fltO STj,
\ PflO^°
HAZARDOUS
SITE CONTROL
DIVISION
Remedial
Planning/
Field
Investigation
(REM/FIT)
ZONE II
'•;:.>:::. ,-. .-..FINAL*
WASTE SOIL. TREATMENT STUDY
CELTOR CHEMICAL WORKS SITE
HOOPA, CALIFORNIA
WA 121.9L280
W69628.00
SEPTEMBER 1986
CONTRACT NO.
68-01-6692
CH2MBHILL.
Ecology&
Environment
-------
FINAL
WASTE SOIL TREATMENT STUDY
CELTOR CHEMICAL WORKS SITE
HOOPA, CALIFORNIA
WA .121.9L280
W69628.00
SEPTEMBER 1986
-------
CONTENTS
Executive Summary ES-1
Previous Investigations ES-1
Treatment Study ES-3
Introduction 1-1
Conceptual Treatment Process and 1-1
Objectives of Study
Scope of Work 1-2
Performance of Extraction Study 2-1
Mechanical Soil Characterization 2-1
Extraction Methodology 2-2
Characterization and Extraction Results 3-1
Soil Characterization , 3-1
Leaching Data 3-6
Extraction Summary • 3-14
Discussion of Results 4-1
Summary 4-1
Conclusions 4-2
Appendix A—Description of Initial Soil
Characterization
Appendix B—Detailed Description of Leaching
Procedure and Evaluation of
Extraction
TABLES
2-1 Sample Identification 2-1
3-1 Raw Soil Characterization 3-2
3-2 STLC Values of Soil Samples 3-6
3-3 Extraction of Soil Sample 1 3-7
3-4 Extraction of Soil Sample 2 3-8
3-5 Extraction of Soil Sample 3 3-9
3-6 Extraction of Combined Sample 486 3-10
-------
CONTENTS (Continued)
TABLES
3-7 Extraction of Soil Sample 5 3-11
3-8 Extraction of Soil Sample 1, 3-15
Extraction Efficiencies
3-9 Extraction of Soil Sample 2, • 3-16
Extraction Efficiencies
3-10 Extraction of Soil Sample 3, 3-17
Extraction Efficiencies
3-11 Extraction of Combined Soil Samples 4 3-18
and 6, Extraction Efficiencies
3-12 Extraction of Soil Sample 5, ' 3-19
Extraction Efficiencies
FIGURES Follows
Page
1-1 Process Schematic for Onsite Treatment 1-1
of Contaminated Celtor Chemical Works Soil
2-1 Soil Sample Locations for Celtor Chemical 2-1
Works Extraction Studies
3-1 Summary of Extraction Efficiencies, 3-19
No. 10 Passing
3-2 Summary of Extraction Efficiencies, 3-19
• No. 10 to 1 inch
RD/R16/031
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EXECUTIVE SUMMARY
The Celtor Chemical Works site is located within the Hoopa
valley Indian Reservation in northwestern California. The
plantsite was leased from the U.S. Bureau of Indian Affairs
(BIA), acting as a representative for the Hoopa Valley
Indian Tribe. The site covers approximately 2.5 acres and
is located at the base of a steep hill and just above a
relatively flat pasture. The Trinity River is located about
800 feet west of the site.
The ore processing plant that operated at this location
between 1957 and 1962 primarily handled sulfide ore from the
nearby Copper Bluff Mine. Ore brought to the plant was
processed for copper, zinc, and precious metals. Ore was
hauled into the plant, unloaded at the upper (eastern) side,
and moved through several processes down to the lower side.
The complete process used at the plant is not known, but
based on the equipment and structures left on the site, it
is thought to have included crushing and vat leaching of the
ore.
Tailings were stored in piles situated at the lower south
corner of the plantsite. Wastewater containing some tail-
ings was reportedly sluiced down the gully northward to a
settling pond on the gravel bar adjacent to the Trinity
River.
The plant operations were suspended in 1962, following
California Pish and Game citations for fishkills apparently
resulting from an uncontrolled discharge from a waste
holding pond located next to the Trinity River. It is not
known if other factors also prompted this closure.
Following closure, some processing wastes (tailings)
remained in the plant area, and apparently contaminated soil
migrated into the adjacent pasture. Ponded water with high
pH was also present in the plant and pasture areas. Pro-
cessing vats and ore bins in the plant contained ore and
tailings. A drainage ditch leading north from the plant to
the Trinity River may have been used as a sluice trench and
had apparently collected deposits of tailings. ,
The present owner of the land on which the site is located
is the Hoopa Valley Indian Tribe.
PREVIOUS INVESTIGATIONS
In July 1981, the site was identified in a California state-
wide abandoned industrial waste facility survey. in August
RD/R34/030 ES-1
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1981, the Indian Health Service submitted to EPA a Notifi-
cation of Hazardous Waste Site under the Comprehensive
Environmental Response, Compensation, and Liability Act of
1980 (CERCLA). Soil sampling on the site and laboratory
analyses were performed in July 1981 by the California
Department of Health Services (DOHS). In February 1982,
soil samples were taken and analyzed by the EPA Field
Investigation Team.
In April 1982, the site was placed on the California State
Priority List, and on December 20, 1982, the site was
proposed for inclusion on the National Priorities List. In
late 1982, DOHS again took surface soil samples. Analyses
of these samples indicated that portions of the site con-
tained soils with concentrations of heavy metals exceeding
the state criteria that defined materials as hazardous.
Metals identified on the site in concentrations exceeding
these limits included arsenic, cadmium, copper, mercury, and
zinc. Concentrations of lead in some areas approached, but
did not exceed, the limits.
To reduce the threat of human exposure of hazardous sub-
stances, EPA decided to expedite removal of all known
sources of contamination. A focused feasibility study to
evaluate and select initial remedial measures (IRM's) for
the Celtor Chemical Works site was completed on August 15,
1983. Results of the focused feasibility study indicated
that removing approximately 1,400 cubic yards of contami-
nated material from the site and adjacent pasture to an
acceptable Class I disposal site was the most cost-
effective solution. Therefore, EPA and the state selected
this removal alternative, and the removal was completed by
December 18, 1983,
During the IRM implementation, material similar in appear-
ance to the tailings was identified in other areas of the
site that had not been identified in the previous samplings.
There also appeared to be contaminated material beneath the
tailings pile. Therefore, it was likely that more work
would be required to provide a permanent remedy. In
October 1984, a remedial investigation (RI) was begun to
further define the extent of remaining hazardous materials.
The RI involved an extensive sampling program to
characterize the soil, surface water, and groundwater at the
site. A total of 181 surface and subsurface soil samples
were taken, 3 monitoring wells were drilled and sampled/ and
19 surface water samples were taken from throughout the site
and the adjacent river.
California Assessment Manual (CAM) TTLC criteria were used
to determine if hazardous materials were present. Metals
most frequently found to be present in excess of CAM limits
RD/R34/030 ES-2
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were cadmium, copper, iron, lead, and zinc. Many of the
soil samples were found to have pH values in the range of 2
to 4.
U.S. EPA 24-Hour Ambient Water Quality Criteria for Aquatic
Life (WQCAL) and Federal Drinking Water Regulations (DWR's)
were used to evaluate water quality for the project. Sur-
face water flowing within and leaving the site exceeds the
DWR's for cadmium, copper, iron, and zinc, and the WQCAL for
cadmium, copper, mercury, silver, and zinc. Water in the
lower drainage gully that discharges into the Trinity River
(combined upgradient and site runoff) exceeds both DWR's and
WQCAL for cadmium, copper, iron, and zinc.
A public health assessment was performed to evaluate the
release mechanisms and the potential for human health and
environmental exposure risks. Based on this assessment,
implementation of the No-Action Alternative (doing nothing
to remedy the site conditions) may result in an excessive
risk of cancer from exposure to arsenic and cadmium and
long-term toxic effects related to copper and lead exposure.
Subsequent to the remedial investigation report, a draft
feasibility study report was issued on June 28, 1985. This
report presented five alternatives which were to be used by
EPA for recommendation for a cost-effective remedial action.
In addition to a summary of previously gathered information
and a recap of site history, the feasibility study provided
a conceptual overview of the five selected alternatives and
a summary of the methodology used to develop these alterna-
tives. The five alternatives selected were:
1. No action
2. Capping
3. Removal
4. Encapsulation
5. Treatment
Although treatment (Alternative 5) appeared to be the most
costly, it had the advantages of permanently removing the
contaminants from access to human contact and possibly pre-
venting the wastes from being taken a great distance to
acceptable landfills. Because of these advantages, a pro-
gram was initiated to study the feasibility of treating the
Celtor wastes.
TREATMENT STUDY
The draft feasibility study indicated that additional
laboratory testing was necessary to define the extraction
process to be used for treatment of hazardous soils. Once
the treatment process was better defined, a more refined
RD/R34/030 ES-3
-------
cost estimate could be developed. The Treatment Alternative
provides benefits to the public health and welfare and to
the environment that are similar to those provided by the
Removal Alternative, and better than those provided by
Capping or Encapsulation. It would comply with all state
and federal environmental laws. Long-term use of the land
for other beneficial uses would be allowed, and no ground-
water or surface water monitoring program would be neces-
sary. Maintenance on the site would only be necessary while
new vegetation was becoming established.
The purpose of the treatment study was to further define the
extraction process needed to remove the hazardous substances
to established cleanup levels and develop a cost estimate to
implement the treatment alternative.
The treatment study was initiated by collecting bulk soil
samples from six locations at the Celtor site. Samples from
two of these locations were combined and tested because of
their similarities, and the remaining four samples were
tested individually. Each of the soil samples was charac-
terized to determine its mass fraction and content of
arsenic, cadmium, copper, lead, and zinc for the following
gradations: No. 10 passing, No. 10 to No. 6, No• 6 to
No. 3, NO. 3 to 1/2-inch, 1/2-inch to 1-inch, and 1-inch
plus. :
Extraction testing was performed on the No. lOrpassing por-
tion and on the No. 10 to 1-inch portion of each soil sample
(five samples total including the one combined sample), No
extractions were attempted for the 1-inch-plus portions of
the soil sample.
Five solutions were used to perform the extraction tests:
1. Sodium gluconate—10 percent by weight aqueous
solution adjusted to a pH of 12 to 13
2. Ethylenediaminetetraacetic acid (EDTA)—13 percent
by weight aqueous solution adjusted to a pH of 6
to 7
3. Acetic acid—10 percent by volume aqueous solution
4. Hydrochloric acid (HCl)—Aqueous solution pH of
1.0 (approximately 1/10 molar)—some of the
extractions were accomplished with a pH
0.8 solution (see text)
Hydrochloric acid/hydrogen peroxide (HCl/H-O-)—
HCl aqueous solution pH o£ 1.0, H202 concentratioi
of approximately 0.05 molar (H-0- aclded to the pH
1.0 solution)
RD/R34/030 ES-4
-------
Except in a few cases, none of the extractants were able to
reduce the concentration of metals in the soil to below
cleanup levels if the soil was initially above ;the cleanup
level. In no case did an extractant reduce the concentra-
tion of more than one metal to below cleanup levels. The
most likely reason that extraction efficiencies were poor is
that a large portion of the metals in the soil are bound up
as insoluble sulfides which require severe conditions (high
temperature oxidation) for mobilization and subsequent
removal of metals.
One goal of this study was to perform a cost estimate of the
full-scale extraction process. Because of the lack of
extraction success, it was decided that a cost estimate
would not be meaningful, and it was .therefore not performed.
RD/R34/030
RD/R34/030 ES_5
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Chapter 1
INTRODUCTION
The draft feasibility study report dated June 28, 1985, for
the Celtor Chemical Works site presented five remedial
action alternatives for the site. These were:
o Alternative 1—No Action
o Alternative 2—Capping
o Alternative 3—Removal
o Alternative 4—Encapsulation
o Alternative 5—Treatment
The draft feasibility study report stated "The Treatment
Alternative is the most expensive to implement, costing an
estimated $5.8 million. Additional laboratory testing is
necessary to define the acid extraction process to be used
for treatment of hazardous soils. Once the treatment pro-
cess is better defined, a more refined cost estimate can be
developed. The Treatment Alternative provides benefits to
the public health and welfare and to the environment that
are similar to those provided by the Removal Alternative,
and better than those provided by Capping or Encapsulation.
It would comply with all state and federal environmental
laws. Long-term use of the land for other beneficial uses
would be allowed, and no groundwater or surface water moni-
toring program would be necessary. Maintenance on the site
would only be necessary while new vegetation was becoming
established."
Although the above quote refers specifically to an acid
extraction process, the scope of the bench-scale extraction
study was not limited to low pH extractants, as will be
described in the following sections. '.
CONCEPTUAL TREATMENT PROCESS AND OBJECTIVES OF STUDY
The conceptual treatment process that was developed during
the preparation of the feasibility study is shown in Figure
1-1. This process is consistent with the technology that is
in the process of development and field verification by the
EPA Office of Research and Development (ORD). The basic
concept is to remove the metals of concern (arsenic,
cadmium, copper, lead, and zinc) from the contaminated soil
by dissolving the metals into a leaching (extractant)
solution. The metals would then be removed from the
leaching solution by precipitating them as insoluble salts
such as sulfides, hydroxides, etc., thus producing a metal
sludge. The metal sludge would be dewatered and hauled to a
landfill. The soil remaining from the extraction process
would be washed and then used as backfill at the site.
RD/R16/026 1-1
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SCtetUIUfr
S
si&i^, ww*oa*
\ MAIEtttAL SLlHttflUt-
/-
warts.
stuetutit
WATER
-f-
If HIT
RtMBVAL
it,
Sept 1986
UU865SJ
£UVa.QliEl
UtCHtUG-
^y
SOIL
7UICKEUEH
ftWWMU
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Figure 1-1
PROCESS SCHEMATIC FOR ON-SITE TREATMENT
OF CONTAMINATED CELTOR CHEMICAL WORKS SOIL
-------
The objective of the treatment process is to reduce the con-
centration of metals in the remaining soils to below the
following site-specific cleanup levels for the Celtor site,
as described in the final feasibility study (issued
January 1986) :
Arsenic
Cadmium
Copper
Lead
Zinc
100 mg/kg
25 mg/kg
2,500 mg/kg
500 mg/kg
5,000 mg/kg
The objective of the laboratory study was to obtain data for
the cost estimate of a leaching (extraction) facility for
the Celtor Chemical Works wastes (raw ore, tailings, and
soils).
Questions to be answered by the laboratory study included:
1. Which of the Celtor wastes are suited for
leaching?
2. What particle sizes of the above wastes are best
suited for leaching, and which are best suited for
direct disposal as solids?
3. Which chemicals are best suited to the leaching
processes?
4. What are the optimum processing methods? What are
the best processing techniques that would be appli-
cable to the wastes, such as type of reactor
(batch, flow, leaching heap), residence time, pH,
mixing energy, chemical dosage, etc.?
5. What are the capital and maintenance costs of the
process?
SCOPE OF WORK
The scope of work to accomplish the above objectives
consisted of six major items, as follows:
1. A literature review and consultation with EPA and
EPA's consultants Science Applications Interna-
tional Corporation (SAIC), who are working on a
similar project, to determine which chemicals
seemed to be best suited for the proposed leaching
studies.
RD/R16/026
1-2
-------
2. Soil sample collection at the Celtor site and soil
characterization at the CH2M HILL laboratory.
3. Performance of bench-scale studies to identify
which of the chemicals selected in Step 1 are
effective extractants, and which soils are best
suited to extraction by these chemicals.
4. Further bench-scale studies to optimize chemical
dosages and contact times with the most effective
chemicals as determined in Step 3.
5. In consultation with EPA and SAIC, development of
a process train for full-scale operation and
bench-scale simulation of this train to obtain
data for a cost estimate of the process.
6. Determine if the EPA mobile soil flushing unit
could potentially be used for onsite soil
extraction.
RD/R16/026
RD/R16/026 1-3
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Chapter 2
PERFORMANCE OF EXTRACTION STUDY
MECHANICAL SOIL CHARACTERIZATION
Soil samples were obtained at the Celtor site and transpor-
ted to the Redding laboratory of CH2M HILL for character-
ization and extraction. The samples were taken from the
locations shown in Figure 2-1 and are described in Table 2-1
("Soil" will be used to mean rock, tailings, and soil
hereinafter.)
Table 2-1
SAMPLE IDENTIFICATION
Sample
Number
Adjacent
Borehole
Number
B-6
B-24
B-22
H-20
Previous
Sample
Numbers
(see RI/FS)
108, 109
001, 002
055, 056
058, 060
157, 177
H-8
H-21
146
168, 171
Depth
(feet)
0-2.5
0-2.5
0-2.5
0-4
1-1.5
0-2
Soil Description
Mixed silt, sand, and
gravel, dark gray-brown,
moist, odor
Sandy gravel with cobbles,
brown, slightly moist,
contains ore materials
Mixed clay, silt, sand,
gravel, and cobbles, rust-
brown, hard, dry
Fine sand, selected tail-
ing material, some phyl-
lite rock pieces and soil
mixed in, gray, dry
Sandy clay, yellow-brown-
gray, nearly dry, selected
layer
Fine sand, selected tail-
ing material, some phyl-
lite rock pieces and soil
mixed in, gray, moist
RD/R16/027
2-1
-------
Sept 1986
Figure 2-1
SOIL SAMPLE LOCATIONS FOR
CELTOR CHEMICAL WORKS
EXTRACTION STUDIES
-------
Each soil sample was analyzed for mass fraction of the
following size gradations:
o No. 10-passing
o No. 10 to No. 6
o No. 6 to No. 3
o No. 3 to 1/2 inch
o 1/2 inch to 1 inch
o 1 inch retained
A complete description of soil,characterization methodology
is given in Appendix A. Note that Samples 4 and 6 were
combined for extraction because of their similar nature.
All other samples were to be extracted separately.
EXTRACTION METHODOLOGY
From discussions with EPA personnel {Region IX and members
of ORD) and SAIC, the following procedure for handling the
soil samples was agreed upon:
1. Leaching tests were to be performed on the frac-
tion of each sample passing a No. 10 sieve (2 mm)
and the fraction between the No. 10 sieve and 1 inch,
These fractions correspond to the fractions treated
in the mobile unit mentioned earlier, with the
exception that the coarse screen on the mobile
unit is 1 inch x 1-1/2 inches, and would therefore
pass some solids larger than 1 inch. The total
metals content of the fraction larger than 1 inch
was to be analyzed, although no extraction studies
were to be performed on this portion, because it
could not be treated by the mobile unit.
2. Duplicate samples of each soil type, at a minimum,
were to be tested for both soil size fractions
(No. 10-passing and No. 10-to-inch) and each
chemical chosen. Where the results of the dupli-
cate testing were not deemed adequate to provide
good confidence in the test data, a third sample
was to be analyzed. (See Chapter 3 tables for
information on actual number of samples taken.)
3. Soluble Threshold Limit Concentration (STLC)
analyses were to be performed on the five soil
types, for arsenic, cadmium, copper, lead, and
zinc.
4. Analysis of a precipitate found in many locations
throughout the site was to be performed. This
precipitate, generally white to whitish-yellow,
was suspected of having been formed from some of
RD/R16/027 2-2
-------
the tailings onsite. It was therefore desirable
to determine its composition. The method chosen
for analysis was digestion and determination of
aluminum and sulfate and also X-ray diffraction.
LEACHING AGENTS
The following chemicals were discussed as being potentially
suitable for leaching of the soil samples:
1. Hydroxylamine
2. Sodium gluconate
3. Ethylenediaminetetraacetic acid (EDTA)
4. Hydroxyethylethylenediaminetriacetic acid (HEDTA)
5. Diethylenetriamine pentaacetic acid
6. Sodium pyrophosphate
7. Sodium dihydrophosphate
8. Disodium hydrogen phosphate
9. Sodium dithionite (sodium hydrosulfite)
10. Citric acid
11. Acetic acid
12. Nitric acid
13. Hydrochloric acid
14. Hydrochloric acid with hydrogen peroxide
15. Hypochlorous acid
Of the above, the following were chosen as the most appro-
priate solutions. (For actual starting and final pH's, see
Tables 3-3 through 3-7.)
1. Sodium gluconate—10 percent by weight solution
adjusted to a pH of 12 to 13. Experience with
this compound indicated that it might be suc-
cessful in extracting arsenic at high'pH, as well
as the remaining metals.
2. EDTA—13 percent by weight adjusted to a pH of
6 to 7. EDTA has been used on similar soil
extraction studies. Its chelating capacity for
metals made it a reasonable candidate for this
study.
3. Acetic acid--10 percent by volume. Acetic acid is
used in the STLC extraction procedure and was
therefore assumed to be a reasonable candidate for
extraction of metals.
4. HC1—Solution pH of approximately 0.8 to 1.0
(approximately 0.16 to 0.1 molar). This acid is
one of the least expensive acids. It was thought
that a very low pH might be ideal for leaching Cd,
Cu, and Zn.
RD/R16/027 2-3
-------
5. HC1/H 0 --HC1 solution pH of 0.8 to 1.0, E20 con-
centration approximately 0.16 to 0.10 molar TH2O2
was added to the HC1 solution).
Some of the reasons for rejecting the remaining chemicals as
potential extractants were as follows:
o Although hydroxylamine was suggested as a poten-
tial extractant, it is a selective extractant for
iron and manganese oxides, and was therefore deemed
to be of questionable value for the Celtor soils.
o HEDTA and diethylenetriamine pentaacetic acid
(Chemicals 4 and 5) are chelating agents, as is
EDTA. It was decided that EDTA would provide
adequate information to determine if a chelant
would be effective for this soil because EDTA has
been shown to be an effective agent in some pre-
vious studies. It was therefore deemed unneces-
sary to use other chelants.
o Chemicals 6, 7, and 8 are effective extractants
primarily for organically bound metals. As the
presence of substantial amounts of organically
bound metals in the Celtor soil was unlikely, this
extractant was rejected.
o Sodium dithionite {Chemical 9) is generally useful
on iron oxides only and was therefore rejected for
the same reasons as hydroxylamine.
o Citric acid (Chemical 10) is generally only useful
for lead extraction and was therefore considered
too specific for the purposes of this:study.
o Nitric acid (Chemical 12) was rejected because of
high cost (as opposed to HCl) and the concern with
potential discharge of nitrogen to the Trinity
River during full-scale operations.
o Hypochlorous acid (Chemical 15) was suggested
because of its oxidizing potential. As the com-
bination of HC1/H?02 was being used for the pur-
pose of obtaining potential oxidation,
hypochlorous acid was rejected.
o For this initial treatment study, only the concen-
trations of the five metals under consideration
were determined. No 'detailed study of the chemi-
cal makeup of the soils was to be performed. The
cation exchange capacity was not determined
because the relatively high concentrations of
extractants used should displace any cations bound
RD/R16/027 2-4
-------
to the soil matrix. !Also, most of the samples
were sand and gravel size. Little fine-grained
soil was present at the site.
LEACHING PROCEDURES
For Samples 1, 2, 3, 5, and Combined Samples 4 and 6, dupli-
cate leaching analyses were made for both the No. 10-passing
and No. 10-to-l-inch portions with each of the five leaching
chemicals. The only exception was Sample 5. Because
Sample 5 contained only a small mass percentage of particles
larger than No. 10, leaching analyses were not run on this
fraction.
For the No. 10-passing portion of each soil type (1, 2,
3, etc.), extractions were performed at ambient temperature
with all five extractants. In addition, extractions were
performed on pulverized (No. 200-passing) portions of each
of Sample 1 and Combined Samples 4 and 6 using EDTA and HC1
at ambient temperatures. Lastly, extractions on pulverized
and unpulverized samples of Sample 1 and Combined Samples 4
and 6 were performed with hot hydrochloric acid.
For the No. 10-to-l-inch portion of each soil sample (1, 2,
3, etc.), extractions were performed at ambient temperatures
with all extractants. No extractions were performed on pul-
verized samples or with hot hydrochloric acid. See
Appendix B for a more detailed description of extraction
procedures.
Sequential leaching by different extractants was not planned
because it was desired to see if, initially, there was a
single extractant that would provide a high degree of
removal efficiency. Use of multiple extractants in the
field would also be complicated and likely expensive; there-
fore, no sequential lab testing was planned.
Analyses of liquid samples (extractant) were performed in
accordance with EPA "Methods for Chemical Analysis of Water
and Wastewater" (EPA 600/4-79-020} and the following methods:
Arsenic - Method 206.3
Cadmium - Method 213.1
Copper - Method 220.0
Lead - Method 239.1 ;
Zinc - Method 289.1
Solids digestion and analyses were performed in accordance
with EPA's "Test Methods for Evaluation of Solid Waste,"
Method SW 846.
RD/R16/027
RD/R16/027 2-5
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Chapter 3
CHARACTERIZATION AND EXTRACTION RESULTS
SOIL CHARACTERIZATION
Table 3-1 is a detailed summary of soil characterization
data for all five soils tested (Samples 1, 2, 3, 5, and
Combined Samples 4 and 6). Listed below is an explanation
of information contained in the table, by column and row,
respectively.
o % of Total Mass—In this column the mass percen-
tage of the various size gradations of the sample
is given. In each'case, the percent refers to
percent of total dry mass of raw, unsieved,
unwashed sample.
o As (mg/kg), Cd (mg/kg), Cu (mg/kg), Pb (mg/kg), Zn
(mg/kg)—These columns give the concentration of
metal in the particular gradation of the sample
referred to by the row heading.
o As (% of total), Cd (% of total), Cu (% of total),
Pb (% of total), Zn (% of total)—These columns
give the amount (as a % of the total content) of
the metal contained in the particular gradation
referred to in the row heading. The value
calculated for the "Total" row is the weighted
average of all gradations, excluding the sieved
portions of the No. 10-to-l-inch fraction. (The
"No. 10-to-l-inch [unsieved]" portion was used for
the weighted average calculation instead of the
unsieved, as it gave more consistent results
with other data, specifically the "analysis of
combined sample" data.)
o >Riffle Sampler—This row presents data for the
soil sample portion that did not pass through the
riffle sampler (^1-1/2 inches x 12 inches). Sam-
ple 1 was the only sample that contained pieces
this large.
o >1 inch,
-------
Table 3-1 ^
RAH SOIL CHARACTERIZATION
» of Totil
Kiss
Rs(q/kg) Of(«g/kg) Cu(«g/kgl Pb(«g/kg) Znl«g/J>g) As I* of tot) Cd It of tot) Cu(toftot) Pb{* of tot) Inl* of tot)
NJ
SUVLl 1
Hiffle Saapler
)l",(Biffll
No. 10-to-r (tnsievEd)
Mo. 10-HH" (sieved)
r-to-1/2'
l/2"-to-Ho. 3
No. 3-to-Ho, 6
No. fc-to-Ho. 10
Total
No. JO-Pjssing
Total (excludes sieved
IMo-KUO)
Analysis of combined
saiple
SWPLE 2
)f, (Riffle
to. 10-to-l1 (urisieved)
to. 10-to-l' (sieved)
r-to-i/21
]/2MoH*>. 3
No. 3-ttHto. 6
No. 6-t(Hto. 10
Totil
No. las5iiw|
Totil (excludes sieved
r-to-*. to
flnalysis of certified
suple
SAMPLE 3
H-, (filfflt
No. 10-to-r (tmirved)
Mo. 10-to-l- (sieved)
r-to-i/j-
l/2'-t
-------
o No. 10-to-l-Inch (Sieved)—The subheadings under
this heading present data on various sized grada-
tions within the No. 10-to-l-inch portion. The
sample that was sieved for these analyses had been
washed only once (see Appendix A). The fines
(
-------
o Fines on the sieved fraction, which would be
expected to be of higher concentration than the
larger size particles, may have affected the
analyses.
o Portions used for analysis may have been unrepre-
sentative of the actual characteristics of the
samples.
CHARACTERIZATION OF SAMPLE 2
As in Sample 1, the weighted average concentration data for
the sieved sample agree fairly well with the analysis of the
unsieved sample which was split off for digestion and analy-
sis. For Sample 2, all metals compare within 25 percent
except for As and Pb. Sample 2 has metals concentrations
below cleanup levels for Cd and Zn, is marginal with
respect to Pb, and is above cleanup levels for As and Cu.
The No. 10-passing portion contains approximately 50 percent
or less of the total Cd, Cu, and Zn, and approximately 82
and 71 percent of the As and Pb, respectively.
The analysis on the sieved fraction of the No. 10-to-l-inch
portion showed higher metals concentrations overall than the
analysis on the unsieved fraction. Also the 1/2-inch-to-
1-inch portion of this fraction contains a disproportion-
ately large amount of Cd, Cu, and Zn.
CHARACTERIZATION OF SAMPLE 3
The weighted average total concentrations and analysis of
the unsieved sample that was split off for analysis compare
rather poorly, except for As. One likely explanation for
this anomaly is that one or more samples were unrepresenta-
tive of the actual soil contents. In addition, it can be
seen that the No. 10-to-l-inch portion contains a small
amount of all metals in comparison to its mass percentage,
while the 1-inch-passing portion contains a disproportion-
ately large amount of metals for its mass fraction. The
soil sample is below cleanup levels for all five metals.
In the sieved No. 10-to-l-inch portion, as was the case for
Samples 1 and 2, the weighted average content of all metals
is greater than shown by the analysis of the unsieved
No. 10-to-l-inch portion, except for As and Pb. The mass
percent content of the metals appears to be rather evenly
distributed by metal and throughout the various gradations
in this fraction.
CHARACTERIZATION OF COMBINED SAMPLES 4 AND 6
For this sample, the weighted average concentrations show
good agreement with the analyses of the combined sample,
RD/R16/029 3-4
-------
except for Pb, which shows only approximately 25 percent
disagreement. As can be seen, more than 95 percent of all
metals in this soil sample are contained in the No. 10-pass-
ing portion, which comprises almost 79 percent of the total
mass fraction of the material. Good agreement was obtained
for the analyses of metals on the unsieved No. 10-to-l-inch
portion as compared to the weighted average of the sieved
material. The soil is above cleanup levels in all metals
except Pb.
CHARACTERIZATION OF SAMPLE 5
All of Sample 5 passed a 1-inch screen, and 98.5 percent
passed the No. 10 screen. After washing, it is unlikely
that more than 1 percent of Sample 5 would have been
retained on a No. 10 screen. Because of this, the
No. 10-to-l-inch portion of Sample 5 was not analyzed. This
soil sample is above cleanup levels in As and Pb.
CHARACTERIZATION OF WHITE PRECIPITATE
As noted, the white precipitate found at the Celtor site was
analyzed by X-ray diffraction to determine its composition.
This sample was found to contain approximately 33 percent
water soluble material consisting of approximately equal
portions of bianchite E(Zn, Fe ) SO4,6H2O] and gunningite
E(Zn, Mn) SO..H-O]. The insoluble portion consisted of the
chlorite rapidolite, a ferroan clinoclore, quartz, and
oliogoclase feldspars. A trace of amphibole was also
present.
Analysis for aluminum and sulfate produced the following
results:
Sample Al (%)
White precipitate 0.9
Soil containing crust of white
precipitate 2.25 17.7
STLC ANALYSIS
Results of the soluble threshold limit concentration (STLC)
analysis on the five soil samples are presented in Table
3-2. This extraction was performed on the'No. 10-passing
portion of the soils.
These values show that the following soils had metal concen-
trations above STLC criteria:
RD/R16/029 3-5
-------
Sample 1—Cd, Pb
Sample 2—Cu
Sample 3—Cu, Pb
Combined Samples 4 and 6—As, Pb
Table 3-2
STLC VALUES OF SOIL SAMPLES
Sample
1
2
3
4 & 6
5
STLC Values
As
mg/kg
3
0
2
8
3
.38
.482
.29
.64
.94
Cd
ing/kg
1
0
0
0
0
.27
.32
.12
.30
.51
Cu
nig/kg
0.
35.
36.
0.
12.
19
6
4
37
9
Pb
mg/kg
8.
3.
8.
26.
1.
30
84
44
5
40
Zn
rog/kg
106
74.
24.
11.
76.
2
2
3
8
LEACHING DATA
EXTRACTION RESULTS
Tables 3-3 through 3-7 present the results of the leaching
studies performed on the five soil samples. Each table
contains information for one soil sample only. All tables
are organized similarly. Following is an explanation of the
data contained in these tables.
o The first section of the table presents a portion
of the soil characterization data contained in
Table 3-1, for comparison of beginning and final
metals concentrations.
o Column headings:
Extractant Solution (After Extraction)—Under this
heading are presented the analyses for the five
metals of concern in the extractant solution.
Note that in some cases hot HC1 was used for
extraction and that some samples were pulverized
before extraction. See the appendixes for more
details.
RD/R16/029 3-6
-------
Celtcr Clinical Worts Evtriction Studies
J.-.c I HI 3628.00
Table 3-3
EXTRACTION OF SOIL SAMPLE 1
Silt
* of total
SOIL PJBLrSIS SU-KAHY
Cdlig/kg) Cu (eg/kg) Pbda/kgl In(«g/kg>
Eitractant
Sodiui Glucorute
No. 10-passing
Suple 1
&uple ?
No. 10-to-r (note 2)
Sacple 1
Suple 2
EDIA
No, 10-passing
¥*}* '
Suple 2
No. 10-to-r
Suple 1
Suple £
No. ID-passing (note 3)
Suple 1 (note 41
Suple I (note 41
Acetic Acrid
No. 10-passing
Suple 1
Suple £
No, 10-to-r
**> Suple 1
1 Suple 2
-J Suple 3
HC1
No. lO-passing
Suple 1
Suple 1
No. l(Mo-l"
Suple 1
Suple 2
No. ID-passing
£77
£71
8.70
10.1
792
856
85.0
55.0
140
144
731
673
59.0
107
38.0
814
821
61.0
67.0
173,0
178.0
22.8
72.0
21.4
75.0
29.5
1110
254.0
1010
847
781
62.0
621
98.0
12.7
12,7
12.0
12.1
5.59
NR
6.14
NR
7.04
7.04
2.47
2.39
2.47
2.73
NO
1.50
1.53
1.32
1.22
0.96
0.96
0.93
0.79
0.92
0.79
1.01
0.86
1.02
0.83
1.53
1.51
1.12
1.13
NR
199.0
185.0
30.2
39.5
197.0
2010
40.7
34.0
Nft
HO
212.0
204.0
46.3
36.0
36.3
165.0
£25.0
46.2
27.4
Nfl
Nfl
HA
Nfl
MA
Nfl
262.0
243.0
45.5
30.6
84.5
83.0
5.25
6.25
61.0
61.8
113
2.78
54
62
57.4
57.3
2.63
3.39
2.38
40.0
61. A
113
3.20
58.3
59.5
58.0
58.0
52.0
51.8
w, a
59.5
3. IB
12.3
1.53
5550
5200
250
475
4980
5060
373
248
4980
4980
4880
4560
238
294
375
3340
4980
398
218
5050
5280
4800
48AO
4800
4AOO
4900
4820
278
273
598
259
26«
31.4
25.1
514
498
£5.4
29.8
403
450
454
413
22.1
22.5
57.3
363
615
31.0
22.9
468
583
335
470
358
288
562
444
37.3
27.5
125
15800
14900
445
523
13200
13400
475
400
13600
. 13900
12400
11903
318
6250
323
6830
13900
615
420
14100
14000
14400
14100
1£800
12600
14000
14000
590
9350
£50
As
0.11
0.76
0.94
1.21
0.67
0.69
1.13
0.95
NR
Nft
0.72
0.70
1.30
1.01
1.02
0.57
0.77
1.32
o.ao
NR
Nfl
Nfl
Nfl
MR
Nfl
0.90
0.83
1.29
0.89
0.£4
Cd
1.04
t.02
0.69
0.82
0.99
1.00
0,69
0.58
0.90
1.01
0.95
0.93
0.59
0.76
0.49
0.76
1.03
0.71
0.70
0.99
0.99
1.06
1.06
0.9?
0.92
1.03
1.00
0.74
£.15
0.51
Cu
1.09
1.02
0.97
1.77
1.02
1.05
1.51
1.02
1.01
1.01
1.00
0.94
0.98
1.20
1.45
0.74
1.05
1.60
0.%
1.07
l.ll
1.12
1.12
1.13
1.11
1.05
1.02
1.22
1.23
2,3!
Pb
o.aa
0.89
1.07
0.9!
0.94
0.92
0.%
1.10
0.81
0.91
0.80
0.73
0.76
0.76
1.97
0.65
1.09
1.33
0. 79
0.87
1.07
0.91
1. 11
0.32
0. ft?
1.00
0.79
1.31
0. fj
*,&
Zn
1 . J7
l.ul
(I.JO
0.4£
(>. 97
0.9-3
0.97
0.77
0.98
I.IK.I
0.91
i>. 8 7
0.66
9./S
(P.M.'
U.M
l.ftj
1.11
0.84
l.iij
LI.IJ
l.fm
•,'i.W
0.9.1
1 . (>2
l.*3
1.02
I.Ofl
15.98
LI.J4
Note I. Initial pH of eirtractant solutions wre is fol lo*s unless other-vise noted: Sodiun 61 uconate-U.40. EDTfl-6.15. flcetic flcid-?. 17, JC1 -1.00, Hot HC1 -0.80, HC1/H202-1.00
. Note £, Initial pH-U. 30
Note 3. Saipie MS pulverupd before ntraction.
Note 4. Initial pH-7.00
-------
Celt or Ctinml Uorhs Extraction Studies
Job I 1119628.00
Table 3-4
EXTRACTION OF SOIL SAMPLE
Sllf
> of Total »s
SOIL twmis swnnr
CdlBj/kgl Culiq'kg)
Pbtag/kj>
OJ
1
oo
Extract ant
Sodii* Glucwutp
No. 10-passina
Simple 1
Saaple 2
S»ple 1
Simple 2
EDTA
No. 10-passiiHi
Ho. 10-to-l1
Eitrictant Sol ut ionlaf ter ertraction)
flslq/1) Cd lug/1)
7.18
7.06
4.77
3.75
0.750
0.700
0.060
0.030
Cudg/1) . Pbliq/D
146
5.3
5.4
13.2
13.8
ii. e
11.6
52.5 311.00 12.0 2930
31. 9 56.20 13.3 3370
EXTRACTION SIMMY
Soil (after eitrjction)
2Mig/ll pHlnotel) Aslog/bg)
106
109
10.0
10.1
NH
12.01
1X06
13.04
267
257
86.6
56.9
S32.0
113.0
2430
220
Cddq/kg) Culvg/kg) Pbl.g/kgt In(«g/k$)
110
11,8
10.8
1-9S
3380
3330
3700
12BO
731
794
92.5
86
2790
2780
1600
423
Mass Balat
fls
0.90
0.87
1.71
1.15
celFraction
Cd
1.21
1.10
0.12
0.15
of Starting
Cu
1.25
1.24
1.10
0.31
Ftaourit Recovered!
Pb
1.42
1.54
1.03
0.97
hi
1.^4
1.23
7.36
i.ol
No. lO-passing (note 2)
Swple t
Sa.pl e 2
Saple 1
Sa.pl e t
flcelic flcid
He, 10-piSSing
San fie 1
Sttple 2
Sa.pl e 1
Saeplef
Satple 3
HCI
No. ID-passing
Sa.pl? 1
Saple 2
*>. lO-to-l"
Saiplf 1
Saul? 2
HC1/H202
No. lO-passinj
Sasple 1
Sarnie 2
No. ItHo-l"
Saiple I
SaupJe 2
Note I. Initial pH of
Note 2. Initial pH-6.
0.137
0.173
0.041
0.034
. 0.073
0.059
0,013
0.013
0.01
0.251
0.237
0.095
0.125
0.03
0.316
0.165
0.131
solutions Here »
9
1:«
0.440
0,420
1.40
1.30
0.310
0.200
o.aoo
1.60
1.37
0!220
0.600
2.23
0.200
0.220
follow,
265
267
59
41
251
232
36.7
30
25.1
273
237
A3
30
294
316
II
K.7
unless othmise
55.2
54.9
9.57
3.30
0.690
0.770
0.910
0.720
0.970
6.33
5.98
11.2
2.49
1. II
6.61
5.94
4.30
noted:
339
343
74.0
70.0
337
291
57.0
39.0
37.0
354
327
83.0
40,0
119
436
36.0
41.0
Sodiui Glunnate-13.
5.65
5.73
5.19
5.18
2.05
2.02
f.+fl
2.64
m
1.39
1.49
1.20
1.28
1.41
1.42
1.23
1.17
40, EDTft-4.15,
274
265
89
41.2
265
280
58.9
69
62.1
J85
201
70.7
123
271
361
69. £
74.4
fleet ic
11.0
II. 0
2.4
9.75
11.0
10.5
2.1
a. 75
3.S
10.0
52. a
19.5
3.0
10.5
12.5
3.48
13.5
(fciil-2.17, IC1-I
3140
3070
4310
3520
2110
2790
1250
3060
76fl
2740
5330
6930
750
2860
3300
1380
1310
.00, HC1/H2Q2-1.
663
664
11B
64
541
655
69.3
115
129
585
253
593
250
500
760
154
106
00.
2130
2200
590
2050
2060
2030
505
1980
193
2060
12300
3600
913
2130
2450
750
2800
0.81
0.85
1.59
0.73
0.85
0,90
1.05
1.23
0.92
0.65
i.at
£.19
0.87
1.16
1.24
1.33
1.16
LIB
0.25
0.80
1.15
1.09
0.20
0,69
0.32
1.10
4.63
1.53
0.26
0.98
1.41
0.29
1.05
1.25
1.23
1.31
1.07
1.13
1.11
0.39
0.93
0.24
1.12
1.99
2.11 '
0.24
1.18
1.34
0.43
0.41
1.45
1.45
0."62
1.02
I.S3
0.63
1.03
1.16
1.12
0.50
5.45
2.25
0.94
1.45
1,47
1.03
l.lb
1.19
3.35
I.IJ
1.07
£.81
9.35
4.40
s!jj
17.12
4.51
0.97
1.37
3.74
13.10
-------
Taile 3-5
EXTRACTION OF SOIL SAMPLE 3
Works Extraction Studies
Site
SOIL flMRLVSIS SUNNfiRV
t of Tcitil Astag/kg) Ctiiag/kg)
Pbtag/kg) Zntog/kg)
Extractant
Sfftlun Eliminate
Ho. 10-passing
Sample 1
Saiplc 2
No. IO-to-1 ' (note £)
Simple 2
SdJiple 2
EDTfl
No- 10-passint]
Ejuplf ! (note 31
Simple 2
No. 10-to-r
Simple 1
Sample 2
Acetic flcid
No. 10-pssing
Sanple 1
NoTio-to-r
Simple 1
Suple 2
Suple 3
HC1
No. 10-passing
Saplel
Sample 2
No. lo-to— 1"
Sample 1
HCl/H2ol *
Ho. 10-pjS5ing
5«ple 1
Saple 2
Mo. 10-to-l"
Siipie 1
Saple 2
S»ple 3
Note 1. Initial pH of «t
Note 2. Initial pH-12.30
Note 3. Initial pH-6.9,
*
Eitractcd Solution
flsUg/l)
5.33
5.01
0.171
0.154
0.543
0.012
0.02!
0.033
0.084
0.016
o.oo8
(0.01
0.143
(.005
0.031
0.03S
0.026
0.034
0.041
0.086
0.033
0.03
0.031
Cdtaj/ll
0.06
0.06
0.01
0.01
0.03
0.5
0.47
0.22
0.13
0.45
0.46
0.75
O.IB
0.15
0.6
0.57
0.31
0.24
O.iS
0.63
0. J2
0.25
0.21
ractant sol tit ions Here as
Cu fij/ll
260
873
46
67
83
232
86
88
207
211
53.2
178
J7B
286
286
301
212
297
ioa
£21
167
137
foil CMS, 1
No. 10-Passing
HO. io-to-r
(after extraction)
Pb(«g/l(
46.3
56
0.18
0.07
1.76
4.65
2.37
3,23
0.95
(0.05
(O.OS
0.18
<0. 05
2.56
0.48
0.44
0.21
0.16
0.57
0.4
0.8
0.61
0.8
57.9
38.7
ZnOg.'ll
15.1
26
4.7
5.1
16.3
89
63.4
26
23
92.8
94.2
124
33
314
126
113
65
46
121
183
52
41
32
89.7
9.34
EXTINCTION SU
6.0
8.1
HMfiY
1880
963
232
147
1280
405
SoiHifter extraction*
pHttote 1) Rstig/kgl
12.39
18.01
12.35
18.11
Nfl
7
5. 87
6.17
6.17
2.67
2.66
3. £7
2.61
MR
1.52
1.49
1.32
1.22
1.6
1.64
1. 13
1.19
MO
mless otherwise noted: Sodiei 6]uconate-13.40,
35.6
41.8
i.as
10.7
3.85
(3.9
58.4
23.9
5.37
60.3
16.8
15.2
7.61
NR
61.9
71.7
6.42
61.6
70.9
5.38
4.73
CdlBg/bj)
5.25
5.75
1.7
1.8
1.25
3.80
4.75
9
0.9
5
2.25
3.28
1.13
MR
3.73
4.75
1
3.33
3,78
1.73
0.95
6.25
Culmj/kg) Pblig/kg)
1280
1300
410
1230
453
12BO
1180
3080
240
1130
1180
435
1080
598
Nfl
1190
1290 '
545
1080
1060
568
438
£18
Ifl
144
4.28
8.55
3.4
240
830
33
4.18
£38
863
20.7
9.6
386
M)
274
£74
6.78
302
228
5.38
55
35
EDTfl-6.15, Bcetic fltid-8. 17, HC1-I.OO, HC1/K
Mass BaiarcetFraction of Starting taount Recovered)
ig/kg)
1150
1260
5£5
£78
213
1110
993
1660
135
9BB
1090
535
780
198
NR
1020
1030
215
1060
1060
370
328
343
As
1.56
1.74
0.34
1.19
0.53
2.15
1.97
£.57
0.58
2.03
0.57
1.63
0.85
NA
Nfl
£.09
7.68
0.69
2.08
2.39
0.5S
0.51
NA
' Cd
0.90
0.98
o.ai
0.57
0.6£
O.AI
0.95
4.43
0.54
0.98
0.99
1.76
1.71
0.67
m
O.B1
2.58
0.69
0.86
0.84
1.02
0.6S
3.13
Cu
O.S6
0.98
0.52
1.42
0.64
0.94
0.64
3.31
0.43
0.82
0.85
0.56
1.49
0,99
NA
0.94
1.%
1.01
0.33
O.S9
1.05
0.34
0.51
Pb
0.92
i.io
0.03
0.06
0.05
1.07
1.01
0.27
0.04
1.03
1.13
0.14
0.07
^6&
m
1.13
1.87
0.05
1.31
0.99
0.04
0. 33
0.24
Zr.
0.92
1.04
1.32
0.71
0.61
1.01
0.91
4.26
u.tt
0.92
l.iXi
1.35
£.0")
Z.(H
Nfl
0.97
2.S6
0.76
.UJ
.!>.'
.17
.Ul
.00
-------
Works Extraction Studies
Table 3-6
EXTRACTION OF COMBINED SAMPLE 486
Size
SOU BNBUSIS SUKWV
of Total fte lag/kg) CdHj/kgl
Culnj/kq) Pb fig/kg) 7.n<«g/kg>
No.
No.
Extractant solution (after extraction)
ID-Passing
10-to-r
78.7 297.0
18. 1 63.6
EtTKCTION SUHWflY
52.0 5240
£.1 328
SoiJ (after eitrtction)
394.0
. 38.0
12200
408
test Balarcelfraction of
Sodiu» tldcwiate Aslng/l) Cd
Saiple 1
Extract ion 1
Extraction 2
Saiple 2
Extraction 1
Extraction 2
HC1/H202
No. 10-passing
Sople 1
Suple 2
No. 10-to-l"
Saipte 1
Sample 2
23.8
24.8
4.67
8.89
0.39
0.3S
0.121
0.113
NA
Nfl
0.923
0.908
0.057
0.051
1.79
1.97
0.1%
0.256
NR
NR
NA
m
Nfl
Nfl
NR
MR
HA
Nfl
1.73
1.77
0.213
0.265
0.32
0.35
0.02
0.02
1.56
1.58
0.27
0.16
0.26
0.3
1.4
1.5
0.24
0.14
l.S
1.58
0.1B
0.43
0.3
0.29
0.34
0.08
0.35
0.07
0.38
0.12
0.4
0.11
1.49
0.15
0.3
0.38
85
%
14.3
19.1
166
158
40.2
36
12.4
14.3
135
145
54
20.3
158
164
26.9
49
25
30.7
40.?
11.1
45.6
10.6
41.7
14.5
47.7
17
165
178
30.7
41
150
143
9.25
6.61
35.1
38.4
3.38
1.28
20.3
25.9
0.13
0.1
0.94
0.05
1.92
2.04
0.22
0.34
1.87
1.75
5.55
10.7
6
10.9
9.75
14.3
8.3
13.7
1.73
1.91
0.25
0.41
73
77
II
9.2
353
350
66
46
60
67.5
288
310
53
31
333
B9
61
51
62
71
17
70.5
IS
71
26.6
79
26.3
331
354
50
60
12.74
12.66
13.19
13.26
NA
5.83
6.13
6.16
7.15
7.2
t.84
1.85
NR
2.51
1.29
1.32
LIB
1.12
0.94
9.94
9.89
0.78
0.88
0.77
0.95
0.79
0.97
0.78
1.39
1.37
1.21
I.ffi
234
275 »
27.4
£4.7
299
301
56.3
40
NR
NR
276
»9
40.2
31.1
270
243
37
32.6
m
NA
NA
NO
NA
NA
265
257
47.5
39.9
52.3
49.5
0.98
1.1
49
48.5
1
0.43
48
59
$0
49.5
1.18
0.3
51.3
51. B
0.3
0.3
47
52
54
54.5
45
51
52.5
0.73
1.33
5080
5270
155
255
5130
5150
253
150
4990
6050
4980
4980
330
168
5100
5180
120
I3S
5400
5200
5050
5200
4850
4950
5050
5000
205
198
286
282
40
41.5
208
332
44
26.7
274
113
341
284
43.8
32.5
445
393
£8 1
£4^3
410
300
153
£50
277
233
503
446
25.3
28.8
11400
11000
243
280
1180
11300
608
IE5
11300
14200
11200
11000
245
133
11800
1900
173
148
12000
12000
12200
12600
11000
1250
11400
11000
1100
268
fe
0.95
1.09
0.58
0.67
1.01
1.02
0.89
0.63
NR
Nfl
0.94
0.91
0.63
0.49
0.92
0.83
0.59
0.52
NR
Nfl
NR
NA
NR
NR
0.90
0.88
0.75
0.64
Cd
1.02
0.97
0.50
0.56
1.00
0.99
0.75
0.37
0,97
1.19
1.02
1.01
0.81
0.28
1.04
1.06
0.32
0.57
0.96
1.06
1.11
1.12
0.95
1.06
1.07
0.95
0.65
i.ce
starting uount recovered)
Cu
1.00
1.04
0.56
0.89
1.04
1.04
uoa
0.68
0.9S
i.ia
1.00
1.01
1.34
0.64
1.03
1.05
0.53
0.71
1.06
1.05
1.05
l.Ofl
1,02
1.05
1.03
1,02
0.81
0.85
Pb
1.49
1.44
1.54
1.44
0,71
1.04
1.34
0.77
1.21
0.94
0.87
0.72
1.20
0.36
1.14
1.01
0.76
0.66
LOT
0.81
0.77
1.03
1.26
1.12
1.29
1.14
0.68
0.78
In
0.35
0.31
•0.66
0. «
0.15
0,98
1.81
0.5J
0.98
j. ^
(', 9/
0.35
0.66
0.46
l.OJ
0.21
0.66
0,66
1.03
1.03
1.06
1,09
0.11
0. 18
0.79
O/*
2.9*
0.35
Hote 1. Initial ph of all e.triCtjnU «?n> as follows, unless otherwise noted:
Note 2. Saiple MS pulvn-izid before extraction.
Note 3. 1ml ul pH-7.00
Sodim Sluttmjtp-13.40. EDFfl-6, 15. Bretic flcid-2. 17, HC1-I.OO. Hot HCI .80, HC1/H202-1.00.
-------
Table 3-7
EXTRACTION OF SOIL SAMPLE 5.
ltorlts
Studies
Size
of rot*l PMig/kql
SOIL (NfiLYSIS SUWflSY
Dldg/kg) Culq/kgl
Pfalig/kg) Zndg/kg>
h->
1— '
Eitrtctaitt
Sodiia Slucorute
No. lO-pjssJra
Sinple 1
Saaple i
Acetic Acid
No. ID-pass irjj
Suple 1
Suple 2
HCI
No. Id-passing
Suplp 1
Sinple 2
EOTfl
No. 10-passinq
S"f|el
Swple 2
HCI/H2JK
No. lO-aassiru)
Simple 1
Satiple 2
No.
No.
Eitrartaitt Solutioolafttr ««tr*ctior)
flstig/l) Cdlng/1) Culig/l) Pb(q/l) I
£8.3
£7.5
0.041
0.032
o.oa
0.062
0,069
0.114
0.099
0.147
0.02
0.01
0.27
0.22
0.36
0.36
0.36
0.34
0.36
0.37
98
73
£98
322
57
61
71
64
£9
70
50
28
(0,05
(0,05
0.09
0,08
1.56
8.08
0.06
0,16
lO-Passinq
10-to-l-
98.5 345 12.5 ESB
1.5 « NR NR
EXTRACTION SUMHY
Soillafttr titrtrtion)
n!»g/ll pHIMote 1) Rs(ig/kg) D
4
2. OB
U.8
46.6
62
65
67
84
70
73
11.73
11.71
2,35
2.35
1.37
1.34
MA
S.B8
1.44
1.55
219
204
£82
280
317
276
299
320
297
Wt
1350
m
2350
m
llBj/kg) Culng/kgl Pfalng/kg) 2n[iq/kg)
8.5
a/5
13
12.5
12.8
12
10.5
ne
to. a
10.75
505
630
755
baa
531
540
518
700
490
650
1190
1110
1310
1260
1350
1200
1190
1340
1310
1340
1950
£080
2250
2180
2430
2330
I960
23BO
2370
2350
Mass BalanetlFractinn of
As
0.80
0.75
0.82
0.81
0.92
0.80
0.87
0.93
0.86
0.76
a
0.68
0.70
1.08
1.04
l.Ofl
1.02
0.90
LOS
0.92
0.92
Starting antxmt Recovered)
Cu
1.07
1.18
S.05
2.02
0.96
1.01
1.00
1.32
0.95
1.20
Pb
0.96
0. B6
0.97
0.93
1.00
0.89
'}. 88
1.00
0.97
0.93
Zn
0.83
O.B9
1. 00
0.9J
1.03
1.1)5
0.90
1.08
1.07
l.(>6
Note l. For inilitl pH of extract ant Solutions, stf Tables 4 through 7.
-------
Soil (After Extraction)—Under this heading are
presented the analyses of metals in the soil that
had undergone extraction. Analyses were performed
on the extracted soil sample after it had been
pressure-filtered on a prefilter paper for removal
of extractant, washed, dried, and pulverized.
Mass Balance—Presented under this heading are
results of a mass balance calculated on each
metal. Values given are the fraction of the total
starting mass that was recovered in the soil and
extractant solutions.
For an example, refer to Table 3-1, and note that
the Cd mass balance for the sodium gluconate
extractant for Sample 1 of the No. 10-passing
fraction equals 1.04. (This indicates greater
than 100 percent recovery which, of course, is not
possible. However, this value is considered to be
within acceptable limits of accuracy.) This value
was calculated as follows:
Beginning Mass
lOOg x £2_ x 87.5 mg/kg (see No. 10-passing
l,000g under Cd in the top
section of the table)
= 8.75 mg
Extractant Solution
3.2 mg/1 x 200 ml x 1 llter
1,000 ml
= 0.64 mg
Soil
8.45 mg + 0.64 rog = 9.09 mg
9.09 mg/8.75 rog = 1.04
EXTRACTION EFFICIENCIES
Extraction efficiencies are summarized in Tables 3-8 through
3-12. These efficiencies were calculated by the formula
E = (M /M + M ) x 100 Equation 1
Go G
RD/R16/029 3-12
-------
where
E = extraction efficiency
M = metal in the extractant, mg
Me = metal in the soil after extraction, mg
s
Referring to the values given in the previous mass balance
example, the efficiency of extraction for the values given
in that example would be
E = (0.64/8.45 + 0.64) x 100 = 7%
There are three potential methods of calculating extraction
efficiencies, as follows:
1) From Equation 1
2) From the equation:
E = (M. - M )/M. Equation 2
_l_ o -L
where M. is equal to the assumed initial concentration
of metal in the soil, as measured by the portion origi-
nally split off for analysis
3) From the equation: Equation 3
E = (M /M.) x 100
C _L
If our assumption that the initial concentration of metal
before extraction is the same in all cases for a given sam-
ple portion is good, and all analyses are 100 percent accu-
rate, all three equations will provide the same results. As
can be seen from Tables 3-8 through 3-12, not all mass
balance values equal 1.0. We therefore decided to use the
first equation for calculation of efficiencies because:
1) If Equation 2 is used, many negative efficiencies
result, which is not possible from the standpoint
of conservation of mass. It is also obvious that
our assumption that all samples have the same
starting concentration is not necessarily true
because of the heterogeneity of the sample.
2) If Equation 3 is used, no negative extraction
efficiencies result. However, this equation still
relies on the assumption that each starting sample
has the same initial metals concentration.
Because of the potential for lab data variations due to
inacurracies within accepted limits, it is impossible to be
certain that the efficiencies calculated by Equation 1 are
completely accurate. Therefore, we have used an asterisk to
RD/R16/029 3-13
-------
highlight those samples whose mass balances show less than a
75 percent closure in Tables 3-8 through 3-12. Even though
mass balance closure does not guarantee accuracy, it is
another cross-check that allows greater confidence in the
data.
EXTRACTION SUMMARY
Refer to Appendix B for a detailed summary and discussion of
extraction results. Presented in Figures 3-1 and 3-2 are
graphical summaries of all extraction testing. Figure 3-1
presents results of testing performed on the No. Id-passing
portion of the samples. Figure 3-2 presents results of
testing performed on the No. 10-to-l-inch portion.
Figures 3-1 and 3-2 illustrate the patterns and differences
that occur between different soils using the same extractant
and between different extractants for the same soil sample.
Presented below is a brief summary of the information illus-
trated in these figures (note that the values given for
removal efficiencies in this figure are averages of the
values given in Tables 3-8 through 3-12).
SUMMARY OF EXTRACTIONS ON NO. 10-PASSING SAMPLE
Sodium Gluconate Extractant
Sodium gluconate was most effective in extracting lead (up
to an average value of 50.8 percent in Combined Samples
4 and 6, copper, (29.3 percent in Sample 3) and arsenic
(21.2 percent in Sample 3). Observing the extraction
efficiencies for the remaining extractants, note that
removals of lead greater than 25 percent were obtained in
only three other cases—hot HC1 extraction on Sample 1 and
Combined Samples 4 and 6, and EDTA extraction on Combined
Samples 4 and 6. Note also that no other extractant removed
a significant amount of arsenic (greatest removal was
2 percent for HC1 in Soil Sample 1). In only one sample did
the sodium gluconate extractant remove sufficient lead to
reduce the level of this metal from above to below cleanup
levels (Sample 1). No other removals to below cleanup
levels were obtained.
EDTA Extractant
This extractant was uniformly inefficient in removing
arsenic from the soils tested (greatest removal was
1 percent in Soil Sample 1). Removals of other constituents
varied significantly depending on which soil was being
extracted and on whether the sample was pulverized before
extraction. Average removals for cadmium were as high as
31 percent, copper 46.2 percent, lead 56 percent
RD/R16/029 3-14
-------
Table 3-8
EXTRACTION OF SOIL SAMPLE 1
EXTRACTION EFFICIENCIES
Extractant
Percent of Metal fisnovec from Sou
Sodium Sluconate
10 Mesh passing
Sanpie 1
Sample 2
SO iiesh to 1"
Sanple 1
Sample 2
EDTft Extractant
10 Mesh passing
Sample 1
Saaple 2
10 mesh to 1"
Sample 1
Saisple 2
410 oassingtPulverized)
Sanple 1
Sample 2
flcetic flcid extractant
10 mesh passing
Sample 1
Sanple 2
10 nesh to 1"
Sample 1
Sample 2
Sanple 2
HC1 extractant
10 nesh Passing
Sanple 1
Sanple £
10 nesh to 1"
Sample I
loWpfssing
Sanple 1
Sanple £
Hot HC1 Extractant
#10 passing (unpulveri red)
Sanple 1
Extraction 1
Extraction 2
Sample 2
Extraction 1
Extraction 2
§10 passing (pulverized)
Sanple 1
Extraction 1
Extraction £
Saaple 2
Extraction 1
Extraction £
HC1/H2G2 extractant
10 flesh passing
Sanple 1
Sample 2
10 nreh to 1"
Sanple 1
Saiple 2
Saaple 3
fls Cd
16 7
18 7
11 2 *
10 1
I * 29
1* 29
I 41*
1 38*
na 3£
na 30
1* 31
1 29
1
1* «*
2 44
1 36*
o* 4t
1 32
3* 43*
5 41 *
na 33
na 32
na 37
na 3fl
na
na
na
na 36
na
na
na 36
na
1 33
1 32
3* 44*
5 36*
10* 61*
Cu
2
2
7
4*
6
7
il*
12
5
5
6
b
13
12
7*
13*
9
11*
19
9
9
ia
17
IB
17
10
10
18
20
7*
Po
46
46
^
S
4
4
12
10
12
12
0
0*
0
i
2*
1*
1
4*
3
5
4
35
£5
31
33
1
1
5*
3
1*
Zn
3
4
4*
4
11
11
£6
22
9
3
11
10
£7*
3*
!9*
IS*
11
' 17
24
ij
11
f
6
10
20
11
10
17
12*
41 *
Mass balance is (0.75, or M.25
3-15
-------
Extract ant
Table 3-9
EXTRACTION OF SOIL SAMPLE 2
EXTRACTION EFFICIENCIES
Percent of Metal Removed fron Soil
Sodium Gluconate
10 mesh massing
Sanple' 1
Sample 2
10 mesh to 1"
Sanple 1
Sanple 2
EDTA
10 nesh passing
Sample' 1
Sample 2
tO nesh to 1"
Sanple 1
Sample 2
flcetic field
10 inesh passing
Sanple !
Sanple £
10 mesh to 1"
Sanple 1
Saraple 3
Sample 3
HC1
EC nesh passing
Saaple 1
Sanple £
10 mesh to 1"
Sample 1
Sample £
HC1/H202
10 mesh passing
Sanple 1
Sanple 2
10 mesh to 1"
Samel e 1
Sample £
3s
2.6
£.7
5.5*
b.2
0.0
0.1
0.1*
0.1*
0.0
0.0
0.0
0.0
0:0
0.1
0.!*
0.1*
0.1*
0.0
0.1
0.2
0.2*
Cd
5.S
5.6
0.6
1.5*
11.5
11.5
15.5*
4.1
11,3
11.0
12.5 *
£.i *
5.0 *
13.8
2.5 *
£.3 *
6.8 *
5.4
15.1 *
5.4 *
1.6
Cu
4.1
4.2
0.1
0.4*
7.3
3.0
1.4*
1.2
B.e
7.7
2.9*
1.0
3.2*
9.1
4.6*
i.e*
3.8*
9.3
3.7*
£,£*
2.4 *
Pb ,
1.3*
1.7*
11.3
li.9
7.7*
7.6*
7.5
4/3*
0.1
0.1
1.3*
0.6
0.7
1.1
2.2 *
1.9*
1.0 *
0.3
0.3 *
3.7 *
3. a
in
3,7
j.a
0.6*
2.3*
13.7
13.5
11.1*
2.3*
13.9
12.5
10. 1*
1.3*
4,0*
14.5
a. 6*
£.3*
4. 2*
5.3
15.1*
4.6*
1.4*
* Mass nalince is (0.75 or H.25
3-16
-------
Table 3-10
EXTRACTION OF SOIL SAMPLE 3
EXTRACTION EFFICIENCIES
Extractant Percent of Metal Removed
Sodium Gluconate
10 rnesri passing
Sample' 1
Sample 2
10 mesh to !•
Sample 2
Sample 2
Sample 3
EDTfl
10 mesh passing
Sanple 1
Sample 2.
10 mesh to 1"
Sample 1
Sample 2
Acetic
.
lO rresh passing
Sasple I
Sample 2
10 mesh to 1"
Sample 1
Saapie 2
Sanple 3
HC1
10 mesh passing
Sample 1
Sanple 2
10 Mesh to 1"
Saiple 1
Saaple 2
HC1/H2G2
10 nesh passing
Sanple 1
SampleS
10 Mesh to 1"
Sample 1
Sample 2
Sanple 3
« .lass balance is <0.75 or J1.25
As
23.0*
113*
10.7*
2.8
22.0*
0.0*
0.1*
0.3*
0.9*
0.1*
0.1*
0.0*
3.6
na
na
0.1*
0.1*
1.0*
0.1*
0.1*
1.2*
1.3*
0.0
Cd
2.2
2.0
1.2
1.6*
4.6 *
20.5
16.5
4.7*
22.4 *
15.3
15.5
40.0 *
9.9 *
21.0 *
na
23.4
11.5 *
32.4 *
25.3
25. 0
20.3
34.5 *
6.3*
Cu
28.9
29.6
13.3*
5.8*
26.8*
27.9
23.3
5.4*
42.3*
26.8
26.3
19.7*
24.8*
37.3
na
32.5
31.8 *
+3.8
35.5
36.3
43.3
46.1
55.7*
Pb
43.4
43.6
7.3*
1.6*
50.9*
3.7
2.0
16.4*
30.3*
0.0
0.0
1.1*
0.0*
1.3*
na
0.3
0.2 *
4.5*
0.4 *
0.3
6.9*
2.2*
1.1*
Zrt
2.6
3.5
1.8*
j.5*
13.3*
13.3
14.4
3.0 *
27.0 *
15.3
14.7
31.7 *
7.3 *
7£.0 *
r.a
IS. i
11.2 *
30.0
16.3
lfl.9
21.9
20.0
15.7
3-17
-------
Table 3-11
EXTRACTION OF COMBINED SOIL SAMPES 4 AND 6
Extractarit Percent of Metal Settoved from
ft* L'lUC
I'} mesh passing
iaraoie 1
SdBDle 2
10 sesh to 1"
Sarnole 2
Saaple 2
EDTfl
10 mesh Dassing
Saaple 1
Sample 8
10 mesh to 1"
Sample 1
Sample 2.
(Pulverized)
Sample 1
Sample 2
elcetic Acid
10 raesh passing
Sample 1
Sample 2
10 mesh to 1"
Sample 1
Sanple £
HC1
10 Mesh passing
Sample 1
Sample £
10 DKSfl tO P
Sample 1
baaple 2
(Pulverized*
Sample 1
Sample 2
Hot HC1
(Unpulverized)
Sanple 1
Extraction 1
Ex traction 2
Saapie 2
Extraction 1
Entraction 2
(Pulverized)
SdBple 1
Extraction 1
Extraction 5
Sanple £
extraction 1
Extraction 2
HC1/H£0£
10 fiesfc passing
Samole 1
Sample £
10 wsh to I1
Sauple 1
Sample 2
HS
Is. 9
iri.j
25.4*
41.8*
0.3
0.2
0.*
0.6*
NA
Nfi
0.7
0.7
0.3*
0.3*
1.3
1.&
1.0*
1.5*
MA
Nfl
NO
Nfl
W)
NA
1.3
1.4
0.9
1.3 *
Cd
1.5
1.4
3.9*
3.5*
6.1
&.J
35.1
42.7*
S.I
4.3
5.3
S.7
£8.9
4fl.3*
5.5
5.7
54.5*
74.1*
6.0
5.3
6.1
£.0
a. 6
7.3
5.4
0.6
45.1*
36.4
Cu
5.8
3.6
•5.6*
13.0
6.1
5,8
24.1
32.4*
2.4
2.3
5.5
5.5
24.7*
19.5*
5.S
6.0
31.0*
42.1 *
4.4
5.6
6.0
a. 5
9.0
!0.0
6.1
6.6
£3.0
£9.3
Po
— • - i
31. Z *
50.4 *
3!. 6 *
d^.i *
S.£ *
ia. a
13.3 *
a. 7
42.6
69.6
0.1
0.1 *
3.7
O.j
0,9
1.0
i.S
2.7*
4.4
5.5
49.7
3fl.&
44.4*
46.1
0. 7*
a. a
1.9*
£.3
Zn
1.3
1.4
3.:*
6.£*
39.1*
5. a
17, a*
42.4*
5.0
4.3
4.9
J. I
30. £
31.8*
5.3
27.0*
SO. 7
45. i*
4.6
4.9
5.7
5,4
7.0
4i.7*
5.3
£.0
3.3 *
30.9
* Mass balance is (0.75 or H.25
3-18
-------
Table 3-12
EXTRACTION OF SOIL SAMPLE 5 -
EXTBACTION EFFICIENCIES
Extractant Percentage of Metal txtractefl from Soil
Na Gi-jc
10 raesh Dassing
Sample i
Samoie 2
Acetic flcid
10 i/iesh Dassing
SaraDle 1
Saaiple 2
HC1
10 mesh passing
Saaoie 1
Sample i
HDTft
10 (flesh passing
Sample 1
Sample 2
HC1/H2Q2
:0 mesh passing
Sauoie 1
Sample £
fls
20,54
21.24
0.03
0.02
0.05
0.06
•J.OS
0.07
0.07
0.11
Cd
— — .
0.47*
0.23*
3.99
3.40
5.33
5.66
6.42
5.04
6,i5
6.44
Cu
27.96
13.31
44. 1£ *
46.35*
17.62
18.43
21. 3S
13.35*
21.37
17.72
Pb
7.75
4.30
0. 00
0. 00
0. 01
0.01
0. 26
0.21
0. 01
0.03
Zn
—
0, 41
0. 20
4.11
4.10
4.36
5.28
6.24
£. 59
3.53
5.S5
* class balance is (0,75 or M.25
3-19
-------
-500IUM &LUCOHATE
Pb Zn A4 W CK fb
CONSTITUENT
Pb Zn A* M Cw
CONSTITUENT
Pb ZK As
C 0 N 5 T i T U EMT
NOTE*
* INMCfiTM WAT Wll SAMPtt WAS
IUITI&LLV AVOt/£ CLEANUP
OULV WE SODIUM
£X7RaC7AH7 (fffOUf 1$
** INDICATES war wuwiTueui was
tLEMOVED IN SUFFICIENT (WAHTI7IES
70 fUZ/UC- MIL FROM fltffl/f 70 JBL0W
ClttW UP CRITERIA FOR 7UIS COfJ-
S7I7U6U7. (TUlSMWHWfONW
0£CU/l£D IH CU£ OF TWO OB. 7tJS££
exTRQCTtou?. oaTa MAV iumc-A7£
LOW r£KCEfJTA£tff£MOt/AtC WHICH
MM M£A?J 7UQT 7U5 ACTUAL
mnn wa$ btiow ut&uw
WI7IRUV - $££ TEXT ALSO).
1.
OR
WITH
£ff/Ct£Ut/£$
6F D37A
9-8 7UROU6U
2 £*7liaCTIQtJ$ W1T1J UOT 1101 W£Z£
HOT PERFORMED QUTUIS SOIL SAMPLE
>. wswii was MOT avAL/ze/) iu TUB
rULI/£Itl2£D EXTRACTED SOIL
Sept 1986
Figure 3-1
SUMMARY OF
EXTRACTION EFFICIENCIES
CELTOR CHEMICAL WORKS
No. 10 PASSING
-------
10
to
10
70
SODIUM GUIGONATE-
20
10
'60
^10-
^ 0
-E 0 T A
I
-ACETIC AND
Pb In A* Cd Ca Pb Z*t A<; W, Cw, Pb Zn A9 Ot
COM*7TITUENT
Pb Zri
CH
C3
Zn A 4 CfiL Cu
fl9 Cd Cu Pb Zn
Cd Cu Pb In ^ Cd Cw, Pb in to Cd Cu Pb In As Cd Cu Fb Zn fl* Cct Cu Pb
CONSTITUENT
Cct Cu Pb 2n
CoC CM, Pb ZK A^ W Cu Pb In
GON
-------
(pulverized sample), and zinc 22.0 percent. Note that with
some exceptions, primarily for lead, removals using EDTA
showed the same overall patterns, and in many instances,
percent removals similar to the remaining extractants
(acetic acid, HC1, hot HC1, and HC1/H202).
In the two cases that showed removals to below action levels
(lead in Sample 1 and zinc in Combined Samples 4 and 6),
other data such as percentage removal and mass balance
indicate that the actual samples tested may have initially
been below cleanup levels or that the percentage recovery of
the metal was not 100 percent.
Acetic Acid Extractant
This extractant was uniformly poor in removing arsenic and
lead (greatest removals were 1 percent for arsenic in
Sample 1 and 0.1 percent for lead in Sample 2 and Combined
Samples 4 and 6). Removals of arsenic, cadmium, copper, and
zinc were similar to those using EDTA, except for copper in
Sample 5. Copper removal in Sample 5 using EDTA was approx-
imately two and one-half times greater than the removal
using acetic acid (approximately 46 percent vs 20 percent).
The only removals to below cleanup levels were for lead in
Sample 1. Mass balance and percentage removal data do not
confirm significant removals for lead in this instance.
Hydrochloric Acid
As with acetic acid, removals with hydrochloric acid were
uniformly poor for arsenic and lead (greatest removals were
2 percent in Sample 1 and 5.5 percent for Combined Samples 4
and 6, pulverized). The removal patterns for hydrochloric
acid and acetic acid were similar, although there were some
differences in actual percentages removed. Some significant
removal differences between pulverized and unpulverized sam-
ples are also evident. Note that the large difference
between average zinc removals in the pulverized versus
unpulverized data for Combined Samples 4 and 6 is the result
of the 27 percent removal shown for the second extraction on
this sample (Table 3-11). Also note that the mass balance
closure for this second extraction is poor (0.21).
In only one instance was a contaminant removed to below
cleanup levels (lead for Sample 1), and, as was the case for
previous lead removals, mass balance and percentage removal
data indicate minor removals.
Hot Hydrochloric Acid
The major removals obtained by hot HC1 were for lead and
cadmium (as high as 48.7 percent for lead in Combined
Samples 4 and 6 and 38 percent for cadmium in Sample 1).
RD/R16/029 3-20
-------
However, cadmium removals were similar to ambient tempera-
ture HC1 removals. Lead removals were significantly higher
than for ambient HC1 (as high as 44 times). Removals of
copper and zinc were as high as 17.5 and 15 percent, respec-
tively. Arsenic analyses were not performed for this
extraction.
Removal to below cleanup levels was obtained for lead
(Sample 1) and zinc {Combined Samples 4 and 6). Note that
other data for lead and zinc in these extractions show poor
mass balance closure, indicating that the sample may have
started out below action levels, or that percentage recovery
of the metals was not 100 percent.
Hydrochloric Acid/Hydrogen Peroxide
The patterns of removal with this extractant were quite
similar to those of HC1; however, mass balance closure data
do not corroborate high zinc removals (mass balance levels
were as low as 0,1 percent). Removals to below cleanup
levels were obtained for lead (Sample 1} and copper
(Sample 1), although percentage removals were minor
(^10 percent).
SUMMARY OF EXTRACTIONS ON NO. 10-TO-l-INCH PORTION
Sodium Gluconate Extractant
Extraction with this chemical showed uniformly poor removals
for both cadmium and zinc (greatest removals were
4.6 percent for cadmium in Sample 1 and 13.3 percent for
zinc in Sample 2). Removals for arsenic were as high as
33.6 percent, copper as high as 18.3 percent, and lead as
high as 27.9 percent. Although final soil concentration
data indicate a removal to below cleanup levels for copper
in Sample 2, percentage removal data and mass balance data
do not indicate large removals.
EDTA Extractant
This extractant showed poor removals of arsenic for all soil
samples (greatest removal was 1 percent). Removals of all
other metals varied considerably, depending on the particu-
lar soil sample. Maximum removals were cadmium
39.5 percent, copper 28.2 percent, lead 23.9 percent, and
zinc 30.1 percent. No removals to below cleanup levels were
obtained.
Acetic Acid Extractant
Removals with this extractant were uniformly poor for both
arsenic and lead (greatest removals were 3.6 percent for
arsenic in Sample 3 and 3.7 percent for lead in Combined
RD/R16/029 3-21
-------
Samples 4 and 6.). Removals for cadmium, copper, and zinc
were as high as 41, 27.3, and 38.5 percent, respectively.
Removal to below cleanup levels was obtained for copper on
Sample 2, although mass balance data and percent removal
data do not indicate significant removals.
HC1 Extractant
As with the acetic acid extractant, HC1 was uniformly poor
in removing arsenic and lead (greatest removals were
5 percent for arsenic in Sample 1 and 4.5 percent for lead
in Sample 3) . Removals of cadmium, copper, and zinc were as
high as 64.3, 37.8, and 47.9 percent, respectively. Removal
to below cleanup critiera were apparently obtained for
copper (Sample 2) . However, mass balance data indicate that
the sample may have been below cleanup levels initially.
O Extractant
The overall pattern of removal for this extractant was quite
similar to that of HC1, although percentage removals dif-
fered substantially in some cases. Removals of arsenic and
lead were uniformly poor (greatest removals were 10 percent
for arsenic in Sample 1 and 6.9 percent for lead in
Sample 3) . Removals of cadmium, copper, and zinc were as
high as 44, 48.5, and 23 percent, respectively. Copper was
below cleanup levels in Sample 2, but mass balance data do
not corroborate large removals.
RD/R16/029
RD/R16/029 3-22
-------
Chapter 4
DISCUSSION OF RESULTS
SUMMARY
Removals of contaminants were marginal for nearly all
metals, soils, and extractants. In very few cases were any
soils treated successfully (reduction of a particular metal
from above cleanup level to below cleanup level). There
were no cases where more than one metal in a soil sample was
reduced from above to below cleanup level. It therefore
appears that none of the extractants used would be effective
in producing a soil which would be below cleanup level in
all metals of concern (if the soil were initially above
cleanup level in more than one metal). The soil remain-
ing after extraction would be nearly the same, or greater,
volume than initially (because of added water). The
extracted soil would remain to be dealt with as a hazardous
waste, requiring one of the remaining actions outlined in
the RI/FS for the site.
Of the five extractants used in this study, sodium gluconate
was the only high pH extractant used. This extractant in
the alkaline form has the ability to remove the four cat-
ionic metals (cadmium, copper, lead, and zinc) by binding
with the chelant portion of the gluconate, and can remove
arsenic by binding with its alkali portion, provided these
constituents are not bound in other forms that make them
chemically insoluble. The remaining four extractants are
capable of extracting the cationic metals as long as they
are not bound in insoluble forms (especially sulfide). The
rationale for using these extractants has been covered in an
earlier chapter.
While some extraction was achieved by all solutions, these
removals were not adequate to meet cleanup levels. It
appears from these test results that the metals are present
primarily as complicated sulfides which are not soluble
unless they are oxidized under severe conditions. The min-
ing industry relies on roasting and high pressure, high
temperature aqueous slurry oxidation to extract metals from
sulfide ores. Although the material was not specifically
analyzed for sulfides, the mining history and study results
suggest strongly that the soils contained significant
amounts of sulfides. The limited extraction that was
observed was most likely the result of slow oxidation pro-
cesses and weathering that have taken place on the exposed
surfaces of the individual particles (acidic runoff from the
site is evidence of this). This weathering makes metals at
the particle surface susceptible to chemical extraction,
while leaving the sulfide-rich interior unaltered and the
sulfide-bound metal unextractable.
RD/R34/031 4-1
-------
Examination of results on the pulverized soil versus unpul-
verized soil extractions tend to corroborate this conjec-
ture, as removals of the two are quite similar. In other
words, exposing the interior, unoxidized portions of the
soil does not significantly increase extraction. A notable
exception to this occurred for lead {which was extracted in
approximately 3 to 5 times the quantity in pulverized versus
unpulverized tests for all but the hot hydrochloric acid
extractants). Lead removals were still minor in all cases
that showed a significant difference between pulverized and
unpulverized extractions (less than 15 percent). Also, note
that for the hot hydrochloric acid extraction on Soil
Sample 1, more zinc was extracted on the pulverized sample,
and for the EDTA extraction on combined Soil Samples 4 and
6, less copper was extracted on the pulverized sample.
There is no apparent explanation for this last phenomenon.
(Samples whose mass balance did not close within 75 percent
of unity are not included in the above discussion.)
In general, extractions with hot hydrochloric acid showed
better or equal removals compared to extractions at ambient
temperatures. The most dramatic example of this was for
lead. The best efficiency for lead extraction at ambient
temperatures was 5.5 percent, whereas with hot HC1, the best
extraction efficiency was almost 50 percent and averaged
38.5 percent. This phenomenon is to be expected as most
sulfides are more soluble at higher temperatures, (As in
the discussion in the preceding paragraph, samples whose
mass balance did not close within 75 percent of unity were
not considered here.)
CONCLUSIONS
Results of attempted extraction of five metals (arsenic,
cadmium, copper, lead, and zinc) from five different soil
types from the Celtor Chemical Works waste were generally
unsuccessful. None of the extractants were capable of pro-
ducing a soil below cleanup level for all metals if the
soil was initially above cleanup level in more than one
metal. The most likely reason for the failure of the
extractants to perform better is that a majority of the
metals in the soils are in insoluble sulfide forms. What
little extraction was obtained was probably due to solubili-
zation of weathered, oxidized surface areas of ore
particles.
Extraction is not recommended as a treatment alternative for
the Celtor Chemical Works wastes. Treatment of this nature
would result in high capital and O&M costs, leaving the site
and soils in substantially no better condition than they are
at present.
RD/R34/031 4-2
-------
Appendix A
DESCRIPTION OP IKITIAL SOIL CHARACTERIZATION
Approximately 150 to 200 pounds of each of the soil samples
shown in Table 2-1 were obtained at the Celtor site. Each
sample consisted of three to four 50-pound bags. Figure 2-1
is a map of the site showing sample locations.
Each of the soil samples was spread out on plywood or sam-
pling pans and allowed to dry for 24 hours. After this dry-
ing period, the samples were broken up by hand to reduce the
size of the clods, but leave all rock intact. Where neces-
sary to obtain an adequate amount of sample, bags of soil
were thoroughly mixed to form a homogeneous composite. A
riffle sampler was then used to split off a representative
portion for crushing, digestion, and subsequent analysis to
determine the metals content of the raw, unsegregated
samples. (The riffle sampler splits any sample that is put
in it into two equal, representative portions.) To obtain a
sample small enough to be easy to work with and pulverize,
the riffle sampler was used to split the original sample in
half, then the half sample into quarters, etc., until the
desired sample size was produced. The openings in the
riffle sampler used are approximately 1-1/2 inches wide by
12 inches long. In all soil samples but Sample I, the
riffle sampler passed the entire sample.
For Sample 1, to obtain a representative portion for crush-
ing, digestion, and subsequent analysis, the weights of the
amount passing and not passing the riffle sampler were
obtained. When the portion split off for digestion was
obtained by passing it through the riffle sampler several
times, it was then weighed, and a proportionate amount of
the "larger than riffle sampler" portion was added to it.
The sample crushing for digestion and metals analysis con-
sisted of pulverizing the sample to No. 200 and smaller.
Each soil sample (1, 2, 3, etc.) was initially sieved into
the following gradations:
o 1 inch and larger
o 1 inch to No. 4
o No. 4-passing
The minus No. 4 portion was sieved into splits of minus
No. 10 and plus No. 10 portions. The plus No. 10 portion
was then combined with the 1-inch-to-No. 4 portion, result-
ing in a combined portion consisting of all the No. 10-to-
1-inch particles of the sample. The entire sample was not
initially sieved through a No. 10 screen because of
equipment limitations.
RD/R34/032 A-l
-------
Next, both the 1-inch-retained and the No. 10-to-l-inch por-
tions were washed with deionized water and the fines
retained for inclusion into the No. 10-passing portion. The
washwater was allowed to settle for 1 to 2 hours and the
supernatant decanted (a portion of the supernatant was saved
for analysis of total solids and metals for later incorpora-
tion into a mass balance). Decanting of the supernatant was
necessary to obtain quick drying of the washwater solids so
they could be incorporated into the No. 10-passing solids,
to allow extraction testing to proceed because of the
necessity to complete testing quickly. After the dry wash-
water solids were blended into the No. 10-passing solids, a
portion of this size fraction was split off from each soil
for digestion and analysis.
Examination of the No. 10-to-l-inch and 1-inch-retained
solids after the initial washing showed a small but signifi-
cant portion of attached soil and fines. Because of these
fines, both of these portions were washed and dried a second
time. The fines from these washings were not saved, but
final weighing of both size fractions (No. 10-to-l-inch and
1-inch-retained) was obtained after drying to determine the
weight of fines removed. The 1-inch-retained portion was
then pulverized for analysis. Part of the No. 10-to-l-inch
portion was also split off for pulverizing and analysis.
Before the second washing, a fraction .of the No. 10-to-l-
inch sample was split off for sieving to characterize it in
terms of particle size distribution and metals content. The
sieves used were No. 3, No. 6, and No. 10. Each of the por-
tions retained was weighed and then bagged for pulverizing
and metals analysis. As might be expected, a portion of
this No. 10-to-l-inch fraction passed the No, 10 sieve. The
portion passing the No. 10 sieve was weighed but not
analyzed. Figure A-l is a schematic of the processing used
for the soils characterization.
RD/R34/032
RD/R34/032 A-2
-------
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Sept 1986
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A-1
SCHEMATIC OF CELTOR CHEMICAL WORKS
SOIL SAMPLE PROCESSING
-------
Appendix B
DETAILED DESCRIPTION OF LEACHING PROCEDURE
AND EVALUATION OF EXTRACTION
EXTRACTION OF NO. 10-PASSING SOIL
To perform each analysis on the No. 10-passing portion, a
100-gram soil sample was first weighed and placed into a
250 ml Nalgene bottle. To assure that samples tested were
representative of the bulk mass, portions to make up the
100-gram sample were taken from different areas of the bulk
sample container. All weighings were done to an accuracy of
±0.1 gram.
Two hundred milliliters of the extractant solution were
added to the bottle which was then capped and placed on a
shaker table for 1 hour. After the 1-hour shaking, each
bottle was set aside and its contents allowed to settle
until the settling rate had slowed significantly
(approximately 1/2 hour to 1 hour).
The supernatant from these samples was centrifuged to remove
fines and allow for easier filtration in subsequent steps.
The supernatant from the centrifuge tubes was vacuum-
filtered through a 0.45-micron filter and the filtrate acidi-
fied and set aside for analysis of As, Cd, Cu, Pb, and Zn.
The solids from the original shaker bottle (containing
residual extractant solution) as well as the solids from the
centrifuge tubes (also containing residual extractant solu-
tion) were washed with deionized water in a pressure filter
apparatus using a piece of prefilter paper. After the
initial filtration was finished, an additional 200 ml of
deionized water was used to wash the solids. No attempt was
made to quantitatively recover the solids from the extrac-
tion; rather, as much of the solid phase as was easily
recoverable was saved. We estimate that the amount of
solids recovered by this process was greater than
95 percent.
This procedure was followed for all samples except the sam-
ples extracted with sodium gluconate. These samples were
extremely difficult to vacuum-filter, so an alternate proce-
dure was followed with these. The entire sample was ini-
tially filtered in the pressure filter on 0.45-micron paper
to collect the extractant. The solids from the pressure
filtration were then transferred to a piece of prefilter
paper and processed as described above.
The rationale for using a 0.45-micron filter for the extrac-
tant supernatant and the second water wash for the solids
was to obtain as total a separation of the phases as pos-
sible. It was thought that this procedure would help to
B-l
-------
ensure closure of a mass balance between the liquid- and
solid-phase metals and the starting sample. Additional
water washes of the solid phase were considered, but were
rejected because of the excessive amount of time this would
have required (some pressure filtrations took up to an hour
to complete).
After filtration, the soil sample was placed in an oven to
dry. After drying, the sample was crushed to No. 200 and
finer and then digested and analyzed for total metals (see
main text for appropriate EPA methods).
EXTRACTION OF NO. 10-TO 1-INCH SOIL
Processing of the No. 10-to-l-inch solids followed a proce-
dure similar to that of the No, 10-passing solids with the
following differences:
o The extracted sample supernatant was not centri-
fuged after shaking; rather, it was filtered
directly. Because the residue on the filter paper
contained significant fines, these fines were
washed back into the solids that were to be
pressure-filtered.
o In weighing out the 100-gram solids sample, it was
apparent that obtaining a representative, uniform
sample would be extremely difficult because of the
heterogeneity of the sample. To help alleviate
this difficulty, for each soil type, a sample of
approximately 1,000 grams was obtained from the
No. 10-to-l-inch portion (enough for 10 bottles,
or duplicates for one of the five soils). The
larger pieces in the 1,000-gram sample were then
separated out and distributed approximately evenly
to each of the 10 sample bottles. The bottles
were then "topped off" to 100 grams with the
smaller mesh particles of the remaining soil.
After separation of the solid and liquid phases, the liquid
phase pH was measured. The color of the extractant solu-
tions was also compared between duplicates. Any of the
No. 10-to-l-inch duplicate samples that showed obvious color
differences or showed pH variations of more than 0.1 unit
were rerun to obtain a third analysis. Figure B-l is a
schematic process diagrams of the leaching process.
SECOND PHASE EXTRACTIONS
After the majority of data was obtained in the previous
phase of leaching experiments/ CH2M HILL, SAIC, and EPA
B-2
-------
90LID9
FIITEB
WASH
ORY
PUUEHIZE
ANALYZE
flDD
1
CLARIFY
SUPEttNAHNT
FOLIOS
$0111)9
1
FILTER
FILTHA7E
AMALYZE
f fa meM MttfM)
OHLY
Sept 1986
Figure B-1
SCHEMATIC OF CHEMICAL
LEACHING PROCESSING OF
CELTOR CHEMICAL WORKS
SOILS (Unheated extractants)
-------
participated in a conference call to determine the procedure
for the next phase of studies, if any. This conference call
occurred on August 2, 1985.
Because of the generally poor performance of all the chemi-
cals on all the soils, it was decided not to proceed with
any optimization studies as originally envisioned (see
"Results" section for a more detailed description of results
of extractions). Rather, it was decided to perform addi-
tional extractions with some of the more promising chemi-
cals, with modifications to the process to increase the
extraction efficiencies. The following additional
extractions were performed:
o Extraction of the No. 10-passing fraction of
Sample 1 and Combined Samples 4 and 6 with EDTA
(13 percent by weight, pH = 7.0) after the soil
sample had been pulverized to finer than No. 200.
o Extraction of the above soil samples (again after
pulverizing to No. 200 and finer) with HC1 (pH =
0.8, approximately 0.16 molar)
o Hot HC1 (pH = 0.8, approximately 0.16 molar)
extraction of the No. 10-passing fractions of
Sample 1 and Combined Samples 4 and 6
(unpulverized)
o Hot HC1 (pH = 0.8, approximately 0.16 molar)
extraction of the No. 10-passing fractions of
Sample 1 and Combined Samples 4 and 6 (pulverized)
The extractions using EDTA and unheated HC1 were performed
in essentially the same manner as the original extractions
on the No. 10-passing samples, with the following
differences:
o Twenty-five grams of soil sample were used.
o Two hundred fifty milliliters of extractant were
added to each sample initially.
o The supernatant from each sample was not centri-
fuged, as the solid and liquid phases separated
fairly well.
o Initial pH of HC1 was 0.8.
The hot HC1 extractions were performed as follows:
o Twenty-five grams of sample were weighed into a
400 ml beaker.
B-3
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o The HC1 extractant was heated to 150°F (initial pH
was 0.8), and then 250 ml of the hot HC1 were
added to the 400 ml beaker using a graduated
cylinder.
o As soon as acid had been added to all samples,
stirring of each sample was initiated to maintain
all solids in suspension.
o A hot plate stirrer was used to maintain the temp-
erature of each solution between 135°F and 155°F.
(Only one hot plate stirrer was available, so each
of the samples was switched between the hot plate
and standard stirrers to maintain its temperature
within the limits noted.)
o After 1 hour of mixing and heating, each sample
was taken off its stirrer and allowed to clarify.
o Two hundred milliliters of the supernatant from
each sample were decanted and filtered through a
0.45-micron filter. The filtrate was saved for
later analysis of As, Cd, Cu, Pb, and Zn.
o Two hundred milliliters of fresh HC1 were added to
each solid sample and the above heating and stir-
ring repeated.
o Approximately 200 ml of the second extractant
solution were filtered through a 0.45-micron
filter and the filtrate saved for later analysis.
o The solid portion was pressure-filtered and washed
with two successive 200 ml/portions of deionized
water.
o The solid phase was dried for later digestion and
analysis (the unpulverized No. 10-passing sample
was pulverized before analysis).
See Figure B-2 for a schematic of these extractions.
EXTRACTION SUMMARY
EVALUATION OF EXTRACTION OF SAMPLE 1
This soil is above cleanup level for all metals in the
No. 10-passing portion. For the No. 10-to-l-inch portion,
the soil is below cleanup level for all metals.
B-4
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SAMPLE
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Figure B-2
SCHEMATIC OF CHEMICAL
LEACHING PROCESSING OF
CELTOR CHEMICAL WORKS SOILS (Hot acid)
t 1986
-------
Extraction with Sodium Gluconate
On the No. 10-passing portion, this extractant showed high
removals of lead only (48 percent) with reduction of lead to
approximately one-half its cleanup level. Removal of arse-
nic was as high as 18 percent, although mass balance closure
for arsenic was 81 percent at best, and concentrations of
arsenic in the soil were not below cleanup level after
extraction. Removals of cadmium, copper, and zinc were
relatively minor (all less than 10 percent), and con-
centrations of these constituents were above cleanup level
after extraction.
For the No. 10-to-l-inch portion of this soil, no signi-
ficant removals of any of the five constituents were
obtained. The best removal was that of arsenic which was a
maximum of 11 percent.
Extraction With EDTA
Extractions were performed on both pulverized and unpulver-
ized samples. Comparing the pulverized and unpulverized
samples, it can be seen that efficiency of extraction of all
metals were similar except for lead. Arsenic was not
measured on the pulverized sample. Removal of lead was
approximately 4 percent in the unpulverized sample and
12 percent in the pulverized sample. Removals of cadmium,
zinc, copper, and arsenic were approximately 30 percent,
10 percent, 6 percent, and 1 percent, respectively. Lead
was the only metal below cleanup level after extraction,
although removal efficiency data do not indicate that a
major portion was extracted.
Data on the No. 10-to-l-inch portion show significant
removals of cadmium and zinc (approximately 40 and 24 per-
cent, respectively) while removal of the remaining three
metals were all 12 percent or less (arsenic removal was only
one percent).
Extraction With Acetic Acid
Extraction of the No. 10-passing portion with this solution
showed approximately 30 percent cadmium removal, but the
soil was still above cadmium cleanup level after extraction.
Removals of the remaining metals were minimal, 10 percent or
less for all instances except the value of 11 percent for
zinc. Although the value for lead in the extracted soil is
below the cleanup level, liquid phase concentrations and
extraction efficiencies indicate little removal.
Data for the No. 10-to-l-inch portion indicate that some
removal of Cd, Cu, and Zn was obtained with little removal
of As and Pb. Removal of Cd was as high as 43 percent.
B-5
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Again, the levels of metals in this portion of the sample
were all below cleanup level initially.
Extraction With HC1 (Ambient Temperature)
For the No. 10-passing portion, extractions were performed
on both pulverized and unpulverized samples. Results for
these samples were similar (arsenic was not analyzed in the
pulverized sample). Cadmium removal ranged from 32 to
41 percent, zinc removal from 11 to 16 percent, and copper
from 9 to 13 percent. Although removal of lead was four to
five times greater for the pulverized sample than the
unpulverized, it was nevertheless only 4 to 5 percent.
Removal of arsenic was minimal (arsenic was not tested for
in the pulverized sample). No metals were removed to below
cleanup level for either the pulverized or unpulverized
sample, except for two instances for lead; and removal
efficiency does not indicate large removals of lead.
The data on the No. 10-to-l-inch portion indicate that 41
to 43 percent of soil Cd was removed, along with 17 to
24 percent of zinc and 11 to 19 percent of copper. Five
percent or less of arsenic and lead was removed.
Extraction with Hot HC1
These extractions were performed on the No. 10-passing por-
tions for both pulverized and unpulverized samples. If
results are compared between the pulverized and unpulverized
samples, removal of all metals appear to be similar. Lead
was the only metal below cleanup level after extraction
(arsenic was not measured). In general, it appears that
more Zn is removed in Extraction 2 than in Extraction 1.
Although a greater percentage of cadmium was removed
compared to lead, cadmium was still above cleanup level
after extraction. Approximately 17.5 percent of the copper
was removed from the soil, and 6 percent to an average of
15 percent of the zinc was removed in extraction of the
unpulverized and pulverized samples, respectively.
HC1/H202 Extractant
For the No. 10-passing portion, this extractant removed
approximately 33 percent of cadmium and approximately
10 percent or less of all other metals. Note the similar-
ities in extraction efficiencies between this extractant and
the HC1 (ambient temperature) extractant. In general,
removal to below cleanup level was not obtained. The soil
was slightly below cleanup level in copper after extraction.
B-6
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Data for the No. 10-to-l-inch portion show some variation,
but in general, removals were significant for cadmium only
(average 44 percent removal), although the third extraction
showed a 41 percent removal of zinc. Average removal of
copper was 15 percent, and removals of arsenic and lead were
both less than 10 percent.
EVALUATION OF EXTRACTION OF SAMPLE 2
In Sample 2, As, Cu, and Pb were above cleanup level in the
No. 10-passing portion. For the No. 10-to-l-inch portion,
Cu was the only metal found to be above cleanup level.
Extraction with Sodium Gluconate
Extractions on the No. 10-passing portion of Sample 2
showed little removal of any metals (less than approximately
6 percent). Note that in general the mass balances for this
extraction do not close within 10 percent, with some excep-
tions. No metals were removed to below cleanup level.
For the No. 10-to-l-inch portion, removals were also gener-
ally minor, and although copper was removed to below its
cleanup level on the average (avg concentration Cu =
2,490 mg/kg), liquid phase copper concentrations and
percentage removal data do not corroborate large removals.
Extraction with EDTA
Removals for all metals for both the No. 10-passing portion
and the No. 10-to-l-inch portions were minor (the largest
removal was 15.5 percent for cadmium on the No. 10-to-l-inch
portion). No removals to below cleanup level were obtained.
Extraction with Acetic Acid
Extraction efficiency for all metals was minor on both the
No. 10-passing and the No. 10-to-l-inch portions (approxi-
mately 14 percent maximum). Again, no removals to below
cleanup level were obtained, with the exception of copper in
the No. 10-to-l-inch portion, and liquid phase and per-
centage removal data do not corroborate significant removals
for copper.
Extraction with HC1
Removals on both the No. 10-passing and the No. 10-to-l-inch
portions were minor (the maximum removal was 14.5 percent
for zinc). Although lead was below cleanup level on the
second extraction on the No. 10-passing portion and copper
was below cleanup level on the second extraction for the
No. 10-to-l-inch portion, mass balance, liquid phase and
extraction efficiency data would indicate that these samples
were probably below cleanup level initially.
B-7
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Extraction with
Again, removals for all metals on both mass fractions were
apparently minor (greatest removals were of cadmium and zinc
in the No. 10-passing fraction, both at 15.1 percent).
Although copper was below cleanup level for the extraction
on the No. 10-to-l-inch portion, the mass balance, liquid
phase, and extraction efficiency data again indicate that
the starting sample was probably initially below the cleanup
level,
EVALUATION OF EXTRACTION OF SAMPLE 3
Sample 3 contained no metals concentrations that were above
cleanup level for the No. 10-passing and No. 10-to-l-inch
portions.
Extraction jtfith j-todium Gluconate
For the No. 10-passing portion, significant removals of
lead, copper, and arsenic were obtained (average of 43.6,
29.3, and 21.2 percent, respectively). Removals of cadmium
and zinc were less than 5 percent.
Removals varied significantly for the extractions performed
on the No. 10-to-l-inch portion. Some significant removals
of lead (up to 51 percent), copper (up to 26.8 percent), and
arsenic (up to 22 percent) were obtained. Removals of
cadmium and zinc were not significant (less than
14 percent).
Extraction with EDTA
Moderate removals were obtained on the No. 10-passing por-
tion for copper, cadmium, and zinc (average removal of 28.6,
18.5, and 14.1 percent, respectively). Removals of arsenic
and lead were small.
In general, there were wide variations in removals between
the two extractions for the No. 10-to-l-inch portion. Aver-
age removals were copper—23.9 percent; lead—23.4 percent;
cadmium—13.6 percent; zinc—15 percent; and
arsenic—0.6 percent.
Extraction with Acetic Acid
For the No. 10-passing portion, moderate removals were
obtained for copper, cadmium, and zinc (approximately 26.6,
15.4, and 15.4 percent, respectively). Little arsenic and
lead were removed.
As with sodium gluconate, removals varied significantly
between extractions for the No. 10-to-l-inch portion.
B-8
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Removals of zinc, cadmium, and copper were as high as
76 percent, 40 percent, and 37 percent, respectively.
Removals of arsenic and lead were small.
Extraction with HC1
Moderate removals were obtained on the No. 10-passing por-
tion of copper, cadmium/ and zinc (32.5, 23.4, and
18.1 percent, respectively). Removals of arsenic and lead
were small.
Removals for the No. 10-to-l-inch portion were similar to
the No. 10-to-l-inch passing portion, although significant
variation was noted between extractions.
Extraction with
Moderate removals were obtained on the No. 10-passing por-
tion for copper, cadmium, and zinc (average removals of
36.2, 25.2, and 18.6 percent, respectively). Removals of
arsenic and lead were minor.
There were some variations in removals between extractions
for the No. 10-to-l-inch portion, with moderate removals of
copper, cadmium, and zinc {average removals of 48.5, 20.4,
and 19.2 percent, respectively). Removals of arsenic and
lead were small, less than 5 percent.
EVALUATION OF EXTRACTION OF COMBINED SAMPLES 4 AND 6
Of the No. 10-passing fraction, the Combined Samples 4 and 6
were above action limits in all metals except for Pb. Of
the No. 10-to-l-inch portion, none of the metals were above
cleanup level. The same extractions performed on Sample 1
were also performed on this sample, including the hot acid
and pulverized sample extraction.
Extraction with Sodium Gluconate
On the No. 10-passing portion, major removals of lead (50
to 51 percent) and moderate removals of arsenic (15 to
17 percent) were obtained. Removals of the remaining metals
were all less than 5 percent, and no removals to below
cleanup level were obtained.
For the No. 10-to-l-inch portion, moderate removals of arse-
nic, lead, and copper were obtained (average removals of
33.6, 27.9, and 14.3 percent, respectively). Removals of
cadmium and zinc were less than 10 percent.
B-9
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Extraction with EDTA
As with Sample 1, extractions were performed on both pulver-
ized and unpulverized samples of the No. 10-passing portion
of the soil. Arsenic was not analyzed in the extractions on
the pulverized portion. Removal of lead was about 2 to
3 times greater in the pulverized versus unpulverized por-
tions, averaging 56.1 and 22 percent, respectively.
Removals were similar for cadmium between pulverized and
unpulverized samples, averaging about 5 to 6 percent.
Except for the apparently anomalous first extraction on the
unpulverized portion, removals of zinc were similar on-both
portions/ averaging slightly above 5 percent. Removal of
copper was approximately 2 to 3 times greater in the unpul-
verized than in the pulverized portion, averaging 6 and
2.4 percent, respectively. Removal of arsenic was less than
1 percent. No removals to below cleanup level were
obtained, except in one case with zinc.
For the No. 10-to-l-inch portion, minor to moderate removals
of all metals but arsenic were obtained (averages for cad-
mium, copper, zinc, and lead were 38.3, 28.2, 30.1, and
11 percent, respectively). Removal of arsenic was less than
1 percent.
Extraction with Acetic Acid
Removals of metals were all approximately 5 percent or less
on the No. 10-passing portion, and no removals to below
cleanup level were obtained.
On the No. 10-to-l-inch portion, moderate removals were
obtained for cadmium, zinc, and copper (average removals of
38.6, 31.0, and 22.1 percent, respectively). Removals of
lead and arsenic were less than 4 percent and 1 percent,
respectively.
Extraction with HC1 (Ambient Temperature)
As with Sample 1, for the No. 10-passing portion, extrac-
tions were performed on both pulverized and unpulverized
samples. Results for the pulverized and unpulverized sam-
ples were generally similar. Generally, removals were
approximately 6 percent or less, with the exception of zinc
in the second extraction on the unpulverized sample, which
showed a removal of 21 percent. Note that for this extrac-
tion, the amount of zinc in the soil after extraction is
shown to be below action limits. Whether this sample was
initially above or below cleanup level in zinc or there is a
possible error in analysis is unknown. Note that lead
removal for the pulverized sample was approximately 4 to
5 times greater than for the unpulverized sample, as was the
case with Sample 1. Except for the case of zinc, no
apparent removals to below cleanup level were obtained.
B-10
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For the No. 10-to-l-inch portion, high to moderate removals
of cadmium, zinc, and copper were obtained (average of 64.3,
48.0, and 36.6 percent, respectively). Removals of arsenic
and lead were less than 3 percent.
Extraction with HC1 (Hot?
As with Sample 1, extractions were performed on both pulver-
ized and unpulverized samples of the soil. Arsenic was not
analyzed in these extractions. Results for both the pulver-
ized and unpulverized portions are quite similar, with the
exception of the value for zinc on the second extraction
of the pulverized sample. The value for zinc in the
extracted soil for this sample indicates that the sample may
have started out low in zinc or that the analysis may be
incorrect. Removals were all approximately 10 percent or
less, except for lead, of which approximately 44.7 percent
was removed, on the average. No removals to below cleanup
level, except in the one case of zinc, were obtained.
Extraction with HC1/H202
For the No. 10-passing portion, removals of all metals were
minor (maximum removal of less than 7 percent). No removals
to below cleanup level were obtained.
On the No. 10-to-l-inch portion, moderate removals of cad-
mium, copper, and zinc were obtained (average of 40.8, 26.2,
and 19,6 percent, respectively). Removals of lead and
arsenic were less than 3 percent,
EVALUATION OF EXTRACTION OF SAMPLE 5
Sample 5 was above cleanup level in lead and arsenic.
Extraction with Sodium Gluconate
Moderate removals of copper and arsenic were obtained (aver-
age of 23.4 and 20.9 percent, respectively). Removals of
cadmium, lead, and zinc were minor, all being less than
8 percent. Removal to below cleanup level was not obtained
for any metal.
Extraction with Acetic Acid
The only moderate removal obtained with acetic acid was with
copper (average of 46.2 percent). Removal of all other
metals was less than approximately 4 percent. Removal to
below cleanup level was not obtained for any metal.
B-ll
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Extraction with HCl, EDTA, and HC1/H2CU
As with acetic acid, the only moderate removal achieved was
on copper (average removal between 17 and 22 percent).
Removal of all other metals was less than 7 percent, and
removal to below cleanup level was not obtained for any
metal.
SUMMARY OF EXTRACTION PERFORMANCE
In the following section, a brief summary of the effective-
ness of each extractant is presented. In this discussion we
have limited examination of extractant performance to those
soils that had metals which were initially above cleanup
level and to the unpulverized samples. This decision was
made in the interest of simplifying this summary and because
the metals and soils that are above cleanup level are of
greatest concern.
Sodium Gluconate
This extractant performed best on arsenic and lead (maximum
removals of approximately 21.2 and 48 percent, respectively),
Removal of cadmium, copper, and zinc were poor, maximum
removals being less than 10 percent.
EDTA
EDTA appeared to be effective for cadmium removal only, and
its maximum extraction efficiency was 30 percent. Note that
the analysis for zinc on the first extraction of the unpul-
verized sample of Combined Samples 4 and 6 was not included
here because of questionable data.
Comparing extraction efficiencies for the pulverized and
unpulverized samples shows little difference in efficiencies
except for the case of copper and lead.
Acetic Acid
Acetic acid was most efficient in the extraction of cadmium,
the maximum removal being 31 percent. Removals of all other
metals were 10 percent or less.
Hydrochloric Acid (Ambient Temperatures)
This extractant was similar to acetic acid in its efficiency
of extraction. Maximum removal of cadmium was 41 percent.
Removals of all other metals were poor, less than
15 percent. The analysis of zinc for the second extraction
on the No. 10-passing portion of Combined Samples 4 and 6
was not considered in this summary because of questionable
data.
B-12
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Comparison of extraction on the pulverized and unpulverized
samples shows similar efficiencies for all metals except
lead (arsenic was not analyzed for the pulverized sample).
Although lead removal was significantly higher for the
pulverized samples, it was still below 6 percent in all
cases.
Hot Hydrochloric Acid
The use of hot HC1 greatly improved efficiency of lead
extraction and improved copper and zinc extraction
efficiency somewhat. Pulverizing the sample seemed to
improve zinc extraction efficiency slightly, but did not
seem to improve extraction of any other metals greatly.
Maximum removals for lead, cadmium, zinc, and copper were
50, 37, 44, and 18 percent, respectively. The analysis for
zinc on the second extraction of the pulverized sample was
not included here because of questionable data.
HC1/H202 Extractant
As was the case with acetic acid and hydrochloric acid, cad-
mium was the only metal removed to any significant extent.
Its maximum removal was 33 percent.
RD/R76/016
B-13
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