.00
0.01
0.02
0.03
0.04
0.05
0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
Time (days)
Figure 5.50 TCE degradation test with PMA present. Symbols represent average of triplicate bottles. The error bars represent one
standard deviation.
94
CHAPTER 6
DISCUSSION
These experiments show that microspheres will release KMnO4 and degrade TCE,
but the rate of degradation is not consistent with predicted TCE degradation based on
batch release tests. The initial rate of degradation is 3 to 4 times faster than the predicted
rate, but observed t0.99 values are greater than predicted. Initial release rates for high
volume drain-daily tests were higher than batch release rates, and so initial degradation
rates based on drain-daily data were better predictors of observed values.
The concentrations of daughter products of the reaction (chloride, potassium, and
permanganate) were measured during and after the reaction and were are all less than
expected based on the stoichiometry (16).
C2Cl3H + 2KMnO4 ==> 2CO2 (aq) + 2MnO2 (s) + 2KCl + HCl
(16)
MnO4- and MnO2 were both identified visually in solution during the degradation of TCE,
indicating that some permanganate was reacting with TCE in solution.
Faster initial degradation rates could occur because the reaction between TCE and
KMnO4 keeps the KMnO4 concentration in solution near zero. This low concentration
maximizes the concentration gradient between the solution and the interior of the
microspheres resulting in a faster release of KMnO4 than was seen in the batch release
tests. In turn, the TCE is oxidized faster than predicted. This is supported by trends in
the drain-daily release tests show double the initial rates of batch tests. It is also likely
that some TCE diffuses into the shell and reacts at the interface between the shell and the
grains of KMnO4. As TCE is consumed by this reaction, a driving gradient for TCE
96
diffusion into the shell is maintained. This gradient is what determines the rate at which
the TCE is removed.
Using drain-daily data to predict TCE degradation can account for a
permanganate concentration gradient affecting release. But using release data does not
consider a driving gradient for TCE into the microspheres.
One explanation for the lower concentrations of daughter products than expected
is that reaction products from TCE degradation by KMnO4 accumulate inside the
microspheres at the interface between the individual KMnO4 grains and the wax.
Assuming conditions favor formation of CO2(g), the gas would form between the grains
and the wax (Figure 6.1), and as KMnO4 reacts, the space formerly occupied by it will be
filled with CO2 (and MnO2). Eventually, CO2 could envelop most of the remaining solid
KMnO4 (Figure 6.2). This gas barrier would limit diffusion of soluble species, including
MnO4-, K+, and Cl- out of the sphere and alter the interface between the grains of KMnO4
and the DDI water containing TCE that diffuses into the sphere. In addition, as the
concentration of CO2 inside the microspheres increases, the reaction rate for KMnO4 and
TCE decreases.
With the reaction slowed due to presence of excess daughter products, the process
relies on the kinetics of diffusion of CO2 out of the microspheres for the reaction to
proceed. This explanation is supported by lower K+ and Cl- concentrations than expected
in solution. Also, the lack of MnO4- in solution at day 85 may indicate inhibition of the
release of residual MnO4- left in the microspheres after complete removal of TCE.
Figure 6.1
Conceptual model step 1.
97
Figure 6.2
Conceptual model step 2.
98
Further experiments are needed to evaluate these explanations. Increased work
with the presence of PMA during TCE degradation could shed light on whether TCE is
diffusing into the spheres and reacting with KMnO4 or reacting in solution. Other key
experiments could include measurement of the diffusion rates of KMnO4 and TCE
through different shell formulations.
Developing an understanding of the processes involved in TCE degradation with
KMnO4 microspheres is the first step toward application of this remediation technology.
Further development of shell composition and manufacturing parameters may extend
release times to as long as 6 to 12 months.
100
CHAPTER 7
CONCLUSIONS
Encapsulated KMnO4 samples were tested in batch release tests and in batch tests
with TCE. Release in a batch system was quantified using an empirical model. TCE
degradation was shown to occur in the presence of encapsulated microspheres. This
represents, to my knowledge, the first report of polymer-encapsulated KMnO4 for
controlled release applications.
Microscopic observation of microspheres 19-230, 19-231, 19-232, 19-233, 19234, 19-235, and 19-236 indicated they are of single grain core (SGC) composition.
Microspheres 19-306, 19-307, 19-308, 19-546, 19-547, 19-548, 19-549, 19-550, 19-551,
19-552, and 19-553 are of multiple grain core (MGC) composition. The majority of SGC
microspheres had a single grain of KMnO4 exposed on one side, whereas MGC
microspheres were more uniformly coated with little noticeable KMnO4 exposed.
Release experiments showed varied release rates and times. The average time
taken to reach maximum concentrations for all samples in batch release tests, tmax, is 27
(±22) days and ranges from 3 to 80 days. The average final concentration ratio, Cr,max, is
0.88 (±0.095) (g KMnO4 released/g KMnO4 initial) for all samples and ranges from 0.80
to 1.05. The average maximum release rate, ko, is 2.70 (±3.64) (g KMnO4 released/g
KMnO4 initial)/day and the range varied from 0.22 to 9.41. Data from batch release tests
with SGC samples showed higher ko values and shorter t0.5 and tmax values than those of
MGC tests. Also, as t0.5 values increase in both SGC and MGC tests, the initial rates of
release, ko consistently decrease.
101
The SGC microspheres had grains that were exposed on one side. When placed
in contact with water, the direct dissolution of KMnO4 was observed. This eccentric core
dominated the release behavior of SGC microspheres. It is expected that SGC material
with uniform shells will release for longer times.
An empirical model, Model C, was used to predict the release in batch tests.
Concentration as a function of time was predicted with an average R2 value of 0.929
(±0.059), and residuals for a majority of fits were uniformly distributed about the x-axis
over the domain.
Initial release rates, ko, are 2 times higher for high volume drain-daily tests than
for batch release tests.
Therefore, based on the high volume tests, keeping a low
concentration in the receiving water increases the rate of release.
Freundlich isotherms were developed experimentally for sample 19-363, boler
wax, and Chlorez 700. The average K value is 0.743 (±1.13) [(l/mg)*(mg/g)], and the
average 1/n value is 1.055 (±0.058) (dimensionless).
TCE was degraded to less than detectable amounts in the presence of the KMnO4
microspheres. In batch TCE tests, the average initial degradation rate is 1.8 (±0.15)
[(mol TCE/day)/ mg KMnO4] and it ranges from 0.07 to 3.8 [(mol TCE/day)/ mg
KMnO4]. The average t0.99 value for all MGC microspheres is 15.5 (±5.2) days, and it
ranges from 1.3 to 30.9 days.
The rate of TCE degradation was predicted using the observed rate of release of
KMnO4 and assuming an ideal reaction stoichiometry. The observed rates of TCE
degradation were 3 to 4 times faster than the predicted rates during the first few days of
the tests. TCE was completely removed in some tests after a few days. However, where
102
TCE was present for longer than a few days, the degradation reaction rate decreased and
was less than predicted based on the release rate.
Chloride measured during the test amounts to 2.56 (±0.05) mol of chloride per
mol of TCE, whereas 3.0 mol Cl- per mol TCE is expected based on the stoichiometry of
the degradation reaction. This suggests that 0.44 mol of chloride per mol of TCE, or 0.15
of the expected chloride is missing.
The concentration of potassium during the degradation of TCE was lower than
expected when assuming K+ is released at the same rate as MnO4- is used to degrade
TCE. The concentration of MnO4- during the degradation of TCE was negligible. Also,
MnO4- concentrations did not increase after degradation of TCE was complete.
The affects of the formulation of microspheres on release and TCE degradation
were evaluated, and two relationships were elucidated. Microspheres 19-549 and 19-553
have the longest maximum release times. These samples contain the highest levels of
Chlorez 700. The fastest initial rates of TCE degradation were achieved by samples 19551 and 19-548. These samples have a KMnO4 mass fraction of 0.5 (the majority of
samples have 0.4).
The important effects of these different formulations are that Chlorez 700 seems
to extend the time of release, and higher mass fractions of KMnO4 seem to increase the
initial rate of TCE degradation.
103
APPENDICES
104
Appendix A
Response Factors
105
Table A.1
Hach DR 2010 spectrophotometer standards for potassium permanganate
Conc. Of KMnO4
(g/L)
0.0500
0.0250
0.0200
0.0167
0.0100
0.0075
0.0050
0.0040
0.0030
0.0010
0.0009
Absorbance @ 528
nm
1.740
0.890
0.709
0.589
0.346
0.268
0.175
0.137
0.101
0.032
0.031
KMnO4 Concentration (g/L)
0.06
0.05
0.04
0.03
y = 0.0285x
2
R = 0.9998
0.02
0.01
0.00
0.0
0.5
1.0
1.5
Absorbance @ 528 nm
Figure A.1
Hach DR 2010 spectrophotometer response factor for potassium
permanganate
2.0
Table A.2
GC standards for 72 ml bottles
Peak Area mol TCE
23328432
339.5
4286499
65.73
Pressure (mm Hg)
874861
308069
82347
34404
13.53
4.081
1.019
0.3504
743.2
o
Temperature ( C)
23
-72 mL serum bottles were used; Vl = 45mL; Vg = 27mL; sample size = 0.1 mL
-TCE retention time = 3.8 minutes
400
mole TCE/bottle
350
300
y = 1.4580E-05x
R2 = 9.9987E-01
250
200
150
100
50
0
0
5000000
10000000
15000000
20000000
25000000
Peak Area
Figure A.2
GC response factor for 72 ml bottles
106
Table A.3
Peak Area
2768618
1391954
554221
280728
65692
21432
GC standards for 160 ml bottles
mol TCE
113.4
55.82
Pressure (mm Hg)
22.5
11.4
2.56
0.853
743.2
Temperature (oC)
23
-160 mL serum bottles were used; Vl = 100mL; Vg = 60mL; sample size = 0.1 mL
-TCE retention time = 3.8 minutes
120
moles TCE
100
80
60
y = 4.07781E-05x
2
R = 9.99878E-01
40
20
0
0
500000
1000000
1500000
2000000
2500000
3000000
Peak Areas
Figure A.3
GC response factor for 160 ml bottles
107
Table A.4
Chloride probe standards
Concentration
log
KCl (M) Concentration
0.0002
0.0005
0.0010
0.0015
0.0020
0.0100
-3.7
-3.3
-3.0
-2.8
-2.7
-2.0
Electric
Potential
(mV)
115.2
94.7
79.6
69.2
62.2
23.0
Electrode Potential (mV)
140
120
y = -54.375x - 84.818
100
2
R = 0.9992
80
60
40
20
0
-3.8
-3.3
-2.8
log Concentration
Figure A.4
Chloride probe response factor
-2.3
-1.8
Table A.5
IC standards for potassium
before
after
Potassium Concentration
(mg/L)
0
0.3
0.6
1.5
3
10
0
0.3
0.6
1.5
3
10
Peak Area
126636
248412
427020
997821
2086967
7014775
148226
261290
442721
1020704
2110313
6999530
+
Concentration K (mg/L)
12
10
8
6
y = 1.4274E-06x
4
2
R = 9.9934E-01
2
0
0
1000000 2000000
3000000
4000000 5000000
Peak Area
Figure A.5
IC response factor for potassium
6000000 7000000
8000000
Table A.6
Beckman spectrophotometer standards for potassium permanganate
ABS @ 525
nm
filtered data
KMnO4 Conc
(g/L)
0.1
0.07
0.05
0.025
0.005
ABS
1.48283
1.01489
0.71722
0.33963
0.04801
unfiltered data
KMnO4 Conc
(g/L)
0.075
0.05
0.03
0.025
0.01
0.005
0.003
0.002
0.001
0.0004
ABS
1.1189
0.7037
0.4567
0.3737
0.1512
0.0954
0.0478
0.0346
0.0213
0.0128
KMnO4 Conc. (g/L)
0.12
0.1
0.08
0.06
y = 6.8357E-02x
0.04
2
R = 9.9832E-01
0.02
0
0
Figure A.6
0.5
1
ABS
1.5
Beckman spectrophotometer response factor for filtered potassium
permanganate solutions
2
KMnO4 Conc. (g/L)
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
y = 6.7736E-02x
2
R = 9.9829E-01
0
0.2
0.4
0.6
0.8
1
ABS
Figure A.7
Beckman spectrophotometer response factor for unfiltered potassium
permanganate solutions
1.2
Appendix B
1-D Diffusion Model Derivation
113
Assume that particles are placed in a fixed volume of fluid and release occurs by
diffusion through the shell. The concentration of permanganate is initially zero, but
increases as a function of time.
Assume 1-D diffusion through shell material, so mass flux of permanganate out of the
capsule is given by Fick’s Law
J  D
dC
dr
(1)
where D is the diffusion coefficient for the shell material. Neglecting the curvature of the
shell, the concentration gradient during steady state conditions must satisfy (Cussler,
1997)
d 2C
0
dr 2
Cs = HCc;
r=0
Cs = HC;
r=T
where H is the ratio of the equilibrium concentration in the shell to the concentration in
the solution. The boundary conditions assume that the concentration in the core is equal
to the saturated concentration of permanganate in water. The partitioning term, H, may
cause the concentrations in the shell to be significantly different than the concentrations
in the solution. We expect that H will be small for compounds, such as permanganate,
that are highly soluble in water.
The concentration in the shell is
 C  Cc 
Cs  H 
 r  HCc
 T 
According to Fick’s Law, the mass flux across the shell is
J
dCs
dM
DH
 D

( C  Cc )
dtA
dr
T
114
dM
dC
DHM DHCc
 D


dtA
dr
TVw
T
J
rearranging
DHACc
dM
DHA

M
dt
TVw
T
gives
DHACc
dM
DHA

M
dt
TVw
T
separate variables
dM
DHACc
DHA

M
TVw
T
 dt
(2)
integrating (2)

TVw
DHACc
DHA
ln( 
M
)  t  Cint
DHA
TVw
T
(3)
and using the initial condition
M = 0 when t = 0
(4)
Gives the integration constant

TVw
DHACc
ln(
)  Cint
DHA
T
substituting (5) into (3)

ln(
and rearranging
DHACc
DHA
M
TVw
T
DHA
)
t
DHACc
TVw
T
(5)
115
ln( 
1
DHA
M  1)  
t
Vw Cc
TVw
gives the mass as a function of time
DHA


t
M  Vw Cc 1  e TVw 


(6)
and the concentration of the water is
DHA


t

Cw  Cc 1  e TVw 


(7)
This release rate is valid while the concentration in the capsule remains equal to C c. It
seems reasonable to assume that Cc = Csat while solid remains in the core. This assumes
that there is no reaction occurring in the core that could reduce Cc, and it assumes that
water occurs in the core. Based on these assumptions, it follows that this release rate
holds while solid remains in the core.
The total surface area of the particles
A  n4r 2
the weight of n particles is
w
4 3
r n
3
so
n
3w
4r 3
and
A
3w
r
(8)
so (7) becomes
DH 3 w

t 


C w  C sat 1  e TrVw 




(9)
116
n: number of particles
unit weight of particles
Cc: concentration in core
A cross section area of capsule
M: mass of permanganate in water
Vw: volume of water
117
Appendix C
Batch Release Data
Table C.1
SGC batch release data sample 19-230
Time Sampled
10/5/99 18:45
10/5/99 19:44
10/5/99 21:07
10/6/99 9:05
10/6/99 19:50
10/8/99 16:44
10/11/99 2:40
10/12/99 1:59
10/17/99 23:40
Table C.2
Time (days)
0.037
0.078
0.136
0.635
1.083
2.954
5.367
6.338
12.242
Amt Sampled(mL) Dilution Rate
1
25
1
25
1
25
1
25
1
25
1
25
1
25
1
25
1
25
ABS
0.144
0.181
0.187
0.221
0.194
0.209
0.212
0.216
0.216
Conc KMnO4(g/L)
0.103
0.129
0.133
0.158
0.138
0.149
0.151
0.154
0.154
C/Co
0.522
0.656
0.677
0.801
0.703
0.757
0.768
0.782
0.782
Conc KMnO4(g/L)
0.093
0.442
0.495
0.615
0.527
0.575
0.586
0.595
0.597
C/Co
0.142
0.676
0.756
0.939
0.804
0.878
0.895
0.909
0.912
SGC batch release data sample 19-231
Time Sampled
10/5/99 18:46
10/5/99 19:46
10/5/99 21:08
10/6/99 9:07
10/6/99 19:52
10/8/99 16:46
10/11/99 2:42
10/12/99 2:03
10/17/99 23:42
Time (days)
0.038
0.079
0.136
0.636
1.084
2.955
5.369
6.342
12.243
Amt Sampled(mL)
1
1
1
1
1
1
1
1
1
Dilution Rate
25
25
25
25
25
25
25
25
25
ABS
0.130
0.620
0.694
0.862
0.738
0.806
0.821
0.834
0.837
118
Table C.3
SGC batch release data sample 19-232
Time Sampled
10/5/99 18:47
10/5/99 19:47
10/5/99 21:09
10/6/99 9:08
10/6/99 19:54
10/8/99 16:48
10/11/99 2:44
10/12/99 2:05
10/17/99 23:44
Table C.4
Time (days)
0.038
0.080
0.137
0.637
1.085
2.956
5.370
6.343
12.245
Amt Sampled(mL) Dilution Rate
1
25
1
25
1
25
1
25
1
25
1
25
1
25
1
25
1
25
ABS Conc KMnO4(g/L)
0.094
0.067
0.47
0.335
0.56
0.400
0.713
0.509
0.613
0.437
0.673
0.480
0.69
0.492
0.72
0.514
0.705
0.503
C/Co
0.137
0.686
0.817
1.041
0.895
0.982
1.007
1.051
1.029
ABS Conc KMnO4(g/L)
0.171
0.122
0.412
0.294
0.516
0.368
0.573
0.409
0.454
0.324
0.548
0.391
0.564
0.403
0.558
0.398
0.56
0.400
C/Co
0.305
0.735
0.921
1.022
0.810
0.978
1.006
0.996
0.999
SGC batch release data sample 19-233
Time Sampled
10/5/99 18:48
10/5/99 19:48
10/5/99 21:10
10/6/99 9:10
10/6/99 19:55
10/8/99 16:49
10/11/99 2:45
10/12/99 2:07
10/17/99 23:46
Time (days)
0.039
0.081
0.138
0.638
1.086
2.957
5.371
6.344
12.246
Amt Sampled(mL) Dilution Rate
1
25
1
25
1
25
1
25
1
25
1
25
1
25
1
25
1
25
119
Table C.5
SGC batch release data sample 19-234
Time Sampled
10/5/99 18:49
10/5/99 19:49
10/5/99 21:12
10/6/99 9:11
10/6/99 19:56
10/8/99 16:51
10/11/99 2:46
10/12/99 2:09
10/17/99 23:48
Table C.6
Time (days)
0.040
0.082
0.139
0.639
1.087
2.958
5.372
6.346
12.247
Dilution Rate
25
25
25
25
25
25
25
25
25
ABS
0.174
0.72
0.751
0.831
0.722
0.787
0.792
0.834
0.806
Conc KMnO4(g/L)
0.124
0.514
0.536
0.593
0.515
0.562
0.565
0.595
0.575
C/Co
0.169
0.698
0.728
0.806
0.700
0.763
0.768
0.809
0.782
Dilution Rate
25
25
25
25
25
25
25
25
25
ABS
0.064
0.199
0.306
0.517
0.434
0.579
0.579
0.578
0.603
Conc KMnO4(g/L)
0.046
0.142
0.218
0.369
0.310
0.413
0.413
0.413
0.430
C/Co
0.088
0.273
0.420
0.710
0.596
0.795
0.795
0.793
0.828
SGC batch release data sample 19-235
Time Sampled
10/5/99 18:50
10/5/99 19:51
10/5/99 21:13
10/6/99 9:13
10/6/99 19:57
10/8/99 16:52
10/11/99 2:48
10/12/99 2:11
10/17/99 23:50
Time (days)
0.041
0.083
0.140
0.640
1.087
2.959
5.373
6.347
12.249
120
Table C.7
SGC batch release data sample 19-236
Time Sampled
10/5/99 18:51
10/5/99 19:52
10/5/99 21:14
10/6/99 9:15
10/6/99 19:58
10/8/99 16:54
10/11/99 2:49
10/12/99 2:13
10/17/99 23:52
Time (days)
0.042
0.084
0.141
0.641
1.088
2.961
5.373
6.348
12.250
Dilution
Rate
25
25
25
25
25
25
25
25
25
ABS
0.026
0.074
0.114
0.231
0.224
0.273
0.299
0.301
0.327
Conc KMnO4(g/L)
0.019
0.053
0.081
0.165
0.160
0.195
0.213
0.215
0.233
C/Co
0.068
0.195
0.300
0.608
0.590
0.719
0.787
0.793
0.861
121
Table C.8
MGC batch release data sample 19-306
Bottle A
Bottle B
Bottle C
Average
Std Dev.
Time
Time (days)
ABS
[KMnO4] (mg/l)
C/Co
ABS
[KMnO4] (mg/l)
C/Co
ABS
[KMnO4] (mg/l)
C/Co
C/Co
C/Co
1/5/00 20:15
0.00
0.000
0.0
0.000
0.000
0.0
0.000
0.000
0.0
0.000
0.000
0.0000
1/6/00 17:20
0.88
0.109
77.8
0.159
0.109
77.8
0.159
0.089
63.5
0.130
0.150
0.0169
1/8/00 3:25
2.30
0.228
162.7
0.333
0.245
174.8
0.358
0.213
152.0
0.311
0.334
0.0234
1/8/00 23:45
3.15
0.326
232.7
0.477
0.351
250.5
0.513
0.314
224.1
0.459
0.483
0.0276
1/10/00 3:00
4.28
0.440
314.0
0.643
0.484
345.4
0.708
0.436
311.2
0.638
0.663
0.0389
1/11/00 19:18
5.96
0.557
397.5
0.815
0.580
413.9
0.848
0.565
403.2
0.826
0.830
0.0171
1/12/00 16:27
6.84
0.580
413.9
0.848
0.623
444.6
0.911
0.595
424.6
0.870
0.876
0.0319
1/14/00 19:00
8.95
0.592
422.5
0.866
0.606
432.5
0.886
0.593
423.2
0.867
0.873
0.0114
1/16/00 20:35
11.01
0.592
422.5
0.866
0.605
431.8
0.885
0.609
434.6
0.891
0.880
0.0130
1/17/00 12:40
11.68
0.595
424.6
0.870
0.609
434.6
0.891
0.596
425.3
0.872
0.877
0.0114
122
Table C.9
MGC batch release data sample 19-307
Bottle D
Bottle E
Bottle F
Average
Std Dev.
Time
time (days)
ABS
[KMnO4] (mg/l)
C/Co
ABS
[KMnO4] (mg/l)
C/Co
ABS
[KMnO4] (mg/l)
C/Co
C/Co
C/Co
1/5/00 20:28
0.00
0.000
0.0
0.000
0.000
0.0
0.000
0.000
0.0
0.000
0.000
0.0000
1/6/00 17:40
0.88
0.026
18.6
0.039
0.024
17.1
0.036
0.018
12.8
0.027
0.034
0.0063
1/8/00 3:40
2.30
0.054
38.5
0.080
0.056
40.0
0.083
0.043
30.7
0.063
0.076
0.0107
1/8/00 23:58
3.15
0.073
52.1
0.109
0.072
51.4
0.107
0.060
42.8
0.088
0.101
0.0112
1/10/00 3:15
4.28
0.095
67.8
0.141
0.096
68.5
0.143
0.078
55.7
0.115
0.133
0.0156
1/11/00 19:34
5.96
0.133
94.9
0.198
0.142
101.3
0.211
0.116
82.8
0.171
0.193
0.0204
1/12/00 16:45
6.84
0.156
111.3
0.232
0.170
121.3
0.253
0.142
101.3
0.209
0.231
0.0217
1/14/00 19:08
8.94
0.250
178.4
0.372
0.280
199.8
0.416
0.240
171.3
0.354
0.381
0.0322
1/16/00 20:50
11.01
0.334
238.4
0.497
0.357
254.8
0.531
0.333
237.7
0.491
0.506
0.0215
1/17/00 14:10
11.74
0.366
261.2
0.544
0.385
274.8
0.572
0.357
254.8
0.526
0.548
0.0232
1/19/00 14:19
13.74
0.446
318.3
0.663
0.466
332.6
0.693
0.446
318.3
0.658
0.671
0.0189
1/23/00 21:25
18.04
0.527
376.1
0.784
0.540
385.4
0.803
0.529
377.5
0.780
0.789
0.0123
1/26/00 15:08
20.78
0.555
396.1
0.825
0.564
402.5
0.839
0.561
400.4
0.827
0.830
0.0072
1/28/00 13:25
22.71
0.567
404.7
0.843
0.575
410.4
0.855
0.568
405.4
0.838
0.845
0.0089
1/31/00 21:10
26.03
0.575
410.4
0.855
0.575
410.4
0.855
0.579
413.2
0.854
0.855
0.0007
123
Table C.10 MGC batch release data sample 19-308
Bottle G
Time
time (days)
ABS
1/5/00 20:36
0.00
1/6/00 17:54
0.89
1/8/00 3:55
Bottle H
[KMnO4] (mg/l)
C/Co
ABS
0.000
0.0
0.000
0.118
84.2
0.175
2.30
0.171
122.0
Average
Std. Dev.
[KMnO4] (mg/l)
Bottle I
C/Co
C/Co
C/Co
0.000
0.0
0.000
0.000
0.0000
0.097
69.2
0.145
0.153
0.0196
0.195
0.134
95.6
0.201
0.217
0.0328
[KMnO4] (mg/l)
C/Co
ABS
0.000
0.0
0.000
0.094
67.1
0.139
0.254
0.132
94.2
1/9/00 0:00
3.14
0.187
133.5
0.278
0.145
103.5
0.214
0.148
105.6
0.222
0.238
0.0350
1/10/00 3:30
4.29
0.207
147.7
0.308
0.161
114.9
0.237
0.161
114.9
0.241
0.262
0.0395
1/11/00 19:49
5.97
0.232
165.6
0.345
0.181
129.2
0.267
0.180
128.5
0.270
0.294
0.0442
1/12/00 17:00
6.85
0.247
176.3
0.367
0.195
139.2
0.288
0.193
137.7
0.289
0.315
0.0455
1/14/00 19:15
8.94
0.275
196.3
0.409
0.221
157.7
0.326
0.214
152.7
0.321
0.352
0.0494
1/16/00 21:30
11.04
0.312
222.7
0.464
0.255
182.0
0.376
0.255
182.0
0.382
0.407
0.0490
1/17/00 14:23
11.74
0.325
231.9
0.483
0.262
187.0
0.386
0.267
190.5
0.400
0.423
0.0524
1/19/00 14:33
13.75
0.367
261.9
0.546
0.298
212.7
0.439
0.298
212.7
0.447
0.477
0.0593
1/23/00 21:45
18.05
0.419
299.0
0.623
0.359
256.2
0.529
0.362
258.3
0.543
0.565
0.0506
1/26/00 15:30
20.79
0.462
329.7
0.687
0.402
286.9
0.593
0.400
285.5
0.600
0.626
0.0525
1/28/00 13:40
22.71
0.490
349.7
0.729
0.429
306.2
0.633
0.427
304.7
0.640
0.667
0.0533
1/31/00 21:20
26.03
0.538
384.0
0.800
0.483
344.7
0.712
0.483
344.7
0.724
0.745
0.0476
2/4/00 12:42
29.67
0.584
416.8
0.868
0.536
382.5
0.790
0.538
384.0
0.807
0.822
0.0411
124
Table C.11 MGC batch release data sample 19-546
Date & Time
10/23/00 14:04
10/23/00 16:30
10/24/00 19:51
10/25/00 19:11
10/26/00 14:16
10/27/00 13:33
10/30/00 10:02
11/1/00 10:36
11/4/00 10:54
11/6/00 12:11
11/8/00 19:23
11/10/00 10:39
11/13/00 9:15
11/15/00 10:38
11/17/00 13:38
11/28/00 13:50
12/1/00 9:57
12/4/00 14:20
12/8/00 13:00
12/12/00 14:52
days
0.00
0.10
1.24
2.21
3.01
3.98
6.83
8.86
11.87
13.92
16.22
17.86
20.80
22.86
24.98
35.99
38.83
42.01
45.96
50.03
ABS
0.000
0.009
0.034
0.043
0.051
0.051
0.068
0.076
0.092
0.102
0.109
0.110
0.114
0.120
0.125
0.135
0.137
0.137
0.138
0.134
19-546-A
KMnO4 Conc (mg/L)
0
32
122
155
183
183
245
273
331
367
392
396
410
432
450
486
493
493
496
482
C/Co
0.00
0.06
0.23
0.29
0.34
0.34
0.46
0.51
0.62
0.69
0.74
0.74
0.77
0.81
0.84
0.91
0.92
0.92
0.93
0.90
ABS
0.000
0.011
0.036
0.043
0.047
0.050
0.070
0.073
0.093
0.101
0.109
0.115
0.113
0.119
0.124
0.141
0.139
0.138
0.144
0.142
19-546-B
KMnO4 Conc (mg/L)
0
40
129
155
169
180
252
263
335
363
392
414
406
428
446
507
500
496
518
511
C/Co
0.00
0.07
0.24
0.29
0.32
0.34
0.47
0.49
0.63
0.68
0.74
0.78
0.76
0.80
0.84
0.95
0.94
0.93
0.97
0.96
Average
C/Co
0
0.07
0.24
0.29
0.33
0.34
0.47
0.50
0.62
0.68
0.74
0.76
0.77
0.81
0.84
0.93
0.93
0.93
0.95
0.93
125
Table C.12 MGC batch release data sample 19-547
19-547-A
Date & Time
10/23/00 14:10
10/23/00 16:34
10/24/00 19:56
10/25/00 19:16
10/26/00 14:21
10/27/00 13:37
10/30/00 10:06
11/1/00 10:40
11/4/00 10:57
11/6/00 12:14
11/8/00 10:26
11/10/00 10:45
11/13/00 9:18
11/15/00 10:41
11/17/00 13:41
11/28/00 13:53
12/1/00 10:07
12/4/00 14:23
12/8/00 13:05
12/12/00 14:55
days
0.00
0.10
1.24
2.21
3.01
3.98
6.83
8.85
11.87
13.92
15.84
17.86
20.80
22.85
24.98
35.99
38.83
42.01
45.95
50.03
ABS
0.000
0.013
0.038
0.047
0.050
0.066
0.082
0.083
0.101
0.110
0.107
0.108
0.108
0.112
0.114
0.122
0.122
0.126
0.123
0.119
19-547-B
KMnO4 Conc
(mg/L)
0
47
137
169
180
237
295
299
363
396
385
388
388
403
410
439
439
453
442
428
C/Co
0.00
0.09
0.26
0.32
0.34
0.45
0.55
0.56
0.68
0.74
0.72
0.73
0.73
0.76
0.77
0.82
0.82
0.85
0.83
0.80
ABS
0.000
0.015
0.033
0.049
0.048
0.070
0.076
0.087
0.085
0.102
0.094
0.098
0.097
0.105
0.105
0.113
0.115
0.116
0.116
0.112
19-547-C
KMnO4 Conc
(mg/L)
C/Co
0
0.00
54
0.10
119
0.22
176
0.33
173
0.32
252
0.47
273
0.51
313
0.59
306
0.57
367
0.69
338
0.63
352
0.66
349
0.65
378
0.71
378
0.71
406
0.76
414
0.78
417
0.78
417
0.78
403
0.76
ABS
0.000
0.015
0.034
0.045
0.048
0.050
0.070
0.076
0.091
0.093
0.100
0.100
0.101
0.105
0.107
0.113
0.114
0.115
0.115
0.120
KMnO4 Conc
(mg/L)
0
54
122
162
173
180
252
273
327
335
360
360
363
378
385
406
410
414
414
432
C/Co
0.00
0.10
0.23
0.30
0.32
0.34
0.47
0.51
0.61
0.63
0.67
0.67
0.68
0.71
0.72
0.76
0.77
0.78
0.78
0.81
avg
std dev
C/Co
0.00
0.10
0.24
0.32
0.33
0.42
0.51
0.55
0.62
0.69
0.68
0.69
0.69
0.72
0.73
0.78
0.79
0.80
0.80
0.79
C/Co
0
0.007788
0.017844
0.013488
0.007788
0.071374
0.040465
0.03755
0.054513
0.057359
0.043881
0.035687
0.03755
0.027256
0.031872
0.035044
0.029397
0.041023
0.029397
0.029397
126
Table C.13 MGC batch release data sample 19-548
19-548-A
Date & Time
10/23/00 14:17
10/23/00 16:40
10/24/00 20:05
10/25/00 19:23
10/26/00 14:33
10/27/00 13:41
10/30/00 10:09
11/1/00 10:42
11/4/00 10:59
11/6/00 12:16
11/8/00 10:28
11/10/00 10:47
11/13/00 9:27
11/15/00 10:44
11/17/00 13:44
11/28/00 13:54
12/1/00 10:10
12/4/00 14:27
12/8/00 13:07
days
0.00
0.10
1.24
2.21
3.01
3.98
6.83
8.85
11.86
13.92
15.84
17.85
20.80
22.85
24.98
35.98
38.83
42.01
45.95
ABS
0.000
0.020
0.066
0.084
0.092
0.102
0.128
0.132
0.143
0.147
0.153
0.155
0.161
0.161
0.164
0.175
0.175
0.175
0.174
KMnO4 Conc (mg/L)
0
72
237
302
331
367
460
475
514
529
550
558
579
579
590
629
629
629
626
C/Co
0.00
0.11
0.36
0.45
0.50
0.55
0.69
0.71
0.77
0.79
0.83
0.84
0.87
0.87
0.88
0.94
0.94
0.94
0.94
127
Table C.14
MGC batch release data sample 19-549
Date & Time
days
ABS
10/23/00 14:17
10/23/00 16:50
10/24/00 20:21
10/25/00 19:38
10/26/00 14:48
10/27/00 13:54
10/30/00 10:37
11/1/00 11:04
11/4/00 11:18
11/6/00 12:30
11/8/00 10:56
11/10/00 11:04
11/13/00 9:39
11/15/00 11:19
11/17/00 14:03
11/28/00 14:11
12/1/00 10:25
12/4/00 14:44
12/8/00 13:20
12/12/00 13:31
12/20/00 16:01
12/28/00 15:48
1/3/01 13:57
1/11/01 16:23
1/20/01 15:12
0.00
0.11
1.25
2.22
3.02
3.98
6.85
8.87
11.88
13.93
15.86
17.87
20.81
22.88
24.99
36.00
38.84
42.02
45.96
49.97
58.07
66.06
71.99
80.09
89.04
0.000
0.008
0.036
0.044
0.049
0.055
0.061
0.079
0.080
0.085
0.085
0.090
0.094
0.098
0.100
0.111
0.114
0.116
0.121
0.123
0.122
0.125
0.126
0.128
0.128
19-549-A
KMnO4
Conc
(mg/L)
0
29
129
158
176
198
219
284
288
306
306
324
338
352
360
399
410
417
435
442
439
450
453
460
460
19-549-B
C/Co
ABS
0.000
0.054
0.243
0.297
0.330
0.371
0.411
0.533
0.540
0.573
0.573
0.607
0.634
0.661
0.674
0.749
0.769
0.782
0.816
0.830
0.823
0.843
0.850
0.863
0.863
0.000
0.007
0.036
0.045
0.050
0.058
0.066
0.073
0.082
0.084
0.086
0.095
0.095
0.100
0.103
0.112
0.115
0.119
0.121
0.119
0.123
0.126
0.128
0.130
0.130
19-549-C
KMnO4
C/Co
Conc (mg/L)
0
25
129
162
180
209
237
263
295
302
309
342
342
360
370
403
414
428
435
428
442
453
460
468
468
0.000
0.047
0.243
0.303
0.337
0.391
0.445
0.492
0.553
0.567
0.580
0.641
0.641
0.674
0.695
0.755
0.776
0.803
0.816
0.803
0.830
0.850
0.863
0.877
0.877
ABS
0.000
0.010
0.042
0.048
0.054
0.067
0.069
0.076
0.085
0.093
0.090
0.095
0.096
0.103
0.109
0.113
0.115
0.118
0.119
0.122
0.124
0.127
0.129
0.133
0.135
KMnO4 Conc
C/Co
(mg/L)
0
36
151
173
194
241
248
273
306
335
324
342
345
370
392
406
414
424
428
439
446
457
464
478
486
0.000
0.067
0.283
0.324
0.364
0.452
0.465
0.513
0.573
0.627
0.607
0.641
0.647
0.695
0.735
0.762
0.776
0.796
0.803
0.823
0.836
0.857
0.870
0.897
0.910
avg
stdev
C/Co
C/Co
0.000
0.056
0.256
0.308
0.344
0.405
0.441
0.513
0.555
0.589
0.587
0.629
0.641
0.677
0.701
0.755
0.773
0.794
0.812
0.818
0.830
0.850
0.861
0.879
0.883
0.0000
0.0103
0.0234
0.0140
0.0178
0.0421
0.0273
0.0202
0.0170
0.0333
0.0178
0.0195
0.0067
0.0170
0.0309
0.0067
0.0039
0.0103
0.0078
0.0140
0.0067
0.0067
0.0103
0.0170
0.0243
128
Table C.15 MGC batch release data sample 19-550
Date & Time
days
ABS
10/23/00 14:30
10/23/00 16:50
10/24/00 20:30
10/25/00 19:48
10/26/00 14:54
10/27/00 14:00
10/30/00 10:40
11/1/00 11:07
11/4/00 11:25
11/6/00 12:33
11/8/00 10:59
11/10/00 11:07
11/13/00 9:44
11/15/00 11:22
11/17/00 14:06
11/28/00 14:14
12/1/00 10:28
12/4/00 14:47
12/8/00 13:45
12/12/00 13:34
12/20/00 16:04
0.00
0.10
1.25
2.22
3.02
3.98
6.84
8.86
11.87
13.92
15.85
17.86
20.80
22.87
24.98
35.99
38.83
42.01
45.97
49.96
58.07
0.000
0.011
0.041
0.048
0.059
0.066
0.077
0.085
0.093
0.106
0.106
0.109
0.113
0.117
0.121
0.131
0.133
0.134
0.138
0.140
0.136
19-550-A
KMnO4 Conc
C/Co
(mg/L)
0.0
39.6
147.5
172.7
212.2
237.4
277.0
305.7
334.5
381.3
381.3
392.1
406.4
420.8
435.2
471.2
478.4
482.0
496.4
503.6
489.2
0.000
0.074
0.277
0.324
0.398
0.445
0.519
0.573
0.627
0.715
0.715
0.735
0.762
0.789
0.816
0.883
0.897
0.904
0.931
0.944
0.917
ABS
0.000
0.012
0.037
0.047
0.052
0.067
0.072
0.078
0.083
0.097
0.106
0.105
0.109
0.114
0.117
0.129
0.129
0.132
0.135
0.134
0.133
19-550-B
KMnO4 Conc
(mg/L)
0.0
43.2
133.1
169.1
187.0
241.0
259.0
280.6
298.5
348.9
381.3
377.7
392.1
410.0
420.8
464.0
464.0
474.8
485.6
482.0
478.4
C/Co
ABS
0.000
0.081
0.250
0.317
0.351
0.452
0.486
0.526
0.560
0.654
0.715
0.708
0.735
0.769
0.789
0.870
0.870
0.890
0.910
0.904
0.897
0.000
0.011
0.041
0.050
0.056
0.063
0.079
0.086
0.097
0.100
0.109
0.111
0.116
0.127
0.123
0.135
0.136
0.137
0.138
0.138
0.138
19-550-C
KMnO4 Conc
(mg/L)
0.0
39.6
147.5
179.8
201.4
226.6
284.2
309.3
348.9
359.7
392.1
399.3
417.2
456.8
442.4
485.6
489.2
492.8
496.4
496.4
496.4
avg
stdev
C/Co
C/Co
C/Co
0.000
0.074
0.277
0.337
0.378
0.425
0.533
0.580
0.654
0.674
0.735
0.749
0.782
0.857
0.830
0.910
0.917
0.924
0.931
0.931
0.931
0.000
0.076
0.268
0.326
0.375
0.441
0.513
0.560
0.614
0.681
0.722
0.731
0.760
0.805
0.812
0.888
0.895
0.906
0.924
0.926
0.915
0.0000
0.0039
0.0156
0.0103
0.0237
0.0140
0.0243
0.0294
0.0486
0.0309
0.0117
0.0206
0.0237
0.0459
0.0206
0.0206
0.0237
0.0170
0.0117
0.0206
0.0170
129
Table C.16 MGC batch release data sample 19-551
19-551-A
19-551-B
19-551-C
avg
stdev
Date & Time
days
ABS
KMnO4 Conc
(mg/L)
C/Co
ABS
KMnO4 Conc
(mg/L)
C/Co
ABS
KMnO4 Conc
(mg/L)
C/Co
C/Co
C/Co
10/23/00 14:37
10/23/00 17:20
10/24/00 20:49
10/25/00 20:09
10/26/00 15:09
10/27/00 14:08
10/30/00 11:02
11/1/00 12:01
11/4/00 11:54
11/6/00 12:49
11/8/00 11:17
11/10/00 11:28
11/13/00 10:00
11/15/00 11:39
11/17/00 14:20
11/28/00 14:31
12/1/00 10:45
12/4/00 15:05
12/8/00 14:00
0.00
0.11
1.26
2.23
3.02
3.98
6.85
8.89
11.89
13.93
15.86
17.87
20.81
22.88
24.99
36.00
38.84
42.02
45.97
0.000
0.043
0.079
0.086
0.087
0.097
0.118
0.128
0.134
0.147
0.139
0.144
0.146
0.148
0.149
0.157
0.162
0.164
0.165
0
155
284
309
313
349
424
460
482
529
500
518
525
532
536
565
583
590
593
0.000
0.232
0.426
0.464
0.469
0.523
0.637
0.691
0.723
0.793
0.750
0.777
0.788
0.799
0.804
0.847
0.874
0.885
0.890
0.000
0.056
0.096
0.105
0.110
0.115
0.138
0.145
0.152
0.154
0.159
0.162
0.164
0.165
0.166
0.170
0.174
0.175
0.172
0
201
345
378
396
414
496
522
547
554
572
583
590
593
597
611
626
629
619
0.000
0.302
0.518
0.567
0.593
0.620
0.745
0.782
0.820
0.831
0.858
0.874
0.885
0.890
0.896
0.917
0.939
0.944
0.928
0.000
0.045
0.083
0.090
0.104
0.112
0.128
0.133
0.136
0.146
0.149
0.150
0.157
0.157
0.159
0.168
0.166
0.170
0.168
0
162
299
324
374
403
460
478
489
525
536
540
565
565
572
604
597
611
604
0.000
0.243
0.448
0.486
0.561
0.604
0.691
0.718
0.734
0.788
0.804
0.809
0.847
0.847
0.858
0.906
0.896
0.917
0.906
0.000
0.259
0.464
0.505
0.541
0.583
0.691
0.730
0.759
0.804
0.804
0.820
0.840
0.845
0.852
0.890
0.903
0.915
0.908
0.0000
0.0378
0.0480
0.0540
0.0644
0.0520
0.0540
0.0471
0.0532
0.0235
0.0540
0.0494
0.0490
0.0459
0.0461
0.0378
0.0330
0.0297
0.0189
130
Table C.17 MGC batch release data sample 19-552
Date & Time
days
ABS
10/23/00 14:45
10/23/00 17:20
10/24/00 21:00
10/25/00 20:30
10/26/00 17:00
10/27/00 14:16
10/30/00 11:06
11/1/00 12:03
11/4/00 11:57
11/6/00 12:59
11/8/00 11:29
11/10/00 11:32
11/13/00 10:03
11/15/00 11:44
11/17/00 14:25
11/28/00 14:34
12/1/00 10:47
12/4/00 15:08
12/8/00 14:15
0.000
0.108
1.260
2.240
3.094
3.980
6.848
8.887
11.883
13.926
15.864
17.866
20.804
22.874
24.986
35.992
38.835
42.016
45.979
0.000
0.006
0.033
0.039
0.046
0.045
0.076
0.092
0.120
0.127
0.135
0.136
0.137
0.138
0.135
0.134
0.133
0.133
0.131
19-552-A
KMnO4 Conc
(mg/L)
0
22
119
140
165
162
273
331
432
457
486
489
493
496
486
482
478
478
471
C/Co
0.000
0.040
0.223
0.263
0.310
0.303
0.513
0.620
0.809
0.857
0.910
0.917
0.924
0.931
0.910
0.904
0.897
0.897
0.883
19-552-B
KMnO4 Conc
ABS
C/Co
(mg/L)
19-552-C
KMnO4 Conc
ABS
C/Co
(mg/L)
0.000
0.010
0.042
0.050
0.063
0.068
0.089
0.114
0.112
0.141
0.145
0.144
0.145
0.145
0.143
0.142
0.142
0.142
0.141
0.000
0.008
0.041
0.049
0.063
0.063
0.086
0.104
0.124
0.128
0.130
0.137
0.130
0.132
0.133
0.135
0.134
0.134
0.133
0
36
151
180
227
245
320
410
403
507
522
518
522
522
514
511
511
511
507
0.000
0.067
0.283
0.337
0.425
0.459
0.600
0.769
0.755
0.951
0.978
0.971
0.978
0.978
0.964
0.958
0.958
0.958
0.951
0
29
147
176
227
227
309
374
446
460
468
493
468
475
478
486
482
482
478
0.000
0.054
0.277
0.330
0.425
0.425
0.580
0.701
0.836
0.863
0.877
0.924
0.877
0.890
0.897
0.910
0.904
0.904
0.897
avg
stdev
C/Co
C/Co
0.000
0.054
0.261
0.310
0.387
0.396
0.564
0.697
0.800
0.890
0.922
0.937
0.926
0.933
0.924
0.924
0.919
0.919
0.910
0.0000
0.0135
0.0333
0.0410
0.0662
0.0816
0.0459
0.0743
0.0412
0.0527
0.0515
0.0294
0.0506
0.0439
0.0357
0.0294
0.0333
0.0333
0.0357
131
Table C.18 MGC batch release data sample 19-553
Date & Time
10/23/00 14:51
10/23/00 17:30
10/24/00 21:12
10/25/00 20:49
10/26/00 18:00
10/27/00 14:28
10/30/00 11:20
11/1/00 12:16
11/4/00 12:14
11/6/00 13:10
11/8/00 11:33
11/10/00 11:47
11/13/00 10:15
11/15/00 11:53
11/17/00 14:43
11/28/00 14:54
12/1/00 10:33
12/4/00 15:19
12/8/00 14:30
12/12/00 14:30
12/20/00 16:13
12/28/00 15:42
1/3/01 13:47
1/7/01 16:01
days
ABS
19-553-A
KMnO4 Conc
(mg/L)
0.000
0.000
0
0.110
0.008
29
1.265
0.039
140
2.249
0.044
158
3.131
0.048
173
3.984
0.052
187
6.853
0.061
219
8.892
0.070
252
11.891 0.077
277
13.930
15.862
17.872
20.808
22.876
24.994
36.002
Experiment ended due
38.821
to leakage from bottle
42.019
45.985
49.985
58.057
66.035
71.956
76.049
C/Co
ABS
0.000
0.054
0.263
0.297
0.324
0.351
0.411
0.472
0.519
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.007
0.040
0.045
0.048
0.050
0.067
0.077
0.082
0.087
0.093
0.099
0.107
0.107
0.109
0.125
0.126
0.128
0.130
0.128
0.133
0.137
0.137
0.137
19-553-B
KMnO4 Conc
(mg/L)
0
25
144
162
173
180
241
277
295
313
335
356
385
385
392
450
453
460
468
460
478
493
493
493
C/Co
ABS
0.000
0.047
0.270
0.303
0.324
0.337
0.452
0.519
0.553
0.587
0.627
0.668
0.722
0.722
0.735
0.843
0.850
0.863
0.877
0.863
0.897
0.924
0.924
0.924
0.000
0.013
0.041
0.048
0.054
0.058
0.070
0.074
0.085
0.089
0.097
0.101
0.107
0.109
0.112
0.124
0.127
0.127
0.131
0.130
0.137
0.142
0.143
0.143
19-553-C
KMnO4 Conc
(mg/L)
0
47
147
173
194
209
252
266
306
320
349
363
385
392
403
446
457
457
471
468
493
511
514
514
avg
stdev
C/Co
C/Co
C/Co
0.000
0.088
0.277
0.324
0.364
0.391
0.472
0.499
0.573
0.600
0.654
0.681
0.722
0.735
0.755
0.836
0.857
0.857
0.883
0.877
0.924
0.958
0.964
0.964
0.000
0.063
0.270
0.308
0.337
0.360
0.445
0.497
0.549
0.593
0.641
0.674
0.722
0.728
0.745
0.840
0.853
0.860
0.880
0.870
0.910
0.941
0.944
0.944
0.00000
0.02168
0.00674
0.01404
0.02336
0.02808
0.03091
0.02368
0.02726
0.00954
0.01908
0.00954
0.00000
0.00954
0.01431
0.00477
0.00477
0.00477
0.00477
0.00954
0.01908
0.02384
0.02861
0.02861
132
133
Appendix D
Drain-Daily Release Data
134
Table D.1
Drain-daily release data for low volume test with sample 19-306
Time
1/5/00 20:49
1/6/00 16:50
1/8/00 4:10
1/9/00 0:20
1/10/00 3:45
1/11/00 20:05
1/12/00 17:12
1/14/00 12:50
1/16/00 21:45
1/17/00 14:45
1/19/00 14:43
1/23/00 21:55
Time (days)
0.00
0.83
2.31
3.15
4.29
5.97
6.85
8.67
11.04
11.75
13.75
18.05
ABS
0.000
0.905
0.855
0.686
0.902
1.267
0.530
0.548
0.055
0.002
0.002
0.000
Conc. KMnO4 (mg/l)
0.000
25.835
24.407
19.583
25.749
36.169
15.130
15.644
1.570
0.057
0.057
0.000
cumulative
cumulative
Mass Released, Mr (mg)
0.000
0.904
1.758
2.444
3.345
4.611
5.141
5.688
5.743
5.745
5.747
5.747
Mr/(mass total)
0.00000
0.11303
0.21981
0.30549
0.41814
0.57638
0.64257
0.71101
0.71788
0.71813
0.71838
0.71838
135
Table D.2
Drain-daily release data for low volume test with sample 19-307
Time
1/5/00 20:49
1/6/00 16:50
1/8/00 4:10
1/9/00 0:20
1/10/00 3:45
1/11/00 20:05
1/12/00 17:12
1/14/00 12:50
1/16/00 21:45
1/17/00 14:45
1/19/00 14:43
1/23/00 21:55
1/26/00 15:45
1/31/00 0:00
0.00
0.83
2.31
3.15
4.29
5.97
6.85
8.67
11.04
11.75
13.75
18.05
20.79
25.13
ABS
0.000
0.761
0.447
0.260
0.462
0.767
0.409
1.012
0.743
0.190
0.459
0.629
0.250
0.210
Conc. KMnO4 (mg/l)
0.000
21.724
12.760
7.422
13.189
21.895
11.676
28.889
21.210
5.424
13.103
17.956
7.137
5.995
cumulative
cumulative
Mass Released, Mr (mg)
0.000
0.760
1.207
1.467
1.928
2.695
3.103
4.114
4.857
5.047
5.505
6.134
6.383
6.593
Mr/(mass total)
0.00000
0.09504
0.15087
0.18334
0.24104
0.33683
0.38791
0.51431
0.60710
0.63083
0.68816
0.76671
0.79794
0.82416
136
Table D.3
Drain-daily release data for low volume test with sample 19-308
Time
1/5/00 20:49
1/6/00 16:50
1/8/00 4:10
1/9/00 0:20
1/10/00 3:45
1/11/00 20:05
1/12/00 17:12
1/14/00 12:50
1/16/00 21:45
1/17/00 14:45
1/19/00 14:43
1/23/00 21:55
1/26/00 15:45
1/31/00 0:00
2/4/00 12:35
0.00
0.83
2.31
3.15
4.29
5.97
6.85
8.67
11.04
11.75
13.75
18.05
20.79
25.13
29.66
ABS
0.000
0.902
0.315
0.120
0.148
0.219
0.118
0.260
0.292
0.087
0.256
0.468
0.330
0.689
0.502
Conc. KMnO4 (mg/l)
0.000
25.749
8.992
3.426
4.225
6.252
3.369
7.422
8.336
2.484
7.308
13.360
9.420
19.669
14.330
cumulative
cumulative
Mass Released, Mr (mg)
0.000
0.901
1.216
1.336
1.484
1.703
1.820
2.080
2.372
2.459
2.715
3.182
3.512
4.200
4.702
Mr/(mass total)
0.00000
0.11265
0.15199
0.16698
0.18546
0.21282
0.22755
0.26003
0.29649
0.30736
0.33933
0.39778
0.43900
0.52505
0.58774
137
Table D.4
Drain-daily release data for high volume test with sample 19-547
Bottle A
Bottle B
Date/Time
Days
ABS
Conc (g/L)
Vol DI
Add/Remo
v.
4/5/01 12:33
0.000
0.000
0.00E+00
0
4/5/01 12:33
0.000
4/5/01 17:05
0.189
4/5/01 17:05
0.189
4/6/01 2:11
0.568
4/6/01 2:11
0.568
4/6/01 12:11
0.985
4/6/01 12:11
0.985
4/7/01 1:31
1.540
4/7/01 1:31
1.540
4/7/01 20:43
2.340
4/7/01 20:43
2.340
4/9/01 0:19
3.490
4/9/01 0:19
3.490
4/10/01 13:15
5.029
4/10/01 13:15
5.029
4/11/01 17:41
6.214
4/11/01 17:41
6.214
4/12/01 17:57
7.225
4/12/01 17:57
7.225
4/13/01 15:13
8.111
4/13/01 15:13
8.111
4/15/01 20:55
10.349
4/15/01 20:55
10.349
4/17/01 18:48
12.260
4/17/01 18:48
12.260
4/19/01 16:25
14.161
4/19/01 16:25
14.161
4/20/01 17:37
15.211
4/20/01 17:37
15.211
4/23/01 20:15
18.321
4/23/01 20:15
18.321
4/25/01 15:05
20.106
4/25/01 15:05
20.106
5/4/01 14:48
29.094
5/4/01 14:48
29.094
5/10/01 12:01
34.978
5/10/01 12:01
34.978
5/21/01 0:45
45.508
5/21/01 0:45
45.508
M/Mo
Date/Time
Days
ABS
Vol DI
Conc (g/L) Add/Remov
.
0
0.000
4/5/01 12:33
0.00
0.000
0.00E+00
4/5/01 12:33
0.00
4/5/01 17:05
0.19
4/5/01 17:05
0.19
4/6/01 2:11
0.57
4/6/01 2:11
0.57
4/6/01 12:11
0.98
4/6/01 12:11
0.98
4/7/01 1:31
1.54
4/7/01 1:31
1.54
4/7/01 20:43
2.34
4/7/01 20:43
2.34
4/9/01 0:19
3.49
4/9/01 0:19
3.49
4/10/01 13:15
5.03
4/10/01 13:15
5.03
4/11/01 17:41
6.21
4/11/01 17:41
6.21
4/12/01 17:57
7.22
4/12/01 17:57
7.22
4/13/01 15:13
8.11
4/13/01 15:13
8.11
4/15/01 20:55
10.35
4/15/01 20:55
10.35
4/17/01 18:48
12.26
4/17/01 18:48
12.26
4/19/01 16:25
14.16
4/19/01 16:25
14.16
4/20/01 17:37
15.21
4/20/01 17:37
15.21
4/23/01 20:15
18.32
4/23/01 20:15
18.32
4/25/01 15:05
20.11
4/25/01 15:05
20.11
5/4/01 14:48
29.09
5/4/01 14:48
29.09
5/10/01 12:01
34.98
5/10/01 12:01
34.98
5/21/01 0:45
45.51
5/21/01 0:45
45.51
0.00E+00
0.561
1.62E-02
750
1.46E-02
0.122
2.71E-03
0.558
1.62E-02
700
2.67E-02
0.223
3.59E-03
0.404
1.17E-02
675
3.40E-02
0.284
2.92E-03
0.373
1.08E-02
650
4.11E-02
0.343
3.00E-03
0.381
1.10E-02
650
4.83E-02
0.403
3.06E-03
0.367
1.06E-02
650
5.51E-02
0.460
2.95E-03
0.332
9.61E-03
650
6.11E-02
0.509
2.67E-03
0.226
6.54E-03
0
6.46E-02
0.539
6.54E-03
0.329
9.53E-03
625
6.73E-02
0.561
400
6.95E-02
0.579
2.91E-03
0.185
5.36E-03
2.98E-03
0.231
6.69E-03
525
7.29E-02
0.607
2.79E-03
0.175
5.07E-03
25
7.49E-02
0.624
4.93E-03
0.226
6.54E-03
0
7.64E-02
0.636
6.54E-03
0.261
7.56E-03
0
7.73E-02
0.644
7.56E-03
0.335
9.70E-03
650
7.92E-02
0.660
2.69E-03
0.140
4.05E-03
0
8.04E-02
0.670
4.05E-03
0.250
7.24E-03
0
8.33E-02
0.694
7.24E-03
0.281
8.14E-03
0
8.41E-02
0.701
8.14E-03
0.299
8.66E-03
8.66E-03
0
Averages
Cum. Mass
Released
8.46E-02
0.705
0
Cum. Mass
Released
M/Mo
0
0.000
avg M/Mo
std dev
M/Mo
avg Conc
std dev Conc
0.000
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
1.57E-02
8.39E-04
2.61E-03
1.40E-04
1.61E-02
8.19E-05
3.58E-03
1.82E-05
1.17E-02
2.05E-05
2.92E-03
5.12E-06
1.08E-02
6.14E-05
3.01E-03
1.71E-05
1.10E-02
2.05E-05
3.06E-03
5.69E-06
1.07E-02
1.64E-04
2.98E-03
4.55E-05
9.96E-03
4.91E-04
2.77E-03
1.36E-04
6.75E-03
2.87E-04
6.75E-03
2.87E-04
9.84E-03
4.50E-04
3.01E-03
1.38E-04
5.56E-03
2.87E-04
3.09E-03
1.59E-04
7.04E-03
4.91E-04
2.93E-03
2.05E-04
5.37E-03
4.30E-04
5.22E-03
4.18E-04
6.86E-03
4.50E-04
6.86E-03
4.50E-04
7.90E-03
4.91E-04
7.90E-03
4.91E-04
1.02E-02
6.96E-04
2.83E-03
1.93E-04
4.26E-03
2.87E-04
4.26E-03
2.87E-04
7.77E-03
7.58E-04
7.77E-03
7.58E-04
8.73E-03
8.39E-04
8.73E-03
8.39E-04
9.21E-03
7.78E-04
9.21E-03
7.78E-04
0.00E+00
0.520
1.51E-02
750
1.36E-02
0.113
0.117
6.30E-03
2.51E-03
0.554
1.60E-02
700
2.57E-02
0.214
0.219
5.86E-03
3.56E-03
0.403
1.17E-02
675
3.30E-02
0.275
0.279
5.88E-03
2.92E-03
0.376
1.09E-02
650
4.02E-02
0.335
0.339
5.38E-03
3.02E-03
0.380
1.10E-02
650
4.74E-02
0.395
0.399
5.66E-03
3.06E-03
0.375
1.09E-02
650
5.44E-02
0.453
0.456
4.39E-03
3.02E-03
0.356
1.03E-02
650
6.10E-02
0.508
0.509
1.05E-03
2.86E-03
0.240
6.95E-03
0
6.46E-02
0.539
0.539
8.10E-05
6.95E-03
0.351
1.02E-02
625
6.75E-02
0.563
0.562
1.31E-03
400
6.99E-02
0.583
0.581
2.43E-03
3.11E-03
0.199
5.76E-03
3.20E-03
0.255
7.38E-03
525
7.37E-02
0.614
0.611
4.92E-03
3.08E-03
0.196
5.68E-03
25
7.60E-02
0.634
0.629
6.61E-03
5.52E-03
0.248
7.18E-03
0
7.75E-02
0.646
0.641
6.85E-03
7.18E-03
0.285
8.25E-03
0
7.85E-02
0.654
0.649
7.16E-03
8.25E-03
0.369
1.07E-02
650
8.07E-02
0.672
0.666
8.69E-03
2.97E-03
0.154
4.46E-03
0
8.20E-02
0.683
0.677
9.39E-03
4.46E-03
0.287
8.31E-03
0
8.55E-02
0.712
0.703
1.29E-02
8.31E-03
0.322
9.32E-03
0
8.64E-02
0.720
0.710
1.35E-02
9.32E-03
0.337
9.76E-03
9.76E-03
0
8.68E-02
0.723
0.714
1.31E-02
138
Table D.5
Drain-daily release data for high volume test with sample 19-551
Bottle A
Bottle B
Date/Time
Days
ABS
Conc (g/L)
Vol DI
Add/Re
mov.
4/5/01 12:44
0.000
0.000
0.00E+00
0
4/5/01 12:44
0.000
4/5/01 17:35
0.202
4/5/01 17:35
0.202
4/6/01 2:29
0.573
4/6/01 2:29
0.573
4/6/01 12:30
0.990
4/6/01 12:30
0.990
4/7/01 1:17
1.523
4/7/01 1:17
1.523
4/7/01 21:04
2.347
4/7/01 21:04
2.347
4/9/01 0:00
3.469
4/9/01 0:00
3.469
4/10/01 13:41
5.040
4/10/01 13:41
5.040
4/11/01 17:26
6.196
4/11/01 17:26
6.196
4/12/01 19:06
7.265
4/12/01 19:06
7.265
4/13/01 15:35
8.119
4/13/01 15:35
8.119
4/15/01 20:27
10.322
4/15/01 20:27
10.322
4/19/01 16:53
14.173
4/19/01 16:53
14.173
4/20/01 17:06
15.182
4/20/01 17:06
15.182
4/23/01 20:48
18.336
4/23/01 20:48
18.336
4/25/01 14:55
20.091
4/25/01 14:55
20.091
4/27/01 14:30
22.074
4/27/01 14:30
22.074
5/4/01 14:39
29.080
5/4/01 14:39
29.080
5/10/01 13:04
35.014
5/10/01 13:04
35.014
6/14/01 14:52
70.089
6/14/01 14:52
70.089
Cum.
Mass
Released
M/Mo
Date/Time
Days
ABS
0
0.000
4/5/01 12:44
0.000
0.000
4/5/01 12:44
0.000
4/5/01 17:35
0.202
4/5/01 17:35
0.202
4/6/01 2:29
0.573
4/6/01 2:29
0.573
4/6/01 12:30
0.990
4/6/01 12:30
0.990
4/7/01 1:17
1.523
4/7/01 1:17
1.523
4/7/01 21:04
2.347
4/7/01 21:04
2.347
4/9/01 0:00
3.469
4/9/01 0:00
3.469
4/10/01 13:41
5.040
4/10/01 13:41
5.040
4/11/01 17:26
6.196
4/11/01 17:26
6.196
4/12/01 19:06
7.265
4/12/01 19:06
7.265
4/13/01 15:35
8.119
4/13/01 15:35
8.119
4/15/01 20:27
10.322
4/15/01 20:27
10.322
4/19/01 16:53
14.173
4/19/01 16:53
14.173
4/20/01 17:06
15.182
4/20/01 17:06
15.182
4/23/01 20:48
18.336
4/23/01 20:48
18.336
4/25/01 14:55
20.091
4/25/01 14:55
20.091
4/27/01 14:30
22.074
4/27/01 14:30
22.074
5/4/01 14:39
29.080
5/4/01 14:39
29.080
5/10/01 13:04
35.014
5/10/01 13:04
35.014
6/14/01 14:52
70.089
6/14/01 14:52
70.089
0.00E+00
1.863
5.39E-02
800
4.85E-02
0.324
5.99E-03
0.649
1.88E-02
750
6.01E-02
0.400
3.13E-03
0.331
9.58E-03
600
6.59E-02
0.439
3.19E-03
0.309
8.95E-03
600
7.11E-02
0.474
2.98E-03
0.331
9.58E-03
650
7.70E-02
0.513
600
8.29E-02
0.553
2.66E-03
0.319
9.24E-03
3.08E-03
0.344
9.96E-03
650
8.91E-02
0.594
2.77E-03
0.229
6.63E-03
0
9.26E-02
0.617
6.63E-03
0.339
9.82E-03
650
9.54E-02
0.636
2.73E-03
0.181
5.24E-03
425
9.77E-02
0.651
2.77E-03
0.246
7.12E-03
550
1.02E-01
0.678
2.77E-03
0.253
7.33E-03
0
1.06E-01
0.705
7.33E-03
0.295
8.54E-03
600
1.07E-01
0.712
2.85E-03
0.193
5.59E-03
0
1.09E-01
0.729
0
1.11E-01
0.737
5.59E-03
0.242
7.01E-03
7.01E-03
0.295
8.54E-03
600
1.12E-01
0.746
2.85E-03
0.238
6.89E-03
0
1.16E-01
0.771
6.89E-03
0.355
1.03E-02
625
1.19E-01
0.791
3.14E-03
0.559
1.62E-02
4.50E-03
650
1.30E-01
0.869
Averages
Conc (g/L)
Vol DI
Add/Re
mov.
Cum. Mass
Released
M/Mo
avg M/Mo
std dev
M/Mo
avg Conc
std dev
Conc
0.00E+00
0
0
0.000
0.000
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
5.32E-02
1.09E-03
5.91E-03
1.21E-04
1.88E-02
4.09E-05
3.13E-03
6.82E-06
9.76E-03
2.46E-04
3.25E-03
8.19E-05
9.16E-03
3.07E-04
3.05E-03
1.02E-04
0.00E+00
1.810
5.24E-02
800
4.72E-02
0.314
0.319
6.51E-03
5.82E-03
0.647
1.87E-02
750
5.88E-02
0.392
0.396
6.03E-03
3.12E-03
0.343
9.93E-03
600
6.49E-02
0.433
0.436
4.52E-03
3.31E-03
0.324
9.38E-03
600
7.04E-02
0.469
0.471
3.17E-03
3.13E-03
0.340
9.84E-03
650
7.64E-02
0.510
0.511
2.68E-03
600
8.23E-02
0.549
0.551
2.98E-03
2.73E-03
0.319
9.24E-03
3.08E-03
0.343
9.93E-03
650
8.84E-02
0.590
0.592
3.11E-03
2.76E-03
0.233
6.75E-03
0
9.20E-02
0.614
0.615
2.58E-03
6.75E-03
0.342
9.90E-03
650
9.49E-02
0.633
0.634
2.70E-03
2.75E-03
0.187
5.41E-03
425
9.73E-02
0.648
0.650
2.07E-03
2.86E-03
0.249
7.21E-03
550
1.01E-01
0.675
0.676
2.09E-03
2.80E-03
0.250
7.24E-03
0
1.05E-01
0.701
0.703
2.60E-03
7.24E-03
0.294
8.51E-03
600
1.06E-01
0.709
0.711
2.35E-03
2.84E-03
0.193
5.59E-03
0
1.09E-01
0.725
0.727
2.31E-03
0
1.10E-01
0.734
0.735
2.56E-03
5.59E-03
0.240
6.95E-03
6.95E-03
0.291
8.43E-03
600
1.11E-01
0.742
0.744
2.81E-03
2.81E-03
0.237
6.86E-03
0
1.15E-01
0.767
0.769
2.76E-03
6.86E-03
0.339
9.82E-03
625
1.18E-01
0.784
0.788
4.61E-03
3.00E-03
0.536
1.55E-02
4.31E-03
650
1.29E-01
0.860
0.864
6.83E-03
9.71E-03
1.84E-04
2.70E-03
5.12E-05
9.24E-03
0.00E+00
3.08E-03
0.00E+00
9.95E-03
2.05E-05
2.76E-03
5.69E-06
6.69E-03
8.19E-05
6.69E-03
8.19E-05
9.86E-03
6.14E-05
2.74E-03
1.71E-05
5.33E-03
1.23E-04
2.81E-03
6.48E-05
7.17E-03
6.14E-05
2.79E-03
2.39E-05
7.28E-03
6.14E-05
7.28E-03
6.14E-05
8.53E-03
2.05E-05
2.84E-03
6.82E-06
5.59E-03
0.00E+00
5.59E-03
0.00E+00
6.98E-03
4.09E-05
6.98E-03
4.09E-05
8.48E-03
8.19E-05
2.83E-03
2.73E-05
6.88E-03
2.05E-05
6.88E-03
2.05E-05
1.00E-02
3.28E-04
3.07E-03
1.00E-04
1.59E-02
4.71E-04
4.40E-03
1.31E-04
139
Table D.6
Drain-daily release data for high volume test with sample 19-552
Bottle A
Date/Time
Days
ABS
Conc (g/L)
4/5/01 12:57
0.000
0.000
0.00E+00
4/5/01 12:57
0.000
4/5/01 17:42
0.198
4/5/01 17:42
0.198
4/6/01 1:46
0.534
4/6/01 1:46
0.534
4/6/01 11:49
0.953
4/6/01 11:49
0.953
4/7/01 1:51
1.537
4/7/01 1:51
1.537
4/7/01 20:19
2.307
4/7/01 20:19
2.307
4/9/01 0:40
3.488
4/9/01 0:40
3.488
4/10/01 12:50
4.995
4/10/01 12:50
4.995
4/11/01 18:01
6.211
4/11/01 18:01
6.211
4/12/01 17:52
7.205
4/12/01 17:52
7.205
4/13/01 15:55
8.124
4/13/01 15:55
8.124
4/15/01 20:03
10.296
4/15/01 20:03
10.296
4/17/01 18:35
12.235
4/17/01 18:35
12.235
4/19/01 16:32
14.149
4/19/01 16:32
14.149
4/20/01 17:47
15.201
4/20/01 17:47
15.201
4/23/01 20:37
18.319
4/23/01 20:37
18.319
4/25/01 14:44
20.074
4/25/01 14:44
20.074
4/27/01 14:30
22.065
4/27/01 14:30
22.065
Bottle B
Vol DI
Cum. Mass
Add/Re
Released
mov.
0
0
M/Mo
Date/Time
Days
ABS
Conc (g/L)
0.000
4/5/01 12:57
0.000
0
0.00E+00
4/5/01 12:57
0.000
4/5/01 17:42
0.198
4/5/01 17:42
0.198
4/6/01 1:46
0.534
4/6/01 1:46
0.534
4/6/01 11:49
0.953
4/6/01 11:49
0.953
0.00E+00
0.511
1.48E-02
600
1.33E-02
0.111
4.93E-03
0.673
1.95E-02
750
2.64E-02
0.220
3.25E-03
0.400
1.16E-02
675
3.39E-02
0.283
2.90E-03
0.376
1.09E-02
650
4.11E-02
0.343
4/7/01 1:51
1.537
4/7/01 1:51
1.537
650
4.78E-02
0.398
4/7/01 20:19
2.307
4/7/01 20:19
2.307
4/9/01 0:40
3.488
4/9/01 0:40
3.488
4/10/01 12:50
4.995
4/10/01 12:50
4.995
4/11/01 18:01
6.211
4/11/01 18:01
6.211
4/12/01 17:52
7.205
4/12/01 17:52
7.205
4/13/01 15:55
8.124
4/13/01 15:55
8.124
4/15/01 20:03
10.296
4/15/01 20:03
10.296
4/17/01 18:35
12.235
4/17/01 18:35
12.235
4/19/01 16:32
14.149
4/19/01 16:32
14.149
4/20/01 17:47
15.201
4/20/01 17:47
15.201
4/23/01 20:37
18.319
4/23/01 20:37
18.319
4/25/01 14:44
20.074
4/25/01 14:44
20.074
4/27/01 14:30
22.065
4/27/01 14:30
22.065
3.02E-03
0.361
1.05E-02
2.90E-03
0.401
1.16E-02
675
5.56E-02
0.464
2.90E-03
0.495
1.43E-02
725
6.59E-02
0.549
2.79E-03
0.517
1.50E-02
725
7.69E-02
0.641
2.91E-03
0.500
1.45E-02
725
8.73E-02
0.727
2.82E-03
0.391
1.13E-02
675
9.49E-02
0.791
2.83E-03
0.411
1.19E-02
675
1.03E-01
0.859
2.98E-03
0.213
6.17E-03
0
1.06E-01
0.883
6.17E-03
0.255
7.38E-03
0
1.07E-01
0.892
7.38E-03
0.281
8.14E-03
25
1.08E-01
0.898
7.91E-03
0.284
8.22E-03
0
1.08E-01
0.900
8.22E-03
0.293
8.48E-03
0
1.08E-01
0.902
8.48E-03
0.300
8.69E-03
2.90E-03
600
1.08E-01
0.904
Averages
Vol DI
Cum. Mass
Add/Rem
Released
ov.
0
0
M/Mo
avg M/Mo
std dev
M/Mo
avg Conc
std dev
Conc
0.000
0.000
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
1.42E-02
7.78E-04
4.75E-03
2.59E-04
1.93E-02
3.28E-04
3.21E-03
5.46E-05
1.16E-02
6.14E-05
0.00E+00
0.473
1.37E-02
600
1.23E-02
0.103
0.107
5.84E-03
4.57E-03
0.657
1.90E-02
750
2.53E-02
0.211
0.216
6.35E-03
3.17E-03
0.403
1.17E-02
675
3.30E-02
0.275
0.279
5.48E-03
2.92E-03
0.376
1.09E-02
650
4.02E-02
0.335
0.339
5.59E-03
650
4.72E-02
0.393
0.396
3.44E-03
3.02E-03
0.375
1.09E-02
3.02E-03
0.412
1.19E-02
675
5.52E-02
0.460
0.462
2.35E-03
2.98E-03
0.512
1.48E-02
725
6.59E-02
0.549
0.549
1.62E-04
2.88E-03
0.489
1.42E-02
725
7.60E-02
0.634
0.637
4.97E-03
2.75E-03
0.507
1.47E-02
725
8.68E-02
0.723
0.725
3.06E-03
2.85E-03
0.401
1.16E-02
675
9.47E-02
0.789
0.790
1.73E-03
2.90E-03
0.414
1.20E-02
675
1.03E-01
0.857
0.858
1.66E-03
3.00E-03
0.204
5.91E-03
0
1.05E-01
0.879
0.881
3.15E-03
5.91E-03
0.235
6.80E-03
0
1.06E-01
0.885
0.889
4.84E-03
6.80E-03
0.258
7.47E-03
25
1.07E-01
0.890
0.894
5.30E-03
7.26E-03
0.259
7.50E-03
0
1.07E-01
0.892
0.896
5.71E-03
7.50E-03
0.265
7.67E-03
0
1.07E-01
0.894
0.898
6.17E-03
7.67E-03
0.266
7.70E-03
2.57E-03
600
1.07E-01
0.894
0.899
7.09E-03
2.91E-03
1.54E-05
1.09E-02
0.00E+00
3.02E-03
0.00E+00
1.07E-02
2.87E-04
2.96E-03
7.96E-05
1.18E-02
2.25E-04
2.94E-03
5.63E-05
1.46E-02
3.48E-04
2.83E-03
6.77E-05
1.46E-02
5.73E-04
2.83E-03
1.11E-04
1.46E-02
1.43E-04
2.83E-03
2.79E-05
1.15E-02
2.05E-04
2.87E-03
5.12E-05
1.19E-02
6.14E-05
2.99E-03
1.54E-05
6.04E-03
1.84E-04
6.04E-03
1.84E-04
7.09E-03
4.09E-04
7.09E-03
4.09E-04
7.80E-03
4.71E-04
7.59E-03
4.58E-04
7.86E-03
5.12E-04
7.86E-03
5.12E-04
8.08E-03
5.73E-04
8.08E-03
5.73E-04
8.19E-03
6.96E-04
2.73E-03
2.32E-04
140
Appendix E
Adsorption Data for Freundlich Isotherms
141
Table E.1
Boler wax batch adsorption data.
Bottle A
Time
6/26/01 6:04
6/26/01 7:04
7/8/01 19:22
7/22/01 14:57
Days
0.00
0.04
12.55
26.37
PA
13105952
8795386
6539552
7291277
mol/bottle
191.0783582
128.2324181
95.34346378
106.3032459
M
3514.472553
2358.5576
1753.636517
1955.217972
Bottle B
Time
6/26/01 6:12
6/26/01 7:28
7/8/01 19:14
7/22/01 13:34
0.00
0.06
12.55
26.31
PA
3501474
2178266
1644789
1798688
mol/bottle
51.0497752
31.75805093
23.98021767
26.22398968
M
938.9500487
584.1205637
441.0641666
482.333493
Bottle C
Time
6/26/01 6:20
6/26/01 7:52
7/8/01 19:07
7/22/01 12:34
8/7/01 2:14
0.00
0.08
12.54
26.27
41.84
PA
699596
433362
315534
356682
304797
mol/bottle
10.19976688
6.318205613
4.600331108
5.200248786
4.443790909
M
187.6026206
116.209708
84.61312712
95.64731347
81.7339092
0.00
0.11
12.54
26.25
41.80
PA
75211
53072
41009
42836
36142
mol/bottle
1.096539527
0.773763755
0.597891126
0.62452789
0.52693265
M
20.16846965
14.23170841
10.99691231
11.48683791
9.691784848
Bottle D
Time
6/26/01 6:28
6/26/01 8:39
7/8/01 19:00
7/22/01 11:57
8/7/01 1:18
Table E.2
Bottle
A
B
C
D
Boler wax calculations for isotherm fit
Ce
256.817881
63.3545043
12.5632746
1.50879616
mg TCE/L
mg TCE/L
mg TCE/L
mg TCE/L
Log Ce
2.40963
1.80178
1.09910
0.17863
qe
11.1307587
3.262171796
0.656621039
0.06194298
mg TCE/g Boler
mg TCE/g Boler
mg TCE/g Boler
mg TCE/g Boler
Log qe
1.04652
0.51351
-0.18269
-1.20801
142
Table E.3
Sample 19-363 batch adsorption data.
Bottle A
Time
6/26/01 6:05
6/26/01 7:10
7/8/01 20:59
7/22/01 14:38
Bottle B
Time
6/26/01 6:14
6/26/01 7:33
7/8/01 20:49
7/22/01 13:50
0.00
0.06
12.61
26.32
-37068.25
PA
13105952
8702458
4971690
5637296
mol/bottle
191.0783582
126.8775734
72.48480407
82.1890134
0
M
3514.472553
2333.638166
1333.20098
1511.688893
0
PA
3501474
2824690
1343666
1418187
mol/bottle
51.0497752
41.1825961
19.58999188
20.67647155
0
M
938.9500487
757.46466
360.3154718
380.298912
0
mol/bottle
10.19976688
7.812182582
4.00876749
4.225200316
3.369485136
M
187.6026206
143.6881786
73.7325956
77.71340867
61.97438128
mol/bottle
1.096539527
0.930828816
0.488996765
0.507191994
0.484550015
M
20.16846965
17.12058004
8.994036407
9.328698227
8.912248061
Bottle C
Time
6/26/01 6:22
6/26/01 7:57
7/8/01 20:25
7/22/01 12:41
8/7/01 2:26
0.00
0.08
12.60
26.28
41.85
PA
699596
535833
274959
289804
231111
Bottle D
Time
6/26/01 6:30
6/26/01 8:44
7/8/01 20:17
7/22/01 12:04
8/7/01 1:37
0.00
0.11
12.59
26.25
41.81
PA
75211
63845
33540
34788
33235
Table E.4
Bottle
A
B
C
D
Days
0.00
0.05
12.62
26.36
-37068.25
Sample 19-363 calculations for isotherm fit
Ce
198.560336
49.9522621
10.2076562
1.22532451
mg TCE/L
mg TCE/L
mg TCE/L
mg TCE/L
Log Ce
2.29789
1.69856
1.00893
0.08825
qe
28.56523955
7.974282299
1.567324382
0.154636034
mg TCE/g 19-363
mg TCE/g 19-363
mg TCE/g 19-363
mg TCE/g 19-363
Log qe
1.45584
0.90169
0.19516
-0.81069
143
Table E.5
Table E.6
Bottle
A
B
C
D
Chlorez 700 batch adsorption data.
Bottle A
Time
6/26/01 6:06
6/26/01 7:16
7/8/01 22:21
7/22/01 14:22
Days
0.00
0.05
12.68
26.34
PA
13105952
927425
2901026
3675054
mol/bottle
191.0783582
13.52140206
42.29553758
53.58048654
M
3514.47255
248.696906
777.934808
985.497003
Bottle B
Time
6/26/01 6:16
6/26/01 7:40
7/8/01 22:03
7/22/01 14:07
0.00
0.07
12.66
26.33
PA
3501474
765068
1009004
992455
mol/bottle
51.0497752
11.15431656
14.71078391
14.4695076
M
938.950049
205.159495
270.573009
266.135253
Bottle C
Time
6/26/01 6:24
6/26/01 8:03
7/8/01 21:50
7/22/01 12:50
8/7/01 2:55
0.00
0.08
12.66
26.28
41.87
PA
699596
457594
293848
269752
200794
mol/bottle
10.19976688
6.671496299
4.284159854
3.932851982
2.927478131
M
187.602621
122.707725
78.7978417
72.3362942
53.8446197
Bottle D
Time
6/26/01 6:32
6/26/01 8:50
7/8/01 21:42
7/22/01 12:10
8/7/01 1:48
0.00
0.11
12.65
26.25
41.82
PA
75211
73455
34997
29626
22929
mol/bottle
1.096539527
1.070937907
0.510239111
0.431932563
0.334293585
M
20.1684697
19.6975833
9.38474336
7.944464
6.14860646
Chlorez 700 calculations for isotherm fit.
Ce
7.03779691
1.90056982
0.51658011
0.05673434
mg TCE/L
mg TCE/L
mg TCE/L
mg TCE/L
Log Ce
0.84744
0.27888
-0.28686
-1.24615
qe
18.038699
4.80097737
0.82357106
0.0872525
mg TCE/g Chlorez
mg TCE/g Chlorez
mg TCE/g Chlorez
mg TCE/g Chlorez
Log qe
1.25621
0.68133
-0.08430
-1.05922
144
Appendix F
TCE Degradation Data
Table F.1
TCE degradation data for sample 19-307
bottle
Response Factor = 1.06550E-05
Time
Time(days)
1/7/00 6:40
0.000
1/7/00 7:40
0.042
1/8/00 21:33
1.621
1/10/00 1:17
2.776
1/12/00 0:36
4.747
1/12/00 23:24
5.697
1/13/00 13:16
6.275
1/17/00 18:01
10.473
1/19/00 17:21
12.446
1/20/00 15:05
13.351
1/24/00 2:37
16.832
1/25/00 18:24
18.489
1/26/00 19:23
19.530
1/28/00 15:06
21.352
1/31/00 16:19
24.402
2/3/00 12:05
27.226
2/7/00 22:15
31.650
2/14/00 19:01
38.515
10
8
10.82000
10.18828
10.10952
9.60343
9.35818
7.81484
8.06877
7.85004
6.23808
5.57051
3.55508
2.96955
2.55612
2.02986
1.19593
0.77659
0.35618
0.00000
10.82000
9.86538
8.77453
8.95931
7.84383
7.02088
7.68329
6.32011
4.87122
4.23678
2.54154
1.98002
1.68624
1.31113
0.64237
0.25989
0.02842
0.00000
Peak Area
956197
948805
901307
878290
733443
757275
736747
585460
522807
333654
278700
239899
190508
112241
72885
33428
0
9
11
mol TCE / Bottle
10.82000
10.82000
9.74961
10.40745
8.15878
9.01902
8.91683
9.16131
8.47717
8.57327
7.61427
7.32589
7.60282
7.95332
7.16282
6.38648
5.45996
4.72108
4.59716
4.11496
2.15427
2.60172
1.47155
2.14991
1.12221
1.79075
0.70761
1.41559
0.16969
0.72242
0.02684
0.39907
0.00000
0.07797
0.00000
0.00000
avg
std dev
10.82000
10.05268
9.01546
9.16022
8.56311
7.44397
7.82705
6.92986
5.32259
4.62985
2.71315
2.14276
1.78883
1.36605
0.68260
0.36560
0.11564
0.00000
0
0.300656
0.814233
0.314132
0.621019
0.346166
0.220087
0.722971
0.688606
0.659677
0.595278
0.621996
0.589818
0.541499
0.420232
0.314095
0.163561
0.00000
145
Table F.2
TCE degradation data for sample 19-308
bottle
Response Factor = 1.06550E-05
Time
Time(days)
1/7/00 6:40
0
1/7/00 7:18
0.026
1/8/00 21:04
1.601
1/10/00 0:46
2.755
1/12/00 0:09
4.729
1/12/00 22:59
5.680
1/13/00 12:50
6.257
1/17/00 17:27
10.449
1/19/00 16:57
12.429
1/20/00 14:41
13.335
1/24/00 1:36
16.789
1/25/00 17:49
18.465
1/26/00 18:56
19.511
1/28/00 14:40
21.334
1/31/00 14:58
24.346
2/3/00 11:41
27.209
2/7/00 21:47
31.630
6
4
10.8200
9.5252
5.7626
5.5997
4.2503
3.5196
3.2921
2.7844
2.2226
1.9669
0.9617
0.4130
0.1766
0.0167
0.0195
0.0000
0.0000
10.8200
8.8076
5.8128
5.8416
4.0070
3.7269
3.6164
3.6509
2.9021
1.0786
0.5993
0.2566
0.0293
0.0000
0.0000
0.0000
0.0000
Peak Area
893962
540835
525551
398904
330325
308971
261328
208600
184603
90256
38764
16573
1567
1829
0
0
5
7
mol TCE / Bottle
10.8200
10.8200
9.8288
9.4930
6.3415
6.6573
6.7900
6.5112
5.5235
5.9758
4.7855
5.1127
4.9023
5.2448
4.7478
4.9080
3.7651
4.2507
3.6641
3.8361
2.5537
2.6733
2.1987
2.2175
1.7916
1.8381
1.1085
1.3014
0.2371
0.5221
0.0126
0.0269
0.0000
0.0000
avg
std dev
10.8200
9.6157
6.2538
6.3003
5.2499
4.4726
4.4797
4.1467
3.4128
3.1557
2.0629
1.6097
1.2688
0.8089
0.2596
0.0131
0.0000
0.0000
0.4314
0.4311
0.5576
0.9591
0.7816
0.9545
0.9968
0.9015
1.3380
1.0697
1.0835
0.9904
0.6954
0.2433
0.0128
0.0000
146
Table F.3
TCE degradation data for water controls (corresponds to Table F.1 and F.2)
Response Factor = 1.06550E-05
Time
Time (days)
1/7/00 8:02
0.00
1/8/00 21:53
1.58
1/10/00 1:39
2.73
1/12/00 0:49
4.70
1/12/00 23:42
5.65
1/13/00 13:29
6.23
1/17/00 18:16
10.43
1/19/00 17:33
12.40
1/20/00 15:16
13.30
1/24/00 2:52
16.78
1/25/00 18:40
18.44
1/26/00 19:36
19.48
1/28/00 15:18
21.30
1/31/00 16:31
24.35
2/3/00 12:24
27.18
2/7/00 22:28
31.60
2/14/00 19:16
38.47
bottle 13
Peak Area mol TCE / Bottle
1032780
11.00427
1057071
11.26309
1045124
11.13580
1048015
11.16660
961685
10.24675
1049538
11.18283
1172002
12.48768
1100864
11.72971
1108160
11.80744
1054324
11.23382
995188
10.60373
958313
10.21083
1027153
10.94432
833058
8.87623
753720
8.03089
692429
7.37783
593323
6.32186
Peak Area
998227
1051915
1057997
1054376
948974
1009979
1159723
1110592
1125131
1068969
1031938
968095
994534
803950
726988
650209
525820
bottle 14
mol TCE / Bottle
10.63611
11.20815
11.27296
11.23438
10.11132
10.76133
12.35685
11.83336
11.98827
11.38986
10.99530
10.31505
10.59676
8.56609
7.74606
6.92798
5.60261
147
Table F.4
TCE degradation data for sample 19-363
Date - Time Time (days)
6/18/01 11:54
0.00
6/18/01 15:59
0.17
6/19/01 5:32
0.74
6/21/01 10:45
2.95
6/25/01 6:57
6.79
7/6/01 9:47
17.91
7/17/01 21:55
29.42
PA
Bottle A
mol/bottle
2382426
2400214
2015328
1828334
1673653
1916488
86.793
87.441
73.420
66.607
60.972
69.819
PA
Bottle B
mol/bottle
2447904
2281573
2138656
1877274
1872280
1930692
89.179
83.119
77.913
68.390
68.208
70.336
PA
Bottle C
mol/bottle
2935856
2478301
2182710
1872294
1814816
1939832
106.955
90.286
79.518
68.209
66.115
70.669
Average
mol/bottle
std dev
94.309
11.017
94.309
11.017
86.949
3.609
76.950
3.161
67.736
0.981
65.099
3.724
70.275
0.429
148
Table F.5
TCE degradation data for sample 19-546
Bottle A
PA
mol/bottle
0.07
1051603
6/18/01 20:07
0.36
6/19/01 2:56
0.64
6/19/01 13:08
Bottle B
PA
mol/bottle
38.311
1299528
546560
19.912
442243
16.111
1.07
298033
Date - Time
Time (days)
6/18/01 11:34
0.00
6/18/01 13:21
Bottle C
Average
Average
mol/bottle
std dev
PA
mol/bottle
84.6
84.6
0
47.343
1437839
52.381
46.012
7.129
863391
31.454
957531
34.884
28.750
7.844
764279
27.843
835420
30.435
24.796
7.632
10.858
568770
20.721
665394
24.241
18.606
6.938
84.6
84.6
6/20/01 8:18
1.86
139726
5.090
448684
16.346
550393
20.051
13.829
7.792
6/20/01 19:21
2.32
113941
4.151
384025
13.990
531767
19.373
12.505
7.719
6/21/01 6:57
2.81
77335
2.817
329990
12.022
452859
16.498
10.446
6.975
6/22/01 5:52
3.76
46680
1.701
285451
10.399
401670
14.633
8.911
6.593
6/23/01 7:57
4.85
26291
0.958
239214
8.715
364902
13.294
7.655
6.236
6/24/01 16:39
6.21
5796
0.211
201860
7.354
325626
11.863
6.476
5.875
6/25/01 8:08
6.86
3929
0.143
174745
6.366
302200
11.009
5.840
5.452
6/26/01 17:18
8.24
0
0.000
167493
6.102
288976
10.528
5.543
5.286
6/27/01 15:32
9.17
0
0.000
150023
5.465
277140
10.096
5.187
5.054
6/28/01 12:54
10.06
0
0.000
175385
6.389
257548
9.383
5.257
4.793
6/29/01 12:10
11.03
0
0.000
110544
4.027
247955
9.033
4.353
4.525
6/30/01 10:46
11.97
0
0.000
114489
4.171
224476
8.178
4.116
4.089
7/1/01 11:55
13.01
0
0.000
86553
3.153
215691
7.858
3.670
3.954
7/2/01 20:30
14.37
0
0.000
61345
2.235
178052
6.487
2.907
3.295
7/3/01 11:42
15.01
0
0.000
60251
2.195
174612
6.361
2.852
3.231
7/4/01 19:14
16.32
0
0.000
49471
1.802
151104
5.505
2.436
2.807
7/5/01 19:54
17.35
0
0.000
37625
1.371
135209
4.926
2.099
2.542
7/7/01 8:04
18.85
0
0.000
27129
0.988
114912
4.186
1.725
2.188
7/8/01 16:32
20.21
0
0.000
15247
0.555
100203
3.650
1.402
1.967
7/9/01 15:50
21.18
0
0.000
10979
0.400
93250
3.397
1.266
1.857
7/10/01 19:33
22.33
0
0.000
8724
0.318
79800
2.907
1.075
1.595
149
Average
Average
Date - Time
Time (days)
PA
Bottle A
mol/bottle
PA
Bottle B
mol/bottle
PA
Bottle C
mol/bottle
mol/bottle
std dev
7/11/01 18:15
23.28
0
0.000
5687
0.207
71343
2.599
0.935
1.444
7/13/01 11:27
25.00
0
0.000
0
0.000
54237
1.976
0.659
1.141
7/14/01 14:10
26.11
0
0.000
0
0.000
57750
2.104
0.701
1.215
7/15/01 22:22
27.45
0
0.000
0
0.000
46841
1.706
0.569
0.985
7/16/01 23:32
28.50
0
0.000
0
0.000
36766
1.339
0.446
0.773
Table F.6
TCE degradation data for sample 19-547
Date - Time
6/18/01 11:36
6/18/01 13:40
6/18/01 20:24
6/19/01 3:31
6/19/01 13:30
6/20/01 8:35
6/21/01 7:14
6/22/01 5:37
Bottle A
Bottle B
Bottle C
Time (days)
PA
PA
PA
mol/bottle
mol/bottle
mol/bottle
0.00
84.6
84.6
84.6
0.09
552178
20.116
858990
31.294
873752
31.831
0.37
182854
6.661
456351
16.625
388034
14.136
0.66
42543
1.550
186447
6.792
164013
5.975
1.08
8193
0.298
50569
1.842
39595
1.442
1.87
3429
0.125
4088
0.149
3209
0.117
2.82
3377
0.123
0
0.000
0
0.000
3.75
0
0.000
0
0.000
0
0.000
Average
mol/bottle
84.6
27.747
12.474
4.772
1.194
0.130
0.041
0.000
std dev
0.000
6.614
5.186
2.821
0.801
0.017
0.071
0.000
150
Table F.7
TCE degradation data for sample 19-548
Date - Time Time (days)
6/18/01 11:38
0.00
6/18/01 14:00
0.10
6/18/01 20:40
0.38
6/19/01 3:49
0.67
6/19/01 13:46
1.09
6/20/01 8:52
1.88
6/20/01 19:47
2.34
6/21/01 7:33
2.83
6/22/01 6:08
3.77
6/23/01 8:16
4.86
6/24/01 16:55
6.22
6/25/01 8:23
6.86
6/26/01 17:40
8.25
6/27/01 15:45
9.17
6/28/01 13:09
10.06
6/29/01 12:22
11.03
6/30/01 11:08
11.98
7/1/01 13:07
13.06
7/2/01 20:41
14.38
7/3/01 11:54
15.01
7/4/01 19:32
16.33
7/5/01 20:05
17.35
7/7/01 8:32
18.87
7/8/01 16:47
20.21
7/9/01 16:16
21.19
7/10/01 19:46
22.34
PA
Bottle A
mol/bottle
1431204
948288
778480
644039
509386
455676
412989
340904
297485
254578
233039
224160
218583
201346
186931
193050
160312
155089
146225
142374
136216
128945
122587
119180
114482
52.140
34.547
28.361
23.463
18.557
16.601
15.045
12.419
10.838
9.274
8.490
8.166
7.963
7.335
6.810
7.033
5.840
5.650
5.327
5.187
4.962
4.698
4.466
4.342
4.171
PA
Bottle B
mol/bottle
1283648
815059
630419
522340
327849
285122
234298
190489
149734
109800
99977
86180
77170
68682
59293
56052
49022
36263
32516
28064
24921
18411
16814
15015
13029
46.764
29.693
22.967
19.029
11.944
10.387
8.536
6.940
5.455
4.000
3.642
3.140
2.811
2.502
2.160
2.042
1.786
1.321
1.185
1.022
0.908
0.671
0.613
0.547
0.475
PA
Bottle C
mol/bottle
1421531
884278
667949
550949
401973
340385
286644
232131
185579
151489
134378
115989
110550
95647
89741
86066
73870
61917
55523
51505
48857
41355
40277
35290
32967
51.787
32.215
24.334
20.071
14.644
12.400
10.443
8.457
6.761
5.519
4.895
4.226
4.027
3.484
3.269
3.135
2.691
2.256
2.023
1.876
1.780
1.507
1.467
1.286
1.201
Average
mol/bottle
std dev
84.6
0
50.230
3.007
32.152
2.427
25.220
2.804
20.854
2.318
15.048
3.325
13.129
3.170
11.341
3.347
9.272
2.829
7.684
2.808
6.264
2.715
5.676
2.516
5.177
2.645
4.934
2.693
4.441
2.554
4.080
2.429
4.070
2.623
3.439
2.128
3.076
2.278
2.845
2.190
2.695
2.200
2.550
2.134
2.292
2.125
2.182
2.024
2.058
2.012
1.949
1.958
151
Date - Time Time (days)
7/11/01 18:37
23.29
7/13/01 11:41
25.00
7/14/01 14:29
26.12
7/16/01 23:47
28.51
Table F.8
Bottle A
PA
mol/bottle
113049
4.118
103328
3.764
128156
4.669
118087
4.302
Bottle B
PA
mol/bottle
11052
0.403
8799
0.321
10343
0.377
8269
0.301
Bottle C
PA
mol/bottle
31987
1.165
26498
0.965
32384
1.180
25956
0.946
Average
mol/bottle
std dev
1.895
1.963
1.683
1.831
2.075
2.282
1.850
2.148
TCE degradation data for sample 19-549
Bottle A
PA
mol/bottle
Date - Time Time (days)
6/18/01 11:41
0.00
6/18/01 14:27
0.12
1104967
6/18/01 20:59
0.39
475501
6/19/01 4:06
0.68
lost
6/19/01 14:02
1.10
lost
6/20/01 9:09
1.89
lost
6/21/01 7:51
2.84
lost
6/22/01 6:24
3.78
lost
6/23/01 8:35
4.87
lost
6/24/01 16:45
6.21
lost
6/25/01 8:33
6.87
lost
6/26/01 18:02
8.26
lost
6/27/01 15:55
9.18
lost
6/28/01 13:38
10.08
lost
6/29/01 12:32
11.04
lost
7/1/01 13:00
13.05
lost
40.255
17.323
Bottle B
PA
mol/bottle
1149213
606742
368194
222387
104640
44503
17868
4589
0
0
0
0
0
0
0
41.867
22.104
13.414
8.102
3.812
1.621
0.651
0.167
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Bottle C
PA
mol/bottle
1398496
1027663
566133
415933
282092
207244
153670
105524
64873
52967
24587
2445
5675
5715
0
50.948
37.438
20.625
15.153
10.277
7.550
5.598
3.844
2.363
1.930
0.896
0.089
0.207
0.208
0.000
Average
std dev
mol/bottle
84.6
0
44.357
5.765
25.622
10.509
17.019
5.099
11.627
4.986
7.044
4.571
4.586
4.192
3.125
3.498
2.006
2.600
1.182
1.671
0.965
1.364
0.448
0.633
0.045
0.063
0.103
0.146
0.104
0.147
0.000
0.000
152
Table F.9
TCE degradation data for sample 19-550
Date - Time Time (days)
6/18/01 11:43
0.00
6/18/01 14:46
0.13
6/18/01 21:26
0.40
6/19/01 4:18
0.69
6/19/01 14:14
1.10
6/20/01 9:30
1.91
6/21/01 8:04
2.85
6/22/01 6:59
3.80
6/24/01 17:14
6.23
6/25/01 8:43
6.88
6/26/01 18:15
8.27
6/27/01 16:09
9.18
6/28/01 13:25
10.07
6/29/01 12:43
11.04
6/30/01 11:35
11.99
7/1/01 15:04
13.14
7/2/01 20:55
14.38
7/3/01 12:11
15.02
7/4/01 20:04
16.35
7/5/01 20:22
17.36
7/7/01 9:25
18.90
7/8/01 17:10
20.23
7/9/01 17:08
21.23
7/10/01 20:08
22.35
7/11/01 19:37
23.33
7/14/01 14:42
26.12
Bottle A
mol/bottle
84.6
1393553
50.768
1012911
36.901
897964
32.713
767653
27.966
638582
23.264
512732
18.679
414614
15.105
307119
11.189
286721
10.445
237990
8.670
217520
7.924
180511
6.576
150942
5.499
???
#VALUE!
92264
3.361
55485
2.021
43547
1.586
23824
0.868
13192
0.481
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
PA
Bottle B
mol/bottle
84.6
1517391
55.280
1156972
42.149
997496
36.339
946699
34.489
810301
29.520
689724
25.127
635713
23.159
476321
17.353
450704
16.419
403627
14.704
376474
13.715
336823
12.271
302409
11.017
285894
10.415
216554
7.889
184583
6.724
166104
6.051
117550
4.282
117145
4.268
79110
2.882
64082
2.335
49673
1.810
38052
1.386
23996
0.874
9999
0.364
PA
Bottle C
mol/bottle
84.6
1422369
51.818
1195694
43.560
974089
35.487
915081
33.337
766969
27.941
654025
23.827
610885
22.255
454444
16.556
419951
15.299
374653
13.649
349138
12.719
311486
11.348
265486
9.672
246921
8.996
193108
7.035
144934
5.280
131631
4.795
98613
3.593
80852
2.945
45290
1.650
30506
1.111
19964
0.727
10706
0.390
5358
0.195
0
0.000
PA
Average
mol/bottle
std dev
84.6
0
52.622
2.361
40.870
3.509
34.847
1.896
31.931
3.481
26.908
3.253
22.544
3.410
20.173
4.413
15.032
3.353
14.055
3.175
12.341
3.223
11.453
3.096
10.065
3.056
8.729
2.877
9.705
1.004
6.095
2.406
4.675
2.409
4.144
2.303
2.914
1.805
2.565
1.922
1.511
1.446
1.149
1.168
0.846
0.911
0.592
0.715
0.356
0.459
0.121
0.210
153
Date - Time Time (days)
7/15/01 22:37
27.45
7/17/01 0:00
28.51
Table F.10
PA
0
0
Bottle A
mol/bottle
0.000
0.000
PA
4333
0
Bottle B
mol/bottle
0.158
0.000
PA
0
0
Bottle C
mol/bottle
0.000
0.000
Average
mol/bottle
std dev
0.053
0.091
0.000
0.000
TCE degradation data for sample 19-551
Date - Time Time (days)
6/18/01 11:45
0.00
6/18/01 15:04
0.14
6/18/01 21:33
0.41
6/19/01 4:33
0.70
6/19/01 14:29
1.11
6/20/01 9:47
1.92
6/21/01 8:21
2.86
6/22/01 7:16
3.81
6/23/01 8:56
4.88
6/24/01 17:30
6.24
6/25/01 9:02
6.89
6/26/01 18:35
8.28
6/27/01 16:19
9.19
6/28/01 13:43
10.08
6/29/01 12:56
11.05
6/30/01 11:48
12.00
7/1/01 15:35
13.16
7/3/01 11:02
14.97
Bottle A
mol/bottle
84.6
710894
25.898
493496
17.978
376852
13.729
351489
12.805
267947
9.761
205394
7.483
178547
6.505
140403
5.115
110817
4.037
100490
3.661
69449
2.530
56419
2.055
41313
1.505
29035
1.058
19172
0.698
8907
0.324
0
0.000
PA
Bottle B
Bottle C
PA
mol/bottle
mol/bottle
84.6
84.6
646115
23.538
581430
21.182
360438
13.131
266072
9.693
247868
9.030
141188
5.144
200646
7.310
83225
3.032
121984
4.444
24161
0.880
66741
2.431
6150
0.224
38384
1.398
0
0.000
17305
0.630
0
0.000
6155
0.224
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
PA
Average
mol/bottle
84.6
23.540
13.601
9.301
7.716
5.029
3.379
2.634
1.915
1.420
1.220
0.843
0.685
0.502
0.353
0.233
0.108
0.000
std dev
0.000
2.358
4.163
4.299
4.899
4.469
3.721
3.424
2.789
2.269
2.114
1.461
1.187
0.869
0.611
0.403
0.187
0.000
154
Table F.11
TCE degradation data for sample 19-552
Date - Time
6/18/01 11:48
6/18/01 15:22
6/18/01 21:50
6/19/01 4:52
6/19/01 14:45
6/20/01 10:10
6/21/01 8:42
6/22/01 7:39
6/23/01 9:07
6/24/01 17:40
6/25/01 9:08
6/26/01 18:44
6/27/01 16:24
6/28/01 13:49
Bottle A
Time (days)
PA
mol/bottle
0.00
84.6
0.15
1327097
48.347
0.42
888704
32.376
0.71
625109
22.773
1.12
488358
17.791
1.93
296300
10.794
2.87
179981
6.557
3.83
128596
4.685
4.89
78181
2.848
6.24
44639
1.626
6.89
35015
1.276
8.29
14773
0.538
9.19
5907
0.215
10.08
0
0.000
Bottle B
PA
mol/bottle
84.6
1328096
48.383
812552
29.602
500245
18.224
351273
12.797
117935
4.296
29798
1.086
6235
0.227
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
Bottle C
PA
mol/bottle
84.6
1346989
49.072
857278
31.231
591183
21.537
544889
19.851
190516
6.941
82767
3.015
37117
1.352
11945
0.435
0
0.000
0
0.000
0
0.000
0
0.000
0
0.000
Average
std dev
mol/bottle
84.6
0
48.601
0.408
31.070
1.394
20.845
2.352
16.813
3.627
7.344
3.268
3.553
2.775
2.088
2.318
1.094
1.534
0.542
0.939
0.425
0.736
0.179
0.311
0.072
0.124
0.000
0.000
155
Table F.12
TCE degradation data for sample 19-553
Date - Time
6/18/01 11:50
6/18/01 15:42
6/18/01 22:14
6/19/01 5:11
6/19/01 15:08
6/20/01 10:30
6/20/01 20:07
6/21/01 9:02
6/22/01 7:56
6/23/01 9:23
6/24/01 17:51
6/25/01 9:18
6/26/01 19:06
6/27/01 16:35
6/28/01 14:01
6/29/01 13:07
6/30/01 12:12
7/1/01 16:09
7/2/01 21:16
7/3/01 11:16
7/4/01 20:52
7/5/01 20:39
7/7/01 11:37
7/8/01 17:18
Time (days)
0.00
0.16
0.43
0.72
1.14
1.94
2.35
2.88
3.84
4.90
6.25
6.89
8.30
9.20
10.09
11.05
12.02
13.18
14.39
14.98
16.38
17.37
18.99
20.23
Bottle A
Bottle B
Bottle C
PA
PA
mol/bottle
mol/bottle
mol/bottle
84.6
84.6
84.6
1396008
50.858
1218467
44.390
1241094 45.21392
1026925
37.412
784929
28.596
982668
35.79928
846670
30.845
600696
21.884
851825
31.03258
729870
26.590
491903
17.920
735520
26.79551
584213
21.283
335282
12.215
576196
20.99122
567839
20.687
304882
11.107
533920
19.45108
491439
17.903
245891
8.958
465040
16.94173
441870
16.098
204835
7.462
447509
16.30307
388559
14.155
148931
5.426
354080
12.89938
353129
12.865
111369
4.057
336914
12.27401
338294
12.324
98434
3.586
298313
10.86775
313900
11.436
67424
2.456
275655
10.04230
288315
10.504
54273
1.977
258846
9.42994
270831
9.867
38019
1.385
231102
8.41921
249448
9.088
25807
0.940
215421
7.84794
248023
9.036
16398
0.597
202648
7.38261
206573
7.526
6967
0.254
170456
6.20983
163722
5.965
3215
0.117
126810
4.61978
155641
5.670
0
0.000
114712
4.17904
132501
4.827
0
0.000
95455
3.47749
125896
4.586
0
0.000
80870
2.94615
85809
3.126
0
0.000
48359
1.76175
82034
2.989
0
0.000
35590
1.29657
PA
Average
std dev
mol/bottle
84.6
0
46.820
3.521
33.935
4.694
27.920
5.229
23.769
5.066
18.163
5.154
17.082
5.211
14.601
4.911
13.288
5.046
10.827
4.720
9.732
4.923
8.926
4.682
7.978
4.832
7.304
4.644
6.557
4.537
5.959
4.390
5.672
4.472
4.663
3.875
3.567
3.063
3.283
2.939
2.768
2.490
2.511
2.324
1.629
1.567
1.428
1.499
156
Date - Time
7/9/01 19:03
7/10/01 20:30
7/11/01 19:50
7/13/01 12:35
7/14/01 15:01
7/15/01 23:00
7/17/01 21:25
Table F.13
Time (days)
21.30
22.36
23.33
25.03
26.13
27.46
29.40
Bottle A
PA
mol/bottle
71058
2.589
55365
2.017
44498
1.621
23332
0.850
20903
0.762
11922
0.434
4271
0.156
PA
0
0
0
0
0
0
0
Bottle B
mol/bottle
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Bottle C
PA
mol/bottle
25230
0.91915
16414
0.59797
10607
0.38642
3524
0.12838
2147
0.07822
0
0.00000
0
0.00000
Average
mol/bottle
std dev
1.169
1.312
0.872
1.036
0.669
0.847
0.326
0.458
0.280
0.419
0.145
0.251
0.052
0.090
TCE degradation data for water controls (corresponds to Table F.4 and F.12)
Date - Time
6/18/01 11:32
6/18/01 13:04
6/19/01 2:37
6/20/01 18:50
6/21/01 10:24
6/23/01 7:40
6/25/01 6:42
6/29/01 13:25
7/6/01 8:04
7/17/01 22:22
Time (days)
0.00
0.06
0.63
2.30
2.95
4.84
6.80
11.08
17.86
29.45
Bottle A
PA
mol/bottle
84.573
2257390
82.238
2618552
95.396
2361029
86.014
2212470
80.602
2269984
82.697
1859354
67.738
2162501
78.781
1987535
72.407
2380318
86.717
Bottle B
PA
mol/bottle
84.573
2287040
83.318
2512606
91.536
2386272
86.934
2261454
82.386
2288088
83.357
2081488
75.830
2154418
78.487
2090692
76.165
2326402
84.752
Bottle C
PA
mol/bottle
84.573
2419992
88.162
2612400
95.172
2375037
86.524
2349470
85.593
2225477
81.076
2064738
75.220
2223634
81.009
2021839
73.657
2248064
81.899
Average
mol/bottle
std dev
84.573
0.000
84.573
3.155
94.034
2.167
86.491
0.461
82.860
2.529
82.376
1.174
72.929
4.506
79.426
1.379
74.077
1.914
84.456
2.423
157
Table F.14
Chloride stoichiometry data from TCE degradation tests.
Average of Triplicates
Sample
19-546-A
19-546-B
19-546-C
19-547-A
19-547-B
19-547-C
19-549-B
19-549-C
19-550-A
19-550-B
19-550-C
19-551-A
19-551-B
19-551-C
19-552-A
19-552-B
19-552-C
19-553-A
19-553-B
19-553-C
meas A
(before
std add.)
conc A
meas B
(after std.
add.)
conc B
mV
60.6
61.9
62.1
63.8
62.1
62.0
62.6
62.2
62.4
62.3
63.0
61.9
62.0
61.5
62.3
61.7
62.4
62.9
62.7
62.8
M
2.319E-03
2.198E-03
2.180E-03
2.032E-03
2.180E-03
2.189E-03
2.135E-03
2.171E-03
2.153E-03
2.162E-03
2.100E-03
2.198E-03
2.189E-03
2.234E-03
2.162E-03
2.216E-03
2.153E-03
2.109E-03
2.127E-03
2.118E-03
mV
47.2
46.4
47.3
47.9
47.2
47.0
46.4
47.5
47.4
47.1
47.9
47.5
47.1
47.3
47.5
47.6
47.3
47.8
47.3
47.9
M
4.026E-03
4.161E-03
4.009E-03
3.911E-03
4.026E-03
4.059E-03
4.161E-03
3.976E-03
3.993E-03
4.042E-03
3.911E-03
3.976E-03
4.042E-03
4.009E-03
3.976E-03
3.960E-03
4.009E-03
3.928E-03
4.009E-03
3.911E-03
sample
vol
% recov
conc A
std dev A
conc B
sample vol
% recov
Cl- Recov.
std dev
Stoic.
mL
7.60
6.96
7.55
7.58
8.02
7.41
7.51
8.07
7.78
7.87
7.62
7.74
7.74
8.11
7.49
7.65
7.62
7.91
7.37
7.96
average
std add.
89.2
93.9
94.7
97.6
101.4
95.1
104.2
99.8
98.1
101.4
94.6
94.5
98.4
98.6
93.3
91.6
97.0
98.5
95.2
97.7
96.7
M
M
M
mL
std add.
2.232E-03 7.552E-05
4.065E-03
7.37
92.8
2.639
0.089
2.134E-03 8.779E-05
3.999E-03
7.67
98.1
2.523
0.104
2.153E-03 2.508E-05
4.069E-03
7.79
102.2
2.546
0.030
2.138E-03 3.320E-05
3.982E-03
7.76
98.0
2.528
0.039
2.207E-03 2.411E-05
4.009E-03
7.86
97.2
2.609
0.029
2.177E-03 3.408E-05
3.982E-03
7.59
94.0
2.574
0.040
2.118E-03 8.720E-06
3.949E-03
7.75
average
97.2
97.1
2.504
0.010
std dev.
3.589403
std dev.
3.1
158
Table F.15
Potassium data from TCE degradation tests.
a
Vial
Sample
Date & Time
b
Date & Time
(GC)
6/18/01 16:00
Time
c
Mass
Mass
Sample +
Sample
Diluent
d = b/(b+c)
e
Dilution
Factor
f=dxe
K+ Conc
IC Peak Area
Inj A
Inj B
average
Un-Diluted
K+ Released
days
g
g
mg/L
mol
A-Dil
BLANK
6/20/01 23:45
6/20/01 18:03
2.323
1.0000
0.0000
1.0000
185575
196976
191276
191276
0.273150429
0.698624823
B-To
BLANK
6/20/01 23:47
6/20/01 18:05
2.324
1.0000
0.0000
1.0000
218051
222762
220407
220407
0.31475087
0.805024438
C-To
BLANK
6/20/01 23:49
6/20/01 18:07
2.326
1.0000
0.0000
1.0000
171069
174574
172822
172822
0.246797247
0.63122245
D-6A
19-546-A
6/20/01 23:52
6/20/01 18:10
2.328
0.3044
4.2828
0.0711
2770646
2765497
2768072
38945784
55.61641498
142.2476552
E-6B
19-546-B
6/21/01 0:00
6/20/01 18:18
2.333
0.2665
3.3166
0.0804
2585989
2577090
2581540
32127332
45.87934391
117.3435774
F-6C
19-546-C
6/21/01 0:08
6/20/01 18:26
2.339
0.2402
3.1747
0.0757
2266670
2282146
2274408
30060629
42.92799496
109.7950421
G-8A
19-548-A
6/21/01 0:28
6/20/01 18:46
2.353
0.2385
3.2278
0.0739
2436545
2428705
2432625
32922545
47.0149459
120.2480566
H-8B
19-548-B
6/21/01 0:42
6/20/01 19:00
2.363
0.2263
3.2578
0.0695
2575009
2585457
2580233
37144866
53.04461865
135.669885
I-8C
19-548-C
6/21/01 0:53
6/20/01 19:11
2.370
0.2133
3.2187
0.0663
2324391
2327685
2326038
35099946
50.12437739
128.2009125
J-3A
19-553-A
6/21/01 1:05
6/20/01 19:23
2.378
0.2148
3.2295
0.0665
1909291
1904222
1906757
28667924
40.9391469
104.7082531
K-3B
19-553-B
6/21/01 1:14
6/20/01 19:32
2.385
0.2160
3.2062
0.0674
2257921
2248610
2253266
33446388
47.76301869
122.1613694
L-3C
19-553-C
6/21/01 1:24
6/20/01 19:42
2.392
0.2143
3.4788
0.0616
1680057
1694209
1687133
27387766
39.11102085
100.0325355
M-7A
19-547-A
6/21/01 19:10
6/21/01 13:28
3.132
0.2413
3.3424
0.0722
4120425
4106173
4113299
56975924
81.36430551
208.1019009
N-7B
19-547-B
6/21/01 19:23
6/21/01 13:41
3.141
0.2269
3.2062
0.0708
4416462
4419099
4417781
62425244
89.14619046
228.0052853
O-7C
19-547-C
6/21/01 19:52
6/21/01 14:10
3.161
0.2435
3.2382
0.0752
3757930
3748519
3753225
49912491
71.27738969
182.3030405
P-0A
19-550-A
6/22/01 14:31
6/22/01 8:49
3.938
0.2286
3.2078
0.0713
2381554
2378151
2379853
33394973
47.68959553
121.9735782
Q-0B
19-550-B
6/22/01 14:41
6/22/01 8:59
3.945
0.2132
3.2476
0.0656
1969927
1964261
1967094
29964045
42.79006904
109.4422751
R-0C
19-550-C
6/22/01 14:50
6/22/01 9:08
3.951
0.2081
3.2131
0.0648
1827633
1831203
1829418
28246530
40.3373767
103.1691319
S-1C
19-551-C
6/22/01 14:58
6/22/01 9:16
3.957
0.2234
3.2236
0.0693
2600231
2588634
2594433
37436941
53.46171612
136.7366768
T-2B
19-552-B
6/23/01 15:36
6/23/01 9:54
4.983
0.2125
3.1804
0.0668
2983100
2964163
2973632
44505118
63.55540641
162.552864
U-9B
19-549-B
6/23/01 15:43
6/23/01 10:01
4.988
0.2264
3.2144
0.0704
3034167
3026578
3030373
43024865
61.44153458
157.1463071
V-6A
19-546-A
6/24/01 22:53
6/24/01 17:11
6.287
0.2238
3.2053
0.0698
3184921
3173830
3179376
45535533
65.0268873
166.3164058
W-1B
19-551-B
6/24/01 23:17
6/24/01 17:35
6.303
0.2421
3.2485
0.0745
3239488
3205137
3222313
43237018
61.7445001
157.9211886
X-2C
19-552-C
6/24/01 23:30
6/24/01 17:48
6.313
0.2326
3.1802
0.0731
3163427
3157395
3160411
43210400
61.7064879
157.8239665
Expected
Expected
K+
K+
TCE
Released Released remaining
TCE
remaining
average
std dev.
average
std dev.
mol
mol
mol
mol
123.1288 16.9822
23.0086
8.4911
128.0396
7.7122
20.5532
3.8561
108.9674 11.6630
30.0893
5.8315
206.1367 22.9144
-18.4954
11.4572
111.5283
28.8088
4.7871
9.5742
159
a
b
c
d = b/(b+c)
e
f=dxe
Vial
Sample
Date & Time
Date & Time
(GC)
Time
Mass
Mass
Sample +
Sample
Diluent
Dilution
Factor
Inj A
Inj B
average
Un-Diluted
Y-6A
19-546-A
6/26/01 23:03
6/26/01 17:21
8.294
0.2345
3.2808
0.0715
3503167
3504703
3503935
K+ Conc
K+ Released
49022217
70.00603673
179.051357
IC Peak Area
Expected
Expected
K+
K+
TCE
Released Released remaining
TCE
remaining
average
Z-6B
19-546-B
6/26/01 23:10
6/26/01 17:28
8.299
0.2394
3.1664
0.0756
3188259
3193946
3191103
42206796
60.27329391
154.1583494
AA-6C
19-546-C
6/26/01 23:18
6/26/01 17:36
8.304
0.2367
3.2291
0.0733
2858148
2880894
2869521
39146473
55.90300908
142.9806643
AB-8A
19-548-A
6/26/01 23:27
6/26/01 17:45
8.310
0.2348
3.2345
0.0726
2978129
2979089
2978609
41031988
58.59561292
149.8674186
AC-8B
19-548-B
6/26/01 23:35
6/26/01 17:53
8.316
0.2088
3.1549
0.0662
3187783
3183766
3185775
48136015
68.74049839
175.8145454
AD-8C
19-548-C
6/26/01 23:43
6/26/01 18:01
8.322
0.2213
3.2090
0.0690
2913621
2936282
2924952
42413779
60.56887588
154.9143464
AE-9C
19-549-C
6/26/01 23:51
6/26/01 18:09
8.327
0.2197
3.3348
0.0659
3281012
3302224
3291618
49963076
71.34962676
182.4877981
AF-0A
19-550-A
6/26/01 23:59
6/26/01 18:17
8.333
0.2182
3.1917
0.0684
2735143
2775535
2755339
40303462
57.5552438
147.2065123
AG-0B
19-550-B
6/27/01 0:11
6/26/01 18:29
8.341
0.1910
3.1400
0.0608
2208054
2226908
2217481
36454923
52.05934856
133.1499031
AH-0C
19-550-C
6/27/01 0:19
6/26/01 18:37
8.347
0.2188
3.1682
0.0691
2509108
2515871
2512490
36380572
51.953172
132.87834
AI-1A
19-551-A
6/27/01 0:33
6/26/01 18:51
8.356
0.2233
3.1897
0.0700
2781390
2793757
2787574
39818734
56.86302816
145.4360628
AJ-1B
19-551-B
6/27/01 0:40
6/26/01 18:58
8.361
0.2144
3.1433
0.0682
3153337
3170089
3161713
46353603
66.19512972
169.304368
AK-1C
19-551-C
6/27/01 0:48
6/26/01 19:06
8.367
0.2241
3.2033
0.0700
2555092
2561829
2558461
36570801
52.22482756
133.5731414
AL-3B
19-553-B
6/27/01 0:59
6/26/01 19:17
8.374
0.2312
3.1995
0.0723
2998050
3001245
2999648
41511125
59.27984344
151.6174449
AM-3C
19-553-C
6/27/01 1:08
6/26/01 19:26
8.381
0.2089
3.1287
0.0668
2464159
2484407
2474283
37057392
52.91970257
135.3503926
AN-2A
19-552-A
6/28/01 19:39
6/28/01 13:57
10.152
0.2338
3.2388
0.0722
3337020
3341852
3339436
46260758
66.06254334
168.9652577
AO-9C
19-549-C
6/29/01 18:27
6/29/01 12:45
11.102
0.2068
3.1734
0.0652
3718857
3730191
3724524
57153793
81.61831061
208.7515585
AP-6B
19-546-B
7/1/01 18:15
7/1/01 12:33
13.094
0.2430
2.2212
0.1094
4886046
5033527
4959787
45336123
64.74211972
165.5880683
AQ-6C
19-546-C
7/1/01 18:30
7/1/01 12:48
13.104
0.2458
3.2006
0.0768
3193164
3204364
3198764
41651603
59.48045242
152.1305336
AR-8A
19-548-A
7/1/01 18:40
7/1/01 12:58
13.111
0.2367
3.1609
0.0749
3256020
3266690
3261355
43552248
62.19466232
159.0725487
AS-8B
19-548-B
7/1/01 19:03
7/1/01 13:21
13.127
0.2255
3.6245
0.0622
14115220
14246556
14180888
227931834
325.4974016
832.510369
AT-8C
19-548-C
7/1/01 20:12
7/1/01 14:30
13.175
0.2899
3.2600
0.0889
3589961
3515397
3552679
39950788
57.05160868
145.9183869
AU-0A
19-550-A
7/1/01 20:23
7/1/01 14:41
13.183
0.2398
3.2371
0.0741
2891043
2827401
2859222
38597112
55.11849553
140.9741486
AV-0B
19-550-B
7/1/01 20:48
7/1/01 15:06
13.200
0.2427
3.1350
0.0774
2839338
2847285
2843312
36727571
52.44870282
134.1457373
AW-0C
19-550-C
7/1/01 21:02
7/1/01 15:20
13.210
0.2311
3.2252
0.0717
2752876
2748928
2750902
38391212
54.82446039
140.2221078
AX-1A
19-551-A
7/1/01 21:19
7/1/01 15:37
13.222
0.2404
3.2845
0.0732
3019402
3010582
3014992
41192767
58.82521296
150.4546565
AY-3A
19-553-A
7/1/01 21:39
7/1/01 15:57
13.235
0.2253
3.3523
0.0672
2447507
2452232
2449870
36452275
52.05556653
133.14023
AZ-3B
19-553-B
7/1/01 21:53
7/1/01 16:11
13.245
0.2335
3.2120
0.0727
2932952
2916062
2924507
40229193
57.44918316
146.9352457
std dev.
average
std dev.
158.7301 18.4648
5.2079
9.2324
137.7449
8.1951
15.7005
4.0976
149.4379 18.1987
9.8541
9.0993
138.4473
15.3493
1.8721
3.7442
160
a
b
c
d = b/(b+c)
e
f=dxe
Mass
Mass
Sample +
Sample
Diluent
Dilution
Factor
Inj A
Inj B
average
Un-Diluted
13.256
0.2493
3.1619
0.0788
2808321
2803633
2805977
Vial
Sample
Date & Time
Date & Time
(GC)
Time
BA-3C
19-553-C
7/1/01 22:09
7/1/01 16:27
Expected
Expected
TCE
remaining
K+ Conc
K+ Released
K+
K+
TCE
Released Released remaining
average
std dev.
average
std dev.
35588523
50.82208756
129.9854151
136.6870
9.0144
16.2295
4.5072
148.6109 10.0698
10.2675
5.0349
146.2155 18.5786
11.4652
9.2893
150.8412
6.3505
9.1524
3.1752
161.7726
6.8329
3.6867
3.4164
160.3191
5.6321
4.4135
2.8161
149.0658
3.6743
10.0401
1.8372
145.2070 12.5788
11.9695
6.2894
IC Peak Area
BB-1A
19-551-A
7/3/01 16:55
7/3/01 11:13
15.038
0.2162
3.1753
0.0681
2793132
2807110
2800121
41124996
58.72843306
150.2071268
BC-3A
19-553-A
7/3/01 17:20
7/3/01 11:38
15.056
0.2282
3.1722
0.0719
2768310
2794481
2781396
38664079
55.21412696
141.2187409
BD-3B
19-553-B
7/3/01 17:27
7/3/01 11:45
15.060
0.2395
3.1798
0.0753
3286235
3315955
3301095
43828066
62.58854436
160.0799635
BE-3C
19-553-C
7/3/01 17:37
7/3/01 11:55
15.067
0.2468
3.1882
0.0774
3044921
3081619
3063270
39571789
56.51037912
144.5341079
BF-8A
19-548-A
7/5/01 1:37
7/4/01 19:55
16.401
0.2926
3.2601
0.0898
3068859
3085579
3077219
34285857
48.96181926
125.2274888
BG-8B
19-548-B
7/5/01 1:42
7/4/01 20:00
16.404
0.2052
2.8684
0.0715
3142882
3146496
3144689
43958216
62.77440429
160.5553292
BH-8C
19-548-C
7/5/01 1:53
7/4/01 20:11
16.412
0.2446
3.1879
0.0767
3204482
3217983
3211233
41852363
59.76714748
152.8638009
BI-0A
19-550-A
7/5/01 2:04
7/4/01 20:22
16.419
0.2559
2.9232
0.0875
3782177
3775995
3779086
43169301
61.64779684
157.673855
BJ-0B
19-550-B
7/5/01 2:08
7/4/01 20:26
16.422
0.2338
3.0517
0.0766
3053401
3034587
3043994
39732064
56.73925957
145.1195054
BK-0C
19-550-C
7/5/01 2:13
7/4/01 20:31
16.426
0.2198
3.0628
0.0718
2937134
2946745
2941940
40994414
58.54195598
149.7301826
BL-Test
DDIWash
BLANK
7/5/01 2:20
7/4/01 20:38
16.431
1.0000
0.0000
1.0000
121095
139666
130381
130381
0.186189499
0.476208682
BLANK
7/5/01 14:00
7/5/01 8:18
16.917
1.0000
0.0000
1.0000
99268
97033
98151
98151
0.14016354
0.358490113
BO-6A
19-546-A
7/7/01 13:59
7/7/01 8:17
18.916
0.2602
2.6414
0.0985
4811412
4617361
4714386.5
47857726.75
61.73019643
157.8846048
BM-6B
19-546-B
7/7/01 13:48
7/7/01 8:06
18.908
0.2364
2.8952
0.0817
4255191
4085613
4170402
51075075.59
66.33504644
169.6622269
BN-6C
19-546-C
7/7/01 13:54
7/7/01 8:12
18.913
0.2518
2.5942
0.0971
4749163
4535204
4642183.5
47826657.81
61.68572881
157.7708719
BP-8A
19-548-A
7/7/01 14:15
7/7/01 8:33
18.927
0.2485
2.7852
0.0892
4389630
4167973
4278801.5
47957013.83
61.87230167
158.2480611
BQ-8B
19-548-B
7/7/01 14:35
7/7/01 8:53
18.941
0.2575
2.7239
0.0945
4831955
4671334
4751644.5
50264094.97
65.17432551
166.693502
BR-8C
19-548-C
7/7/01 14:39
7/7/01 8:57
18.944
0.2676
2.8787
0.0930
4490917
4311738
4401327.5
47347165.45
60.99945247
156.0156131
BS-DDI
BLANK
7/7/01 14:45
7/7/01 9:03
18.948
1.0000
0.0000
1.0000
292077
266874
279475.5
279475.5
-6.36646381
-16.2832241
BT-0A
19-550-A
7/7/01 14:58
7/7/01 9:16
18.957
0.2711
2.6662
0.1017
4786509
4668773
4727641
46495154.68
59.7800069
152.8966909
BU-0B
19-550-B
7/7/01 15:09
7/7/01 9:27
18.965
0.2614
2.8970
0.0902
4146487
4038712
4092599.5
45356774.11
58.15069281
148.729466
BV-0C
19-550-C
7/7/01 15:20
7/7/01 9:38
18.972
0.2577
2.8367
0.0908
4084022
4000095
4042058.5
44494013.76
56.91586184
145.5711932
BW-3A
19-553-A
7/7/01 17:07
7/7/01 11:25
19.047
0.2662
2.7517
0.0967
4407564
4305379
4356471.5
45032692.06
57.68684842
147.5431116
BX-3B
19-553-B
7/7/01 17:32
7/7/01 11:50
19.064
0.2585
2.5829
0.1001
4790648
4710454
4750551
47466917.52
61.17084834
156.4539848
BY-3C
19-553-C
7/7/01 17:22
7/7/01 11:40
19.057
0.2638
2.7637
0.0955
3938044
3828671
3883357.5
40683984.54
51.46273445
131.6239695
BZ-6A
19-546-A
7/13/01 17:25
7/13/01 11:43
25.059
0.2772
3.0377
0.0913
4475750
4367538
4421644
48454646.39
68.95531102
176.3639622
CA-6B
19-546-B
7/13/01 17:28
7/13/01 11:46
25.061
0.2724
3.0557
0.0891
4824606
4734547
4779576.5
53615829.34
76.34228537
195.2573011
161
a
b
c
d = b/(b+c)
e
f=dxe
Mass
Mass
Sample +
Sample
Diluent
Dilution
Factor
Inj A
Inj B
average
Un-Diluted
25.063
0.2905
3.0908
0.0940
4761418
4702736
4732077
7/15/01 23:02
27.531
0.2896
2.8020
0.1034
4883891
4829637
7/15/01 23:05
27.533
0.2842
2.9297
0.0970
4556465
4466414
7/16/01 4:49
7/15/01 23:07
27.534
0.3080
2.9097
0.1059
4945287
4874630
4909958.5
BLANK
7/16/01 4:59
7/15/01 23:17
27.541
1.0000
0.0000
1.0000
264876
266292
19-550-A
7/17/01 5:55
7/17/01 0:13
28.580
0.2922
2.9151
0.1002
4772726
4754465
19-550-B
7/17/01 5:59
7/17/01 0:17
28.583
0.3039
2.8065
0.1083
5620682
5592020
CI-0C
19-550-C
7/17/01 6:03
7/17/01 0:21
28.585
0.2649
2.8507
0.0929
5392873
Vial
Sample
Date & Time
Date & Time
(GC)
Time
CB-6C
19-546-C
7/13/01 17:30
7/13/01 11:48
CC-3A
19-553-A
7/16/01 4:44
CD-3B
19-553-B
7/16/01 4:47
CE-3C
19-553-C
CF-DDI
CG-0A
CH-0B
Expected
Expected
TCE
remaining
K+ Conc
K+ Released
K+
K+
TCE
Released Released remaining
average
std dev.
average
std dev.
50347344.55
71.66424672
183.2924877
184.9713
9.5579
-7.9126
4.7789
4856764
46991204.17
60.43852064
154.5809425
4511439.5
46506559.83
59.74487049
152.8068241
46384760.54
59.57054453
152.3609582
153.2496
1.1744
7.9482
0.5872
265584
265584
-6.437806199
-16.46569339
4763595.5
47523467.63
67.62255578
172.9552328
5606351
51774347.09
73.70665275
188.5162597
5374993
5383933
57938761.05
82.52950757
211.0820869
190.8512 19.1704
-10.8526
9.5852
170.3653
-0.6096
3.2698
IC Peak Area
CJ-3A
19-553-A
7/22/01 16:25
7/22/01 10:43
34.017
0.2815
2.9078
0.0968
4700113
4694412
4697262.5
48521136.4
69.16031056
176.8882805
CK-3B
19-553-B
7/22/01 16:30
7/22/01 10:48
34.021
0.2712
2.9119
0.0931
4186589
4185926
4186257.5
44948241.94
64.04658372
163.8091265
CL-3C
19-553-C
7/22/01 16:34
7/22/01 10:52
34.024
0.2868
2.9070
0.0987
4607461
4616763
4612112
46748290.04
66.62291347
170.3984917
CM-DDI
BLANK
7/22/01 16:40
7/22/01 10:58
34.028
1.0000
0.0000
1.0000
208091
220703
214397
214397
0.020997242
0.053703721
Blank
BLANK
8/7/01 0:00
8/6/01 18:18
49.333
1.0000
0.0000
1.0000
187778
211675
199726.5
199726.5
-0.109835305
-0.280920923
6.5396
162
Table F.16
Sample
19-546
19-547
19-548
Permanganate data from TCE degradation tests.
Bottle Date and Time Time
Mass
Mass
Sample +
Sample
Diluent
6/18/01 16:00
days
g
g
Dilution
Factor
ABS
KMnO4
KMnO4
(Avg of
triplicates)
Std Dev
KMnO4
KMnO4
(Avg of
triplicates)
Std Dev
g/l
g/l
g/l
umol/bottle
umol/bottle
umol/bottle
B
7/1/01 17:40
13.1
1.0000
0
1.0000
-0.0043
0.00E+00
0.000
0.000
0.000
C
7/1/01 17:56
13.1
0.5000
0
1.0000
-0.0037
0.00E+00
0.000
0.000
0.000
A
7/7/01 13:59
18.9
0.2602
2.6414
0.0985
-0.0091
0.00E+00
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
B
7/7/01 13:48
18.9
0.2364
2.8952
0.0817
-0.0047
0.00E+00
C
7/7/01 13:54
18.9
0.2518
2.5942
0.0971
-0.0071
0.00E+00
A
7/13/01 17:25
25.1
0.2772
3.0377
0.0913
-0.0044
0.00E+00
0.000
0.000
0.000
B
7/13/01 17:28
25.1
0.2724
3.0557
0.0891
-0.0085
0.00E+00
0.000
0.000
0.000
C
7/13/01 17:30
25.1
0.2905
3.0908
0.0940
-0.0085
0.00E+00
0.000
0.000
0.000
A
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0112
0.00E+00
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
1.311
0.000
0.000
0.082
0.000
0.000
0.000
0.464
0.734
B
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0014
0.00E+00
C
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0049
0.00E+00
A
9/12/01 14:00
85.9
2.0000
0
1.0000
0.0303
2.07E-03
0.00E+00 0.00E+00
0.00E+00 0.00E+00
0.00E+00 0.00E+00
B
9/12/01 14:00
85.9
2.0000
0
1.0000
0.0019
1.30E-04
C
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0002
0.00E+00
A
7/1/01 18:40
13.1
0.5000
0
1.0000
-0.0011
0.00E+00
0.000
0.000
0.000
B
7/1/01 19:03
13.1
0.5000
0
1.0000
-0.0052
0.00E+00
0.000
0.000
0.000
C
7/1/01 20:12
13.2
0.5000
0
1.0000
-0.0014
0.00E+00
0.000
0.000
0.000
A
7/7/01 14:15
18.9
0.2485
2.7852
0.0892
-0.0051
0.00E+00
0.000
0.000
0.000
B
7/7/01 14:35
18.9
0.2572
2.7239
0.0944
-0.0051
0.00E+00
0.000
0.000
0.000
C
7/7/01 14:39
18.9
0.2676
2.8787
0.0930
-0.0045
0.00E+00
0.000
0.000
0.000
A
9/12/01 14:00
85.9
2.0000
0
1.0000
0.016
1.09E-03
0.692
0.000
0.000
B
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0129
0.00E+00
0.000
0.000
0.000
C
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0099
0.00E+00
0.000
0.231
0.400
7.34E-04
1.16E-03
0.00E+00 0.00E+00
0.00E+00 0.00E+00
3.65E-04
6.31E-04
163
Sample
19-549
19-550
19-551
19-552
19-553
Bottle Date and Time Time
Mass
Mass
Sample +
Sample
Diluent
6/18/01 16:00
days
g
g
Dilution
Factor
ABS
KMnO4
KMnO4
(Avg of
triplicates)
Std Dev
KMnO4
KMnO4
(Avg of
triplicates)
Std Dev
g/l
g/l
g/l
umol/bottle
umol/bottle
umol/bottle
0.000
0.000
0.000
0.000
0.000
0.000
B
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0044
0.00E+00
C
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0004
0.00E+00
A
7/1/01 20:23
13.2
0.5000
0
1.0000
0.0004
2.73E-05
0.017
0.000
0.000
B
7/1/01 20:48
13.2
0.5000
0
1.0000
-0.0005
0.00E+00
0.000
0.000
0.000
C
7/1/01 21:02
13.2
0.5000
0
1.0000
0.0003
2.05E-05
0.013
0.010
0.009
A
7/7/01 14:58
19.0
0.2711
2.6662
0.1017
-0.0055
0.00E+00
0.000
0.000
0.000
B
7/7/01 15:09
19.0
0.2614
2.897
0.0902
-0.0019
0.00E+00
0.000
0.000
0.000
C
7/7/01 15:20
19.0
0.2577
2.8367
0.0908
-0.0025
0.00E+00
0.000
0.000
0.000
A
7/17/01 5:55
28.6
0.2922
2.9151
0.1002
0.0161
1.10E-02
6.949
0.000
0.000
B
7/17/01 5:59
28.6
0.3039
2.8065
0.1083
0.0052
3.28E-03
C
7/17/01 6:03
28.6
0.2649
2.8507
0.0929
0.0234
1.72E-02
A
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.01
0.00E+00
B
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0059
0.00E+00
C
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0098
0.00E+00
A
7/1/01 21:29
13.2
0
1.0000
-0.0018
A
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0091
0.00E+00 0.00E+00
1.60E-05
1.42E-05
0.00E+00 0.00E+00
2.078
0.000
0.000
10.895
6.641
4.417
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.00E+00
0.000
0.000
0.000
0.00E+00
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
1.05E-02
6.98E-03
0.00E+00 0.00E+00
B
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0106
0.00E+00
C
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0089
0.00E+00
A
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.014
0.00E+00
0.000
0.000
0.000
B
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0131
0.00E+00
0.000
0.000
0.000
C
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.013
0.00E+00
0.000
0.000
0.000
A
7/1/01 21:39
13.2
0.5000
0
1.0000
-0.0026
0.00E+00
0.000
0.000
0.000
B
7/1/01 21:53
13.2
0.5000
0
1.0000
-0.0032
0.00E+00
0.000
0.000
0.000
C
7/1/01 22:09
13.3
0.5000
0
1.0000
-0.0031
0.00E+00
0.000
0.000
0.000
A
7/7/01 17:07
19.0
0.2662
2.7517
0.0967
-0.0054
0.00E+00
0.000
0.000
0.000
B
7/7/01 17:32
19.1
0.2585
2.5829
0.1001
0.0044
3.01E-03
1.902
0.000
0.000
C
7/7/01 17:22
19.1
0.2638
2.7637
0.0955
0.0021
1.50E-03
0.952
0.951
0.951
0.00E+00 0.00E+00
0.00E+00 0.00E+00
0.00E+00 0.00E+00
1.50E-03
1.50E-03
164
Sample
Bottle Date and Time Time
Mass
Mass
Sample +
Sample
Diluent
Dilution
Factor
ABS
g
KMnO4
KMnO4
(Avg of
triplicates)
Std Dev
KMnO4
KMnO4
(Avg of
triplicates)
Std Dev
g/l
g/l
g/l
umol/bottle
umol/bottle
umol/bottle
6/18/01 16:00
days
g
A
7/16/01 4:44
27.5
0.2896
2.802
0.1034
0.0233
1.54E-02
9.754
0.000
0.000
B
7/16/01 4:47
27.5
0.2842
2.9297
0.0970
0.0072
5.07E-03
3.211
0.000
0.000
C
7/16/01 4:59
27.5
0.3080
2.9097
0.1059
0.0054
3.49E-03
2.207
5.057
4.098
A
7/22/01 16:25
34.0
0.2815
2.9078
0.0968
0.0063
4.45E-03
2.816
0.000
0.000
B
7/22/01 16:30
34.0
0.2712
2.9119
0.0931
0.0057
4.18E-03
2.648
0.000
0.000
C
7/22/01 16:34
34.0
0.2968
2.907
0.1021
0.009
6.03E-03
3.814
3.092
0.630
A
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0137
0.00E+00
0.000
0.000
0.000
B
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0103
0.00E+00
0.000
0.000
0.000
C
9/12/01 14:00
85.9
2.0000
0
1.0000
-0.0092
0.00E+00
0.000
0.000
0.000
7.99E-03
4.89E-03
6.47E-03
9.96E-04
0.00E+00 0.00E+00
165
166
Appendix G
Polymaleic Acid Addition
Table 0.1
Preliminary data for PMA experiment.
Humic A (2671 mg/L)
Humic C
(1179 mg/L)
Humic B (1870 mg/L)
Time
PA
umol/Bottle
Time
PA
umol/Bottle
Time
PA
umol/Bottle
9/10/01 18:44
2373886
86.48233
9/10/01 18:44
2373886
86.48233
9/10/01 18:44
2373886
86.48233
9/10/01 19:04
2343862
85.38853
9/10/01 19:11
2022614
73.68524
9/10/01 19:18
1619789
59.01005
9/10/01 20:23
2370493
86.35872
9/10/01 20:31
2202997
80.25672
9/10/01 20:38
1705365
62.12764
9/11/01 9:59
2151854
78.39355
9/11/01 10:08
2214525
80.67670
9/11/01 10:15
1629037
59.34696
Humic D (497 mg/L)
Time
PA
umol/Bottle
9/10/01 18:44 2373886
86.48233
9/10/01 19:26
260565
9.49257
9/10/01 20:45
147892
5.38781
9/11/01 10:31
174169
6.34510
Humic G (Water Control)
Time
PA
umol/Bottle
9/10/01 18:44 2373886
86.48233
9/10/01 20:23 2373886
86.48233
9/11/01 10:38 2308698
84.10748
Humic E (112 mg/L)
Time
9/10/01 18:44
9/10/01 19:32
9/10/01 21:08
PA
2373886
25263
0
umol/Bottle
86.48233
0.92035
0.00000
Humic F (0 mg/L)
Time
9/10/01 18:44
9/10/01 19:38
PA
2373886
0
umol/Bottle
86.48233
0.00000
167
Table 0.2
TCE and PMA degradation experiment data.
Bottle
A
B
Water controls
C
D
Humic (1.9g/L)
+ TCE
E
F
Time
Time
TCE
TCE
date and time
9/15/01 10:19
9/15/01 10:39
9/15/01 12:54
9/16/01 6:02
9/15/01 10:25
9/15/01 10:45
9/15/01 13:00
9/16/01 6:12
9/15/01 10:31
9/15/01 10:51
9/15/01 13:10
9/16/01 6:19
9/15/01 10:37
9/15/01 10:57
9/15/01 13:20
9/15/01 22:30
9/16/01 6:27
9/17/01 5:42
9/15/01 10:43
9/15/01 11:03
9/15/01 13:30
9/15/01 22:39
9/16/01 6:35
9/17/01 5:49
9/15/01 10:48
days
0.000
0.014
0.107
0.822
0.000
0.014
0.108
0.824
0.000
0.014
0.111
0.825
0.000
0.014
0.113
0.495
0.827
1.795
0.000
0.014
0.117
0.497
0.828
1.796
0.000
PA
2447626
2447626
2381208
2121142
2365533
2365533
2398354
2163037
2379394
2379394
2278664
2109594
2397518
1928692
2285168
2075563
2073509
2033101
2397518
2156346
2308270
2234768
2495142
2140294
2397518
mol/bottle
89.16872852
89.16872852
86.74907429
77.27468786
86.17802306
86.17802306
87.37371507
78.80095204
86.682989
86.682989
83.01332458
76.85398614
87.34324686
70.26359964
83.25026986
75.61421298
75.53938433
74.0672926
87.34324686
78.55719422
84.09189189
81.41416258
90.89976966
77.97240863
87.34324686
time
days
Average of triplicates
TCE
std dev
mol/bottle
0.000
0.014
0.109
0.824
87.34
87.34
85.71
77.64
1.600948192
1.600948192
2.357930134
1.024463152
0.000

87.34
1.600948192
168
Bottle
G
H
Microspheres +
TCE
I
J
Microspheres +
Humic (1.9g/L)
+ TCE
Time
date and time
9/15/01 11:08
9/15/01 13:37
9/15/01 22:47
9/16/01 6:44
9/17/01 5:56
9/15/01 10:54
9/15/01 11:14
9/15/01 13:11
9/15/01 22:54
9/16/01 6:51
9/17/01 6:04
9/15/01 11:02
9/15/01 11:22
9/15/01 13:51
9/15/01 23:01
9/16/01 6:59
9/17/01 6:11
9/15/01 11:08
9/15/01 11:28
9/15/01 13:57
9/15/01 23:09
9/16/01 7:06
9/17/01 6:17
9/15/01 11:14
9/15/01 11:34
9/15/01 14:24
9/15/01 23:16
9/16/01 7:12
9/17/01 6:23
Time
days
0.014
0.117
0.499
0.830
1.797
0.000
0.014
0.095
0.500
0.831
1.799
0.000
0.014
0.117
0.499
0.831
1.798
0.000
0.014
0.118
0.501
0.832
1.798
0.000
0.014
0.132
0.502
0.832
1.798
TCE
PA
2151971
2213115
2197477
2104674
2186038
2397518
1901935
689612
105671
14868
5078
2397518
1811659
752681
149709
26357
0
2397518
1917008
811216
233357
78745
3126
2397518
2195606
2086488
1970641
1896226
1865488
TCE
mol/bottle
78.39780991
80.62532863
80.05562534
76.67474709
79.63889457
87.34324686
69.2888234
25.12304789
3.8496685
0.541651648
0.184995095
87.34324686
66.00000553
27.42069571
5.454003666
0.96020396
0
87.34324686
69.83794335
29.55316673
8.50135886
2.868735472
0.113882368
87.34324686
79.9874635
76.01221838
71.79183108
69.08084054
67.96103368
time
days
0.014
0.116
0.497
0.828
1.796
0.000
0.014
0.110
0.500
0.831
1.798
Average of triplicates
TCE
std dev
mol/bottle
75.74
4.742968322
82.66
1.808116189
79.03
3.033457391
81.04
8.55941736
77.23
2.859774322

87.34
68.38
27.37
5.94
1.46
0.10
1.600948192
2.075557049
2.215572579
2.362854496
1.240497057
0.093317914
169
Bottle
K
L
Time
date and time
9/15/01 11:19
9/15/01 11:39
9/15/01 14:31
9/15/01 23:23
9/16/01 7:19
9/17/01 6:31
9/15/01 11:25
9/15/01 11:45
9/15/01 14:38
9/15/01 23:32
9/16/01 7:27
9/17/01 6:38
Time
days
0.000
0.014
0.133
0.503
0.834
1.800
0.000
0.014
0.134
0.505
0.834
1.801
TCE
PA
2397518
2381208
2111258
2043625
1985301
1952728
2397518
1948326
1978937
1840127
1897915
1823678
TCE
mol/bottle
87.34324686
86.74907429
76.91460682
74.45068929
72.32590514
71.13924795
87.34324686
70.97888001
72.09406017
67.0371147
69.14237199
66.43786611
time
days
0.000
0.014
0.133
0.503
0.833
1.800
Average of triplicates
TCE
std dev
mol/bottle

87.34
79.24
75.01
71.09
70.18
68.51
1.600948192
7.911731632
2.562678896
3.755838633
1.856031327
2.398752333
170
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