Professional Documents
Culture Documents
A Thesis
Presented in Partial Fulfillment of the Requirements for the
Degree of Master of Science
with a
Major in Environmental Science
in the
College of Graduate Studies
University of Idaho
by
Melanie M. Bond
14 February, 2000
This thesis of Melanie M. Bond, submitted for the degree of Master of Science with a
Releases from Mining in the Idaho Phosphate Region,” has been reviewed in final
form, as indicated by the signatures and dates given below. Permission is now
granted to submit final copies to the College of Graduate Studies for approval.
Committee
Members Date
Donald Crawford, Ph. D.
Date
Keith Prisbrey, Ph. D.
Date
Phil Druker
Department
Administrator Date
Margrit von Braun, Ph. D.
Dean, College of
Letters and Science Date
Kurt Olsson, Ph. D.
Date
Jean’ne M. Shreeve, Ph. D.
iv
ABSTRACT
Idaho to investigate selenium releases from its Smoky Canyon phosphate mine in
Idaho. Site sampling provided collection of water from up- and down-gradient of
characterization.
drain which underlies the overburden piles vary from below detection limits at the
inlet to near 0.0086 mM (680 µg/L) at the outlet. Analyses conducted on the
overburden indicated that sulfide minerals comprise about 0.2 volume percent of
of the siltstones showed that selenium is substituting for approximately 1.28% of the
sulfur in the pyrite lattice (by weight). The oxidation of these reactive sulfides is
Several water and soil treatments were then investigated for effectiveness in
ineffective due to storage aging of the water samples in which selenite (SeO32-)
oxidized to the less treatable selenate (SeO42-). Saturated soil paste studies with
most amendments. Application of potato waste was the most effective, followed by
use of granular iron. Field studies with selected amendments are currently
underway.
v
ACKNOWLEDGMENTS
Shokes for their guidance and showing me the ropes, and to the staff of the U of I
Analytical Sciences Laboratory for taking such great care of my samples. I would
also like to thank the J. R. Simplot Company for making this research possible in the
first place. I am grateful to Dr. Prisbrey, Dr. Crawford and Mr. Druker for their careful
critique of this thesis; without their help it would not have gone together quite as
smoothly as it has. And finally, although certainly not the least of my thanks goes to
my family - Mom, Dick, Kirstin, Anna, Dad, Meri, and everyone else that believed I
TABLE OF CONTENTS
ABSTRACT .......................................................................................................................................... IV
ACKNOWLEDGMENTS........................................................................................................................ V
3.3.2 Soil.......................................................................................................................................20
3.5.2 Soil.......................................................................................................................................25
A.1.1 Chloride...............................................................................................................................71
A.1.4 Phosphorous:......................................................................................................................71
REFERENCES .....................................................................................................................................92
ix
LIST OF FIGURES
Figure 4. Map showing sample locations along the Pole Canyon overburden
pile and creek. Adapted from Montgomery-Watson, 1998 (69)..........................14
LIST OF TABLES
Table 6. Results of general soil screen performed on the -3/8 in. soil fraction
of Pole Canyon overburden samples. .................................................................35
Table 7. Results of total soil microelement screen of samples from the Pole
Canyon overburden dump. .................................................................................36
Table 13. Results of agitation leach of Pole Canyon overburden samples with
Pole Creek water as leachate. ............................................................................42
Table 14. Results of agitation leach of Pole Canyon overburden with 18 MΩ-
cm water as leachate. .........................................................................................43
In the fall of 1996, livestock in the areas down gradient of regional phosphate
included hair loss, hoof disorders and the most severe cases resulted in the animals
the forages and surface water in the livestock pastures indicated higher than
drainage from phosphate mining waste rock dumps may have been the source of
the selenium.
Compensation, and Liability Act of 1980 (CERCLA) by the United States Forest
study of the source, extent, cycling, and possible control methods for the selenium
releases in the phosphate lease area began, involving five mining companies and
leases in the area, partnered with the University of Idaho to characterize selenium
releases at the Smoky Canyon Mine and examine control strategies. This
partnership provided the opportunity for the research contained in this thesis. This
research pursues two main objectives: first, to characterize the selenium release and
Figure 1. United States Geological Survey (USGS) topographic map of the western US
phosphate resource area. Encircled area approximates the study area of concern.
characterization of soil and water samples from mining overburden piles at the
Smoky Canyon Mine. It included aqueous metals screens, domestic water screens,
overburden leachate tests, neutron activation analysis, and thin section microprobe
the second objective of this work. The second chapter provides a summary of
treatment approaches for selenium-affected waters and soil and the fifth chapter
contains the further analysis of those experiments deemed applicable to the site.
3
2.0 SELENIUM
Selenium is a metalloid found in group VIB of the periodic table, as are sulfur
and tellurium. It commonly occurs with tellurium and acts as a sulfur analog in
nature. The atomic weight of selenium is 78.96 g/mole. It has five naturally
occurring cold isotopes and two beta particle emitting radioactive isotopes, 75Se and
79
Se (1). It has four oxidation states in nature: -2, 0, +4, and +6, of which the +4 and
+6 will form the oxyanions selenite (SeO32-) and selenate (SeO42-) in aqueous
solution. When found in its elemental form, it is a red amorphous or black crystalline
solid (2). In the precipitation of elemental selenium from solution, the red form
precipitates first and then transforms into the black crystalline form with aging or the
bornite, but few deposits contain high enough concentrations for economic mining of
selenium alone. Therefore, the most common method for obtaining selenium is from
the refining of anode slimes, a product from the electrowinning of copper. One other
source of selenium is from the leaching of flue dusts from sulfide ore smelter
operations (4). According to the USGS Mineral Industry Survey: Selenium and
Tellurium (5), worldwide production of selenium reached over 2100 metric tons.
alloy production, and in chemical and pigment production. Demand for selenium
4
may increase in the future due to the possibility of using selenium to replace lead in
Selenium is found not only in products used in everyday life, but it is also
humans) to maintain good health (6). Plants will uptake selenium and make it
(SeGSHpx), which assists in the conversion of free radicals into other harmless
Conversely, too much selenium in the diet of animals (3-15 mg Se/kg food)
can cause chronic or acute selenosis and death. Horses are especially susceptible
disorders, hair loss, tender joints, stillbirths, and malformation of offspring. Effects of
acute selenosis vary greatly by dose, bioavailability of the selenium form, and animal
species affected. The most bioavailable form of selenium is selenite (SeO32-), which
and concentrations causing toxic effects, the United States Environmental Protection
drinking water maximum contaminant level (MCL) is 10 µg/L and water-quality based
criteria for protection of aquatic life is 5 µg/L for chronic exposure (7, 8). Waters
containing more than 1000 µg/L are considered toxic waste by the EPA (9).
The EPA is currently updating water quality criteria and on December 10,
Federal Register. Recommended chronic criteria are at 5.0 µg/L and acute criteria
are given as an equation relating the fraction selenite to fraction selenate present:
1
Acute =
( fselenite / 185.9) + ( fselenate / 12.83)
These regulations apply to all states that do not have regulations meeting federal
While there is evidence to support having MCLs of lower values, there are
numerous problems with accurate detection of total selenium at low levels in water
duplicates of seven industrial and natural water samples for analysis of total
selenium in water. Results of the study indicated large variation in minimum and
are found in the sedimentary uranium and phosphatic vanadium deposits of the
western U.S. (4). Siltstones and shales are common sedimentary rocks that host
Formation of Idaho, Wyoming, Montana, Utah, and Nevada (11, 12) (Figure 1). The
Meade Peak member of the Phosphoria Formation is being mined for phosphate
release of heavy metals and the production of sulfuric acid, which is generally the
main concern associated with acid rock drainage (13). Sulfur oxidizes to form
oxyanions such as sulfate (SO42-), and selenium behaves in a similar way, producing
selenite (SeO32-) and selenate (SeO42-) anions. Kinetically favored selenate is the
most common in oxidized waters, but neutral to acidic environments will favor the
selenite and biselenite forms (Figure 2). Selenate is much more mobile in an
1.0
0.8 0
H2SeO3
0.6
-
HSeO3
0.4
0.2 2-
SeO3
0.0 Se
-0.2 0
H2Se
-0.4
-
-0.6 HSe
-0.8
-1.0
0 2 4 6 8 10 12 14
pH
the Kesterson National Wildlife Refuge in the San Joaquin Valley (14, 15).
Agricultural practices in the San Joaquin Valley area have concentrated selenium
released from cretaceous marine shales of the Coast Ranges. The practice of
concentrates the salts when evaporation outpaces the influx of water. This results in
high levels of selenium in the water, sediments, and biota, which in turn
aquatic birds led to deformities and death of embryos and hatchlings reaching 64%
8
of the population. Elevated levels of selenium are also observed in the local fish
(15).
Based on the USGS studies, areas of similar geology and hydrology that
Utah; Kendrick, Wyoming; Sun River, Montana; and Stillwater, Nevada (15).
Selenium source rocks of similar composition occur in parts of Arizona, New Mexico,
Many recent articles, books, and patents discuss the treatment of soil and
approaches for immobilizing or removing selenium oxyanions from water and soil
Iron co-precipitation is by far the most successful and widely used method of
contaminant removal from water and soils. Iron(II) salts, such as ferrous chloride,
and the resulting ferric oxyhydroxide precipitate incorporates the oxyanions into its
lattice (16, 17). In addition to entrapment of these oxyanions into the lattice, the
oxidation of ferrous ions to ferric ions may have the capability of reducing some of
the selenium to its elemental form (18). The resulting FeOOH and Fe2(SeO3)3
precipitates are largely insoluble and to some extent can control selenium solubility
9
the addition of a zero-valent metal (20, 21, 22). The oxidation of the metal in an
aqueous acidic to neutral solution is the driving force behind this method. Zero-
valent iron is unstable in water, and its oxidation will cause the release of electrons
with the production of the more stable Fe2+ and Fe3+. Half-reactions for this process
are
Oxidation:
Fe ⇔ Fe2+ + 2e-
Fe2+ ⇔ Fe3+ + e-
Reduction:
The electrons produced in this reaction are responsible for the reduction of aqueous
Marchant’s (21) work showed that the direct reduction of selenium oxyanions
to elemental selenium (or selenide) through the use of zero-valent iron must be done
under acidic conditions. This acidic medium prevents the formation of iron oxy-
hydroxides while the redox couple of ferrous-ferric iron reduces the selenium
species. Work by Baldwin et al. (22) and Murphy (18) demonstrated that allowing
the production of hydroxyl ions from the corrosion of the iron can cause the selenium
Ion exchange and adsorption are two more processes that can also
process involving the reversible exchange of ions between a liquid and a solid (24).
A strong base resin removes selenium oxyanions, but there is competition between
selenium oxyanions and sulfate ions if they are present. This makes the application
of ion exchange to wastewater difficult (25). Most applications of ion exchange are
present (26, 27). However, recent developments in ion exchange processes, which
are cheaper and more selective for selenium species, may increase the likelihood of
Currently, physical and chemical adsorption are the two most common
the van der Waals forces between the solute and adsorbent are greater than the
forces between the solute and solvent. This is a reversible process. Chemical
adsorption involves a reaction between the adsorbent and the solute, and this
utilizing amorphous iron oxyhydroxides, manganese dioxide, retorted oil shale, and
reverse osmosis (RO) methods are too expensive for use in the treatment of
industrial and agricultural wastewater due to pretreatment and energy costs (36).
wastewater prior to treatment and have much lower pressure requirements for water
to pass through them (37, 38). Nanofiltration is a proven method for removing
the last decade (45). Microbial processes in a passive remediation scheme that is
low in operating costs may have long-term applicability for mine drainage treatment.
The use of bacteria of the genus Clostridium in bioreactors for the remediation of
selenium contaminated waters is one proven treatment approach (46, 47). Other
soils such as irrigated farmland are a newer approach to remediation (52). Studies
indicate that the wetting-drying cycle combined with an added carbon source for
soil.
12
treatment, pharmaceuticals, and the agricultural industry (53). The main uses of tpA
are corrosion inhibition and nutrient absorption enhancement. The compound can
has chelating properties which allow it to bind with positively charged ions when its
acid groups are displaced. TpA chelated with ferric iron has demonstrated the ability
water or air from moving through contaminated soils, thus preventing the initial
prevent penetration and flow of water. Segregation is not examined in this study.
NH NH
O
OH OH
O
O
α=0.3 n β=0.7n
Prior to sampling, the materials to be used for the collection and storage of
the water and soils were washed and rinsed with deionized water to prevent cross
contamination. The wash consisted of soaking and scrubbing all materials with hot
Micro® detergent solution and triple rinsing with deionized water. A final rinse was
made with 18 MΩ-cm distilled water. A 2.5 gallon cubitainer of deionized rinse water
and a bottle of micro solution were prepared for quick clean-up of equipment
Four 2.5 gallon water samples were collected from the Pole Canyon
overburden dump, two at the inlet end (PCW1a, b) of the french drain and two at the
outlet end (PCW2a, b; See Figure 4). Samples were collected by allowing the creek
water to flow into the cubitainers, which were then sealed with plastic under the
made on site, and the water was packed into coolers for same-day transportation to
the University of Idaho. Upon arrival at the University of Idaho Analytical Sciences
Five soil samples in five-gallon buckets were taken from the overburden piles
in Pole Canyon. Two samples were collected at the upstream (upper) end of the
taken from the downstream (lower) end above the French drain which had slumped
in the spring of 1997 (PCO-03). Prior to the slump, this sample site had been at a
Figure 4. Map showing sample locations along the Pole Canyon overburden pile and creek. Adapted from Montgomery-
Watson, 1998 (69).
15
‘unweathered’ overburden sample. The fourth site was on an upper bench at the
downstream end of the pile where topsoil application required excavation to about a
one foot depth to reach overburden (PCO-04). A fifth sample was a channel sample
taken from the central area on the top of the overburden pile (PC-CH). All of these
samples were stored refrigerated and sent to the University by air transport two days
after collection, upon arrival at the University the soil samples were stored at 4°C.
compliance with Good Laboratory Practice standards (55). Quality control for the
for analysis. Standard reference water containing trace metals was used for quality
recommended statistical performance limits were followed for batch data quality
acceptance criteria. All standards used in the analyses are traceable to the US
Analytical instruments used by the ASL for this study included: Leeman 2000
inductively coupled argon plasma spectrophotometer (ICP), Perkin Elmer P-40 ICP,
Dionex DX-100 Ion Chromatograph, YSI model 31Conductivity Bridge, Orion model
525A pH-Eh multimeter, Milton Roy Spectronic 301, Alpkem Rapid Flow Analyzer,
16
TurboVap evaporator.
The following chemicals were reagent grade or better and used as received.
neutral alumina (Fisher Scientific), activated carbon (J. T. Baker Inc.), colloidal iron
(micropowder iron, 1-3 µm, grade S-3700, ISP Technologies, Inc.) and industrial
mixed mesh scrap iron (100% passing 8 US Sieve; Master Builders, Inc.).
Enhancer™ (Amilar International Inc.), food grade potato starch (AVEBE Veendam,
the Netherlands), and potato processing waste (J. R. Simplot Company) were also
by the ASL for aqueous and soil sample analysis. A brief explanation of the sources
3.3.1 W ATER
EPA and can be found in EPA Methods for Chemical Analysis of Water and Wastes
the ASL, is modeled after research conducted at the University of California, Davis
(57).
17
method involves the titration of a known aliquot of sample with 0.01N sulfuric acid.
325.3. Acidified samples are titrated with silver nitrate in the presence of potassium
and a change of solution color from bright yellow to reddish brown indicates the
not interfere.
method 120.1 using a YSI Conductivity Bridge, model 31. The measurement probe
is placed within the sample of interest and the range and sensitivity of the instrument
is manually adjusted so the conductance can be read directly from the instrument
dial.
18
of trace elements in solution using EPA method 200.7. A Leeman 2000 ICP is used
aliquot of water that will pass through a glass fiber filter (EPA 160.1). After vacuum
dried residue (>4 mg/L) are weighed to determine the total filterable residue in the
water.
the sample which also contains Eriochrome Black T indicator. When the endpoint is
reached, the indicator changes from red to blue. A calculation based on the amount
nitrite nitrogen in water samples using EPA 353.2. Filtered aqueous samples pass
through a tube containing copper and cadmium, which reduces all nitrates to nitrite.
an azo dye and the concentration is read colorimetrically by an Alpkem Rapid Flow
Analyzer. Addition of EDTA can eliminate interference from iron, copper, or other
metals.
19
by the EPA 365.4 method. Samples are digested with persulfate and sulfuric acid to
Spectronic 301.
(HG-ICP). Samples are digested with nitric acid and then boiled in perchloric and
injection of undigested water. Selenite is the only species present that can be
crystals are precipitated from mixing sulfate ions in an acetic acid medium with
Turbidimeter DRT 100B and compared to a curve prepared from standard sulfate
solutions.
following a vigorous digestion using concentrated trace metal grade nitric acid and
3.3.2 SOIL
Methods of Soil Analysis, 1st edition edited by C.A. Black (58), 2nd edition edited by
A.L. Page (59); and other sources. A full list of sources can be obtained from the UI
ASL.
has been allowed to come to equilibrium. The reading is taken in the soil
bicarbonate, and chloride in a soil. The extract of a saturated soil paste is titrated to
chromatography.
Boron – Air-dried and ground soil is placed into a plastic zip-lock bag in
which the soil is mixed with CaCl2 and then brought to the boiling point.
method.
a pH 8.2 is used to leach the soil and saturate the exchange sites with ammonium
21
ion. The excess ammonium is removed with alcohol and then acidified sodium
determine the conductivity attributable to the major soil anions CO32-, HCO3-, Cl-,
Nitrogen – nitrate and ammonium – Five grams of air-dried and ground soil
is mixed with 2M KCl, and the extract is analyzed by automated colorimeter and/or
Sulfuric acid is then added to the sample while external heat is applied. A ferroin
indicator is added and the mixture is titrated with FeSO4 until the endpoint is
sodium ion in a 0.5 M sodium bicarbonate solution and potassium in the extract is
sulfuric acid, ammonium molybdate, ascorbic acid and antimony potassium tartrate.
spectrophotometer.
The sample is initially digested by heating with nitric acid and boiling with a mixture
of sulfuric and perchloric acids. This digestion converts all selenium species to
selenate, Se(VI). The selenate is then reduced to selenite, Se(IV), with hydrochloric
acid and heat. Selenite is then reduced by acidic sodium borohydride to hydrogen
needed.
is digested in nitric acid and hydrogen peroxide at 150°C. The digestate is then
refluxed at 150°C with hydrochloric acid, filtered if necessary, and analyzed for
characterizations of the overburden were carried out for this research. The methods
grams of a sample were placed into a 1L polyethylene bottle and the leachable
elements were extracted by rotary agitation in 18 MΩ-cm water for 18 ± 2 hrs. The
mixture was then filtered under pressure through a glass fiber filter and a dissolved
multi-element screen, selenium, and sulfate analyses were run on the filtrate.
Procedure was then repeated with Pole Creek inlet water as leach solution.
15 kV electron beam was used, and intensities were converted to concentrations via
a PAP correction scheme. Spot analyses of two microns in size were conducted
Neutron activation analysis – One air dried and ground sample from each
sample location was analyzed for 75Se and 65Zn using the TRIGA III reactor at
Washington State University. This reactor irradiates the soil samples, and then the
chloride in a 150 mL beaker. Enough methylene chloride was used so that the
sonifier probe could extend at least a centimeter below the surface of the methylene
chloride without touching the soil. The sonicator was run at full pulsed output for 3
minutes. Following sonication the liquid was vacuum filtered and collected for
Each sample was washed in this way three times. The three wash liquids
This liquid was transferred to a container usable for selenium analysis and the
were also transferred to the selenium analysis tubes. Evaporation to dryness using
nitrogen evaporation left a yellow film in the tubes, which were submitted for
overburden followed the sequential extraction outlined by Martens and Suarez (60).
steps, each followed by centrifuging and decanting. Water soluble selenium species
phosphate buffer (pH 7.00) extracted the selenium adsorbed to the soil, followed by
3.5.1 W ATER
each run, 100 mL of the PCW2a water was mixed in 200 mL Erlenmeyer flasks with
shaker for 24 hrs. Samples were treated with 5, 10, and 25 mg/L Fe3+. An
additional run with Fe3+ was conducted at 10 mg/L plus an equimolar concentration
of thermal polyaspartate (tpA), a product which we call ferric tpA. At the conclusion
25
of the 24 hrs, 10 mL of solution were filtered through a 0.2 micron syringe filter,
runs, 100 mL of the PCW2a water was treated with colloidal iron (c-Fe) at
concentrations of 0.1%, 1.0% and 10% by weight and agitated on an orbiting shaker
for 24 hrs. At the conclusion of 24 hrs, 10 mL of the solution were filtered through a
0.2 micron syringe filter, acidified, and submitted for total selenium analysis.
Adsorption – Four treatment runs were performed in triplicate. For each run,
100 mL of the PCW2a water was mixed with 1 or 10 mg/L of either neutral activated
alumina or activated carbon and agitated on an orbiting shaker for 24 hrs. At the
conclusion, 10 mL of the solution were filtered with a 0.2 micron syringe filter,
3.5.2 SOIL
duplicate. For each of the runs 5 grams of PCO-03 overburden soil and 25 mL of
soil amendment enriched water were mixed and then shaken lightly for one hour.
The mixtures were centrifuged and the liquid portion of each was decanted. To the
remaining soil, 25 mL of 18 MΩ-cm water was added and the mixture was then
shaken lightly for 24 hours. Following shaking, they were again centrifuged, and 10
The remaining liquid was mixed back into the soil and allowed to sit
undisturbed for an additional 48 hours after which it was again centrifuged and 10
mL were decanted and submitted for selenite analysis. Added to the remaining soil
26
solution was mixed into the soil and gently shaken for 24 hours. The mixture was
then centrifuged and 10 mL were decanted and submitted for selenite analysis.
Amendments tested included 5.0% tpA (w/w), 0.5% tpA (w/w), 0.05% tpA (w/w),
1000 mg/L Fe3+, 100 mg/L Fe3+, 10 mg/L Fe3+, 1.0% ferric tpA (w/w), and 18 MΩ-cm
water as a control.
Saturated paste with amendments – Ten treatment runs and one control
run were performed in triplicate for two periods of time, 14 days and 28 days. For
each run, 12.5 g of each soil (PCO-01, -02, -03, -04) were measured into a saturated
paste cup and mixed with 30 mL of 18MΩ-cm water. Dry amendments were added
to the soil prior to addition of the water, wet amendments were added to the water
5.0% (by wet weight). Approximately 10,000 cells/mL suspension of a 50:50 mixed
inoculate some pastes. Pastes were sealed under nitrogen and two layers of
parafilm and placed into an incubator at 25° C for either 14 days or 28 days. At the
conclusion of the run, pastes were mixed and filtered. Filtrate was analyzed for
selenium, dissolved multi-elements, and sulfate if there was enough filtrate left.
Amendments tested included sulfate reducing bacteria inoculum (SRB), c-Fe, mb-
Fe, mb-Fe plus SRB, potato starch, potato starch plus SRB, ferric ion chelated
27
thermal polyaspartate (ferric tpA), ferric tpA plus SRB, potato processing waste, and
Canyon give insight into the nature and extent of the selenium releases from Idaho’s
regional phosphate mines. Data from these water and soil analyses allow us to
draw conclusions as to what the source of the selenium in the study area is and thus
aid in development of a control strategy for the selenium releases. Results of water
analyses are unique to this sampling period and will vary with precipitation and
drainage conditions.
use these detection limits as needed. The concentration data is reported in units of
dissolved elements, and total recoverable elements. Since Pole Creek drains into
grazing and agricultural lands, a domestic/livestock water screen for samples from
both the inlet and outlet of the overburden drain was also appropriate.
This analysis involved water collected from two sample locations and
(61). The water from in the inlet of the overburden piles was designated as PCW1
and the outlet water as PCW2. Preservation methods included filtered (F), filtered
and acidified (FP), and acidified (P). If a sample was not filtered or acidified it is
29
designated with -N, and all preservation methods included continuous refrigeration
at 4°C.
the creek inlet of the overburden french drain, PCW1, to 8.61 µM (680 µg/L) at the
creek outlet below the overburden pile, PCW2. Selenium has a seven times greater
increase than any other ion or metal in the study. This illustrates that the selenium
problems in this particular area are influenced by the overburden piles, and it is not
The anion screen (Table 2) shows large increases in fluoride, chloride, nitrate,
and sulfate, although the levels of fluoride, chloride, and nitrate in the outlet water
are not considered higher than normal. Fluoride is a constituent of the phosphoria
(fluorapatite – Ca5(PO4)3F) mined in the study area, and sulfate can substitute into
the lattice where phosphate is found (62). It is likely that weathering of the
fluorapatite is the cause of the increase in fluoride in the outlet water and a source of
source for selenium oxyanions in the waters. However, an increase in sulfate this
large cannot solely be a result of sulfide oxidation and is likely a result of both
phosphorous species are detected in the outlet water even though the overburden
contains large amounts of low-grade ore (12%-17% P2O5). This may be related to
the presence of iron in the overburden, which can form stable iron phosphate
element screen (TMS) were conducted on the Pole Creek waters to assist in
identifying the major components of the system. The DMS results show that calcium
between the inlet and outlet of the drain (Table 3). Calcium is a component of
fluorapatite, and both calcium and magnesium are components of limestone. Their
presence is most likely a result of both the weathering of the fluorapatite and the
Dissolved zinc (33x), nickel (16x), and cadmium (5x) all show an increase in
concentration at the outlet. All three of these elements are commonly found as
sulfides and may be present in the overburden. Sphalerite (ZnS) has been
beryllium, iron, and manganese decrease from inlet to outlet. It is interesting that the
iron concentrations decrease since the most common reactive sulfide in these
deposits is normally pyrite, FeS2. Again, this may be due to the presence of
phosphate ions in solution, which form stable compounds with ferrous and ferric
ions.
32
The TMS shows similar results as the DMS, with calcium and magnesium
comprising the majority of the cations present in the outlet water (Table 4). Zinc,
nickel, and cadmium show increases again, but the increase in zinc is much greater
than that measured in the DMS. This indicates the possible presence of zinc in the
element.
The domestic livestock water screen, like the previous tests, indicates that
chloride slightly increases and sulfate shows a large increase within the drain (Table
5). At over 3 mM, sulfate is the dominant oxyanion in the dissolved solids of the exit
water. There is also a 0.7 unit reduction in pH over the length of the drain. The
33
combination of a decrease in pH and the large increase in sulfate also supports the
nitrate/nitrite levels are again normal to low for natural waters, and phosphorous
concentrations again show a decrease in the drain and are considered low for
natural waters.
Table 5. Results of screen for domestic livestock water performed on Pole Canyon
overburden french drain water.
Results in Table 5 also show that total dissolved solids increase by 230%
throughout the length of the drain, of which dissolved CaSO4 accounts for 78% of
the increase. The pH drop may be an effect of acid rock drainage production. The
drain, reflecting the increase in type and concentration of dissolved ions. Total
For the following soil screens, the air-dried, ground, -3/8 inch fraction of the
overburden from each sample location was used. While some of these analyses are
generally reserved for agricultural soils, this study applied them to the overburden
because the piles are reclaimed for grazing purposes. Other analyses within this
selenium and its possible release from minerals into the water.
A general soil screen of the overburden samples revealed the selenium and
Fertility test results on the air-dried and ground -3/8 inch fraction of the
overburden give us information about whether the overburden is suitable for use as
The soil testing facility at the ASL analyzed and gave recommendations
concerning soil fertility (Table 6). This analysis reported that plant available
phosphorous is slightly higher than normal, which is expected given that the soils
contain low-grade phosphate ore. Levels of plant available potassium, however, are
low and would require application of fertilizer. Extractable nitrogen levels are normal
for these soils but additional application could increase fertility. Soil boron levels are
reported as normal.
3
Table 6. Results of general soil screen performed on the - /8 in. soil fraction of
Pole Canyon overburden samples.
PCO-03 shows high levels of sulfate, the sample with the most weathering (PC-CH)
36
shows normal concentrations, and all others are slightly elevated. Alkalinity
(carbonate/ bicarbonate) typifies this soil type and pH range. Percent organic
carbon, total carbon, and total nitrogen levels are slightly high, while hydrogen levels
are normal. For southeastern Idaho soils of this soil texture and type, the electrical
Table 7. Results of total soil microelement screen of samples from the Pole Canyon
overburden dump.
magnesium (Table 7). This correlates well with the knowledge that the overburden
from this section of the Meade Peak member consists of a mixture of fluorapatite,
calcite, dolomite, pyrite, and other minor minerals (62). There are also relatively
mmol/kg of soil; typical values for this soil type are <0.0063 mmol/kg soil (Table 8).
This confirms that the origin of the selenium is the overburden but still does not
shows selenium concentrations that range from 0.218 mmol/kg in sample PCCH to
0.922 mmol/kg in sample PCO-04. These numbers do not correlate well with the
PCO-03, also slightly higher than the acid digestion method. Zinc results indicate
contain no visible sulfide and little organic matter, however, it appears that the
siltstones are the host rock for pyrite (FeS2) and sphalerite (ZnS) minerals and also
contain hydrocarbons.
of iron, zinc, selenium, and sulfur from one sample (Figure 5). Pyrite comprises
about 0.2%, by volume, of the siltstones, and sphalerite is even more scarce at only
The analytical results show that the concentration of selenium in the pyrite
grains (Figure 5, Table 10) is sufficient to account for most of the selenium
concentration in the overburden. These results also support the theory that acid
rock drainage is most likely occurring in the overburden even though there is no
of acid rock drainage resulting from oxidation of the pyrite, and its presence is
different extractable selenium species in a sample (Table 11). Results from applying
this method to sample PCO-03 indicate that about 2% of the mass of selenium
selenite, SeO32-. After all of the oxidation/extraction steps of the SES about 0.016
mmol-Se/kg soil is extracted. This is an order of magnitude less than half the bulk
the total soil selenium determined by NAA, 2% is extractable selenite with the
remaining selenium in the soil present as either selenide (-II) or zero-valent selenium
(67).
This analysis revealed that for the weathered samples, methylene chloride
(MeCl) extractable organo-selenium compounds account for less than one percent
account for approximately 2.5 percent of the total overburden selenium. Further
The agitation leach provided information from leachate samples of the five
overburden soils collected from the Pole Canyon site. This analysis determined the
weathered and/or soluble minerals may be present in the overburden. Leaching with
water from upper Pole Creek allowed the use of water that has natural carbonate
allowed a leach with no interference of natural buffering, acidity, and other ions.
Table 13. Results of agitation leach of Pole Canyon overburden samples with Pole
Creek water as leachate.
With the Pole Creek water as leach solution (Table 13), selenium, barium,
manganese, and nickel did leach into the water in all samples. Other elements such
as aluminum, cadmium, and chromium were below detection limits in all screens.
43
Copper, molybdenum, vanadium, and zinc was detected in some of the leachates,
but not all. With 18 MΩ-cm water as leach solution (Table 14), selenium, aluminum,
barium, manganese, and zinc were found in all leachates. The only other element of
concern (See 5.1) that was above detection limits in at least one solution was
cadmium.
Ω-cm water
Table 14. Results of agitation leach of Pole Canyon overburden with 18 MΩ
as leachate.
Cov( X , Y )
ρxy =
σx ⋅ σy
1 n
Where − 1 ≤ ρxy ≤ 1 and Cov( X , Y ) = ∑ ( xj − µx)( yj − µy) .
n j −1
This correlation analysis was completed utilizing the five overburden samples (n =
5), giving the analysis 3 degrees of freedom. For three degrees of freedom, a 5%
0.959 (68).
levels (via agitation leach) correlate with total selenium by digestion just outside of
the 5% level of significance (ρ = 0.859), but do not correlate well with total selenium
0.337) between total selenium determined by digestion and that determined by NAA.
correlation coefficient also falls within the 1% and 5% levels of significance for water
carbon (ρ=-0.290) or total carbon (ρ=0.017). Even with higher ρ values, correlation
45
remains low between total selenium by digestion and organic carbon (ρ=0.475) as
• Selenium is not detected in Pole Creek waters before it enters the french drain.
• Sulfate concentrations show a large increase (190 to 2920 µM) and may indicate
• Phosphorous species are not detected in the drainage even though the
• The dissolved metals screen shows large increases in cadmium (BDL to 0.100
µM), calcium (1500 to 4500 µM), nickel (BDL to 2.00 µM), and zinc (0.2 to 7.30
concentrations (0.08 to 10.2 µM), and shows increases in barium (0.23 to 2.30
• The pH of the system is near neutral; however, the slight pH decrease observed
from the inlet to the exit of the drain (8.10 to 7.30) is consistent with increased
• There is a relative absence of dissolved iron in the exit water, even though pyrite
• The soil fraction of the overburden has low to reasonable fertility and may need N
• The soils contain a range of 0.218–0.922 mmol/kg (17-73 µg/g (ppm)) total
• Speciation and geochemical studies of waste rock soil and leachate indicate that
• Correlation analyses for total selenium in the overburden soils by digestion and
water extractable selenium show a correlation coefficient of 0.859, just under the
sulfate is 0.946, just under the 1% level of significance. The coefficient for water
extractable selenium and soil sulfate-sulfur is 0.927, which falls within the 1% to
5% levels of significance.
47
treatment are currently under investigation at the University of Idaho’s Center for
Hazardous Waste Remediation Research and are being field-tested at J.R. Simplot
received the Sampling and Analysis Plan: Southeast Idaho Phosphate Resource
development of aquatic screening criteria for both aquatic populations and possible
selenium that should be addressed at this site can be identified (Table 15). In
addition to selenium, those metals that may be above the MCL (at this sampling) for
search were applied to water from the Pole Canyon french drain outlet water. In the
following treatment studies, it was assumed that selenium oxyanions were present in
49
their most oxidized state; thus, analyses determined only total selenium in the
samples used for these treatment studies have since revealed that the species in the
have been conducted on samples field frozen on dry ice at the site. Analyses of the
field frozen samples identified the species in the outlet water as approximately 85%
(PCW1 and PCW2) having been exposed to air, causing the selenite that had been
determining which of the methods tested here were best suited for field studies, the
5.2.1 SELENIUM
the drainage must be reduced by 74%-92% to fall within the allowable MCL range.
Of the three concentrations of ferric ion tested, none of them reduced selenium
concentrations in the outlet water by more than 6% (Figure 6). This is disappointing
since ferric salts have shown much success in conventional wastewater treatment
50
for removal of similar oxyanions. One concentration of ferric-tpA was tested and
9.0
8.0
Concentration of Se (µM)
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
T
Fe
3+
3+
3+
Fe
A
Fe
on
a
a
on
N
in
in
tp
rb
Fe
Fe
Fe
c-
rb
c-
c-
um
um
I)-
ca
ca
1%
%
1%
(II
L
L
L
al
al
g/
g/
g/
10
L
Fe
L
0.
L
L
g/
g/
m
m
m
g/
g/
L
10
1
10
25
5
g/
10
1
m
10
alumina at 1 g/L removed less than 5% of the selenium while the 10 g/L
concentration removed 14%. Activated carbon at 1 g/L was more effective than the
10 g/L alumina, and larger decreases in the concentration of selenium occurred with
the 10 g/L.
Direct reduction from the use of zero-valent, micropowder iron had the
removed a similar amount of dissolved selenium as the activated carbon, while the
51
1% treatment removed close to 80% of the selenium and the 10% treatment
that the elements cadmium, copper, nickel and zinc were also above aquatic criteria.
Water treatment studies that were conducted for removal of selenium from the water
were repeated on refrigerated lower Pole Creek samples and analyzed for total
metals.
5.2.2.1 Cadmium
cadmium in the Pole Creek Outlet water should be reduced by at least 92% in order
0.25
0.20
Cd concentration (µM)
0.15
0.10
0.05
0.00
T
a
Fe
Fe
n
Fe
n
L
L
L
in
in
bo
g/
g/
bo
g/
N
tp
c-
c-
c-
um
um
m
m
5m
I)-
ar
ar
10
25
1%
0%
(II
C
Al
Al
I)
.0
Fe
/L
L
I)
I)
(II
0.
1.
/L
L
10
g/
(II
(II
1g
g/
Fe
1g
10
Fe
Fe
10
to meet aquatic criteria. Of the five water treatments studied, the two that exhibit the
most potential are ferric iron co-precipitation and cementation onto metallic iron
(Figure 7).
The highest reduction reached by either of these treatments nears 90% and
concentrations. This indicates that the amount of reactant needed to remove the
contaminants can be low. Better mixing of the reagents and water may increase
removal. Adsorption treatments and use of Fe(III)-tpA all had similar results ranging
5.2.2.2 Copper
Creek water. Of the treatment methods studied, none reached above 48% although
lab conditions were not ideal and better mixing has a chance to increase removal
1.40
1.20
Cu concentration (µM)
1.00
0.80
0.60
0.40
0.20
0.00
T
L
L
A
Fe
Fe
n
Fe
g/
g/
g/
in
in
bo
N
bo
tp
c-
c-
c-
um
um
m
m
5m
I)-
ar
ar
10
25
1%
0%
(II
C
Al
Al
I)
.0
Fe
/L
L
I)
I)
(II
0.
1.
/L
L
10
g/
(II
(II
1g
g/
Fe
1g
10
Fe
Fe
10
rates (Figure 8). The most promising treatment is using zero-valent, colloidal iron
which showed removal nearing 50%. Ferric ion co-precipitation at 25 mg/L showed
removal near 30% as did adsorption with alumina. The least effective treatments
5.2.2.3 Nickel
Creek to below aquatic MCLs (Figure 9). The most effective removal was achieved
3.50
3.00
2.50
Ni concentration (µM)
2.00
1.50
1.00
0.50
0.00
L
L
L
T
A
Fe
Fe
a
a
Fe
n
n
g/
g/
g/
in
in
bo
bo
N
tp
c-
c-
c-
um
um
m
m
5m
I)-
ar
ar
10
25
1%
0%
(II
C
C
Al
Al
I)
.0
Fe
L
/L
I)
I)
(II
0.
1.
L
/L
10
g/
(II
(II
1g
g/
Fe
1g
10
Fe
Fe
10
5.2.2.4 Zinc
order to meet the determined MCLs. All of the treatments except one exhibited the
54
ability to reduce concentrations of zinc by over 90% (Figure 10). The most effective
treatment was the use of zero-valent colloidal iron, although all treatments
9.00
8.00
7.00
Zn concentration (µM)
6.00
5.00
4.00
3.00
2.00
1.00
0.00
-1.00
L
L
L
T
A
Fe
Fe
a
a
Fe
n
n
g/
g/
g/
in
in
bo
bo
N
tp
c-
c-
c-
um
um
m
m
5m
I)-
ar
ar
10
25
1%
0%
(II
C
C
Al
Al
I)
.0
Fe
L
/L
I)
I)
(II
0.
1.
L
/L
10
g/
(II
(II
1g
g/
Fe
1g
10
Fe
Fe
10
Figure 10. Effects of various water treatments on the concentration of zinc in Pole
Creek outlet water. Error bars represent sample S.D., n=3.
Results of the chemical armoring study were used to examine the effect of
rock soils. The goal of the saturated soil paste study was to compare and contrast
the effects of ten different soil amendments on selenium and COPC leaching.
5.3.1 SELENIUM
been identified as the species selenite (SeO32-). In the following armoring studies,
55
analysis for selenite was performed on the leachate samples after treatment, with no
digestion for total selenium. In the saturated paste studies, analysis for total
selenium was performed. Once the concentration of selenium in the paste pore
water was determined, the amount of selenium leached per kilogram of overburden
This experiment examined the soil particle armoring effects of three different
Surface treatment of soil particles has the potential to limit short-term selenite
the end the study to remove any remaining soluble or exchangeable selenite (s/e
At the completion of this trial, it was apparent that the highest concentration of
each amendment was the most effective prior to addition of phosphate (Figure 11).
The high concentrations of tpA, Fe(III), and Fe(III)-tpA reduced the amount of s/e
selenite leached over 24 hours from the soil by at least 80%. As the amendment
concentration decreased, the leached amount approached that of not having been
treated. Twenty-four hours later, all of the leached amounts increased, but the 1000
mg/L Fe(III) and 1% Fe(III)-tpA treatments did not increase as much as either the
0.1000
0.0100
mmol selenite leached
per kg soil
0.0010
0.0001
0.0000
control 5.0% tpA 0.5% tpA 0.05% tpA 1000mg/L 100mg/L 10mg/L 1.0%
Fe(III) Fe(III) Fe(III) Fe(III)-tpA
Figure 11. Amount of soluble/exchangeable selenite leached from soil after three
consecutive leach periods; water/24 hrs, water/24hrs, and phosphate buffer/24 hrs.
Soluble and exchangeable selenite was further leached from the same soil
samples after the remaining water was replaced with the phosphate buffer solution.
In this sequential extraction, the greatest amount of s/e selenite leached from the
soils was after this 24-hour extraction. This not only illustrated that phosphate will
enhance s/e selenite leaching, but also showed that all samples contained similar
The primary goal of this study was to reduce the amount of selenium leaching
from the overburden. Secondary goals included reducing or not affecting the
leaching of other potential contaminants (COPC) within the overburden. The ten soil
colloidal iron (c-Fe), mixed mesh scrap iron (mb-Fe), mb-Fe/SRB, potato starch
waste (PW), and PW/SRB. Figures 12 and 13 show the effects of the ten soil
100.00
10.00
µmoles Se leached
per kg soil
1.00
0.10
0.01
B
B
te
B
Fe
B
Fe
t
ch
A
tm
SR
SR
SR
SR
SR
tp
as
ar
c-
b-
I)-
no
st
m
+
+
+
(II
to
to
pw
ps
A
Fe
Fe
ta
tp
ta
b-
po
I)-
po
m
(II
Fe
amount of selenium leached by over 99%. In the same time mb-Fe/SRB, PS, and
reduced the selenium leached from 56% to 84%. During this 14 day trial, the
amendments that were mixed with SRBs outperformed those same treatments
100.00
10.00
µmoles Se leached
per kg soil
1.00
0.10
0.01
B
B
B
t
ch
Fe
Fe
B
te
tm
SR
tp
SR
SR
SR
SR
as
ar
c-
b-
I)-
no
st
m
+
+
+
(II
to
to
Fe
ps
pw
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
After 28 days, with the exception of PS, there was little difference between
the amount of selenium leached in the samples treated with an amendment plus
SRB and those with just the amendment (Figure 13). In some trials, the absence of
SRB inoculation appears to have had a slightly lower Se concentration result. This
may be due to the gradual infiltration of oxygen into the inoculated pastes, which
limits the ability of the anaerobic SRBs to maintain a viable population. Conversely,
within the time frame of the experiment, and none of the approaches showed
significant reversal of positive effects within the time frame of the study. In four
weeks, all treatments except c-Fe (86%) and SRB (82%) showed the ability to inhibit
59
selenium releases by at least 98%. Potato waste demonstrated the most rapid and
reduction of other COPC leaching is also a concern. Figures 14-21 summarize the
effects of the ten soil amendments on the leaching of these elements. Manganese
leaching (Figures 22 and 23) was also included because it appears to increase
enough (>10X) from some treatments to raise creek concentrations above the MCL.
Other elements were removed from further consideration after it was determined that
than 92% to comply with the MCLs. After the 14 day study (Figure 14), there was no
overburden and that overburden amended with c-Fe, SRB and mb-Fe. Samples
tpA/SRB samples showed a 180% increase, possibly due to the acidity of tpA.
18%), potato waste (-84%), PW/SRB (-89%) and potato starch (-14%) amendments.
The 28 day data showed a large standard deviation in the cadmium leached
from the unamended sample, which in turn made it difficult to assess whether
60
3.00E-04
2.50E-04
2.00E-04
µmoles Cd leached
per kg soil
1.50E-04
1.00E-04
5.00E-05
0.00E+00
B
B
Fe
B
Fe
t
te
B
ch
A
B
tm
SR
SR
SR
SR
tp
SR
as
ar
c-
b-
I)-
no
st
m
+
+
+
(II
to
to
pw
ps
Fe
A
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
3.00E-04
2.50E-04
2.00E-04
µmoles Cd leached
per kg soil
1.50E-04
1.00E-04
5.00E-05
0.00E+00
B
B
Fe
B
ch
Fe
t
te
B
tm
SR
SR
SR
SR
tp
SR
as
ar
c-
b-
I)-
no
st
m
+
+
+
+
(II
to
to
pw
Fe
ps
A
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
amendments effects were significant (Figure 15). Colloidal iron treatment appeared
cadmium leaching was apparent with potato waste and PW/SRB, and some
inhibition was possible from amendment with mb-Fe, mb-Fe/SRB, potato starch and
PS/SRB.
meet the MCLs determined in this study. However, the best reduction within the
span of this study was 30-40%. After 28 days (Figure 16), there was little change in
the amount of copper leached from the overburden amended with c-Fe, SRB, mb-Fe
8.00E-04
7.00E-04
6.00E-04
µmoles Cu leached
5.00E-04
per kg soil
4.00E-04
3.00E-04
2.00E-04
1.00E-04
0.00E+00
B
B
Fe
B
Fe
t
te
B
ch
A
B
tm
SR
SR
SR
SR
tp
SR
as
ar
c-
b-
I)-
no
st
m
+
+
+
(II
to
to
pw
ps
Fe
A
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
180%, respectively. Slight reductions were observed with potato waste (-20%) and
potato starch (-12%) amendments, and the best inhibition was exemplified by
PW/SRB (-42%) and PS/SRB (-47%) amendment. After 28 days, there was not
much change in effectiveness of most amendments (Figure 17). The only change
was with potato waste amendment, which enhanced copper leaching by 140%.
9.00E-04
8.00E-04
7.00E-04
6.00E-04
µmoles Cu leached
per kg soil
5.00E-04
4.00E-04
3.00E-04
2.00E-04
1.00E-04
0.00E+00
B
B
Fe
B
ch
Fe
t
te
B
tm
SR
SR
SR
SR
tp
SR
as
ar
c-
b-
I)-
no
st
m
+
+
+
+
(II
to
to
pw
Fe
ps
A
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
Nickel is just slightly over the recommended MCL and concentrations should
be reduced by about 6%. After 14 days, the only amendment treatments to have a
significant effect on the amount of nickel leached were the Fe(III)-tpA and potato
waste, with and without SRB (Figure 18). Fe(III)-tpA (890%) and Fe(III)-tpA/SRB
(990%) showed drastic increases while potato waste (180%) and potato waste/SRB
0.012
0.010
µmoles Ni leached
0.008
per kg soil
0.006
0.004
0.002
0.000
B
B
Fe
B
Fe
t
te
B
ch
A
B
tm
SR
SR
SR
SR
tp
SR
as
ar
c-
b-
I)-
no
st
m
+
+
+
(II
to
to
pw
ps
Fe
A
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
The 28 day study had no treatments that significantly inhibited the leaching of
nickel from the overburden (Figure 19). Amendment with Fe(III)-tpA, at over 1000%,
was not as strong as in the 14 day study. Potato waste and PW/SRB showed
similar effects as in the 14 day study, while potato starch and PS/SRB showed an
Pole Creek. After 14 days, the amount of zinc leached was reduced by addition of
potato waste (-49%), but was essentially not affected by amendment with c-Fe,
the amount of zinc leached occurred with mb-Fe (150%) and both Fe(III)
0.010
0.008
µmoles Ni leached
per kg soil
0.006
0.004
0.002
0.000
Fe
t
ch
B
B
Fe
B
B
te
A
B
tm
SR
SR
SR
SR
tp
SR
as
ar
b-
c-
I)-
no
st
w
m
+
+
+
(II
to
to
Fe
ps
A
pw
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
0.005
0.004
µmoles Zn leached
per kg soil
0.003
0.002
0.001
0.000
t
Fe
B
Fe
B
A
ch
B
te
tm
SR
SR
SR
SR
tp
SR
as
ar
c-
b-
I)-
no
st
m
+
+
+
+
(II
to
to
ps
pw
Fe
A
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
SRB and the two Fe(III) amendments increased leaching of zinc over the 28
days, although the amount being leached was considerably less than at 14 days.
Potato starch and PS/SRB amendment still had little effect on the leaching of zinc
after 28 days (Figure 21). However, c-Fe, mb-Fe, mb-Fe/SRB, potato waste, and
PW/SRB all reduced the amount leached by 57 to 65%. While this did not reach the
targeted 84% reduction for meeting MCLs in Pole Creek, the potential for further
0.005
0.004
µmoles Zn leached
0.003
per kg soil
0.002
0.001
0.000
t
ch
A
Fe
B
Fe
B
B
te
B
tm
SR
tp
SR
SR
SR
SR
as
ar
c-
b-
I)-
no
st
m
+
+
+
(II
to
to
A
Fe
pw
ps
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
Of the remaining elements for which the overburden outlet water was tested,
none were above MCLs as calculated in this study. With the exception of
exceed MCLs.
66
0.100
0.090
0.080
0.070
µmoles Mn leached
0.060
per kg soil
0.050
0.040
0.030
0.020
0.010
0.000
t
Fe
B
B
B
ch
Fe
te
tm
SR
SR
tp
SR
SR
SR
as
ar
c-
b-
I)-
no
st
m
+
+
+
+
(II
to
to
pw
Fe
ps
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
reducing conditions produced by amendment materials used in this study, they all
leaching was not significantly increased by amendment with c-Fe, SRB, mb-Fe, mb-
Fe/SRB, potato starch, and PS/SRB (Figure 22). However, the Fe(III)-tpA (870%),
showed larger increases and would most likely cause outlet concentrations to
exceed MCLs.
67
Conditions did not improve after the initial 14 days, with only c-Fe, SRB, mb-
Fe, and mb-Fe/SRB treatments remaining below the 1000% increase mark (Figure
1400% to 3800%.
0.080
0.070
0.060
µmoles Mn leached
0.050
per kg soil
0.040
0.030
0.020
0.010
0.000
ch
Fe
Fe
A
B
B
t
te
B
B
B
tm
tp
SR
SR
SR
SR
SR
as
ar
c-
b-
I)-
no
st
m
+
(II
to
to
Fe
pw
ps
Fe
ta
ta
tp
b-
po
po
I)-
m
(II
Fe
• Water treatment studies show the most promise for selenium and COPC removal
with zero-valent iron treatment. Activated carbon is also effective but may be
cost prohibitive.
68
• Treatments performed on aged outlet water samples could have differing results
on freshly collected outlet water or leachate in which the selenite has not yet
oxidized to selenate.
• Fe(III)-tpA demonstrates the best soil particle chemical armoring activity against
reversal of positive effects within the 28 day time frame of the experiment.
• Potato waste amendments demonstrated the most rapid and effective selenium
• Over the 28 day saturated soil paste study, mb-Fe, Fe(III)-tpA, potato waste, and
potato starch, with and without SRB inoculation, all showed the ability to stabilize
• Over the 28 day saturated soil paste study, potato waste, potato starch and mb-
Fe, with and without SRB inoculation all demonstrated the ability to reduce
• Potato waste demonstrated the best overall combined selenium and other COPC
• Fe(III)-tpA enhanced the release of all metals of concern from the saturated
pastes.
increase from amendment with Fe(III)-tpA, potato waste, and potato starch could
6.0 CONCLUSIONS
detectable amounts in Pole Creek prior to influence of the overburden french drain.
The french drain is overlain by waste rocks and low grade phosphate ore from the
Although this work does not explore reaction pathway in detail, the data
suggest that the overburden selenium release results from the oxidation of minerals
such as pyrite in the middle waste shales of the Meade Peak member. Associated
acid rock drainage acidity is controlled by the limestone fraction of the overburden.
The absence of soluble iron in this system likely results from availability of
phosphate from the low grade ore; this has the effect of limiting the selenite solubility
of sampling, not only was selenium above water quality criteria, but cadmium,
copper, nickel and zinc were as well. Treating the french drain outlet water directly
concentrations. Since several months passed between sampling Pole Creek and
(selenate being more difficult to treat than selenite). Repeat testing of treatment
water treatments.
70
potential control strategies for the release of selenium and other contaminants.
Most significantly, the data from the treatment study suggest that the
selenium release from the phosphate resource area overburden may be controlled
in-situ with chemical or microbial reductive approaches. This is in large part due to
leachable and adsorbed form on the overburden soils. Topical application of the
Fe(III)-tpA solution shows potential for short-term armoring of soils against the
studied in this work were successful. Analysis of COPC in associated pore water of
amended soils suggests that potato waste and granular iron (mb-Fe) offer the best
overall inhibition of contaminant release. The mb-Fe, potato waste, and potato
A.1 WATER
A.1.1 CHLORIDE
Results:
PCW1-Na PCW2-Na units EDL
-
Cl 8.20 9.80 mg/L 2.0
A.1.2 SULFATE
Results:
PCW1-Na PCW2-Na units EDL
SO42- 19.0 290 mg/L 2.0
Results:
PCW1-Na PCW2-Na units EDL
N as NO32- 0.100 0.300 mg/L 0.10
+ NO22-
A.1.4 PHOSPHOROUS:
Results:
PCW1-Na PCW2-Na units EDL
total P 0.0800 0.0300 mg/L 0.010
72
A.1.5 ANIONS
Method: EPA 300.0: Anion Concentrations in Water Using the Dionex DX-100 Ion
Chromatograph
Results (mg/L):
PCW1-Nb PCW2-Nb units EDL
Fluoride 0.0500 0.180 mg/L 0.050
Chloride 1.60 3.60 mg/L 0.050
Nitrite 0.0500 0.0500 mg/L 0.050
Bromide 0.100 0.100 mg/L 0.10
Nitrate 0.0500 0.790 mg/L 0.050
o-Phosphate 0.0500 0.0500 mg/L 0.050
Sulfate 18.0 280 mg/L 0.10
Oxalate 0.100 0.100 mg/L 0.10
Sulfite 5.00 5.00 mg/L 5.0
Results:
PCW1-FP PCW2-FP Units EDL
Al 0.0890 0.0890 mg/L 0.089
Ba 0.0580 0.0420 mg/L 0.00060
Be 0.00210 0.000100 mg/L 0.00010
Cd 0.00230 0.0130 mg/L 0.0023
Ca 60.0 180 mg/L 0.0099
Cr 0.00440 0.00440 mg/L 0.0044
Co 0.00800 0.00800 mg/L 0.0080
Cu 0.00840 0.0140 mg/L 0.0084
Fe 0.0320 0.00370 mg/L 0.0037
Mg 16.0 28.0 mg/L 0.0047
Mn 0.0280 0.0200 mg/L 0.0012
Mo 0.0270 0.0480 mg/L 0.027
Ni 0.00700 0.120 mg/L 0.0070
K 0.610 1.20 mg/L 0.61
Na 4.00 5.10 mg/L 0.12
V 0.0150 0.0150 mg/L 0.015
Zn 0.0140 0.480 mg/L 0.0025
Ag 0.0300 0.0300 mg/L 0.010
Si 4.30 4.40 mg/L 0.29
73
Results:
PCW1-Nb PCW2-Nb units EDL
Ba 0.0320 0.310 mg/L 0.0040
Be 0.000900 0.00120 mg/L 0.00040
Cd 0.00300 0.0140 mg/L 0.0030
Ca 58.0 190 mg/L 0.031
Cr 0.0130 0.0220 mg/L 0.013
Co 0.0170 0.0200 mg/L 0.011
Cu 0.0350 0.0780 mg/L 0.035
Fe 0.0120 0.0120 mg/L 0.012
Mg 15.0 30.0 mg/L 0.0020
Mn 0.00900 0.0140 mg/L 0.0020
Mo 0.0400 0.1000 mg/L 0.040
Ni 0.0200 0.170 mg/L 0.020
K 1.60 3.20 mg/L 1.60
Ag 0.100 0.100 mg/L 0.10
Na 4.30 6.10 mg/L 0.55
V 0.0280 0.0280 mg/L 0.028
Zn 0.00500 0.670 mg/L 0.0030
A.1.8 SELENIUM
Results:
PCW1-P PCW2-P Units EDL
Se 0.000700 0.680 mg/L 0.00070
74
Results:
A.2.2 SULFATE-SULFUR
Results:
Results:
Results:
Results:
A.2.6 SELENIUM
Results:
Results:
Se (mg/kg) Zn (mg/kg)
PCO-01 34.0 ± 3.0 1430 ± 50
PCO-02 38.2 ± 3.3 804 ± 26
PCO-03 53.8 ± 4.4 2130 ± 70
PCO-04 72.8 ± 5.8 1720 ± 50
PCCH 17.2 ± 1.6 1200 ± 40
Results:
Results:
Sample ID Organo-Selenium Percentage of
mg-Se/kg-soil total Se by NAA
PCO-01a 0.513 0.96 %
PCO-01b 0.490 0.91 %
PCO-02a 0.142 0.26 %
PCO-02b 0.221 0.41 %
PCO-03a 0.142 2.65 %
PCO-03b 1.18 2.21 %
Method: Modified EPA 1311 Toxicity Characteristic Leaching Procedure for Metals
in Soil
77
Results: PCO-01
mg/L PCW-01 PCW-02 18MΩ-cm 18MΩ-cm Units EDL
01 02
Se 0.06100 0.06500 0.0780 0.0820 mg/L 0.0007
Al 0.0890 0.0890 0.2800 0.2600 mg/L 0.0890
Ba 0.2600 0.2600 0.1700 0.1700 mg/L 0.0006
Be 0.0001 0.0001 0.0001 0.0001 mg/L 0.0001
Cd 0.0023 0.0023 0.0023 0.0023 mg/L 0.0023
Ca 66.0000 67.0000 17.0000 16.0000 mg/L 0.0099
Cr 0.0044 0.0044 0.0088 0.0094 mg/L 0.0044
Co 0.0080 0.0080 0.0080 0.0080 mg/L 0.0080
Cu 0.0084 0.0084 0.0084 0.0084 mg/L 0.0084
Fe 0.0037 0.0037 0.2700 0.2600 mg/L 0.0037
Mg 14.0000 14.0000 1.6000 1.6000 mg/L 0.0047
Mn 0.0110 0.0048 0.0020 0.0024 mg/L 0.0012
Mo 0.0270 0.0270 0.0270 0.0270 mg/L 0.0270
Ni 0.0140 0.0100 0.0070 0.0070 mg/L 0.0070
K 0.7200 0.6100 0.6100 0.6100 mg/L 0.6100
Na 5.7000 5.8000 2.0000 2.1000 mg/L 0.1200
V 0.0150 0.0150 0.0150 0.0150 mg/L 0.0150
Zn 0.0025 0.0025 0.0240 0.0240 mg/L 0.0025
Results: PCO-02
mg/L PCW-01 PCW-02 18MΩ-cm 18MΩ-cm Units EDL
01 02
Se 0.0310 0.0290 0.0380 0.0400 mg/L 0.0007
Al 0.0890 0.0890 2.8000 2.5000 mg/L 0.0890
Ba 0.3000 0.2900 0.2000 0.1900 mg/L 0.0006
Be 0.0001 0.0001 0.0001 0.0001 mg/L 0.0001
Cd 0.0023 0.0023 0.0023 0.0023 mg/L 0.0023
Ca 59.0000 59.0000 9.6000 9.9000 mg/L 0.0099
Cr 0.0044 0.0044 0.0760 0.0780 mg/L 0.0044
Co 0.0080 0.0080 0.0080 0.0080 mg/L 0.0080
Cu 0.0084 0.0084 0.0084 0.0084 mg/L 0.0084
Fe 0.0037 0.0037 2.0000 1.8000 mg/L 0.0037
Mg 13.0000 13.0000 1.2000 1.2000 mg/L 0.0047
Mn 0.0017 0.0012 0.0270 0.0260 mg/L 0.0012
Mo 0.0270 0.0270 0.0270 0.0270 mg/L 0.0270
Ni 0.0070 0.0070 0.0140 0.0140 mg/L 0.0070
K 0.6100 0.6100 0.6100 0.6100 mg/L 0.6100
Na 5.7000 5.7000 2.1000 2.3000 mg/L 0.1200
V 0.0150 0.0150 0.0370 0.0360 mg/L 0.0150
Zn 0.0025 0.0025 0.0870 0.0780 mg/L 0.0025
78
Results: PCO-03
mg/L PCW-01 PCW-02 18MΩ-cm 18MΩ-cm Units EDL
01 02
Se 0.1900 0.1900 0.1900 0.2100 mg/L 0.0007
Al 0.0890 0.0890 0.0930 0.1700 mg/L 0.0890
Ba 0.1400 0.1200 0.0990 0.0960 mg/L 0.0006
Be 0.0001 0.0001 0.0001 0.0001 mg/L 0.0001
Cd 0.0023 0.0023 0.0023 0.0023 mg/L 0.0023
Ca 140.00 140.00 88.00 99.00 mg/L 0.0099
Cr 0.0044 0.0044 0.0044 0.0044 mg/L 0.0044
Co 0.0080 0.0080 0.0080 0.0090 mg/L 0.0080
Cu 0.0084 0.0120 0.0230 0.0340 mg/L 0.0084
Fe 0.0037 0.0037 0.0037 0.0037 mg/L 0.0037
Mg 16.0000 16.0000 3.6000 3.9000 mg/L 0.0047
Mn 0.0059 0.0052 0.0034 0.0042 mg/L 0.0012
Mo 0.0800 0.0770 0.1000 0.0850 mg/L 0.0270
Ni 0.0430 0.0460 0.0180 0.0280 mg/L 0.0070
K 0.6200 1.1000 1.0000 1.7000 mg/L 0.6100
Na 5.8000 5.9000 2.6000 2.7000 mg/L 0.1200
V 0.0150 0.0150 0.0150 0.0160 mg/L 0.0150
Zn 0.0380 0.0091 0.0025 0.0034 mg/L 0.0025
Results: PCO-04
PCW-01 PCW-02 18MΩ-cm 18MΩ-cm Units EDL
01 02
Se 0.0720 0.0710 0.0790 0.0770 mg/L 0.0007
Al 0.1600 0.1000 1.0000 0.8900 mg/L 0.0890
Ba 0.2300 0.2800 0.1900 0.1900 mg/L 0.0006
Be 0.0001 0.0001 0.0001 0.0001 mg/L 0.0001
Cd 0.0023 0.0023 0.0023 0.0023 mg/L 0.0023
Ca 59.0000 60.0000 11.0000 11.0000 mg/L 0.0099
Cr 0.0044 0.0044 0.0900 0.0830 mg/L 0.0044
Co 0.0080 0.0080 0.0080 0.0080 mg/L 0.0080
Cu 0.0250 0.0200 0.0210 0.0170 mg/L 0.0084
Fe 0.0037 0.0037 0.7300 0.6600 mg/L 0.0037
Mg 11.0000 11.0000 1.1000 1.1000 mg/L 0.0047
Mn 0.0041 0.0028 0.0062 0.0059 mg/L 0.0012
Mo 0.0270 0.0270 0.0270 0.0270 mg/L 0.0270
Ni 0.0220 0.0230 0.0310 0.0270 mg/L 0.0070
K 1.9000 2.2000 0.9000 1.8000 mg/L 0.6100
Na 5.5000 5.7000 2.4000 2.3000 mg/L 0.1200
V 0.1200 0.1200 0.1500 0.1500 mg/L 0.0150
Zn 0.0097 0.0073 0.0760 0.0690 mg/L 0.0025
79
Results: PC-CH
PCW-01 PCW-02 18MΩ-cm 18MΩ-cm Units EDL
01 02
Se 0.0007 0.0007 0.0025 0.0020 mg/L 0.0007
Al 0.0890 0.0890 2.8000 2.4000 mg/L 0.0890
Ba 0.3500 0.3300 0.3300 0.3700 mg/L 0.0006
Be 0.0001 0.0001 0.0001 0.0001 mg/L 0.0001
Cd 0.0023 0.0023 0.0023 0.0023 mg/L 0.0023
Ca 44.0000 44.0000 3.2000 3.1000 mg/L 0.0099
Cr 0.0044 0.0044 0.2500 0.2100 mg/L 0.0044
Co 0.0080 0.0080 0.0080 0.0080 mg/L 0.0080
Cu 0.0084 0.0084 0.0084 0.0084 mg/L 0.0084
Fe 0.0037 0.0037 1.9000 1.6000 mg/L 0.0037
Mg 11.0000 11.0000 0.6400 0.6200 mg/L 0.0047
Mn 0.0016 0.0026 0.0015 0.0022 mg/L 0.0012
Mo 0.0270 0.0270 0.0270 0.0270 mg/L 0.0270
Ni 0.0220 0.0280 0.0220 0.0200 mg/L 0.0070
K 0.6100 0.6100 0.6100 0.6100 mg/L 0.6100
Na 6.4000 6.4000 2.4000 3.0000 mg/L 0.1200
V 0.0150 0.0170 0.0620 0.0530 mg/L 0.0150
Zn 0.0410 0.0460 0.1100 0.4100 mg/L 0.0025
80
B.1 WATER
14 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 2700 1600 700 180 17.0 8.00 30.0 120 15.0 7.70 32.0 µg/L
B 2600 950 300 250 18.0 9.40 38.0 79.0 15.0 8.90 37.0 µg/L
C 2700 810 360 720 19.0 11.0 50.0 120 12.0 8.80 40.0 µg/L
Avg 2667 1120 453 383 18.0 9.47 39.3 106 14.0 8.47 36.3 µg/L
mole 33.8 14.2 5.74 4.85 0.228 0.120 0.498 1.35 0.177 0.107 0.460 µmol/L
per mL 0.0338 0.0142 0.00574 0.00485 0.000228 0.000120 0.000498 0.00135 0.000177 0.000107 0.000460 µmol
per sample 0.608 0.265 0.111 0.0971 0.00433 0.00252 0.00863 0.0265 0.00349 0.00236 0.00782 µmol
12.2 5.30 2.22 1.94 0.0866 0.0504 0.173 0.530 0.0698 0.0472 0.156 µmol/kg
soil
28 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 3100 530 480 27.0 16.0 6.90 16.0 33.0 15.0 5.80 23.0 µg/L
B 2800 440 150 43.0 19.0 6.70 8.80 38.0 16.0 6.80 26.0 µg/L
C 2500 400 430 24.0 14.0 7.70 12.0 41.0 17.0 7.60 24.0 µg/L
Avg 2800 457 353 31.3 16.3 7.10 12.3 37.3 16.0 6.73 24.3 µg/L
mole 35.5 5.78 4.48 0.397 0.207 0.0900 0.155 0.473 0.203 0.0850 0.308 µmol/L
per mL 0.0355 0.00578 0.00448 0.000397 0.000207 0.0000900 0.000155 0.000473 0.000203 0.0000850 0.000308 µmol
per sample 0.567 0.0983 0.0791 0.00781 0.00366 0.00183 0.00254 0.00819 0.00344 0.00173 0.00545 µmol
11.3 1.97 1.58 0.156 0.0731 0.0366 0.0507 0.164 0.0689 0.0347 0.109 µmol/kg
soil
Cadmium
14 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 0.0330 0.0320 0.0270 0.0260 0.0820 0.00470 0.0230 0.0200 0.0550 0.00290 0.0260 µg/L
B 0.0310 0.0250 0.0290 0.0260 0.0780 0.00510 0.0230 0.0240 0.0630 0.00260 0.0270 µg/L
C 0.0290 0.0290 0.0270 0.0260 0.0750 0.00330 0.0260 0.0260 0.0400 0.00270 0.0320 µg/L
Avg 0.0310 0.0287 0.0277 0.0260 0.0783 0.00437 0.0240 0.0233 0.0527 0.00273 0.0283 µg/L
mole 0.000276 0.000255 0.000246 0.000231 0.000697 0.0000388 0.000214 0.000208 0.000469 0.0000243 0.000252 µmol/L
per mL 2.76E-07 2.55E-07 2.46E-07 2.31E-07 6.97E-07 3.88E-08 2.14E-07 2.08E-07 4.69E-07 2.43E-08 2.52E-07 µmol
per sample 4.96E-06 4.76E-06 4.76E-06 4.63E-06 1.32E-05 8.16E-07 3.70E-06 4.08E-06 9.22E-06 5.35E-07 4.28E-06 µmol
9.93E-05 9.52E-05 9.52E-05 9.25E-05 0.000265 1.63E-05 7.40E-05 8.17E-05 0.000184 1.07E-05 8.57E-05 µmol/kg
soil
no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 0.0160 0.0460 0.0370 0.0160 0.0880 0.00400 0.0230 0.0220 0.0860 0.00370 0.0230 µg/L
B 0.0360 0.0420 0.0260 0.0250 0.0760 0.00880 0.0210 0.0240 0.0750 0.00360 0.0260 µg/L
C 0.0560 0.0610 0.0290 0.0240 0.0830 0.00810 0.0290 0.0290 0.0730 0.00250 0.0250 µg/L
Avg 0.0360 0.0497 0.0307 0.0217 0.0823 0.00697 0.0243 0.0250 0.0780 0.00327 0.0247 µg/L
mole 0.000320 0.000442 0.000273 0.000193 0.000732 0.0000620 0.000216 0.000222 0.000694 0.0000291 0.000219 µmol/L
per mL 3.20E-07 4.42E-07 2.73E-07 1.93E-07 7.32E-07 6.20E-08 2.16E-07 2.22E-07 6.94E-07 2.91E-08 2.19E-07 µmol
per sample 5.12E-06 7.51E-06 4.82E-06 3.79E-06 1.29E-05 1.26E-06 3.53E-06 3.85E-06 1.18E-05 5.91E-07 3.88E-06 µmol
1.02E-04 1.50E-04 9.64E-05 7.58E-05 2.59E-04 2.52E-05 7.07E-05 7.71E-05 2.36E-04 1.18E-05 7.75E-05 µmol/kg
soil
Copper
14 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 0.0660 0.0610 0.0540 0.0530 0.120 0.0400 0.0540 0.0430 0.100 0.0240 0.0350 µg/L
B 0.0540 0.0370 0.0430 0.0440 0.120 0.0400 0.0530 0.0580 0.100 0.0330 0.0320 µg/L
C 0.0580 0.0550 0.0530 0.0460 0.130 0.0410 0.0540 0.0390 0.0920 0.0260 0.0320 µg/L
Avg 0.0593 0.0510 0.0500 0.0477 0.123 0.0403 0.0537 0.0467 0.0973 0.0277 0.0330 µg/L
mole 0.000934 0.000803 0.000787 0.000750 0.00194 0.000635 0.000844 0.000734 0.00153 0.000435 0.000519 µmol/L
per mL 9.34E-07 8.03E-07 7.87E-07 7.50E-07 1.94E-06 6.35E-07 8.44E-07 7.34E-07 1.53E-06 4.35E-07 5.19E-07 µmol
per sample 1.68E-05 1.50E-05 1.52E-05 1.50E-05 3.69E-05 1.33E-05 1.46E-05 1.44E-05 3.01E-05 9.58E-06 8.83E-06 µmol
0.000336 0.000300 0.000304 0.000300 0.000737 0.000267 0.000293 0.000289 0.000603 0.000192 0.000177 µmol/kg
soil
28 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 0.0420 0.0680 0.0790 0.0420 0.140 0.0520 0.0650 0.0550 0.120 0.0300 0.0350 µg/L
B 0.0590 0.0560 0.0470 0.0490 0.150 0.0700 0.0490 0.0610 0.100 0.0300 0.0400 µg/L
C 0.0710 0.0620 0.0550 0.0600 0.130 0.0630 0.0730 0.0540 0.0980 0.0330 0.0310 µg/L
Avg 0.0573 0.0620 0.0603 0.0503 0.140 0.0617 0.0623 0.0567 0.106 0.0310 0.0353 µg/L
mole 0.000902 0.00098 0.000949 0.000792 0.00220 0.00097 0.00098 0.000892 0.00167 0.000488 0.000556 µmol/L
per mL 9.02E-07 9.76E-07 9.49E-07 7.92E-07 2.20E-06 9.70E-07 9.81E-07 8.92E-07 1.67E-06 4.88E-07 5.56E-07 µmol
per 1.44E-05 1.66E-05 1.68E-05 1.56E-05 3.89E-05 1.97E-05 1.60E-05 1.55E-05 2.84E-05 9.92E-06 9.82E-06 µmol
sample
2.89E-04 3.32E-04 3.36E-04 3.12E-04 7.79E-04 3.95E-04 3.20E-04 3.09E-04 5.67E-04 1.98E-04 1.96E-04 µmol/kg
soil
Nickel
14 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 0.220 0.190 0.170 0.160 1.70 0.290 0.200 0.140 1.60 0.240 0.190 µg/L
B 0.180 0.170 0.170 0.180 1.60 0.320 0.180 0.160 1.90 0.310 0.220 µg/L
C 0.180 0.190 0.180 0.170 1.60 0.280 0.200 0.160 1.80 0.290 0.220 µg/L
Avg 0.193 0.183 0.173 0.170 1.63 0.297 0.193 0.153 1.77 0.280 0.210 µg/L
mole 0.00329 0.00312 0.00295 0.00290 0.0278 0.00505 0.00329 0.00261 0.0301 0.00477 0.00358 µmol/L
per mL 3.29E-06 3.12E-06 2.95E-06 2.90E-06 2.78E-05 5.05E-06 3.29E-06 2.61E-06 3.01E-05 4.77E-06 3.58E-06 µmol
per sample 5.93E-05 5.83E-05 5.71E-05 5.79E-05 0.000529 0.000106 5.71E-05 5.14E-05 0.000592 0.000105 6.08E-05 µmol
0.00119 0.00117 0.00114 0.00116 0.0106 0.00212 0.00114 0.00103 0.0118 0.00210 0.00122 µmol/kg
soil
28 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 0.100 0.230 0.250 0.110 1.70 0.210 0.480 0.140 1.20 0.280 0.290 µg/L
B 0.180 0.230 0.160 0.150 1.60 0.290 0.380 0.150 1.30 0.240 0.290 µg/L
C 0.230 0.320 0.160 0.160 1.60 0.250 0.420 0.170 1.00 0.230 0.280 µg/L
Avg 0.170 0.260 0.190 0.140 1.63 0.250 0.427 0.153 1.17 0.250 0.287 µg/L
mole 0.00290 0.00443 0.00324 0.00239 0.0278 0.00426 0.00727 0.00261 0.0199 0.00426 0.00488 µmol/L
per mL 2.90E-06 4.43E-06 3.24E-06 2.39E-06 2.78E-05 4.26E-06 7.27E-06 2.61E-06 1.99E-05 4.26E-06 4.88E-06 µmol
per sample 4.63E-05 7.53E-05 5.72E-05 4.69E-05 0.000492 8.66E-05 0.000119 4.53E-05 0.000338 8.66E-05 8.63E-05 µmol
9.27E-04 1.51E-03 1.14E-03 9.38E-04 9.83E-03 1.73E-03 2.37E-03 9.05E-04 6.76E-03 1.73E-03 1.73E-03 µmol/kg
soil
Zinc
14 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 0.280 0.200 0.230 0.220 0.830 0.110 0.150 0.220 0.760 0.190 0.260 µg/L
B 0.220 0.230 0.220 0.460 0.910 0.110 0.230 0.290 0.820 0.240 0.300 µg/L
C 0.160 0.240 0.180 0.200 0.810 0.0710 0.220 0.250 0.540 0.170 0.310 µg/L
Avg 0.220 0.223 0.210 0.293 0.850 0.0970 0.200 0.253 0.707 0.200 0.290 µg/L
mole 0.00336 0.00342 0.00321 0.00449 0.0130 0.00148 0.00306 0.00387 0.0108 0.00306 0.00444 µmol/L
per mL 3.36E-06 3.42E-06 3.21E-06 4.49E-06 1.30E-05 1.48E-06 3.06E-06 3.87E-06 1.08E-05 3.06E-06 4.44E-06 µmol
per sample 6.06E-05 6.38E-05 6.21E-05 8.97E-05 0.000247 3.12E-05 5.3E-05 7.62E-05 0.000213 6.73E-05 7.54E-05 µmol
0.00121 0.00128 0.00124 0.00179 0.00494 0.000623 0.00106 0.00152 0.00425 0.00135 0.00151 µmol/kg
soil
28 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 0.170 0.550 0.190 0.150 0.600 0.120 0.340 0.160 0.660 0.170 0.280 µg/L
B 0.500 0.640 0.220 0.170 0.560 0.160 0.340 0.190 0.570 0.0990 0.290 µg/L
C 0.790 0.970 0.150 0.150 0.620 0.120 0.350 0.210 0.660 0.150 0.310 µg/L
Avg 0.487 0.720 0.187 0.157 0.593 0.133 0.343 0.187 0.630 0.140 0.293 µg/L
mole 0.00744 0.0110 0.00286 0.00240 0.00908 0.00204 0.00525 0.00286 0.00964 0.00214 0.00449 µmol/L
per mL 7.44E-06 1.10E-05 2.86E-06 2.40E-06 9.08E-06 2.04E-06 5.25E-06 2.86E-06 9.64E-06 2.14E-06 4.49E-06 µmol
per sample 0.000119 0.000187 5.04E-05 4.71E-05 0.000160 4.15E-05 8.58E-05 4.95E-05 0.000164 4.34E-05 7.93E-05 µmol
2.38E-03 3.74E-03 1.01E-03 9.43E-04 3.21E-03 8.29E-04 1.72E-03 9.90E-04 3.28E-03 8.69E-04 1.59E-03 µmol/kg
soil
Manganese
14 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 0.340 0.600 0.700 0.500 3.10 11.0 2.60 1.50 4.00 10.0 2.70 µg/L
B 0.330 0.760 0.890 1.00 3.10 13.0 2.30 1.60 4.70 11.0 2.70 µg/L
C 0.310 0.670 1.10 0.590 2.80 12.0 2.30 1.50 4.40 12.0 2.60 µg/L
Avg 0.327 0.677 0.897 0.697 3.00 12.0 2.40 1.53 4.37 11.0 2.67 µg/L
mole 0.00595 0.0123 0.0163 0.0127 0.0546 0.218 0.0437 0.0279 0.0795 0.200 0.0485 µmol/L
per mL 5.95E-06 1.23E-05 1.63E-05 1.27E-05 5.46E-05 2.18E-04 4.37E-05 2.79E-05 7.95E-05 2.00E-04 4.85E-05 µmol
per sample 0.000107 0.000230 0.000315 0.000254 0.00104 0.00459 0.000757 0.000549 0.00156 0.00440 0.000825 µmol
0.00214 0.00460 0.00631 0.00507 0.0207 0.0917 0.0151 0.0110 0.0313 0.0881 0.0165 µmol/kg
soil
28 day no tmt SRB c-Fe mb-Fe Fe(III)-tpA PW PS mb- Fe(III)-tpA PW/SRB PS/SRB units
Fe/SRB /SRB
A 0.150 0.780 0.970 1.60 4.20 8.70 11.0 2.10 4.20 9.30 5.10 µg/L
B 0.320 0.800 1.20 1.40 3.70 9.60 8.50 1.60 4.00 8.70 5.10 µg/L
C 0.400 0.950 0.740 1.60 4.20 8.60 9.60 1.80 4.30 7.30 4.50 µg/L
Avg 0.290 0.843 0.970 1.53 4.03 8.97 9.70 1.83 4.17 8.43 4.90 µg/L
mole 0.00528 0.0154 0.0177 0.0279 0.0734 0.163 0.177 0.0334 0.0758 0.154 0.0892 µmol/L
per mL 5.28E-06 1.54E-05 1.77E-05 2.79E-05 7.34E-05 1.63E-04 1.77E-04 3.34E-05 7.58E-05 1.54E-04 8.92E-05 µmol
per sample 8.45E-05 0.000261 0.000312 0.000549 0.00130 0.00332 0.00288 0.000578 0.00129 0.00312 0.00158 µmol
1.69E-03 5.22E-03 6.24E-03 1.10E-02 2.59E-02 6.64E-02 5.77E-02 1.16E-02 2.58E-02 6.24E-02 3.15E-02 µmol/kg
soil
92
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