Toxicity Characteristic Leaching Procedure (TCLP) for Inorganics

Standard Operating Procedure

Soil Environmental Chemistry Program, The Ohio State University
Version 1

1.0 Scope of Method

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

2.0 Definitions

2.1 Duplicate Samples: A duplicate test involves splitting a sample two sub-samples
and processing each through the same sample preparation procedure in order to
determine the precision of the method.

2.2 Preparation Blank: The Preparation Blank is a sample that contains only the
reagents used in the extraction procedure. The preparation blanks is processed
through the same preparation procedures as the samples and therefore gives an
indication of any contamination picked up during the sample preparation process.

2.3 Matrix Spike: A duplicate sample is spiked after to the extraction procedure in order
to provide information about the effect of the sample matrix on the measurement
methodology.

2.4 ICP-AES: Inductively Coupled Plasma-Atomic Emission Spectrometry.

3.0 Equipment and Supplies

3.1 Agitation apparatus

3.2 high density polyethylene (HDPE), polypropylene (PP), or polyvinyl chloride(PVC)

extraction vessels

3.3 pH Meter accurate to 0.05 units

3.4 Laboratory Balance: Any laboratory balance accurate to within + 0.01 grams may be
used (all weight measurements are to be within + 0.1 grams).

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

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

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

3.8 Glacial acetic acid, CH3CH2OOH, ACS reagent grade.

3.9 ≥18 MΩ deionized water (DI).

 Toxicity Characteristic Leaching Procedure (TCLP) for Inorganics
Standard Operating Procedure
Soil Environmental Chemistry Program, The Ohio State University
Version 1

3.10 Parafilm

4.0 Procedure
Review SOP for handling acids (attached) prior to beginning the procedure.

4.1 Oven dry sample at 60°C.

4.2 Grind solid sample until it is capable of passing through a 9.5 mm sieve.

4.3 Determine the correct extraction solution for the sample.

4.3.1 Weigh 5g of sample into a 500 mL beaker or Erlenmeyer flask. 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. 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 °C, and hold at 50 EC for 10 minutes.
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.

4.4 Prepare appropriate extraction solution.

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.

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

4.5 Weigh 1.5g of sample into extraction vessel.

4.6 Add 30ml of extraction fluid

4.7 Close the extractor bottle tightly, secure in agitation device, and agitate for 18 ± 2
hours.

4.8 Remove from rotary agitation device and 0.45um nylon syringe filter (aprox. 12ml)
into falcon tubes for ICP analysis. Samples should be preserved <pH 2 by the
addition of 1 drop of concentrated HNO3.

5.0 Instrumental Analysis by ICP-OES

 Toxicity Characteristic Leaching Procedure (TCLP) for Inorganics
Standard Operating Procedure
Soil Environmental Chemistry Program, The Ohio State University
Version 1

5.1 Instrumentation: ICP-AES and ICP-HG-AES analysis are carried out on a Varian
Vista-MPX ICP-OES (Varian Inc., Walnut Creek, CA). Determination by ICP-MS is
done on a Perkin-Elmer Sciex ELAN 6000 (Perkin-Elmer Inc., Waltham, MA)

5.2 Stock standards are prepared using ICP grade standards (SPEX CertiPrep Group,
Metuchen, NJ, Assurance ICP Standards). Calibration standards are prepared daily
by serial dilution from at least two independent stock standards. The dilutions
should be done into a matrix comparable to the samples.

5.3 Nebulizer optimization should be performed before each calibration. Nebulizer

optimization should be carried out according to manufacturer specifications.

5.4 Instruments shall be calibrated daily and each time the instrument is set up.
Calibrate the instrument according to instrument manufacturer's recommended
procedures. At least four standards shall be used for ICP calibration. One of the
standards shall be a blank. Linear calibration must meet the criteria of: r2 = 0.995,
and calculated concentrations from the regression within 10% for each standard in
the calibration.

5.5 Initial calibration verification (ICV) is an independent certified mixed QC standard

(SPEX CertiPrep Group LPC standard 1, Fisher Cat. No. LPC-1-100N) run
immediately after instrument calibration. Standards must fall within ± 10% of
certified value. An independent standard is defined as a standard composed of the
analytes from a different source than those used in the standards for the instrument
calibration.

5.6 Continuing calibration verification (CCV) is a dilution of the ICV QC standard and is
run after every ten samples. Standards must fall within ± 10% of certified value.

5.7 Initial calibration blank (ICB) is a calibration blank run just prior to the first sample.
The calibration blank must fall below the method detection limit (MDL) detection
limit. If the calibration blank is above the MDL, the problem should be fixed and
instrument re-calibrated.

5.8 Continuing calibration blank (CCB) is a calibration blank run after every ten samples
with the CCV. The calibration blank must fall below the MDL. If a calibration blank
is above the detection limit, the instrument must be recalibrated and the previous
samples to the last CCB re-run.

5.9 Limit of quantitation (LOQ) is a check standard used to verify linearity at the MDL for
ICP analysis. The LOQ standards at a concentration equal to the MDL are
analyzed at the beginning of each sample analysis.
 Toxicity Characteristic Leaching Procedure (TCLP) for Inorganics
Standard Operating Procedure
Soil Environmental Chemistry Program, The Ohio State University
Version 1

5.10 A linear range verification check standard shall be analyzed for each wavelength
concentrations that exceed the highest calibration standard by more than 20%. The
standard shall be analyzed during the analytical run. The analytically determined
concentration of this standard shall be within 10% of the true value. This
concentration is the upper limit of the ICP linear range beyond which results cannot
be reported without dilution of the analytical sample

5.11 Potential interferences are determined by calibration of all potential lines used for
analysis followed by the analysis of single element standards as samples containing
10 to 500mg/L. Interferences were identified as a signal greater than the IDL on
any line other than the element in the standard. The single element standards
investigated included; Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na,
Ni, P, Pb, Sb, Se, Tl, V, Zn.

6.0 Quality Control

6.1 Sample Duplicates: The relative percent difference (RPD) must be no more than
20%. One sample duplicate must be run every 20 samples.

RPD = 100 x |S – D|
Avg. (S,D)

6.2 Matrix Spike: Spikes should be performed such that the end concentration is within
the linear range for the instrument. Spike recoveries for analytes of interest must
fall within the limits of 75-125%. At least one spike analyses (matrix spikes) shall be
performed on each group of samples of a similar matrix type.

6.3 Preparation Blank: If any analyte concentration is above the LOQ, in the
preparation blank, the lowest concentration of the analyte reported in associated
samples must be ≥ 10 times the preparation blank concentration. A preparation
blank must be performed with each batch of microwave digests.

7.0 Reporting

7.1 If the QC limits are not met for any element or sample, the effect on the data set will
be evaluated by the project manager and analyst.

8.0 References

8.1 United States Environmental Protection Agency. Method 1311. Toxicity

Characteristic Leaching Procedure. In SW-846; U.S. EPA: Washington, DC, 2007.
 Toxicity Characteristic Leaching Procedure (TCLP) for Inorganics
Standard Operating Procedure
Soil Environmental Chemistry Program, The Ohio State University
Version 1

8.2 United States Environmental Protection Agency. Method 6010C. Inductively

Coupled Plasma-Atomic Emission Spectrometry. In SW-846; U.S. EPA:
Washington, DC, 2007.

8.3 United States Environmental Protection Agency. Document number ILM04.0b.

Contract Laboratory Program Statement of work for inorganic analysis, multi-media,
multi-concentration. U.S. EPA: Washington, DC.