BaCl -Triethanolamine, pH 8.

2 Extraction (4B2) 2 Centrifuge (4B2b) Automatic Titrator (4B2b1) Back Titration with HCl (4B2b1a) Extractable Acidity (4B2b1a1) Air-Dry or Field-Moist, <2 mm (4B2b1a1a-b1) 1. Application The extractable acidity is the acidity released from the soil by a barium chloridetriethanolamine (BaCl2-TEA) solution buffered at pH 8.2 and includes all the acidity generated by replacement of the H and Al from permanent and pH dependent exchange sites. Extractable acidity may be measured at any pH, and a variety of methods have been used to measure it. The Soil Conservation Service adopted a pH of 8.2 because it approximates the calculated pH of a soil containing free CaCO3 in equilibrium with the normal CO2 content (0.03%) of the atmosphere. A pH of 8.2 also closely corresponds to the pH of complete neutralization of soil hydroxy-Al compounds. Although other pH values are valid for some types of soils, and the BaCl2-TEA, pH 8.2 method (4B2b1a1) may not always accurately reflect the nature of soils as they occur in the environment, this method has become a standard reference to which other methods are compared. 2. Summary of Method A soil sample is leached with a BaCl2-TEA solution buffered at pH 8.2. Sample is allowed to stand overnight, shaken, and centrifuged. The extract is back-titrated with HCl. The difference between a blank and the extract is the extractable acidity. Extractable acidity is reported in meq 100 g-1 soil or (cmol (+) kg-1). 3. Interferences No significant interferences are known to exist with this method. However, for some very acid soils, the buffer capacity of the BaCl2-TEA solution may be exceeded. 4. Safety Wear protective clothing (coats, aprons, sleeve guards, and gloves) and eye protection (face shields, goggles, or safety glasses) when preparing reagents, especially concentrated acids and bases. Dispense concentrated acids in a fume hood. Thoroughly wash hands after handling reagents. Use the safety showers and eyewash stations to dilute spilled acids and bases. Use sodium bicarbonate and water to neutralize and dilute spilled acids. 5.1 Electronic balance, 1.0-mg sensitivity 5.2 Pipettes or dispenser, adjustable volume to 40 mL 5.3 Vortexer, mini, Analog, VRW Scientific Products 5.4 Centrifuge tubes, 50-mL, polyethylene 5.5 Centrifuge, Centra, GP-8, Thermo IEC, Needham Heights, MA 5.6 Titration beakers, 250-mL, plastic, Metrohm Ltd., Brinkmann Instruments Inc. 5.7 Automatic titrator, with control unit, sample changer, and dispenser, Metrohm Ltd., Brinkmann Instruments, Inc. 5.8 Combination pH-reference electrode, Metrohm Ltd., Brinkmann Instruments, Inc. 5.9 Computer, with Titrino Workcell software, Metrohom Ltd., Brinkmann Instruments, Inc., and printer 6. Reagents 6.1 Reverse osmosis deionized (RODI) water 6.2 Hydrochloric acid (HCl), concentrated, 12 N 6.3 HCl, 0.13 N, standardized. Dilute 193 mL of concentrated HCl to 16-L volume with RODI water. 6.4 Buffer solution (0.5 N BaCl2, 0.2 N Triethanolamine (TEA), pH 8.2). Dissolve 977 g of BaCl22H2O in 8 L of RODI water. Dissolve 477 g of TEA in 4 L of RODI water. Mix two solutions and bring to nearly 16-L volume with RODI water. Adjust to pH 8.2 with 33 mL of concentrated HCl or barium hydroxide. Bring to 16-L volume with RODI water.

6.5 Replacement solution. Dissolve 977 g of BaCl22H2O in 8 L of RODI water. Add 80 mL of buffer solution and dilute to 16-L volume with RODI water. 7. Procedure Extraction of Acidity 7.1 Weigh 5 g of <2-mm or fine-grind, air-dry soil to the nearest mg and place in a centrifuge tube. If sample is moist, weigh enough soil to achieve 5 g of air-dry soil. Prepare at least two reagent blanks (no sample in tube) and one quality control check sample per 21 samples. 7.2 Add 40.00 mL of BaCl2-TEA solution to sample. Cap the tube and shake to ensure all soil is wetted. Place tube in a rack. 7.3 Place tube rack on its side and gently shake to stratify the mixture lengthwise along the tube. Allow to stand overnight on its side. 7.4 Centrifuge sample at 2000 rpm for 5 min. 7.5 Decant extract into numbered titration beakers. 7.6 Add 40 mL of replacement solution to sample. 7.7 Cap tube and use a vortexer to loosen soil. Manually shake. 7.8 Repeat Sections 7.4 7.7. 7.9 Repeat Sections 7.4 7.5. Total volume in titration beaker should be 120 mL. Titration of BaCl2-TEA Extract 7.10 Place titration beakers on automatic sample changer. 7.11 Refer to the manufacturers manual for operation of the automatic titrator. 7.12 Calibrate the titrator meter with 9.18, 7.00 and 4.00 pH buffers. Set-up the automatic titrator to sent end point mode. The Set pH parameters are listed as follows: Parameter Value Ep1 pH 4.60 Dyn change pH 1.5 units Drift 0.4 mV s-1 Time delay 10 s Drift 0.4 mV s-1 Temp 25C Stop Volume 75 mL 7.13 If pre-titration pH is 0.3 units lower than the average pH of the blanks, re-run using a 0.5-g sample. 7.14 Record the titer to the nearest 0.01 mL. Record the normality of the HCl solution. Average the titer of the reagent blanks and record. 8. Calculations Extractable acidity (meq 100 g-1) = {[(B T) x N x R]/C} x 100 where: B = Average reagent blank titer (mL) T = Sample titer (mL) N = Normality of HCl C = Sample Weight (g) 100 = Conversion factor (100-g basis) R = Air-dry/oven-dry ratio (procedure 3D1) or field-moist/oven-dry ratio (procedure 3D2) 9. Report Report extractable acidity to the nearest 0.1 meq 100 g-1 (cmol (+) kg-1). 10. Precision and Accuracy Precision and accuracy data are available from the SSL upon request. 11. References Holmgren, G.G.S., R.L. Juve, and R.C. Geschwender. 1977. A mechanically controlled variable rate leaching device. Soil Sci. Am. J. 41:1207-1208.