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LIBRARY
Michigan State
University

 

 

 

This is to certify that the

thesis entitled

HEAVY METAL PARTITIONING IN SOILS OF VARIABLE
TEXTURE AND REDOX POTENTIAL: AN EVALUATION
OF SEQUENTIAL CHEMICAL EXTRACTIONS

presented by

Robert J. Ellis

has been accepted towards fulfillment
of the requirements for

M.S. degree in Geological Sciences

 

    

Major professor

DateW

0-7639 MS U is an Affirmative Action/Equal Opportunity Institution

PLACE IN RETURN BOX to remove this checkout from your record.

TO AVOID FINES return on or before date due.

MAY BE RECAU£D with earlier due date if requested.

 

  
 

h
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\
DU

DATE DUE

DATE DUE

DATE DUE

 

i003

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

1M WW“

 

 

HEAVY METAL PARTITIONING IN SOILS OF VARIABLE
TEXTURE AND REDOX POTENTIAL:
AN EVALUATION OF SEQUENTIAL CHEMICAL EXTRACTIONS

By

Robert J. Ellis

A THESIS

Submitted to

Michigan State University
in partial fulfillment of the requirements
for the degree of
MASTER OF SCIENCE

Department of Geological Sciences

1999

 

The fa
Iannery site. 1
state. organic
OPNHUHII)‘ to
and sequesten’
Chemical emr
partitioning it

gained from s

 

In oxit

(MR‘FC Oxi:

 

 

ABSTRACT
HEAVY METAL PARTITIONING 1N sons OF VARIABLE
TEXTURE AND REDOX POTENTIAL:

AN EVALUATION OF SEQUENTIAL CHEMICAL EXTRACTIONS
By

Robert J. Ellis

The fates of metals (e. g. Fe, Cu, and Zn) have been studied in soils at a former
tannery site. Soil at the site varied in degree of water saturation, oxidation-reduction
state, organic matter content, and metals concentrations. These conditions afforded the
opportunity to study how biogeochemical soil conditions affect the formation, alteration,
and sequestering ability of environmentally reactive metal binding phases. Sequential
chemical extractions (SCEs) and porewater chemistry were used to determine metal
partitioning within soil, and between solid and fluid phases, respectively. Information
gained from SCEs, developed for oxic systems, was evaluated for anoxic systems.

In oxic soils, the easily reducible (ER - reactive Fe oxides), moderately reducible
(MR - Fe oxides), and basic oxidizable (OX1 - organic matter) were the most important
sequestering phases of metals. In anoxic soils these three phases were also important, but
the mineralogical substrates comprising the ER and MR phases were unclear. Detailed
analyses of meta-stable, water saturated, anoxic soils including: porewater redox potential
determination; geochemical modeling; SCEs; acid volatile sulfide extractions; magnetic
mineral fractionation; and x-ray diffraction, were preformed to determine mineralogical
substrates comprising the ER and MR phases. SCEs performed on pure minerals,
identified in anoxic soils, demonstrated that the SCE method used could not selectively

distinguish between substrates that were found to comprise the ER and MR phases.

For my mother,
Janet M. Friske,
who has struggled for many years to support our family,
and has shown me, by example,
the value of hard work, dedication and perseverance

-- R.J.E

iii

ACKNOWLEDGEMENTS

My development as a geologist has been guided by several teachers and fellow
students. Foremost among them, my advisor, David T. Long, who has been very
influential at several critical stages of my academic career. Others include: my thesis
committee members, Michael Velbel, Sharidan Haack, and Duncan Sibley, who provided
helpful reviews of early drafts of this thesis; and my good friends, Jon Kolak and Gary
leapini, fellow graduate students, who provided technical guidance and encouragement
that helped me accomplish the goals of this research. Several others assisted with
laboratory work and sample analyses during this research. Among them were Jennifer
McGuire, Nathan Mellot, Sarah Hayes, Raullie Casteel, Page Vassar, Jeff Vought,
Michael Klug, Michael Roberts, Jane Matty, Paul Laconto, and Susan Sipple. I thank
them all.

This research was funded by a grant from a corporate sponsor who wishes to

remain anonymous.

iv

‘nm

LIST OF T.~‘
LIST OF F I
I. [\TRODI

II. BACKGI
2.1 -1

I‘d
IQ

I
PH

 

TABLE OF CONTENTS

LIST OF TABLES ................................................................................................... viii
LIST OF FIGURES ................................................................................................. xi
I. INTRODUCTION ................................................................................................ 1
H. BACKGROUND INFORMATION
2.1 - Site Description ..................................................................................... 6
2.1.1 - study site location ................................................................... 6
2.1.2 - site history ............................................................................... 8
2.1.3 - topography land surface characteristics .................................. 9
2.1.4 - soil characteristics ................................................................... 10
2.2 - Environmental Chemistry of Metals and Substrates ............................. 11
2.2.1 - soil constituents and distribution of metals in soils ................ 11
2.2.2 - surface functional groups and surface charge ......................... 12
2.2.3 - metal ions in solution .............................................................. 13
2.2.4 - adsorption, complexation and co-precipitation ...................... 14
2.2.5 - geochemistry of iron, copper, zinc, sulfur and carbonate ....... 15
2.3 - Metal Cycling In Response to Changes in Redox Conditions .............. 19
III. METHODS
3.1 - Sample Grid Development, Surveying, and Site Locations .................. 21
3.2 - Soil Sample Collection .......................................................................... 23
3.3 - Clean Procedures ................................................................................... 23
3.4 - Sequential Chemical Extractions ........................................................... 24
3.5 - Procedure for Metals Analysis .............................................................. 26
3.6 - Organic Matter Determination ............................................................... 27
3.7 - Porewater Samplers ............................................................................... 27
3.8 - Porewater Field Measurements ............................................................. 31
3.9 - Measuring Redox Potential ................................................................... 31
3.10 - Geochemical Modeling ........................................................................ 32
3.11 - Acid Volatile Sulfide (AVS)Analysis ................................................. 32
3.12 - Magnetic Fraction Separation .............................................................. 33
3.13 - X-ray Diffraction ................................................................................. 35
3.14 - Pure Mineral Extractions ..................................................................... 36

11'. RESULTS A.‘
4.1 ~3011T
42-51613}

4.2. I
4.2.

4.2.
4.2.

4.3- Pure .‘l
4.4- Pores
4.4 '

4.4

4.5 - 5616-.“
4.6 - Geoc?
4.6

4.6

4.7- Acid
4.3 - Mag.“
4-9 - X-ra‘.
4.9

4.9
410'SUH
4.11 - C03:
E1111

Ext:

4.12 - F31;

VI. CONCLLSli
5.1 - Prir.

5.2 ' EVa:

Em;

REFERENCES

“Fusions
Append

 

IV. RESULTS AND DISCUSSION

4.1 - Soil Textures Descriptions ..................................................................... 37
4.2 - Metal Partitioning .................................................................................. 44
4.2.1 - general metal partitioning results ........................................... 44
4.2.2 - detailed metal partitioning results ........................................... 44
4.2.3 - comparison of partitioning from this study to other studies 59
4.2.4 - identifying phases not targeted by sequential chemical
extractions ............................................................................... 59
4.3 - Pure Mineral Extractions ...................................................................... 61
4.4 - Porewater Chemistry Results ................................................................. 66
4.4.1 - porewater chemistry ................................................................ 66
4.4.2 - redox conditions and terminal electron accepting processes. 70
4.5 - Selected Site Sequential Chemical Extraction Results .......................... 74
4.6 - Geochemical Modeling Results ............................................................. 78
4.6.1 - mineral saturation indices ....................................................... 78
4.6.2 - prediction of mineral precipitation and dissolution ............... 81
4.7 - Acid Volatile Sulfide/Simultaneously Extracted Metals Results .......... 83
4.8 - Magnetic Separation Results ................................................................. 87
4.9 - X-ray diffraction Results ....................................................................... 90
4.9.1 - x-ray diffraction results for samples from anoxic soils .......... 90
4.9.2 - effect of ER and MR extractions on carbonates and silicates 90
4.10 - Summary of the Search for Fe-Bearing Minerals in Anoxic Soils ...... 91
4.11 - Composition of Phases Identified by Sequential Chemical
Extractions: Interpreting Results of Sequential Chemical
Extractions .......................................................................................... 93
4.12 - Fate on Fe Cu and Zn in Soil at the Site .............................................. 99
VI. CONCLUSIONS
5.1 — Principle Findings ................................................................................. 101
5.2 - Evaluating the Use of Sequential Chemical Extractions in Anoxic
Environments ........................................................................................ 103
REFERENCES ......................................................................................................... 105
APPENDICIES
Appendix 1 - Solid Phase Sample Descriptions
A - sample location and core descriptions ........................................ 112
B - organic matter content .................................................................. 124
C - samples sorted by soil texture classifications ............................. 126
Appendix 2 - Supplemental Description of Methods
2A - sequential chemical extraction procedures ............................... 128
ZB - pore water sampling and analytical methods ............................. 132
2C - method for determination acid volatile sulfide and
simultaneously extracted metals ............................................... 136

vi

~ 1
. ndxx.
AW 3A
3A

3B»

 

3C
3C
3D

3E
3F
30

 

Appendix 3 - Supplemental Data Tables

3A—l - iron sequential chemical extraction data ............................... 140
3A-2 - replicate sample analysis for iron ........................................... 150
3B-1 - copper sequential chemical extraction data ........................... 154
3B-2 - replicate sample analysis for copper ....................................... 165
3C—1 - zinc sequential chemical extraction data ................................ 169
3C-2 - replicate sample analysis for zinc ........................................... 181
3D - acid volatile sulfide/simultaneously extracted metal

calculations ............................................................................. 185
3B - porewater data .......................................................................... 187
3F - sequential chemical extraction data for pure minerals ............. 191
3G - x-ray diffraction peak interpretations and mineral identification 193

vii

 

Table l. Summzu

Tessier

  
  

Table 2.. Soil text

LIST OF TABLES

Table 1. Summary of Sequential Chemical Extraction Procedure (modified after
Tessier et al. (1979)). ..................................................................................

Table 2. Soil texture descriptions and classifications with general location of
each, number of samples, and avarage organic matter (OM) content for
each texture. ................................................................................................

Table 3. Summary of relative partitioning of Fe, Cu, and Zn, as determined by
sequential chemical extractions among, oxic soils (Brown silty sand,
Rusty silty sand, Tan silty sand (unsaturated) and gravel/debris) and
anoxic soils (OM>50%. Silty sand with abundant OM, and Tan silty
sand (saturated)). .........................................................................................

Table 4. Summary of partitioning results from selected studies that used similar
selective chemical extraction schemes modified after Tessier etal., 1979.

Table 5: Summary of results from sequential chemical extractions of pure minerals.

Results are given as average per cent of metal recovered from each
extraction with respect to the sum total metal recovered. Values in bold
indicate the extraction that yielded the highest percentage of metal from
that particular mineral. ................................................................................

Table 6. Summary of selected pore water chemistry data for sites selected for
detailed solid phase analysis (November 1997) ..........................................

Table 7. Organic matter content (%), total Fe (umol/g) and partitioning for
selected sites ................................................................................................

Table 8. Organic matter content (%), total Cu (umol/g) and partitioning for
selected sites ................................................................................................

Table 9. Organic matter content (%), total Zn (umng) and partitioning for
selected sites ................................................................................................

Table 10. Saturation indices (SI = log IAP/Ksp) of selected minerals calculated by
PHREEQC with the Minteq database for pore waters at sites J23, K22,
N23, P25, and 022 ....................................................................................

Table lla. Concentrations of AVS measured simultaneously extracted metals (SEM)

for J19, J23, K22, N23, 022, and P25 in pmol/g dry weight soil. .........

viii

25

43

45

63

69

76

76

76

80

84

Table 11b. Calcu I
concer
the se.

 

Table 12. Solubi’.
1991 I

Table 13. Concer
the m.
dry so
deterr.

Table 14. Sum..
total 1’
attrlb':

Table 15. Calcul
by St"

Table 1A.]. 53L...

Table 13.1 01‘:

 

 

Table llb. Calculations of FeS, and Fe Othenmin) and Fe Othenm) and
concentration of total extractable Fe as determined by the sum of
the sequential extractions for comparison ................................................

Table 12. Solubility product constants of selected sulfides at 25°C (from Faure,
1991). .......................................................................................................

Table 13. Concentrations of Fe, Cu and Zn in leachate samples from extraction of
the magnetically separated fraction of selected soils, reported in 1.1111ng
dry soil used for the magnetic seperation. Total extractable Fe as

determined by sequential chemical extractions is shown for comparison.

Table 14. Summary of Fe concentrations in selected samples including the sum
total from sequential extractions; the ER-t- MR fractions; amount
attributed to FeS; magnetite; and amount from unidentified phases. ......

Table 15. Calculations of the amount of Fe in fluid portion of samples extracted
by sequential extractions along with values of Fe in EX phase ..............

Table lA-l. Sample Location and Soil Core Descriptions .......................................
Table lB-l. Organic Matter Content .........................................................................
Table lC-l. Samples Sorted by Soil Texture Classifications. ..................................
Table 3A-l. Sequential Chemical Extraction Data for Iron. .....................................
Table 3A-2. Replicate Sample Analysis for Iron. ....................................................
Table 3B-1. Sequential Chemical Extraction Data for Copper. ................................
Table 3B-2. Replicate Sample Analysis for Copper. ................................................
Table 301. Sequential Chemical Extraction Data for Zinc ....................................
Table 3C-2. Replicate Sample Analysis for Zinc. ....................................................

Table 3D-l. Calculation of 82‘ in NaOH Trap for Acid Volatile Sulfide
Determination. ......................................................................................

Table 3D-2 . Concentrations of simultaneously extracted metals (SEM) from
AVS/SEM analysis. .............................................................................

Table 3E-l. Pore water data for samples collected on 7/26/97 .................................

Table 3E-2. Pore water data for samples collected on 8/26/97 .................................

ix

84

86

89

92

95

112

124

126

140

150

154

165

169

181

185

185

187

188

Table 3E-3. POW
Table 312-4. Pore

Table 3F-l. Seq1

 

Table 3E-3. Pore water data for samples collected 10/8/97 ...................................... 189
Table 3E-4. Pore Water Data Collected on 11/20/97 ................................................ 190

Table 3F-l. Sequential Chemical Extraction Data for Pure Minerals ...................... 191

Figure 1. Site 1

Figure 2. Drag
mono

Figure 3. Loca‘
Figure 4. Schel
figure 5. Schei
Figure 6. Schet
Flgun: 7. Maps
Figure 8. Orgm
Flgut-e 9. Land
Figure 10a. P1.
Fianna 10b. P1.
Flgurm. Tril
“gm 12a. P1.
Flgure 12b. Pi:

“$11113. Re]
Cu.

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Figure 151). P;

mm, ,6. ml

Plgllre 17. P01

 

LIST OF FIGURES

Figure l. Site Layout ................................................................................................

Figure 2. Diagrammatic representation of the overall process of FeS, metal
monosulfide, and pyrite formation. (modified after Bemer,1984). ...........

Figure 3. Locations of soil samples collected in September and October, 1996.
Figure 4. Schematic diagram of a “peeper” pore water sampler. ............................
Figure 5. Schematic diagrams of a “barrel” pore water sampler. ............................
Figure 6. Schematic diagram of the acid volatile sulfide analytical apparatus. .......
Figure 7. Maps of soil textures for the three depth intervals. ..................................
Figure 8. Organic matter content (weight %) for three depth intervals. ..................
Figure 9. Land surface characteristics ......................................................................
Figure 108. Pie diagrams showing Fe partitioning in oxic soils. .............................
Figure 10b. Pie diagrams showing Fe partitioning in anoxic soils. .........................
Figure 11. Trilinear plot of Fe partitioning data in ER-MR-OXl space ..................
Figure 12a. Pie diagrams showing Cu partitioning in oxic soils. ............................
Figure 12b. Pie diagrams showing Cu partitioning in anoxic soils. ........................

Figure 13. Relationship between soil organic matter content and OX1 extractable
Cu. ...........................................................................................................

Figure 14. Trilinear plot of Cu partitioning data in ER-MR-OXI space. ................
Figure 15a. Pie diagrams showing Zn partitioning in oxic soils. ............................
Figure 15b. Pie diagrams showing Zn partitioning in anoxic soils. ........................
Figure 16. Trilinear plot of Zn partitioning data in ER-MR-OXI space. ................

Figure 17. Porewater sampling locations. ................................................................

xi

18

22

29

30

34

40

41

42

48

49

50

51

52

53

54

56

57

58

67

figure MIC-1.1..

 

Figure A2C-1. Low and normal range calibration curves for acid volitile
sulfide (AVS) method. .................................................................... 139

xii

Concern
contaminated of
gain insight into
6131., 1979; Luc
Gibson and Fan
al.. 1994). The
contain Comple.
amorPhOUS Oxic
imponafll Sinks
TEACHER“ HOV
(e.g. dissolutio:

 

haw meta-15 a.

f .
OMOD, 21116 I

 

I. INTRODUCTION

 

Concern over possible human health risk and ecological effects of heavy metal
contaminated of soil due to improper disposal of industrial waste has prompted studies to
gain insight into the fate of heavy metals in soil environments (e. g. Jenne, 1977; Tessier
et al., 1979; Luoma and Bryan, 1981; Harrison et al., 1981; Hickey and Kittrick, 1984;
Gibson and Farmer, 1986; Shannon and White, 1991; Yong et al., 1993; and Fielder et
al., 1994). The fate of heavy metals is difficult to access because soils and sediments
contain complex mixtures of sequestering phases. The exchangeable, carbonate,
amorphous oxide, crystalline oxide, organic matter, and sulfide phases are considered
important sinks for heavy metals due to their ubiquitous nature and environmental
reactivity. However, their reactivity also makes these phases susceptible to alteration
(e.g. dissolution) during natural biogeochemical processes (Jenne, 1977; Tessier et al.,
1979; Nirel and Thompson, 1987). Since the reactive phases have different affinities for
heavy metals and some are more susceptible to alterations than others, knowledge of the
relative partitioning of metals among the reactive phases of soil is necessary to predict
their potential mobility and bioavailability. Therefore, the purpose of this study is to
investigate how variable and dynamic biogeochemical soil conditions affect the

formation, alteration, and sequestering ability Of environmentally reactive metal binding

phases. This 5
magical med
The U3
has been the us
are applied to s
sediment samp
phase is based
Consequently.
relative partitio
Fecxides. cry».
concentrations .
Criticisr
cm’flCUOns and
1984; Tipping e
1986; Gmeel t
”traction Cfitig

during a Panic

 

 

 

phases. This study will also evaluate the effect different phases in soils have on
analytical methods used to determine metal partitioning.

The traditional method for investigating metal partitioning in soils and sediments
has been the use of sequential chemical extractions. In this procedure, chemical reagents
are applied to solid samples in sequence to remove metals from target phases of a soil or
sediment sample. The selectivity of each extraction for a targeted mineral or organic
phase is based on the chemical environment created by the various reagents.
Consequently, the phases are only “operationally defined” by the reagents chosen. The
relative partitioning Of metals among targeted phases (e. g., carbonates, poorly crystalline
Fe-oxides, crystalline-Fe oxides, organic matter and sulfides) is calculated from the
concentrations of metals measured in the extraction leachate fluids.

Criticism of this approach has focused on the possible non-specific nature of the
extractions and possible re-adsorption of metals during the procedure (e. g. Robinson
1984; Tipping et al., 1985; Nirel et al., 1985; Nirel and Thompson, 1987; Rapin et al.,
1986; Gruebel et al.,1988; Rauret et al., 1989). Examples of potential non-specific
extraction criticisms are the partial dissolution or destruction of phases not being targeted
during a particular extraction. Evidence has suggested that some of these arguments have
merit, but several researchers have shown the application of sequential chemical
extractions to oxic sediments can be useful for determining metal partitioning and gaining
insight into biogeochemical cycling of metals, as long as the limitations are recognized
and interpretations are made accordingly (Tessier et al., 197 9; Gephart, 1982; Chao,
1984;Be1zile et al., 1989; and Fielder et al., 1994).

The most common extraction procedure, developed by Tessier et al. (1979) and

modified by others including Tessier et al. (1982) and Belize et a1. (1989), has been

5110‘“) [Q glw
soil and sedil
has also been
environments
sediments has
reagents for pl
Martin et al., 1
reductively dis
previous Studit
metals in soils
oxides are unlj
minerals are be
from using SCq
Answering the:
Itsuhs because
Comprising 38C

T0 eva]

Informatiofl ga

 

3110ij SYSICmJ

. . , 1|
Eta] 133111110:

benchmark T1

{EXTUIES that 0,1

 

shown to give reproducible and fairly accurate information about metal partitioning in
soil and sediment samples collected from oxic environments. This extraction procedure
has also been routinely applied to soil and sediment samples collected from anoxic
environments. However, extension of sequential chemical extractions to anoxic soils and
sediments has proven to be a bit more tenuous due to problems with selectivity of the
reagents for phases present in anoxic systems (Tessier et al., 1979; Rapin et al., 1983; and
Martin et al., 1987). Two of the extractions within the procedure were designed to
reductively dissolve iron (Fe) and manganese (Mn) oxides. Partitioning results from
previous studies indicate that these two extractions Often yield the highest percentage of
metals in soils and sediments from both oxic and anoxic systems. Since Fe- and Mn-
oxides are unlikely to form or persist under anoxic conditions, questions arise as to what
minerals are being dissolved during these two extractions and what information is gained
from using sequential extractions on soil or sediment samples from anoxic environments.
Answering these questions is essential to accurate interpretation of metal partitioning
results because the interpretations depend on the ability to identify the substrates
comprising each operationally defined phase.

To evaluate the substrates comprising the operationally defined phases and
information gained from use of sequential chemical extractions on soil samples from
anoxic environments, investigation of metal partitioning behavior in well constrained
anoxic systems that have been rigorously characterized is necessary. Knowledge of
metal partitioning in similar materials existing under oxic conditions is also needed as a
benchmark. The site chosen for this study is unique in that it contains similar soil

textures that originated from the same parent material currently existing under a wide

range of environ
existing under (1:
lDV’CSllg.:|
among the soil 1;
events in Septen
were subjected t
determine partit

phases.

 

Several l

to collect soil p
Work was to de
in direct comat-
i”Sight into the
water saw-316‘
chums"? date
[0 be Stable an
Result

“‘0” detailed
millet-a] phaSe

SepaIanOn‘ an

range of environmental conditions, thus allowing comparison between similar materials
existing under different oxidation-reduction (redox) conditions.

Investigation of the soils, to characterize the variability in metal partitioning
among the soil types and textures encountered at the site, began with initial soil sampling
events in September and October 1996. Soil samples collected during this initial effort
were subjected to sequential chemical extractions and leachate fluids were analyzed to
determine partitioning of iron (Fe), copper (Cu), and zinc (Zn) among sequestering
phases.

Several more sampling events in the late summer and fall of 1997 were conducted
to collect soil porewater samples from a wetland area at the site. The purpose of this
work was to determine the redox chemistry and the disequilibrium state of the porewater
in direct contact with solid soil phases. Evaluation of the pore water data provided
insight into the geochemical and microbiological processes controlling the redox state in
water saturated wetland soil environments. In addition, analysis of the porewater
chemistry data by geochemical modeling helped predict mineral phases that were likely
to be stable and actively forming in the anoxic water saturated soils at the site.

Results from the pore water analysis and the geochemical modeling prompted
more detailed solid phase analyses in an attempt to verify the presence of predicted
mineral phases. These analyses included acid volatile sulfide determination, magnetic
separation, and x-ray diffraction on samples collected in November 1997. Once mineral
phases were identified, either by direct and/or indirect lines Of evidence, pure forms of
selected minerals were subjected to the same sequential extraction procedure to give
some indication as to how they respond to the chemical reactants in the sequential

extraction procedure. Information gained from the combination of analyses aided the

4

 

interpretation 0
the limitations .
systems. Resul
chemistry and l

partitioning bai

 

 

interpretation of metal partitioning in soil samples from the site and illustrated some of
the limitations of using sequential chemical extractions on samples collected from anoxic
systems. Results of this study emphasize the importance of fully characterizing the redox
chemistry and mineralogy of soil environments when making interpretations of metal

partitioning based on sequential chemical extraction results.

The foil
characteristics.

description of t

comrale SpOns

2.1.1 . Study S

The Stu
layout includi:
Shoreline, roatj
mlestigmom
Smdl area at {3

backgTOUTld s;

 

 

II. BACKGROUND INFORMATION

 

2.1 Site Description

The following sections describe the study site location, site history, land surface
characteristics, and general soil characteristics at the study site. The name and
description of the site location purposefully lack detail at the request of the anonymous

corporate sponsor that owns the property.

2.1.1 - Study Site Location:

The study site is located along a major water way in northern Michigan. The site
layout including, property fence lines, study area boundary within the site property,
shoreline, roads, and locations of former buildings is presented in Figure 1. Field
investigations in support of this research were conducted both within and outside the
study area at the site. Field activities outside the study area were conducted to obtain

background samples and increase diversity of sample populations.

.5993 35 .H 2:3...—

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2.1.2 - Site His
Historic
late 1890's unti
animal hides in
acid [HClll tha
dichromate salt
strongly basic 1
sugar) to reduc
chromium hyd:
salts on the sur
durable leather
inherently inef
lVln'ch contain
the animal hid.
the SUI’faces of
to transport th.
may have Con'
made of gals/g,
vats in the tar.
A 10“
tButtery Waste-I

drainage Pipe

 

2.1.2 - Site History

Historically, the property was the location of a leather tannery operated from the
late 1890’s until approximately 1958. Typical tanning processes included, placing
animal hides in large metal vats containing strongly acidic solutions (e.g. hydrochloric
acid [HC1]) that cleaned and conditioned the hides, followed by the addition of a
dichromate salt (c. g. sodium dichromate [NaZCrzO7+]), and finally the addition of a
strongly basic solution (e. g. sodium dithionate [Na28203], sodium hydroxide [NaOH], or
sugar) to reduce the NazCr207+, to chromic salts (e.g. chromium sulfate [Cr2(SO4)3] or
chromium hydroxide [Cr(OH) 3]) (T.C.Thorstensen, 1958). The precipitation of chromic
salts on the surface of the hides helped cross-link the collagen fibers to form a stable,
durable leather product (E.B.Thorstensen, 1958). This chrome tanning technique was
inherently inefficient and resulted in the production of large volumes of liquid waste,
which contained chromic salts and dissolved organic-chromium complexes released from
the animal hide. The acidic chromium (Cr) solutions could have solublized metals from
the surfaces of the large metal vats in which the tanning occurred and/or any piping used
to transport the acidic and/or basic solution into and out of the vats. The liquid waste
may have contained Fe, Zn, Cu and other metals if the vats used to soak the hides were
made of galvanized metal and if the pipes used to transport the tannery solutions to the
vats in the tannery buildings were made of Cu.

A low-lying area along the river was used as a disposal area for liquid and solid
tannery waste. Liquid waste was also discharged directly from the tannery buildings via

drainage pipes to three locations in the low-lying area.

Previo
generated fror
contaminatior
approximatel}
investigations
and magnitud
extractions ha
Therefore. res
concentration
each metal. 1

long-term pre

2.1.3 - Site 51

A 15-
Si"Panties are;
lying area) to

Surface eleva

Previous investigations at this site have concluded that disposal of waste
generated from leather tanning Operations resulted in significant heavy metal
contamination, especially Cr, of the near surface soils to a maximum depth of
approximately six feet below land surface (ft bls). As a result, site assessments and field
investigations by previous investigators at the site have focused on determining the extent
and magnitude Of metals impacted soils at the site. However, sequential chemical
extractions have not been used to investigate partitioning of metals in soils at the site.
Therefore, results from this study will enhance information about the total metal
concentrations of Fe, Cu and Zn by identifying phases that are important in sequestering
each metal. Understanding what phases of the soil are sequestering metals will aid in the

long-term prediction of heavy metal behavior at the site.

2.1.3 - Site Specific H ydrogeolog and Landswface Topography:

A 15-foot high ridge, extending east to west across the middle of the site,
separates areas of higher elevation (upland area) to the south and lower elevation (low-
lying area) to the north. Due to its proximity to the river, the low-lying area has land
surface elevations at or below the groundwater table. This, along with the engineered
embankment along the shoreline, has resulted in an extensive wetland containing poorly
drained, water-saturated soil. In some areas of slightly higher elevation the soil is only
occasionally water-saturated.

Stone rip-rap was installed along the shoreline of the site property in the early
1990’s to eliminate erosion and transport of heavy metals impacted soil from the site by
the river flowing adjacent to the site. The rip-rap has altered the natural hydrology at site

by restricting the natural flow of surface water from the low lying area to the river. The

open gr;
wooflan
two diffe
is limited
these soils
weathering
more devel:

Of Woodlant

2-1-4 - Soil C

Soil tj
quartz Sand It
in Search 4, 1_
15TH) 5011 is be i
“COIlsolidatec

Wetland areas

 

causing saturated conditions. Wooded and grassy wetland areas make up the bulk of the
low-lying portion of the site. Four small ponds, some with stagnant water and some with
running water supported by natural springs are present within the wetland.

The area south of the ridge, and away from the river, contains woodlands and
open grassy meadows with well-drained soils. The distinction between grassy and
woodland areas is made because of the difference in soil development that occurs in the
two different areas. Less water is available for soil leaching in unshaded areas and there
is limited production of mobile organic acids during decomposition of organic matter in
these soils. These conditions may yield slower rates of weathering and reduce the loss of
weathering products through the soil (Schlesinger, 1991). These drier soils may have
more developed accumulation of oxide coatings on mineral grains at depth than in soils

of woodland origin.

2.1.4 - Soil Characteristics:

Soil types and textures at the site are spatially heterogeneous, ranging from oxic
quartz sand to anoxic organic rich peat. Detailed description of the soil textures is given
in Section 4.1. To avoid confusion with the sediments of the river adjacent to the site, the
term soil is being used here and throughout the text to describe the near surface
unconsolidated geologic and detrital organic material in both upland areas and low-lying

wetland areas of the site.

10

 

I“

2.2.! -Soi1 Con
Soil is a

one or more ph:

l.) dissc
2.) occu
3.1 speci
4.) an

 

 

2.2 Environmental Chemistg of Metals and Substrates

2.2.1 - Soil Constituents and Distribution of Metals in Soils:

Soil is a complex system of competing phases. As a result, metals can exist in
one or more phase, as described by Shuman (1991):

1.) dissolved in an aqueous soil solution,

2.) occupying exchanges sites on inorganic soil constituents,

3.) specifically adsorbed on inorganic soil constituents,

4.) associated with insoluble soil organic matter,

5.) precipitated as pure or mixed solids,

6.) present in the structure Of secondary, and/or

7.) present in the structure of primary minerals.

The aqueous fraction and those solid phases that are in disequilibrium with it are
of primary importance when considering metal partitioning because they are the most
environmentally reactive. In fact, it is these environmentally reactive phases that are
target by sequential chemical extractions. The particle surfaces on reactive soil phases
also play an important role in the cycling of metals. Thus, understanding processes that
occur at the particle level will help explain how and why solid phases of soil sequester
metal ions from soil solutions. The next three sections will briefly describe the physical
nature of the particle surfaces, the different forms metals ions take in an aqueous solution,
and finally, the physiochemical attraction between particle surfaces and metal ions.

Section 2.2.5 will discuss general geochemical properties of Fe, Cu, and Zn and potential

co-precipitating substrates in soil environments.

11

22.2 - Surfac
Weati
precipitates o
of mineral gn
organic matte
al., 1995). Bt
Mn- oxides a:
for many hea‘
occurrence 01
that occur at I
discussion of
discussed.
Solid
SLu'face fun“
functional gr
fluid interfac
fluid. Each I

dependng Or

811ng
cations fOr h'

2.2.2 - Surface Functional Groups and Surface Charge:

Weathering reactions in soils produce a complex mixture of oxide and/or silicate
precipitates on surfaces Of soil grains (Sposito, 1984; Coston et al., 1995). The surfaces
of mineral grains and weathering products are further altered by the accumulation of
organic matter and/or poorly crystalline hydroxides (J enne, 1977; Davis, 1982; Coston et
al., 1995). Because of the density of functional groups present at their surfaces, Fe- and
Mn- oxides and organic matter are thought to be the most important sequestering phases
for many heavy metals in the environment. Therefore, an understanding of the origin and
occurrence of reactive surfaces on soil particles is important. There are many processes
that occur at the particle-pore fluid interface which affect the mobility of metals;
discussion of all of them is beyond the scope of this study and only a few will be
discussed.

Solid phases that comprise a soil and sequester metals have a variety of reactive
surface functional groups to which metals are attracted to varying degrees. Surface
functional groups are molecular entities that are part of a solid but located at the particle-
fluid interface and are reactive toward ions and molecules present in the surrounding
fluid. Each surface functional group contributes to the net surface charge Of the solid,
depending on the origin of the functional group and the pH of the surrounding fluid.

Surface charge can be created by isomorphous substitution of lower charged
cations for higher charged cations in tetrahedral (At-1" for Si“) and/or octahedral (M for
Fe2+ for Al”) layers of (2:1) aluminosilicate clays. Charge derived in this manner is
termed permanent charge and is always net negative (Sposito, 1989; McLean and

Bledsoe, 1992). Inorganic -OH groups also provide pH dependant surface and edge

12

.hmwm
oxy‘b)’d1011d€'
gbbsite). 01%
net negatil'Cll'
alcboholic. by
Schnitzer. 195
monosultide [1
energy (e.g. re
microfractures
replace atoms
reactions. Als

solution tletm

223 - Metal 1

Metals
soluble comp}
colloidal mate

more SPlates

1011 increases

 

 

 

charge in some clays (e. g. kaolinite, smectite, and illite) and metal oxides, hydroxides and
oxyhydroxides (e. g. ferrihydrite, goethite, hematite, lepidocrocite, magnetite, and
gibbsite). Organic matter contains biochemicals and humic substances, which provide
net negatively charged sites (acid functional groups, such as carboxylic, phenolics,
alchoholic, hydroxide (OH'), and amino groups) for metal sorption (Kerndorf and
Schnitzer, 1980; Sposito, 1989; and McLean and Bledsoe, 1992). Sulfide minerals (iron
monosulfide [FeS] and pyrite [Fe28]) have also been found to have sites with high surface
energy (e.g. regions of excess strain associated with crystal defects, dislocations,
microfractures, etc) where surface reactions can take place. Metals in solution can
replace atoms at etch pits, fracture lines and grain edges by oxidization-reduction
reactions. Also, these high surface energy sites function as nucleation sites for metals in

solution (Jean and Bancroft, 1986; Hyland and Bancroft, 1990).

2.2.3 - Metal Ions in Solution:

Metals exist in aqueous solutions as uncomplexed metals ions (free ions), in
Soluble complexes with soluble inorganic or organic ligands, or associated with mobile
Colloidal material (McLean and Bledsoe, 1992). Free ions can be hydrated by one or
more spheres of water and the affinity of a cation for water increases as the charge of the
ion increases and the radius of the ion decreases. This affinity for water molecules
affects the type of bond an ion creates with reactive surfaces. Some metal ions form
Soluble complexes with inorganic anions, such as chloride (Cl'), sulfate (8042*), OH', and
Carbonate (C03'), or organic molecules, such as aliphatics, aromatics, amino acids and

Soluble fulvic acids. Metal ions can also be associated with mobile colloidal material

Such as Fe-oxide, clay, or organic particles by the same mechanisms as for larger,

13

 

immobile panic;

swim.

I
2.2.4 - Adsorpti

The prin

 

 

 

 

surface function
complexation, (I
(Sposito, 1989,
between the so
site. An inner
water molecul
“SOCiation be
Diffu$c km 5‘
Purely an elec
surface and U

Inner

Mews adSorl

immobile particle surfaces (McLean and Bledsoe, 1992), which are described in the next

section.

2.2.4 - Adsorption, Complexation and Co-precipitation:

The principal mechanisms of adsorption, a general term for reaction between
surface functional groups and ions or molecules in an aqueous solution, are inner-sphere
complexation, outer-sphere complexation, and association with a diffuse ion swarm
(Sposito, 1989). Adsorption-desorption reactions affect the partitioning of metals
between the solid and liquid phase in soils, and hence the mobility of metals at the study
site. An inner sphere complex is an association between a surface and an ion with no
water molecules between the surface and the ion. An outer sphere complex is an
association between a surface and an ion with one or more hydration spheres in between.
Diffuse ion swarm adsorption is an association between an ion and a surface that is
purely an electrostatic attraction. Several layers of water separate the ion from the
surface and the adsorption is not with any particular functional group.

Inner sphere complexes have ionic and/or covalent character to their binding.
Metals adsorbed in this manner, termed specific adsorption, are relatively immobile.
With increasing concentration, adsorbing metals saturate the available specific sites and
the non-specific or exchange sites are filled. Non-specific adsorption results in a higher
potential for exchange by other common cations (e. g. potassium [K+], magnesium
[Mg2*], and calcium [Ca2*]), and hence greater potential for mobility. Soils at the site
with elevated concentrations of metals may exhibit this increased potential for mobility,
which should be evident from the partitioning results of the sequential chemical

extractions.

l4

Surface

 

group that resu‘.

   
   
 

Structure (Sposr
fluid immCdiat;
respect to the it
may not reilec
solubility of m

amorphous pre

2.2.5 - Geoch
This 5
Cu. and Zn :
immune, c
Chemistry c
PreviOUS tl’
Tlr
Solid Pha
SmCateS,
interdep
metals“
allow t
of Fer’ f

utiliz;

Surface precipitation is an association between an ion and a surface functional
group that results in polymerization and precipitation of a three dimensional mineral
structure (Sposito, 1989 and McLean and Bledsoe, 1992). For this to occur, only the
fluid immediately surrounding the surface needs to be at or beyond saturation with
respect to the mineral that is precipitating, so measurement of bulk solution chemistry
may not reflect interfacial conditions. Also, formation of co-precipitates can lower the
solubility of metals as predicted by the thermodynamic equilibrium with pure minerals or

amorphous precipitates (McBride, 1994).

2.2.5 - Geochemistry of Iron, Copper, Zinc and Sulfur and Carbonate:

This section will give a general description of the geochemical behavior of Fe,
Cu, and Zn and common substrates that these metals are likely to react with, given the
porewater chemistry at the study site. These generalizations are based on the surface
chemistry of particles and attraction between ions and reactive surfaces discussed in the
previous three sections.

The ubiquitous nature, large surface areas, and surface chemical reactivity of Fe
solid phases such as (Fe (11,111) oxyhydroxides, FeSz, FeS, siderite (FeC03) and Fe-
silicates, facilitate adsorption of various solutes. These properties result in the
interdependency of the Fe cycle with that of many other elements, especially heavy
metals, sulfur and carbonate. The solid state and surface chemistry of some Fe phases
allow the inorganic catalysis of redox reactions (Stumm, 1992). The high redox potential
of Fe(III), and the rapidity of the inter-conversion of Fe(III) to Fe(II) also promote the
utilization of Fe (III) by microorganisms in their metabolic activities (Myers and

Nealson, 1991).

15

 

 

 

become water l

I
identify the for
environments r

Copper

+3 cation. but

 

il sulfide ions
adsorb Cuz’ gr
COPPCr is bou
has a high af‘
Complexes {1
Zinc

0Xicles. A5

f”matron

mObility.

Reduced Fe phases are produced directly and indirectly by reactions coupled to
the oxidation of organic matter (OM) by microorganisms (Lovley, 1991). The reduction
of Fe oxides can lead to considerable redistribution of heavy metals in soils when they
become water saturated (McBride, 1994). It was therefore considered important to
identify the form of iron in various soil types at the study site, especially soil
environments where these transformations have occurred or are presently occurring.

Copper is a chalcophile, which usually occurs in soils and aqueous solutions as a
+2 cation, but reduction to Cu+ and Cu0 is possible under reducing conditions, especially
if sulfide ions are present. In reducing environments, most organic material in soils
adsorb Cu2+ strongly thus restricting its mobility dramatically. Organically adsorbed
copper is bound more strongly than any other divalent metal (McBride, 1994). Cu also
has a high affinity for soluble organic ligands and at high pH the formation of these
complexes may also increase its mobility (McLean and Bledsoe, 1992).

Zinc is readily adsorbed onto clay minerals, carbonates, sulfides, and hydrous
oxides. As with most trace metals, Zn adsorption increases with increasing pH, and
formation of complexes with inorganic and organic ligands also tends to increase
mobility. Zinc hydrolyzes at pH 7.7 and the resulting species generally sorb strongly to
soil particle surfaces. Under oxidizing conditions, Zn2+ is highly soluble and thus very
mobile. As conditions change from oxidizing to reducing, such as during a soil flooding
event, release of Zn from reduction of Fe oxides may increase its mobility, but this
mobility is ultimately controlled by the extreme insolubility of wurtzite (ZnS) (McBride,
1994 and McLean and Bledsoe, 1992).

Sulfide (82') is generated by sulfate reduction as microbes utilize 8042' as a

terminal electron acceptor during OM oxidation (Bertolin et al., 1995). Under reducing

l6

conditions. iron
tencrated react

grrigite {F638;

 

1994.). Sulfid:
2112‘) to form ll
monosulfrdes. ‘
anoxic systems

The ma

chzl can form

 

I
mnabiliiy of

rePresentation
Sulfate and 12‘
the Various, fc
Micrr
C0m'en Orga
“mil dioi
Walked dl

H20 and re

conditions, iron oxides and oxyhydroxides are reduced and the ferrous iron ions
generated react with the $2- to produce a variety of sulfide minerals including FeS,
greigite (Fe384), and eventually FeS; (Morse and Comwell, 1987; Casas and Crecelius,
1994,). Sulfide may also react with many other metal heavy metal cations (e.g. Cu2+ and
Zn”) to form insoluble monosulfides. Due to the relative insolubility of these metal
monosulfides, pore water concentrations of the transition row metal ions are low in
anoxic systems where sulfide is present (Allen et al., 1993).

The major factors controlling how much metal monosulfide (e. g. FeS, CuS, and
FeS;) can form are the amounts of organic matter, reactive Fe minerals present and the
availability of dissolved sulfide (Bemer, 1984). Figure 2 is a diagrammatic
representation of the overall process of FeS, metal monosulfide, and Fezs formation.
Sulfate and Fe (III) reducing microorganisms play key roles in the interaction between
the various forms of sulfur and Fe.

Microorganisms also drive the carbon cycle. Heterotrophic microorganisms
convert organic carbon bound up in complex organic matter to inorganic forms of carbon
(carbon dioxide (C02), carbonic acid (H2C03), bicarbonate (HC03')). Carbonic acid is
produced during the complete oxidation of organic carbon by microorganisms to C02 and

H20 and resulting reactions that follow (Bemer and Bemer, 1996):

CH20 + 02 69 C02 +H20
C02 + H2 (—) H2CO3

H2CO3 H H+ + HCO3-

17

Mic
OC‘

 

 

Noe: 5163*

mezt
and Write it

 

Organic matter

 

 

 

 
 
 
   

 

 

SO Fe Oxides

 

 

 

 

 

 

   
 

Microbial
activity

Microbial
activity

  
    

 

Microbial

activity H25 Fe“ 4 » Fe3+
4
r
r
r
r
l

S0 FeS l Me2+
l
r
r
r
F8384 MeS
F882

Note: Me2+ represents any metal cation that forms a more soluble sulfide than FeS.

Figure 2. Diagrammatic representation of the overall process of FeS, metal monosulfide,
and pyrite formation (modified after Bemer,1984).

l8

Tne carbonic ac
minerals during

yielding carbor

g;
The sr
redox conditi
Thus. consicl
and solid ph
“he
catalyzed rt
concentrarl
and carer
minerals c
until micr
COIldrtiOn
deem)“ :
lefininal
l’ertical }
adVanta;
metabol
and Bar

more in.

The carbonic acid produced can then react with and dissolve silicate, carbonate and oxide
minerals during chemical weathering or the H+ can be displaced by ions in solution

yielding carbonate precipitates (e. g. calcite (CaC03) and FeC03).

2.3 - Metal Cycling in Resmnse to Changes in Redox Conditions

The solid phases and surface chemical properties that developed under one set of
redox conditions are unlikely to be preserved once a change in redox potential occurs.
Thus, considerable redistribution of metals can occur as the solution chemistry changes
and solid phases re-precipitate under the new conditions (McBride, 1994).

When soil becomes saturated with water, a sequence of microbiologically
catalyzed redox reactions occur that exert control over the solution pH, redox, and
concentration of important geochemical elements such as oxygen, nitrogen, iron, sulfur,
and carbon (Stone, 1987). Initially, metal species exist in solution and on surfaces (e. g.
minerals or organic matter coatings) primarily as oxides, hydroxides, or oxyhydroxides
until microbial activity depletes the aqueous system of oxygen (02) and a shift to anoxic
conditions occurs. Anaerobic microorganisms then begin to utilize alternative terminal
electron acceptors in their metabolism. In soils and sediments, the sequence of dominant
terminal electron accepting processes (TEAPs) can be observed spatially in horizontal or
vertical layers. The dominance of one TEAP over others is based on the competitive
advantage groups of organisms have over others resulting from utilization of available
metabolic substrates and terminal electron acceptors that maximize energy yield (Atlas
and Bartha, 1993). Although one TEAP may dominate at a particular time and location,

more than one TEAP can occur simultaneously. The result of the succession of TEAPs is

19

 

 

direCt biogenic
surfaces. and or
aqueous specie

Due to
anoxic conditir

mineral phases

 

 

 

 

When the soil
forming oxide
into oxides du
have more re;
1994'). These
Upland soils :
metal partitir

S‘i‘lll'éntial cl

direct biogenic and indirect geochemical transformation of oxic aqueous species, mineral
surfaces, and organic matter functional groups, which resulting in the reduction of
aqueous species and minerals. The rates of these transformations are quite variable.

Due to direct and indirect microbial reduction of Fe oxides under water saturated
anoxic conditions, Fe and absorbed metals become mobilized, then re-precipitate as
mineral phases stable in the new redox environment (carbonates and metal sulfides).
When the soil becomes unsaturated, or oxic again, reduced phases can be re-oxidized
forming oxides, hydroxides, and oxyhydroxides. The potential for incorporating metals
into oxides during redox/saturation cycles is increased because freshly precipitated oxides
have more reactive surfaces and are more effective absorbents for metals (McBride,
1994). These processes, driven by microorganisms, are most likely occurring in the
upland soils and cyclically water saturated wetland soils at the site and the effects on
metal partitioning in different soil types should be observable in the results of the

sequential chemical extractions.

20

 

A gr
would give
characteriz
generated
the grid pt

82
surveying
Marker a
location
10Cail0ng
Which re

III. METHODS

 

3.1 - Sample Grid Development1 Surveying, and Site Locations
A grid of equally spaced sampling locations was developed in a manner that

would give the best spatial coverage, reduce bias in the sample population and best
characterize the variability in soil conditions at the site. First, a grid of points was
generated graphically. Then, the grid was overlain on an existing site map so that one of
the grid points corresponded to a pre-existing land survey marker.

Sample locations were located by measuring linear and angular distances with
surveying equipment and a 200 foot steel tape starting from the existing land survey
marker and continuing to successive sampling locations. Once located, each sampling
location was marked with a labeled wooden staked. The locations of the 80 sampling
locations that resulted are shown in Figure 3. One area of the site near the shoreline,
which received the highest loading of tannery waste, had restricted access. As a result no

field activities were conducted in this area.

21

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22

L’ndis

solid phase a
stainless stee
advanced int
were attache
Ate
intervals (0.
horizons at
discontinue
gmtl prev
disassembl
paper tow:
CONS Wer
frozen (-2
E;

Ellen one
organic c

distilled (

disriumg

3.2 - Soil Sample Collection

Undisturbed soil cores collected for sequential chemical extractions and other
solid phase analyses were obtained using an AMSTM two-inch diameter spilt-spoon
stainless steel coring device with 6-inch plastic liner tubes. The coring device was
advanced into the ground with an AMSTM weighted hand slide hammer. Extension bars
were attached to the slide hammer to take cores at depth.

At each sampling location an attempt was made to retrieve cores from three
intervals (O-O.5 ft bls, 1-1.5 ft bls, and 3-3.5 ft bls) corresponding to observed soil
horizons at each of the 80 sampling locations. At several sample locations, however,
discontinuous layers of solid waste (e.g. cans, scrap metal), wood boards, and coarse
gravel prevented the retrieval of cores at depth. The split-spoon coring device was
disassembled then cleaned with plastic brushes, rinsed with distilled water and dried with
paper towels between each coring to prevent cross contamination between samples.
Cores were sealed with end caps, which were secured with electrical tape, then stored
frozen (-20° F) within one to six hours.

Each of the soil samples were described in the field upon retrieval, then later
given one of seven descriptive soil texture classifications based on field descriptions and
organic carbon results. Field descriptions of cores and organic matter content results are

shown in Appendices 1A and IE.

3.3 - Clean Procedures
Water used for preparing solutions, mixing reagents, and washing glassware was
distilled deionized water (DDW) manufactured using house deionized water and further

distilling it in a CorningTM water still (model AG-22). All glassware was rinsed three

23

times with D
with DDW. i
were placed
Once dry. gl
sample bott?
plastic bags
filters (0.4 r
cleaned by :
finally soak
polyethylen

filters durin

in this stud
Belzile et ;
Procedure
l'hich util:
‘0 PH =9.
metals ass
Work On pr
hlPOchlon'
mailer [h an

typically u.

times with DDW, acid-washed in 10 % HCl for 24 hours then rinsed again three times
with DDW, and then soaked in DDW for 24 hours. After the DDW water soak, items
were placed in lined polyethylene containers and dried completely in a class 100 hood.
Once dry, glassware was capped and placed in lined drawers until needed. Capped
sample bottles, filtration components, and other reusable parts were sealed in acid washed
plastic bags and then placed in lined drawers. Nucleopore polycarbonate membrane
filters (0.4 micrometer (pm)) used for filtering extraction leachate from samples were
cleaned by a 24 hour dilute HNO3 soak, then rinsed three to five times with DDW, and
finally soaked in DDW for 24 hours. Filters were stored soaking in DDW in acid-washed
polyethylene containers until use. Acid-washed plastic forceps were used to handle the

filters during loading of Millipore Swinex filter holders.

3.4 - Sguential Chemical Extractions

The sequential chemical extraction procedure used to determine metal partioning
in this study was similar to that developed by Tessier et al. (1979), with modifications by
Belzile et al. (1989). An outline of the procedure is presented in Table 1. The extraction
procedure used is described in detail in Appendix 2A. An additional extraction (0X1),
which utilized a five to seven per cent solution of sodium hypochlirite (N aOCl) acidified
to pH = 9.5 with hydrochloric acid (HCl), was included to help distinguish between
metals associated with soil organic matter and those associated with sulfides. In their
work on peat samples and pure minerals Papp et al. (1991) showed that sodium
hypochlorite (N aOCl) (pH = 9.5) is more selective in releasing metals bound to organic
matter than the hydrogen peroxide (H202, pH = 2 with nitric acid (HNO3)) solution

typically used in the Tessier et al. (1979) method. They also demonstrated that NaOCl

24

L_

Sub

 

Exchar

Cart

Reactive
and .\l:

Crystallir.

Table 1. Summary of Sequential Chemical Extraction Procedure
(modified after Tessier et al. (1979)).

 

 

Target Operationally Defined Extraction Extraction
Substrate Extraction Phase Solution“ Conditions
Exchange Sites Exchangeable 1.0M MgCl2, pH 7 20°C, 1 hour
(EX) 10 milliliters (mL)
Carbonates Weakly Acid Soluble 1.0M NaOAc, pH 5 20° C, 5 hours
(WAS) 10 mL
Reactive Fe—Oxides Easily Reducible 0.1M NH2OHHCl 25° C, 5 hours
and Mn- Oxides (ER) in 0.1M I'INO3
25 mL
Crystalline Fe-Oxides Moderately Reducible 0.04M NH2OHHCL 96° C, 6 hours
(MR) v/v 25%HOAc
20 mL
Organic Matter Basic Oxidizable NaOCl, pH 9.5 96° C, 15 min.
(OX1) 3 times, 6 mL
then 3.2M NH40Ac 25° C, 1 hour
5 mL
Pyrite Acid Oxidizable 0.02M HNOg 85° C, 5 hours
(0X2) 3 mL
30% H202, pH2
8mL
3.2M NH40Ac 25° C, 1 hour
5mL
then add DDW to
make 25mL

 

* volumes optimized for 1.0g samples

25

 

did not sigr
to the Tessi
water satur

section 4.3

Met
were deterr
(MS). Fe
samples tva

Cali
the extracti
liter (mg/L
Standards a
belli'een sa
0! better.

Ana
three conce
acCUracy w‘
lNlST) Stan

“RM 1a

 

did not significantly dissolve selected oxides and sulfides. This was an attractive addition
to the Tessier method primarily because much of this site is comprised of organic rich,
water saturated, anoxic soils. Metal partitioning results are presented and discussed in

section 4.2

3.5 - Procedures for Metals Analysis

Metal concentrations in sequential chemical extraction leachate fluid samples
were determined using a Perkin Elmer 5100pc atomic absorption spectrophotometer
(AAS). Fe and Zn in leachate samples were analyzed by flame-AAS. Cu in leachate
samples was analyzed by graphite furnace-AAS with Zeeman background correction.

Calibration standards for leachate sample analyses were prepared using DDW and
the extraction chemicals to form the background matrix and certified 1000 milligrams per
liter (mg/L) stock solutions (J .T. Baker Analyzed). Care was taken when making
standards and necessary dilutions of leachate samples to maintain similar matrices
between samples and standards. All chemicals and reagents used were analytical grade
or better.

Analytical precision, in terms of the relative standard deviation of response for
three concentration determinations, was set at less than 15 % for all AAS. Analytical
accuracy was assessed by comparison to National Institute of Standards and Testing
(NIST) standard reference materials (SRM). Standard calibration curves were compared

to SRM 1643c or 1643d (Trace Elements in Water) values, which were required to be

26

 

within 15 9‘

converted ‘

Or
taken prio
method w;
Soil Scien.
were subrr
analysis. 1

Section 4.]

P01
principal C
1976; Cat
long blocl
drawing 0
compartm
Sheet of a‘
membrane
thin acrylic

Was taken

 

within 15 % of certified values. Metals concentration in the leachate fluids were

converted to solid phase concentrations and reported on a dry weight basis.

3.6 - Organic Matter Content Determination

Organic matter content of soils was determined, on sub-splits of homogenized soil
taken prior to the sequential chemical extractions, by a loss on ignition method. The
method was modified after a procedure developed by researchers from the Department of
Soil Science at the University of Wisconsin, Madison, WI (Shulte et al., 1991). Samples
were submitted to the Plant and Soil Testing Lab at Michigan State University for
analysis. Results of the organic matter determinations are presented and discussed in

Section 4.1.

3.7 - Porewater Sampling

Porewater was obtained using two different types of samplers, both based on the
principal of in-situ dialysis membrane equilibration. The “Peeper” samplers (Hesslein,
1976; Carignan, 1984; Carignan and Nriagu, 1985; Carignan, et al. 1985) consist of a 2 ft
long block of acrylic with twenty—eight individual sample compartments. A schematic
drawing of a pepper is shown in Figure 4. To prepare a peeper for deployment, sample
compartments were filled with deoxygenated, distilled-deionized water (DDDW), then a
sheet of acid washed dialysis membrane (02le pore diameter Biodyne BTM nylon
membrane, Pall Corp.) was carefully placed over the sample compartments followed by
thin acrylic faceplate. The faceplate was secured to the sampler with nylon screws. Care

was taken to avoid trapping air bubbles under the nylon membrane.

27

Tl
apparatus
hollow pc
um nylon
complete

Or
DDDW a
before tra
the cylind
introducir
three wee
1985). D
into equi]

Pitsented

The “barrel” samplers were modified from dialysis membrane multilevel sampler
apparatus designed by US. Filter/Johnson Screens Corp. Each barrel consists of a
hollow polyethylene tube (one-inch in diameter, three-inches in length) with screw-on 0.2
pm nylon filters at both ends. A schematic drawing of a pepper is shown in Figure 5. To
complete the assembly, three barrels were strapped together with plastic cable ties.

Once assembled, both types of samplers were submerged in a cylinder filled with
DDDW and deoxygenated by bubbling with N2 or Ar gas for a minimum of three days
before transport to the site and deployment. At each site, the samplers were taken from
the cylinder and inserted into water-saturated soils within two minutes to avoid
introducing oxygen to the compartments. Samplers were left in place for period of two to
three weeks (Hesslein, 1976; Carignan, 1984; Carignan et al., 1985; and Tessier et al.,
1985). During this time, dissolved ions and molecules ((211m) in the porewater came
into equilibrium with the DDDW inside the sampler. Porewater analytical results are

presented and discussed in Section 4.4

28

Front

:HO.O.O.O.O.O .OWU 0.0 .0 O .0 0‘:

 

Ii
r“.

3-D View

Front View

Acrylic Sampler

Dialysis Membrane

Screws

- Face Plate
Nylon

00000000000000
eoeeooeoeeeoee

s s

 

 

 

Compartments

Sample

\

 

!

 

 

000m0000000009
00000000000099

 

 

 

 

 

 

Figure 4. Schematic diagram of a “Peeper” pore water sampler.

29

3-D View

Membrane screw cover

 

Side View

 

 

 

 

 

MI]

Figure 5. Schematic diagrams of a “barrel” porewater sampler.

30

A t
the pore is
sampled a
strapped tr
measured
Fey, and t
metals). at
Niel). in
sampling :

Porewater

Redox p01
electrons 1
bl introdt
these mea
geOChemji
rm)" rear
usual), m.
mulls t Li
redox COUI
ConditionS

aSsessltltfn

3.8 - Porewa_ter Field Measuremflts

A complete geochemical analysis was performed on the equilibrated fluids within
the pore water samplers. To obtain enough fluid, groups of four to six peeper ports were
sampled as if they were the one compartment and the group of three barrels that were
strapped together were sampled as a single compartment. Geochemical parameters
measured in the field included: temperature, pH, redox (Eh) potential, alkalinity, 82',
Fe”, and Cr°+. Aliquots were collected for cations (majors and transition row trace
metals), anions (cr, bromide [Br'], nitrate [N03'], nitrite [N02], 5042', and ammonia
[NI-14]), methane (CH4), and dissolved organic carbon (DOC). Detailed methodology for
sampling and analyzing each parameter is given in Appendix 2B. Results of the

porewater field measurements are presented and discussed in Section 4.4.

3.9 - Measuring Redox Potential

Redox potential is a measure of the ability of a solution to donate electrons to or accept
electrons from a chemical species. This potential can be measured directly as Eh (mV)
by introducing an electrode into a solution. However, investigators have discovered that
these measurements are problematic because electrodes respond to few of the
geochemically important redox couples and low temperature aqueous environments
rarely reach redox equilibrium. The redox potentials observed in natural waters are
usually mixed potentials, which are impossible to relate to a single dominant redox
couple (Lindberg and Runnels, 1984). An alternative approach is to measure specific
redox couples such as Fe2+lFe3+, NHf/NOg'lNO2‘, and 82'IS042'. Interpretations of redox
conditions in this study were based on electrode measured Eh values for general

assessment of redox potential, while more refined statements about redox state are based

31

k.

 

on anaIVSlS

metabolic e

Ge
PllREEQt
stability 0
program t
calculatio
complexir
porential l
informant
The MTV
MNEQ
compose.

diSCUSsec

detenm'n
and Casa
Altltendi'r
addition C

”Sits

on analysis of aqueous species of coupled redox processes and accumulated microbial

metabolic end-products (e. g. S2”).

3.10 - Geochemical Modeling

Geochemical modeling of pore water chemistry data was performed using
PHREEQC (Parkhurst 1995) with the MINTEQ database to predict the presence and
stability of minerals in the water saturated anoxic soils. PHREEQC is a computer
program that was designed to use known water chemistry data to perform thermodynamic
calculations which predict the level of mineral disequilibrium, charge balance, metal
complexing, Eh from measured redox couples, possible aqueous redox species, and the
potential for minerals to precipitate or dissolve. Parkhurst (1995) gives background
information on the development of this model and the algebraic equations used within it.
The MINTEQ database was selected over the more traditional WATEQ database because
MINTEQ has a more robust assemblage of thermodynamic reactions for minerals
composed of Fe, Cu and Zn. Results of the geochemical modeling are presented and

discussed in Section 4.6.

3.11 - Acid Volatile Sulfide Analysis
Acid volatile sulfide (AVS) and simultaneously extracted metals (SEM)

determinations were preformed by methods described by Allen et al. (1993) and Lasorsa
and Casas (1996). The procedure is only summarized here but explained in depth in
Appendix 2C. Briefly, AVS in a sample is converted to hydrogen sulfide (H28) by
addition of 1M hydrochloric acid at room temperature. The sulfide evolved is trapped in

a 0.5 M NaOH solution and reacted with mixed diamine reagent (MDR) to create

32

methylene
dissolve A
extracted ‘
noted that
therefore
sulfides (

1993; am

Figure 6.

saved fro
DDW in

slurry w;

 

methylene blue, which is then measured colorimetrically. The acid solution used to
dissolve AVS and evolve hydrogen sulfide (H2S) is filtered and the simultaneously
extracted metals (SEM) in the fluid measured by flame or furnace AAS. It has been
noted that Fe2S and organic-sulfur compounds are not soluble in IN HCl (25° C) and
therefore it is generally assumed that only amorphous iron sulfide and other metal
sulfides (with the exception of CuS) are being attacked (DiToro et al., 1990; Allen et al.,
1993; and Lasorsa and Casas, 1996). The AVS/SEM reaction apparatus used is shown in

Figure 6. Results of the AVS/SEM analyses are presented and discussed in Section 4.7.

3.12 - Magetic Fraction Separations

The magnetic mineral fraction was separated from sub-splits of homogenized soil
saved from the AVS/SEM analysis. Three to five grams of wet soil were mixed with
DDW in an Erlenmeyer flask to create a slurry. A magnetic stir bar was added and the
slurry was magnetically stirred for 10 minutes, with occasional gentle shaking of the
flask. A magnetic rod was then used to remove the stir bar from the flask. Gentle drips
of DDW were used to remove any nonmagnetic material from the stir bar. The recovered
magnetic minerals were then leached with concentrated HN03 at 96° C for several hours.
The leachate was filtered through acid washed 0.4 um Nucleopore filters into acid

washed Nalgene polypropylene bottles. The leachate samples were analyzed for metals

by FAAS as described in Section 3.5.

33

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34

 

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3.13 - X-ray Diffraction

X—ray diffraction of oriented samples were analyzed to determine the mineralogy
of the clay and fine silt size fractions (<20um). An estimation of the amount of clay in
samples was used to calculate the amount of sample that will be required to yield about
0.5 gram (g) of clay (Soil Survey Staff 1975). Clay, silt, and sand size particles were
separated by a cylinder sedimentation method and settling times were calculated using
Stoke’s Law. Samples having greater than five per cent organic matter were subjected to
successive extractions with NaOCl (pH 9.5) to remove organic matter prior to grain size
separation.

Mounts were made according to one of two methods outlined by Moore and
Reynolds (1989). Particle suspensions were decanted into a Millipore filtration system
and the particles were collected by vacuum suction of the suspension through a 0.4 pm
Millipore filter. Magnesium chloride (MgCl2) and potasium chloride (KCl) saturation
was achieved on separate sample splits by adding one molar (M) solutions to the filtration
system at the end of the suspension filtration. Then the filter cake was rinsed with DDW
to remove most of the Cl'. Before all of the DDW rinse water passed through the filter
the vacuum was removed and the system was brought back to atmospheric pressure. The
remaining DDW was decanted and the moist filter cake was carefully placed upside
down on a microscope slide. After three to five minutes, the filter was peeled off leaving
the oriented clay and/or silt size particles on the slide. Results of the XRD analyses are

presented and discussed in Section 4.9.

35

 

Pt
CaC03. P
chenucal
raon us
presented
sequentia
pure mint
to avoid (

Results 0

 

3.14 - Pure Mineral Extractions

Pure powdered minerals (FeS, CuS, ZnS, PbS from Aldrich Chemical Co. and
CaCO3, Fe304, FeS2 from Wards Geology Catalogue) were subjected to sequential
chemical extractions. Sequential extraction of some of these minerals (CuS, ZnS, PbS
Fe304) using the Tessier (1979) method have not previously been conducted so the results
presented in Section 4.3 are the first of their kind. The procedure for the pure mineral
sequential extractions followed exactly that for samples described in Section 3.4. The
pure minerals were handled and extracted under a nitrogen (N2) or argon (Ar) atmosphere
to avoid oxidation of the monosulfides. All extractions were preformed in triplicate.

Results of the pure mineral extractions are presented in Section 4.8.

36

L... ..__—»«_En_- ._

30:
samples dr
the site inc

peat and a

IV. RESULTS AND DISCUSSION

 

4.1 Soil Texture Descriptions

Soil textures were described in the field during soil boring and collection of soil
samples during the initial site characterization. Two distinct soil types were observed at
the site including a histosol in the low lying wetland area, characterized by organic rich
peat, and a spodosol in the upland area with well developed 0, A, and B and C horizons.

Solid waste generated from leather tannery processes and industrial and domestic
trash (fill), was laterally discontinuous and ranged from zero to at least six ft bls within
the upland and wetland areas of the site. The fill was comprised of scrap leather, animal
hair, scrap wood, bricks, concrete, scrap metal, glass, cans, etc. In areas that were
intensely impacted with tannery waste (near soil borings 014, E16 and E18) contained
green colored soils to depths of at least three ft bls.

The peaty soil in the wetland area was comprised of dark brown to black,
decaying organic matter varying amounts of fine to medium grained quartz sand (20-50
%) and silt (IO-30%) with trace mafic mineral grains. There was a sharp contact, which
ranged from one to four ft bls throughout the wetland area, between the peaty soil interval
and silty sand glacial/fluvial sediments below. The lower interval consisted of tan to dark
gray, fine to coarse grained, quartz sand (60-90%) and silt (IO-40%) with minor clays and
mafic mineral grains. The water table was observed to fluctuate from several inches

above land surface to not more than six inches below land surface (bls) soil in the

37

wetland
redox cc
several 7

Section

which e
decomp
inches tr
angular.
(15%).
This hor
and silt i
interpret
Carbon c
tannery
C horizr
compOS.
dlSconti;
from 0.2
Winery
appearec
matenay J
the first t

the “Plan.

 

wetland area generally resulting in generally saturated conditions most of the year. Soil
redox conditions in the wetland area were determined by analysis of the porewater at
several locations. Results of the porewater analysis are presented and discussed in
Section 4.4.

Soil in the upland area had developed soil horizons beginning with an O horizon,
which extended from land surface to about three inches bls and contained mainly
decomposing organic material. The A soil horizon extended from approximately three
inches to one ft bls and was comprised of well-sorted, fine to coarse, rounded to sub-
angular, quartz sand (70-90%), silt and clays (IO-30%), and organic matter ranging from
(1-5%). The B soil horizon extended from one to three ft bls throughout the upland area.
This horizon contained rusty-orange, well-sorted, fine to coarse, quartz sand (60-90%),
and silt (10-40 %) with discontinuous lenses of clayey silt. The rusty-orange color was
interpreted to indicate the presence of Fe-oxides on the quartz grain surfaces. Organic
carbon content in this interval ranged from 0.5 to 3 % in areas that were not impacted by
tannery waste. Grain size within the B soil horizon generally coarsened with depth in the
C horizon. The C soil horizon was generally encountered at three ft bls and was
composed of tan, medium to coarse grained quartz sand (60-100%) and silt (040%) with
discontinuous lenses of fine gravel. The organic carbon content in this horizon range
from 0.2 to 1.1% in areas that were not impacted with tannery waste. Soils containing
tannery waste generally contained greater than 20 percent organic matter, most of which
appeared to originate from the tannery waste (e. g. scraps of leather and unrecognizable
material), as opposed to detrital of plant material. In general, soils were moist throughout
the first three and a half ft bls, but no groundwater was encountered during soil borings in

the upland area of the site. Soil redox conditions were not directly measured, but these

38

well drain
indicate tl
S
geochern
2 summa
collected
Field des
Appendi:
illustratir
R
directly r.
drained 5
possibly
color Fe.
position.
and in ge

ill the WC

 

well drained soils had rusty orange staining on quartz grains, which was interpreted too
indicate the presence of Fe-oxides and oxic conditions.

Soil samples collected represent a full spectrum of soil textures as well as
geochemical and microbiological conditions found in near surface soils at the site. Table
2 summarizes these texture descriptions. General location at the site, number of samples
collected, and average organic matter content for each soil type are also given in Table 2.
Field descriptions of individual cores and organic matter content results are presented in
Appendix 1A. Soil texture and organic matter content and ecological interpretation maps
illustrating spatial variability throughout the site are shown in Figures 7-9, respectively.

Redox conditions in unsaturated soils from the upland area of the site were not
directly measured. However, due to the observed unsaturated conditions of these well-
drained soils, it is assumed that 02 (g) is commonly present in the soil at depth, except
possibly during heavy rain or spring thaw flooding events. The intense rusty orange
color Fe-oxides on sand grains as deep as three feet below land surface supports this
position. Redox conditions in water saturated soils in the wetland area were measured
and in general suggest anoxia occurs within one inch of the soil-air or soil-water interface

in the wetland. These results are discussed in Section 4.4.

39

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42

Table 2. Sol
number of s:

Soil
Textu

 

Brown :
sane

t_—

l Rusty silt

 

Tan silty
(unsatur

 

Tan silty
(satura

K

OM>5

Silty san
abundar

L\
Gravelf

 

 

 

 

\tm

 

 

Table 2. Soil texture descriptions and classifications with general location of each,
number of samples, and average organic matter (OM) content for each texture.

 

 

 

 

 

 

 

 

 

Soil Soil Horizon General Number Average
T And Description Location of OM
exture
Samples Content
Brown silty O and A horizon Upland area 31 3.9%
sand soils, rich in humus (topsoil)
B-horizon soils with Upland area 47 2.8%
Rusty silty sand rusty stains on quartz (1-1.5’)
sanigrains
, C horizon soils, Upland area 25 1.94%
T“ 8'“? sand devoid of visible (3-3.5’)
(unsaturated) oxide staining
. Silty sand, devoid Wetland 21 6.0%
Ti: 31:: 3d of oxide stains, area below
permanently water peat (3-3.5’)
Black or dark brown Wetland 47 58.1%
OM>50% peat cyclically or area
permanently water
saturated
Soil with significant Wetland 35 21.4%
Silty sand with OM that is cyclically area
abundant OM or permanently water
saturated
Gravel/Debris Tannery waste or Old tannery l5 29.6%
(fill) construction scrap area

 

 

 

 

 

43

 

4.2 - Metal Partitioning

Results of the sequential chemical extractions performed on the 240 soil samples
collected for the initial site characterization are discussed in this section. Metal
partitioning among target phases was evaluated for each metal after metal concentrations
detected in the leachate fluids from each extraction were converted to solid phase

concentrations. Solid phase concentrations are reported on a dry weight basis.

4.2.1 - General Metal Partitioning Results:

In general, the relative partitioning of Cu, Fe, and Zn among dominant
sequestering phases (operationally defined) is similar between the oxic soils of the upland
area and the anoxic, water saturated soils in the wetland area of the study site. However,
variations in the relative importance of the dominant phases and the partitioning among
less dominant phases were identified among the different soil textures, The three most
dominant sequestering phases for Cu are the OX1, MR, and ER, as shown in the
summary of metal partitioning in Table 3. The most dominant phases sequestering Fe
and Zn also include the ER and MR phases, but the third most dominant phase varies

between the WAS and OX1 among different soil types.

4.2.2 - Detailed Metal Partitioning Results:

Metal partitioning trends are presented using two types of graphical diagrams. Pie
diagrams are used to show average partitioning results among all of the extraction phases.
Ternary diagrams are used to show individual data points plotted in ternary space with
the three most dominant sequestering phases at the vertices. One advantage of presenting

partitioning data in ternary space is that it allowed clearer visualization and recognition of

44

Table 3. Summary of relative partitioning of Fe, Cu, and Zn, as determined by

sequential chemical extractions among, target phases of the soil.

 

 

 

Soil
F Zn
Texture e C“
Brown silty MR>>ER>WAS> OX1=ER>MR> MR>ER>EX>
sand 0x1, EX and ox2=o 0X2>WAS WAS>0X1>OX2
Rusty silty MR>>ER>WAS MR 5 ER> MR>ER>WAS>
sand EX, 0x1, 0x2 = o 0X1>0X2>WAS OX1>EX>0X2
Tan silty sand MR>>ER>WAS’ MR>ER>0X1> I'"°WAS>ER>
(unsaturated) EX’ OXI’ and OX2>WAS 0X1>EX’ and
0x2 = o ox2=o
Gravel/Debris MR>ER>0X2>WAS 0X1>ER>MR ER>MR>OX1>
>ox 1, EX=0 =OX2>WAS WAS>EX>0X2
Tan silty sand I'H°:EE§(>WAS 0X1>ER>MR> MR>ER>WAS>
(saturated) 0x1 and 0x2 = 0 0X2>WAS 0X1=EX>0X2
0M>50% MR>ER>0X1>EX ox 1 >>ER>MR> ER>MR>WAS>
>WAS=0X2 0X2>WAS OX1>EX>OX2
wifélgbmim MR>ER>WAS>0X1 0X1>ER>MR> ER>MR>0X1>
0M >EX>0X2 0X2>WAS WAS>EX>OX2

 

EX Exchangeable

WAS Weakly Acid Soluble

ER Easily Reducible

MR Moderately Reducible
OX1
OX2

another

Basic Oxidizable (OM) OM organic matter
Acid Oxidizable

45

MR>ER indicates one phase more dominant than

OX2=0 indicates metal was not detected
in leachate fluid for this phase

the don
advantz
could b
trends i.

camber]

and red
of the se
and diag
Table 1.
3B, and

'1
Figure 1
average
most im;
become 1
are bOth

COUU‘ibu

 

 

the dominance, or lack of dominance, of one sequestering phase over the others. Another
advantage is that individual sample rather than average values for sample populations
could be viewed graphically. A third advantage of using ternary plots is that spatial
trends in partitioning could be discerned because individual samples or groups of samples
can be labeled within the plots.

It was thought that trends in metal partitioning might be related to the soil texture
and redox conditions. Consequently, metal partitioning is presented graphically in terms
of the seven soil textures described in Table 2. The abbreviations (e. g. ER) in the tables
and diagrams refer to the target phases of the sequential chemical extractions given in
Table 1. Tables of partitioning results for Fe, Cu and Zn are given in Appendices 3A,
3B, and 3C, respectively.

The relative partitioning of Fe among all soil types is similar as can be seen in
Figure 10a and 10b. The MR phase (Fe-oxides) dominates the sequestering, up to an
average of 92 % for unsaturated tan silty sand. The ER phase is consistently the second
most important sequestering phase for all soil types. Phases other than the ER and MR
become more important in silty sand with abundant OM and soils with OM>50%, which
are both generally anoxic, as well as gravel/debris soils. The EX and 0X2 phases
contribute to Fe partitioning only in the wetland area soils, but almost not at all in the
upland area soils. The increased Fe in the EX may reflect Fe in pore water, as well as Fe
associated with clays and exchange sites. The importance of the OX1 and OX2 for the
silty sand with abundant OM and soils with OM>50% could indicate increased

sequestering ability of OM at high soil OM concentrations and/or a difference in the

46

forrntS)

will be C

space. i
show sig
soils wit

axis tow

shows m
sequeste
Silt),r 5am
imperial:

increases

 

form(s) that inorganically bound Fe exists in these anoxic soils vs. oxic soils. The latter
will be discussed further in Sections 4.10 and 4.11.

Figure 11 is a trilinear diagram of Fe partitioning results plotted in ER-MR-OXl
space. Most of the data points fall on or along the ER-MR axis. The only soil types that
show significant deviation from this pattern are the silty sand with abundant OM and
soils with OM>50% in which some samples trend away from the center of the ER-MR
axis toward the OX1 vertex.

The pattern of relative partitioning for Cu, presented in Figures 12a and 12b,
shows more complex distributions than that of Fe. The OX1 and ER are the dominant
sequestering phases of Cu in all soil types except for rusty silty sand and unsaturated tan
silty sand. The MR is the dominant sequestering phase of Cu in these soil types. The
importance of the OX1 phase in sequestering Cu increases as the OM content of the soil

increases.

47

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$ Rusty silty sand A Silty sand with OM>10%

O Tan silty sand (unsaturated) 0 Tan silty sand (saturated)

+ Gravel/ Debris (fill)

 

 

 

Figure 11. Trilinear plot of Fe partitioning data in ER-MR—OXI space.

50

 

 

 

 

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52

The OX1 accounts for up to 66 % of the Cu in soils with greater the 50 percent OM.
Interestingly, even when the OM content is low (e.g. brown silty sand, rusty silty sand,
and tan silty sand-unsaturated) the importance of the OX1 phase remains significant,
demonstrating the attraction of Cu by organic matter. The relationship between organic
matter and Cu in the OX1 is shown in Figure 13. The WAS and OX2 combined account
for less than or equal to 10 % of the Cu partitioning in all soils, with no distinguishable

trends. Concentrations of Cu in the EX fraction were below detection for all samples

 

 

 

 

 

 

 

analyzed.
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Soil Organic Matter Content (weight %)

Figure 13. Relationships between soil organic matter content and percent of Cu in the
OX1 Cu.

Figure 14 is a trilinear diagram of Cu partitioning results plotted in ER-MR-OXI space.
Most of the gravel/debris, brown silty sand, silty sand with OM and soil with OM >50%
data points plot along the ER-OXI axis. Rusty silty sand points plot along both the ER-
OXl and ER-MR axes, but not along the MR-OXl axis. The association between Cu and
the MR phase in rusty silty sand indicates the sequestering ability of crystalline Fe-oxides

when organic matter content is low and oxide surface coatings are prevalent.

53

 

 

 

 

 

 

 

 

 

 

I Brown silty sand x Organic matter >50%

'3 Rusty silty sand A Silty sand with OM>10%
O Tan silty sand (unsaturated) . Tan silty sand (saturated)

+ Gravel/ Debris (fill)

 

 

Figure 14. Trilinear plot of Cu partitioning data in ER-MR-OXI space.

54

 

 

 

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The relative partitioning of Zn among the six target phases is similar for all soil
types in that the ER and MR phases are consistently the dominant sequestering phases
(FigurelSa and 15b). The MR phase is most important in sequestering Zn in brown silty
sand, rusty silty sand, and tan silty sand (unsaturated) and tan silty sand (saturated). The
ER is the most important phase in the gravel/debris, soils with OM>50% and silty sand
with abundant organic matter. The EX and WAS phases are slightly more important in
sequestering Zn in the unsaturated oxic soils than in the anoxic saturated soils indicating
that Zn in the oxic soils may potentially be more reactive and mobile under unsaturated
oxic conditions. The sequestering ability of the OX1 phase, which generally accounts for
10 to 15 % of the total Zn, is similar among the different soil types, with the exception of
tan silty sand (saturated) in which the OX1 accounts for only three per cent of the total.
The OX2 phase is relatively unimportant in the sequestering of Zn accounting for two per
cent, or less, of the extractable Zn in all soil types.

Figure 16 shows a trilinear diagram of Zn partitioning in ER-MR-OXI space.
Most of the data points plot along or near the ER- MR axis. This diagram illustrates the
importance of the ER and MR in sequestering Zn. Several silty sand with OM, OM>50%
and brown silty sand points trend away from the ER-MR axis toward the OX1 vertex
indicating a relationship between organic matter content and Zn associated with the OX1

for some samples.

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It Rusty silty sand A Silty sand with OM>10%
. Tan silty sand (unsaturated) C Tan silty sand (saturated)

+ Gravel/ Debris (fill)

 

 

 

Figure 16. Trilinear plot of Zn partitioning data in ER-MR-OXl space.

58

4.2.3 - Comparison of partitioning from this study to other studies:

The dominant sequestering phases for Cu, Fe, and Zn at this study site are similar
to those found for soil and sediments from both oxic and anoxic environments at other
sites. A summary of partitioning results from selected studies that used the sequential
chemical extraction scheme modified after the Tessier et al. (1979) procedure is
presented in Table 4. Although sample collection, pretreatment, and some extraction
procedures varied slightly among each of these studies, general comparisons can be
made. It is clear from this and other studies that the ER, MR and organic matter phases
are generally the most dominant in sequestering metals in both oxic and anoxic
environments. But because of differences between mineral phases stable in oxic and
anoxic soil environments, it is not clear what these results mean. For example, in oxic
environments, for which the extractions were designed, the ER and MR phases are
generally considered to be comprised of poorly crystalline Fe-oxides (and Mn-oxides)
and crystalline Fe-oxides, respectively. However, the lack of oxygen in anoxic pore
waters and the capability of anaerobic microorganisms to directly, or indirectly, dissolve
oxides would imply that Fe-oxides (especially reactive poorly crystalline forms) are not
likely to form and/or persist for long periods. Furthermore, the production of reduced
elemental species (e. g. 82') make alternative substrates energetically favorable and

available to precipitate out of solution with dissolved metals in the pore water.
4.2.4 - Identifying Phases Not Targeted By Sequential Chemical Extractions:

The operational definitions for phases targeted in these extractions do not include

reduced forms, other than pyrite. Other solids commonly found in anoxic environments

59

Table 4. Summary of partitioning results from selected studies that used similar selective
chemical extraction schemes modified after Tessier et al., 1979.

 

 

 

 

Study Environmental Setting General Partitioning Results

Lion et al., Estuarine particulate Fe - MR>OX>WAS>EX
1982 matter Cu - OX>WAS>MR>EX
Rapin et al., Oxic and anoxic Fe- X>WAS>EX
1983 Marine sediments 2“ ' I'fibWAsmbEX
Cu - OX>WAS>MR>EX

mlgilifrilcind Contaminated soils C“ - OX) WAS>EX

1984 ’ Zn - MR>WAS>EX>OX

 

Tessier et al.,
1985

Oxic and anoxic sediments
From three small lakes

Fe - MR>OX>ER>WAS>EX

Cu - ER>OX>MR>WAS>EX
Cu - OX>MR>ER>WAS>EX
Cu - OX>MR>ER>WAS>EX

Zn - OX>MR>EX>ER>WAS
Zn - MR>WAS>OX>ER>EX
Zn - MR>OX>ER>WAS>EX

 

Gibson and Farmer,
1986

Contaminated soils

Cu — OX>MR>WAS>EX>ER
Zn — OX>MR>ER>WAS>EX

 

 

McKee,
1990

 

Oxic and anoxic sediments
from Lake Superior

 

Fe — MR>>OX>>ER>EX>WAS
Cu - OX>>MR>>WASzER>EX
Zn — MR>>WASzOX>ER>EX

 

 

 

 

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include minerals such as FeC03, magnetite (F6304) marcasite (FeS), covellite (CuS), or

sphalerite (ZnS).

At this point in the study two questions needed to be addressed. First, how does
the presence of reduced solid phases influence the results of sequential chemical
extractions, and second, how do these substrates that form under reducing conditions
influence metal partitioning and metal cycling at the study site? In order to investigate
these questions several methods of analyses were pursued during a second phase of field
sampling events and laboratory analyses. The first was to subject pure minerals that form
in reduced environments to the same sequential extraction procedure used for soil
samples. The results of these extractions were used to determine the potential for the
selected minerals to be dissolved by each chemical extractant within the procedure. The
second step was to analyze the pore water geochemistry and identify terminal electron
accepting processes (TEAPs) occurring in the wetland area of the site. This information
was used to identify the presence of substrates that control metal cycling and characterize

the thermodynamic equilibrium state with respect to reduced mineral phases.

4.3 - Pure Mineral Extractions
Knowledge of how individual mineral phases are effected by the chemical
reactants that make up sequential chemical extraction procedures has traditionally been
interpreted from a variety of studies that have looked at how a particular mineral or small
set of minerals respond to treatment by a single extractant. The results of these studies
have been interpreted and extrapolated to predict how minerals respond to a sequence of

chemical additions. The type of extractant, reaction conditions (e.g., temperature,

61

duration, etc.) and sequence of the extractions has been designed in part by identifying
which set of chemical conditions effect or do not effect a particular mineral phase. For
example, early work by Arrhenius and Korkish (1959), Chester and Hughes (1967), Choa
(1972), Choa and Theobald (1976), Chao and Zhou (1983), and Gruebel et al. (1988),
demonstrated that hydroxylarnine hydrochloride mixed with dilute HNO3 and
hydroxylamine hydrochloride mixed acetic acid can be used to dissolve amorphous and
crystalline Fe oxides (ER and MR extractions, respectively) with relatively good
effectiveness and selectivity. Nirel et al. (1986) applied the sequential extraction method
designed by Tessier et al. (1979) to individual substrates including montrnorillonite,
CaC03, Fe oxides, Mn oxides, humic acids and quartz that had been spiked with various
trace metals. Their work showed that, CaCO3 was completely dissolved after the sodium
hydroxide N aOAc extraction (pH=5). Heron et al. (1994) used several reagents to
determine the most effective and selective extractant for various Fe-bearing minerals and
found that FeCO3 was not significantly effected by the NaOAc (pH=5) extraction, but
could be dissolved with more acidic and higher temperature extractions. More recently,
Papp et el. (1991) showed that both NaOCl (pH=9) and H202 (pH=2) do not significantly
effect goethite (FeOOH). The effect of the extractions on selected carbonate and silicate
minerals (quartz, calcite, feldspar amphibole, mica, and chlorite; kaolinite, vermiculite
and hydroxy interlayer vermiculite) identified in a soil sample was also addressed in this
study and the results are discussed in Section 4.9.2.

Prior to this study, pure forms of metal monosulfides, other than FeS, had not
been subjected to sequential chemical extractions. While FeS has been found to be
dissolved during the MR extraction (Tessier et al., 1979), other metal monosulfides have

apparently been thought to be oxidized during a peroxide (H202) (pH=2) extraction (the

62

OX2 extraction designed to dissolve Fe2S). Other minerals that have not been well
characterized in terms of their response to sequential chemical extractions include FeC03
and magnetic minerals such as magnetite.

In an effort to characterize how these minerals may affect the results of sequential
chemical extractions on soil samples collected from reduced environments, extractions
were performed on pure forms of selected minerals. The sequential extraction of pure
minerals may or may not reflect what occurs during the sequential extraction of an actual
soil sample containing mixtures of these minerals. The presence of multiple mineral
phases and organic matter in a soil sample probably has some affects on the capacity of
the chemical extractants to dissolve individual minerals. However, this approach has
been used to give indication of the effectiveness and selectivity of an extraction for
minerals that form in oxic environments (e. g., Fe-oxides).

Results of pure mineral extractions from this study, summarized in Table 5 and
presented in full in Appendix 3F-1, indicate that sequential extractions exhibit varying
degrees of selectivity for dissolution of these pure minerals. This means that some
minerals were dissolved almost exclusively during one extraction while others were
partially dissolved during two or more extractions in the procedure. Extractions were
performed on sub-splits of varying masses of powdered or granulated minerals with little
effect on the results, even though the largest sub-splits were not completely dissolved
during the extractions. Relatively large masses of mineral samples were used to assure
that mineral grains were still present during the extractions at the end of the sequential
chemical extraction procedure so that the partitioning trends were not biased by complete

dissolution of the minerals during extractions early in the procedure.

63

Table 5: Summary of results from sequential chemical extractions of pure
minerals. Results are given as average per cent of metal recovered from each extraction
with respect to the sum total metal recovered. Values in bold indicate the extraction that
yielded the highest percentage of metal from that particular mineral.

 

 

Siderite n.d. 0.4 7.8 83.8 2.0 6.0

Magnetite n.d. 0.5 2.3 91.0 4.1 2.1
Pyrite 0.1 0.2 0.7 2.7 1 1.9 83.3
FeS 1.1 5.6 11.3 62.9 16.4 2.8
CuS n.d. n.d. 0.1 0.1 87.9 12.0
ZnS n.d. n.d. 21.6 5.7 72.5 n.d.

 

Extraction results indicate a slightly progressive attack of FeS with 70.9% of the
total Fe recovered in the first four steps of the extraction from FeS. The MR extraction
released the highest percentage of Fe (62.9%) from FeS. The progressive release of Fe
from FeS prior to the MR extraction could be an artifact of impurities in the FeS or
sample handling not necessarily a lack of selectivity of the method. The partitioning
pattern (or selectivity) was independent of the amount used in the extractions over the
range of 79 mo] to 238 ttmol FeS.

The MR extraction, which was designed to dissolve Fe oxides, exhibited fairly
selective dissolution of FeCO3 and magnetite, yielding 83.8 % and 91.0 % of the total
extracted Fe, respectively. This finding suggests that soil samples containing trace metals
adsorbed to the surface FeCO3 and/or magnetite could yield similar partitioning results to
soil samples containing trace metals adsorbed to Fe(III)-oxides and/or Fe(III)-

oxyhydroxides. Therefore, rnisinterpretations of trace metal partitioning results could

 

 

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occur if Fe(III)-oxides are not present in soil sample, yet trace metals are found to be
associated with the MR phase.

Sequential chemical extraction of Fe2S also resulted in selective dissolution with
83.3% of the total Fe recovered being released during the OX2 extraction. The partial
dissolution from Fe2S during the OX1 extraction was not expected based on work of
Papp et al. (1991), who found NaOCl (extraction chemical in OX1, this study) not to
significantly dissolve Fe2S. Differences in the Fe2S used in the two studies may explain
these data. An alternative explanation for the difference may be related to the choice of
chemicals used to dissolve any recently precipitated Fe-oxides. Papp et al. (1991) used
an HCl (pH 2) acid wash after NaOCl treatments, while NHnOAc (pH 2 with HNO3) was
used in this study. The choice of NHaOAc over HCl was based on knowledge of the
conditions under which Fe2S dissolves (e. g. oxidizing, low pH). To avoid these
conditions and specifically target the recently precipitated Fe-oxides the addition of
NHaOAc (pH=2), after organic matter extraction with NaOCl, was used to create a low
pH reducing wash solution. Another alternative is that the four extractions prior to the
OX1 (e. g. EX, WAS, ER, and MR) changed the surface properties of the Fe2S which
resulted in release of Fe from surface coatings that may not have the mineral structure of
Fe2S. This would not have been observed by Papp et a1. (1991) because their work did
not include any extractions prior to their NaOCl treatment. Whatever the case, Fe
released from Fe2S during an OX1 extraction of a real soil sample will be relatively
minor and dependent on the amount of Fe2S and organic matter in the sample. Presence
of fresh organic matter would likely reduce the capacity of the NaOCl to affect any Fe2S
because the organic matter would be preferentially oxidized. For samples with little or

no Fe2S, this would not be an issue.

65

Extraction results show selective dissolution of CuS with 87.9% of the total Cu
recovered being associated with the OX1 extraction. The release of 12 % of the Cu
during the OX2 could be due to saturation of the OX1 fluids with respect to CuS or
conversion of the CuS to other forms during the first couple of extractions in the
procedure. The OX1 extraction also yielded the most Zn (72.5%) from ZnS. However,
the selectivity of the OX1 for Zn was lower due to significant release of Zn (21.6%)
during the ER extraction. This could be due to impure or mixed forms of ZnS in the
purchased stock powder or due to partial oxidation of the ZnS to another more reactive

form during the EX and WAS extractions.

4.4 - Porewater Chemistgy
4.4.1 - Porewater Results:

Geochemical parameters measured during porewater sampling events include
temperature, pH, redox potential (Eh), alkalinity, NH3, NO3’, 32', so}; CH4, Fe“, Cr”,
Br', Cl', and total cations (Ca, K, Na, Mg, Fe, Cd, Co, Cr, Mn, Pb, and Zn). Data from
four different pore water sampling events are presented in Appendix 3E and locations for
pore water sampling are shown in Figure 17. Many locations (122, K28, L27, M22, M24,
M28, P23, Q26, $26 and U26) were sampled only once to get a snap shot of the pore
water geochemistry of the wetland soils (Ellis et al., 1997 and Icopini et al., 1997). Other
locations were sampled once in support of this initial characterization and later
resampled.

The final pore water sampling event occurred in November 1997. During this
sampling event porewater field measurements and pore water samples were collected

from peepers within approximately 20 minutes of collecting soil samples for solid phase

66

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67

analyses. The peeper interval sampled for pore water corresponded to the depth interval
from which the soil samples were taken. The objective was to obtain geochemical data
for porewaters in direct contact with solid phase samples collected at locations selected
for another round of sequential extractions as well as more detailed analyses (J 19, J 23,
K22, N23, 022 and P25). These detailed analyses, discussed in the following sections,
were designed to further investigate how substrates that form in reducing environments
influence the results of sequential chemical extractions and metal cycling at the site.
Consequently, emphasis is placed on interpreting data from that porewater sampling
event. A summary of pore water data from the November 1997 sampling is shown in
Table 6.

The soil textures at sites chosen for this detailed work range in physical character
from an organic rich A horizon soil containing tannery waste (J 19) to peat comprised of
decaying organic matter with varying amounts of silt and clay (123, K22, N23 and P25)
to gray silty sand (022). All of these sites were sampled for both porewater and solid
material from two inches to eight inches bls except for 022 at which the sampling
interval was three to three and a half feet bls. The two to eight inch interval was selected
to avoid oxidized soil and porewater existing in the top two inches of the wetland
sediments, as indicated in previous porewater sampling events. The land surface at J 19
was a bit higher in elevation than the other sites and unsaturated so porewater sampling
was not conducted.

Measurement and analysis of porewater chemistry was used to gain insight into
the conditions under which minerals were precipitating or dissolving, as well as,

microbial processes that may be influencing the local environment. However, due to the

68

Table 6. Summary of selected pore water chemistry data for sites selected for detailed

solid phase analysis (November 1997).

 

 

Parameter 1 19 123 K22 N23 022 P25
pH -- 6.80 6.75 6.43 7.19 6.57

Eh (mV) —- -82 58 -17 47 42
AIR. (mg/L) -- 156.7 141.4 141.4 428.1 122.3
CH4(mg/L) -- 0.07 1.98 1.75 8.48 1.17
sz' (mg/L) -- 0.66 n.d. n.d. 0.17 n.d.
8042'(mg/L) -- 12.94 5.23 0.66 5.72 n.d.
N113 (mg/L) -- 0.61 0.61 0.22 12.99 1.09
Fe to... (mg/L) -- 0.32 1.98 13.66 1.56 7.44
Fe2+ (mg/L) -- 0.21 1.59 12.43 1.49 7.09
Fe3+ (mg/L) -- n.d. 0.39 1.23 n.d. 0.35
1=e3+ll=e2+ -- 0 0.24 0.1 0 0.05

Mn (pg/L) -- 73.48 392.61 517.20 404.66 350.16
Ni (pg/L) -- 2.11 1.60 1.88 1.72 2.27
Zn (pg/L) -- 10.82 14.05 83.51 2.34 17.87
Cu (pg/L) -- 5.35 3.44 4.44 9.16 1.99
Cd (pg/L) -- 3.91 1.26 1.19 1.10 1.17
Pb (pg/L) -- 0.64 n.d. 0.32 0.73 1.46
2- 2- -
Inferred TEAP Resp?rzation Refleétion Rfdtgtlihn ngtggihn 3420;212:112: R5598;

 

design of the peeper samplers and volume of fluid required to conduct field

measurements and pore water sampling, three pairs of ports were sampled for different

geochemical parameters over a six inch interval. It is possible that this approach may

have resulted in sampling different redox zones if the zones changed rapidly with depth.

Pore water pH values were generally very slightly acidic with values for 123,

K22, N23 and P25 ranging from 6.43 to 6.80. Only one site (022) had a slightly basic

pH of 7.19. This range of values is similar to those measured previously for these sites

(Icopini et al., 1997, and Ellis et al., 1997). Alkalinity, as bicarbonate (HCO3'), values

were similar among all sites, ranging from 122.3 - 156.7 mg/L, except 022, which had a

69

concentration of 428.1 mg/L, more than three times that of the other sites. The solid
phase material in contact with porewater at each of the sites may contribute to the
differences observed in the pH and alkalinity. The solid phase material at 022 had by far
the lowest organic matter content of all the sites and this site has the highest pH and
alkalinity. The significantly alkalinity in the porewater sample from 022 is unique
among the sites investigated and may reflect a different solid phase geochemistry and/or
different microbial community. The greater amount of decaying organic matter present
at the other sites likely results in lower pH values because greater amounts of organic

acids were being released to the surrounding porewater.

4.4.2 - Porewater Redox Conditions and Terminal Electron Accepting Processes

Pore water redox conditions and concentrations of microbial metabolic end
products were used to infer the dominant terminal electron accepting processes occurring
in the saturated soil environment. However, it was recognized that the presence of a
particular TEAP end product might not necessarily indicate that a TEAP was occurring at
the time of sampling, rather that it had occurred and the end products had not been
consumed, precipitated, or transported away. Electrode measurements of the soil pore
fluid redox potential were used only as a general indication of redox conditions, because
electrode measurements have been found to not accurately predict predominant TEAPs
(Lindberg and Runnels, 1984 and Lovley and Goodwin, 1988).

Electrode-measurements of redox potential (Eh) were slightly higher during the
November, 1997 sampling than they had been for previous sampling events, but still
generally indicate anoxic conditions. Electrode-measured redox potential values in pore

waters of saturated soils for all sampling events ranged from +50 to —188 mV. These

70

values generally fall in the range that has been reported for Fe- reduction and sulfate
reduction in flooded soils (Yoshida, 1975; Watanabe and Furusaka, 1980; Lovley and
Goodwin, 1988). The ambient air and pore water temperatures during the November,
1997 sampling (2-5°C) may have affected the performance of the electrode. These near
freezing conditions probably also affected the microbial activity and rates of TEAPs, thus
resulting in lowered production of metabolites. This was reflected in the concentrations
of CH4 and 82', which were lower for this sampling than previously measured for most
locations. Minor amounts of S2' were detected in pore waters at K22, N23 and P25
during previous events but not this sampling event.

Concentrations of Fe3+ in pore water at K22, N23, and P25 were relatively minor
compared to the concentration of Fe”. Fe” was not directly measured, but rather
calculated by the difference between Fem] and Fe“. The detection limit of both the Fe2+
and the Few] methods was about 0.1 mg/L so calculated Fe3+ concentrations below this
value were considered non-detect. The Fey/Fe2+ ratios indicate that Fe2+ was the
dominant aqueous species of Fe in pore water at all of the locations. The presence of
Fe3+ in otherwise anoxic pore waters may reflect active dissolution of Fe(IIl) oxides or
mixed valence minerals such as magnetite Fe(III)[Fe(II)Fe(III)]O4. Dissolved Fe2+
concentrations were elevated at K22, N23, and P25 and Eh values in were the range
reported for Fe reduction.

The location with the highest measured redox potential during the November
1997 sampling event was K22 (Eh = +58). This site did not have any detectable 82', but
did have a fair amount dissolved SO42' (5.23 mg/L). Concentrations of CH4, NH3, Fem],

and Fe2+ were low (1.98, 0.61, 1.98, 1.59 mg/L, respectively) as were concentrations of

71

most trace metals. This pore water chemistry suggests that the dominant TEAP process
occurring at the time of sampling was likely Fe reduction.

The Eh value measured in porewater from N23 was —17. Pore water
concentrations of CH4, 8042', NH3, were all relatively low (1.75, 0.66, and 0.22,
respectively), and 82' was not detected. Concentrations of Fen“, Fe“, Fe”, Mn and Zn
were the highest of all the sites during the last sampling (13.66, 12.43, 1.23, 0.517 and
0.083 mg/L respectively). However, concentrations of the other trace metals were
relatively low. This pore water chemistry suggests that the dominant TEAP process
occurring at the time of sampling was likely iron reduction.

Pore water at P25 had a measured Eh value of —42. Low concentrations of CH4,
and NH3 (1.17 and 1.09 mg/L) were detected in this sample. Neither 82°,nor SO42} were
detected in pore water in this sample. Relatively high concentrations of Fem,“ and Fe2+
(7.44 and 7.09mg/L) were detected, but trace metal concentrations were low. This pore
water chemistry suggests that the dominant TEAP process occurring at the time of
sampling was likely iron reduction.

The lowest dissolved Fem. concentrations occur in samples with the lowest Eh
values and the highest measured 82' concentrations (J23 and 022), possibly indicating
that sulfate reduction was the dominant TEAP occurring at the time of sampling.

During the November 1997 sampling of pore water, 123 had the lowest Eh (-82)
of all the locations sampled. This location also had the highest dissolved 82' (0.66 mg/L)
and 5042' (12.94 mg/L) concentrations. Pore water concentrations of CH4, NH3, Fem],
and Fe2+ at 123 were the lowest of all the sites (0.07, 0.61, 0.32 and 0.21 mg/L,
respectively) and Fe3+ was not detected. Trace metal concentrations were also low. The

presence of 82‘ and the relatively low concentrations of Fe and trace metals suggests that

72

sulfate reduction was the dominant TEAP occurring at the time of sampling. This
porewater chemistry also suggests that the precipitation of metal monosulfides may have
occurred.

The apparent Fe-reducing conditions may have caused reduced Fe bearing
minerals, including FeS, Fe304, or FeCO3, to become supersaturated with respect to pore
water chemistry, resulting in precipitation of one or more of these minerals. Precipitation
of the FeC03 may be most likely at 022, which has the highest alkalinity and pH
measured at the site, 428.1 mg/L (as HCO3’) and 7.19, respectively. FeCO3 can compete
with magnetite formation for Fe(H) in environments with high bicarbonate concentrations

and elevated pH by the following reaction:

Fe2+ + HCO3' (—) FeC03 + H”

Since Fe(III) reduction occurs in anoxic environments prior to 8042' reduction the
formation of R30; and FeCO3 could occur prior to 82' accumulation and subsequent
precipitation of Fe2+ as FeS, thus explaining the presence of three different reduced Fe-
bearing minerals (Lovley, 1991).

The interpretation of the dominant TEAP at 022 is complicated by presence of a
significant amounts of 82', CH4, and NH3+ in pore water (0.17mg/L, 8.48 mg/L and 12.99
mg/L, respectively). Several scenarios could explain the simultaneous presence of three
TEAP end products in porewater. The presence of significant concentrations of CH4, 82',
and NH3 at site 022 may indicate that three different TEAPs had occurred, or that more
than one was occurring concurrently. Ammonia may have been produced via

dissimilatory nitrate reduction concurrent with the other TEAPs or may have occurred

73

prior to sampling and the accumulated end-product had not been utilized or transported
away. The S2' in the pore water could result from previous and, or concurrent sulfate
reduction or from the oxidation of S0 to 8042’ and subsequent reduction to 82'. The
presence of CH4 may indicate concurrent methanogenesis, or diffusion of CH4 from
deeper layers of the water-saturated soil. Interestingly, this location had an electrode
measured Eh value of +47, which was higher than expected given its pore water
chemistry and may have been the result of electrode malfunction at low temperatures.
In summary, analyses of pore water from the sites sampled in November 1997 are
similar to those of previous sampling events and indicate that iron and sulfate reduction
are the dominant TEAPs occurring in the wetland area of the site. These microbial
processes influence the cycling of metals at the site by changing the redox potential and

the substrates available for precipitation and/or adsorption.

4.5 - Selected Site Sguential Chemical Extraction Results

With the redox conditions of the porewater sampling locations characterized,
sequential extractions were performed on soil samples collected from these locations
selected for detailed analysis (119, 123, K22, N23, 022, and P25). The objective for
collecting more soil samples from the wetland area further investigation was to identify
differences in partitioning among sites from differing environments and correlate, if
possible, these findings to measured physical, chemical and microbiological parameters
(e.g. soil type, porewater chemistry, TEAP). Most of the sites selected for this detailed
work were from the wetland area because metal partitioning in soils from the oxic upland
area is thought to be relatively straightforward in comparison to the water saturated

anoxic soils area. Again, the ER and MR phases are known to comprise Fe-oxides and

74

the OX1 is likely comprised of organic matter in oxic soils, but these phases are still in
question for anoxic soils.

Partitioning results for the six sites selected for detailed analysis are shown in
Tables 7-9. As discussed in the previous section, pore water in direct contact with the
solid phase indicates that anoxic (reducing) conditions exist at each of the sites except
119, which is unsaturated. The dominant sequestering phases for Fe, Cu, and Zn in these
individual samples are similar to those identified in the initial partitioning investigation.
The ER and MR are the dominant sequestering phases for Fe and Zn and the OX1 is the
dominant sequestering phase of Cu followed by the ER and MR.

There is a distinct difference in the partitioning of Fe, Cu, and Zn among the six
samples analyzed in this portion of the study. The most striking difference in partitioning
is between the unsaturated sample (119) and the water-saturated anoxic samples. Fe is
predominantly associated with the MR and ER fractions for all six samples, but samples
from K22, N23 and P25 had significant Fe associated with the EX phase, 23.8, 27.8, and
28.3%, respectively. 022 had a significant proportion of its total Fe associated with the
WAS and OX2 phases, 17.0 and 16.5%, respectively. In contrast, the unsaturated oxic
location, 119, did not exhibit much variation in Fe partitioning with the EX, WAS,
OXland OX2 combined accounting for only seven per cent of the total Fe. Cu was
predominantly associated with the OX1 phase for all samples, except 119 in which the
ER and MR were most important. 123, K22, N23, 022, and P25 all had greater than 86%
of the Cu associated with the OX1 phase, while at 119 the ER, MR, and OX1 accounted
for 47.8%, 25.7 and 24.9% of the total Cu, respectively. Zn is primarily associated with

the MR, and OX1 phases for 119, the ER and MR for 123 and K22, the ER, MR, and

75

Table 7. Organic matter content (%), total Fe micromoles per gram (umol/g) and
partitioning for selected sites.

 

OM ZFe EX WAS ER MR OX1 OX2

 

samP'em % (umol/g) % % % % % %
119 31.4 96.3 0.2 2.7 15.0 78.7 2.3 1.2
123 35.9 68.4 1.8 3.4 36.5 41.4 3.6 13.3
K22 36.8 115.0 23.8 3.4 31.6 30.9 5.3 5.0
N23 10.3 118.3 27.8 8.8 25.0 28.0 2.7 7.7
022avg 5.5 77.8 0.2 17.0 213 34.3 9.7 16.5
P25 36.3 113.2 28.3 7.0 24.5 34.3 2.0 3.8

 

Table 8. Organic matter content (%), total Cu (umol/g) and partitioning for selected sites.

 

OM ZCu EX WAS ER MR OX1 OX2

 

5mm“ m % (umol/g) % % % % % %
119 31.4 3.25 n.d. 1.0 47.8 25.7 24.9 0.6
123 35.9 2.25 n.d. n.d. 6.1 1.9 90.0 2.0
K22 36.8 1.25 n.d. n.d. 10.2 2.8 86.5 0.4
N23 10.3 1.03 n.d. n.d. 3.1 4.5 91.5 0.9
O22avg 5.5 0.39 n.d. n.d. n.d. 2.8 94.1 3.1
P25 36.3 1.13 n.d. n.d. 10.5 2.7 86.6 0.2

 

Table 9. Organic matter content (%), total Zn (umol/g) and partitioning for selected sites.

 

OM ZZn EX WAS ER MR OX1 OX2

 

S‘m‘p'em % (umol/g) % % % % % %
J19 31.4 1.09 3.0 9.2 9.2 42.1 25.5 11.1
123 35.9 3.40 0.7 10.1 36.9 38.3 11.6 2.5
K22 36.8 8.12 3.0 13.1 57.7 195 5.7 0.9
N23 10.3 4.82 1.2 6.7 52.1 21.6 17.2 1.1
O22avg 5.5 5.41 0.1 4.1 12.9 12.9 69.2 0.8
P25 36.3 1.93 n.d. 17.2 35.8 30.5 16.5 n.d.

 

76

Oleor N23 and P25. The sample from 022 is the only one of this group to have only
the OX1 dominate the partitioning of Zn.

The pattern of Cu partitioning among this group of samples was consistent with
what would be expected based on the traditional interpretations of sequential extraction
results. Cu was strongly associated with OX1 phase of the soil for those samples with
high organic matter content and little apparent probability of Fe oxides present (123, [(22,
N23, and P25). The one sample that was unsaturated and likely contained some Fe-
oxides (119) showed a much different pattern of partitioning in that the ER and MR
phases became relatively more important in sequestering Cu.

The pattern of Zn partitioning in this group of samples was a little less consistent
with what was expected given the soil type and conditions. There was more variability in
the pattern among the water saturated wetland samples suggesting that partitioning may
be controlled by factors that were more sample specific than for the partitioning of Cu.
Before more detailed interpretations concerning Zn partitioning can be made some
discussion about the form(s) of Fe that make up the ER and MR phases would be
necessary. The concentration of Fe found in the ER and MR fractions was somewhat
surprising considering that no Fe-oxides were thought to be present in the wetland soils.
To investigate this further and also explain the differences in partitioning found among
these wetland area samples, the pore water chemistry associated with the solid phase
samples was considered a first.

Solid phase Fe partitioning appears to be related to the degree of water saturation,
Fe3+and Sz' porewater concentrations and Fe3+lFe2+ porewater ratio. The ER and MR
accounted for greater than 90% of the total Fe for the sample from 119, which was

unsaturated. This pattern is similar to that expected for soil having Fe-oxides as the

77

dominant form of solid phase Fe. In contrast, the water saturated samples exhibit a
pattern of Fe partitioning in which other phases were relatively important in sequestering
Fe.

The two samples with detectable dissolved 82' concentrations and non detectable
Fe“, 123 and O22, exhibit similar partitioning in that the OX2 fraction accounts for a
relatively significant portion of the solid phase Fe. In contrast, sequential extraction
results for the other samples (K22, N 23, and P25) indicate that the EX, ER, and MR
phases were about equally important in Fe partitioning, each accounting for 25-30% of
the total extracted Fe. This difference in the Fe partitioning among samples from the six

sites seemed curious and deserving of further investigation.

4.6 - Geochemical Modeling Results

To continue to investigate the partitioning patterns observed for the water
saturated samples geochemical modeling was performed to identify or predict the
presence of solid phases that may affect the results of the sequential chemical extractions.
Perhaps a phase or phases other than Fe-oxides were present in the samples that could
yield a sequential extraction partitioning pattern similar to that of Fe—oxides (eg. ER and
MR most important phases), resulting in a misinterpretation of the phases which make up

the ER and MR phases.
4. 6.1 - Mineral Saturation Indices

Pore water analytical data for samples collected during the November 1997

porewater sampling event were used for geochemical modeling. All geochemical

78

parameters shown in Appendix 3E (Table 3E-4) were used to create input files for
geochemical modeling with PHREEQC (Parkhurst, 1995), with the exception of CH4.
Selected mineral saturation indices determined by PHREEQC modeling of
the pore water data are shown in Table 10. Saturation indices (SI) were determined
during the modeling by dividing the log of the calculated ion activity product (IAP) of

aqueous species needed to form a mineral by the log of the calculated solubility product
(Ksp) for that mineral. Mineral saturation indices indicated whether a mineral phase was

thermodynamically under-saturated (SI<0), saturated (81:0), or supersaturated (SI>0)
with respect to the fluid chemistry at the time of sampling. From this information,
interpretations were made concerning what minerals were likely to precipitate or dissolve
in this system.

In the manner that PHREEQC was used in this study, it did not account for the
microbially mediated process that drive many of the precipitation/dissolution reactions
involving redox sensitive elements. Also, the MINTEQ database, in the form used for
this modeling, did not accept input for CH4. Consequently, the Eh value calculated by
the model and used to determine aqueous speciation and mineral saturation indices does
not reflect the HC03'/ CH4(aq) redox couple. Therefore, the results of the modeling may
not be accurate for those locations where methanogenesis Controlled or contributes to the
redox conditions. Also, calculation of mineral disequilibrium was not possible in cases
where a parameter necessary for the formation of that mineral had an aqueous
concentration of zero. For instance, FeS disequilibrium could not be calculated when the

porewater concentration of 82' was zero.

79

Table 10. Saturation indices (S1 = log IAP/Ksp) of selected minerals calculated by

PHREEQC with the Minteq database for pore waters at sites 123, K22, N23, P25, and

 

 

 

022.

Saturation Indices
Mineral Phase Formula .123 K22 N 23 P25 022
Aragonite CaC03 -1.29 -1.37 -1.8 -1.83 0.02
Calcite CaC03 -1.13 -1.2 -1.63 - l .66 0.18
Chalocite Cqu 1 1.52 -- -- -- l 1.57
Chalcopyrite CuFeSz 17.04 -- -- -- 18.76
Covellite CuS 8.05 -- -- -- 9.26
Cuprousferrite CuFeOz 1.63 15.25 -- -- --
Fe3(OH)g FC3(OH)3 -12.25 3.01 3.66 2.89 --
Ferrihydrite Fe(OH)3 -5.01 2.3 l -- 2. l --
FeS (ppt) FeS(ppt) —0.01 -- -- -- --
Galena PbS 4.64 -- -- -- 5.34
Geothite FeOOH -1.48 5.85 6 5.58 --
Greigite Fe3S4 4.46 -- -- -- --
Hematite Fe203 1.94 16.59 16.9 16.06 --
Lepidocrocite FeOOH -1.49 5.83 6.03 5.62 --
Mackinawite FeS 0.73 -- - -- 1.34
Maghernite Fe203 -- 8.02 8.41 7.6 --
Magnesite MgC03 -2. 17 -2.22 -- -- -1 .82
Magnetite F6304 1.25 16.51 -- 16.21 --
Millerite MS 1.56 -- -- -- --
Pyrite Fe2S 13.67 -- -- -- 16.57
Siderite FeCO3 1.56 -0.59 -- -0.55 -0.03
Sphalerite ZnS 2.53 -- -- -- 2.59
Sulfur S 0.3 -- -- -- 2.72
Wurtzite ZnS 0.4 -- -- -- 0.5
ZnS(a) ZnS(a) -0.31 -- -- -- -0.21

 

-- indicates a saturation index for that mineral was not calculated by the model.

80

4.6.2 - Predictions of mineral precipitation and dissolution:

Mineral saturation indices for pore water at 123 and 022 indicate that soil pore
fluids are supersaturated with respect to many metal sulfides, which were likely to be
precipitating out of solution. This was expected given the concentration of 82° and
insolubility of metal sulfides. Pore fluids have negative saturation indices for ferric Fe-
bearing minerals such as goethite and ferrihydrite, indicating that they were
undersaturated with respect to these minerals. If goethite and ferrihydrite were present as
minerals in the solid phase, the modeling predicts that they were dissolving. Pore fluids
were supersaturated with respect to the mixed Fe(H)/Fe(III) oxide at 123, but not at 022.
Pore water at 123 had both Fe2+ and Fe“, but 022 did not have detectable Fe3+ so the
calculation of magnetite disequilibrium was not possible at 022. Pore fluid was
supersaturated with respect to FeCO3 at J 23 and very close to saturation with respect to
FeC03 at 022.

Results of the geochemical modeling for K22, N 23, and P25 indicate that the
fluids were supersaturated with respect to Fe(III) oxides. The lack of 82' in porewater at
these locations makes the precipitation of metal sulfides unlikely, as predicted by the
model. However, the model cannot predict whether precipitation of sulfides had occurred
prior to sampling. Pore fluid was very close to saturation with respect to FeC03 at K22
and P25. Pore fluids were supersaturated with respect to magnetite at K22 and P25.

The modeling suggests that there may have been forms of Fe-bearing minerals
present in the samples that are not included in the operational definitions of the sequential

chemical extractions. It also suggests that Fe(III)-oxides may have been present in some

81

of the wetland samples that were thought to be reducing beyond the point were oxides
would persist. The next three sections describe efforts to positively identify phases of Fe
that make up the total mass of extractable Fe in the soils. Identifying these phases will
help interpret the results of the sequential chemical extractions and indicate which phases
in an anoxic soil make up the ER and MR fractions.

Initially it was assumed that no Fe oxides were present in the wetland soils and
that the extractable Fe was composed of phases containing only reduced forms of Fe. As
each phase was independently identified and measured (when possible) the contribution

of that phase to the total mass of Fe was evaluated.

82

4.7 - Acid Volatile Sulfide and Simultaneously Extracted Metals Results

The detection of sulfide in porewater at some locations in the wetland area and
results of the geochemical modeling prompted investigation into the presence of metal
sulfides in the anoxic soils. It was thought that if a significant mass of sulfide was
present in the soil that a significant amount of Fe could be bound to it.

Sulfide minerals are generally classified as either acid volatile sulfides (AVS),
which includes amorphous iron monosulfide and monosulfides of other metals (e. g.
cadmium, lead, mercury, nickel, silver, zinc), or more crystalline forms such as FeZS
(Morse and Comwell, 1987 and Lasorsa and Casas, 1996).

A summary of the AVS extraction results for six soil samples is presented in
Tables 11a and 11b. Calculations for these data are shown in Appendix 3D. The soil
sample from 119 had no detectable AVS and P25 had an AVS concentration just above
detection. Site 119 was not expected to have any detectable AVS given that this location
is generally unsaturated and probably has 02 in soil gas within the pore spaces. Given
these conditions, it is unlikely that microbially mediated sulfate reduction occurred at
rates significant enough to yield detectable soil AVS. The lack of AVS and dissolved
5042' and 82' at P25 suggests that either the soil at this site is sulfur limited or the sulfur is

bound up in an unreactive phase such as FeZS. Soil samples from 123, K22, N23, and

83

Table 11a. Concentrations of AVS measured simultaneously extracted metals (SEM) for

119, 123, K22, N23, 022, and P25 in umol/g dry weight soil.

 

 

E [SEMlTM

Sample [AVS] ‘0" ”A“ [AVS] - 2[SEM]1~M [SEM]p.

ID (umol/g) (umollg) (umollg) (umol/g)
119 AVS n.d. 33.41 -33.40 66.96
123 AVS 10.58 7.30 3.28 33.15
K22 AVS 6.69 8.53 -1.84 110.43
N23 AVS 11.61 4.26 7.35 76.10
022 AVS 11.87 2.34 9.53 24.95
925 AVS n.d 1.87 -1.78 101.70

 

Table 11b. Calculations of FeS, and Fe Othermin) and Fe Othenm) and concentration of

total extractable Fe as determined by the sum of the sequential chemical extractions
(SCEs) for comparison.

 

 

[SEM]Fe '-
Sample [AVS] - 2 [SEerM ([AVS] -[SEM]m) [SEere- [AVS] til: 111
= F eS = Fe Other (max) =F e Other (min) SCES
ID (umol/g) (umoI/g) (umol/g) (umol/g)
119 AVS 0 66.96 66.96 96.3
123 AVS 3.28 29.87 22.57 68.4
K22 AVS 0 1 10.43 103.74 115.0
N23 AVS 7.35 68.75 64.49 1 18.3
022 AVS 9.53 15.42 13.08 77.78
P25 AVS 0 101.70 101.70 113.2

 

84

022 had significant concentrations of AVS. This is in good agreement with the redox
measurements and dissolved Fe2+ and 82' concentrations from 123 and 022. However,
the pore water chemistry did not suggest, and the geochemical modeling did not predict,
the presence of sulfides at K22 and N23. As mentioned in Section 4.4.2, minor amounts
of 82' were detected at these sites during sampling events prior to the November 1997
porewater/solid phase sampling event. It is probable that the AVS formed and
accumulated some time prior to a shift in redox caused by a change in the dominant
TEAP.

It is difficult to determine the exact concentration of each metal monosulfide
present in a particular sample because of the complex nature of sulfide geochemistry and
the potential for metals to be released by the AVS/SEM extraction from phases other than
monosulfides. It is known that preferential binding of trace metals by 82' occurs when a
system is at equilibrium, because the 82' ion successfully out-competes all commonly
present dissolved or particulate ligands to form insoluble metal sulfides (DiToro et al.
1992). Also, more soluble metal sulfides, such as FeS, can be converted to more

insoluble sulfides (e.g. PbS and CuS) by direct displacement reactions:

FeS + Me2+ —> MeS + Fez”,

where Me2+ is any cation which forms a more insoluble metal sulfide (see Table 12).

Because Fe forms one of the most soluble sulfides, this approach seemed an appropriate

way to estimate the concentration of FeS in soil samples.

85

Table 12. Solubility product constants of selected sulfides at 25°C (from Faure, 1991).

 

 

Mineral (szp) Mineral (szp)
MnS (green) 13.5 a-ZnS Sphalerite 24.7
FeS or-triolite 16.2 CdS Greenockite 27.0
PbS galena 17.5 CuS Covellite 36.1
a-NiS 19.4 FeS; Marcasite 41.8
B-ZnS wurtzite 22.5 FeSz Pyrite 42.5
y-NiS 26.6 FezS3 Greigite 88.0

 

With this in mind, the sum of the simultaneously extracted metal (SEM)
concentrations of the trace metals (TM) (2 [SEM]m(Cd, Ni, pb, 2m), was subtracted from the
AVS concentrations, on a molar basis ([AVS] - 2 [SEM]TM). The difference yielded the
amount of sulfide that would theoretically be available to form FeS. It should be noted
that CuS is not considered an AVS because it has been shown to not dissolve in IN HCl
at 25°C (Allen et al., 1993). Consequently, the concentration of Cu measured in the
AVS/SEM leachate was not included in the [SEMhM

Three of the six samples analyzed (119, K22, and P25) had no AVS remaining
after accounting for the more insoluble metal sulfides (see Table 11a). The typical
calculations performed with AVS/SEM data end here, but some AVS was still
unaccounted for and the amount of Fe released during the AVS/SEM analysis appeared

to be significant and worthy of further investigation. Continuing on, the amount of

86

[SEMFC] and the remaining AVS were used to calculate the amount of FeS that could be

present in the soils. Next, the amount of [SEM]p¢ that could not be attributed to FeS, was
calculated as Fe-Othenm). This value is one end-member estimate for Fe that was likely
not associated with sulfide but may originate from other easily dissolved Fe-bearing
minerals that comprise the ER and MR phases, and assumes that all [SEM]1~M originate
from monosulfides. The Fe-Othenm) end-member assumes that all of the trace metals
extracted as SEM originated from metal monosulfides. The final calculation represents
the other theoretical end-member, Fe-Othenmin), in which the SEM trace metals are
assumed to be not associated with monosulfides. For Fe-Othermin), all of the AVS was
subtracted from the SEM Fe. Both theoretical end-member calculations yielded similar
values for Fe-other.

The AVS/SEM results indicate the presence of metal monosulfides in samples
from the wetland area of the site. Calculations with the AVS and SEM;:.: suggest that FeS
is likely present in the wetland soils but the mass of FeS is small in comparison to the
total mass of extractable Fe determined by summation of sequential extraction data. This
means that another phase (or phases) must account for the majority of the Fe in the

wetland soil.

4.8 Magnetic Mineral Separations

To continue the search for phases that might contribute Fe to the ER and MR
phases, magnetic separations were performed on soil samples from 119, 123, K22, N23,
022, and P25. The separations yielded detectable amounts of one or more fine-grained

magnetic minerals. The data generated is likely an underestimation of the magnetic

87

fraction present in the soil because due to the rather crude method used very fine-grained
minerals may not have been effectively separated and collected.

Visual inspection under low magnification revealed they had irregular, flake, and
needle shapes grains, ranging in diameter or length from barely visible to approximately
three millimeters (mm). This apparent structural and size difference may indicate the
presence of different magnetic minerals and/or different genesis of the same mineral.
The exact mineralogy of this magnetic fraction was not investigated, but the most likely
candidates given the conditions of the soil were magnetite (Fe(III) [Fe(II)Fe(III)]O4) and
biogenically produced magnetic Fe-sulfides including greigite, (Fe3S4), or pyrrhotite
(Fe-183) (Bazylinski et. a1, 1991). Presence of magnetic minerals in soils could be the
result of exogenic weathering, transport, and subsequent deposition; authigenic inorganic
processes (Maher 1991); magnetotactic dissimilatory Fe(II) reduction (Lovley, 1991); or
biogenically derived by magnotactic bacteria (Bzylinski et al., 1991).

Fe, Cu and Zn concentrations in leachate samples from extraction of the
magnetically separated fraction are shown in Table 13. It was assumed that most of this
fraction would consist of Fe-bearing magnetic minerals. Cu and Zn were analyzed in an
attempt to determine the importance of adsorption onto magnetic minerals. Fe was the
only metal present in detectable concentrations in the leachate samples.

Site K22 had both the largest observable magnetic fraction and the highest
detected concentration of Fe in leachate fluid ( 12.07 tunol/g dry soil used for the
separation). This is in good agreement with the interpretation of the dominant TEAP
occurring at this location and presence of both Fe2+ and Fe3+ in the pore water. The
concentrations of Fe in leachate fluids for samples from the other five locations was

significantly lower indicating less magnetite in the soil at those locations.

88

Table 13. Concentrations of Fe, Cu and Zn in leachate samples from extraction of the
magnetically separated fraction of selected soils, reported in 11111ng dry soil used for the
magnetic separation. Total extractable Fe as determined by sequential chemical
extractions is shown for comparison.

 

 

Sample Fe Cu Zn EFe from
ID SCEs
(umollg) (lanai/g) (umollg) (umollg)
119 0.64 n.d. n.d. 96.3
123 2.53 n.d. n.d. 68.4
K22 12.07 n.d. n.d. 115.0
N 23 1.66 n.d. n.d. 1 18.3
022 0.63 n.d. n.d. 77.78
P25 0.06 n.d. n.d. 1 13.2

 

n.d. indicates constituent was not detected

Similar to the AVS/SEM work, the mass of Fe associated with the magnetic fraction
is small in comparison to the total amount of extractable Fe as determined by summing
the sequential chemical extractions. This indicated that some other phase must account
for the Fe in the ER and MR leachates. Other Fe bearing minerals that would likely form
or exist under reducing conditions are FeC03, chlorite, and Fe bearing amphiboles,
pyroxenes and feldspars. The only available technique to identify the presence of these

minerals was x-ray diffraction.

89

4.9 - X-ray Diffraction Results
4.9.1 - XRD results for samples from anoxic soils:

Several soil samples were analyzed by X-ray diffraction (XRD) in an attempt to
identify the presence of carbonates (e. g. FeC03), Fe-oxides, layered silicate minerals
(e. g., chlorite), chain silicates (e.g., amphibole, pyroxenes) and framework silicates (e.g.,
feldspar). Detailed x-ray diffractogram peak identifications and mineral identifications
for these samples are given in Appendix 3G and are only briefly summarized below.

X-ray diffraction of samples from 119, 123, K22, N23 and 022 did not show
evidence for the presence of chlorite, amphibole, pyroxene, feldspar or Fe-oxides. Low
concentrations, poor crystal structures, and/or sample pretreatment could have resulted in
non-detection by XRD methods. If FeC03 or crystalline Fe-oxides were present in the
samples it would likely be only minor amounts. However, poorly crystalline Fe-oxides
cannot be ruled out because their amorphous character causes them to be unidentifiable

by XRD.

4. 9.2 - Effect of ER and MR extractions on carbonate and silicates

One sample outside the wetland area, D11 1-1.5, was subjected to selected
extractions within the sequential chemical extraction procedure used in this study in an
attempt to determine the effect of these extractions on carbonate and silicate minerals.
Sample D11 1-1.5 was selected for analysis because it was very low in organic matter

content (0.3 % of dry soil weight) and had a moderate clay size fraction. This reduced

90

the number of variables and avoided the need for pre—treatment prior to XRD analysis
that could alter the samples and allowed several sub-splits for analysis.

Minerals identified in the <10p.m fraction of sample D11 1-1.5 prior to chemical
extractions include: quartz, calcite, feldspar (possibly both plagioclase and microcline),
amphibole, mica (muscovite and/or illite), and chlorite; and there was suggestive
evidence for kaolinite, vermiculite and hydroxy interlayer vermiculite. Of all the
minerals identified initially, only calcite was not present after the WAS extraction. This
demonstrates the specificity of N aOAc (pH 5) for dissolution of carbonate minerals.

No significant decrease or loss of peaks was observed after the ER or MR extractions for
this sample, suggesting that the silicate and clay minerals (including chlorite) identified

in the untreated sample were not significantly dissolved by these extractions.

4.10 - SW of the Search for Fe-Bearing Minerals Present in Anoxic Soils
The relatively small mass of Fe attributable to the AVS and magnetically

separated fractions in samples from the wetland area, along with the non-detection of Fe
bearing carbonates and silicates was somewhat perplexing given the anoxic soil
conditions and the significance of the ER and MR fractions in Fe partitioning. A
summary of Fe concentrations from the ER and MR phases and identified minerals for
the samples from the wetland area is given in Table 14. The ER and MR phases account
for 50 to 80% of the extracted Fe for samples from the wetland area. The ER and MR
phases account for about 94% of the extracted Fe for the sample from 119, the only
unsaturated sample. Subtracting the masses of Fe attributable to FeS and magnetite
yields the mass of Fe that was unaccounted for by these reduced forms of Fe that were

presumably precipitated under anoxic conditions.

91

Table 14. Summary of Fe concentrations in selected samples including the sum total
from sequential chemical extractions (ZSCE); the percent of total Fe extracted by ER +
MR, the concentration of Fe extracted by ER+ MR fractions; Fe attributed to FeS; Fe
attributed by magnetite; and Fe from unidentified phases extracted by ER and MR.

 

 

 

sample (ZFicmEj) BR-l-MR ER+MR Fe as Fe Mag. F6 Unidentified F6 Unidentified

ID (umol/g) (%) (umol/g) (umol/g) (umol/g) (umollg) % of Fe...
1 19 96.3 93.7 90.2 0.0 0.6 89.6 93.0
123 68.4 77.9 53.3 3.3 2.5 47.5 69.4
K22 1 15.0 62. 71.9 0.0 12.1 59.8 52.0
N23 118.3 53.0 62.7 7.4 1.7 53.6 45.4
022 113.2 55.6 62.9 9.5 0.6 52.8 46.6
P25 77.8 58.8 45.7 0.0 0.1 45.6 58.7

 

Since the most likely reactive reduced phases have been identified and found to be
insufficient to account for the mass of Fe released from these anoxic samples, other
possible substrates and environmentally reactive phases must be considered and include

the following:

0 pH sensitive Fe-organic matter-complexes/coatings,
o Fe-oxides that persist under anoxic conditions,

0 less common Fe phases such as Fe phosphate (e.g. FePO4-2H20).

The first two possibilities would be consistent with the results of the sequential chemical
extraction results. This would mean that Fe released during the ER extraction could
originate from pH sensitive organic matter coatings, while the Fe released during the MR

phase could originate from continued release from the organic coating or relic Fe-oxides.

92

Agitation of the samples during the first couple of extractions could have resulted in
removal of some of the organic coatings on soil grains. Preservation of Fe oxides under
anoxic conditions may have been facilitated by organic matter coatings which inhibited
microbial reduction of the Fe-oxides. The final alternative phase suggested would have
depended on the amount of available substrate (e.g. P04) present in the anoxic soil
environment. This less common substrate was not identified in the course of this
research and it is not known whether or not it would have contributed Fe to the ER or MR

phases.

4.11 - Comflition of Phases Identified by Seguential Chemical Extractions:

Interpreting Results of Sguential Chemical Extractions

The samples chosen and methods employed in this study allow an evaluation of
the composition of phases that are targeted during sequential chemical extractions.
Potential for phases that form under one set of environmental conditions (e.g. oxidizing
or reducing) to persist after conditions have changed has been recognized and
underscores the importance of complementary analysis of both porewater and solid phase
mineralogy when applying sequential chemical extractions to anoxic or cyclically
oxic/anoxic soils or sediments. Porewater geochemistry at the study site suggested
anoxic conditions exist throughout the wetland area soils. Consequently, Fe-oxides were
originally thought to be absent in the wetland area of the site, where these anoxic
porewater conditions were shown to exist. However, because Fe reduction was one of
the dominant TEAPs, would there not need to be Fe-oxides present to support this
apparent metabolically favored process? If Fe-oxides were present in anoxic soils (and

sediments) and other phases have been created in response to the changes in redox

93

conditions (e.g. [Fe(III)2Fe(II)]O4 and FeS), the question that followed was how does this
affect interpretations of sequential chemical extraction results? Also, if trace metals are
found in leachates of the ER and MR extractions, were they associated with Fe—oxides
currently undergoing microbial reductive dissolution or did they originate from phases
that formed under the anoxic conditions (e. g. metal-monosulfides) that dissolve in
response to the low pH of the ER and MR extractions?

Identifying where the trace metals originate has important implications if results
of sequential chemical extractions are to be used to predict trace metal behavior at this
site or any other site. If the trace metals were associated with the oxide surfaces existing
under anoxic conditions, then continued reducing conditions would presumably result in
the continued release of trace metals to the surrounding porewater. The concentration of
metals in porewater (and hence bioavailability and toxicity) would then be dependent on
the microbial production of substrates, such as 82', to precipitate the metals out of
solution. On the other hand, if the trace metals were associated with reduced phases, then
the trace metals would likely not be released to the surrounding porewater or soil solution
until a shift back to oxidizing conditions was experienced.

It is possible that some soils are too complex for sequential chemical extractions
to be used to accurately predict the behavior of trace metals in the environment. With
these concerns in mind, a discussion of the composition of phases that can be present in
wetland soils follows.

Data from this study show that in water saturated, anoxic soils, Fe in the EX
phase increases as the pore water concentration of Fe increases. This is true especially
when the molar concentrations of dissolved metals exceed the molar concentration of

available sulfide, which ordinarily controls the solubility of metals in anoxic systems.

94

However, it was found that the actual contribution of Fe from pore water to the
EX phase is insignificant. This can be seen by calculating the volume of pore fluid in a
mass of soil used for extractions (assuming a fluid density of one gram/milliliter), then
dividing by the concentration of metal measured in pore water in the field. These
calculations are shown in Table 15. The amount of Fe that the pore water contributes to
the EX is one to two orders of magnitude less than the amount of Fe derived from solid

phase exchange sites.

Table 15. Calculations of the amount of Fe in fluid portion of samples extracted by
sequential extractions along with values of Fe in EX phase.

Vol. of

 

Soil Percent

 

Sample wet fluid in fluid Fe cone. in Fe in fluid of Fe cone.
weight wet soil in wet soil pore water ~lg sample in EX

(umollg (14111ng

(g) (% water) (mL) (umollL) wet soil) wet soil)
1 19 1. 1 0.65 0.72 -- -- 0.052
123 1.16 0.88 1.02 5.73 0.005 0.142
022avg 1.03 0.49 0.51 27.93 0.014 0.043
K22 1.07 0.86 0.92 35.45 0.032 3.855
P25 1.1 0.85 0.93 133.21 0.124 4.834
N23 1.04 0.80 0.83 244.58 0.202 6.708

 

X-ray diffraction results from this study agree with those of Tessier et al. (1979)
who reported low concentrations of Si, S, Al and OM in the MgClz solution after the EX
extraction indicating no significant destruction of silicates, sulfides or organic matter.
Results of the pure mineral extractions in this study show very little or no dissolution of
FeS, FeC03, magnetite, Fezs, CuS and ZnS, which supports the observations of Tessier et

a1. (1979). Thermodynamic calculations and observations by Tessier et al. (1979)

95

suggest that Fe and Mn oxides should not be significantly solubilized by this pH 7
extraction fluid. It is likely that metals released during the EX extraction probably
originate from some form of outer-sphere complexes or exchange sites on clays.

The chemical reagent used in the WAS extraction, NaOAc (pH 5), has been
successfully used for dissolution of CaC03 and MgCO; in many applications, most
notably in pretreatment of samples for XRD analysis (Jackson, 1969; Kunze and Dixon
1986). X-ray diffraction results from this study support the effectiveness of this
extraction. Analysis of the diffraction peaks indicates the presence of calcite in soil
samples prior to treatment with NaOAc (pH 5) and disappearance of the calcite peaks
after treatment.

The WAS extraction appears to be relatively selective for dissolution of calcite.
However, an undesirable effect of this extraction, rarely discussed by current researchers,
is the effect this extraction may have on metals adsorbed to Fe- and Mn- oxides. Tessier
et al. (1982) suggest that metals released during a N aOAc (pH=5) extraction are mainly
adsorbed rather than carbonate bound. Potential phases affected are pH dependant Fe-
oxide edge sites and organic matter functional groups. Metals may be released during
this extraction due to the slight acidity (pH 5) of the extraction fluid resulting in
competition between metal ions and H+ at pH dependent adsorption sites. Dissolution of
the Fe-oxide edge sites is also pH dependent and has been shown to begin below ~ pH 6
(Essen and El Bassam, 1981 and McLean and Bledsoe, 1992). As a result, metals
released during the WAS extraction could be derived from specifically adsorption surface
sites on Fe-oxides and organic matter, in addition to those associated with calcite and
dolomite. Studies of adsorption of metals onto humic materials have generated

adsorption curves as a function of pH that indicate differences in the affinity of humic

96

materials for heavy metals. Fe and Cu appear to reach maximum sorption to humic
materials around pH 5, while Zn does not even begin to plateau at pH 6 (Kemdorf and
Schnitzer 1980). This suggests that the NaOAc (pH 5) extraction may affect metals
associated with humic substances as well. The appreciable amounts of Fe released during
the extractions on samples in this study likely originate from Fe-oxides rather than
carbonate bound Fe.

Data from the pure mineral extractions in this study show that FeC03 should not
be included as a phase in the WAS as had been previously speculated, but not tested, by
Tessier et a1. (1979). Dissolution of FeCO; by NaOAc (pH 5) was not observed in this
study. This finding is in agreement with results from Heron et al. (1994) who also found
NaOAc ( pH 5) to not significantly dissolve FeCO3. This extraction also does not appear
to significantly affect CuS, FeS, FeSz, ZnS, or Fe3O4.

Low temperature leaching with acidified hydroxylamine hydrochloride (ER
extraction) has been reported to cause specific and effective dissolution of Mn-oxides
(Chao, 1972) and amorphous Fe oxides without significant dissolution of crystalline Fe-
oxides in oxic soils and sediments and pure mineral substrates (Chao and Zhou, 1983 and
Gruebel et al. 1988). Results from the pure mineral extractions in this study show this
extraction caused partial dissolution of FeS, ZnS, FeC03 and magnetite. Consequently,
use of this extraction on anoxic soils and sediments containing these minerals could cause
misinterpretation of the partitioning of Fe, Zn and any other metal adsorbed to the
mineral surfaces.

The MR extraction hydroxylamine hydrochloride in acetic acid at high
temperature has been shown to completely dissolve crystalline Fe oxides with little or no

destruction of silicate and clay minerals (T essier et al. 1979). X-ray diffraction results

97

from this study show no decrease in peaks representing feldspar, amphibole, mica,
kaolinite, vermiculite and chlorite after this extraction. Tessier et al. (1979) also reported
similar results for mica and chlorite but noted a slight decrease in XRD peaks for
smectite. The MR extraction exhibited fairly selective dissolution of FeC03 and R304
and continued partial dissolution of FeS according to results in this study. Up to 40 mol
of FeCO3 could be dissolved by this extraction (See Appendix 3F—1). It is apparent that
different Fe bearing minerals formed in both oxic and anoxic environments could
potentially comprise the MR phase, thus complicating the interpretation of metal
partitioning. This might be especially true for studies of soils and sediments from
locations with variable or cyclic redox conditions.

In the study by Papp et al. (1991), comparing the selectivity and effectiveness of
NaOCl (pH 9.5) and three other common reagents used in partial extraction procedures,
peat samples with up to 40% Corg were extracted with no reported difficulties. Papp et a1
(1991) found extraction with NaOCl was the most selective for releasing metals from
organic matter and not sulfides. However, they noted that the alkaline conditions may
promote precipitation of some metals from samples with low OM content.

The dissolution of CuS and ZnS primarily in the OX1 (N aOCl pH 9.5) in this
study demonstrates that this extraction is not as selective toward organic matter as Papp
et al. (1991) had shown. Their study based the selectivity of NaOCl (pH 9.5) for organic
matter in part on extraction of silica mixtures with FeOOH, Fe2S, CuFeSz, and FeS but
their study did not include other sulfides such as CuS and ZnS. The release of CuS and
ZnS during the NaOCl extraction in this study indicates a possible overestimation of the
importance of organic matter in sequestering Cu and Zn in anoxic systems. Data from

this study do agree well with the Papp et al. (1991) results in terms of limited dissolution

98

of FeS; by NaOCl (pH 9.5). However, the surface chemistry of FeZS may not be
preserved after this extraction due to formation of a protective surface coating, possibly
Fe-oxide or RG3, observed visually during the pure mineral extractions.

The largest percentage of Fe released from FeZS during pure mineral extractions
was in the OX2 (HzOz, pH 2), which indicates relative selectivity of this extraction for
FeS; by the sequential chemical extraction scheme used for this study. It was determined
that this extraction could dissolve up to approximately 15 mo] of FeZS (see Appendix
3F-1). Continued oxidation of refractory organic matter probably occurs during this
extraction. This may or may not result in significant release in metals depending on the
ability of this refractory material to adsorb metals. Of more concern is the potential
decrease in the ability of this extraction to effectively dissolve FeSz caused by the

decreased oxidizing capacity of the H202.

4.12 Fate on Fe, Cu, and Zn in Soil at the Site

Despite the problems associated with the specificity of the sequential chemical
extraction method, their use along with the additional biogeochemical analyses have
given valuable insight into the sequestering substrates and natural processes that control
the mobility of Fe, Cu and Zn in soils at the site. In general, organic matter and reactive
Fe-bearing mineral surfaces play a very important role in limiting the mobility of metals.
Organic matter has a strong affinity for Cu among all soil textures and in all soil
environments at the study site. Reactive Fe-oxide surfaces have a strong influence on the
mobility of Fe and Zn in the upland forested and grassy soils. Anaerobic metabolism of
organic carbon in reducing soil environments causes dissolution of Fe-oxides, releasing

adsorbed metals, and produces alternative substrates, such as sulfide, to precipitate with

99

metals that are released to pore water when the soils become saturated and redox
conditions favor dissolution of substrates that sequestered metals under oxic conditions.
Low concentrations of Cu and Zn in porewater at the sampling locations in the
wetland area indicate that these metals are immobilized, probably due to adsorption by
reactive sequestering phases and/or co-precipitation with substrates such as sulfide.
Porewater concentrations of Fe ranged from almost non-detect to more than ten
milligrams per liter indicating that adsorption and/or precipitation of reduced Fe bearing
minerals does not equal the reductive dissolution of reactive Fe bearing minerals in dis-
equilibrium with the pore fluids. The porewater data suggests that the production of
sulfide by microbial sulfate reduction, is not sufficient to equal the flux of Fe to the

porewater.

100

V. CONCLUSIONS

 

5.1 Principle Findings

During the initial site characterization, approximately 200 soil samples from three
depths at 80 sampling boring locations were collected and described. The study site was
found to be diverse with respect to soil types and textures. Two soil types with several
soil textural differences exit across the site resulting from topographic variability and soil
horizon development.

Results of the sequential chemical extractions performed the 200 samples
indicated that Fe, Cu and Zn were predominantly sequestered by the ER, MR and OX1
operationally defined phases regardless of soil redox conditions, which is similar results
reported in other studies. However, variations in patterns of metal partitioning among
operationally defined phases, were observed among the different soil textures across the
site. The variability in metal partitioning was correlated to the presence of soil
porewater, the amount of organic carbon, and soil redox conditions, which are driven by
microbial metabolic terminal electron accepting processes. Specifically, Fe was found to
be associated mostly with the MR fraction for all soil textures and types, but the relative
importance of the other fractions (ER, WAS, OX1, EX and OX2) increased in samples
from areas that had reducing conditions. Copper was found to be associated
predominantly with the OX1 phase in samples with significant amounts of organic
matter, but the ER and MR phases were important sequestering phases in samples with

lower amounts of organic carbon. Zinc was found to be associated primarily with the

101

MR followed by ER phases with the importance of the ER increasing over the MR in
samples taken from reducing conditions or with higher organic matter content.

After the initial characterization of metal partitioning in soil samples from across
the study site, a smaller set of sampling locations were analyzed in more detail to identify
minerals that comprise the ER and MR phases in samples from anoxic soils to help
interpret the sequential chemical extraction results. Porewater sampling and analyses
indicated the presence of reduced aqueous species and TEAP indicators of anoxic
conditions in the water-saturated wetland area of the site. Evidence for Fe-reduction,
sulfate reduction, and methanogenesis was found at several sites within inches below
land surface. Geochemical modeling of the porewater chemistry indicated that conditions
were favorable for reduced mineralogical species to be present in the solid phase. Acid
volatile sulfide/simultaneously extracted metal, magnetic separation and X-ray diffraction
analytical methods performed on solid phase samples confirmed the presence of these
reduced species. Metal mono-sulfides and a magnetic mineral, possibly magnetite, were
identified and attempt was made to quantify the amounts of Fe mono-sulfide and
magnetite and then compare those values to amounts of Fe partitioned among ER and
MR phases of the soil as determined by sequential chemical extractions. Calculations
revealed that the masses of the identified Fe bearing minerals could not account for all of
the Fe released from soil samples during the ER and MR extractions. This was
interpreted to mean that other forms, possibly oxidized forms, of Fe bearing minerals or
phases must have been present in the soils from the wetland area of the study site.
Potential alternative environmentally reactive phases include pH sensitive Fe- bearing
organic matter-complexes/coatings, Fe-oxides that persist under anoxic conditions, and/or

Fe-phosphate.

102

Some of the reduced mineral phases (e. g., FeCO3, R304, and metal mono-
sulfides), that were predicted and/or identified by pore water and solid phase
biogeochemical analyses are not generally included in the operational definitions for
phases targeted by sequential chemical extractions. In order to predict which
operationally defined phases these reduced minerals would likely be associated with in a
soil sample, pure mineral samples were subjected to the same sequential extracted
procedure used for soil samples. Siderite, magnetite, and FeS were found to be dissolved
most significantly by the MR extraction. CuS and ZnS were dissolved/oxidized most
significantly by the OX1 extraction and FeZS was most significantly dissolved/oxidized
by the OX2 extraction. The EX, WAS and ER extractions appeared to be ineffective in
degrading the integrity of these mineral structures, with the exception of ZnS which was

slightly affected by the ER extraction.

5.2 Evaluating the Use of Muential Chemical Extractions in Anoxic Environments

Potential problems with the use of sequential chemical extractions on samples
collected from anoxic soils have been identified during the course of this research. The
ability of Fe(III)oxides, Fe oxyhydroxides, Fe(II)oxide minerals, Fe (II)carbonate, and Fe
(H) sulfides to exist simultaneously in meta-stable anoxic (or cyclically oxic-anoxic)
environments complicates interpretations of the results of sequential chemical
extractions, because the operational definitions for phases targeted in these extractions do
not include minerals such as FCCO3, FeS, and Fe304, which are common in anoxic
environments. In addition, metal monosulfides (e.g. FeS, CuS, and ZnS) do not exhibit
the same partitioning behavior so they cannot be operationally defined together as a

group as has been done traditionally. It is clear that hydroxylamine hydrochloride

103

extractable Fe in oxic soils and sediments (ER and MR) likely originates mainly from Fe-
oxides. Hydroxylamine hydrochloride extractable Fe in anoxic soils and sediments does
not exclusively indicate the presence of reactive Fe-oxides, because dissolution of pure
FeS, FeCO3, and F6304 has been shown to occur.

It has been demonstrated that the sequential chemical extraction procedure used in
this study cannot selectively distinguish between these different Fe-bearing minerals and
that they all likely comprise the most important operationally defined phase (MR) for
sequestering some metals. If the underlying goal for the use of information derived by
sequential chemical extractions is to gain insight into cycling and potential mobility of
metals, distinction between metals associated with an Fe(III) oxides, Fe(H)-mineral or a
sulfide is essential. Just as these mineral phases form under different conditions, they
dissolve and/or are transformed differently in response to environmental changes caused
by chemical and biological activity. Consequently, metals associated with each mineral
will be released under different conditions and at different rates, thus complicating

prediction of metal mobility.

104

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111

APPENDIX 1

Solid Phase Sample Descriptions

 

 

 

 

 

 

 

 

 

 

 

 

.6 mm... .....a ...... .58.. ...... 2...... as... 863.58.198.55 ....
....a ...... as 5.4... ......
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9.8 9:. E65 .92... x30 ...—.0.—
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9.8 9:. .3... m.m.o.m
9.8 9:. .3. o. .92... o. .09...» 9.8 9:. .565 Em: .92...— 5.9%—
93. 9:. .565 Em: .92:— WI...
9.8 9:. .565 .92... ..3: 6. E65 539 ...—-2.
9.8 9:. .565 530 ndéd 003 509.63 0 .5 52.5 E 2 05m 2m
9.8 9:. .3... neared
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9.8 9:. .565 53.. ..05. E65 .2... :30 ...—-md
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0.60 .o no. :6: .050... 00.5. .:. .565 5.5. 88.6.. m3... :0... 9.8 9:. .3... n.m.o.m
9.8 .9:. .3. o. .239 9.8 9:. 52.565 .92.”— c.m-m._
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30.0... ....50 9.63 5.3 .6... 9.8 9:. .3. ......50... .92.. 9.5m:m n.d..
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...... ...... .52.. ...... ......
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5.3. 9:. .565 .92.. ......505. 0......
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.... .538 .3. 9.... 3 6.... .053.m .565 ..30 9.6.5
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.... 9.3 9.8 0...... 5.5. ..35 E65 ..30 n.m.c.m
..35 5.5. E65 ..35 o. ..35 .... .....5. .... .565 Em: o. .053.m .3. 9.30.0 o.m-n..
5.3. .335... 9.30.0 5.55 .0338 ...35. 53.3.3... .565 53A. 0......

 

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2.3 E: .59 3-2
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Organic Matter Content

Emptem 70M amPleID «mm ‘ . Sampnem «70M
B3a0-05 2.2 B31-1.5 5.2 B33-35 1.0
B50-05 0.8 B51-1.5 0.7 B53-35 1.1
B70-0.5 0.6 B7 1-15 0.6 B73-3.5 0.3
B9a0-05 2.4 B91-15 2.8 B93-35 0.3
B110-05 NA B111-15 0.8 B 1 13-35 0.9
B 130-05 2.3 B13a1-15 1.8 B 133-35 0.5
B150-05 5.3 B151-15 15.2 B 153-35 35.8
B170-05 5.5 B 171-15 0.6 B 173-35 21.5
C20-05 2.3 C21-1.5 0.3 C23-35 0.3
C40-0.5 2.3 C4l-15 1.1 C43-35 0.6
C60-0.5 0.4 C61-15 1.0 C63-35 0.1
C80-05 4.2 C81-1.5 0.7 683-35 0.9
C100-05 2.1 C101-l5 1.3 ClO3-35 2.0
C120-05 2.9 C121-15 0.4 6123-35 0.2
C140-05 5.2 C141-1 .5 0.3 C143-35 0.4
C160-05 1.8 C161-1.5 NA 6163-35 NA
D50-05 1.8 D51-15 1.1 D53-35 0.7
D70-0.5 4.2 D71-15 0.4 D73-35 0.7
D90-05 3.7 D91-l5 0.7 D9a3-35 0.6
D110-05 0.7 D11 1-15 0.3 D1 13-35 0.2
D130-05 3.7 D131-1.5 0.5 D133-35 0.6
D150-05 2.1 D151-15 1.8 D153-35 0.8
D170-05 32.1 D171-1.5 30.6 D173-35 4.3
D190-05 19.2 D191-15 71.0 D193-35 18.8
E140-05 1.9 E141-15 3.5 E143-3.5 0.4
E160-05 28.2 E161-15 49.8 E163-35 35.8
E180-05 34.5 E18 1-15 55.7 E183-35 NA
E200-05 2.2 E201-15 1.8 B20335 NA
F130—05 1.8 F13 1-1.5 0.9 F133-35 0.3
F150-05 20.7 F151-15 20.4 F153-35 0.3
F170-05 5.5 F171-1.5 0.6 F17a3-35 0.2
F190-05 5.4 F191-15 1.4 F193-35 0.5
F210-05 0.7 F211-15 0.6 F213-35 0.8
6140-05 7 6141-15 4.5 6143-35 0.6
6160-05 65.8 6161-15 8 6163-35 6.4
6180-05 4.9 6181-15 0.6 6183-35 0.3
6200-05 2.8 6201-15 0.8 6203-35 0.3
6220-05 1.9 6221-15 2.3 6223-35 0.4
H150-05 14.8 H151-1.5 5.9 H153-35 15.8
H170-05 34.2 H17l-15 56.7 H173—35 5.8
H190-05 22.9 H191-15 23.1 H193-35 70.2

 

 

 

 

 

 

 

 

 

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Emmet]: am new 70M ; Sampler]; ‘ ;
H210-05 0.2 H211-1.5 8.5 H213-35
H23aO-05 2 H23 1-1.5 0.5 H233-35
1200-05 48.9 1201-15 79.4 1203-35
1220-05 65.3 1221-15 74.5 1223-35
1240-05 3 1241-15 0.3 1243-35
1260-05 16.7 126al-15 5.1 1263-35
1 19:10-05 65.3 1191-15 76.3 1193-35
1210-05 2.6 1211-15 1.2 1213-35
1230-05 74.4 123 1- 1.5 70.7 1233-35
1250-05 23.8 1251-15 96 1253-35
1270-05 9.6 1271-15 0.5 1273-35
K200-05 81.3 K201-1 .5 NA K203-35
K220-05 76.5 K221- l .5 81.7 K223-35 .
K240-05 72.2 K241- l .5 77.7 K243-35 1.1
K260-05 4.7 K261-15 60.3 K263-35 30.1
K280-05 25.8 K281-l5 35.8 K28-3.5 NA
L210-05 2.1 L21 1- 1.5 2.9 L2 1 3-35 NA
L230-05 77.3 L23 1-15 86.6 L233-35 1.2
L250-05 2.1 L25 1- 1.5 76.1 L25a3-35 49.5
L270-05 77.5 L271-15 12.8 L273-35 0.3
M200-05 2.7 M201-1.5 22.2 M203-35 NA
M220-05 12.5 M221-l.5 13.5 M223-35 2.1
M240-05 25.0 M24 1- l .5 75.0 M243-35 0.2
M260-05 35.3 M26l-15 50.0 M263-35 NA
M280-05 19.3 M281-l .5 15.2 M283-35 0.6
N210-05 68.4 N211-15 58.0 N213-35 NA
N230-0.5 77.3 N231-l5 2.2 N233-35 4.6
N250-0.5 3.4 N251-15 34.9 N253-35 3.7
0220-05 69.9 022al- l .5 38.1 0223-35 4.5
0240-05 54.3 0241-15 18.8 0243-35 3.2
P230-05 61.9 P23 1-15 2.1 P23a3-35 8.4
P250-05 62.1 P251-15 58.2 P253-35 4.4
(2240-05 54.4 Q24a1-15 25.0 Q243-35 34.4
260-05 15.7 Q261-l5 NA Q263-35 NA
R250-05 51.5 R251-15 17.4 R253-35 2.7
R270-05 37.2 R271-15 59.4 R273-35 51.2
8260-05 35.8 8261-15 66.1 3263-35 NA
T270-05 46.7 T27l-15 60.3 1273-35 NA
U260-05 1.0 U261-15 5.6 U263-35 3.1

 

NA - indicates that no sample was taken for that interval

125

 

Table 1C-l.

Samples Sorted by Soil Texture Classifications

 

 

Brown Rusty Tan Silty Silty sand Tan Gravel!
silty silty sand OM>50% W IOM silty sand Debris
sand sand (unsaL) (sat.) (fill)

B30-0.5 B33-35 B53-35 D19l-15 B 153-35 1233-35 D170-0.5

B31-15 B5 1-15 B73-35 6160-05 D171-1.5 1253-35 Dl73-35

BSD-0.5 B71-l.5 B93-3.5 6161-15 6163-35 1271-15 D190-05

B70-05 B91-1.5 B 1 13-35 H171-15 H150-05 K203-35 D193-35

B90-05 B111-15 B133-35 11193-35 H151-15 K223-35 E161-15

B110-05 B131-15 C63-35 1201-15 H153-35 K243-35 El63-35
B 130-05 B 151-15 C83-3.5 1220-05 H170-05 L211-1.5 E180-05
B150-05 B171-1.5 C103-35 1221-15 H173-35 L233-35 13181-15
B 170-05 B 173-35 C123-3.5 1223-35 11191-15 L273-35 F150-05

620-05 C21-1.5 C 143-35 1230-05 1200-05 M223-35 6140-05

640-05 623-35 D53-35 1231-15 1190-05 M243-35 6141-15

C60-05 C41-15 D113-35 1250-05 1191-15 M283-35 6143-35

C80-05 643-35 D133-35 1251-15 1210-05 N233-35 H 190-05

6100-05 C61-15 D153-35 K200-05 J211-15 N253-35 1203-35
C 120-05 (381-15 E143-35 K220-05 K260-O5 0223-35 1193-35
C 140-05 C101-l .5 F133-35 K221-15 K263-35 0243-35 M281-15
C160-05 C121-15 F153-35 K240-05 K280-05 P233-35
D50-05 C14l-1.5 Fl73-35 K241-15 K281-15 P253-35
D70-0.5 D51-1.5 F193-35 K261-15 L210-05 R253-35
D90-0.5 D7 1-1 .5 F213-35 L230-05 L27 1- 1.5 U263-35
D110-05 D73-35 6183-35 L231-15 M200-05
D130-05 D91-15 6203-35 L250-05 M201-15
D150—05 D93-3.5 6223-35 L253-35 M221-15
E 140-05 D11 1-15 11233-35 L270-0.5 M221-15
E160-05 D131-1.5 M220-05 M260-05
F130—05 D151-15 M240-05 M280-05
F170-0.5 El41-1.5 M241-l.5 N23l-15
F190-05 E200-05 M261-15 N251-1.5
6180-05 13201-15 N210-05 0221- 1 .5
6200-05 F131-15 N211-15 0241-15
H210-05 F151-1.5 N230-05 P231-15
1270-05 F17 1-1 .5 N250-05 Q241-15
F191-15 0220-05 Q243-35
F210-05 0240-05 R251-15
F21 1-15 P230-05 U260-05
6181-15 P250-05 U261-15
6201-15 P251-15
6220-05 Q240-05

 

126

Table lC-l (con’L!

 

 

Brown Rusty Tan Silty OM>50% Silty sand Tan Gravel!
silty silty sand WIOM silty sand Debris
sand sand (unsaL) (sat.) (fim

6221-15 Q260-05
H211-1.5 R250-05
11213-35 R270-05
H230-05 R27 1-1 .5
H233-35 R273-35
1240-05 8260-05
1241-15 8261-15
1243-35 T270-05
1260-05 T271-15
1261-15

 

127

APPENDIX 2

Supplemental Description of Methods

APPENDIX 2A:

Sequential Chemical Extraction Procedure
Sample preparation:

Due to the high number of samples taken for the initial investigation, three groups
of eight cores were processed each week for a period of ten weeks. 0n subsequent
sampling events for more detailed work, fewer cores were taken allowing less of a delay
before extractions were performed. In all cases, soil cores were frozen (-20°C) until just
before chemical extractions were to begin.

After the cores were thawed, they were placed in a glove bag, which was then
evacuated and purged twice with N2 (g) or Ar (g) to ensure an inert atmosphere. A Teflon
stirrer was used to transfer about 50 grams of soil from the bottom of each core into acid
washed 120mL plastic vials for homogenization. Visible debris, wood, and roots were
excluded in the transfer. After homogenization, five grams (:1: 0.5g) of wet soil were
weighed out on an acid washed watch glass for wet weight/ dry weight determination. A
separate one gram (:1: 0.2 g) aliquot was placed into an acid washed 30 ml centrifuge tube
for sequential chemical extractions (SCE). The remaining homogenized soil was saved
for organic carbon (Cars) determination by loss on combustion. Once the weighing was
completed in the glove bag the watch glasses were placed in a convection oven for 24
hours at 50°C to completely dry the soils.

Method for Sequential Chemical Extractions of Metals:

Each sequential chemical extraction step began with addition of a chemical
reagent under an inert atmosphere, followed by agitation of the tightly secured centrifuge
tubes to completely mix the soil/chemical mixture. Each chemical addition reacts with

the soil to strip off the bound metals from targeted solid phases. After each prescribed

128

reaction time the leachate was separated from the soil by centrifugation at 15,000 rpm for
20 minutes. Leachate fluids were siphoned off or decanted into acid washed 30 ml
syringes, then filtered through 0.4u.m acid washed Nucleopore membrane filters into acid
washed NalgeneTM polypropylene bottles and acidified to pH< 2 to prevent adsorption to
the container walls and precipitation of metals from solution. Samples were stored in a

dark 4°C refrigerator until analysis.

129

Methods for Sequential Chemical Extractions of Metals (modified from Matty,1992):

From each homogenous sample remove two aliquots.
Aliquot 1: place on tared watch glass; dry in oven at 50°C for 24 hours; reweigh

and record percent water; perform HNO3 microwave digestion.

Aliquot 2: place in taxed centrifuge tube; perform sequential chemical extractions

under N2 using the following procedures:

I. Exchangeable Fraction

1.
2.

3.
4.

5.

Place 1.0 g wet sediment into acid-washed tared centrifuge tube.

To each sample, SRM, and blank, add 10 mL 1.0M MgClz (pH 7); with wrist
action shaker agitate continuously for 1 hour at 20°C.

Centrifuge for 20 minutes at 15,000 rpm.

Remove leachate with a syringe and filter through 0.4pm Nuclepore filter into
an acid-washed 8 or 30 mL bottle. Acidify to pH<2 with optima HNO3.
Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes
at 15,000 revolutions per minute (rpm); remove supernatant and discard.

II. Weak-Acid Soluble Fraction

1.

.U'

To sediment from (I) add 10 mL of 1.0M NaOAc (pH 5 with HOAc) and
agitate with shaker for 5 hours at 20°C.

Centrifuge for 20 minutes at 15,000 rpm.

Remove leachate with a syringe and filter through 0.4um N uclepore filter into
an acid-washed 8 or 30 mL bottle. Acidify to pH<2 with optima HNO3.
Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes
at 15,000 rpm; remove supernatant and discard.

III. Easily Reducible Fraction

1.

To sediment from (11) add 25 mL of 0.1M NHZOH-HCI in 0.01N HNO3 and
agitate in shaker for 0.5 hours at 20°C.

Centrifuge for 20 minutes at 15,000 rpm.

Remove leachate with a syringe and filter through 0.4um Nuclepore filter into
an acid-washed 30 mL bottle.

Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes
at 15 ,000 rpm; remove supernatant and discard.

IV. Moderately Reducible Fraction

1. To sediment from (111) add 20 mL of 0.04M NH20H-HC1 in 25% (v/v) HOAc. Place
sample in a water bath at 96°C for 6 hours; agitate every 30 minutes.
2. Centrifuge for 20 minutes at 15,000 rpm.

130

Remove leachate with a syringe and filter through 0.4pm Nuclepore filter into an

acid-washed 30 mL bottle.

Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes at

15,000 rpm; remove supernatant and discard.

1.

99‘

Oxidizable Fraction 1 (not done under N2)

To sediment from (IV) add 6 mL of NaOCl (pH 9.5 with HCl just prior to
use). Place sample in a water bath at 96°C for 15 minutes.

Centrifuge for 20 minutes at 15,000 rpm.

Remove leachate with a syringe and filter through 0.4um Nuclepore filter into
an acid-washed 30 mL bottle.

Repeat steps 1 through 3 two more times (except for the third step of the third
addition), using the vortex mixer to resuspend the sample after each addition
of NaOCl.

Add 5 mL of 3.2M N1140Ac (pH 2 with HN03) to the solution-sample
mixture of the last NaOCl addition. Agitate with shaker for 1 hour at 20°C.
Centrifuge for 20 minutes at 15,000 rpm.

Remove leachate with a syringe and filter through 0.4|.I.m Nuclepore filter into
an acid-washed 30 mL bottle.

Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes
at 15,000 rpm; remove supernatant and discard.

VI. Oxidizable Fraction I] (not done under N 2)

1.

3”!"

3":‘3

To sediment from (V) add 3 mL of 0.02N HNO3 and 8 mL of 30% H202 (pH
2 with HNO3) in 500 “L aliquots; agitate every 30 minutes for 5 hours in a
water bath heated to 85°C; leave caps unscrewed.

Place samples in Wrist Action Shaker to cool.

Add 5 mL of 3.2M NH40Ac(pH 2 with HNO3). Agitate with shaker for 1
hour at 20°C.

Centrifuge for 20 minutes at 15,000 rpm.

Remove leachate with a syringe, empty the syringe into an acid-washed 25
m1. volumetric flask and dilute up to 25 mL with DDW. Filter the diluted
solution through a 0.4m Nuclepore filter. Transfer solution to an acid
washed 30 mL bottle.

Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes
at 15,000 rpm; remove supernatant and discard.

131

APPENDIX 2B:
Porewater Sampling and Analytical Methods
Pore Water Sampling

Geochemical parameters measured in the field included: temperature, pH,
alkalinity, SZ', Fe“, and Cr“. Sampler fluid preserved for laboratory analyses included
separate aliquots for cations (majors and trace metals), anions (Cl‘, Br', N03',N02’,
SO42), NH4, CH4, and dissolved organic carbon (DOC).

Filtration of fluid in the samplers was unnecessary because the 0.2 pm
membranes used during the dialysis equilibration excluded particles from the sampler
during the equilibration period.

Peeper samplers were sampled immediately upon removal from sediments at each
sample location. To ensure enough fluid for analysis, four to six peeper compartments
were sampled as a unit representative of an interval rather than a discrete level below the
land surface. The barrel samplers were capped with air tight end caps to prevent changes
in redox sensitive parameters, then returned to a central processing location for sampling.
Similarly, the group of three barrels was treated as a unit.

The most redox sensitive parameters were sampled and, or, analyzed first.
Aliquots for dissolved gasses CH4, NH4, and Sz', and iron speciation were taken first,
followed by aliquots for cations, anions, pH, alkalinity, dissolved organic carbon (DOC).
Usually the complete sampling of a peeper was achieved within 10 minutes by a team of

three to four personnel.

132

Analytical measurements

Temperature was measured in-situ with a digital thermometer or a conventional
mercury thermometer.

An aliquot of fluid from the samplers was taken for pH measurement with a glass
electrode calibrated with standard pH 4 and pH 7 buffers. The same aliquot was also
titrated to below pH 4.5 with a standardized H2804 solution to determine alkalinity as
HCOg'. Eh was measured using a silver-silver chloride single junction electrode. Redox
state measurements using electrodes have often been viewed with suspicion due to the
potential for disequilibrium between the redox couples in the fluid of interest (Lindberg
and Runnels, 1984). Therefore, in addition to the electrode measured Eh, the
concentrations of several aqueous redox couples were measured including, ferrous (Fe2+)-
ferric (Fe3+) iron, sulfide (82')-sulfate (3042'), and the nitrate (N03‘)-nitrite(N02')-
ammonia(NH4+) triad, as well as dissolved methane(CH4).

Ferrous iron was analyzed by the phenanthroline method (Chin 1994). The
method begins by pipetting 2.5 ml of sample fluid into a spectrophotometer cuvette pre-
acidified with 100 pl of Optima HCl. Then, 1 ml of phenanthroline solution, 0.5 ml of
ammonium acetate, and 1 ml of DDW was added. After two to five minutes, the
absorbance were measured with a Spectronic Spec 20D+ at 625 nm and compared to a
three point calibration curve created in the lab by plotting concentration versus
absorbance

Sulfide was analde by one of two methylene-blue colorimetric methods. In one
procedure, 7.3 ml of sample was transferred to two Milton RoyTM 1 cm path length

spectrophotometer cells. To one cell, 0.5 ml amino sulfuric acid reagent (N ,N dimethyl-

133

p-phenylenediamine oxalate in diluted H2SO4) and to the other (the method blank) 0.5 ml
H2804 1+1 with DDW was added. To both cells 0.15 ml FeCl3 solution was added. The
cells were inverted once to mix the solutions. Color developed in the first cell, if sulfide
was present, by creation of methylene blue. After 3-5 minutes 1.6 ml of (NH4)2H P04
was added to both cells to reduce potential interference of excess FeCl3. After 5-10
minutes the method blank cell was used to zero the instrument and then the absorbance of
the sample cell was measured. Absorbances were measured with a Spectronic Spec
20D+ at 625 nm and compared to an 8 point calibration curve created in the lab by
plotting concentration obtained from a tinimetric iodine procedure versus absorbance
obtained from the methylene blue procedure (Cline 1979, AWWA et al., 1986).

The second procedure utilized Chemetrics Vacu-Vialsm which are self filling ampoules
containing appropriate mixtures of reagents. The difference in the two analytical
methods was found to be less than 10%.

Fluid samples for methane analysis were taken by simultaneously piercing the
nylon membrane of a sampler and the butyl rubber septum of a scintillation vial with a
double-ended needle. This method allowed the sample to be taken without the fluid
coming in contact with air. A syringe and single ended needle were used to evacuate air
from the scintillation vial allowing fluid to be drawn into the vial by partial vacuum.

Aliquots for NH; determination were stored in 10ml polypropylene Nalgene
bottles and frozen on dry ice in the field. In the lab, samples were thawed and analyzed
by ion selective electrode after conversion of NH4 to NH3+ with a buffer solution and an

ionic strength adjuster.

134

 

 

 

Aliquots for cations were pipetted into pre-acidified acid washed NalgeneTM

polyethane bottles and stored at (4°C). Cation samples were acidified (pHd) with
OptimaTM HNO3. Anion samples were analyzed by ion chromatography.

Heavy metals (Cu, Mn, Pb, Zn) and major cations (Mg, Na, K) in pore water
samples were analde on a V6-Elemental Plasma Quad 1 inductively coupled plasma-
mass spectrometry (ICP-MS). Ca and Fe were determined by flame atomic absorption
(FAA) spectrophotometry (Perkin-Elmer model 5100) because of interference caused by

similarities in mass between 40Ca and the 40Ar carrier gas used in ICP-MS.

135

Apmndix 2C:

Method for Determination of Acid Volatile Sulfide
and Simultaneously Extracted Metals

Acid volatile sulfide (AVS) and simultaneously extracted metals (SEM)
determinations were preformed as described by Allen et al. (1993) and Lasorsa and Casas

(1996). A schematic diagram of the AVS/SEM analytical apparatus is shown in Figure 6.

Apparatus description:

Nitrogen gas was used to purge the apparatus of oxygen prior to beginning the
extractions and to act as a carrier gas for the H28 generated during the reaction. A
vanadous chloride solution was used to scrub the N2 free of oxygen prior to entering the
reaction vessel. Vanadous chloride solution was prepared by adding 4g of ammonium
metavanadate boiled with 50 ml concentrated hydrochloric acid to a 500 ml volumetric
flask and diluting to the mark. Amalgamated zinc, prepared by placing 15g of zinc metal
in 10-20 ml distilled deionized water (DDW) before adding three drops (0.15mi) of
concentrated hydrochloric acid and then adding a small amount of elemental mercury to
complete the amalgamation, was added to the vanadous chloride solution (Di Toro et al.

1990). All glassware was connected with minimum lengths of Tygon tubing.

Method Development and Calibration:
The nitrogen flow rates and reaction times were varied during initial method
development to determine the most efficient conditions for 82' recovery. Many trial runs

were performed with NaS2-9H2O solutions of varying concentrations to determine

136

trapping efficiency of the apparatus and overall performance of the method prior to
sample analysis.

Low range (0-5 umol 82'/100ml) and normal range (0-25 pmol 82'/100ml)
calibration curves were made relating absorbance to concentration (Figure A2C1).
Calibration standards, each made from a 0.05 M (50pmol Sz'llml) NaS2-9H2O stock
solution, were made in triplicate by adding known amounts of 82' to 100ml flasks filled
with 80ml of 0.5 M NaOH trapping solution, adding 10 ml of mixed diamine solution
(MDR), and diluting to the mark with DDDW. The MDR was prepared by mixing two
solutions. For the first, 2.25 g of N,N dimethyl-p-phenylenediamine oxalate was added to
660ml H2804 + 340 ml DDDW after the acid cooled. The second solution was made by
adding 5.4g FeCl3-9H2O to 100 ml HCl, then diluting to 200 ml with DDDW (Allen et al.
1993). After 30 minutes, but not more than 2 hours, standards were diluted by a factor of
10 with l M H2804 in a Milton Roy Spectronic cell. After another 30 minutes absorbance
was measured at 670nm in a Spectronic 20D+ spectrophotometer. The average of three
measurements was used to define points in the calibration curves. All standards and

samples were analyzed within 3 hours.

137

AVS Calibration AVS Calibration
Low Range Normal Range

 

 

 

 

 

 

 

l 0 4 Abs. = 0.0108 + 02441" Cone. ' 1 g 5 l Abs. = 0'2 + 00226. Conc. .. '7
- 4 '- 0. ~ 1
1 r-squared = 0.997 /' . é ‘ r-squared = 0.99] i, ,w
u 0.84 1,“ 7°: 0,4. /
i 0,; ,r i z 03 r
I. . , -
9. . ’ [ E r
3 // ' "
0.4 ~ ‘ IE 02 . /./ ,x
1 L 1 ,x/
0'24 E 0.1 " /
l i ‘C 1 ,
G.OtF—fifv-vflvvev-rtw—fi' 0.011 , 4+1
0 l 2 3 4 5 o 5 lo 15 20 25 3o
Sulfide (ml/100ml) Sulfide (ml/100ml)

Figure A2Cl. Low and normal range calibration curves for AVS method.

Sample A VS/SEM Analysis:

Undisturbed soil cores for AVS/SEM analyses were retrieved as described
previously in section 3.2. Samples were frozen (-20 °C) within one hour of collection
and stored for no more than three weeks. Samples were thawed, homogenized, sub-split,
and weighed in a glove bag under a N2 atmosphere.

To begin the procedure one hundred m1 of DDDW and a magnetic stirring bar
were added to a 250ml round ball flask in which the AVS liberation reaction would
occur. Each bubbler trap was filled with 80 ml of 0.5 M NaOH. The apparatus was
purged with N2 for 10 minutes at a flow rate if 100 cm3/min.

Three to five gram sub-splits of sediment were delivered to the reaction chamber
on a piece of Parafilmm. The remaining homogenized soil was saved for sequential
chemical extractions and other detailed work described below.

The reaction apparatus was purged for 10 minutes at a flow rate of 45 cm3/min.

Then 20 ml of deoxygenated 6N hydrochloric acid was injected into the reaction chamber

138

from a syringe attached to the tubing above the reaction vessel. This yielded a final
concentration of 1N hydrochloric, causing the conversion of AVS to H28. Nitrogen was
bubbled through the sample-acid mixture at a flow rate of 45 cm3/min while the mixture
was magnetically stirred for 35-40 minutes.

After the prescribed reaction time had elapsed, 10 ml of MDR was added to each
N aOH bubblers to create methylene blue by reaction with the trapped 82'. The solution
was transferred to a 100 ml volumetric flask and diluted to the mark with DDDW. After
30 minutes an aliquot of this solution was either measured directly with a Spectronic”
Spec 20D+ at 670nm or diluted by a factor of ten with 1M H2804 and then measured
after another 30 minutes. Methylene blue is produced by reaction between 82' and the
MDR. The leachate fluid in the reaction vessel containing the SEM was decanted and

filtered through a 0.4um acid washed NucleporeTM filter into acid washed 30 ml

Nalgene” bottles.

139

APPENDIX 3

Supplemental Data Tables

 

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186

Table 315-1:
Pore water data for samnlw taken g 7126/97.

 

187

Table 313-2:
Pore water data for samples taken on 7/26/97.

 

188

 

Table 3E-3:
Pore water data for samgles collected 10/8/97

 

189

Table 3E-4:
Pore Water Data Collected on 11I20/97

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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192

Appendix 36:

X-ray Diffraction Peak Integpretations and Mineral Identification

Peak Identification and mineral identification is described in detail for sample
D11 1-1-5 prior to a modified sequential chemical extraction (WAS, ER and MR
extractions only). Brief comments are given if mineralogy changed after a given
extraction within the sequence. All minerals present in the sample prior to extractions
were found to be present after extractions with the exception notable exception of calcite

not present after the WAS, NaOAc (pH 5) extraction

Sample D11 l-l.5
Quartz is present as evident by several peaks a couple of hkl reflections (112) at 1.82 A,

(200) at 2.12 A, as well as more common peaks at 3.33 A, and 4.23 A.

Calcite is present as evident by a 2.27 A peak (this disappears after extraction with

NaOAc (pH 5), a common extraction to remove carbonates).

Several feldspar-s are present. Peaks at 3.12 A and 3.18 A are indicative of plagioclases.

A peak at 3.23 A indicates that a potassium feldspar is also present possibly microcline.

An Amphibole of some kind is present as evident by an 8.38 A peak.

Mica is present as evident by a (001) peak at 9.81 A and a broad (002) peak at 4.9 A. Fe

in octahedral sites of mica (biotite) causes the (002) peak to be missing or very weak

193

relative to the (001) peak. Relatively strong (002) peaks indicate the presence of Mg or
Al micas (muscovite). In this case the (002) is relatively weak but still noticeable

suggesting the presence of illite which can have Fe substitution in octahedral sites.

Kaolinite may be present as evident by a peak at 7.07 A (001), and a peak on the shoulder
of a broad peak at 3.5 A. Positive identification of kaolinite is hindered by the presence of

chlorite. There appears to be three separate peaks near 3.5 A which may be vermiculite

(004), chlorite (004) at 3.53 A, and kaolinite (002) at 3.56 A.

Chlarite is present as evident by a (001) peak at 14.0 A for Mg-saturated, K-saturated
and K 550°C treatments. Also, higher order peaks are found at (002) peak at 7 A, a (003)
peak at 4.7 A, and a (004) peak at 3.53 A. The three peaks around 3.5 A may indicate

vermiculite (004), chlorite (004) at 3.53 A, and kaolinite (002) at 3.56 A peaks.

Venniculite may be present as evident by 14 A peak and an (004) peak at 3.48 A. The
three peaks around 3.5 A indicate chlorite (004), vermiculite (004), and kaolinite (002)
peaks. However, vermiculite collapses to 10A when K—saturated. The 10 AIM A peak
ratios for the K-saturated sample should be larger than that for the Mg saturated sample if
vermiculite is present.

HIV may be present as evident by broad intensity between the 10 A an 14 A peaks for all
treatments and high order peaks of vermiculite around 3.5. The three peaks around 3.5
A may indicate vermiculite (004) at 3.48 A, chlorite (004) at 3.53 A, and kaolinite (002)

at 3.56 A peaks.

194

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