To: VCP Date: October 28, 1998

Thru: Charles Epperson, Section Manager

Voluntary Cleanup Section

From: Otu Ekpo-Otu Project Manager

Voluntary Cleanup Section

Subject: When to use Toxicity Characteristic Leachate Procedure (TCLP) Test or Synthetic
Precipitation Leaching Procedure (SPLP) Test to demonstrate the leaching potential
of contaminants

This memo evaluates the above analytical methodologies and their suitability as a leachate test for the
different contaminant categories. Contaminants from similar lithology at the same site, subjected to both
test have yielded significantly different results. Considering the fact that the difference in these results have
contributed to sites being closed or remediated, the analytical method employed is critical.

TCLP method 1311; This method is designed to determine the mobility of both organic and inorganic
compounds present in liquid, solid and multi phase waste. It is used to classify waste (hazardous or non
hazardous) for purposes of disposal in a landfill. TCLP analysis mimics the acidic conditions in a landfill.
For volatile organic compounds (VOCs), Zero Head space Extraction (ZHE) vessels should be used to
prevent extract from coming in contact with the atmosphere. Only extraction fluid #1 (glacial acetic acid
at a pH of 4.93) should be used for VOC analyses. For non VOC analyses, extraction fluid #1 should be
used if the initial pH of the sample is less than 5. Extraction fluid #2 should be used for non VOCs when
the sample persist at a pH greater than 5 even after the addition of hydrochloric acid. Extracts for metallic
compound determinations must be acidified with nitric acid to a pH of less than 2.

SPLP method 1312; This method is designed to detennine the mobility of both organic and inorganic
compounds present in liquid, soils, and waste. It is used to detennine the leaching potential of soils, waste
and wastewater. The extraction fluid employed is a function of the region of the country where the soil
sample is located. Extraction fluid #1 is made by adding 60/40 weight % mixture of sulphuric and nitric
acids to reagent water until a pH of 4.2 is achieved. It is used to detennine the leaching potential of soils
east of the Mississippi river (high organic content), as well as waste and wastewater. For extraction fluid
#2, the same mixture is used but at a pH of 5.00 for soils west of the Mississippi (low organic content).
Extraction fluid #3 is made by bubbling an inert gas (Nitrogen) through water maintained at 90 degrees
Celsius. It is used to detennine cyanide and volatile leaching potential. Leaching of cyanide containing
waste under acidic conditions may result in the fonnation of hydrogen cyanide gas.

TCLP versus SPLP; TCLP evaluates metal mobility in sanitary landfills. The TCLP extraction fluid
recipes were developed to stimulate a worst case scenario, where the waste is disposed with municipal solid
waste. The primary extraction fluid is a buffered organic acid solution at pH 4.98. A buffer is a substance
capable in solution of neutralizing both acids and bases and thereby maintaining the original acidity or
basicity of the solution. If the waste is highly alkaline a different extraction fluid at pH 2.88 is used. The
combination of highly alkaline waste and a weak organic acid produces a buffered solution similar to the
first fluid ( the pH remains constant). TCLP is the only leaching procedure for characterizing waste
under RCRA.
The SPLP test is used to evaluate the potential for leaching metals into ground and surface waters. The
SPLP extraction fluid is intended to simulate precipitation. East of the Mississippi River the fluid is slightly
more acidic at a pH of 4.20 reflecting the air pollution impacts of heavy industrialization and coal
utilization. A pH of 5.00 is used west of the Mississippi reflecting less industrialization and smaller
population densities. The SPLP extraction fluid is not buffered (the pH level fluctuates). Inter laboratory
comparison of TCLP and SPLP by EPAtLas Vegas indicates that non buffered extraction fluids used in the
SPLP test readily absorb Carbon dioxide which will quickly dissociate to the bicarbonate the!eby driving
the pH higher. Another laboratory prepared a n SPLP extraction fluid with a phosphate buffer at a pH of
4.2. The phosphate may also complex with lead therefore biasing the results high with respect to lead. The
SPLP test method provides a more realistic assessmentof metal mobility under actual field conditions,
that is, what happens when it rains or snows. The SPLP test is a method of choice when evaluating
fate and transport of metals in a properly engineered waste land disposal facility from which
municipal waste is excluded.

The effect of pH on the partitioning of inorganic and organic compounds; The soil- water distribution
coefficient (Kd) for metals and other inorganic compounds is affected by numerous geochemical parameters
including pH. More metal would dissolving under acidic conditions than otherwise. An exception to this
rule is chromium +6 which will dissolving more under basic conditions. The partitioning of ionizing
organic compounds is significantly influenced by soil pH. Certain organic compounds e.g. , phenols contain
functional groups that ionize under subsurface pH conditions. Most subsurface solids (soil and aquifer
material) have a negative net surface charge, therefore, positively charged chemicals have a greater
tendency to sorb than neutral forms , and neutral speciessorb more readily than negatively charged forms.
Thus predictions for the total sorption of any organic compound capable of ionizing, must consider the
extent to which it ionizes over the range of subsurface pH conditions. pH conditions determine the relative
concentrations of neutral and ionized species in the system.

Comparison of TCLP and SPLP for lead; In 1988 research Triangle Institute performed an inter
laboratory study of the above methods for EPA. The results show that the differences in extract lead
concentration are correlated with both the extracting fluid and bulk lead concentration. The report indicated
that pH stable extracting fluid for SPLP could not be prepared due to the fact that unbuffered solutions
in the range 4.2-5.0 will revert to 5.8 soon after they are made. TCLP test, made with an acetic/acetate
buffer solution, extracted measurable quantities of lead from all samples except those with little lead in
the bulk soil. The addition of acetic acid to the extraction fluid to adjust the pH, increased the solubility
of lead. The buffering capacity of these soils easily overwhelmed the non buffered acidity of the extracting
fluid used in the SPLP test, resulting in a final pH that was greater than seven. At such high pH, little lead
is expected to dissolve. TCLP was clearly more effective at dissolving lead than SPLP .

Comparison of TCLP and SPLP on VCP Sites; Confirmatory soil samples from a site in Dallas
contaminated with Perchloroethylene were subjected to both TCLP and SPLP analyses, the SPLP test
results were three times higher than the TCLP results from the same sample. In another VCP site in Dallas,
the difference in analytical results from the above two methodologies was the difference between closing
and remediating a lead contaminated site.

References:
Certes Enviromnental Laboratories; TCLP versus SPLP
Marcia Alforque (EPA); Synthetic Precipitation Leaching Procedure
Research Triangle Institute; Inter laboratory Comparison of Methods 1310, 1311, and 1312 for lead
in soils.
Solid Waste Regulations 846; Synthetic Precipitation Leaching Procedure, Method 1312
Solid Waste Regulations 846; Toxicity Characteristic Leaching Procedure, Method 1311
EP A Soil Screening Guidance; Technical Background Document
 Synthetic Precipitation Leaching Procedure

versus

ToXicity CharacteriStic Leaching Procedure

Synthetic Toxicity Characteristic Comments

Precipitation Leachate Procedure
Leachate Procedure Method 1311
Method 1312
I
I Purpose Used to determine the Used to classify waste SPLP is preferred to TCLP in
leachability of soils, (Hazardous or non evaluating fate and transport of
waste, and waste hazardous) for contaminants in a disposal
water purposes of disposal in facility without municipal solid
a landfill waste. SPLP provides a more
realistic assessmentof mobility
under actual field conditions.
TCLP is the only leaching
procedure for characterizing
waste under RCRA.

action 60/40 H2S041HN03 Glacial Acetic Acid The choice of extracting fluid
Fluid #1 pH 4.20 pH 4.98 has significant effect on the
concentration of metal dissolved.
Use #1 if Sample is from east Initial pH < 5.0 Use only for VOCs and non
of the Mississippi VOCs when the pH < 5 (SW-
River 846) .pH conditions determine
the relative concentration of
neutral and ionized species in a
system. Anion are more easily
solubilized than cations.

Extraction Fluid #2 60/40 H2S041HN03 Glacial Acetic Acid Use only for non VOCs when the
pH 5.00 . pH 2.88 pH >5

Use #2 if Sample is from west Initial pH > 5.0

of the Mississippi
River
 Synthetic Precipitation Leaching Procedure

versus

T oXicity CharacteriStic Leaching Procedure

Synthetic Toxicity Characteristic Comments

Precipitation Leachate Procedure
Leachate Procedure Method 1311
Method 1312

Purpose Usedto determine the Used to classify waste SPLP is preferred to TCLP in
leachability of soils, (Hazardous or non evaluating fate and transport of
waste, and waste hazardous) for contaminants in a disposal
water purposes of disposal in facility without municipal solid
a landfill waste. SPLP provides a more
realistic assessmentof mobility
under actual field conditions.
TCLP is the only leaching
procedure for characterizing
waste under RCRA.

action 60/40 H2S041HN03 Glacial Acetic Acid The choice of extracting fluid
Fluid #1 pH 4.20 pH 4.98 has significant effect on the
concentration of metal dissolved.
Use #1 if Sampleis from east Initial pH < 5.0 Use only for VOCs and non
of the Mississippi VOCs when the pH < 5 (SW-
River 846) .pH conditions determine
the relative concentration of
neutral and ionized species in a
system. Anion are more easily
solubilized than cations.
I Extraction Fluid #2 60/40 H2S04/HN03 Glacial Acetic Acid Use only for non VOCs when the
pH 5.00 . pH 2.88 pH >5
Use #2 if Sampleis from west Initial pH > 5.0
of the Mississippi
River