00411
&EPA
United StatfS
Environmental Protection
Agpncy
Great Lakes National
Program Office
536 South Clark Street
Chicago, Illinois 60604
RCRA EP Toxcity
Test Applied To
Dredged Material
905F84100
Reprinted from Proceedings of the
Conference Dredging '84, ASCE,
Clearwater Beach, Florida, November 1984
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U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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RCRA EP Toxicity Test Applied to Dredged Material
Anthony G. Kizlauskas '
and
David Homer 2
ABSTRACT
A set of 25 Great Lakes harbor sediment samples were subjected to
bulk sediment analysis and the EP Toxicity Test. Based on the
results of this pilot study, there appears to be little, if any,
correlation between the contaminant concentrations in the EP
Toxicity Test extract and the bulk sediment concentrations of cadmium
chromium, and lead. None of the sample extracts exhibited the EP
toxicity characteristic of hazardous wastes for cadmium, chromium,
lead, and mercury despite the fact that the bulk sediment concen-
trations of these contaminants were amonq the highest typically
encountered in Great Lakes dredged sediments.
INTRODUCTION
Industrial and population centers are typically located along navi-
qable rivers and harbors since the availability of water-borne com-
merce is frequently one of the siting requirements. Regular dredging
is usually necessary to keep the rivers and harbors navigable. An
average of 4.1 million cubic meters (5.4 million cubic yards) of
sediments are dredged annually in the U.S. Great Lakes alone (2).
The high concentrations of industry and population lead to con-
centration of sources discharging pollutants to the waterways.
Sediments typically concentrate contaminants to many times the
concentration of the contaminant in the effluent or the water
column. In order to protect the environment and the public
health against damage from the careless dredging and disposal of
contaminated sediments in inland waters, Congress included Section
404 in the federal Water Pollution Control Act to regulate these
activities.
U.S. Environmental Protection Agency, Great Lakes National Program
Office, 536 South Clark Street, Chicago, Illinois 60605.
U.S. Environmental Protection Agency, Waste Management Division,
230 South Dearborn Street, Chicago, II1 i rib 1s'r 60604' - : *"-."
lot
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362 DRI.IKiU) MA 11 KIAL DISPOSAL
The Section 404 regulations are the primary tool used by the USEPA
and the U.S. Anny Corps of Engineers to regulate the discharge of
dredged or fill material in the inland waters of the U.S.
Passage of the Resource Conservation and Recovery Act (RCRA) in 1976
and promulgation of the applicable regulations introduced an additional
set of regulations to which dredged material is subject.
Resource Conservation and Recovery Act
Congress passed the Resource Conservation and Recovery Act (RCRA) on
October 21, 1976. as Public Law 94-580, to provide for the recovery
of energy and other resources from discarded materials, to provide
for the safe disposal of discarded materials, and to regulate the
management of hazardous waste. Subtitle C of the Act established a
federal program to regulate the management of hazardous solid waste
from "cradle to grave." USEPA promulgated the first phase of reg-
ulations in February and Nay 1980 to initiate the Subtitle C program.
The generator of a solid waste is required to determine if the waste
is hazardous (40 CFR Part 262.1).
Solid waste may be defined as hazardous by two methods. First, the
waste may be listed as a hazardous waste by the Aguncy based on infor-
mation about the waste.
Wastes listed as hazardous under RCRA regulations (40CFR Part 261,
Subpart 0} include:
1) Generic wastes from non-specific sources (13 sources)
This includes spent solvents, electroplating wastes, and metal
heat-treating wastes.
2) Wastes from specific sources (72 sources)
This includes specific wastes from the following industries - wood
preservation, inorganic pigments, organic chemicals, inorganic
chemicals, pesticides, explosives, petroleum refining, iron and
steel, secondary lead, veterinary Pharmaceuticals, ink formulation,
and coking.
3) Discarded commercial chemical products, off-specification species,
containers and spill residues
(i) Acute hazardous wastes (106 wastes)
(ii) Toxic Wastes (230 wastes)
If a waste is not listed as a hazardous waste, it may still be hazardous
because it exhibits a characteristic of a hazardous waste. The charac-
teristics are Ignitability, corrosivity, reactivity, and Extraction
Procedure (EP) Toxicity, and are determined by specific tests (40 CFR
Part 261 Subpart C and Appendix II) or by knowledge of the chemical
and physical properties of the waste.
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KCKA I-.P lOXICIIY I LSI K)
If a waste is defined as hazardous under RCRA, the transportation,
storage, and disposal of that waste is subject to stringent and, there-
fore, costly requirements (40 CFR Parts 124, ?60 to 267 and 2/0).
Due to the very larqe quantities of material involved, there has been
a great deal of concern over whether dredged material could be defined
as a hazardous waste and, therefore, whether its management could be
subject to the RCRA regulations. Certain wastes are specifically ex-
cluded from the definition of solid waste and, therefore, are exempt
from RCRA regulation (40CFR Part 261.4). Dredged material, however,
does not have this exclusion. Dredged material meets the definition
of a solid waste, so it must be evaluated to determine if it is
hazardous. The characteristic dredged material is most likely to
exhibit is EP Toxictty.
The EP Toxicity Test
The EP Toxicity Test is intended to simulate the leaching of con-
taminants from waste co-disposed in a municipal landfill. The first
step in the test Is to separate the waste (minimum of 100 g) into its
solid and liquid fractions. Next, the solid portion is reduced in
particle size (if necessary) to pass through a 9.5 mm standard sieve,
and diluted with 16 times its weight In deionized water. Then, 0..5N
acetic acid is added to the solution to adjust the pH to 5.0 ^ 0.2,
maintained at that level (with an upper limit of 4 ml of acid per gram
of sample), and is shaken for 24 hours at ambient temperature (20°C -
40"C). After shaking, additional deionized water is added to bring
the total volume (mi 11iliters) of the solution to 20 times the sample
weight (grams). The sample is filtered through a 0.45 pm filter, the
filtrate (the "extract") is combined with the initial liquid fraction
and the combined liquid Is analyzed for the contaminants in Table I.
If the concentrations exceed any of the levels listed in Table 1, the
waste is classified as a hazardous waste.
The question of when to require testing of dredged material for hazar-
dous waste characteristics (EP Toxicity) is important in view of the
thousands of 404 permits issued and the millions of cubic yards of
material dredged annually. One potential approach to this question
is to examine results from the bulk analysis of sediments to be dredged.
Certain assumptions can be made: 1) that contaminants competely dis-
associate from the sediment and dissolve in the extract during the
EP Toxicity Test, and 2) that the dilution ratio that occurs in the
EP Toxicity Test is 20 to 1. Based on these assumptions, screening
levels (Table 2) may be established for the bulk chemical concen-
trations, below which it would be Impossible for a sediment to
fail the EP Toxicity Test (1). A pilot study was undertaken to
address the question of the practical applicability or reasonable-
ness of these screening levels.
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OKlilKil.D MAII.KIAI. DISPOSAL
Table 1
Maximum Concentration of Contaminants
for Characteristic of EP Toxicity
EPA Maximum
Hazardous Concentration
Waste Contaminant (Milligrams
Number Per liter)
D004 Arsenic 5.0
0005 Bari urn 100.0
0006 Cadmi urn 1.0
D007 Chromium 5.0
0008 Lead 5.0
0009 Mercury 0.2
0010 Selenium 1.0
0011 Silver 5.0
0012 Endnn(l,2,3,4,10,10- 0.02
hexachloro-1,7-epoxy-
1.4.4a. 5.6,7.8.8a-
octahydro-l,4-endo,endo-
5,8-dimethano naphthalene).
0013 Llndane(1.2.3.4.6.6- 0.4
hexachlorocy1hexane.
gawwa isoiner)
0014 Methoxychl or{ 1,1,1- 10.0
Trichloro-2,2-bis[p-
methoxyphenyt]ethane)
0016 Toxaphene (CjoHioCla 0.5
technical chlorinated
camphene, 67-69 percent
chlorine).
0016 2.4-0(2,4- 10.0
Dichlorophenoxyacetic
acid).
0107 2,4.5-TP Silvex (2.4.5- 1.0
TrUMorophenoxyproplonic
acid).
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RCKA hi' IOXICIIY II.ST .165
Table 2
Suggested Screpning Levels to Determine the Need for EP Toxicity
Testing of Sediments.!1) Values are bulk sediment contaminant con-
centrations.
Arsenic 100.0 mg/kg
Barium 2000.0 mg/kg
Cadmium 20.0 mg/kg
Chromium 100.0 mg/kq
Lead 100.0 mg/kg
Mercury 4.0 mg/kg
Selenium 20.0 mg/kg
Silver 100.0 mg/kg
Endrin 0.4 mg/kg
Lindane 8.0 mg/kg
Methoxychlor 200.0 mg/kg
Toxaphene 10.0 mg/kg
2,4-D 200.0 mg/kg
2,4,5-TP Silvex 20.0 mg/kg
THE PILOT STUDY
The Great Lakes National Program Office Harbor Sediment Program (3)
provided an ideal inventory of Great Lakes Harbor sediments from
which to choose samples to subject to th'e EP Toxicity Test. A
total of 25 samples from this Inventory were selected using the
suggested screening levels (Table 2). To get the maximum amount
of Information for the pilot study out of the least number of EP
extractions, samples were selected which exceeded the screening
levels for more than one contaminant at a time, and which covered a
wide range of bulk sediment concentration values (I.e., Ix, 2x, 3x, 4x
the screening levels for each contaminant). Because of this selection
process, the bulk sediment concentrations in the samples (Table 3)
do not necessarily exceed the screening levels for all contaminants
simultaneously. In the case of mercury, only one sample In the set
exceeded the mercury screening level. Therefore, mercury was only
analyzed in the EP extract of that single sample.
Bulk chemistry levels of cadmium, chromium, and lead were frequently
found in excess of the screening levels. Only one sample in the
inventory was found that exceeded the screening level for mercury.
None of the samples in the Inventory exceeded the screening levels
for the other contaminants specified in the EP Toxicity Test (Table 1).
The levels of cadmium, chromium, and lead in the samples selected
for the pilot study are among the highest typically encountered in
Great Lakes dredging projects. Therefore, the pilot study results
should represent a worst case situation. The samples selected for
the study consisted of:
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166 DKMXJkl) MA 11 KIAI. DISPOSAL
-9 from the Grand Calumet River. Indiana, collected in December 1980;
-4 from Milwaukee Harbor, Wisconsin, collected in July 1980; and
-12 from the Buffalo River, New York, collected in May and September
1981 .
The sediment samples had been stored at 4°C since collection. The
effects of holding time and preservation method on the results of
the FP Toxicity Test are not known. This adds an unknown amount of
uncertainty to the pilot study results.
RESULTS
Rocky Mountain Analytical, a U.S. EPA HWI sample contractor, analyzed
the samples for the EP Toxicity characteristic in November 198?.
Region V Central Regional Laboratory personnel reviewed the contract
laboratory's guality control data for these samples and found it accept-
able. The results are presented in Table 3.
Cadmium
Total cadmium concentrations of the sediments varied front 0.?? to 64
mg/kg or 0.01 to 3.2 times the suggested screening level of 20 mq/kg
(Table 2). Although leaching of cadmium occurred (Table 3), none of
the extract concentrations exceeded the 1 mg/1 EP maximum concentration
(Table 1). The highest extract concentration was 35 ug/1, or about
3.5% of the Table 1 value. A plot of the data (Figure 1) shows no
apparent relationship between bulk sediment concentrations and con-
centrations in the extracts. Assuming the detection limit con-
centration for the extracts that were below the detection limit, a
correlation of bulk sediment concentration and extract concentration
was made. This resulted in a correlation coefficient of 0.272,
and yielded a t-statistic of 1.36 (with 23 degrees of freedom),
indicating that there is no statistically significant correlation
between these parameters at the 95% confidence level.
Chromium
The bulk sediment concentrations of chromium ranged from 18 to 2.000
mq/kg or 0.18 to 20 times the suggested screening level of 100 mg/kg
(Table 2). No chromium was detected in any of the extracts above the
laboratory's 10 ug/1 detection limit.
Lead
Bulk sediment concentrations of lead ranged from 120 to 15,000 mg/kg
or 1.2 to 150 times the suggested screening level of 100 mg/kg
(Table 2). No lead was detected in any of the extracts above the
laboratory's 5 ug/1 detection limit.
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KCRA tl' TOXICJTY TbSl
Table 3
Bulk Sediment Concentrations and EP Extract Concentrations for 25
Selected Great Lakes Harbor Sediments.
.167
Cadmium
Bulk'/
Sample Number Extract?
GCR-1
GCR-2
GCR-3
GCR-4
GCR-S
GCR-6
GCR-7
GCR-8
GCR-9
MIL-1
MIL-2
MIL-3
MIL-4
BUF-1
BUF-2
BUF-3
BUF-4
BUF-5
BUF-6
BUF-7
BUF-8
BUF-9
BUF-10
BUF-11
BUF-12
Extract
Detection
1. Bulk
2. RCRA
3. I/NO
31 /NO
64/17
10/5
7.3/9
12/6
11/9
8/5
8/NO
17.8/ND
19.4/8
45.7/ND
11.6/7
0.64/ND
2. 8/NO
4.5/NO
12/35
25/ND
4.5/NO
B.9/ND
2.3/ND
4.2/NO
3.4/NO
5.9/ND
0.22/ND
Limits 1 ug/1
Chromium
Bulk*/
Extract2
160/ND
28/NO
1 300/ND
410/NO
470/NO
1 700/ND
2000/ND
1 000/ND
480/ND
386/ND
330/ND
423/ND
234/ND
18/NO
1 30/ND
54 /NO
1 80/ND
260/ND
68/ND
1 30/NO
45/NO
78/ND
92/NO
120/ND
18/NO
10 ug/1
sediment concentration in nig/kg
Lead
Bulk1/
Extract2
5?0/ND
4000/ND
1600/NO
1 5000/NO
1 400/NO
2100/NO
1 500/ND
1 300/NO
750/NO
634/NO
436/ND
477/NO
298/NO
140/ND
360/ND
300/NO
950/NO
840/ND
'2 30/ND
420/ND
130/ND
1100/NO
460/ND
180/NO
2100/NO
5 uq/1
dry weiqht.
Mercury
Bulk*/
Extract2
NA
12.0/ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.2 ug/1
EP Toxicity Test extract in ug/1.
NA * Not analyzed for this contaminant
NO - Below laboratory's detection limit
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368
ORtlXJbl) MAIURIAL DISPOSAL
o
I
o
o
«•*
o
X
UJ
*•*
w
0)
Q.
UJ
35 i
30
25
15 -
10
XX
223
XXXXXX XX
10 20 30 40 50 60
Bulk Sediment Concentration (mg/Kg)
Figure 1. Bulk Sediment Concentration v^_. EP Toxicity Test
Extract Concentration in Pilot Study for Cadmium.
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KCKA u' loxioi'Y it:Si 109
The data base for mercury was much more limited since only one of the
samples hdd d bulk sediment concentration (12 mq/ki)) that exceeded the
suggested screening level of 4 rog/kq. No mercury was detected in the
extract above the laboratory's 0.2 ug/1 detection limit.
CONCLUSIONS
Since the effect of sediment storage and preservation method on the
results of the EP Toxicity Test is not known, the study results contain
an unknown degree of uncertainty. With this caveat, based on the
results of this pilot study, the following conclusions can be drawn:
1) In sediments in the Great Lakes Basin only sediment concentrations
of cadmium, chromium, lead, and occasionally, mercury are likely
to exceed the suggested screening levels (Table 2).
2) There appears to be little, if any, correlation between the con-
taminant concentrations in the EP Toxicity Test extract and the
bulk sediment concentrations of cadmium, chromium, and lead.
(The results for mercury are less conclusive since there was
only one sample in the pilot study for that contaminant).
3) None of the sample extracts exhibited the EP toxicity character-
istic of hazardous wastes for cadmium, chromium, lead, and mercury
despite the fact that the bulk sediment concentrations of these
contaminants were among the highest typically encountered in
Great Lakes dredged sediments.
ACKNOULEOGEMENT
The results and conclusions presented in this paper are based upon work
conducted at Region V of the United States Environmental Protection
Agency. Mr. Vacys Saulys of the Great Lakes National Program Office
provided encouragement and support on the Study. Mr. Charles Elly
and Ms. Andrea Jirka of the Central Regional Laboratory provided
support for the laboratory analyses. Messrs. Alan S. Carson and
David Friedman of the U.S. Environmental Protection Agency Office
of Solid Waste and Messrs. Curtis Ross, Charles Elly, and Y.J. Kim
of Region V critically reviewed the manuscript. Ms. Gaynell Uhatley
provided tireless typing support.
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.170 UKhDGhU MAM:KIAL DISPOSAL
APPENDIX - REFERENCES
1. Homer, 0., U.S. Environmental Protection Agency, Region V, Waste
Management Division, Chicago, Ilinois, unpublished data, February
1981.
2. International Joint Commission, "Guidelines and Register for
Evaluation of Great Lakes Dredging Projects - Report of the
Dredging Subcommittee to the Water Quality Programs Committee
of the Great Lakes Water Quality Board," Windsor, Ontario,
January 1982.
3. Palmer. M.F., and Rockwell, D.C.. "1981-1982 Sediment Surveys."
U.S. Environmental Protection Agency, Great Lakes National
Program Office, Chicago, Illinois, December 1982, unpublished.
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U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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Ur>MM« Sldlt'S
EnvuoftnienUtl PrnU-riiu'i
Ag«'nry
Gtedl L,ikes National
Protjiam OHicc
536 South Clark SlriMM
CIIK.JQU Illinois 6O6O5
S300
* Pfiv.ti.- Use
es P.nc*
Aqpncy
tPA 33b
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