CD-ROM 1311- 1 Revision 0 July 1992 METHOD 1311 TOXICITY CHARACTERISTIC LEACHING PROCEDURE

1.0 SCOPE AND APPLICATION

1.1 The TCLP is designed to determine the mobility of both organ ic and inorganic analytes present in liquid, solid, and multiphasic wastes.

1.2 If a total analysis of the waste demonstrates that individua l analytes are not present in the waste, or that the y are present but at such low concen trations that the appropriate regulatory levels could not possibly b e exceeded, the TCLP need not be run.

1.3 Ifan anal ysis of any one of the liquid fractions of the TCL Pextract 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 remainin g fractions of the extract.

1.4 If an anal ysis of extract obtained using a bottle extractor shows that the concentration of any regulated volatile a nalyte exceeds the regulatory level for that compound, then the waste is hazardous and extraction using the ZH E is not nece ssary. However, extract from a bottle extractor cannot be used t o demonstrate that the concentration of volatile compounds is below the regulator y level. 2.0 SUMMARY OF METHOD

2.1 For liquid wastes ( i.e. , those containing less than 0.5% drysolid material ), the waste, after filtration through a 0.6 to 0.8 μm glass fibe r filter, is defined as the TCLP extract.

2.2 For wastes containing greater than or equal to 0.5% solids, th e liquid, if any, is separated from the solid phase and stored for later analysis ; the particle size of the solid phase is reduced, i f necessary. The solid phase is extracted with an amount of extraction fluid eq ual to 20 times the weight of the solid phase. The extraction fluid employed is a function of the alkalinity ofthe solid phase of the waste. A special extractor vessel is used when testin g forvolatile analytes (see Table 1 for a list of volatile compounds). Followin g 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 Ifcompatible ( i.e. , multiple phases will not form on combination) , the initial liquid phase of the waste is added to the liquid extract, and these areanalyzed together. If incompatible, the liquids are analyzed separately an d th e results are mathematically combined to yield a volume-weighted averag e concentration.VITON is a trademark of Du Pont. 1 ® CD-ROM 1311- 2 Revision 0 July 1992 3.0 INTERFERENCES 3.1 Potential interferences that may be encountered during analysis ar e discussed in the individual analytical methods. 4.0 APPARATUS AND MATERIALS 4.1 Agita tion apparatus: The agitation apparatus must be capable o f rotatin g the extraction vessel in an end-over-end fashion (see Figure 1) a t 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 i s 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 effectivel y precludes headspace. This type of vessel allows f or initial liquid/solid separation, extraction, and final extract filtration without opening the vessel (see Section 4.3.1). The vessels shall hav e an internal volume of 500-600mL, and be equipped to accommodate a 90-110 mm filter. The device s contain VITON O-rings which should be replaced frequen tly. Suitable ZHE ®1 devices known to EPA are identified in Table 3.

For the ZHE to be acceptable for use, the piston within the ZH E should be able to be moved with approximately 15 psi or less. If it take s more p ressure to move the piston, the O-rings in the device should b e replaced. If this does not solve the problem, the ZHE is unacceptable fo r TCLP analyses and the manufacturer should be contacted.

TheZHE should be checked for leaks after every extraction. If th e device contains a built-in pressure gauge, pressurize the device t o 50 psi, allow it to stand unattended for 1 hour, and recheck the pressure

. Ifthe device does not have a built-in pressure gauge, pressurize th e 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 al l fittings and inspect and replace O-rings, if necessary. Retest th e device. If leakage problems cannot be solved, the manufacturer should be contacted.

SomeZHEs use gas pressure to actuate the ZHE piston, while other s use mechanical pressure (see Table 3). Whereas the volatiles procedur e (see Sect ion 7.3) refers to pounds per square inch (psi), for th e mechan icallyactuated piston, the pressure applied is measured i n torqu e-inch-pounds. Refer to the manufacturer's instructions as to th e proper conversion.CD-ROM 1311- 3 Revision 0 July 1992 4.2.2 Bott le Extraction Vessel. When the waste is bein g evaluated using the nonvolatile extraction, a jar with sufficient capacit y to hold the sample and the extraction fluid is needed. Headspace i s allowed in this vessel.

The extraction bottles may be constructed from various materials, depending on the analytes to be analyzed and the n ature of the waste (see Section 4.3.3). It is recommended that borosilicate glass bottles be use d instead of other types of glass, especially when inorganics are o f concern. Plastic bottles, other than polytetrafluoroethylene, shall not be used if organics are to be investigated. Bottl es are available from a number of laboratory suppliers. When this type of extraction vessel i s used, the filtration device discussed in Section 4.3.2 is used for initia l liquid/solid separation and final extract filtration. 4.3 Filtra tion Devices: It is recommended that all filtrations b e 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 i n Sectio n 4.2.1 is used for filtration. The device shall be capable o f suppor ting and keeping in place the glass fiber filter and be able t o 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 materia l within the ZHE. 4.3.2 FilterHolder: When the waste is evaluated for other tha n volatile analytes, any filter holder capable of supporting a glass fiber filter and able to withstand the pressure needed t o accomplish separation ma ybe used. Suitable filter holders range from simple vacuum units t o relatively complex systems capable of exerting pressures of up to 50 psi or more. The type of filter holder used depends o n the properties of the material to be filtered (see Section 4.3.3). These devices shall have a minimuminternal volume of 300 mL and be equipped to accommodate a minimu m filter size of 47 mm (filter holders having an int ernal capacity of 1.5 L or grea ter, and equipped to accommodate a 142 mm diameter filter, ar e recommended). Vacuum filtration can only be used for wastes with lo w solids content (<10%) and for highly granular, liquid-containing wastes. All other types of wastes should be filtered using positive pressur e filtration. Suitable filter holders known to EPA are shown in Table 4.

4.3.3 Materials of Construction: Extraction vessels an d filtration devices shall be made of inert materials which will not leach or a bsorb waste components. Glass, polytetrafluoroethylene (PTFE), o r type 316 stainless steel equipment may be used when evaluating th e mobility of both organic and inorganic components. Devices made of high de nsitypolyethylene (HDPE), polypropylene (PP), or polyvinyl chlorid e (PVC) may be used only when evaluating the mobilit y of metals. Borosili-TEDLAR is a registered trademark of Du Pont. 2 ®

CD-ROM 1311- 4 Revision 0 July 1992 ca te glass bottles are recommended for use over other types of glas s bottles, especially when inorganics are analytes of concern. 4.4 Filters: Filters shall be made of borosilicate gl ass fiber, shall contain n o binder materials, and shall have an effective pore size of 0.6 t o 0.8 μm, or equivalent. Filters known to EPA which meet these specifications ar e ident ified in Table 5. Pre-filters must not be used. When evaluating th e mobilityof metals, filters shall be acid-washed prior to use by rinsing with 1 N nitric acid followed by three consecutive rinses w ith deionized distilled water (a minimum of 1 L per rinse is recommended). Glass fiber filters are fragile an d should be handled with care. 4.5 pH Meters: The meter should be accurate t o +0.05 units at 25 E C. 4.6 ZHE Extr act Collection Devices: TEDLAR bags or glass, stainless ® 2 steel or PTFE gas-tight syringes are used to collect the initial liquid phase an d thefinal extract of the waste when using the ZHE device. The devices listed ar e 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 collec t ® and combine the initial liquid and solid extract.

4.6.2 Ifa waste contains a significant amount of nonaqueou s liquid in the initial liquid phase ( i.e. , >1% of total waste), the syring e orthe TEDLAR bag may be used for both the initial solid/liquid separatio n ® andthe final extract filtration. However, analysts should use one or th e 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 th e TEDLAR bag or the syringe may be used. If the syringe is used, discar d

® the first 5 mL of liquid expressed from the device. The remainin g aliquots are used for analysis. 4.7 ZH EExtraction Fluid Transfer Devices: Any device capable o f transferringthe extraction fluid into the ZHE without changing the nature of th e extraction fluid is acceptable ( e.g. , a positive displacement or peristalti c pump, a gas tight syringe, pressure filtration unit (see Section 4.3.2), or othe r ZHE device). 4.8 Labora toryBalance: Any laboratory balance accurate to withi n +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.CD-ROM 1311- 5 Revision 0 July 1992 4.10 Wat chglass, appropriate diameter to cover beaker or Erlenmeye r flask. 4.11 Magnetic stirrer. 5.0 REAGENTS 5.1 Reagentgrade chemicals shall be used in all tests. Unles s ot herwise indicated, it is intended that all reagents shall conform to th e specifications of the Committee on Analytical Reag ents 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 purit y to permit its use without lessening the accuracy of the determination. 5.2 Re agentWater. Reagent water is defined as water in which a n interf erantis not observed at or above the method's detection limit of th e analyte (s) of interest. For nonvolatile extractions, ASTM Type II water o r 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 pass ing tap water through a carbon filter bed containing about 50 0 grams of activated carbon (Calgon Corp., Filtrasorb-300 or equivalent).

5.2.2 A water purification system (Millipore Super-Q o r equivalent) may also be used to generate reagent water for volatil e extractions.

5.2.3 Reagen twater for volatile extractions may also b e prepared by boiling water for 15 minutes. Subsequently, while maintainin g thewater temperature at 90 +5 degrees C, bubble a contaminant-free iner t gas ( e.g . nitrogen) through the water for 1 hour. While still hot , transferthe water to a narrow mouth screw-cap bottle under zero-headspac e 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), HNO , made from ACS reagent grade. 3 5.5 Sodium hydroxide (1N), NaOH, made from ACS reagent grade. 5.6 Glacial acetic acid, CH CH OOH, ACS reagent grade. 3 2 5.7 Extraction fluid.

5.7.1 Ex traction fluid # 1: Add 5.7 mL glacial CH CH OOH t o 3 2 50 0 mL of reagent water (See Section 5.2), add 64.3 mL of 1N NaOH, an d dilute t o a volume of 1 liter. When correctly prepared, the pH of thi s fluid will be 4.93 +0.05.CD-ROM 1311- 6 Revision 0 July 1992 5.7.2 Extraction fluid # 2: Dilute 5.7 mL glacial CH CH OOH wit h 3 2 reagent wat er (See Section 5.2) to a volume of 1 liter. When correctl y prepared, the pH of this fluid will be 2.88 +0.05. NOTE: These extraction fluids should be monitored frequently fo r

impurities. The pH should be checked prior to use to ensure that these fluids are made up accurately. If impurities are found o r 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 appropriat e analytical method. 6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING 6.1 All samples shall be collected using an appropriat e sampling plan. 6.2 The TC LP may place requirements on the minimal size of the fiel d sample, depending upon the physical state or states of the waste and the analyte s ofconcern. An aliquot is needed for preliminary evaluation of which extractio n fluid is to be used for the nonvolatile analyte extraction procedure. Another aliquotmay be needed to actually conduct the nonvolatile extraction (see Sectio n 1.4 co ncerning the use of this extract for volatile organics). If volatil e organics are of concern, another aliquot may be needed. Quality control measure s may require additional aliquots. Further, it is always wise to collect mor e samplejust in case something goes wrong with the initial attempt to conduct th e test. 6.3 Preservatives shall not be added to samples before extraction. 6.4 Sample s may be refrigerated unless refrigeration results i n irreversible physical change to the waste. If pre cipitation occurs, the entire sample (including precipitate) should be extracted. 6.5 When the waste is to be evaluated for volatile analytes, care shal l be take n to minimize the loss of volatiles. Samples shall be collected an d stored in a manner intended to prevent the loss of volatile analytes ( e.g. , samples should be collected in Teflon-lined septumcapped vials and stored at 4

E C. 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 metalli c analyte det erminations must be acidified with nitric acid to a pH < 2, unles s precipitation occurs (see Section 7.2.14 if precipitation occurs). Extract s sh ould be preserved for other analytes according to the guidance given in th e individual analysis methods. Extracts or portions of extracts for organi c analyte determinations shall not be allowed to come into contact with th e atmospher e ( i.e. , no headspace) to prevent losses. See Section 8.0 (Q A requirements) for acceptable sample and extract holding times.CD-ROM 1311- 7 Revision 0 July 1992 7.0 PROCEDURE 7.1 Preliminary Evaluations Performpreliminary TCLP evaluations on a minimum 100 gram aliquot o f waste. This aliquot may not actually undergo TCLP extraction. These preliminar y 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 (Sect ion 7.1.2); (3) determination ofwhether the solid portion of the waste requires particle size reductio n (Section 7.1.3); and (4) determination of which of the two extraction fluids ar e to be used for the nonvolatile TCLP extraction of the waste (Section 7.1.4).

7.1.1 Preliminarydetermination of percent solids: Percen t 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 applie d pressure, as described below.

7.1.1.1 Ifthe waste will obviously yield no liquid whe n subjected to pressure filtration ( i.e. , is 100% solids) proceed t o Section 7.1.3.

7.1.1.2 Ifthe sample is liquid or multiphasic , liq uid/solid separation to make a preliminary determination o f perce ntsolids is required. This involves the filtration devic e descri bed 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 wil l receive the filtrate.

7.1.1.4 Assemblethe filter holder and filter followin g the manufacturer's instructions. Place the filter on the support screen and secure.

7.1.1.5 Weig h out a subsample of the waste (100 gra m minimum) and record the weight.

7.1.1.6 All owslurries to stand to permit the soli d phase to settle. Wastes that settle slowly may be centrifuge d prior to filtration. Centrifugation is to be used only as an aid to filtration. If used, the liquid should be decanted and filtere d followed by filtration of the solid portion of the waste throug h the same filtration system.

7.1.1.7 Quantitativelytransfer the waste sample to th e filter holder (liquid and solid phases). Spread the waste sample evenly over the surface of the filter. If filtration of the waste at4 E C 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.CD-ROM 1311- 8 Revision 0 July 1992 NOTE: If waste material (>1% of original sample weight) has obviousl y

adhered to the container used to transfer the sample to th e filtra tion apparatus, determine the weight of this residue an d subtractit from the sample weight determined in Section 7.1.1.5 t o determine the weight of the waste sample that will be filtered.

Grad uallyapply vacuum or gentle pressure of 1-10 psi , until air or pressurizing gas moves through the filter. If thi s point is not reached under 10 psi, and if no addit ional liquid has passed through the filter in any 2 minute interval, slowly increas e the pressur e in 10 psi increments to a maximum of 50 psi. Afte r each incremental increase of 10 psi, if the pressurizing gas ha s notmoved through the filter, and if no additional liquid ha s passed through the filter in any 2 minute interval , proceed to the next 1 0 psi increment. When the pressurizing gas begins to mov e through the filter, or when liquid flow has ceased at 50 psi ( i.e. , filtration does not result in any additional filtr ate within any 2 minute period), stop the filtration. NOTE: In stantaneous application of high pressure can degrade the glas s

fiber filter and may cause premature plugging.

7.1.1.8 Thematerial in the filter holder is defined a s th e solid phase of the waste, and the filtrate is defined as th e liquid phase. NOTE: Some wastes, such as oily wastes and some paint wastes, wil l

obviously contain some material that appears to be a liquid. Even af ter applying vacuum or pressure filtration, as outlined i n Section 7.1.1.7, this material may not filter. If this is th e case, the material within the filtration device is defined as a solid. Do not replace the original filter with a fresh filte r under any circumstances. Use only one filter.

7.1.1.9 Det ermine the weight of the liquid phase b y subtracting the weight of the filtrate container (see Sectio n 7. 1.1.3) from the total weight of the filtrate-filled container

. Determi ne the weight of the solid phase of the waste sample b y 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 Ift he percent solids determined in Section 7.1.1.9 i s equa l to or greater than 0.5%, then proceed either to Section 7.1.3 t oCD-ROM 1311- 9 Revision 0 July 1992 determine whether the solid material requires particle size reduction or toSection 7.1.2.1 if it is noticed that a small amount of the filtrate i s entrained in wetting of the filter. If the percent solids determined in Se ction 7.1.1.9 is less than 0.5%, then proceed to Section 7.2.9 if th e nonvolatil e TCLP is to be performed and to Section 7.3 with a fres h portion of the waste if the volatile TCLP is to be performed.

7.1.2.1 Remo ve the solid phase and filter from th e filtration apparatus.

7.1.2.2 Dry the filter and solid phase at 100 +20 E C 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 u pon heating. It is recommended that the drying oven b e 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 Percentdry solids = x 10 0 Initial wt. of waste (Section 7.1.1.5 or 7.1.1.7) 7.1.2.4 Ift he percent dry solids is less than 0.5% , then pr oceed to Section 7.2.9 if the nonvolatile TCLP is to b e per formed, and to Section 7.3 if the volatile TCLP is to b e 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 th e beginning of this Section (7.1) and, with a fresh portion of waste , de termine whether particle size reduction is necessary (Sectio n 7.1 .3) and determine the appropriate extraction fluid (Sectio n 7.1.4). If only the volatile TCLP is to be performed, see the not e in Section 7.1.4. 7.1.3 Determination of whether the waste requires partic le size reduct ion (particle size is reduced during this step): Using the soli d portion of the waste, evaluate the solid for particle size. Particle siz e redu ction is required, unless the solid has a surface area per gram o f 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 particl e size larger than described above, prepare the solid portion of the waste for ex traction by crushing, cutting, or grinding the waste to a surfac e area or particle size as described above. If the solids are prepared for organicvolatiles extraction, special precautions must be taken (se e 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 no t required, nor is it recommended. For materials tha t do not obviously meetCD-ROM 1311- 10 Revision 0 July 1992 the criteria, sample specific methods would need to be developed an d employed to measure the surface area. Such methodology is currently no t available.

7.1.4 De termination of appropriate extraction fluid: If th e so lid content of the waste is greater than or equal to 0.5% and if th e sample will be extracted for nonvolatile constituents (Section 7.2) , dete rmine the appropriate fluid (Section 5.7) for the nonvolatile s extraction as follows: NOTE: TCL P extraction for volatile constituents uses only extractio n

fluid # 1 (Section 5.7.1). Therefore, if TCLP extraction fo r nonvolatiles is not required, proceed to Section 7.3.

7.1.4.1 Weigh out a small subsample of the solid phase ofthe waste, reduce the solid (if necessary) to a particle size o f approximately 1 mm in diameter or less, and transfer 5.0 grams of the soli d phase of the waste to a 500 mL beaker or Erlenmeye r 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 Ifthe pH from Section 7.1.4.2 is >5.0, ad d 3.5 mL 1N HCl, slurry briefly, cover with a watchg lass, heat to 50

E C, and hold at 50 E C for 10 minutes.

7.1.4.4 Let the solution cool to room temperature an d record the pH. If the pH is <5.0, use extraction fluid #1. If th e pH is >5.0, use extraction fluid #2. Proceed to Section 7.2. 7.1.5 Ifthe aliquot of the waste used for the preliminar y evaluation (Sections 7.1.1 - 7.1.4) was determined to be 100% solid a t Section 7.1.1.1, then it can be used for the Section 7.2 extractio n (assuming at least 100 grams remain), and the Section 7.3 extractio n (assuming at least 25 grams remain). If the aliqu ot was subjected to the procedure in Section 7.1.1.7, then another aliquot shall be used for the volati le extraction procedure in Section 7.3. The aliquot of the wast e subjected to the procedure in Section 7.1.1.7 might be appropriate for us e for the S ection 7.2 extraction if an adequate amount of solid (a s determined by Section 7.1.1.9) was obtained. The amount of soli d necessaryis dependent upon whether a sufficient amount of extract will b e 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 Aminimum sample size of 100 grams (solid and liquid phases) is recommend

ed. In some cases, a larger sample size may be appropriate, depending on th eCD-ROM 1311- 11 Revision 0 July 1992 solids content of the waste sample (percent solids , See Section 7.1.1), whether the initial liquid phase of the waste will be misc ible with the aqueous extract of the solid, and whether inorganics, semivolatile organics, pesticides, an d 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 al l of the analyses required. If the amount of extract generated by a single TCLP extraction will not be sufficient to perform all o f the analyses, more than one extraction may be performed and the extracts from each combined and aliquoted fo r analysis. 7.2.1 Ifthe waste will obviously yield no liquid when subjecte d topressure filtration ( i.e. , is 100% solid, see Section 7.1.1), weigh ou t a subsample of the waste (100 gram minimum) and pr oceed to Section 7.2.9.

7.2.2 Ift he sample is liquid or multiphasic, liquid/soli d separation is required. This involves the filtrat ion 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 Assem ble the filter holder and filter following th e manufacturer's instructions. Place the filter on the support screen and se cure. Acid wash the filter if evaluating the mobility of metals (se e Section 4.4). NOTE: Acid washed filters may be used for all nonvolatile extraction s

even when metals are not of concern. 7.2.5 Weigh out a subsample of the waste (100 gram minim um) and record t he weight. If the waste contains <0.5% dry solids (Sectio n 7.1.2), the liquid portion of the waste, after filtration, is defined as the TC LP extract. Therefore, enough of the sample should be filtered s o that the amount of filtered liquid will support all of the analyse s required of the TCLP extract. For wastes containing >0.5% dry solid s (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 suppor t the analyses to be performed on the TCLP extract.

7.2.6 Al lowslurries to stand to permit the solid phase t o settle. Wastes that settle slowly may be centrifuged prior to filtration

. Us e centrifugation only as an aid to filtration. If the waste i s centrif uged, the liquid should be decanted and filtered followed b y filtration of the solid portion of the waste through the same filtration system. 7.2.7 Quantitatively transfer the waste sample (liquid and soli d phases) to the filter holder (see Section 4.3.2). Spread the waste sampl e evenlyover the surface of the filter. If filtration of the waste at 4 E C reduces the amount of expressed liquid over what would be expressed a tCD-ROM 1311- 12 Revision 0 July 1992 room temperature, then allow the sample to warm upto room temperature in the device before filtering. NOTE: Ifwaste material (>1% of the original sample weight) has obviousl y

adhered to the container used to transfer the sample to th e filtra tion apparatus, determine the weight of this residue an d subtract it from the sample weight determined in S ection 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 o r 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 i n any 2 minute interval, slowly increase the pressure in 10 psi increments toa maximum of 50 psi. After each incremental increase of 10 psi, if th e pressu rizing gas has not moved through the filter, and if no additiona l liquid has passed through the filter in any 2 minu te interval, proceed to the next 10 psi increment. When the pressurizing gas begins to mov e through the filter, or when the liquid flow has ceased at 50 psi ( i.e. , filtra tion does not result in any additional filtrate within a 2 minut e period), stop the filtration. NOTE: In stantaneous application of high pressure can degrade the glas s

fiber filter and may cause premature plugging. 7.2.8 The material in the filter holder is defined as th e solid phase ofthe waste, and the filtrate is defined as the liquid phase

. We igh the filtrate. The liquid phase may now be either analyzed (Se e Section 7.2.12) or stored at 4 E C until time of analysis. NOTE: Some wastes, such as oily wastes and some paint wastes, wil l

obviously contain some material that appears to be a liquid. Even af ter applying vacuum or pressure filtration, as outlined i n Section 7.2.7, this material may not filter. If t his is the case, the material within the filtration device is defined as a solid an d 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 Ifthe waste contains <0.5% dry solids (see Sectio n 7.1.2), proceed to Section 7.2.13. If the waste contains >0.5% dry solid s (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 materia l in to the extractor bottle along with the filter used to separate th e 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 particl e size as described in Section 7.1.3. When the surface area or particl e size has been appropriately altered, quantitatively transfer the soli dCD-ROM 1311- 13 Revision 0 July 1992 material into an extractor bottle. Include the filter used to separate th e initial liquid from the solid phase. NOTE: Sieving of the waste is not normally required. Surface are a

requ irements are meant for filamentous ( e.g. , paper, cloth) an d similarwaste materials. Actual measurement of surface area is no t recommended. If sieving is necessary, a Teflon coated sieve shoul d be used to avoid contamination of the sample. 7.2.11 Determine the amount of extraction fluid to add to th e 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

Slowlyadd this amount of appropriate extraction fluid (see Sectio n 7.1.4) to the extractor vessel. Close the extractor bottle tightly (it i s re commended that Teflon tape be used to ensure a tight seal), secure i n rotary agita tion 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 E C during the extraction period. NOTE: As agitation continues, pressure may build up with in the extractor

bottle for some types of wastes ( e.g. , limed or calcium carbonate containing waste may evolve gases such as carbon dioxide). T o 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 Foll owing the 18 +2 hour extraction, separate th e material in the extractor vessel into its component liquid and soli d ph ases by filtering through a new glass fiber filter, as outlined i n Section 7.2.7. For final filtration of the TCLP e xtract, 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 o f metals. 7.2.13 Prepare the TCLP extract as follows:

7.2.13.1 Ift he waste contained no initial liqui d phase, the filtered liquid material obtained from Section 7.2.12 i s 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 liqui d resulting from Section 7.2.12 with the initial liquid phase of th e waste obtained in Sect ion 7.2.7. This combined liquid is defined as the TCL P extract. Proceed to Section 7.2.14.CD-ROM 1311- 14 Revision 0 July 1992 7.2.13.3 Ift he initial liquid phase of the waste, a s 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, collectivel y defined as the TCLP extract, and combine the results mathematical ly, as described in Section 7.2.14. 7.2.14 Follo wing collection of the TCLP extract, the pH of th e extract should be recorded. Immediately aliquot a nd preserve the extract fo r analysis. Metals aliquots must be acidified with nitric acid t o pH <2. I f precipitation is observed upon addition of nitric acid to a small aliquot of the extract, then the remaining portion of the extrac t for meta ls analyses shall not be acidified and the extract shall b e anal yzed as soon as possible. All other aliquots must be stored unde r refrigeration (4 E C) until analyzed. The TCLP extract shall be prepared andanalyzed according to appropriate analytical methods. TCLP extracts t o be ana lyzed for metals shall be acid digested except in those instance s where digestion causes loss of metallic analytes. If an analysis of the undigested extract shows that the concentration ofany regulated metallic analyte exceeds the regulatory level, then the waste is hazardous an d digest ion of the extract is not necessary. However, data on undigeste d ext racts alone cannot be used to demonstrate that the waste is no t hazardous. If the individual phases are to be analyzed separately , determine the volume of the individual phases (to +0.5%), conduct th e appro priate analyses, and combine the results mathematically by using a simple volume-weighted average: (V ) (C ) + (V ) (C ) 1 1 2 2 Final Analyte Concentration = V + V 1 2 where:
V = The volume of the first phase (L). 1 C = The concentration of the analyte of concern in the first phase (mg/L)

. 1 V = The volume of the second phase (L). 2 C = The concentration of the analyte of concern in the second phase 2 (mg/L).

7.2.15 Co mpare the analyte concentrations in the TCLP extrac t with the levels identified in the appropriate regulations. Refer t o 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 volatil e compounds only. Extract resulting from the use ofthe 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 aCD-ROM 1311- 15 Revision 0 July 1992 sample from which no additional liquid may be forc ed out by an applied pressure of5 0 psi), due to the need to add an amount of extraction fluid equal to 2 0 times the weight of the solid phase. Charge the ZHE with sample only once and do not op en the device until the final extract (of the solid) has been collected. Repeated filling of the ZHE t o obtain 25 grams of solid is not permitted.
Do not al low the waste, the initial liquid phase, or the extract to b e exposed to the atmosphere for any more time than is absolutely necessary. Any manipulation of these materials should be done when cold (4 E C) to minimize los s of volatiles. 7.3.1 Pre-weigh the (evacuated) filtrate collection containe r (S ee Section 4.6) and set aside. If using a TEDLAR bag, express al l ® liquid from the ZHE device into the bag, whether f or the initial or final liquid /solid separation, and take an aliquot from the liquid in the ba g for an alysis. The containers listed in Section 4.6 are recommended fo r use under the conditions stated in Sections 4.6.1 - 4.6.3.

7.3.2 Placethe ZHE piston within the body of the ZHE (it may b e he lpful first to moisten the piston O-rings slightly with extractio n fluid ). Adjust the piston within the ZHE body to a height that wil l minimize the distance the piston will have to move once the ZHE is charge d 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 flang e (bottomflange) 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), we igh 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 liq uid portion of waste, after filtration, is defined as the TCL P extract. Filter enough of the sample so that the amount of filtere d liquid will support all of the volatile analyses required. For waste s containing > 0.5% dry solids (Sections 7.1.1 and/or 7.1.2), use th e percen tsolids information obtained in Section 7.1.1 to determine th e optimum sample size to charge into the ZHE. The recommended sample size is as follows: 7.3.4.1 Forwastes containing < 5% solids (see Sectio n

7.1.1), weigh out a 500 gram subsample of waste and record th e weight. 7.3.4.2 Forwastes containing >5% solids (see Sectio n 7.1.1), determine the amount of waste to charge into the ZHE a s follows:CD-ROM 1311- 16 Revision 0 July 1992 25 Weight of waste to charge ZHE = x 100 percent solids (Section 7.1.1)

Weigh o ut a subsample of the waste of the appropriate size an d record the weight. 7.3.5 If particle size reduction of the solid portion of th e was te was required in Section 7.1.3, proceed to Section 7.3.6. I f particle size reduction was not required in Section 7.1.3, proceed t o Section 7.3.7.

7.3.6 Prepare the waste for extraction by crushing, cutt ing, or grinding the solid portion of the waste to a surface area or particle siz e as described in Section 7.1.3. Wastes and appropriate reduction equipmen t shoul d be refrigerated, if possible, to 4 E C prior to particle siz e reducti on. The means used to effect particle size reduction must no t generate heat in and of itself. If reduction of the solid phase of th e waste i s necessary, exposure of the waste to the atmosphere should b e avoided to the extent possible. NOTE: Sieving of the waste is not recommended due to the possibility tha t

volatiles may be lost. The use of an appropriately graduated rule r is rec ommended as an acceptable alternative. Surface are a requ irements are meant for filamentous ( e.g. , paper, cloth) an d similarwaste materials. Actual measurement of surface area is no t recommended. Wh en the surface area or particle size has been appropriatel y altered, proceed to Section 7.3.7.

7.3.7 Waste slurries need not be allowed to stand to per mit the solid phase to settle. Do not centrifuge wastes prior to filtration.

7.3.8 Quantitativelytransfer the entire sample (liquid an d solid phases) quickly to the ZHE. Secure the filter and support screens on to the top flange of the device and secure the top flange to the ZH E body in accordance with the manufacturer's instruc tions. 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 th e top plate. NOTE: If waste material (>1% of original sample weight) has obviousl y

adhere d to the container used to transfer the sample to the ZHE , determine the weight of this residue and subtract it from th e 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 flang e) open, begin applying gentle pressure of 1-10 psi (or more if necessary) to force all headspaceCD-ROM 1311- 17 Revision 0 July 1992 slowly out of the ZHE device into a hood. At the first appearance o f liquid from the liquid inlet/outlet valve, quickly close the valve an d di scontinue pressure. If filtration of the waste at 4 E C reduces th eamount 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 th e headspace out of the device and proceed to Section 7.3.12.

7.3.9 Attach the evacuated pre-weighed filtrate collectio n contain er to the liquid inlet/outlet valve and open the valve. Begi n applyi ng gentle pressure of 1-10 psi to force the liquid phase of th e sample into the filtrate collection container. If no additional liqui d has pa ssed through the filter in any 2 minute interval, slowly increas e the pressu re in 10 psi increments to a maximum of 50 psi. After eac h incremental increase of 10 psi, if no additional liquid has passed throug h the filter in any 2 minute interval, proceed to the next 10 psi increment

. When liquid flow has ceased such that continued pr essure 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, discontinu e pressure to the piston, and disconnect and weigh the filtrate collection container. NOTE: In stantaneous application of high pressure can degrade the glas s

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, wil l

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. Ifthe original waste contained <0.5% dry solids (see Sectio n 7. 1.2), this filtrate is defined as the TCLP extract and is analyze d directly. Proceed to Section 7.3.15.

7.3.11 Th e liquid phase may now be either analyzed immediatel y (See Secti ons 7.3.13 through 7.3.15) or stored at 4 E C under minima l headspace conditions until time of analysis. Determine the weight o f 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 = 100CD-ROM 1311- 18 Revision 0 July 1992 7.3.12 The following Sections detail how to add the appropriate amount o f extraction fluid to the solid material within the ZHE an d agitation of the ZHE vessel. Extraction fluid #1 is used in all case s (See Section 5.7).

7.3.12.1 With the ZHE in the vertical p osition, attach a line from the extraction fluid reservoir to the liquid in

let/outlet valve. The line used shall contain fresh extractio n fluid and should be preflushed with fluid to eliminate any ai r pockets in the line. Release gas pressure on the ZHE piston (from th e gas inlet/outlet valve), open the liquid inlet/outlet valve , and be gin transferring extraction fluid (by pumping or simila r means) into the ZHE. Continue pumping extraction fluid into th e 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 an d disconnect the extraction fluid line. Check the ZHE to ensure that all valves ar e in their closed positions. Manually rotate the device in a n en d-over-end fashion 2 or 3 times. Reposition the ZHE in th e ve rtical 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 headspa ce (into a hood) thatmay have been introduced due to the addition of extractio n fluid. This bleeding shall be done quickly and shall be stopped a t the first appearance of liquid from the valve. Re-pressurize the ZH Ewith 5-10 psi and check all ZHE fittings to ensure that the y are closed.

7.3.12.3 Place the ZHE in the rotary ag itation 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 E C during agitation. 7.3.13 Follow ing the 18 +2 hour agitation period, check th e pressur e behind the ZHE piston by quickly opening and closing the ga s 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 soli d phases. If the waste contained an initial liquid phase, the liquid may be filtered directl y intothe same filtrate collection container ( i.e. , TEDLAR bag) holding th e ® initial liquid phase of the waste. A separate filtrate collectio n containermust be used if combining would create multiple phases, or ther e is not enough volume left within the filtrate collection container

. Filter through the glass fiber filter, using the Z HE device as discussed in Sec tion 7.3.9. All extract shall be filtered and collected if th eCD-ROM 1311- 19 Revision 0 July 1992 TEDLAR bag is used, if the extract is multiphasic, or if the wast e

® 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 materia l

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 a s the TCLP extract. If the waste contained an initial liquid phase, th e filter ed liquid material obtained from Section 7.3.13 and the initia l liquid phase (Section 7.3.9) are collectively defined as the TCLP extract

.

7.3.15 Following collection of the TCLP extract, immediatel y prepare the extract for analysis and store with minimal headspace at 4 E C until analyzed. Analyze the TCLP extract according to the appropriat e analytical methods. If the individual phases are to be analyze d sepa rately( i.e. , are not miscible), determine the volume of th e individual phases (to 0.5%), conduct the appropriate analyses, and combin e the results mathematically by using a simple volume-weighted average:

(V ) (C ) + (V ) (C ) 1 1 2 2 Final Analyte = Concentration V + V 1 2 where:
V = The volume of the first phases (L). 1 C = The concentration of the analyte of concern in the first phase (mg/L)

. 1 V = The volume of the second phase (L). 2 C = The concentration of the analyte of concern in the second phase 2 (mg/L).

7.3.16 Co mpare the analyte concentrations in the TCLP extrac t with the levels identified in the appropriate regulations. Refer t o Section 8.0 for quality assurance requirements. 8.0 QUALITY ASSURANCE 8.1 Aminimum of one blank (using the same extraction fluid as used fo r the samples) must be analyzed for every 20 extract ions that have been conducted in an extraction vessel. 8.2 Amatrix spike shall be performed for each waste type ( e.g. , wastewater treatment sludge, contaminated soil, et c.) unless the result exceeds the regulatory level and the data are being used s olely to demonstrate that the wasteproperty exceeds the regulatory level. A minimum of one matrix spike mus t be analyzed for each analytical batch. As a minimum, follow the matrix spik e addition guidance provided in each analytical method.CD-ROM 1311- 20 Revision 0 July 1992 8.2.1 Matrixspikes are to be added after filtration of the TCL P extract and before preservation. Matrix spikes sh ould not be added prior to TCLP extraction of the sample.

8.2.2 In most cases, matrix spikes should be added at a conce ntration equivalent to the corresponding regulatory level. If th e analyte concentration is less than one half the regulatory level, th e sp ike concentration may be as low as one half of the analyte concentra

tion, 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 b e added to the same nominal volume of TCLP extract as that which wa s analyzed for the unspiked sample.

8.2.3 The purp ose of the matrix spike is to monitor th e pe rformance of the analytical methods used, and to determine whethe r matri xinterferences exist. Use of other internal calibration methods , modification of the analytical methods, or use of alternate analytica l methods may be needed to accurately measure the analyte concentration in the TCLP e xtract when the recovery of the matrix spike is below th e expected analytical method performance.

8.2.4 Matrix spike recoveries are calculated by the followin g formula: %R (%Recovery) = 100 (X - X )/K s u where: X = measured value for the spiked sample, s X = measured value for the unspiked sample, and u K = known value of the spike in the sample. 8.3 All quality control measures described in the appropriate analytica l methods shall be followed. 8.4 The use of internal calibration quantitation methods shall b e employed for a metallic contaminant if: (1) Recovery of the contaminant from th e TCLP extract is not at least 50% and the concentration does not exceed th e 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 preparin g calibration standards in the sample matrix rather than reagent water o r blanksolution. It requires taking four identical aliquots of th e solution and adding known amounts of standard to t hree of these aliquots. The forth aliquot is the unknown. Preferably, the first addition should be prepared so that the resulting concentration is approximately 50% o f the expected concentration of the sample. The sec ond and third additions should be prepared so that the concentrations are approximately 100% andCD-ROM 1311- 21 Revision 0 July 1992 150% of the expected concentration of the sample. All four aliquots are main tained at the same final volume by adding reagent water or a blan k solution, and may need dilution adjustment to main tain the signals in the linearrange 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 depend antvariable (y-axis) versus concentrations of the additions o f standard as the independent variable (x-axis). Solve for the intercept o f theabscissa (the independent variable, x-axis) which is the concentratio n in the unknown.

8.4.4 Alternately, subtract the instrumental signal or external

calibration-derived concentration of the unknown (unspiked) sample fro m theinstrumental signals or external-calibration-derived concentrations o f th e standard additions. Plot or subject to linear regression of th e corrected instrument signals or external-calibration-derived concentra

tions as the dependant variable versus the independent variable. Derive concentrations for unknowns using the internal cal ibration curve as if it were an external calibration curve.

8.5 Sample s must undergo TCLP extraction within the following tim e 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 considere d minimal concentrations. Exceeding the holding time is not acceptable i n establishing that a waste does not exceed the regulatory level. Exceeding the holding time will not invalidate characterization if the waste exceeds th e regulatory level.CD-ROM 1311- 22 Revision 0 July 1992 9.0 METHOD PERFORMANCE 9.1 Ruggedness. Two ruggedness studies have been performed to determin e the effect of various perturbations on specific elements of the TCLP protocol. Rugg edness testing determines the sensitivity of small procedural variation s which might be expected to occur during routine laboratory application.

9.1.1 Metals - The following conditions were used when l eaching 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 o f the extraction fluid had the greatest impact on the results. Four of 13 metals from an API se parator sludge/electroplating waste (API/EW) mixture and two o f three metals from an ammonia lime still bottom waste were extracted a t higher levels by the more acidic buffer. Because of the sensitivity to p H changes, the method requires that the extraction fluids be prepared s o that the final pH is within +0.05 units as specified.

9.1.2 Volatile Organic Compounds - The following conditions wer e 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 psiCD-ROM 1311- 23 Revision 0 July 1992 None of the parameters had a significant effect on the results of the ruggedness test. 9.2 Precision. Many TCLP precision (reproducibility) studies have bee n performed, and have shown that, in general, the precision of the TCLP i s comparable to or exceeds that of the EP toxicity t est and that method precision is adequate. One of the more significant contributions to poor precision appear s 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 show n in Table 6 , and indicate that a single analysis of a waste may not b e adequate for waste characterization and identification requirements.

9.2.2 Semi -Volatile Organic Compounds - The results of tw o studie s are shown in Tables 7 and 8. Single laboratory precision wa s excell entwith greater than 90 percent of the results exhibiting an RS D less than 25 percent. Over 85 percent of all indi vidual compounds in the multi-labor atorystudy fell in the RSD range of 20 - 120 percent. Bot h 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 laboratorie s participated in a collaborative study of the use of the ZHE with two wast e types whi ch were fortified with a mixture of VOCs. The results of th e collaborativestudy are shown in Table 9. Precision results for VOCs ten d to occur over a considerable range. However, the range and mean RS D compared very closely to the same collaborative study metals results i nTable 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 ) ea ch laboratory showed the same pattern of recovery for each of the tw o samples. 10.0 REFERENCES 1. Blackburn, W.B. and Show, I. "Collaborative Study of the Toxicit y Characteristics Leaching Procedure (TCLP)." Draft Final Report, Contract No. 68

- 03-1958, S-Cubed, November 1986. 2. Newcome r, L.R., Blackburn, W.B., Kimmell, T.A. "Performance of th e ToxicityCharacteristic 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.CD-ROM 1311- 24 Revision 0 July 1992 Table 1. Volatile Analytes 1,2

_______________________________________________________________________ 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.CD-ROM 1311- 25 Revision 0 July 1992 Table 2. Suitable Rotary Agitation Apparatus 1

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.CD-ROM 1311- 26 Revision 0 July 1992 Table 3. Suitable Zero-Headspace Extractor Vessels 1

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. 2CD-ROM 1311- 27 Revision 0 July 1992 Table 4. Suitable Filter Holders 1

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.CD-ROM 1311- 28 Revision 0 July 1992 Table 5. Suitable Filter Media 1

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.CD-ROM 1311- 29 Revision 0 July 1992 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 2.9CD-ROM 1311- 30 Revision 0 July 1992 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 = μ g/L Extractions were performed in triplicate All results were at least 2x the detection limit Extraction Fluid #1 = pH 4.9 #2 = pH 2.9CD-ROM 1311- 31 Revision 0 July 1992 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: U nits = μ g/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 - 164CD-ROM 1311- 32 Revision 0 July 1992 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 = μ g/LCD-ROM 1311- 33 Revision 0 July 1992 Figure 1. Rotary Agitation Apparatus

Figure 2. Zero-Headspace Extractor (ZHE)CD-ROM 1311- 34 Revision 0 July 1992 METHOD 1311 TOXICITY CHARACTERISTIC LEACHATE PROCEDURECD-ROM 1311- 35 Revision 0 July 1992 METHOD 1311 (CONTINUED) TOXICITY CHARACTERISTIC LEACHATE PROCEDURE