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

-------
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL  60604-3590

-------
              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

-------
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.

-------
                         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.

-------
                      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).

-------
                         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:

-------
 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.

-------
                         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

-------
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.

-------
                         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.

-------
.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.

-------

-------
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL  60604-3590

-------

-------
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

-------