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METHOD 1311

TOXICITY CHARACTERISTIC LEACHING PROCEDURE

1.0 SCOPE AND APPLICATION

1.1 The TCLP is designed to determine the mobility of both organic and

inorganic analytes present in liquid, solid, and multiphasic wastes.

1.2 If a total analysis of the waste demonstrates that individual

analytes are not present in the waste, or that they are present but at such low

concentrations that the appropriate regulatory levels could not possibly be

exceeded, the TCLP need not be run.

1.3 If an analysis of any one of the liquid fractions of the TCLP

extract indicates that a regulated compound is present at such high concentrations that, even after accounting for dilution from the other fractions of the

extract, the concentration would be above the regulatory level for that compound,

then the waste is hazardous and it is not necessary to analyze the remaining

fractions of the extract.

1.4 If an analysis of extract obtained using a bottle extractor shows

that the concentration of any regulated volatile analyte exceeds the regulatory

level for that compound, then the waste is hazardous and extraction using the ZHE

is not necessary. However, extract from a bottle extractor cannot be used to

demonstrate that the concentration of volatile compounds is below the regulatory

level.

2.0 SUMMARY OF METHOD 

2.1 For liquid wastes (i.e., those containing less than 0.5% dry solid

material), the waste, after filtration through a 0.6 to 0.8 μm glass fiber

filter, is defined as the TCLP extract.

2.2 For wastes containing greater than or equal to 0.5% solids, the

liquid, if any, is separated from the solid phase and stored for later analysis;

the particle size of the solid phase is reduced, if necessary. The solid phase

is extracted with an amount of extraction fluid equal to 20 times the weight of

the solid phase. The extraction fluid employed is a function of the alkalinity

of the solid phase of the waste. A special extractor vessel is used when testing

for volatile analytes (see Table 1 for a list of volatile compounds). Following

extraction, the liquid extract is separated from the solid phase by filtration

through a 0.6 to 0.8 μm glass fiber filter.

2.3 If compatible (i.e., multiple phases will not form on combination),

the initial liquid phase of the waste is added to the liquid extract, and these

are analyzed together. If incompatible, the liquids are analyzed separately and

the results are mathematically combined to yield a volume-weighted average

concentration.
 VITON is a trademark of Du Pont. 1 ®

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3.0 INTERFERENCES

3.1 Potential interferences that may be encountered during analysis are

discussed in the individual analytical methods.

4.0 APPARATUS AND MATERIALS

4.1 Agitation apparatus: The agitation apparatus must be capable of

rotating the extraction vessel in an end-over-end fashion (see Figure 1) at

30 + 2 rpm. Suitable devices known to EPA are identified in Table 2.

4.2 Extraction Vessels

4.2.1 Zero-Headspace Extraction Vessel (ZHE). This device is

for use only when the waste is being tested for the mobility of volatile

analytes (i.e., those listed in Table 1). The ZHE (depicted in Figure 2)

allows for liquid/solid separation within the device, and effectively

precludes headspace. This type of vessel allows for initial liquid/solid

separation, extraction, and final extract filtration without opening the

vessel (see Section 4.3.1). The vessels shall have an internal volume of

500-600 mL, and be equipped to accommodate a 90-110 mm filter. The devices

contain VITON O-rings which should be replaced frequently. Suitable ZHE ®1

devices known to EPA are identified in Table 3.

For the ZHE to be acceptable for use, the piston within the ZHE

should be able to be moved with approximately 15 psi or less. If it takes

more pressure to move the piston, the O-rings in the device should be

replaced. If this does not solve the problem, the ZHE is unacceptable for

TCLP analyses and the manufacturer should be contacted.

The ZHE should be checked for leaks after every extraction. If the

device contains a built-in pressure gauge, pressurize the device to

50 psi, allow it to stand unattended for 1 hour, and recheck the pressure.

If the device does not have a built-in pressure gauge, pressurize the

device to 50 psi, submerge it in water, and check for the presence of air

bubbles escaping from any of the fittings. If pressure is lost, check all

fittings and inspect and replace O-rings, if necessary. Retest the

device. If leakage problems cannot be solved, the manufacturer should be

contacted.

Some ZHEs use gas pressure to actuate the ZHE piston, while others

use mechanical pressure (see Table 3). Whereas the volatiles procedure

(see Section 7.3) refers to pounds per square inch (psi), for the

mechanically actuated piston, the pressure applied is measured in

torque-inch-pounds. Refer to the manufacturer's instructions as to the

proper conversion.
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4.2.2 Bottle Extraction Vessel. When the waste is being

evaluated using the nonvolatile extraction, a jar with sufficient capacity

to hold the sample and the extraction fluid is needed. Headspace is

allowed in this vessel.

The extraction bottles may be constructed from various materials,

depending on the analytes to be analyzed and the nature of the waste (see

Section 4.3.3). It is recommended that borosilicate glass bottles be used

instead of other types of glass, especially when inorganics are of

concern. Plastic bottles, other than polytetrafluoroethylene, shall not

be used if organics are to be investigated. Bottles are available from a

number of laboratory suppliers. When this type of extraction vessel is

used, the filtration device discussed in Section 4.3.2 is used for initial

liquid/solid separation and final extract filtration.

4.3 Filtration Devices: It is recommended that all filtrations be

performed in a hood.

4.3.1 Zero-Headspace Extractor Vessel (ZHE): When the waste is

evaluated for volatiles, the zero-headspace extraction vessel described in

Section 4.2.1 is used for filtration. The device shall be capable of

supporting and keeping in place the glass fiber filter and be able to

withstand the pressure needed to accomplish separation (50 psi).

NOTE: When it is suspected that the glass fiber filter has been ruptured,

an in-line glass fiber filter may be used to filter the material

within the ZHE.

4.3.2 Filter Holder: When the waste is evaluated for other than

volatile analytes, any filter holder capable of supporting a glass fiber

filter and able to withstand the pressure needed to accomplish separation

may be used. Suitable filter holders range from simple vacuum units to

relatively complex systems capable of exerting pressures of up to 50 psi

or more. The type of filter holder used depends on the properties of the

material to be filtered (see Section 4.3.3). These devices shall have a

minimum internal volume of 300 mL and be equipped to accommodate a minimum

filter size of 47 mm (filter holders having an internal capacity of 1.5 L

or greater, and equipped to accommodate a 142 mm diameter filter, are

recommended). Vacuum filtration can only be used for wastes with low

solids content (<10%) and for highly granular, liquid-containing wastes.

All other types of wastes should be filtered using positive pressure

filtration. Suitable filter holders known to EPA are shown in Table 4.

4.3.3 Materials of Construction: Extraction vessels and

filtration devices shall be made of inert materials which will not leach

or absorb waste components. Glass, polytetrafluoroethylene (PTFE), or

type 316 stainless steel equipment may be used when evaluating the

mobility of both organic and inorganic components. Devices made of high

density polyethylene (HDPE), polypropylene (PP), or polyvinyl chloride

(PVC) may be used only when evaluating the mobility of metals. Borosili-
 TEDLAR is a registered trademark of Du Pont. 2 ®

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cate glass bottles are recommended for use over other types of glass

bottles, especially when inorganics are analytes of concern.

4.4 Filters: Filters shall be made of borosilicate glass fiber, shall

contain no binder materials, and shall have an effective pore size of 0.6 to

0.8 μm, or equivalent. Filters known to EPA which meet these specifications are

identified in Table 5. Pre-filters must not be used. When evaluating the

mobility of metals, filters shall be acid-washed prior to use by rinsing with 1N

nitric acid followed by three consecutive rinses with deionized distilled water

(a minimum of 1 L per rinse is recommended). Glass fiber filters are fragile and

should be handled with care.

4.5 pH Meters: The meter should be accurate to + 0.05 units at 25 EC.

4.6 ZHE Extract Collection Devices: TEDLAR bags or glass, stainless ®2

steel or PTFE gas-tight syringes are used to collect the initial liquid phase and

the final extract of the waste when using the ZHE device. The devices listed are

recommended for use under the following conditions:

4.6.1 If a waste contains an aqueous liquid phase or if a waste

does not contain a significant amount of nonaqueous liquid (i.e., <1% of

total waste), the TEDLAR bag or a 600 mL syringe should be used to collect

®

and combine the initial liquid and solid extract.

4.6.2 If a waste contains a significant amount of nonaqueous

liquid in the initial liquid phase (i.e., >1% of total waste), the syringe

or the TEDLAR bag may be used for both the initial solid/liquid separation

®

and the final extract filtration. However, analysts should use one or the

other, not both.

4.6.3 If the waste contains no initial liquid phase (is 100%

solid) or has no significant solid phase (is 100% liquid), either the

TEDLAR bag or the syringe may be used. If the syringe is used, discard

®

the first 5 mL of liquid expressed from the device. The remaining

aliquots are used for analysis.

4.7 ZHE Extraction Fluid Transfer Devices: Any device capable of

transferring the extraction fluid into the ZHE without changing the nature of the

extraction fluid is acceptable (e.g., a positive displacement or peristaltic

pump, a gas tight syringe, pressure filtration unit (see Section 4.3.2), or other

ZHE device).

4.8 Laboratory Balance: Any laboratory balance accurate to within

+ 0.01 grams may be used (all weight measurements are to be within + 0.1 grams).

4.9 Beaker or Erlenmeyer flask, glass, 500 mL.
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4.10 Watchglass, appropriate diameter to cover beaker or Erlenmeyer

flask.

4.11 Magnetic stirrer. 

5.0 REAGENTS

5.1 Reagent grade chemicals shall be used in all tests. Unless

otherwise indicated, it is intended that all reagents shall conform to the

specifications of the Committee on Analytical Reagents of the American Chemical

Society, where such specifications are available. Other grades may be used,

provided it is first ascertained that the reagent is of sufficiently high purity

to permit its use without lessening the accuracy of the determination.

5.2 Reagent Water. Reagent water is defined as water in which an

interferant is not observed at or above the method's detection limit of the

analyte(s) of interest. For nonvolatile extractions, ASTM Type II water or

equivalent meets the definition of reagent water. For volatile extractions, it

is recommended that reagent water be generated by any of the following methods.

Reagent water should be monitored periodically for impurities.

5.2.1 Reagent water for volatile extractions may be generated

by passing tap water through a carbon filter bed containing about 500

grams of activated carbon (Calgon Corp., Filtrasorb-300 or equivalent).

5.2.2 A water purification system (Millipore Super-Q or

equivalent) may also be used to generate reagent water for volatile

extractions.

5.2.3 Reagent water for volatile extractions may also be

prepared by boiling water for 15 minutes. Subsequently, while maintaining

the water temperature at 90 + 5 degrees C, bubble a contaminant-free inert

gas (e.g. nitrogen) through the water for 1 hour. While still hot,

transfer the water to a narrow mouth screw-cap bottle under zero-headspace

and seal with a Teflon-lined septum and cap.

5.3 Hydrochloric acid (1N), HCl, made from ACS reagent grade.

5.4 Nitric acid (1N), HNO3, made from ACS reagent grade.

5.5 Sodium hydroxide (1N), NaOH, made from ACS reagent grade.

5.6 Glacial acetic acid, CH3CH2OOH, ACS reagent grade.

5.7 Extraction fluid.

5.7.1 Extraction fluid # 1: Add 5.7 mL glacial CH3CH2OOH to

500 mL of reagent water (See Section 5.2), add 64.3 mL of 1N NaOH, and

dilute to a volume of 1 liter. When correctly prepared, the pH of this

fluid will be 4.93 + 0.05.
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5.7.2 Extraction fluid # 2: Dilute 5.7 mL glacial CH3CH2OOH with

reagent water (See Section 5.2) to a volume of 1 liter. When correctly

prepared, the pH of this fluid will be 2.88 + 0.05.

NOTE: These extraction fluids should be monitored frequently for

impurities. The pH should be checked prior to use to ensure that

these fluids are made up accurately. If impurities are found or

the pH is not within the above specifications, the fluid shall be

discarded and fresh extraction fluid prepared.

5.8 Analytical standards shall be prepared according to the appropriate

analytical method.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 All samples shall be collected using an appropriate sampling plan.

6.2 The TCLP may place requirements on the minimal size of the field

sample, depending upon the physical state or states of the waste and the analytes

of concern. An aliquot is needed for preliminary evaluation of which extraction

fluid is to be used for the nonvolatile analyte extraction procedure. Another

aliquot may be needed to actually conduct the nonvolatile extraction (see Section

1.4 concerning the use of this extract for volatile organics). If volatile

organics are of concern, another aliquot may be needed. Quality control measures

may require additional aliquots. Further, it is always wise to collect more

sample just in case something goes wrong with the initial attempt to conduct the

test.

6.3 Preservatives shall not be added to samples before extraction.

6.4 Samples may be refrigerated unless refrigeration results in

irreversible physical change to the waste. If precipitation occurs, the entire

sample (including precipitate) should be extracted.

6.5 When the waste is to be evaluated for volatile analytes, care shall

be taken to minimize the loss of volatiles. Samples shall be collected and

stored in a manner intended to prevent the loss of volatile analytes (e.g.,

samples should be collected in Teflon-lined septum capped vials and stored at 4

EC. Samples should be opened only immediately prior to extraction).

6.6 TCLP extracts should be prepared for analysis and analyzed as soon

as possible following extraction. Extracts or portions of extracts for metallic

analyte determinations must be acidified with nitric acid to a pH < 2, unless

precipitation occurs (see Section 7.2.14 if precipitation occurs). Extracts

should be preserved for other analytes according to the guidance given in the

individual analysis methods. Extracts or portions of extracts for organic

analyte determinations shall not be allowed to come into contact with the

atmosphere (i.e., no headspace) to prevent losses. See Section 8.0 (QA

requirements) for acceptable sample and extract holding times.
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7.0 PROCEDURE

7.1 Preliminary Evaluations

Perform preliminary TCLP evaluations on a minimum 100 gram aliquot of

waste. This aliquot may not actually undergo TCLP extraction. These preliminary

evaluations include: (1) determination of the percent solids (Section 7.1.1);

(2) determination of whether the waste contains insignificant solids and is,

therefore, its own extract after filtration (Section 7.1.2); (3) determination

of whether the solid portion of the waste requires particle size reduction

(Section 7.1.3); and (4) determination of which of the two extraction fluids are

to be used for the nonvolatile TCLP extraction of the waste (Section 7.1.4).

7.1.1 Preliminary determination of percent solids: Percent

solids is defined as that fraction of a waste sample (as a percentage of

the total sample) from which no liquid may be forced out by an applied

pressure, as described below.

7.1.1.1 If the waste will obviously yield no liquid when

subjected to pressure filtration (i.e., is 100% solids) proceed to

Section 7.1.3.

7.1.1.2 If the sample is liquid or multiphasic,

liquid/solid separation to make a preliminary determination of

percent solids is required. This involves the filtration device

described in Section 4.3.2 and is outlined in Sections 7.1.1.3

through 7.1.1.9.

7.1.1.3 Pre-weigh the filter and the container that will

receive the filtrate.

7.1.1.4 Assemble the filter holder and filter following

the manufacturer's instructions. Place the filter on the support

screen and secure.

7.1.1.5 Weigh out a subsample of the waste (100 gram

minimum) and record the weight.

7.1.1.6 Allow slurries to stand to permit the solid

phase to settle. Wastes that settle slowly may be centrifuged

prior to filtration. Centrifugation is to be used only as an aid

to filtration. If used, the liquid should be decanted and filtered

followed by filtration of the solid portion of the waste through

the same filtration system.

7.1.1.7 Quantitatively transfer the waste sample to the

filter holder (liquid and solid phases). Spread the waste sample

evenly over the surface of the filter. If filtration of the waste

at 4 EC reduces the amount of expressed liquid over what would be

expressed at room temperature then allow the sample to warm up to

room temperature in the device before filtering.
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NOTE: If waste material (>1% of original sample weight) has obviously

adhered to the container used to transfer the sample to the

filtration apparatus, determine the weight of this residue and

subtract it from the sample weight determined in Section 7.1.1.5 to

determine the weight of the waste sample that will be filtered.

Gradually apply vacuum or gentle pressure of 1-10 psi,

until air or pressurizing gas moves through the filter. If this

point is not reached under 10 psi, and if no additional liquid has

passed through the filter in any 2 minute interval, slowly increase

the pressure in 10 psi increments to a maximum of 50 psi. After

each incremental increase of 10 psi, if the pressurizing gas has

not moved through the filter, and if no additional liquid has

passed through the filter in any 2 minute interval, proceed to the

next 10 psi increment. When the pressurizing gas begins to move

through the filter, or when liquid flow has ceased at 50 psi (i.e.,

filtration does not result in any additional filtrate within any 2

minute period), stop the filtration. 

NOTE: Instantaneous application of high pressure can degrade the glass

fiber filter and may cause premature plugging.

7.1.1.8 The material in the filter holder is defined as

the solid phase of the waste, and the filtrate is defined as the

liquid phase.

NOTE: Some wastes, such as oily wastes and some paint wastes, will

obviously contain some material that appears to be a liquid. Even

after applying vacuum or pressure filtration, as outlined in

Section 7.1.1.7, this material may not filter. If this is the

case, the material within the filtration device is defined as a

solid. Do not replace the original filter with a fresh filter

under any circumstances. Use only one filter. 

7.1.1.9 Determine the weight of the liquid phase by

subtracting the weight of the filtrate container (see Section

7.1.1.3) from the total weight of the filtrate-filled container.

Determine the weight of the solid phase of the waste sample by

subtracting the weight of the liquid phase from the weight of the

total waste sample, as determined in Section 7.1.1.5 or 7.1.1.7.

Record the weight of the liquid and solid phases.

Calculate the percent solids as follows:

 Weight of solid (Section 7.1.1.9)

Percent solids = x 100 

 Total weight of waste (Section 7.1.1.5 or 7.1.1.7)

7.1.2 If the percent solids determined in Section 7.1.1.9 is

equal to or greater than 0.5%, then proceed either to Section 7.1.3 to
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determine whether the solid material requires particle size reduction or

to Section 7.1.2.1 if it is noticed that a small amount of the filtrate is

entrained in wetting of the filter. If the percent solids determined in

Section 7.1.1.9 is less than 0.5%, then proceed to Section 7.2.9 if the

nonvolatile TCLP is to be performed and to Section 7.3 with a fresh

portion of the waste if the volatile TCLP is to be performed.

7.1.2.1 Remove the solid phase and filter from the

filtration apparatus.

7.1.2.2 Dry the filter and solid phase at 100 + 20 EC

until two successive weighing yield the same value within + 1%.

Record the final weight.

NOTE: Caution should be taken to ensure that the subject solid will not

flash upon heating. It is recommended that the drying oven be

vented to a hood or other appropriate device.

7.1.2.3 Calculate the percent dry solids as follows:

 (Wt. of dry waste + filter) - tared wt. of filter

Percent dry solids = x 100

 

 Initial wt. of waste (Section 7.1.1.5 or 7.1.1.7)

7.1.2.4 If the percent dry solids is less than 0.5%,

then proceed to Section 7.2.9 if the nonvolatile TCLP is to be

performed, and to Section 7.3 if the volatile TCLP is to be

performed. If the percent dry solids is greater than or equal to

0.5%, and if the nonvolatile TCLP is to be performed, return to the

beginning of this Section (7.1) and, with a fresh portion of waste,

determine whether particle size reduction is necessary (Section

7.1.3) and determine the appropriate extraction fluid (Section

7.1.4). If only the volatile TCLP is to be performed, see the note

in Section 7.1.4.

7.1.3 Determination of whether the waste requires particle size

reduction (particle size is reduced during this step): Using the solid

portion of the waste, evaluate the solid for particle size. Particle size

reduction is required, unless the solid has a surface area per gram of

material equal to or greater than 3.1 cm , or is smaller than 1 cm in its 2

narrowest dimension (i.e., is capable of passing through a 9.5 mm (0.375

inch) standard sieve). If the surface area is smaller or the particle

size larger than described above, prepare the solid portion of the waste

for extraction by crushing, cutting, or grinding the waste to a surface

area or particle size as described above. If the solids are prepared for

organic volatiles extraction, special precautions must be taken (see

Section 7.3.6).

NOTE: Surface area criteria are meant for filamentous (e.g., paper, cloth, and

similar) waste materials. Actual measurement of surface area is not

required, nor is it recommended. For materials that do not obviously meet
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the criteria, sample specific methods would need to be developed and

employed to measure the surface area. Such methodology is currently not

available.

7.1.4 Determination of appropriate extraction fluid: If the

solid content of the waste is greater than or equal to 0.5% and if the

sample will be extracted for nonvolatile constituents (Section 7.2),

determine the appropriate fluid (Section 5.7) for the nonvolatiles

extraction as follows:

NOTE: TCLP extraction for volatile constituents uses only extraction

fluid #1 (Section 5.7.1). Therefore, if TCLP extraction for

nonvolatiles is not required, proceed to Section 7.3.

7.1.4.1 Weigh out a small subsample of the solid phase

of the waste, reduce the solid (if necessary) to a particle size of

approximately 1 mm in diameter or less, and transfer 5.0 grams of

the solid phase of the waste to a 500 mL beaker or Erlenmeyer

flask.

7.1.4.2 Add 96.5 mL of reagent water to the beaker,

cover with a watchglass, and stir vigorously for 5 minutes using a

magnetic stirrer. Measure and record the pH. If the pH is <5.0,

use extraction fluid #1. Proceed to Section 7.2.

7.1.4.3 If the pH from Section 7.1.4.2 is >5.0, add

3.5 mL 1N HCl, slurry briefly, cover with a watchglass, heat to 50

EC, and hold at 50 EC for 10 minutes.

7.1.4.4 Let the solution cool to room temperature and

record the pH. If the pH is <5.0, use extraction fluid #1. If the

pH is >5.0, use extraction fluid #2. Proceed to Section 7.2.

7.1.5 If the aliquot of the waste used for the preliminary

evaluation (Sections 7.1.1 - 7.1.4) was determined to be 100% solid at

Section 7.1.1.1, then it can be used for the Section 7.2 extraction

(assuming at least 100 grams remain), and the Section 7.3 extraction

(assuming at least 25 grams remain). If the aliquot was subjected to the

procedure in Section 7.1.1.7, then another aliquot shall be used for the

volatile extraction procedure in Section 7.3. The aliquot of the waste

subjected to the procedure in Section 7.1.1.7 might be appropriate for use

for the Section 7.2 extraction if an adequate amount of solid (as

determined by Section 7.1.1.9) was obtained. The amount of solid

necessary is dependent upon whether a sufficient amount of extract will be

produced to support the analyses. If an adequate amount of solid remains,

proceed to Section 7.2.10 of the nonvolatile TCLP extraction.

7.2 Procedure When Volatiles are not Involved

A minimum sample size of 100 grams (solid and liquid phases) is recommended. In some cases, a larger sample size may be appropriate, depending on the
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solids content of the waste sample (percent solids, See Section 7.1.1), whether

the initial liquid phase of the waste will be miscible with the aqueous extract

of the solid, and whether inorganics, semivolatile organics, pesticides, and

herbicides are all analytes of concern. Enough solids should be generated for

extraction such that the volume of TCLP extract will be sufficient to support all

of the analyses required. If the amount of extract generated by a single TCLP

extraction will not be sufficient to perform all of the analyses, more than one

extraction may be performed and the extracts from each combined and aliquoted for

analysis.

7.2.1 If the waste will obviously yield no liquid when subjected

to pressure filtration (i.e., is 100% solid, see Section 7.1.1), weigh out

a subsample of the waste (100 gram minimum) and proceed to Section 7.2.9.

7.2.2 If the sample is liquid or multiphasic, liquid/solid

separation is required. This involves the filtration device described in

Section 4.3.2 and is outlined in Sections 7.2.3 to 7.2.8.

7.2.3 Pre-weigh the container that will receive the filtrate.

7.2.4 Assemble the filter holder and filter following the

manufacturer's instructions. Place the filter on the support screen and

secure. Acid wash the filter if evaluating the mobility of metals (see

Section 4.4).

NOTE: Acid washed filters may be used for all nonvolatile extractions

even when metals are not of concern.

7.2.5 Weigh out a subsample of the waste (100 gram minimum) and

record the weight. If the waste contains <0.5% dry solids (Section

7.1.2), the liquid portion of the waste, after filtration, is defined as

the TCLP extract. Therefore, enough of the sample should be filtered so

that the amount of filtered liquid will support all of the analyses

required of the TCLP extract. For wastes containing >0.5% dry solids

(Sections 7.1.1 or 7.1.2), use the percent solids information obtained in

Section 7.1.1 to determine the optimum sample size (100 gram minimum) for

filtration. Enough solids should be generated by filtration to support

the analyses to be performed on the TCLP extract.

7.2.6 Allow slurries to stand to permit the solid phase to

settle. Wastes that settle slowly may be centrifuged prior to filtration.

Use centrifugation only as an aid to filtration. If the waste is

centrifuged, the liquid should be decanted and filtered followed by

filtration of the solid portion of the waste through the same filtration

system.

7.2.7 Quantitatively transfer the waste sample (liquid and solid

phases) to the filter holder (see Section 4.3.2). Spread the waste sample

evenly over the surface of the filter. If filtration of the waste at 4 EC

reduces the amount of expressed liquid over what would be expressed at
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room temperature, then allow the sample to warm up to room temperature in

the device before filtering.

NOTE: If waste material (>1% of the original sample weight) has obviously

adhered to the container used to transfer the sample to the

filtration apparatus, determine the weight of this residue and

subtract it from the sample weight determined in Section 7.2.5, to

determine the weight of the waste sample that will be filtered.

Gradually apply vacuum or gentle pressure of 1-10 psi, until air or

pressurizing gas moves through the filter. If this point is not reached

under 10 psi, and if no additional liquid has passed through the filter in

any 2 minute interval, slowly increase the pressure in 10 psi increments

to a maximum of 50 psi. After each incremental increase of 10 psi, if the

pressurizing gas has not moved through the filter, and if no additional

liquid has passed through the filter in any 2 minute interval, proceed to

the next 10 psi increment. When the pressurizing gas begins to move

through the filter, or when the liquid flow has ceased at 50 psi (i.e.,

filtration does not result in any additional filtrate within a 2 minute

period), stop the filtration.

NOTE: Instantaneous application of high pressure can degrade the glass

fiber filter and may cause premature plugging.

7.2.8 The material in the filter holder is defined as the solid

phase of the waste, and the filtrate is defined as the liquid phase.

Weigh the filtrate. The liquid phase may now be either analyzed (See

Section 7.2.12) or stored at 4 EC until time of analysis.

NOTE: Some wastes, such as oily wastes and some paint wastes, will

obviously contain some material that appears to be a liquid. Even

after applying vacuum or pressure filtration, as outlined in

Section 7.2.7, this material may not filter. If this is the case,

the material within the filtration device is defined as a solid and

is carried through the extraction as a solid. Do not replace the

original filter with a fresh filter under any circumstances. Use

only one filter.

7.2.9 If the waste contains <0.5% dry solids (see Section

7.1.2), proceed to Section 7.2.13. If the waste contains >0.5% dry solids

(see Section 7.1.1 or 7.1.2), and if particle size reduction of the solid

was needed in Section 7.1.3, proceed to Section 7.2.10. If the waste as

received passes a 9.5 mm sieve, quantitatively transfer the solid material

into the extractor bottle along with the filter used to separate the

initial liquid from the solid phase, and proceed to Section 7.2.11.

7.2.10 Prepare the solid portion of the waste for extraction by

crushing, cutting, or grinding the waste to a surface area or particle

size as described in Section 7.1.3. When the surface area or particle

size has been appropriately altered, quantitatively transfer the solid
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material into an extractor bottle. Include the filter used to separate the

initial liquid from the solid phase.

NOTE: Sieving of the waste is not normally required. Surface area

requirements are meant for filamentous (e.g., paper, cloth) and

similar waste materials. Actual measurement of surface area is not

recommended. If sieving is necessary, a Teflon coated sieve should

be used to avoid contamination of the sample.

7.2.11 Determine the amount of extraction fluid to add to the

extractor vessel as follows:

20 x percent solids (Section 7.1.1) x weight of waste

 filtered (Section 7.2.5 or 7.2.7) 

Weight of = 

extraction fluid 100 

Slowly add this amount of appropriate extraction fluid (see Section

7.1.4) to the extractor vessel. Close the extractor bottle tightly (it is

recommended that Teflon tape be used to ensure a tight seal), secure in

rotary agitation device, and rotate at 30 + 2 rpm for 18 + 2 hours.

Ambient temperature (i.e., temperature of room in which extraction takes

place) shall be maintained at 23 + 2 EC during the extraction period.

NOTE: As agitation continues, pressure may build up within the extractor

bottle for some types of wastes (e.g., limed or calcium carbonate

containing waste may evolve gases such as carbon dioxide). To

relieve excess pressure, the extractor bottle may be periodically

opened (e.g., after 15 minutes, 30 minutes, and 1 hour) and vented

into a hood.

7.2.12 Following the 18 + 2 hour extraction, separate the

material in the extractor vessel into its component liquid and solid

phases by filtering through a new glass fiber filter, as outlined in

Section 7.2.7. For final filtration of the TCLP extract, the glass fiber

filter may be changed, if necessary, to facilitate filtration. Filter(s)

shall be acid-washed (see Section 4.4) if evaluating the mobility of

metals.

7.2.13 Prepare the TCLP extract as follows:

7.2.13.1 If the waste contained no initial liquid

phase, the filtered liquid material obtained from Section 7.2.12 is

defined as the TCLP extract. Proceed to Section 7.2.14.

7.2.13.2 If compatible (e.g., multiple phases will not

result on combination), combine the filtered liquid resulting from

Section 7.2.12 with the initial liquid phase of the waste obtained

in Section 7.2.7. This combined liquid is defined as the TCLP

extract. Proceed to Section 7.2.14.
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7.2.13.3 If the initial liquid phase of the waste, as

obtained from Section 7.2.7, is not or may not be compatible with

the filtered liquid resulting from Section 7.2.12, do not combine

these liquids. Analyze these liquids, collectively defined as the

TCLP extract, and combine the results mathematically, as described

in Section 7.2.14.

7.2.14 Following collection of the TCLP extract, the pH of the

extract should be recorded. Immediately aliquot and preserve the extract

for analysis. Metals aliquots must be acidified with nitric acid to

pH <2. If precipitation is observed upon addition of nitric acid to a

small aliquot of the extract, then the remaining portion of the extract

for metals analyses shall not be acidified and the extract shall be

analyzed as soon as possible. All other aliquots must be stored under

refrigeration (4 EC) until analyzed. The TCLP extract shall be prepared

and analyzed according to appropriate analytical methods. TCLP extracts to

be analyzed for metals shall be acid digested except in those instances

where digestion causes loss of metallic analytes. If an analysis of the

undigested extract shows that the concentration of any regulated metallic

analyte exceeds the regulatory level, then the waste is hazardous and

digestion of the extract is not necessary. However, data on undigested

extracts alone cannot be used to demonstrate that the waste is not

hazardous. If the individual phases are to be analyzed separately,

determine the volume of the individual phases (to + 0.5%), conduct the

appropriate analyses, and combine the results mathematically by using a

simple volume-weighted average:

 (V1) (C1) + (V2) (C2)

Final Analyte Concentration = 

 V1 + V2

where:

V1 = The volume of the first phase (L).

C1 = The concentration of the analyte of concern in the first phase (mg/L).

V2 = The volume of the second phase (L).

C2 = The concentration of the analyte of concern in the second phase

 (mg/L).

7.2.15 Compare the analyte concentrations in the TCLP extract

with the levels identified in the appropriate regulations. Refer to

Section 8.0 for quality assurance requirements.

7.3 Procedure When Volatiles are Involved

Use the ZHE device to obtain TCLP extract for analysis of volatile

compounds only. Extract resulting from the use of the ZHE shall not be used to

evaluate the mobility of nonvolatile analytes (e.g., metals, pesticides, etc.).

The ZHE device has approximately a 500 mL internal capacity. The ZHE can

thus accommodate a maximum of 25 grams of solid (defined as that fraction of a
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sample from which no additional liquid may be forced out by an applied pressure

of 50 psi), due to the need to add an amount of extraction fluid equal to 20

times the weight of the solid phase.

Charge the ZHE with sample only once and do not open the device until the

final extract (of the solid) has been collected. Repeated filling of the ZHE to

obtain 25 grams of solid is not permitted.

Do not allow the waste, the initial liquid phase, or the extract to be

exposed to the atmosphere for any more time than is absolutely necessary. Any

manipulation of these materials should be done when cold (4 EC) to minimize loss

of volatiles.

7.3.1 Pre-weigh the (evacuated) filtrate collection container

(See Section 4.6) and set aside. If using a TEDLAR bag, express all

®

liquid from the ZHE device into the bag, whether for the initial or final

liquid/solid separation, and take an aliquot from the liquid in the bag

for analysis. The containers listed in Section 4.6 are recommended for

use under the conditions stated in Sections 4.6.1 - 4.6.3.

7.3.2 Place the ZHE piston within the body of the ZHE (it may be

helpful first to moisten the piston O-rings slightly with extraction

fluid). Adjust the piston within the ZHE body to a height that will

minimize the distance the piston will have to move once the ZHE is charged

with sample (based upon sample size requirements determined from Section

7.3, Section 7.1.1 and/or 7.1.2). Secure the gas inlet/outlet flange

(bottom flange) onto the ZHE body in accordance with the manufacturer's

instructions. Secure the glass fiber filter between the support screens

and set aside. Set liquid inlet/outlet flange (top flange) aside.

7.3.3 If the waste is 100% solid (see Section 7.1.1), weigh out

a subsample (25 gram maximum) of the waste, record weight, and proceed to

Section 7.3.5.

7.3.4 If the waste contains < 0.5% dry solids (Section 7.1.2),

the liquid portion of waste, after filtration, is defined as the TCLP

extract. Filter enough of the sample so that the amount of filtered

liquid will support all of the volatile analyses required. For wastes

containing > 0.5% dry solids (Sections 7.1.1 and/or 7.1.2), use the

percent solids information obtained in Section 7.1.1 to determine the

optimum sample size to charge into the ZHE. The recommended sample size

is as follows:

7.3.4.1 For wastes containing < 5% solids (see Section

7.1.1), weigh out a 500 gram subsample of waste and record the

weight.

7.3.4.2 For wastes containing > 5% solids (see Section

7.1.1), determine the amount of waste to charge into the ZHE as

follows:
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 25 

Weight of waste to charge ZHE = x 100 

 percent solids (Section 7.1.1)

Weigh out a subsample of the waste of the appropriate size and

record the weight.

7.3.5 If particle size reduction of the solid portion of the

waste was required in Section 7.1.3, proceed to Section 7.3.6. If

particle size reduction was not required in Section 7.1.3, proceed to

Section 7.3.7.

7.3.6 Prepare the waste for extraction by crushing, cutting, or

grinding the solid portion of the waste to a surface area or particle size

as described in Section 7.1.3. Wastes and appropriate reduction equipment

should be refrigerated, if possible, to 4 EC prior to particle size

reduction. The means used to effect particle size reduction must not

generate heat in and of itself. If reduction of the solid phase of the

waste is necessary, exposure of the waste to the atmosphere should be

avoided to the extent possible.

NOTE: Sieving of the waste is not recommended due to the possibility that

volatiles may be lost. The use of an appropriately graduated ruler

is recommended as an acceptable alternative. Surface area

requirements are meant for filamentous (e.g., paper, cloth) and

similar waste materials. Actual measurement of surface area is not

recommended.

When the surface area or particle size has been appropriately

altered, proceed to Section 7.3.7.

7.3.7 Waste slurries need not be allowed to stand to permit the

solid phase to settle. Do not centrifuge wastes prior to filtration.

7.3.8 Quantitatively transfer the entire sample (liquid and

solid phases) quickly to the ZHE. Secure the filter and support screens

onto the top flange of the device and secure the top flange to the ZHE

body in accordance with the manufacturer's instructions. Tighten all ZHE

fittings and place the device in the vertical position (gas inlet/outlet

flange on the bottom). Do not attach the extract collection device to the

top plate.

NOTE: If waste material (>1% of original sample weight) has obviously

adhered to the container used to transfer the sample to the ZHE,

determine the weight of this residue and subtract it from the

sample weight determined in Section 7.3.4 to determine the weight

of the waste sample that will be filtered.

Attach a gas line to the gas inlet/outlet valve (bottom flange)

and, with the liquid inlet/outlet valve (top flange) open, begin applying

gentle pressure of 1-10 psi (or more if necessary) to force all headspace
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slowly out of the ZHE device into a hood. At the first appearance of

liquid from the liquid inlet/outlet valve, quickly close the valve and

discontinue pressure. If filtration of the waste at 4 EC reduces the

amount of expressed liquid over what would be expressed at room temperature, then allow the sample to warm up to room temperature in the device

before filtering. If the waste is 100% solid (see Section 7.1.1), slowly

increase the pressure to a maximum of 50 psi to force most of the

headspace out of the device and proceed to Section 7.3.12.

7.3.9 Attach the evacuated pre-weighed filtrate collection

container to the liquid inlet/outlet valve and open the valve. Begin

applying gentle pressure of 1-10 psi to force the liquid phase of the

sample into the filtrate collection container. If no additional liquid

has passed through the filter in any 2 minute interval, slowly increase

the pressure in 10 psi increments to a maximum of 50 psi. After each

incremental increase of 10 psi, if no additional liquid has passed through

the filter in any 2 minute interval, proceed to the next 10 psi increment.

When liquid flow has ceased such that continued pressure filtration at 50

psi does not result in any additional filtrate within a 2 minute period,

stop the filtration. Close the liquid inlet/outlet valve, discontinue

pressure to the piston, and disconnect and weigh the filtrate collection

container.

NOTE: Instantaneous application of high pressure can degrade the glass

fiber filter and may cause premature plugging.

7.3.10 The material in the ZHE is defined as the solid phase of

the waste and the filtrate is defined as the liquid phase.

NOTE: Some wastes, such as oily wastes and some paint wastes, will

obviously contain some material that appears to be a liquid. Even

after applying pressure filtration, this material will not filter.

If this is the case, the material within the filtration device is

defined as a solid and is carried through the TCLP extraction as a

solid.

If the original waste contained <0.5% dry solids (see Section

7.1.2), this filtrate is defined as the TCLP extract and is analyzed

directly. Proceed to Section 7.3.15.

7.3.11 The liquid phase may now be either analyzed immediately

(See Sections 7.3.13 through 7.3.15) or stored at 4 EC under minimal

headspace conditions until time of analysis. Determine the weight of

extraction fluid #1 to add to the ZHE as follows:

 20 x percent solids (Section 7.1.1) x weight

 of waste filtered (Section 7.3.4 or 7.3.8)

Weight of extraction fluid = 

 100
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7.3.12 The following Sections detail how to add the appropriate

amount of extraction fluid to the solid material within the ZHE and

agitation of the ZHE vessel. Extraction fluid #1 is used in all cases

(See Section 5.7).

7.3.12.1 With the ZHE in the vertical position, attach

a line from the extraction fluid reservoir to the liquid inlet/outlet valve. The line used shall contain fresh extraction

fluid and should be preflushed with fluid to eliminate any air

pockets in the line. Release gas pressure on the ZHE piston (from

the gas inlet/outlet valve), open the liquid inlet/outlet valve,

and begin transferring extraction fluid (by pumping or similar

means) into the ZHE. Continue pumping extraction fluid into the

ZHE until the appropriate amount of fluid has been introduced into

the device.

7.3.12.2 After the extraction fluid has been added,

immediately close the liquid inlet/outlet valve and disconnect the

extraction fluid line. Check the ZHE to ensure that all valves are

in their closed positions. Manually rotate the device in an

end-over-end fashion 2 or 3 times. Reposition the ZHE in the

vertical position with the liquid inlet/outlet valve on top.

Pressurize the ZHE to 5-10 psi (if necessary) and slowly open the

liquid inlet/outlet valve to bleed out any headspace (into a hood)

that may have been introduced due to the addition of extraction

fluid. This bleeding shall be done quickly and shall be stopped at

the first appearance of liquid from the valve. Re-pressurize the

ZHE with 5-10 psi and check all ZHE fittings to ensure that they

are closed.

7.3.12.3 Place the ZHE in the rotary agitation apparatus (if it is not already there) and rotate at 30 + 2 rpm for 18 +

2 hours. Ambient temperature (i.e., temperature of room in which

extraction occurs) shall be maintained at 23 + 2 EC during agitation.

7.3.13 Following the 18 + 2 hour agitation period, check the

pressure behind the ZHE piston by quickly opening and closing the gas

inlet/outlet valve and noting the escape of gas. If the pressure has not

been maintained (i.e., no gas release observed), the device is leaking.

Check the ZHE for leaking as specified in Section 4.2.1, and perform the

extraction again with a new sample of waste. If the pressure within the

device has been maintained, the material in the extractor vessel is once

again separated into its component liquid and solid phases. If the waste

contained an initial liquid phase, the liquid may be filtered directly

into the same filtrate collection container (i.e., TEDLAR bag) holding the

®

initial liquid phase of the waste. A separate filtrate collection

container must be used if combining would create multiple phases, or there

is not enough volume left within the filtrate collection container.

Filter through the glass fiber filter, using the ZHE device as discussed

in Section 7.3.9. All extract shall be filtered and collected if the
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TEDLAR bag is used, if the extract is multiphasic, or if the waste

®

contained an initial liquid phase (see Sections 4.6 and 7.3.1).

NOTE: An in-line glass fiber filter may be used to filter the material

within the ZHE if it is suspected that the glass fiber filter has

been ruptured.

7.3.14 If the original waste contained no initial liquid phase,

the filtered liquid material obtained from Section 7.3.13 is defined as

the TCLP extract. If the waste contained an initial liquid phase, the

filtered liquid material obtained from Section 7.3.13 and the initial

liquid phase (Section 7.3.9) are collectively defined as the TCLP extract.

7.3.15 Following collection of the TCLP extract, immediately

prepare the extract for analysis and store with minimal headspace at 4 EC

until analyzed. Analyze the TCLP extract according to the appropriate

analytical methods. If the individual phases are to be analyzed

separately (i.e., are not miscible), determine the volume of the

individual phases (to 0.5%), conduct the appropriate analyses, and combine

the results mathematically by using a simple volume-weighted average:

 (V1) (C1) + (V2) (C2) 

Final Analyte = 

Concentration V1+ V2

where:

V1 = The volume of the first phases (L).

C1 = The concentration of the analyte of concern in the first phase (mg/L).

V2 = The volume of the second phase (L).

C2 = The concentration of the analyte of concern in the second phase

 (mg/L).

7.3.16 Compare the analyte concentrations in the TCLP extract

with the levels identified in the appropriate regulations. Refer to

Section 8.0 for quality assurance requirements.

8.0 QUALITY ASSURANCE

8.1 A minimum of one blank (using the same extraction fluid as used for

the samples) must be analyzed for every 20 extractions that have been conducted

in an extraction vessel. 

8.2 A matrix spike shall be performed for each waste type (e.g.,

wastewater treatment sludge, contaminated soil, etc.) unless the result exceeds

the regulatory level and the data are being used solely to demonstrate that the

waste property exceeds the regulatory level. A minimum of one matrix spike must

be analyzed for each analytical batch. As a minimum, follow the matrix spike

addition guidance provided in each analytical method.
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8.2.1 Matrix spikes are to be added after filtration of the TCLP

extract and before preservation. Matrix spikes should not be added prior

to TCLP extraction of the sample.

8.2.2 In most cases, matrix spikes should be added at a

concentration equivalent to the corresponding regulatory level. If the

analyte concentration is less than one half the regulatory level, the

spike concentration may be as low as one half of the analyte concentration, but may not be not less than five times the method detection limit.

In order to avoid differences in matrix effects, the matrix spikes must be

added to the same nominal volume of TCLP extract as that which was

analyzed for the unspiked sample.

8.2.3 The purpose of the matrix spike is to monitor the

performance of the analytical methods used, and to determine whether

matrix interferences exist. Use of other internal calibration methods,

modification of the analytical methods, or use of alternate analytical

methods may be needed to accurately measure the analyte concentration in

the TCLP extract when the recovery of the matrix spike is below the

expected analytical method performance.

8.2.4 Matrix spike recoveries are calculated by the following

formula:

%R (%Recovery) = 100 (Xs - Xu)/K

where:

Xs = measured value for the spiked sample,

Xu = measured value for the unspiked sample, and

K = known value of the spike in the sample. 

8.3 All quality control measures described in the appropriate analytical

methods shall be followed.

8.4 The use of internal calibration quantitation methods shall be

employed for a metallic contaminant if: (1) Recovery of the contaminant from the

TCLP extract is not at least 50% and the concentration does not exceed the

regulatory level, and (2) The concentration of the contaminant measured in the

extract is within 20% of the appropriate regulatory level.

8.4.1. The method of standard additions shall be employed as the

internal calibration quantitation method for each metallic contaminant.

8.4.2 The method of standard additions requires preparing

calibration standards in the sample matrix rather than reagent water or

blank solution. It requires taking four identical aliquots of the

solution and adding known amounts of standard to three of these aliquots.

The forth aliquot is the unknown. Preferably, the first addition should

be prepared so that the resulting concentration is approximately 50% of

the expected concentration of the sample. The second and third additions

should be prepared so that the concentrations are approximately 100% and
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150% of the expected concentration of the sample. All four aliquots are

maintained at the same final volume by adding reagent water or a blank

solution, and may need dilution adjustment to maintain the signals in the

linear range of the instrument technique. All four aliquots are analyzed.

8.4.3 Prepare a plot, or subject data to linear regression, of

instrument signals or external-calibration-derived concentrations as the

dependant variable (y-axis) versus concentrations of the additions of

standard as the independent variable (x-axis). Solve for the intercept of

the abscissa (the independent variable, x-axis) which is the concentration

in the unknown.

8.4.4 Alternately, subtract the instrumental signal or externalcalibration-derived concentration of the unknown (unspiked) sample from

the instrumental signals or external-calibration-derived concentrations of

the standard additions. Plot or subject to linear regression of the

corrected instrument signals or external-calibration-derived concentrations as the dependant variable versus the independent variable. Derive

concentrations for unknowns using the internal calibration curve as if it

were an external calibration curve.

8.5 Samples must undergo TCLP extraction within the following time

periods: 

SAMPLE MAXIMUM HOLDING TIMES [DAYS]

From: From: From:

Field TCLP Preparative

collection extraction extraction

To: To: To: Total 

TCLP Preparative Determinative elapsed

extraction extraction analysis time

Volatiles 14 NA 14 28

Semi-volatiles 14 7 40 61

Mercury 28 NA 28 56

Metals, except 180 NA 180 360

mercury

NA = Not applicable

If sample holding times are exceeded, the values obtained will be considered

minimal concentrations. Exceeding the holding time is not acceptable in

establishing that a waste does not exceed the regulatory level. Exceeding the

holding time will not invalidate characterization if the waste exceeds the

regulatory level.
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9.0 METHOD PERFORMANCE

9.1 Ruggedness. Two ruggedness studies have been performed to determine

the effect of various perturbations on specific elements of the TCLP protocol.

Ruggedness testing determines the sensitivity of small procedural variations

which might be expected to occur during routine laboratory application. 

9.1.1 Metals - The following conditions were used when leaching

a waste for metals analysis:

 Varying Conditions

 Liquid/Solid ratio 19:1 vs. 21:1

 Extraction time 16 hours vs. 18 hours

 Headspace 20% vs. 60%

 Buffer #2 acidity 190 meq vs. 210 meq

 Acid-washed filters yes vs. no

 Filter type 0.7 μm glass fiber vs. 0.45 μm

 vs. polycarbonate

 Bottle type borosilicate vs. flint glass

Of the seven method variations examined, acidity of the extraction

fluid had the greatest impact on the results. Four of 13 metals from an

API separator sludge/electroplating waste (API/EW) mixture and two of

three metals from an ammonia lime still bottom waste were extracted at

higher levels by the more acidic buffer. Because of the sensitivity to pH

changes, the method requires that the extraction fluids be prepared so

that the final pH is within + 0.05 units as specified.

9.1.2 Volatile Organic Compounds - The following conditions were

used when leaching a waste for VOC analysis:

 Varying Conditions

 Liquid/Solid ratio 19:1 vs. 21:1

 Headspace 0% vs. 5%

 Buffer #1 acidity 60 meq vs. 80 meq

 Method of storing extract Syringe vs. Tedlar bag ®

 Aliquotting yes vs. no

 Pressure behind piston 0 psi vs. 20 psi
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None of the parameters had a significant effect on the results of

the ruggedness test.

9.2 Precision. Many TCLP precision (reproducibility) studies have been

performed, and have shown that, in general, the precision of the TCLP is

comparable to or exceeds that of the EP toxicity test and that method precision

is adequate. One of the more significant contributions to poor precision appears

to be related to sample homogeneity and inter-laboratory variation (due to the

nature of waste materials).

9.2.1 Metals - The results of a multi-laboratory study are shown

in Table 6, and indicate that a single analysis of a waste may not be

adequate for waste characterization and identification requirements.

9.2.2 Semi-Volatile Organic Compounds - The results of two

studies are shown in Tables 7 and 8. Single laboratory precision was

excellent with greater than 90 percent of the results exhibiting an RSD

less than 25 percent. Over 85 percent of all individual compounds in the

multi-laboratory study fell in the RSD range of 20 - 120 percent. Both

studies concluded that the TCLP provides adequate precision. It was also

determined that the high acetate content of the extraction fluid did not

present problems (i.e., column degradation of the gas chromatograph) for

the analytical conditions used.

9.2.3 Volatile Organic Compounds - Eleven laboratories

participated in a collaborative study of the use of the ZHE with two waste

types which were fortified with a mixture of VOCs. The results of the

collaborative study are shown in Table 9. Precision results for VOCs tend

to occur over a considerable range. However, the range and mean RSD

compared very closely to the same collaborative study metals results in

Table 6. Blackburn and Show concluded that at the 95% level of significance: 1) recoveries among laboratories were statistically similar, 2)

recoveries did not vary significantly between the two sample types, and 3)

each laboratory showed the same pattern of recovery for each of the two

samples.

10.0 REFERENCES

1. Blackburn, W.B. and Show, I. "Collaborative Study of the Toxicity

Characteristics Leaching Procedure (TCLP)." Draft Final Report, Contract No. 68-

03-1958, S-Cubed, November 1986.

2. Newcomer, L.R., Blackburn, W.B., Kimmell, T.A. "Performance of the

Toxicity Characteristic Leaching Procedure." Wilson Laboratories, S-Cubed, U.S.

EPA, December 1986.

3. Williams, L.R., Francis, C.W.; Maskarinec, M.P., Taylor D.R., and Rothman,

N. "Single-Laboratory Evaluation of Mobility Procedure for Solid Waste." EMSL,

ORNL, S-Cubed, ENSECO.
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Table 1.

Volatile Analytes1,2

_______________________________________________________________________

Compound CAS No.

 

Acetone 67-64-1

Benzene 71-43-2

n-Butyl alcohol 71-36-3

Carbon disulfide 75-15-0

Carbon tetrachloride 56-23-5

Chlorobenzene 108-90-7

Chloroform 67-66-3

1,2-Dichloroethane 107-06-2

1,1-Dichloroethylene 75-35-4

Ethyl acetate 141-78-6

Ethyl benzene 100-41-4

Ethyl ether 60-29-7

Isobutanol 78-83-1

Methanol 67-56-1

Methylene chloride 75-09-2

Methyl ethyl ketone 78-93-3

Methyl isobutyl ketone 108-10-1

Tetrachloroethylene 127-18-4

Toluene 108-88-3

1,1,1,-Trichloroethane 71-55-6

Trichloroethylene 79-01-6

Trichlorofluoromethane 75-69-4

1,1,2-Trichloro-1,2,2-trifluoroethane 76-13-1

Vinyl chloride 75-01-4

Xylene 1330-20-7

_______________________________________________________________________

 When testing for any or all of these analytes, the zero-headspace 1

 extractor vessel shall be used instead of the bottle extractor. 

 Benzene, carbon tetrachloride, chlorobenzene, chloroform, 2

 1,2-dichloroethane, 1,1-dichloroethylene, methyl ethyl ketone,

 tetrachloroethylene, and vinyl chloride are toxicity characteristic

 constituents.
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Table 2.

Suitable Rotary Agitation Apparatus1

 

Company Location Model No. 

Analytical Testing and Warrington, PA 4-vessel extractor (DC20S)

 Consulting Services, (215) 343-4490 8-vessel extractor (DC20)

 Inc. 12-vessel extractor (DC20B)

 24-vessel extractor (DC24C) 

 

Associated Design and Alexandria, VA 2-vessel (3740-2-BRE)

 Manufacturing Company (703) 549-5999 4-vessel (3740-4-BRE)

 6-vessel (3740-6-BRE)

 8-vessel (3740-8-BRE)

 12-vessel (3740-12-BRE)

 24-vessel (3740-24-BRE)

Environmental Machine and Lynchburg, VA 8-vessel (08-00-00)

 Design, Inc. (804) 845-6424 4-vessel (04-00-00)

IRA Machine Shop and Santurce, PR 8-vessel (011001)

 Laboratory (809) 752-4004

Lars Lande Manufacturing Whitmore Lake, MI 10-vessel (10VRE)

 (313) 449-4116 5-vessel (5VRE)

 6-vessel (6VRE)

Millipore Corp. Bedford, MA 4-ZHE or

 (800) 225-3384 4 2-liter bottle 

 extractor (YT31ORAHW)

 

 Any device that rotates the extraction vessel in an end-over-end fashion at 1

30 + 2 rpm is acceptable.
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Table 3.

Suitable Zero-Headspace Extractor Vessels1

 

Company Location Model No.

Analytical Testing & Warrington, PA C1O2, Mechanical 

 Consulting Services, Inc. (215) 343-4490 Pressure Device

Associated Design and Alexandria, VA 3745-ZHE, Gas

 Manufacturing Company (703) 549-5999 Pressure Device

Lars Lande Manufacturing Whitmore Lake, MI ZHE-11, Gas 2

 (313) 449-4116 Pressure Device 

 

Millipore Corporation Bedford, MA YT30O9OHW, Gas

 (800) 225-3384 Pressure Device

Environmental Machine Lynchburg, VA VOLA-TOX1, Gas

and Design, Inc. (804) 845-6424 Pressure Device

Gelman Science Ann Arbor, MI 15400 Gas Pressure

 (800) 521-1520 Device

 

 Any device that meets the specifications listed in Section 4.2.1 of the 1

method is suitable.

 This device uses a 110 mm filter. 2
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Table 4.

Suitable Filter Holders1

 

 Model/

Company Location Catalogue No. Size

 

Nucleopore Corporation Pleasanton, CA 425910 142 mm

(800) 882-7711 410400 47 mm

Micro Filtration Dublin, CA 302400 142 mm

Systems (800) 334-7132 311400 47 mm

(415) 828-6010

Millipore Corporation Bedford, MA YT30142HW 142 mm

(800) 225-3384 XX1004700 47 mm

 

 Any device capable of separating the liquid from the solid phase of the 1

waste is suitable, providing that it is chemically compatible with the waste

and the constituents to be analyzed. Plastic devices (not listed above) may

be used when only inorganic analytes are of concern. The 142 mm size filter

holder is recommended.
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Table 5.

Suitable Filter Media1

 

Pore

Size

Company Location Model (μm)

 

Millipore Corporation Bedford, MA AP40 0.7

(800) 225-3384

Nucleopore Corporation Pleasanton, CA 211625 0.7

(415) 463-2530

Whatman Laboratory Clifton, NJ GFF 0.7

 Products, Inc. (201) 773-5800

Micro Filtration Dublin, CA GF75 0.7

Systems (800) 334-7132

(415) 828-6010

Gelman Science Ann Arbor, MI 66256 (90mm) 0.7

(800) 521-1520 66257 (142mm)

 

 Any filter that meets the specifications in Section 4.4 of the Method is 1

suitable.
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Table 6. Multi-Laboratory TCLP Metals, Precision

 Waste Fluid Metal X S %RSD

 Extraction 

 Ammonia #1 Cadmium 0.053 0.031 60

 Lime Still #2 0.023 0.017 76

 Bottoms #1 Chromium 0.015 0.0014 93

 API/EW #1 Cadmium 0.0046 0.0028 61

 Mixture #2 0.0005 0.0004 77

 Fossil #1 Cadmium 0.080 0.069 86

 Fuel Fly #2 0.093 0.067 72

 Ash #1 Chromium 0.017 0.014 85

 #2 0.0032 0.0037 118

 #1 Lead 0.0030 0.0027 90

 #2 0.0032 0.0028 87

 #1 Chromium 0.0561 0.0227 40

 #2 0.105 0.018 17

 #1 Lead 0.0031 0.0031 100

 #2 0.0124 0.0136 110

 #2 0.070 0.040 57

 #1 Lead 0.0087 0.0074 85

 #2 0.0457 0.0083 18

 %RSD Range = 17 - 118

 Mean %RSD = 74

 

NOTE: X = Mean results from 6 - 12 different laboratories

Units = mg/L

Extraction Fluid #1 = pH 4.9

 #2 = pH 2.9
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Table 7. Single-Laboratory Semi-Volatiles, Precision

 Waste Compound Fluid X S %RSD

 Extraction 

 Ammonia Phenol #1 19000 2230 11.6

 Lime Still #2 19400 929 4.8

 Bottoms 2-Methylphenol #1 2000 297 14.9

 API/EW Phenol #1 40.7 13.5 33.0

 Mixture #2 19.0 1.76 9.3

 4-Methylphenol #1 7940 1380 17.4

 2,4-Dimethylphenol #1 321 46.8 14.6

 Naphthalene #1 3920 413 10.5

 2-Methylnaphthalene #1 290 44.8 15.5

 Dibenzofuran #1 187 22.7 12.1

 Acenaphthylene #1 703 89.2 12.7

 Fluorene #1 151 17.6 11.7

 Phenanthrene #1 241 22.7 9.4

 Anthracene #1 33.2 6.19 18.6

 Fluoranthrene #1 25.3 1.8 7.1

 2,4-Dimethylphenol #1 33.0 9.35 28.3

 Naphthalene #1 185 29.4 15.8

 2-Methylnaphthalene #1 265 61.2 23.1

 #2 1860 52.9 2.8

 #2 7490 200 2.7

 #2 307 45.8 14.9

 #2 3827 176 4.6

 #2 273 19.3 7.1

 #2 187 7.2 3.9

 #2 663 20.1 3.0

 #2 156 2.1 1.3

 #2 243 7.9 3.3

 #2 34.6 1.55 4.5

 #2 26.0 1.8 7.1

 #2 43.3 8.61 19.9

 #2 165 24.8 15.0

 #2 200 18.9 9.5

 %RSD Range = 1 - 33

 Mean %RSD = 12

NOTE: Units = μg/L

Extractions were performed in triplicate

All results were at least 2x the detection limit

Extraction Fluid #1 = pH 4.9

 #2 = pH 2.9
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Table 8. Multi-Laboratory Semi-Volatiles, Precision

 Extraction 

 Waste Compound Fluid X S %RSD

 Ammonia Lime BNAs #1 10043 7680 76.5

 Still Bottoms (A) #2 10376 6552 63.1

 API/EW BNAs #1 1624 675 41.6

 Mixture (B) #2 2074 1463 70.5

 Fossil Fuel BNAs #1 750 175 23.4

 Fly Ash (C) #2 739 342 46.3

 Mean %RSD = 54

NOTE: Units = μg/L

X = Mean results from 3 - 10 labs

Extraction Fluid #1 = pH 4.9

 #2 = pH 2.9

%RSD Range for Individual Compounds

 A, #1 0 - 113

 A, #2 28 - 108

 B, #1 20 - 156

 B, #2 49 - 128

 C, #1 36 - 143

 C, #2 61 - 164
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Table 9. Multi-Laboratory (11 Labs) VOCs, Precision

 Waste Compound X S %RSD

 

 Mine Vinyl chloride 6.36 6.36 100

 Tailings Methylene chloride 12.1 11.8 98

 Ammonia Vinyl chloride 5.00 4.71 94

 Lime Still Methylene chloride 14.3 13.1 92

 Bottoms Carbon disulfide 3.37 2.07 61

 Carbon disulfide 5.57 2.83 51

 1,1-Dichloroethene 21.9 27.7 127

 1,1-Dichloroethane 31.4 25.4 81

 Chloroform 46.6 29.2 63

 1,2-Dichloroethane 47.8 33.6 70

 2-Butanone 43.5 36.9 85

 1,1,1-Trichloroethane 20.9 20.9 100

 Carbon tetrachloride 12.0 8.2 68 

 Trichloroethene 24.7 21.2 86

 1,1,2-Trichloroethene 19.6 10.9 56

 Benzene 37.9 28.7 76

 1,1,2,2-Tetrachloroethane 34.9 25.6 73

 Toluene 29.3 11.2 38

 Chlorobenzene 35.6 19.3 54

 Ethylbenzene 4.27 2.80 66

 Trichlorofluoromethane 3.82 4.40 115

 Acrylonitrile 76.7 110.8 144

 1,1-Dichloroethene 52.1 38.8 75

 1,1-Dichloroethane 52.8 25.6 49

 Chloroform 64.7 28.4 44

 1,2-Dichloroethane 43.1 31.5 73

 2-Butanone 59.0 39.6 67

 1,1,1-Trichloroethane 53.6 40.9 76

 Carbon tetrachloride 7.10 6.1 86

 Trichloroethene 57.3 34.2 60

 1,1,2-Trichloroethene 6.7 4.7 70

 Benzene 61.3 26.8 44

 1,1,2,2-Tetrachloroethane 3.16 2.1 66

 Toluene 69.0 18.5 27

 Chlorobenzene 71.8 12.0 17

 Ethylbenzene 3.70 2.2 58

 Trichlorofluoromethane 4.05 4.8 119

 Acrylonitrile 29.4 34.8 118

 %RSD Range = 17 - 144 

 Mean %RSD = 75

NOTE: Units = μg/L
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Figure 1. Rotary Agitation Apparatus

Figure 2. Zero-Headspace Extractor (ZHE)
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METHOD 1311

TOXICITY CHARACTERISTIC LEACHATE PROCEDURE
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METHOD 1311 (CONTINUED)

TOXICITY CHARACTERISTIC LEACHATE PROCEDURE