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This is to certify that the
thesis entitled

The Effects of Wetting and Drying on Chromium and Other
Metal Mobility

presented by

Matthew Robert Harold

has been accepted towards fulfillment
of the requirements for the

M§._____ degree in Environmental Geosciences

Major Profesfqg Signature

”4&5 Pfc’ /c o 31.

Date

  

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6/01 cJCIRC/DateDuepss-pJS

THE EFFECTS OF WETTING AND DRYING ON CHROMIUM
' AND OTHER METAL MOBILITY

By

Matthew Robert Harold

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Geological Sciences

2003

ABSTRACT

THE EFFECTS OF WETTING AND DRYING ON CHROMIUM
AND OTHER METAL MOBILITY

By

Matthew Robert Harold

This study looks at the effects that wetting and drying has on Cr mobility in
wetland soils. The source of the chromium was a former leather tannery that
operated from the early 1900’s to 1958. At the wetland site, the dominant form of Cr
is Cr (III). A previous study done at the wetland site reported that soils that
underwent saturation changes in the field released higher levels of chromium to
solution during laboratory leaching studies. This study investigated four questions
(1) is there evidence that wetting and drying enhances chromium mobility? (2) does
the duration of drying affect chromium mobility? (3) do aerobic microbes play a role
in chromium mobility during wetting and drying? (4) how does chromium behavior
compare to other elements?

The results of this study indicate that wetting and drying affects chromium
mobility. Concentrations of chromium increased under wetting and drying cycles
and concentrations of chromium decreased when the soils are always wet. Soils that
were not completely dried did not behave the same as samples that were always wet
or completely dried From the results of this study, the role of microbes in the
mobilization of chromium can neither be supported nor denied. Finally, chromium

behaves differently than Fe, Mn, and Sr under wetting and drying conditions.

To my wife Donna and to my parents and my brother Dave, without whose support

and patience I could not have maintained the will to see this project to its conclusion.

iii

I would like to acknowledge my fellow Geology T.A.s with whom I shared an office
and many good times. I would like to thank the geology faculty for providing me
with a quality education both in the classroom and in the field. I would like to thank
Gary Icopini for his help in the laboratory and the field. I would like to thank Terry
Marsh for his input towards the microbiological portion of this thesis. I would like
to thank my committee members Dr. Hyndman and Dr. Patino for their contributions
in developing and editing my thesis. I would also like to thank Dr. Patino for her
countless hours spent helping me with sample analysis. Finally, I would like to

thank my advisor Dr. David Long for his guidance throughout my Master’s program.

iv

TABLE OF CONTENTS

List ofTahles

List ofFigures.........

Introduction

General Introduction...

IOBaCkground ofthe Suite .

2..00bjectives.. .
3.0 Approach

Site Description..............................

Methods

1.0 Sample Collection...
2.0 DryingCabinet De51gn

3 0 Sample Preparation...

4.0 Total Extractions... .

5 0 Duration of Drying Treatment .

6.0 Chemical Sterilizer Treatments and Distilled Detomzed

Autoclaved WaterTreatment........................
7.0 Always Wet Treatment.............

8.0 Spectrophotometric Methods...

90D‘SSOIVCd0rganlcCaI-b0nAnalys15

10.0 ICP- HEX-MS“

Results and Discussion

1.0 Does wetting and drying increase chromium mobility?... ....
2.0 Does the duration of drying effect chromium mobility?...

3.0 Do aerobic microbes play a role in chromium mobilization
during wetting and drying?...

5.0 Summary of results and discussion...

.vii-xviii

.xix-xx

...l-2

”...2-8

. 8-9

....913

14-16

1 7-20

..21
21-22
22

"...:2223
...23 24

.24-25

.25-26
...26- 27

.27

”.....27" 28

4.0 How does chromium behavior compare to other elements?. ......41-63

Summary and Conclusions

10..Summary.
2. 0 Environmental S1gntficance and Sources of Error...

3. 0 Future research... ..

4.0 Questions for future research...

Appendix I. Method for Nitric Acid Microwave Digestion of Soils...
Appendix II. Method for TOC 5000A: Organic Carbon Analyzer...
Appendix III. ICP-HEX-MS Data Tables...

Appendix IV. ICP-HEX-MS Standard Preparation......

Appendix V. Detailed results for DDAW, formaldehyde, glutaraldehyde,
always wet, and bimonthly treatments for the four elements

(chromium, iron, maganese, and strontium)...

AppendixVI. Dissolved organic carbon results...

Appendix VII. Concentrated nitric acidleaching...

vi

.... ....65-66
.... ..66-68
....68-69
...69-70

73-74

76-80

82-129

131

133-164

166-168

..170-171

173-175

Table 1.

Table 2.

Table 3.

Table 4.

Table 5.

Table 6.

Table 7.

Table 8.

Table 9.

Table 10.

Table 1 1.

LIST OF TABLES

Microcosm site characterization... .....20

Aqueous results for chromium for the four treatments DDAW,
Formaldehyde, Glutaraldehyde, Always Wet, and Bimonthly
forthesamplelocations... . 30

Aqueous results for distilled deionized water (DDAW) treatment
for the four elements investigated chromium, iron, manganese,
and strontium... ......42

Aqueous results for the formaldehyde treatment for the four elements
investigated chromium, iron, manganese, and strontium ............... 42

Aqueous results for the glutaraldehyde treatment for the four elements
investigated chromium, iron, manganese, and strontium... ...43

Aqueous results for the always wet treatment for the four elements
investigated chromium, iron, manganese, and strontium ............... 43

Aqueous results for the bimonthly treatment for the four
elements investigated chromium, iron, manganese, and
strontium ....44

Aqueous results for iron for the four treatments DDAW,
formaldehyde (F), glutaraldehyde (G), always wet (AW), and
bimonthly (BM) for the sample locations... .. .. ...44

Aqueous results for manganese for the four treatments DDAW,
formaldehyde (F), glutaraldehyde (G), always wet (AW) and
bimonthly (BM) for the sample locations... . . ...45

Aqueous results for strontium for the four treatments DDAW,
formaldehyde (F), glutaraldehyde (G), always wet (AW) and
bimonthly (BM) for the sample location... .. .....46

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site J19 weekly wetting and drying experiment for sampling
intervals 1-24... .82

vii

Table 12.

Table 13.

Table 14.

Table 15.

Table 16.

Table 17.

Table 18.

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site J19
weekly wetting and drying experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (A5), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site 123 weekly wetting and drying experiment for sampling
intervalsl-24... . . . . ..........84

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (N 1), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site 123
weekly wetting and drying experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site K22 weekly wetting and drying experiment for sampling
intervalsl-24... . 86

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site K22
weekly wetting and drying experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site N23 weekly wetting and dryrng experiment for sampling
intervals 1-24... .. . . . . 88

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scanditun (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site N23
weekly wetting and drying experiment for sampling intervals

viii

Table 19.

Table 20.

Table 21.

Table 22.

Table 23.

Table 24.

Table 25.

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site 022 weekly wetting and drying experiment for sampling
intervals 1-24... .90

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site 022
weekly wetting and drying experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site P25 weekly wetting and drying experiment for sampling
intervalsl-24... 92

ICP-MS-I-IEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site P25
weekly wetting and drying experiment for sampling intervals

1-24... .. . . .. 93

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site J19 bimonthly wetting and drying experiment for sampling
intervals 1-13... ....94

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scanditun (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site J 19
bimonthly wetting and drying experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmitun (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site J23 bimonthly wetting and “drying experiment for sampling
intervalsl- 13.. . ......96

ix

Table 26.

Table 27.

Table 28.

Table 29.

Table 30.

Table 31.

Table 32.

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site J23
bimonthly wetting and drying experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site K22 bimonthly wetting and drying experiment for sampling
intervalsl- 13.. . .. 98

ICP-MS-I—IEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site [(22
bimonthly wetting and drying experiment for sampling intervals

ICP-MS-I-IEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site N23 bimonthly wetting and drying expenment for sampling
intervalsl- 13.. ....100

lCP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site N23
bimonthly wetting anddrying experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (A5), baritun (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron We), and magnesium (Mg) in ug/L for

site 022 bimonthly wetting and drying expenment for sampling
intervalsl- 13. ......102

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontitun (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site 022
bimonthly wetting and drying experiment for sampling intervals

Table 33.

Table 34.

Table 35.

Table 36.

Table 37.

Table 38.

Table 39.

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site P25 bimonthly wetting and drying experiment for sampling
intervalsl- 13.. .. . 104

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site P25
bimonthly wetting and drying experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium Mg) in ug/L for

site J19 bimonthly DDAW wetting and drying experiment for
samplrngrntervals 1-7 .........106

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in pig/L for site .119
bimonthly DDAW wetting and drying experiment for sampling
intervals] 7. .....106

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (A5), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site J23 bimonthly DDAW wetting and drying expertment for
sampling intervals 1-7... .. .. . 107

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scanditnn (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site J23
bimonthly DDAW wetting and drying expenment for sampling
intervals 1-7... . .....107

ICP-MS-I-IEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site K22 bimonthly DDAW wetting and drying experiment for
sampl1ng1ntervalsl-7.. .........108

xi

Table 40.

Table 41.

Table 42.

Table 43.

Table 44.

Table 45.

Table 46.

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site K22
bimonthly DDAW wetting and drying expenment for sampling
intervalsl-7... .....108

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site N23 bimonthly DDAW wetting and drying experiment for
sampling intervals 1-7... . ........109

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site N23
bimonthly DDAW wetting and drying experiment for sampling
intervals 1-7... . .....109

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site 022 bimonthly DDAW wetting and drying expenment for
sampling intervals 1 7. . .... .1 10

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site 022
bimonthly DDAW wetting and drying experiment for sampling
intervals 1-7... .....110

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site P25 bimonthly DDAW wetting and drying experiment for
samplingintervals 1-7... ..... . .........lll

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site P25
bimonthly DDAW wetting and drying expenment for sampling
intervalsl-7... .....111

xii

le 47.

le 48.

le 49.

[e 50.

le 51.

ie 52.

e 53.

ICP-MS-HEX data of aqueous concentrations of aluminum (Al ),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site .119 bimonthly formaldehyde treatment wetting and drying
experiment for sampling intervals 1-7... . ...112

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in rig/L for site J 19
bimonthly formaldehyde treatment wetting and drying experiment for
sampling intervals l-7..... ...1 12

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site J 23 bimonthly formaldehyde treatment wetting and drying
experiment for sampling intervals l-7...... . 1 13

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site 123
bimonthly formaldehyde treatment wetting and drying experiment for
samplingintervalsl-7... . ..113

ICP-MS-HEX data of aqueous concentrations of aluminum (Al ),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site K22 bimonthly formaldehyde treatment wetting and drying
experiment for sampling intervals l-7...... .........1 14

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site K22
bimonthly formaldehyde treatment wetting and drying experiment for
samplingintervalsl-7... ...114

lCP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site N23 bimonthly formaldehyde treatment wetting and drying
experiment for samplingintervals l -...7 ..........115

xiii

Table 54.

Table 55.

Table 56.

Table 57.

Table 58.

Table 59.

Table 60.

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site N23
bimonthly formaldehyde treatment wetting and drying experiment for
samplingintervalsl- 7. ..115

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site 022 bimonthly formaldehyde treatment wetting and drying
experiment for samplingintervalsl -7... . ......116

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site 022
bimonthly formaldehyde treatment wetting and drying experiment for
sampling intervals 1-7116

lCP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site P25 bimonthly formaldehyde treatment wetting and drying
experiment for sampling intervals 1-7... .... .1 l7

ICP-MS-l-{EX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site P25
bimonthly formaldehyde treatment wetting and drying experiment for
sampling intervals 1-7..... ....117

lCP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site J 19 bimonthly glutaraldehyde treatment wetting and drying
experimentforsamplingintervals1-7.. .......118

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in rig/L for site .119
bimonthly glutaraldehyde treatment wetting and drying experiment
for sampling intervals 1-7..... ......118

xiv

Table 61.

Table 62.

Table 63.

Table 64.

Table 65.

Table 66.

Table 67.

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium

(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for

site J 23 bimonthly glutaraldehyde treatment wetting and drying
experiment for sampling intervals 1-7...... ..1 19

lCP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site J23
bimonthly glutaraldehyde treatment wetting and drying experiment
for sampling intervalsl- 7... ...119

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in rig/L for

site K22 bimonthly glutaraldehyde treatment wetting and drying
experiment for sampling intervals 1-7...... .....120

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site K22
bimonthly glutaraldehyde treatment wetting and drying experiment
forsamplingintervalsl -...7 ..120

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in pg/L for

site N23 bimonthly glutaraldehyde treatment wetting and drying
experiment for sampling intervals 1-7 .................................... 121

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site N23
bimonthly glutaraldehyde treatment wetting and drying experiment
forsamplingintervalsl-7... ...121

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in rig/L for

site 022 bimonthly glutaraldehyde treatment wetting and drying
experiment for sampling intervals l-7...... 122

XV

Table 68.

Table 69.

Table 70.

Table 71.

Table 72.

Table 73.

Table 74.

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in pg/L for site 022
bimonthly glutaraldehyde treatment wetting and drying experiment
for sampling intervals l-7.. .... ..122

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in rig/L for

site P25 bimonthly glutaraldehyde treatment wetting and drying
experiment for sampling intervals] -...7 .. .. .....123

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in rig/L for site P25
bimonthly glutaraldehyde treatment wetting and drying experiment
for samplingintervals 1-7... .123

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for
site J 19 bimonthly always wet experiment for sampling intervals

lCP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site .119
bimonthly always wet experiment for sampling intervals 2-7. .. .. 124

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for
site .123 bimonthly always wet experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in rig/L for site .123
bimonthly always wet experiment for sampling intervals 2-7. .. .. 125

xvi

Table 75.

Table 76.

Table 77.

Table 78.

Table 79.

Table 80.

Table 81.

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for
site K22 bimonthly always wet experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of manganese Gun),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site K22
bimonthly always wet experiment for sampling intervals 2-7. .. ..... 126

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in rig/L for
site N23 bimonthly always wet experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site N23
bimonthly always wet experiment for sampling intervals 2-7. .. .. 127

ICP-MS-HEX data of aqueous concentrations of aluminum (A1),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for
site 022 bimonthly always wet experiment for sampling intervals

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site 022
bimonthly always wet experiment for sampling intervals 2-7.. . .. 128

ICP-MS-HEX data of aqueous concentrations of aluminum (Al),
arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium
(Cr), copper (Cu), iron (Fe), and magnesium (Mg) in ug/L for
site P25 bimonthly always wet experiment for sampling intervals

xvii

Table 82.

Table 83.

ICP-MS-HEX data of aqueous concentrations of manganese (Mn),
nickel (Ni), lead (Pb), selenium (Se), scandium (Sc), strontium (Sr),
titanium (Ti), Vanadium (V), and zinc (Zn) in ug/L for site P25
bimonthly always wet experiment for sampling intervals 2-7. .. .. 129

Concentration of chromium from concentrated nitric acid leaching
including the order from highest concentration (1) to lowest
concentration (6) of chromium in soil and in the solution from the
distilled deionized autoclaved water treatment... 171

xviii

rel.

re 2.

re 3.

re 4.

re 5.

re 6.

re 7.

re 8.

re 9.

re 10.

rell.

re 12.

re 13.

re 14.

re 15.

re 16.

re 17.

re 18.

re 19.

LIST OF FIGURES

Conceptual Model of Chromium Geochemistry in Oxic

Aqueous Systems

Total concentration of chromium in the soil ananged in order
of highest to lowest amount of chromium present in the

microcosm exchange water...

Graphs of chromium concentration vs. time for exchange fluids

from the intact soil core microcosm............
Sampling grid with experiment sites starred...

Sampling grid with soil types...

Chromium vs. time for DDAW (Distilled Deionized Autoclaved

Water)treatment...................................
Chromium vs. time foralways wet treatment...
Chromium vs. time for formaldehyde treatment... ..
Chromium vs. time for the glutaraldehyde treatment... ..

Chromium vs. time for bimonthly treatment...

Iron vs. time forDDAW treatment... .. .. ..

Iron vs. time foralways wettreatment... ..

Iron vs. time for formaldehyde treatment......

Iron vs. time for glutaraldehyde treatment... ..

Iron vs. time forbimonthly treatment...

Manganese vs. time for DDAW treatment...

Manganese vs. time for the always wet treatment...
Manganese vs. time for the formaldehyde treatment ..................

Manganese vs. time for the glutaraldehyde treatment... ..

xix

l8

19

32

.33

36

.37

...38

...47

.48

.49

...50

51

....52

53

54

55

,_:‘r.. 1..“ ‘. he

Figure 20.
Figure 21.
Figure 22.
Figure 23.
Figure 24.
Figure 25.

Figure 26.

Figure 27.

Manganese vs. time for bimonthly treatment... ...56

Strontium vs. time for DDAW treatment...... ....57
Strontium vs. time forthe always wet treatment........ .....58
Strontium vs. time for the formaldehyde treatment... ..59
Strontium vs. time forthe glutaraldehyde treatment... ...60
Strontium vs. time for bimonthly treatment... ....61

Graph of chromium concentrations vs. dissolved organic matter
concentrations for the weekly sampling interval... ..167

Graph of chromium vs. dissolved organic matter concentrations
for the bimonthly sampling interval... .. 168

INTRODUCTION

Chromium, mainly in the form of Cr (III), was discharged as waste from a
tannery into a wetland from the early 1900’s to 195 8. The elevated concentrations
of chromium in the wetland soils and sediments were a cause for concern because
the negative impact of chromium on the ecosystem and human health (Ellis, 1999).
Chromium has two redox states, C1 (111) and Cr (V1). C1 (111) is the less toxic form
of chromium found in the environment. Cr(HI) was the dominant form discharged at
the former tannery site (Icopini et al., 1997, 1998, and 1999). In the aqueous phase,
trivalent chromium is kinetically stable and is found as Cr(OH)2+ and organic
complexes (Hem, 1985). In the aqueous phase, trivalent chromium can become
hexavalent chromium via slow oxidation (Takacs, 1988). Manganese oxides can
also oxidize trivalent chromium (Hem, 1985). Hexavalent chromium is
thermodynamically stable, and hexavalent chromium can become trivalent chromium
in the aqueous phase via reduction by 82', F e2+, and organic acids (Takacs, 1988).

Chromium concentrations near the tannery were evaluated because of the
location of the contamination. The site’s close proximity to a major Great Lakes
waterway lead to concern for increased mobility of chromium in solution In
addition to being close to a major waterway, there was increased interest for
contamination in wetland areas. The hydrology and soils associated with wetland
areas pose a greater threat for mobility than sites associated to upland hydrology and
soils. The water table was near the surface and in contact to areas contaminated with

chromium. Furthermore, wetland soils have a high percent of organic matter relative

to upland soils. The high percent of organic matter was of interest because
chromium complexes with organic matter. Degradation of the organic matter could
lead to an increase in chromium mobility. Processes that would impact the state and
mobility of chromium are important for this wetland. One possible process that
would impact chromium mobility is wetting and drying. This study investigated the

role of wetting and drying on chromium mobility.

1.0 Background of the Site

This section will describe the procedures and findings of Ellis (1999) and
Icopini et al. (1997, 1998, and 1999) at the same site location as this study. The site
is located in Michigan’s Upper Peninsula. It is situated in a wetland area adjacent to
a major waterway. Two remediation strategies that were proposed for the wetland
were the (l) removal of the soil from the site and (2) in situ stabilization of the
chromium in the soils. To assess the feasibility of in situ stabilization of chromium
in the soils, Ellis (1999) and Icopini et al. (1997, 1998, and 1999) utilized field and
laboratory tests to investigate the cunent state of chromium at the wetland and
possible mechanisms for its release from the soil.

Ellis (1999) and Icopini et al. (1997, 1998, and 1999) took soil samples
throughout the wetland at three depth intervals (O-O.5 ft, 1-1.5 ft, and 3-3.5 ft) to
determine the oxidation state and spatial distribution of chromium. In addition, Ellis
(1999) and Icopini et al. (1997, 1998, and 1999) did selective chemical extractions
on the sediments to assess the partitioning of chromium among soil phases at the

wetland. From that work, the substrates that control chromium immobilization were

determined to be iron oxides, Cr(OH)3, and organic matter. An illustration of the
possible roles of these substrates in the cycling of chromium in oxic systems based
on theoretical considerations and laboratory studies is presented in Takacs (1988).
Figure 1 shows the mechanisms associated with the sequestering of chromium with
different phases (e. g. iron oxides, organic matter, and manganese oxides). Across the
sediment/water interface, trivalent chromium is sequestered by Cr (OH); and (Fe,
Cr)(OH)3 by precipitation in the solid phase. Adsorption is the means by which
trivalent chromium is sequestered by iron oxides, clays, solid organics, and
manganese oxides. In the sediment, manganese oxides rapidly oxidize and return
trivalent chromium to solution as hexavalent chromium. In the sediment, oxidation
and re-adsorption can transfer chromium (VI) from manganese oxides to iron oxides.
Hexavalent chromium in the aqueous phase is sequestered by iron oxides via
adsorption when chromium moves across the sediment/water interface. The findings
of Ellis (1999) and Icopini et al. (1997, 1998, and 1999) support Takacs’ (1988)
model of chromium aqueous geochemistry in oxic systems. The two studies find
that chromium associates with similar’phases (e. g. iron oxides and organic matter).
This study will investigate which phase (e.g. iron oxides and organic matter) controls
chromium mobility in wetting and drying cycles.

Icopini et al. (1998 and 1999) compared the concentration of chromium in
microcosm fluids with the concentration of chromium in the soil. Chromium
concentrations in the soil were determined by summing the concentrations of
chromium found in the various phases of the soil. The results of this comparison are

presented graphically in figure 2. The x-axis of figure 2 is labeled with the six

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microcosm sites. The sites are arranged left to right in order of highest to lowest
amount of chromium present in the microcosm exchange fluid. On the y-axis, the
concentration of total chromium in the soil is represented in mg/kg. The highest
chromium concentration in the soil was found in sample K22. However, compared
to J19, J23, N23, 022, and P25, K22 had a lower chromium concentration in the
microcosm exchange fluid than J19, P25, and N23. Thus, the concentration of
chromium in the soil (Figure 2) does not determine its concentration in the exchange
fluids, which is presented in color in Figure 3.

In addition, Icopini et al. (1998, 1999) assessed the possible factors that could
limit chromium mobility from the soil. They utilized an intact soil core microcosm
in the laboratory to evaluate the effects of acid rain on metal mobility. Soils used for
the microcosm were acquired, using a split spoon corer, from six different locations
at the wetland site that represented the difl’erent redox conditions and saturation
states. Results of the acid rain simulation showed that chromium concentrations in
the microcosm solutions were initially high and then decreased over time (Figure 3).

From observations presented by Ellis (1999) and Icopini et al. (1997, 1998,
and 1999), the field saturation state of the soils collected for the microcosm
experiments can be divided into three categories (always dry, cyclicly wet and dry,
and always wet). Site J19 was always dry, sites N23 and P25 were periodically wet
and dry; and sites K22, 123, and 022 were always wet.

A connection was found between the total concentration of chromium in the
soil (Figure 2) and the microcosm exchange fluids from the intact soil core

microcosm (Figure 3). The highest concentrations of chromium in the microcosm

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exchange fluids were associated to the sites whose field saturation state was either
always dry or cyclicly wet and dry. There was no correlation found between the
total concentration of chromium in the soil with the chromium concentration in the
microcosm exchange fluids. When the soils were analyzed using sequential chemical
extractions, Icopini et al. (1998) noted that P25 and N23 had lower chromium
concentrations than J19, J23, and K22. However, the results from the microcosm
exchange fluids showed that the chromium concentrations from P25 and N23
(cyclicly wet and dry sites) were higher than the concentrations from K22, J23 and
022 (always wet sites). These results were interpreted to indicate that soils that were
always wet would tend to have the greatest capacity to immobilize chromium,
perhaps through the formation of Cr(OH)3 or by sorption on organic matter. On the
other hand drying or decreasing the saturation state and then subsequent rewetting

may increase chromium mobility.

2.0 Objectives

Field observations by Ellis (1999) and Icopini (1997, 1998, and 1999) noted
that some sites would be wet during some observation periods. Additional studies
reported that soils from the sites that underwent saturation changes in the field
released higher levels of chromium to solution during laboratory leaching studies.
The intact soil core microcosm work performed by Icopini et al. (1998 and 1999),
showed a possible correlation between the field saturation state of the soil and the

ease of metals (e. g. chromium) to mobilize. The field observations and laboratory

results from the intact soil core microcosm led to the questions that are the focus of
this research.

The objective of this thesis is to address the role of wetting and drying on
chromium mobility. The mechanisms of chromium mobility will be evaluated by (l)
aerobic microbes degrading organic matter releasing chromium to solution, (2) the
cycling of iron oxides liberating chromium when the soil is re-wet, and (3) the
solubility or detachment of soil particles containing chromium. The questions
addressed in this study were (1) is there evidence that wetting and drying enhances
chromium mobility? (2) are microbes, through aerobic processes, degrading organic
matter and releasing chromium to solution? (3) does the cycling of iron oxides
liberate chromium when the soil is re-wet? (4) is solubility or detachment from

particles the main mechanism for chromium mobility from soil?

3.0 Approach

Various researchers have investigated the effect of wetting and drying on the
biogeochemistry of soils (e.g. nitrogen accumulation and Te mobility). Haynes and
Swift (1989) looked at changes in the accumulation of nitrogen and pH in air-dried
soils that had been re-wet. This was done because re-wetting soil results in higher
microbial activity which leads to an accumulation of nitrogen in the soil. Eight
different non-hydric soils, seven silt-loams and one clay-loam, were used in the
experiment to evaluate the influence of wetting and drying on different soil types.
Soil samples were dried in a drying cabinet for 48 hours at 22°C. The duration of the

experiment was six weeks. At the end of each 48-hour drying period, the soil

samples were analyzed for pH, ammonium, microbial activity, and nitrate. Microbial
activity was limited in some samples by means of fumigation with chloroform. Two
major conclusions were reached from this study. First, concentrations of nitrate
and/or ammonium increased after every re-wetting event. Second, the pH of soils
was not affected by the microbial community and the processes of re-wetting air-
dried soils. Crozier et al. (1995) looked at the production of methane and reduced
sulfur gas from dried and re-wet wetland soils and noted that methane production
increased upon re-wetting. Alter re-wetting an increase in available carbon for
methane production was also noted which agrees with the work done by Hall and
Hall (1996).

Westfall et al. (1973) investigated the effects of wetting and drying on the
concentration of aluminum in acidic soils. The soils were dried for seven days at
105°C. The duration of re-wetting period was also seven days. From their research,
they noted that aluminum concentrations decreased after one wetting and drying
cycle. Furthermore, they concluded that organic matter influences the amount of
aluminum that can be extracted from soils. Haynes and Swift (1991) looked at the
change in the mobility of Cu, Zn, Fe, and Mn in soils that were both air-dried and
oven-dried and then re-wet. The air-dried soils were maintained in a 22°C cabinet
that had air circulation for a 48-hour period. The oven-dried soils were maintained at
100°C for 48 hours. Sequential extractions were performed on the air dried, and
oven dried soils. Soil samples were re-wet on weeks one, two, four, and eight of the
experiment. Haynes and Swifi (1991) noted that the mobility of Cu and Zn increased

following the drying. From the sequential chemical extractions, Cu and Zn

10

concentrations decreased in the soil after drying. Tagami and Uchida (1996)
evaluated the mobility of Tc in waterlogged soils from rice paddy fields. Tc (VII) is
the most mobile and plant available form of To which is a contaminant from nuclear
weapons and power facilities. The soils were air-dried, sieved and then saturated and
analyzed. Tagami and Uchida (1996) concluded that under saturated conditions, Eh
values are low indicating reducing conditions, and Tc (VII) was transformed to To
(IV) by the microorganisms in the soil. Thus under reducing conditions, the
availability of Te to plants is lowered. Tagami and Uchida (1999) continued their
work on the rice paddy soils. In the next set of experiments, they kept the soils at
5°C before use. The soils were then waterlogged and kept in a dark room for 52
days. The soils were then sampled at day 1, 5, 14, 30, and 52 using selective and
sequential extraction methods. They also performed an air-drying experiment on the
waterlogged soil. Tagami and Uchida (1999) concluded that once Tc (VII) was
transformed to its less mobile forms such as TcOz, TcSz, or organically bound Tc via
microbial processes, Tc would not re-mobilize under wetting and drying cycles.

A generalized conclusion is that wetting and drying does have an impact on
the concentration of metals in the soil (e. g. Cu, Zn, Al, Tc). From these studies it
was shown that wetting and drying released Cu, Zn (Haynes and Swift, 1991) and To
(Tagami and Uchida, 1996). However, the studies varied in their approach and
execution (e. g. type of soil, drying techniques, drying/wetting periods). The
variability of experimental parameters makes it difficult to compare these studies.

To assess the role of microbes in chromium mobility as it pertains to wetting

and drying, sterilizing agents were used to kill the microbes during every

11

wetting/drying interval. Past wetting and drying experiments have used chloroform

and autoclaving as sterilizers. Sterilizers have been evaluated for their effectiveness

in killing certain classes of microorganisms (O’Leary, 1989). Haynes and Swift

(1989, 1991) used chloroform. Chlorofonn is a bacterialcidal agent, but is not

effective against spore formers. Alef and Nannipieri (1995) concluded that

chloroform might not be appropriate for element mobility studies because
chloroform accelerates the decomposition of soil organic matter. Jenkinson and

Powlson (1976) concluded that fumigation destroys the fine structure of the soil.

Tagami and Uchida (1996) autoclaved the soils to inhibit microbial activity.

Autoclaving is a procedure that uses steam under pressure destroying the structure of

the soil, and liberating high concentrations of organic substances (Alef and

Nannipieri, 1995).

Another method for sterilization is applying a liquid sterilizer. Formaldehyde
and glutaraldehyde are effective against all bacteria, viruses, fungi, and spore
formers (O’Leary, 1989).

Previous studies on wetting and drying were used as a guide in the design of this
study. For this project the methods were evaluated from the previous studies and
were modified to fit our objectives.

I Previous studies only examined the solid phase (Haynes and Swift, 1989; Crozier
et al., 1995; Hall and Hall, 1996; Westfall et al., 1973; Haynes and Swift, 1991;
Tagami and Uchida, 1996; and Tagami and Uchida, 1999). This study evaluated
metals in the aqueous phase because the aqueous phase is more sensitive to

subtle changes in the mobility of chromium.

12

The duration of the experiment was expanded to evaluate the effects of wetting
and drying over a longer period of time. Other scientists ended their studies at 52
days. This study continued for 90 days.
Of the previous studies, only one, Tagami and Uchida (1999), studied what
happened when a soil remained saturated for the duration of the experiment. The
continually saturated study was expanded to both hydric and non-hydric soils in
this study.

Testing both hydric and non-hydric soils allows us to investigate the role of
organic matter in chromium mobility during wetting and drying cycles.
An air-dried approach was used in this project because room temperature falls
within the environmental range of temperatures at the field site. In addition,
using oven dried soils would impact the soil structure differently than drying
soils within the normal environmental range of temperatures for the wetland site.
Release of chromium from organic matter by degradation induced by aerobic
microbes is evaluated Other studies used a furnigant or a physical process to kill
the microbes in the soil. In this study formaldehyde and glutaraldehyde, which
are both chemical sterilizers, were used to kill microbes.
Research has been presented on the importance of wetting and drying for several
elements including Tc, Cu, Zn, Fe, and Mn. For this study, the mobility of
several elements was investigated. The elements of interest were chromium,
iron, manganese, and strontium. These elements were selected for their
concentrations and environmental behavior. Chromium and strontium have not

been studied before in the context of wetting and drying.

13

THIS STUDY

As was illustrated in the early discussion on wetting and drying of soils,
research groups have performed wetting and drying experiments to ascertain a
variety of parameters including mobility of metals at room temperature or at higher
temperatures using an oven. An oven was not used in this study because the fine
structure of the soil would be damaged thereby restricting the evaluation of the
microbial activity on metal mobility. For this study, the soils were dried at room
temperature. This was done because room temperature falls within the normal
environmental range of temperatures found at the wetland site. The air temperature
at the site can range from below 0°C to a high around 30°C; therefore, using a drying
cabinet at 22°C is within the normal temperature range at the site. Four aspects of
this experiment are presented in this section.

The first aspect to be evaluated is the analysis of the liquid phase. Previous
works (Westfall et al., 1973; Crozier et al., 1995; Hall and Hall, 1996; Haynes and
Swift, 1991; and Tagami and Uchida, 1999) analyzed the solid phase in their
experiments. Using the liquid phase in this study allows us to observe/examine
small-scale variations and elements of low concentration. The instrument used to
analyze the liquid filtrate was the Micromass Platform Inductively Coupled Plasma
Mass Spectrometer with a hexapole collision cell (ICP-HEX-MS) where
concentrations can be quantified in the ng/L range. In addition to the liquid phase,

the solid phase was evaluated using concentrated nitric acid extractions.

l4

A second aspect investigated was the microbial inhibitors used in the
experiment. In this study, the chemicals used for sterilization were formaldehyde
and glutaraldehyde. Neither formaldehyde nor glutaraldehyde had been used in
previous wetting and drying studies (Haynes and Swift, 1991and Tagami and
Uchida, 1999). Formaldehyde and glutaraldehyde were selected on the basis of their
ability to kill microbes without disturbing the texture of the soil.

Another aspect of this experiment was the duration of the experiments. The
first experiment (weekly and bimonthly drying treatments) lasted for six months, and
the second experiment (DDAW, formaldehyde, glutaraldehyde, and always wet
treatments) lasted for three months. Of the previous wetting and drying studies the
longest duration of a wetting and drying experiment was 52 days by Tagami and
Uchida (1999). The longer duration of the experiment allowed for an evaluation of
the effects of wetting and drying over time.

Previous studies concentrated on one or two elements. Multi-element analysis
using the Micromass Platform ICP-HEX—MS allows for comparisons between a host
of redox sensitive and non-redox sensitive elements. The complete list of elements
analyzed is presented in the methods section. For this study, the elements of
particular interest were chromium, iron, manganese, and strontium. Each was
selected for unique geochemical characteristics that could be used in evaluating the
controlling factors of chromium mobility. Chromium (III) and (VI) are the two
dominant valence states for chromium in the environment where chromium (V1) is
the more toxic and mobile (Bartlet and James, 1979 and Hem, 1985). At the

wetland site, the dominant form of chromium is chromium (III) (Ellis, 1999). In

15

soils, chromium favors the chromium (Ill) valence state and complexes with organic
matter (McBride, 1994). In addition to chromium’s tendency to complex with
organic matter, chromium will substitute for iron and form an insoluble precipitate
Cr(OH)3. Mechanisms that may induce chromium to liberate from the soil need to
be evaluated Iron and manganese were selected for being elements that undergo
oxidation-reduction and for their sequestering of chromium to iron and manganese
oxy-hydroxides (Ellis, 1999). Manganese complexes with carbonates and oxides not
associated with chromium, but it is a redox sensitive element (Hem, 1985 and
McBride, I994). Manganese oxides convert Cr (III), the less toxic state, to Cr (VI),
the toxic state. Iron is important to study because Fe-oxides commonly sequester
chromium. Finally, strontium was selected because it is not an oxidation/reduction
sensitive element. Strontium represents the entire class of redox independent
elements. Strontium is commonly found in carbonates, and its concentration is
controlled by carbonate solubility. Strontium can replace calciwn in carbonate
minerals due to similar chemical characteristics (Hem, 1985).

Images in this thesis are presented in color.

16

SITE DESCRIPTION

The site of investigation is a former tannery in Northern Michigan that
operated from the early 1900’s to 1958. A wetland area is adjacent to the waste
disposal site for the tannery (Ellis, 1999). The wetland area is a classified as a mix
of unconsolidated bottom, forested, and scrub-shrub wetlands (Cowardin et al.,
1979). The sampling grid used is presented in Figure 4, and soil types present at the
site are represented in Figure 5. Six locations were chosen for this study. These
locations were the same sites used in the intact soil core microcosm experiments
done by Ic0pini (1998, 1999).

The six sites selected for investigation were J19 (005 feet), J23 (0-0.5 feet),
[(22 (0-0.5 feet), N23 (0-0.5 feet), 022 (3-3.5 feet), and P25 (005 feet). The sites
are characterized further by pH, percent soil organic matter, iron concentration,
chromium concentration, saturation state, and depths in Table l. Site J19 is always
dry, contains a high percentage of organic matter, and has relatively high chromium
concentrations. Sites N23 and P25 exhibit cyclic wet and dry conditions in the field,
contain a high percentage of organic matter, and have relatively high chromium
concentrations. Sites J23 and K22 are continuously water saturated in the field,
contain a high percentage of organic matter, and have relatively high chromium
concentrations. Site 022 is always water saturated, contains a low percentage of

organic matter, and has relatively low chromium concentrations.

17

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METHODS

1.0 Sample Collection

Soil samples were collected on October 12, 1998, and were taken from the
same depths as the samples collected for the microcosm experiments performed by
Icopini et al. (1997, 1998, and 1999) and Ellis (1999). The samples collected from
0-0.5 feet depth were scooped using a clean plastic cup. The sites sampled at this
shallow depth were J19, J23, K22, N23, and P25. Sediment at each site was
homogenized using a plastic bucket and transferred into nine separate plastic
urinalysis cups. Each cup held approximately 250 grams of saturated sediment A
hand corer was used to excavate a hole to a depth of 3-3.5 feet to collect the samples
at site 022. The sediment from 022 was homogenized in a plastic bucket and
separated into nine plastic cups. The 54 cups of sediment were stored on dry ice for
transport back to the laboratory, where they were placed in a freezer until the

experiments were carried out.

2.0 Drying Cabinet Design

A cabinet was designed for the experiments to house the drying vessels and
to circulate filtered air that would come in contact with the soils. The drying cabinet
was a RubbermaidTM 33.5 x 21 x 10.8 inch jumbo clear plastic box with a removable
snap on lid. Two holes were cut at one end of the cabinet. A sterile plastic filter cup
made by Corning containing a 0.45 pm filter was inserted into one of the holes. The

filter cup had a plastic attachment where a vacuum could be attached to pull air

21

through the filter. A fan was placed in front of the filter cup cap to circulate air
throughout the cabinet. A hose was placed through a second hole in the cabinet and

attached to a second vacuum to remove the filtered, excess air out of the box.

3.0 Sample Preparation

The samples were thawed and placed in a glove bag filled with nitrogen. The
nine plastic cups for each site were combined and homogenized in a bucket inside
the glove bag. Centrifuge tubes and watch glasses used for the wetting and drying
experiments and for total extractions were weighed using a scale inside the glove
bag. Exactly fifteen grams of homogenized sample were then separated into 50-
milliliter centrifuge tubes for the experiments. Since 30 milliliters of water were
necessary for experiments, 15 grams of saturated soil was the maximum amount of
soil that could be placed in the centrifuge tube. Six to ten grams of saturated soil

were weighed on watch glasses for total extractions (Appendix I).

4.0 Total Extractions

Three splits fi'om each homogenized sample were analyzed for the nitric acid
extractable concentration of metals in the soil using the method after Hewitt and
Reynolds ( I 990) presented in Appendix II. Wet sediment was placed on the watch
glasses and dried in an oven at 50°C for approximately 24 hours. The oven-dried
sediments were ground into a fine powder using a ceramic mortar and pestle. One
half gram of sediment was placed into a CEM MDS 81D Teflon digestion vessel.

For each set of twelve samples a blank and a standard reference material (Buffalo

22

River Sediment SRM 2704) were digested. The blank consisted of ten milliliters of
concentrated HNO; added to the Teflon digestion vessel.

The vessels were then placed in the CEM MDS 81D microwave. The
pressure monitor was connected to the vessel that contained the sample with the
highest amount of organic matter. The samples with the highest organic matter were
listed in Table 7, 8, and 9 found in Ellis (1999). The microwave was set for 15
minutes at 100% power, followed by a cool down period of 0% power for 20
minutes. The vessels remained in the microwave until they reached a pressure of
less than 20 psi, at this point they were removed from the microwave. Under a fume
hood, the vessels were then disassembled and 90 milliliters of distilled deionized
water were added to each vessel. The samples were filtered through a 0.4 pm acid
washed Nucleopore filter into acid washed 6O milliliter bottles. The filtrate was
analyzed for total metal concentrations on an inductively coupled plasma-hexapole-

mass spectrometer (Micromass Platform ICP-I—IEX—M S).

5.0 Duration of Drying Treatment (weekly and bimonthly drying)

For six months, samples underwent a wetting and drying procedure. F ifty-
milliliter centrifuge tubes containing exactly fifteen grams of sediment were used for
this experiment. The experiment was designed to assess the effect of two different
drying intervals (one week and bi-monthly) had on the release of metals from
wetland soils. Before starting the experiment the soils were initially saturated.
Thirty milliliters of distilled, deionized, autoclaved water were added to each

centrifuge tube and allowed to sit in the centrifuge tube for three hours. The

23

supernatant water was removed from each vessel using a 30-milliliter syringe. The
supernatant water was filtered using an acid washed Nucleopore 0.4 11m filter, and
the filtrate was split into two separate acid washed bottles and three couvets. Five
milliliters of filtrate were collected for dissolved organic carbon analysis. Eight and
a half milliliters of filtrate were added to couvets for Cr (VI) and Fe (II) analysis.
Remaining filtrate was acidified with optima HNO3 to a pH of less than two and
analyzed for cations. After the filtrate was removed the centrifuge tubes with the
sediment were placed inside the drying cabinet. Each centrifuge tube was covered
with a filter to filter air that would come in contact with the soil. Centrifirge tubes
remained in the cabinet for their respective drying intervals and removed from the
cabinet at the appropriate time. Samples were again saturated using 30 milliliters of
distilled, deionized, autoclaved water and sampled the same as the initial saturation

event. These steps were repeated for six months.

6.0 Chemical Sterilizer Treatments (formaldehyde and glutaraldehyde) and
Distilled Deionized Autoclaved Water Treatment

Chemical sterilizer treatments compared to the DDAW (distilled, deionized,
autoclaved water) treatment was used to assess the role of microorganisms in
releasing metals to the environment. Three sets of centrifuge tubes containing fifteen
grams of sediment were separated into three categories: DDAW treatment,
formaldehyde treatment, and glutaraldehyde treatment. The three sets of soils
underwent the same wetting and drying procedure, only varying in the treatment

solution used to saturate the soils. The DDAW solution consisted of distilled,

24

deionized, autoclaved water. The formaldehyde treatment solution was an 8%
formaldehyde solution made with distilled, deionized, autoclaved water. The
glutaraldehyde treatment solution was a 2% glutaraldehyde solution made with
distilled, deionized, autoclaved water (O’Leary 1989). The soils in the centrifuge
tubes were first saturated for three hours with 30 milliliters of their respective
treatment solution for an initial (time zero) evaluation). The treatment solutions
were removed from the centrifuge tubes and filtered. The filtrate was analyzed for
cations, dissolved organic matter, Cr (VI), and Fe (II). The centrifuge tubes were
placed uncapped in the drying cabinet for fifteen days. After fifteen days, the soil
samples were saturated again for three hours using the treatment solutions, and the
same analysis was done as in the time zero saturation. The pH of the samples was

analyzed at two saturation events. The experiment continued for three months.

7.0 Always Wet Treatment

The other experiment that was conducted was an always wet treatment. This
treatment was conducted simultaneously with the chemical sterilizer treatment;
therefore, the DDAW treatment was compared to the always wet treatment. For this
treatment, the same parameters were evaluated for the extracted solution. Soil in the
centrifuge tubes remained saturated throughout the three-month duration of the
experiment. Thirty milliliters of distilled, deionized, autoclaved water were added to
each centrifuge tube. The centrifuge tube was capped and placed into the drying
cabinet for fifteen days. Alter fifteen days, the remaining water was removed and

filtered The filtrate was analyzed for cations, dissolved organic carbon, Cr (VI), and

25

Fe (II) and used as the starting concentration. After the remaining water was
extracted, thirty more milliliters of distilled, deionized, autoclaved water were added
to the centrifuge tube. This water was allowed to sit in the centrifirge tube for three
hours. After three hours, the water was removed from the centrifuge tube and
filtered using an acid washed 0.4 pm filter. The filtrate was analyzed for cations,
dissolved organic carbon, Cr (VI), and Fe (II). The pH of the water was analyzed for
two saturation events. The sample was then re-saturated, re-capped, and placed back

into the drying cabinet. This experiment continued for three months.

8.0 Spectrophotometric Methods
Cr (VI)

Hexavalent chromium was analyzed using a Spectronic Spec 20d at a
wavelength of 540 nm. A solution of 0.3 mL of 1.2 M H2804 and 0.15 mL of
diphenylcarbazide solution were added to 3.0 mL of filtrate. The 1.2 M H2804 is
made by slowly adding 6.5 mL concentrated H2804 to DDW and diluting to 100 mL.
The 0.15 mL of diphenylcarbazide is made by dissolving 0.2 grams of
diphenylcarbazide and 1.0 grams of phthalic anhydride in 200 mL of ethanol

(AWWA, 1971).

Fe (11)

Ferrous iron (Fe II) was analyzed using a Spectronic Spec 20d at a

wavelength of 508 nm. A solution of 100 11L of trace metal grade HCl, 1.0 mL of

26

phenanthroline, and 0.5 mL of ammonium acetate were added to 2.5 mL of filtrate

(AWWA, 1971).

9.0 Dissolved Organic Carbon Analysis

Samples for dissolved organic carbon were analyzed on a Shimadzu TOC
5000A: Organic Carbon Analyzer. Details of this method are presented in Appendix
II. The TOC analyzer requires two solutions for calibration when analyzing for
organic carbon. The first solution is an inorganic carbon solution. The inorganic
carbon (IC) solution was prepared by dissolving 3.5 grams of sodium hydrogen
carbonate and 4.1 grams of sodium carbonate into one liter of E-pure water. The
organic carbon (0C) solution was prepared by dissolving 2.125 grams of reagent
grade potassium hydrogen phthalate in one liter of E-pure water. Samples were
diluted one to one for analysis prior to analysis.

The carrier gas (ultra zero pure air) is set at 4-5 Kg/cm, and the gas flow is
150 mL/min. The furnace must warm up for approximately one hour to 680°C.
Before running samples the IC reagent (25% phosphoric acid) and the glass
humidifier bottle need to be checked to make sure they are properly filled. A

calibration is done using both IC (Inorganic carbon) and 0C (organic carbon).

10.0 ICP-HEX-MS
The concentrations of metals were measured using a Platform Inductively
Coupled Plasma Mass Spectrophotometer with a hexapole collision cell from

Micromass (ICP-HEX-MS). The elements analyzed on the ICP-HEX-MS were

27

”Co, 60Ni, 63C“, 51V, 114C (1, zospb, 75 As, 47“, 4586, 662m 888 r, 8086, 27 Al, 52Cr, 138821,
44Ca, 54 Fe, 56 Fe, 24Mg, and 5 5 Mn. Of these elements, only a few will be discussed in
this thesis: 52Cr, 56 Fe, ”Mn, and 888t. Chromium is the objective of the study and
selected because of its abundance at the wetland site. Iron and Manganese were
selected because they are associated with chromium cycling and are sensitive to
changes in redox conditions. Strontium was selected because it is not affected by
variations in the redox conditions. Complete results are presented in Appendix [11.
Elements were divided into groups based on their expected aqueous
concentrations: low concentration group ”Co, 6"Ni, 63Cu, “V, “4Cd, 208Pb, 75As,
47Ti, and 45 Sc; intermediate concentration group 66Zn, 88Sr, 80Se, and 27Al; and high
concentration group 52Cr, I38Ba, “Ca, 54Fe, 56Fe, 24Mg, and 55Mn. Multi-element
standards were used to calibrate the ICP-HEX-MS analyses. The method for
standard preparation is presented in Appendix IV. NIST 1643d was analde during
every run as an aqueous standard reference material (SRM). A run consists of
approximately 120 samples, blanks, standards, and SRMs. All solutions were
combined with a one-milliliter of a solution that contained 20 ug/L of indium and
bismuth, which were used as internal standards. A concentric nebulizer and an
autosampler (Cetac ASX-SOO) were used during the analyses. The concentrations of
the different analytes in the aqueous solutions are reported in ug/L. Digested soil
samples were diluted one to one hundred for analysis on the ICP-HEX-MS allowing
their concentration to be in the range of the detector. Data was collected using single

ion recording mode (peak jumping).

28

RESULTS AND DISCUSSION

In this section of the thesis, the results of the experiments will be
summarized, discussed, and interpreted. Four questions were investigated. (1) Does
wetting and drying of sediment increase chromium mobility? (2) Does the duration
of drying affect chromium mobility? (3) Do aerobic microbes play a role in
chromium mobilization during wetting and drying? (4) How does chromium

behavior compare to other elements? The data tables are located in appendix V.

1.0 Does wetting and drying of sediment increase chromium mobility?

There is a definite link between wetting and drying of sediment and
chromium mobility. Aqueous chromium concentrations were greater in samples that
underwent wetting and drying (DDAW treatment) as opposed to samples that
remained saturated (always wet treatment). The two treatments differed only by the
duration of time that the sample remained saturated. Comparing results from the
always wet treatment and the distilled deionized autoclaved water (DDAW)
treatment illustrates the influence of wetting and drying of sediment on chromium
mobility.

Chromium concentrations are compared between individual samples and
between treatments. The results are summarized in Table 2. Table 2 shows a
comparison of chromium concentration trends for the DDAW treatment and the
always wet treatment. The general trend for the DDAW samples was continually
increasing. The only site that did not exhibit a continual increase was 022 where the

general trend was a decrease followed by an increase. The percent of change for the

29

 

 

 

 

 

 

 

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DDAW samples ranged between a 96% increase for J19 to a 1373% increase for
N23. In the always wet treatment, the general trends for all the samples was a
continual decrease. All of the samples experienced some degree of decrease.
Overall the greatest decrease was found in the samples from site .119 where the
percent decrease was 77%. The smallest amount of decrease was found in samples
from site K22 where the percent decrease was 34%. From the general trends and the
percent of increase and decrease, it is evident that cyclic wetting and drying affects
chromium mobility.

In comparing the DDAW treatment and the always wet treatment graphs
presented in Figure 6 and Figure 7 respectively, evidence of the impact of wetting
and drying can be seen. Chromium concentrations increased over time in the
DDAW treatment (Figure 6). Conversely, chromium concentrations decreased over
time in the always wet treatment (Figure 7). In addition to the trends being different,
maximum chromium concentrations in the graphs for the DDAW treatment (Figure
6) are higher than the maximum chromium concentrations in the graphs for the
always wet treatment (Figure 7). F urtherrnore, the results from the always wet
treatment are similar to the intact soil core microcosm results (Figure 3) where
chromium concentrations decrease over time (Icopini et al. 1997, 1998, and 1999).
This illustrates that wetting and drying influenced chromium concentrations in
solution.

In summation, the differences between the two treatments (DDAW and
always wet) illustrate the impact that wetting and drying has on chromium mobility.

When samples underwent changes in their saturation state, the chromium found in

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solution was higher. There are a number of mechanisms that control chromium
mobility. Some of the possible mechanisms are the degradation of organic matter by
aerobic microbes, cycling of iron oxides, and solubility or detachment from soil
particles. This study illustrates that wetting and drying influences chromium
mobility, and the amount of chromium released increases over time.

This research supports the findings of Icopini et al, (1997, 1998, and 1999).
Increased concentrations of chromium were seen in sites that were cyclicly wet and
dry (sites P25 and N23) in the field The pore water samples collected from the
peepers and barrels in the field were higher in P25 and N23 in comparison to J23 and

K22 (e. g. always wet sites).

2.0 Does the duration of drying affect chromium mobility?

There is conclusive evidence that the duration of drying affects chromium
mobility. The results of the duration of drying experiment for chromium are
presented in appendix V.

Concentrations and trends are tied to the field saturation state. When the
always dry site J 19 was subjected to cyclic wetting and drying conditions it exhibited
the highest amount of chromium eluded in the bimonthly drying experiment.
Furthermore, the amount of chromium eluded from 119 decreased over the span of
the bimonthly experiment, similar to the results of the intact soil core microcosm
presented in Icopini et al. (1998). For sites that undergo cyclic wetting and drying in
the field (N23 and P25), the concentrations of chromium eluded in the bimonthly

drying experiment increased for 60 days and then decreased to a steady state. The

34

general trends for chromium for all the sites studied are located in table 2. After the
initial 60 days, the trends were similar to the intact soil core microcosm results. The
intact soil core microcosm experiment (Icopini et al., 1998) show a flushing
experiment where chromium concentration decreased over time afler being
continually saturated with a solution (Figure 2). The field saturation state influences
the chromium mobility.

The results of the bimonthly treatment experiment cannot be compared to the
DDAW experiment. The time that the two samples dried were similar; however, the
conditions under which they dried were completely different. The DDAW samples
were dried without a filter covering the sample in the drying cabinet while the
bimonthly drying samples were covered with a 0.4 pm filter. The filter prevented
the complete drying of the samples. The degree of wetness makes a difference. The
semi-saturated soils of the drying experiment show similar results to the intact soil
core microcosm experiment and the always wet experiment which validates the

influence of wetting and drying on chromium mobility.

3.0 Do aerobic microbes play a role in chromium mobilization during wetting
and drying?

From research presented by Tagami and Uchida (1996 and 1999) the role of
microorganisms in the mobility of chromium was studied. Their results were
summarized in the introduction. The role of microbes was evaluated using two
different microbial sterilizers formaldehyde and glutaraldehyde. The formaldehyde

treatment (Figure 8) and the glutaraldehyde treatment (Figure 9) are compared to the

35

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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treatment where microbes were not killed (Figure 6). A summary of all the figures 6,
8, and 9 are located in Table 2. The DDAW treatment acts as the control in this
experiment. For chromium concentrations in solution, all of the sites except 022
exhibited an increase over time. The results from 022 show a decrease followed by
an increase.

With the influence of wetting and drying established, the possible role of
aerobic microbes was investigated. The first microbial sterilizer investigated was
formaldehyde. The results of the formaldehyde treatment can be seen in Table 2 and
Figure 8. The general results for the formaldehyde treatment were not consistent
amongst all the sites. Four different types of trends were seen. The graphs for site
J 19 and site 022 showed a decrease over time of chromium concentration in
solution. The graphs for N23, P25, and K22 had one peak. Finally, the graph for
123 showed a decrease followed by an increase of chromium in solution. The
DDAW treatment and the formaldehyde treatment do not exhibit similar trends.
Possible microbial influences could be inferred by the decreases found in site J19.
The percent decrease in chromium concentration in solution was 34% for the site J 19
in the formaldehyde treatment. However, the remaining five sites do not illustrate
that same general trend. The percent change of chromium concentration in solution
in the other five sites is much lower in the formaldehyde treatment than in the
DDAW treatment. The percent increase of chromium in solution ranges from 8% to
330%, and the percent decrease 34% to 46% in the formaldehyde treatment. The

percent increase of chromium in solution in the DDAW treatment ranges from 96%

39

to 1373%. Therefore, the influence of microbes on chromium mobility is not
supported by the data.

Results from the glutaraldehyde treatment are presented in Table 2 and
Figure 9. Two general trends can be seen in the glutaraldehyde results. The first
trend is a step increase in chromium released to solution, which can be found in sites
J 19, N23, P25, and K22. The other general trend is a decrease in chromium released
to solution, which can be found in sites J23 and 022. The similarities between the
DDAW treatment and the glutaraldehyde treatment can be seen for four sites.
However, two sites (J23 and 022) exhibit a decrease in chromium released to
solution in the glutaraldehyde treatment. With the differences seen within the
glutaraldehyde samples, the influence of microbes is not supported by the data.

The previous work evaluating the influence of microbes on mobility includes
the work done by Tagami and Uchida (1996 and 1999). This work does not support
nor deny their conclusions that microbes play a role in organically bound metal
mobility. The use of formaldehyde and glutaraldehyde as compared to chloroform
used by Tagami and Uchida (1996 and 1999) as the microbial inhibitor may account
for the changes seen in this project’s data. Following the research presented in Alef
and Nannipieri (1995) and Jenkinson and Powlson (1976), the furnigants used in the
Tagami and Uchida experiments would have destroyed the fine structure of the soil.
This study used chemical sterilizers that were suggested for their ability to inhibit a
broad spectrum of microorganisms but not destroy the fine soil structure. However,
the definite connections seen in the Tagami and Uchida experiments (1996 and

1999) could not be supported by this data. In addition, the data may not be

40

consistent with Tagami and Uchida (1996 and 1999) because of possible complexes
that formaldehyde or glutaraldehyde could have formed with iron or manganese in

the experiment.

4.0 How does chromium behavior compare to other elements?

The comparisons of chromium to other metal mobility in the presence of
wetting and drying are presented in Tables 3 through 10 and Figures 11 through 25.
Iron, manganese, and strontium were evaluated for the effects of wetting and drying.
Iron and manganese are redox sensitive elements. On the other hand, strontium is
controlled by solubility not oxidation reduction reactions. The comparison of the
aforementioned elements to chromium for the DDAW treatment is presented in
Table 3. The concentration of iron in the DDAW treatment decreases over time for
the sites that were always wet and were found at locations where the water table was
near the surface (00.5 feet) in the field (J23 and K22) (Figure 11). A percent
change of 98% for site 123 and a percent change 96% for site K22 mark the sharp
decrease of iron concentration The sites that were either always wet or underwent
wetting and drying in the field show a general decreasing trend of iron released to
solution (Figure 11). The cyclicly wet and dry field sites (N23 and P25) and the
always dry field site (119) have percent decreases of iron concentration of 30%, 61%,
and 55% respectively. Furthermore, the concentrations of iron in the formaldehyde
treatment (Figure 13 and Table 8) and the concentration of iron in the glutaraldehyde

treatment (Figure 14 and Table 9) decrease over time.

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Manganese concentrations in the DDAW treatment increase over time in
samples N23 and K22 (Figure 16). The percent increase of manganese concentration
for sites N23 and K22 were 285% and 362% respectively. J 19, 123, P25, and 022
have a portion of their graphs of manganese concentration vs. time that increases
during the experiment. Manganese concentrations for the formaldehyde and
glutaraldhyde treatments initially increase in sites J19 and N23 (Figures 18 and 19).
In the formaldehyde treatment, P25 manganese concentration in solution increases
after a decrease between time zero and time equal to 15 days. After the increase the
concentration of manganese decreases in P25 for the remainder of the experiment.

Strontium concentrations decrwse over time after an increase that peaks
between day 30 and 60 depending on the sample for the DDAW treatment (Figure
21). The formaldehyde treatment (Figure 22) and the glutaraldehyde treatment
(Figure 23) had a more variable trend over time.

Iron cycling is a possible mechanism that controls chromium mobility in
wetting and drying. Iron cycles between the +2 and +3 states. The reduced state of
iron, Fe (II), oxidizes to Fe (1H). This oxidation and subsequent precipitation of
ferric hydroxide occurs rapidly in the presence of oxygen (McBride, 1994).
Dissolved Fe (H) undergoes oxidation in the drying phase of the experiment where
the completely saturated soil becomes completely dry. The oxic phase of iron is Fe
(III) which forms an insoluble precipitate of Fe (hydro)oxides (e. g. Fe(OH)3)
(Stumm and Morgan, 1996). Chromium is adsorbed by Fe (hydro)oxides (Stumm
and Morgan, 1996). Therefore, the cycling of iron could impact the liberation of

chromium to solution. The increase in iron concentration in the rewetting water

62

could indicate that the sensitive redox boundary described in McBride (1994) was
reached, and the Fe (III) (hydro)oxide that adsorbs Cr (III) released the chromium to
solution Furthermore, chromium may also be adsorbed by Mn (hydro)oxides
(Stumm and Morgan, 1996). Mn (III/IV) reduces to Mn (11) at a higher redox
potential tlmn Fe (HI) to Fe (II) (Stumm and Morgan, 1996). Therefore, the cycling
of manganese could also affect the amount of chromium in solution. From the
manganese data in Figure 17, some increased concentrations of manganese in
solution, especially in site N23, leads to a conclusion that manganese cycling has an

impact on chromium mobility in wetting and drying environments.

5.0 Summary of Results and Discussion

Is there evidence that wetting and drying enhances chromium mobility? Yes,
the research points to a definite influence and enhancement of chromium mobility
from wetting and drying. Does the duration of drying affect chromium mobility?
Yes, the degree of saturation validates the importance of wetting and drying. The
more that the soils are dried out the more chromium is eluded to solution when re-
wet. Soils that were dried without a filter over the drying vessel showed an increase
in chromium over time while on the other hand semi-dried soils that were capped
with a filter or always wet soils decreased in chromium concentration in solution
over time. Do aerobic microbes play a role in chromium mobility during wetting and
drying? There was no conclusive evidence about the role of aerobic microbes in
wetting and drying. How does chromium behave compared to other elements? The

other elements investigated behaved differently than chromium. Chromium

63

concentrations in solution increased over time while strontium concentrations in
solution decreased over time. The redox sensitive elements, iron and manganese,
behaved for the most part differently than chromium in solution with the exception
of a few samples and/or treatments (e.g. sample N23 in the DDAW treatment for"

manganese and chromium) that behaved similarly.

64

CONCLUSION

1.0 Summary

The research examined the role of wetting and drying of soils on chromium
and other metal mobility in soils. Past research (Haynes and Swifi, 1989 and 1991;
Westfall et al., 1973; Crozier et al., 1995; Hall and Hall 1996; Tagamiand Uchida,
1996 and 1999; Icopini et al., 1997, 1998, and 1999; and Ellis 1999) provided the
framework for this project. Results from the treatments indicate that wetting and
drying increases chromium concentrations in solution from soils that are dried and
re-wet.

This study used multi-element analysis on the ICP-HEX-MS to study a
variety of elements and their response to wetting and drying including chromium,
iron, manganese, and strontium. From previous researchers (Icopini et al., 1997,
1998, and 1999; Ellis, 1999; and Haynes and Swifi, 1991) and this study, four
questions were addressed (1) Is their evidence that wetting and drying enhances
chromium mobility? (2) Does the duration of drying affect chromium mobility? (3)
Do aerobic microbes play a role in chromium mobility during wetting and drying?
(4) How does chromium behave compared to other elements?

Chromium released to solution during organic matter degradation may be an
important mechanism enhancing chromium mobility during wetting and drying.
This was inferred from the DDAW treatment where chromium concentrations in
solution increased and strontium concentrations in solution decreased Chromium,

which is mainly associated with organic matter, was released to solution during

65

wetting and drying cycles, and strontium, which is mainly associated with
carbonates, was not released to solution during wetting and drying cycles.

Iron and manganese cycling may be important in chromium mobility. The
possible liberation of chromium by iron and/or manganese cycling was studied by
observing the concentrations and trends of iron and manganese. Chromium
concentrations in solution increased when undergoing wetting and drying and
decreased under always wet conditions. The increase of chromium in solution
coincides with the description of iron and manganese cycling by McBride (1994),
Stumm and Morgan (1996). From the results, iron cycling plays a role in chromium
mobility; however, manganese cycling may be more important in chromium
adsorption and subsequent release in wetting and drying environments.

The solubilization or detachment of soil particles containing chromium may be a
mechanism of enhancing chromium mobility. This mechanism could be inferred
from the increase in chromium concentration in solution in the DDAW treatment.
These results correspond to the initial observations of the intact soil core microcosm
(Icopini et al., 1998) where they concluded that the initial high concentrations of
chromium were due to solubilization or detachment of soil particles containing

chromium.

2.0 Environmental Significance and Sources of Error
Chromium is naturally found in two valence states Cr (III) and Cr (VI).
Chromium (III) is required by humans along with insulin to maintain proper blood

sugar levels (Harte et al., 1991). Cr (III) is considered safe and necessary to a daily

66

intake of 0.20 mg/day (Harte et al., 1991). However, Cr (V1) is highly toxic and
guidelines regarding Cr (VI) exposure has been set the EPA. The primary drinking
water standard is 50 ppb. The water quality standard for the protection freshwater
aquatic life is 11 ppb (Harte et al., 1991).

Ellis (1999) and Icopini et al. (1997, 1998, and 1999) evaluated soil
partitioning. From their work, the soil partitioning at the site was linked to two
major phases. Those phases were the moderately reducible phase, which targets Fe-
oxides/hydroxides, and the oxidizable phase that targets organic matter. The
mechanisms that control chromium mobility discussed in the results and discussion
section are consistent with the environmental assessment of the partitioning of
chromium in the environment at the wetland site presented by Ellis (1999) and
Icopini et al. (1997, 1998, and 1999).

Variability and error analysis will be discussed in this section. The first issue
is re-freezing. The fine structure of the soil may have been affected by the freezing
procedure. Since the concentrations of metals in solution are very small in
comparison to the concentration of the soil the fine structure and small-scale
variations in the soil become important.

Dying times and sediment heterogeneity are variable in this experiment.
Variations in the soil itself would cause replication to be difficult. Sediments were
homogenized on site to ensure a relative sample of sediment from each site for the
laboratory experiments. Drying times could have caused more variability. The
degree of drying/degree of wetness would greatly affect results as was seen in the

duration of drying experiments where the sediments were capped with filters and the

67

DDAW treatment where the sediments were open to the filtered air of the drying
cabinet.

Analytical error and sensitivity was a function of the parameters and
limitations of the ICP-HEX-MS. Standards were prepared according to the method
presented in appendix IV. All samples were run on the ICP-HEX-MS, and the
concentrations of the samples were between the highest and lowest standard
concentration. The magnitude of change was presented in the results and discussion
section. Some of the overall changes were within the possible error of the ICP-HEX-
MS, however, the majority of the samples had an overall percent change of over
30%.

Other factors beyond the microbialcidal effects of the chemical sterilizers that
influence metal mobility are difficult to assess. For example, studies have shown
propylene oxide, an effective microbial inhibitor, increases all metal concentrations
released to solution. In this experiment, iron and manganese may have complexed
with glutaraldehyde and/or formaldehyde, which could have altered the
concentration of chromium in solution. Further studies would need to be done on
possible complexing between iron and manganese with glutaraldehyde and

formaldehyde.

3.0 Future Research
Phytoremediation and other in situ techniques are possible remediation
strategies for the wetland site. Remediation strategies for the wetland site were

discussed in Icopini et al. (1997, 1998, and 1999). The dominant remediation

68

strategy discussed was in situ remediation. This strategy requires that transformation
or loss of contaminants occurs. One remediation strategy that has documented
transformation potential is phytoremediation. Phytoremediation is the use of green
plants to remove or contain contaminants in the environment. Some of the dominant
wetland species that are used in constructed wetlands when phytoremediation is
desired are cattail (Typha latifolia), bulrush (Scripus lacustris) and reed (Phragmites
australis). Those wetland plants have high primary productivity (Buddhawong et al.,
2002). Wetland plants in association with aerobic microbes have been found to
uptake and convert Cr (VI) to Cr (III). Other possible suggestions for remediation
for the wetland site are to keep saturated areas saturated and unsaturated areas

unsaturated so as not to induce the mobility of chromium through wetting and

drying.

4.0 Questions for further research.

0 Would rain in a desert environment act as a catalyst to enhance chromium
mobility similar to the cyclic wetting and drying process in wetland
environments?

0 What are the effects of formaldehyde and glutaraldehyde complexing with iron
and manganese?

o What is the best microbial inhibitor to use in metal mobility studies? And in
what cases should one utilize fumigants, chemical sterilizers, and/or autoclaving?

0 Would phytoremediation decrease the amount of chromium in solution when the

wetland is subjected to wetting and drying conditions?

69

0 Would a field study with a broader study of more diverse sites with additional
parameters like Eh provide a definite conclusion to the major mechanism

controlling chromium mobility in wetting and drying cycles?

70

APPENDICES

71

APPENDIX I

72

APPENDIX I

Method for Nitric Acid Microwave Digestion of Soils (Hewitt and Reynolds,

1990)

I. Weigh and label a watch glass.

2. Place at least 5 grams of soil on a watch glass.

3. Weigh the watch glass and soil.

4. Place the watch glass in a 50°C oven for 24 hours.

5. Re-weigh the watch glass and soil.

6. Place the dried sample into ceramic mortar. Grind into a fine powder with a
pestle.

7. Carefully weigh out 0.500 grams of ground sample and place into a teflon
digestion vessel.

8. Repeat for each sample and wash the mortar and pestle between each grinding to
prevent cross-contamination.

9. Do the same for the Standard Reference Material (SRM)

10. To each sample and the SRM add 10 mL of ISN HNO3. Make sure no sample
remains on the side of the vessel.

1 I. The blank is a vessel with just nitric acid added for digestion.

12. Seat the pressure membranes in the caps of all the samples, the blank, and the
SRM.

13. Screw caps on all vessels.

l4. Attach the pressure monitor to any sample not the blank or SRM.

73

15. A CEM MDS 81D microwave with pressure regulation is used for digestions.
Place vessels into a rotary tray inside the microwave. Rotate the tray a few times
before starting to assure that the pressure hose will not get caught on any of the
vessels.

16. Program the microwave to run 15 minutes at 100% power with pressure
regulated to 150 psig maximum and then 20 minutes (0% power) cool down
period to allow pressure in the vessels to fall below 10 psig.

17. To each sample, blank, and SRM add 90 mL of distilled deionized water (DDW)
after digestion and cool down period.

18. Filter samples through a 0.4 pm Nucleopore filter into an acid washed 120 mL

bottle. Condition filter with 10 mL of leacbate/DDW.

74

APPENDIX [1

75

APPENDIX II

Method for TOC 5000A: Organic Carbon Analyzer

1.0 Daily Maintenance:

1.

2.

Check paper. Lifi cover on top of machine to view paper, if low replace.
Check acid in [C reagent container (25% phosphoric), if the acid is low replace

with additional acid that can be made using the following formula

(Concentrated dilute acid (25%) x volume being made (250 mL)) / (Concentrated

stock phosphoric acid)

3.

Check water level in glass humidifier bottle, water level should be between white
lines, if not, unscrew black cap on the side of bottle and fill with E-pure water.
Make sure drain tubes are not submerged in wastewater.

Check amount of water in the rinse/wash bottle, if the water level is low fill with

E—pure water.

2.0 Periodic Maintenance:

1.

2.

Replace gas cylinder with ultra pure zero air when the gauge reaches 200 psi.
Replace COz absorber after 1 year of use.

Replace halogen scrubber annually or when discoloration reaches the tip of the
tube.

Replace microsyringe plunger tip if leakage appears in the syringe barrel.
Replace white O-ring on sliding sample injector if running mor than 125

injections per day.

76

9‘

>1

>0

Replace dark O-ring every 6 months.
Adjust NDIR zero when baseline drift occurs.
Check to see if TC catalyst is discolored, and if so replace.

Replace TC combustion tube 0 ring annually.

10. Clean humidifier bottle and replace water yearly, when cleaning add 3 pellets of

NaOH.

3.0 Preparation of 1C stock solution (1000 ppm)

Dissolve precisely 3.50 grams of Sodium Hydrogen Carbonate and 4.10 grams of

Sodium Carbonate Anhydrous, which have both been placed in a 285°C oven for at

least 1 hour, into 1 L of E-pure water.

4.0 Preparation of 0C stock solution (1000 ppm)

Dissolve precisely 2.125 grams of reagent grade potassium hydrogen phthalate in 1 L

of E-pure water.

5.0 Sample Preparation

1.

2.

Samples are filtered using an acid washed 0.4 pm filter.

Between 5 - 8 mL ofthe filtrate is placed in an acid washed 8 mL bottle.

The samples are then immediately frozen until analysis

Thaw samples before analysis.

In the small glass containers add 100 uL of Shimadu’s Hydrochloric Acid, 2 mL

of e-pure water, and 2 mL of sample.

77

9.

After every 15 samples insert a check standard.

Place parafilm tightly over all the small glass sample containers.

Prepare standards using the IC and OC stock solutions and place in the large
glass containers.

Place parafilm tightly over all the large glass sample containers.

10. Place all the containers in the auto-sampler tray.

6.0 Beginning a run

(all commands other than function commands must be confirmed by pressing the

return key)

1.

2.

8.

9.

Carrier gas pressure should be set at 4-5 kg/cm.

Carrier gas flow should be at 150 mL/min.

Turn power on.

Must press F5 to Initialize auto sampler.

Afier initializing is complete select F 1 next to access main menu screen.
Select #3 General Conditions

Turn furnace on by entering 1 (TOC) then press return

Furnace takes approximately 1 hour to heat to the proper temperature (680°C)

The machine needs to be on 24 hours in advance of running standards or samples

10. From print out options, choose Data & Peak plots or just Data).

11. Press F2 to return to main menu

12. Choose #9 auto sampler

13. Choose type of measurement to be performed (1-5)

78

14.

15.

Enter under IS (initial sample) the location of the first sample vial, then press
return. Next enter the location of your final sample (FS).

Enter the calibration curve under Cl then press return.

7.0 Calibration/Conditions

l.

2.

10.

ll.

12.

Select type of curve (1=TC and 2=IC)

Enter values for the lSt standard concentration and press return, then enter the
standard position that it is in (SI-S8).

Repeat for 2nd, 3“, and 4th standards, depending on how many you have (a re-
calibration should be done every 15 samples).

Set number of injects and maximum number of injects (recommended 4 out of
7).

If doing NPOC with IC check, set sparge time to 2 minutes.

Repeat these steps as many times as necessary.

All curves will be under the C1 column.

Before starting a run check the ready state conditions choose #6 monitor

Make sure the baseline is at or near zero.

To adjust the baseline, move small square cover at top of machine labeled optical
zero to access the adj ustrnent screw. The screw is in the opening with the copper
tube, closest to the front of the machine.

Make sure the furnace is at the appropriate temperature.

Choose F2 to go back to main menu

79

13. Set needle washes (W) equal to 3 and number (NO) and maximum number
(MAX) of sample injections (recommended 3 out of 5).

14. Make sure the arrows on the machine and the carousel line up.

15. Choose F 1 NEXT

16. Press the START button.

8.0 Shutdown Procedures

1. To shutdown first go to General Conditions and turn furnace off, than return to
the main menu F2.

2. Choose #7 Standby Options and select finish.

3. A proper shutdown will take approximately 30 minutes

4. Turn of? the power switch.

80

APPENDIX III

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129

APPENDIX IV

130

APPENDIX IV

ICP-HEX—MS Standard Preparation (after Icopini et al. 1998)

All standards are prepared in a 100mL volumetric flask with 500ug/L ultra pure
nitric acid

Solution A: 1mg/L Co, Ni, Cu, V, Cd, Pb, As, Ti, Hg, Sc (1001.11 of each element)
Solution B: lOmg/L Zn, Sr, Se, Al (1000ul of each element)

Solution C: 10mg/L Cr, Ba, Mn, Fe, K, Mg (1000ul of each element)

Solution D: 1mg/L In, Bi, Tb, Ge (100141 of each element)

Solution E: 20ug/L in 500ml flask at 4% nitric acid

Formula for Solution E: ml of HNO; = (4% HN01X500ml)
70% HNO3 solution

Standard 1: Soul Solution A, 250ul Solution B, 1001.11 Solution C
Standard 2: lOOul Solution A, 500ul Solution B, lOOOul Solution C
Standard 3: 500m Solution A, 1000p] Solution B, SOpI Solution C
Standard 4: 1000ul Solution A, 2000ul Solution B, 100ul Solution C

Standard 5: 2000ul Solution A, 3000ul Solution B, 200ul Solution C

131

APPENDIX V

132

APPENDIX V

Detailed results for DDAW, formaldehyde, glutaraldehyde, always wet, and
bimonthly treatments for the four elements (chromium, iron, maganese, and
strontium)

1.0 Chromium

DDAWjDistilled Deionized Autoclaved Water) Treatment (Figure 6)

J 19: At time zero, chromium concentrations were 209 ppb. The concentration of
chromium released ranges between 200 and 400 ppb over the 90 days, with a trend
of increasing concentration over time.

N23: Chromium concentration for time zero was 11 ppb. Chromium concentrations
always increased. At 90 days, the chromium concentration was 161 ppb.

P25: The chromium concentration at time zero was 27 ppb. The concentration of
chromium released from the sample decreased to 14 ppb at day 30. Alter day 30, the
concentration increased for the remainder of the experiment where the final
concentration was 165 ppb.

J 23: Chromium concentration for time zero was 27 ppb. After a decrease to 9 ppb at
day 15, the graph illustrates a general increasing trend to 116 ppb.

K22: The chromium concentration at time zero was 38 ppb. The chromium
concentration decreased to 9 ppb on day 15. For the remainder of the experiment,
the chromium concentration increased where the final concentration was 67 ppb.
022: At time zero, chromium concentration was 21 ppb. Chromium concentration

decreased to a low concentration of 3 ppb on day 30. Beyond 30 days, the chromium

concentration increased to a final concentration of 17 ppb.

133

Always Wet Treatment (Figure 7)

For J 19 always wet treatment, the amount of chromium released began 743
ppb and steadily decreased over the duration of the experiment to 173 ppb. In
contrast, J19 DDAW treatment (Figure 6) began at a lower concentration (209 ppb)
and the trend increased over time.

In the always wet treatment for N23 and P25, chromium concentrations
began at 86 ppb and 113 ppb respectively. The chromium released decreased to a
steady state at 45 days to a concentration of 43 ppb and 58 ppb respectively.
However, in the DDAW treatment N23 and P25, chromium concentrations began at
a lower concentration and increased over time.

The chromium concentration for 123, K22, and 022 always wet treatment
decreased over time to a steady state concentration. The concentration range for J 23
was 110 to 51 ppb. The concentrations of K22 ranged from 63 to 43 ppb. Finally
the concentrations at 022 ranged from 22 to 8 ppb. However, the DDAW treatment
J 23 and K22 chromium concentrations increased over the duration of the experiment
For 022 the concentration (in the DDAW) at the end was approximately equal to the
starting concentration. The pattern was a “v” shape rather than the steady increase

noted by the other always wet treatments J 23 and K22.

F ormafllehyde Treatment (Figure 8)
J 19: At time zero, chromium concentrations were at 777 ppb. Over time, there was
a slight decrease in the concentration of chromium released with the final

concentration of 551 ppb.

134

In contrast to the DDAW treatment (Figure 6), the sample treated with the

formaldehyde treatment decreased over time whereas the sample with the DDAW
treatment increased over time. The concentrations of chromium eluded were
different between the two treatments. Higher concentrations of chromium were
eluded in the sample treated with the formaldehyde concentration approximately
double the concentration of chromium in the sample treated with DDAW.
N23: The concentration of chromium at time zero was 62 ppb. Afier 15 days of
drying, the chromium released decreased to a concentration of 38 ppb. For the
following 45 days, there was an increase in chromium eluded resulting in a peak
concentration of 243 ppb at day 60. Alter this peak, chromium concentrations
decreased to 67 ppb by day 90 the final concentration.

For the first 45 days, both the formaldehyde (Figure 8) and DDAW (Figure
6) treatment samples showed an increasing trend, however, the samples from the
formaldehyde treatment exhibited higher chromium concentrations. At day 60, the
trends for the two treatments diverge. Chromium concentrations for samples that
underwent the DDAW treatment increased by 50%. However, chromium
concentrations for samples that underwent the formaldehyde treatment, there was a
peak at day 60 with a subsequent decline of 50%.

P25: The chromium concentration at time zero was 30 ppb. This remained
relatively constant until after day 30 where there was an increase in concentration of
chromium released The chromium concentration peaks at day 75 at 135 ppb

followed by a decrease in chromium to a concentration of 87 ppb.

135

Chromium concentrations eluded from the formaldehyde (Figure 8) and

DDAW (Figure 6) treatment samples were similar at time zero. Both treatments
show a slight decrease in chromium concentrations to day 30 followed by an
increase. However, the soil that underwent the formaldehyde treatment had a peak in
chromium concentration released at day 75; whereas, the soil that underwent the
DDAW treatment continued to increase to day 90.
J23: The concentration of the fluid collected at time zero was 275 ppb. Chromium
concentrations decreased rapidly to a concentration of 29 ppb at day 15. From day
15, there is a gradual increase in chromium concentrations eluded from the soil at
site J23 with a peak concentration (170 ppb) of chromium on day 75. However, by
day 90, the chromium released had returned to a lower concentration of 35 ppb.

Initial concentrations of the formaldehyde treatment (Figure 8) and the
DDAW treatment (Figure 6) differed The concentration of the DDAW treatment
was lower than the concentration of the formaldehyde treatment at time zero. The
formaldehyde treatment ranged in concentrations from 29 to 275 ppb. Concentration
ranges for the DDAW treatment were from 10 to 70 ppb. Both treatments
demonstrated an initial lS-day decrease in chromium concentrations. Following the
initial decrease, the concentration increased in both treatments with a 17% increase
in the DDAW treatment and a 7% increase in the formaldehyde treatment; however,
the formaldehyde treatment shows a peak at day 75 followed by a decrease; whereas,
the DDAW treatment exhibits a continual increase.

K22: Chromium concentrations at time zero were 51 ppb. This amount released

remained relatively constant until day 45 where the chromium concentrations peaked

I36

at 221 ppb and remained at that level until day 60. After day 60, there was a
decrease to 129 ppb to day 90.

In comparison to the DDAW treatment, both the DDAW (Figure 6) and
formaldehyde (Figure 8) treatments released similar concentrations in the early
stages of the experiment. Concentrations in the DDAW treatment increased over
time but did not result in chromium concentration as high as those seen in the
formaldehyde treatment. Furthermore, there was no peak in chromium
concentrations in the DDAW treatment, whereas, there was a peak present between
days 60 and 75 in the formaldehyde treatment.

022: At time zero, the chromium concentration was 24 ppb. Alter 30 days, there
was a decline in the chromium eluded to a low of 6 ppb. Following day 30,
chromium concentrations released increased until day 75 where it peaked at 17 ppb.

After this chromium peak, the concentration decreased to 13 ppb at day 90.

Glutaraldehvde Treatment (Figure 9)
J19: The concentration of chromium released at time zero was 436 ppb. Initially,
there was a decrease in chromium concentration to a low of 342 ppb at day 15.
Following the low at day 15, there was an increase in chromium concentrations to
day 60 where the concentration was 689 ppb. After the peak at day 60, the
chromium concentrations decreased to 573 ppb and then increased to a final
concentration of 61 8 ppb at day 90.

Chromium concentrations at time zero differ between the formaldehyde

(Figure 8) and glutaraldehyde (Figure 9) treatments, where the glutaraldehyde

137

samples exhibited lower concentrations. An overall increase can be seen in the
glutaraldehyde treatment where as the formaldehyde treatment was closer to steady
state over time.

In comparison to the DDAW treatment (Figure 6), the glutaraldehyde

treatment sample (Figure 9) had a higher concentration at time zero. Both the
glutaraldehyde and DDAW treatment samples had an increase in concentration over
the duration of the experiment.
N23: The concentration at time zero was 22 ppb. There is an increase to 15 days
where the chromium concentration was 51 ppb. A decrease of 12 ppb occurs
between 15 and 30 days. After 30 days, there is an increase to a peak at 45 days
where the concentration was 124 ppb. The concentration then decreases to a steady
state starting at 60 days and continuing the duration of the experiment.

N23 graph from the DDAW treatment (Figure 6) exhibits a constant increase
over the duration of the experiment. However, the graph from the glutaraldehyde
treatment (Figure 9) shows a series of increases and decreases over the duration of
the experiment Furthermore, the initial concentrations of N23 for the DDAW
treatment and the glutaraldehyde treatment differ significantly.

P25: At time zero, the concentration of chromimn was 59 ppb. The trend decreased
t027ppbonday15. Themflrerewasanincreasetoapeakat30daysata
concentration of 225 ppb. Finally, it reached a steady state of 158 ppb afier 60 days.

The formaldehyde treatment trend (Figure 8) increases afier day 30 to a peak
at day 75; however, the glutaraldehyde treatment graph (Figure 9) peaks at day 30

and then decreases before reaching a steady state.

138

The DDAW graph for P25 (Figure 6) illustrates an increase for the duration
of the experiment starting at 30 days. Once again, the glutaraldehyde graph (Figure
9) reaches a steady state after 60 days.

J23: At time zero the chromium concentration was 209 ppb. Afier the first drying
interval, the concentration of chromium reached a low of 40 ppb. There, the
concentration of chromium increased to a peak of 121 ppb at day.

In comparison to the formaldehyde treatment (Figure 8), the glutaraldehyde
treatment sample (Figure 9) had a lower chromium concentrations. The trends vary
between the two treatments with the formaldehyde having a longer period of increase
to a peak at 75 days followed by a decrease to day 90. However, the glutaraldehyde
treatment graph (Figure 9) shows a curve with two peaks and three lows following
the initial high at time zero.

The chromium concentrations for time zero were higher in the glutaraldehyde
treatment samples (Figure 9) than in the DDAW treatment samples (Figure 6). The
DDAW treatment samples increased over the duration of the experiment; whereas,
the glutaraldehyde treatment samples exhibited a drastic decrease at the beginning,
followed by smaller increases and decreases in the concentration
K22: The chromimn concentrations at time zero was 38 ppb. The concentration of
chromitun decreases to a low at day 15 and then increases to a peak of 164 ppb at
day 45. Following the peak, the concentration decreased 50 ppb to day 60 followed
by an increase of 12 ppb the next sampling interval. Between the second peak at day

75 and day 90 there was a final decrease of 31 ppb.

139

Both the formaldehyde (Figure 8) and glutaraldehyde (Figure 9) treatments
increase the concentrations eluded after day 45 in the formaldehyde treatment and
day 30 in the glutaraldehyde treatment.

The DDAW treatment graph (Figure 6) shows an increase from time 30 to
time 90 days. In comparison, the glutaraldehyde treatment graph (Figure 9) showed
chromium concentrations increasing after day 30 to a peak and then decreasing.

022: The concentration of chromium at time zero was 68 ppb. At day 15, a sharp
decline in the concentration occurred. After the decline, a small increase of 18 ppb
occurred between day 30 and day 75.

Both the formaldehyde (Figure 8) and glutaraldehyde (Figure 9) treatment
graphs have a sharp decline between day 0 and day 15. Both the formaldehyde
(Figure 8) and glutaraldehyde (Figure 9) treatment graphs illustrate an increase in
chromium concentrations after day 30 and with the highest concentration being at
day 75.

In comparison, the DDAW (Figure 6) and glutaraldehyde (Figure 9)
treatments exhibited similar curves with a sharp decline at the start, the lowest

concentration at 30 days, and the peak concentration at 75 days.

Bimonthly DryingTfiatrnentfligure 10)

The plots represent a six-month monitoring of chromium released from the
cyclic wetting and drying of soils. The sample for J19 bimonthly drying treatment
was 60 ppb at time zero (Figure 10) and peaked at a concentration of 403 ppb at

approximately 30 days. After the peak, the chromium concentration declines to a

140

steady state of approximately 40 ppb. Chromium released from soils representing
cyclic wetting and drying in the field (N23 and P25) had an initial concentration of 3
ppb and 7 ppb respectively. The chromium released in the soils increased and then
decreased over time. The peaks occurred at approximately the same time for both
soils. However, the percent increase and decrease was greater in P25 then N23.
Chromium released from soils representing continuously wet field conditions with
high organic matter, J23 and K22, had initial concentrations of 4 ppb and 8 ppb
respectively (Figure 10). They behaved similarly by increasing to peak
concentrations of 36 ppb and 58 ppb respectively after the first drying interval and
then decreasing to a steady state. However, K22 bimonthly drying treatment
increases at the end of the experiment where J23 bimonthly drying treatment
remained at steady state. Chromium concentrations eluded from the site with
continuously wet field conditions and low organic matter (O22) decreased from 14
ppb at time zero to a steady state with chromium concentrations fluctuating between

5 and 8 ppb.

2.0 Iron

DDAW Treatment (Figure 11)

119: At time zero, the concentration of iron was 103 ppb. The concentration of iron
decreased to a minimum concentration at day 45 of 33 ppb. The concentration

increased 13 ppb over the remaining 45 days of the experiment.

141

N23: Iron concentration for time zero was 262 ppb. The graph illustrates a decrease
of 200 ppb to the minimum concentration at day 30. After day 30, the concentration
increases to 185 ppb on day 90.

P25: The initial concentration of iron was 433 ppb. The graph illustrates a drastic
decrease in concentration to 27 ppb on day 30. After day 30 the concentration
increases to 170 ppb on day 90.

J 23: Iron concentration for time zero was 78 ppb. The concentration decreased to
approximately 10 ppb and reached a steady-state for the remainder of the
experiment.

K22: At time zero, the concentration of iron was 657 ppb. The graph illustrates a
decrease to a concentration of 30 ppb at day 15. There was an increase to 86 ppb at
day 30. After day 30, the concentration of iron remained at steady-state for the
remainder of the experiment.

022: Iron concentration for time zero was 50 ppb. There was a decrease in
concentration to day 45. There was an increase to 71 ppb at day 60, and then the

concentration decreased for the remainder of the experiment.

Always Wet Treatment (Figure 12)

J 19: The concentration of iron was above 3000 ppb for 30 days. Afier 30 days, the
concentration started to decrease to 820 ppb on day 45. The concentration increased
from day 45 to day 60 to a concentration of 1610 ppb. Afier day 60, the

concentration of iron decreased to a steady-state of 285 ppb.

142

N23: Initial concentration of iron was 3806 ppb. The concentration of iron
decreased over the duration of the experiment to 1363 ppb. Between days 75 and 90,
the concentration started to achieve a steady-state 1400 ppb.

P25: The concentration of iron at the start of the experiment was 1576 ppb. The
concentration acreased to day 75 where the concentration reached a steady-state.
The final concentration of iron was 109 ppb.

J23: The initial concentration was 187 ppb. The concentration increased at day 30
to 210 ppb. After day 30, the concentration woreased and reached a steady-state of
approximately 19 ppb at day 45.

K22: Initial concentration of iron was 431 ppb. The concentration of iron decreased
until day 45 where a steady-state was reached at approximately 67 ppb.

022: The initial concentration of iron was 115 ppb. The graph illustrates a decrease
to day 45. After day 45, a steady-state was reached. The final concentration of iron

was 12 ppb.

Formaldehyde Treatment (Figure 13)
J 19: At time zero, the iron concentration was 189 ppb. The concentration of iron
decreased for the remainder of the experiment.

In comparison to the DDAW treatment (Figure 11), the concentration of iron
at time zero was higher in the formaldehyde treatment The trends differed after 45
days where the formaldehyde treatment continued to decrease and the DDAW

treatment slightly increased.

143

N23: The initial concentration of iron at time zero was 457 ppb. The concentration
decreased to 78 ppb at time 15 days. The concentration of iron then increased to 335
ppb at time 60 days. Finally, the concentration decreased for the remainder of the
experiment with a final concentration of 90 ppb.

The concentration of iron at time zero was higher for the formaldehyde
treatment (Figure 13) than the DDAW treatment (Figure 11). The trends of the two
treatments are different. The graph of the DDAW treatment (Figure 11) shows a
decrease followed by an increase. On the other hand, the graph of the formaldehyde
treatment shows an additional decrease after the increase at 60 days.

P25: At time zero, the concentration of iron was 2361 ppb. There was a significant
decrease in iron concentration to 38 ppb on day 30. After day 30, the concentration
of iron increased to 128 ppb on day 75. The concentration decreased between day 75
and day 90 with a final concentration of 75 ppb. The trends of both the DDAW
treatment (Figure 11) and the formaldehyde treatment (Figure 13) were similar.

J 23: The initial concentration of iron was 54 ppb. The concentration decreased to
14 ppb on day 30. There was an increase in iron concentration to 162 ppb on day 45 .
The graph illustrates a decrease to day 60 followed by an increase to 36 ppb at day
90.

In comparison to the graph of the DDAW treatment (Figure 11), the graph of
the formaldehyde treatment had a series of decreases and increases where the
DDAW treatment graph showed a decrease to a steady-state.

K22: At time zero, the concentration of iron was 569 ppb. The graph illustrates a

decrease in iron to 41 ppb on day 30. The concentration of iron increased from day

144

30 to a concentration of 162 ppb on day 60. Finally, the graph shows a‘decrease for
the remainder of the experiment.

The DDAW treatment graph (Figure 11) is similar to the formaldehyde
treatment graph except for the increase and subsequent decrease surrounding day 60
in the formaldehyde treatment.

022: The time zero concentration was 660 ppb. The concentration decreased
between time zero and 15 days. At 15 days the concentration reached a steady-state
of approximately 10 ppb for the remaining 75 days.

A high concentration of iron at day 60 of the DDAW treatment and the initial
concentration of iron in the formaldehyde treatment were the only two differences
between the graphs. The initial concentration of the formaldehyde treatment (Figure
13) was 10 times higher than the initial concentration of iron in the DDAW

treatment.

Glutzflrldehvde Treatment (Figure 14)
J19: The concentration of iron at time zero was 2476 ppb. After time zero, there
was a decrease to day 15 where the graph remained at steady-state for the remaining
75 days with a final concentration of 50 ppb.

The trends are similar to the graph of the DDAW treatment (Figure 11) and
the formaldehyde treatment (Figure 13). The initial concentration was much higher
in the glutaraldehyde treatment, but after time zero, the graph illustrates a steady-

state similar to the formaldehyde treatment with similar concentrations.

145

N23: At time zero, the concentration of iron was 425 ppb. The concentration of iron
decreased from time zero to day 30 where the concentration was 70 ppb. After day
30, the concentration of iron increased to 250 ppb on day 45. After day 60, the
concentration of iron reached a steady-state of approximately 160 ppb.

In comparison to the graph of the formaldehyde treatment (Figure 13), the
graph of the glutaraldehyde treatment (Figure 14) had similar concentrations of iron.
The trends, however, were different. Both exhibited an initial decrease after time
zero. A second high point was reached a different times according for each
treatment. For the formaldehyde treatment (Figure 13), the second peak was reached
at 60 days. The second peak was reached at 45 days in the graph of the
glutaraldehyde treatment (Figure 14). In the glutaraldehyde treatment, the graph
(Figure 14) shows the iron concentration reaching a steady-state after the second
peak On the other hand, in the formaldehyde treatment, the graph (Figure 13) shows
the iron concentration continuing to decrease after the second peak.

The graph of the DDAW treatment (Figure 11) has a decrease to day 30

followed by an increase for the remainder of the experiment. This is different than
the steady-state shown in the graph of the glutaraldehyde treatment (Figure 14).
P25: The initial concentration was 592 ppb. The concentration of iron decreased to
60 ppb on day 15. After day 15, the concentration of iron increased to a second high
point at day 30 of 325 ppb. After the second high point, the graph shows the
concentration of iron reaching a steady-state of approximately 160 ppb.

In comparison to the graph of the formaldehyde treatment (Figure 13) and the

graph of the DDAW treatment (Figure 1 l), the graph of the glutaraldehyde treatment

146

is different. The graphs of the glutaraldehyde treatment had a peak concentration at
day 30.

J23: At time zero, the concentration of iron was 297 ppb. After time zero, the
concentration decreased to a steady-state of approximately 14 ppb.

The graph of the glutaraldehyde treatment (Figure 14) is similar to the graph

of the DDAW treatment (Figure 11). The graph of the formaldehyde treatment
(Figure 13) does not reach a steady-state like the graphs of the DDAW treatment
(Figure 11) and the glutaraldehyde treatment (Figure 14).
K22: The initial concentration of iron was 2039 ppb. There was a decrease to 30
days where the concentration was 31 ppb. The concentration of iron increased to
107 ppb at 45 days. The concentration decreased to 73 ppb on day 60. The
concentration increased again to day 75 . Finally, the concentration decreased to 52
ppb on day 90.

In comparison to graphs for the DDAW treatment (Figure 11) and the
formaldehyde treatment (Figure 13), the initial concentration of iron was higher in
the glutaraldehyde treatment (Figure 14). The three graphs have different trends.
However, a general trend of a sharp decrease followed by increases and decreases
can be found in all three graphs.

022: At time zero, the concentration of iron was 1128 ppb. Alter time zero, the
concentration of iron decreased and then reached steady-state of approximately 10
ppb.

The graphs of the glutaraldehyde treatment (Figure 14) and the formaldehyde

treatment (Figure 13) are similar. They both differ from the DDAW treatment by the

147

peak at day 60 in the DDAW treatment graph (Figure 11). Initial concentrations of
iron are also different where the glutaraldehyde treatment sample is double the
formaldehyde treatment sample, which is ten times higher than the DDAW

treatment.

Bimonthly DflinLTreatment (F igure 15)

J 19: This site is always dry in the field. For the first 30 days the concentration of
total iron decreased. On day 45, the peak on the trend is reached. The
concentrations weline alter the peak with a few smaller increases for the duration of
the experiment.

N23: After a short decline for the first 30 days, the concentrations increase to a peak
at 60 days. After the peak, the concentrations decrease for the duration of the
experiment.

P25: The concentration starts high and then the concentrations decrease to day 30.
Between days 30 and 60 the concentrations increase to a second smaller peak. After
the second peak, the concentrations decrease for the remainder of the experiment.
J23: The graph starts with small increases and decreases followed by a peak of 97
ppb at day 60. After day 60 there is a sharp decline to day 75 followed by a small
increase for 30 days. The graph then decreases for 15 days followed by a small
increase for the remainder of the experiment.

K22: The graph increases from time zero to 127 ppb on day 45. After day 45, the
graph decreases followed by a series of small-scale increases and decreases for the

remainder of the experiment.

148

022: The graph peaks after 15 days of drying and is followed by a sharp decline.

The remainder of the graph consists of small scale increases and decreases.

3.0 Manganese

DDAW Treatment (Figure 16)

J 19: Initially, the concentration of manganese was 11 ppb. The concentration
increased to a concentration of 41 ppb on day 60. The concentration then slightly
decreased for the remaining 30 days.

N23: The initial concentration of manganese was 8 ppb. The concentration of
manganese increased for the entire 90 days of the experiment to 27 ppb.

P25: At time zero, the concentration of manganese was 13 ppb. The concentration
decreased to 4 ppb on day 15. The concentration increased to 22 ppb on day 45.
The concentration then decreased for the remaining 45 days to 5 ppb.

J23: The initial concentration of manganese was 0.44 ppb. The concentration
increased to day 45 where the concentration was 1.44 ppb. From day 45 to day 90
the concentration decreased to 0.8 ppb.

K22: At time zero, the concentration of manganese was 8 ppb. The concentration of
manganese increased to 36 ppb on day 45. The concentration then decreased to day
60. After day 60, the concentration increased to 53 ppb on day 75 and then

decreased to 38 ppb on day 90.

149

022: The manganese concentration at time zero was 5 ppb. The concentration
decreased to 1 ppb on day 15 . After day 15, the concentration increased to 7 ppb on

day 60. The concentration then decreased for the remaining 30 days.

Always Wet Treatment (Figure 17)

119: The initial concentration of magnesium was 436 ppb. The concentration
decreased to a steady-state of approximately 43 ppb on day 75.

N23: Initially, the concentration of manganese was 622 ppb. The concentration
decreased 530 ppb for the 90 days of the experiment.

P25: The initial manganese concentration was 134 ppb. The concentration of
chromium decreased to a final concentration of 18 ppb on day 90.

123: Initially, the manganese concentration was 12 ppb. The concentration
decreased 11% for the duration of the experiment.

K22: The initial manganese concentration was 75 ppb. The concentration decreased
to 9 ppb on day 75. After day 75, the concentration of manganese increased to 14
ppb on day 90.

022: The initial concentration of manganese was 39 ppb. The concentration of
manganese decreased for the remainder of the 90 days where the final concentration

was 2 ppb.
F ormaldehyde Treatment (Figure 18)
119: Initially, the concentration of manganese was 179 ppb. The concentration

increased to the highest concentration of 790 ppb on day 15. After day 15, the

150

concentration decreased for the remaining 75 days with a final concentration of 177
ppb.

In comparison to the DDAW treatment graph (Figure 16), the graph of
formaldehyde treatment (Figure 18) illustrated the opposite trend. The DDAW
treatment concentrations increased to day 60 and then decreased, where the graph of
formaldehyde treatment increased to day 15 and then decreased for the remaining 75
days. The formaldehyde treatment samples had higher concentrations than the
DDAW treatment samples for the entire experiment
N23: The initial concentration of manganese was 482 ppb. The concentration
increased 19% to day 60 with a small decrease at day 45. After day 60, the
concentration decreased to remaining 30 days to a final concentration of 92 ppb.

Manganese concentrations for the formaldehyde treatment samples were

higher than the DDAW treatment samples. The DDAW treatment concentrations
(Figure 16) increased for the entire experiment. On the other hand, the
concentrations of the formaldehyde treatment (Figure 18) increased to day 60 and
then decreased for the remaining 30 days.
P25: At time zero, the concentration of manganese was 15 ppb. The concentration
decreased to day 15 with a concentration of 4 ppb. After day 15, the concentration
increased to 16 ppb on day 45. The concentration then decreased for the remaining
45 days.

In comparison, the DDAW treatment graphs (Figure 16) and formaldehyde

treatment graphs (Figure 18) display similar in trends. The concentrations both

151

decrease for the first 15 days, increase for the next 30 days, and decrease for the
remaining 45 days.

123: The manganese concentration at time zero was 14 ppb. The concentration
increased to 38 ppb on day 75. After day 75, the concentration of manganese
decreased to 8 ppb on day 90.

The concentrations of manganese in the formaldehyde treatment samples

(Figure 18) were higher than the concentration of manganese in the DDAW
treatment samples (Figure 16). In comparison, the two graphs exhibited different
trends. The DDAW treatment concentrations (Figure 16) had a peak at day 45
followed by a general steady-state trend for the entire experiment On the other
hand, the formaldehyde treatment graph (Figure 18) increased to day 75 and then
decreased to day 90.
K22: Initially, the concentration of manganese was 72 ppb. The concentration
increased to 550 ppb on day 15. After day 15, the concentration wereased to 203
ppb at day 45. The concentration increased again to 795 ppb on day 60. Manganese
concentrations decreased for the remaining 30 days.

In comparison, the concentrations of manganese were higher in the
formaldehyde treatment samples (Figure 18) than in the DDAW treatment samples
(Figure 16). The DDAW treatment concentrations showed an increased for the 90
days. Conversely, the concentrations of the formaldehyde treatment showed an
initial increased followed by a series of increases and decreases.

022: At time zero, the concentration was 39 ppb. The concentration decreased to 6

ppb on day 15, and then the concentration increased to day 30. After day 30, the

152

concentration reached a steady-state of approximately 17 ppb until day 60. After day
60, the concentration decreased for remaining 30 days.

Concentrations of manganese are higher in formaldehyde treatment samples
(Figure 18) than in the DDAW treatment (Figure 16). The trends of both graphs are
similar. The graphs are at steady-state for the majority of the experiment. The
concentration ranges for the formaldehyde treatment is between 6 and 19 ppb for all
concentrations except for the initial concentration, and the range of manganese

concentration for DDAW treatment was between 1 and 7 ppb.

glam—raldehyde Treatment (figure 19)

119: Initially, the concentration of manganese was 81 ppb. The concentration
increased to 175 ppb to day 45 with a small decrease at day 30. The concentration of
manganese than decreased to a steady-state of approximately 1 19 ppb on day 75 .

In comparison to the DDAW treatment and the formaldehyde treatment
graphs, the concentration of manganese in the glutaraldehyde treatment samples are
intermediate. All three of the graphs have trends that increase and then decrease
over time.

N23: At time zero, the concentration of manganese was 28 ppb. The concentration
increased to 377 ppb at 45 days. The concentration decreased for the remaining 45
days to a final concentration of 52 ppb.

The concentrations of glutaraldehyde treatment samples (Figure 19) are
intermediate between those of the formaldehyde treatment samples (Figure 18) and

DDAW treatment samples (Figure 16). The formaldehyde and glutaraldehyde

153

treatment concentrations (Figure 18 and 19 respectively) increase followed by a
decrease. On the other hand, the DDAW treatment graph (Figure 16) increased for
the entire 90 days.

P25: The initial concentration of manganese was 43 ppb. The concentration
increased to 296 ppb on day 30. The concentration decreased to a steady-state at day
45.

The highest concentration of manganese was in the glutaraldehyde treatment

samples (Figure 19). The general trend of all the treatments is a high concentration
at day 30 or day 45 followed by a decrease or steady-state.
123: At time zero, the concentration of manganese was 4 ppb. The concentration
decreased to 2 ppb on day 15. After day 15, the concentration increased to the
highest concentration of 8 ppb on day 30. The concentration decreased to day 60
where the concentration reached a steady-state of approximately 3 ppb.

The concentrations of the glutaraldehyde treatment samples (Figure 19) are
intermediate between the formaldehyde treatment (Figure 18) and the DDAW
treatment (Figure 16) samples. The trends of the glutaraldehyde treatment graph
(Figure 19) are similar to the trends of the DDAW treatment graph (Figure 17).

K22: The initial concentration of manganese was 31 ppb. The concentration
increased to day 45 where the concentration was 210 ppb. The concentration
decreased for the remaining 45 days to a final concentration of 81 ppb.

The trends of the glutaraldehyde treatment graph (Figure 19) were different
than the formaldehyde treatment graph (Figure 18) and the DDAW treatment graph

(Figure 16). It differs from the formaldehyde treatment graph (Figure 18) by the lack

154

of two peaks of that graph, instead a single peak at day 45 was observed (Figure 19).
The DDAW treatment graph (Figure 16) differs because the concentrations increase
for all 90 days.
022: Initially, the concentration of manganese was 22 ppb. The concentration
decreased to 2 ppb on day 15. The concentration then increased to a steady-state
where the concentrations ranged between 5 and 8 ppb.

In comparison, the glutaraldehyde treatment and formaldehyde treatment
were similar in concentration and trends. However, the DDAW treatment
concentrations had a peak at day 90 and the concentrations were higher than the

glutaraldehyde treatment.

Bimonthly DryingTrgrtment (Figure 20)

119: The initial concentration of manganese was 12 ppb. The highest concentration
of manganese was 127 ppb on day 15. After day 15, the concentration of manganese
decreased with small increases at days 45 and 75.

N23: The initial concentration of manganese was 6 ppb. The concentration of
manganese increased from day 15 to a peak of 14 ppb on day 60. From day 60 to
day 75 the concentration decreased followed by an increase to the highest peak of 17
ppb. After the second peak, the concentration decreased for the remainder of the
experiment.

P25: The initial concentration of manganese was 5 ppb. After an initial decrease

from time zero to day 15, the concentration increases to 13 ppb on day 90. After day

155

90, the concentration of manganese decreases for the remainder of the experiment to
a concentration of 3 ppb.

1 23: The concentrations of manganese vary between 0 and 2 ppb for the entire
experiment. There were two peaks of approximately 2 ppb on day 45 and 75 .

K22: The initial concentration of manganese was 4 ppb. The concentration of
manganese increases to a peak of 15 ppb on day 60. After day 60, the concentration
of manganese decreases for the remainder of the experiment.

022: The initial concentration of manganese was 2.37 ppb. The concentration
increases to 3 ppb and is followed by a decrease. There is one smaller peak before

the decrease to the final concentration, which was less than 1 ppb.

4.0 Strontium

DDAW Treatment (F ige 21)

119: The initial concentration of strontium was 8 ppb. The concentration increased
to 15 ppb on day 60. The concentration decreased from day 60 to day 75 followed
by an increase over the last 15 days to a final concentration of 12 ppb.

N23: At time zero, the concentration of strontium was 2 ppb. The concentration
increased to 24 ppb on day 45. After day 45, the concentration decreased to a
steady-state of approximately 14 ppb.

P25: Initially, the strontium concentration was 4 ppb. From time zero to day 15, the

concentration decreased to 1 ppb. After day 15 , the concentration increased to 25

156

ppb on day 45. The concentration decreased for the remaining 45 day to a final
concentration of 3 ppb.

1 23: The initial strontium concentration was 10 ppb. The concentration increased to
144 ppb on day 30. After day 30, the concentration decreased to a steady-state of
approximately 23 ppb.

K22: Initially, the strontium concentration was 12 ppb. From time zero to day 45,
the concentration increased to 148 ppb. After day 45, the concentration decreased
for the remaining 45 days to 35 ppb.

022: At time zero, the strontium concentration was 24 ppb. The concentration of
strontium decreased for the entire 90 days with a small increase at day 30 to a final

concentration of 9 ppb.

Always Wet Treatment (Figure 22)

119: The initial concentration of strontium was 80 ppb. The concentration increased
to 101 ppb on day 30, and decreased to 89 ppb on day 45. After day 45, the
concentration of strontium increased to 95 ppb on day 60. After day 60, the
concentration decreased for the remaining 30 days to a final concentration of 67 ppb.
N23: Initially, the concentration of strontium was 95, ppb. The concentration of
strontium decreased for the entire duration of the experiment to 22 ppb.

P25: The initial strontium concentration was 36 ppb. The strontium concentration
decreased for the remaining 75 days to 3 ppb.

123: The initial concentration of strontium was 110 ppb. The concentration stayed

at a steady-state to day 30. After day 30, the concentration of strontium reached a

157

second steady-state to day 75 of approximately 76 ppb. After day 75, the
concentration decreased to 56 ppb on day 90.

K22: Initially, the concentration of strontium was 86 ppb. The concentration
decreased to 54 ppb on day 45. At day 45 the concentration was at a steady-state of
approximately 54 ppb for 30 days. After day 75, the concentration decreased to 41
ppb-

022: Initially, the strontium concentration was 112 ppb. The concentration
decreased to 78 ppb on day 45. The concentration increased to 92 ppb on day 60.
Following the increase, the concentration decreased for the remaining 30 days to a

final concentration of 72 ppb.

Formaldehyde Treatment figure 23)

119: The initial strontium concentration was 53 ppb. The concentration increased
from time zero to 65 ppb on day 15 . After day 15, the concentration decreased for
the remaining 75 days to a final concentration of 16 ppb.

The formaldehyde treatment (Figure 23) concentrations decreased for most of
the experiment. This is different from the general increasing trend of the DDAW
treatment (Figure 21).

N23: Initially, the strontium concentration was 69 ppb. The concentration increased
to 204 ppb on day 30. The concentration decreased at day 45; however, the
concentration increased again to 237 ppb on day 60. After day 60, the concentration

decreased for the remaining 30 days to 14 ppb.

158

In comparison to the DDAW treatment graph (Figure 21 ), both graphs had an

increase followed by a decrease. The peak before the decrease was 15 days later in
the formaldehyde treatment graph (Figure 23).
P25: At time zero, the strontium concentration was 4 ppb. The concentration
initially decreased to 2 ppb on day 15. After day 15, the concentration increased to
day 45 where the concentration was 22 ppb. The concentration then decreased to 8
ppb on day 75. There was a final increase after day 75 to day 90.

Except for the final increase, the DDAW treatment graph (Figure 21) and the
formaldehyde treatment graph (Figure 23) were similar in trends and concentrations.
1 23: Initially, the strontium concentration was 118 ppb. The concentration of
strontium increased to a peak at day 75 where the concentration was 368 ppb. After
day 75, the concentration decreased to 82 ppb on day 90.

The concentration of strontium in the formaldehyde treatment graph (Figure

23) was higher than the concentration of strontium in the DDAW treatment graph
(Figure 21). The peak concentration was 45 days later in the formaldehyde treatment
graph (Figure 23) in comparison to the DDAW treatment graph (Figure 21).
K22: At time zero, the strontium concentration was 43 ppb. The concentration of
strontium increased to 269 ppb on day 15. After day 15, the concentration decreased
to 91 ppb on day 45. The strontium concentration increased to day 75 to a maximum
of 37 1 ppb and, finally, the concentration decreased to 41 ppb on day 90.

In comparing the DDAW treatment graph (Figure 21) and the formaldehyde
treatment graph (Figure 23), the concentrations are higher in the formaldehyde

treatment graph (Figure 23). Another difference is the two peaks present in the

159

formaldehyde treatment graph (Figure 23) versus the single peak present in the
DDAW treatment graph (Figure 21 ).

022: The initial concentration of strontium was 53 ppb. The strontium
concentration decreased from time zero to 29 ppb on day 15. After day 15, the
concentration increased to a steady-state of approximately 62 ppb for 45 days. After
day 75, the strontium concentration decreased to 40 ppb on day 90.

In comparison, the concentration of the formaldehyde treatment graph
(Figure 23) was higher than the concentration of the DDAW treatment graph (Figure
21). In contrast, the DDAW treatment graph (Figure 21) decreased for the duration
of the experiment while the formaldehyde treatment graph (Figure 23) was at a

steady-state for the majority of the experiment.

Glutaraldehyde Treatment 1 F igrre 24)
119: At time zero, the strontium concentration was 24 ppb. The concentration of
strontium decreased for all 90 days to a final concentration of 12 ppb.

In comparison to the DDAW treatment graph (Figure 21), the concentrations
are similar while the trends are opposite. The DDAW treatment graph (Figure 21)
increases over the duration of the experiment, which is in contrast to the decreasing
trend of the glutaraldehyde treatment (Figure 24). Both the formaldehyde treatment
graph (Figure 23) and the glutaraldehyde treatment graph (Figure 24) have the

decreasing for the 90 days.

160

N23: Initially, the strontium concentration was 6 ppb. The concentration increased
to 77 ppb on day 45 . After day 45, the concentration decreased for the remaining 45
days to 10 ppb.

The glutaraldehyde treatment graph (Figure 24) has a similar trend to the
DDAW treatment graph (Figure 21). Both the aforementioned graphs have the peak
present at 45 days. On the other hand, the formaldehyde treatment graph (Figure 23)
has two peaks. The concentration is highest in the formaldehyde treatment graph
(Figure 23) followed in decreasing concentration by the glutaraldehyde treatment
graph (Figure 24) and the DDAW treatment graph (Figure 21).

P25: The initial strontium concentration was 11 ppb. The concentration increased to
72 ppb on day 30. After day 30, the concentration decreased to a steady-state of
approximately 14 ppb for the remainder of the experiment.

In comparison to the DDAW treatment graph (Figure 21) and the
formaldehyde treatment graph (Figure 23 ), the glutaraldehyde treatment graph
(Figure 24) has a similar trend of a single peak leading to a steady-state. However,
the peak occurred 15 days earlier in the glutaraldehyde treatment graph (Figure 24)
than the DDAW treatment.

123: Initially, the strontium concentration was 52 ppb. The concentration of
strontium increased to 182 ppb on day 30. After day 30, the concentration of
strontium decreased to a steady-state of approximately 51 ppb.

The glutaraldehyde treatment graph (Figure 24) has similar trends to the
DDAW treatment graph (Figure 21 ). In contrast, the glutaraldehyde treatment graph

(Figure 24) peaked earlier than the formaldehyde treatment graph (Figure 23), and

161

the glutaraldehyde treatment graph (Figure 24) has a lower concentration of
strontium than the formaldehyde treatment graph (Figure 23).

K22: At time zero, the strontium concentration was 22 ppb. The concentration
increased from time zero to 45 days where the concentration was 162 ppb. After day
45, the concentration decreased for the remaining 45 days to a concentration of 49
ppb.

Comparing the DDAW treatment graph (Figure 21) to the glutaraldehyde

treatment graph (Figure 24), the trends and concentrations of the two graphs were
similar. In contrast, the formaldehyde treatment graph (Figure 23) had two peaks to
the one peak of the glutaraldehyde treatment graph (Figure 24).
022: The initial concentration of strontium was 41 ppb. The concentration
decreased to day 15. After day 15, the concentration increased to 39 ppb on day 60.
After day 60, the concentration of strontium decreased for the remaining 30 days to a
final concentration of 25 ppb.

The trends and concentration of glutaraldehyde treatment (Figure 24) were
similar to the trends of the formaldehyde treatment (Figure 23 ). However, the trends
are not the same as the DDAW treatment graph (Figure 21) where the concentration
decreased over the entire experiment in the DDAW treatment graph and the
concentration increased for 45 days before the decrease in the glutaral dehyde

treatment graph (Figure 24).

162

Bimonthly Drying Treatment (Figure 25)

119: The initial concentration of strontium was 4.16 ppb. From time zero to day 15
the concentration of strontium eluded increased to 27 ppb. After day 15, the
concentration of strontium decreased in a step fashion and the concentration of
strontium eventually went to zero.

N23: The initial concentration of strontium was 1.2 ppb. The concentration of
strontium in solution increased from time zero to a concentration of 16 ppb on day
75 . The concentration of strontium then decreased to day 135 where the
concentration of strontium eluded was zero ppb.

P25: The initial concentration of strontium was 1.26 ppb. The concentration of
strontium in solution increased to 16 ppb on day 90. After day 90, the concentration
of strontium in solution decreased to zero ppb on dayl35.

123: The initial concentration of strontium was 6.62 ppb. From time zero to day 15
the concentration of strontium in solution increased to 47 ppb. From day 15 to day
45 the concentration of strontium eluded decreased to 16 ppb. The concentration of
strontium increased again from day 45 to day 75 to a concentration of 33 ppb. There
was a decrease in strontium concentration to 13 ppb on day 105. After day 105, the
concentration of strontium eluded increased to 22 ppb on day 120. After day 120,
the concentration of strontium in solution was zero ppb.

K22: The initial concentration of strontium was 5.27 ppb. From time zero to day 15,
the concentration of strontium in solution increased to 55 ppb. From day 15 to day
45, the concentration of strontium in solution decreased to 31 ppb. The

concentration of strontium in solution increased to 61 ppb on day 60. From day 60

163

to day 135, the concentration of strontium decreased to 38 ppb. The final
concentration of strontium was zero ppb.

022: The initial concentration of strontium was 11 ppb. The concentration of
strontium eluded increased to 20 ppb on day 15. From day 15 to day 45, the
concentration of strontium decreased to 8 ppb. From day 45 to day 60, there was an
increase in strontium concentration to 14 ppb. After day 60, the concentration of
strontium in solution decreased. After day 135, the concentration of strontium in

solution was zero ppb.

164

APPENDIX VI

165

APPENDIX VI

Dissolved Organic Carbon Results

Icopini and Long (1999) demonstrated that dissolved organic carbon (DOC)
is important in controlling chromium concentrations in water. In the present
experiment, the DOC relation to chromium was studied in samples that were not
treated with microbialcidal fluids. In this experiment, there is not a correlation
between DOC and chromium for the majority of the sites. Only one site (119) shows
a significant correlation between DOC and chromium; the R2 values for 119 weekly
(Figure 26) and bimonthly (Figure 27) are 0.7648 and 0.8736 respectively. The R2

values for the other sites range from 0.0004 to 0.6732.

166

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168

APPENDIX VII

169

APPENDIX VII

Concentrated Nitric Acid Leaching

Concentrated nitric acid leaching was performed on the soils used in the
wetting and drying experiments. The values for the concentrations of chromium in
the soil are presented in Table 6. From the results, it is clear that the amount of
chromium in the soil does not influence the amount of chromium eluded during
wetting and drying experiments. The values from the concentrated nitric acid
leaching are similar to the summation of sequential extractions (Table 1) presented
by Icopini et al. (1997, 1998, 1999) and Ellis (1999). The sites can be divided into
three high concentration sites (.119, .123, and K22) and three lower concentration sites
(N23, 022, and P25). The amount of chromium in solution does not correspond to
the same concentration breaks. Concentrations from the wetting and drying
experiments presented in Table 83 were placed in decreasing order of chromium
concentration in solution: .119, N23, P25, K22, J23, and 022. Grouping sites
according to the field saturation state was the best indicator of the relative

concentration of chromium in solution.

170

 

 

 

 

 

 

 

 

 

 

 

 

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171

BIBLIOGRAPHY

172

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175