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1、AS 4969.1220091 AS 4969.122009Australian StandardAnalysis of acid sulfate soilDried samples Methods of testMethod 12: Complete suspension peroxide oxidation combined acidity and sulfur (SPOCAS) methodPREFACEThis Standard was prepared by the Australian members of the Joint Standards Australia/Standar
2、ds New Zealand Committee EV-009, Sampling and Analysis of Soil and Biota and Working Group EV-009-02-01, Analysis of Acid Sulfate Soil.The objective of this Standard is to encompass the determination of the various components of soil acidity and/or alkalinity, depending on pH, into a combined method
3、 to streamline the process of acid base accounting. It specifies methods for the determination of pHKCl, titratable actual acidity (TAA), potassium chloride extractable sulfur (SKCl), calcium (CaKCl) and magnesium (MgKCl) in acid sulfate soil (ASS), as well as for the determination of pHOX, titratab
4、le peroxide acidity (TPA), excess acid neutralizing capacity (ANCE), peroxide sulfur (SP), calcium (CaP), magnesium (MgP) and residual acid soluble sulfur (SRAS). These results can be used to calculate titratable sulfidic acidity (TSA), reacted calcium (CaA), reacted magnesium (MgA) and peroxide oxi
5、dizable sulfur (SPOS).The term informative has been used in this Standard to define the application of the appendix to which it applies. An informative appendix is only for information and guidance.METHOD1 SCOPEThis Standard specifies a method for the determination of pH in a 1 M KCl soil suspension
6、, and, where required, titratable actual acidity (TAA) in acid sulfate soil. Following this, potassium chloride extractable sulfur (SKCl), calcium (CaKCl) and magnesium (MgKCl) are determined. On a separate test portion, peroxide pH (pHOX), titratable peroxide acidity (TPA) and excess acid neutraliz
7、ing capacity (ANCE) are determined following digestion with 30% hydrogen peroxide. Following this, peroxide sulfur (SP), calcium (CaP) and magnesium (MgP) are determined. On samples where jarosite is present, or pHKCl 4.5, residual acid soluble sulfur (SRAS) is determined on the soil residue remaini
8、ng after peroxide digestion. Standards Australia19AS 4969.122009The Standard is downloaded from Standard Sharing2 REFERENCED DOCUMENTSThe following documents are referred to in this Standard: AS1006Solid-stem general purpose thermometers2162Verification and use of volumetric apparatus2162.1Part 1:
9、GeneralVolumetric glassware2162.2Part 2: Guide to the use of piston-operated volumetric apparatus (POVA)2164Laboratory glasswareOne-mark volumetric flasks2165Laboratory glasswareBurettes2166Laboratory glasswareOne-mark pipettes2167Graduated straight pipettes4969Analysis of acid sulfate soilDried sam
10、plesMethods of Test4969.0Part 0: Introduction and definitions, symbols and acronyms4969.1Method 1: Pre-treatment of samples4969.8Method 8: Determination of hydrochloric acid extractable sulfur (SHCl), calcium (CaHCl) and magnesium (MgHCl)4969.11Method 11: Calculation of net acid-soluble sulfur (SNAS
11、), calcium (CaNAS) and magnesium (MgNAS)AS/NZS2243Safety in laboratories2243.1Part 1: Planning and operational aspects2243.2Part 2: Chemical aspects2243.8Part 8: Fume cupboardsISO3696Water for analytical laboratory useSpecification and test methods3 DEFINITIONSFor the purpose of this Standard the te
12、rms and definitions set out in AS 4969.0 apply.4 PRINCIPLEA suspension of soil in KCl solution is shaken for 4 h and allowed to stand overnight. The suspension is then briefly shaken prior to determining pH (pHKCl). If pHKCl is less than 6.5, titratable actual acidity (TAA) is determined by titratin
13、g the soil suspension to pH 6.5. After appropriate dilution of the soil suspension, potassium chloride extractable sulfur (SKCl), calcium (CaKCl) and magnesium (MgKCl) are measured by suitable analytical technique(s).A separate test portion of soil is digested with 30% hydrogen peroxide and acidity
14、is generated from the oxidation of sulfides (and organic matter where present). Following digestion, pHOX is measured on the digest solution. If the pH after peroxide digestion is greater than 6.5, a HCl titration is performed, followed by an additional peroxide digest step. This allows the calculat
15、ion of excess acid neutralizing capacity (ANCE). Titratable peroxide acidity (TPA) is then determined by titration to pH 6.5 in a KCl suspension. After appropriate dilution of the soil suspension, peroxide sulfur (SP), calcium (CaP) and magnesium (MgP) are measured by suitable analytical techniques.
16、 After appropriate washing of the soil residue, the sulfur is extracted with hydrochloric acid and the residual acid soluble sulfur (SRAS) is measured by a suitable analytical technique on samples where pHKCl 4.5, or where the presence of jarosite has been noted in the submitted sample. Standards Au
17、straliawww.standards.org.au5 REAGENTS5.1 GeneralAll reagents shall be of analytical grade (AR grade). Deionized or glass distilled water of grade 2 as defined in ISO 3696 shall be used throughout.The purity of all reagents (for sulfur, calcium and magnesium) should be verified by performing a blank
18、test. Reagents should also be tested for the presence of these elements whenever a change in source is made (e.g. brand or batch).5.2 Calibration solutions for the pH meter5.2.1 GeneralFor pH determinations, buffer solutions as specified in Clauses 5.2.2 and 5.2.3 are sufficient for calibrating the
19、pH meter. It is the responsibility of the analytical laboratory to verify the accuracy of the buffer solutions.NOTE: Commercially available buffer solutions covering a comparable pH range may be used.5.2.2 Buffer solution, pH 4.00 at 20CDissolve 10.21 g of potassium hydrogen phthalate (C8H5O4K) in w
20、ater and dilute to1000 mL at 20C.The potassium hydrogen phthalate shall be dried before use for 4 h at 105C.5.2.3 Buffer solution, pH 6.88 at 20CDissolve 3.40 g of potassium dihydrogen phosphate (KH2PO4) and 3.55 g of disodium hydrogen phosphate (Na2HPO4) in water and dilute to 1000 mL at 20C.Both s
21、alts shall be dried before use for 4 h at 105C.5.2.4 Buffer solution, pH 9.22 at 20CDissolve 3.81 g of disodium tetraborate decahydrate (Na2B4O7.10H2O) in water and dilute to 1000 mL at 20C.NOTES:1Disodium tetraborate decahydrate may lose water of crystallization when stored for a long time.2The buf
22、fer solutions as specified in Clauses 5.2.2, 5.2.3 and 5.2.4 are stable for one month when stored in polyethylene bottles.3The pH 9.22 buffer solution (5.2.4) is used when calibrating the pH meter prior to standardizing the sodium hydroxide solution (5.11) and/or when alkaline or lime-treated sample
23、s are analysed.5.3 Copper chloride solution, 400 mg Cu/L as CuCl2.2H2ODissolve 1.073 g of copper (II) chloride dihydrate (CuCl2.2H2O) in water and dilute to1000 mL at 20C.5.4 Hydrochloric acid, 20 1.16 g/mL (HCl)WARNING: CONCENTRATED HYDROCHLORIC ACID IS A CORROSIVE AGENT. AVOID CONTACT WITH SKIN AN
24、D EYES. SAFETY GLASSES AND GLOVES ANDOTHER SUITABLE PROTECTIVE CLOTHING AND FOOTWEAR SHALL BE WORN AND SHALL COMPLY WITH AS/NZS 2243, PARTS 1 AND 2.5.5 Hydrochloric acid solution, 0.5 M (Standardized)Add 50 mL of concentrated HCl (5.4) with stirring to approximately 700 mL of water. Cool to room tem
25、perature, transfer to a 1 L volumetric flask and fill to the mark with water.The Standard is downloaded from Standard SharingStandardize against disodium tetraborate decahydrate (Na2B4O7.10H2O) and calculate molarity of HCl solution (C3).Solutions made by diluting commercially available ampoules ma
26、y also be used.NOTE: The molarity (C3) of the standardized HCl solution should be used in the calculations (seeClause 12.3).5.6 Hydrochloric acid solution 4 MAdd 400 mL of hydrochloric acid (5.4) with stirring to approximately 400 mL of water. Cool to room temperature, transfer to a 1 L volumetric f
27、lask and fill to the mark with water.WARNING: HYDROCHLORIC ACID IS A CORROSIVE AGENT. AVOID CONTACT WITH SKIN AND EYES. SAFETY GLASSES, GLOVES AND OTHER SUITABLE PROTECTIVE CLOTHING AND FOOTWEAR SHALL BE WORN AND SHALL COMPLY WITH AS/NZS 2243, PARTS 1 AND 2.5.7 Hydrogen peroxide, 30% (w/w) H2O2 (bul
28、k peroxide for digestion)WARNING: HYDROGEN PEROXIDE IS A CORROSIVE OXIDIZING AGENT. CONTACT WITH COMBUSTIBLE MATERIAL MAY CAUSE FIRE. AVOID CONTACT WITH SKIN AND EYES. SAFETY GLASSES AND GLOVES AND OTHER SUITABLE PROTECTIVE CLOTHING AND FOOTWEAR SHALL BE WORN AND COMPLY WITH AS/NZS 2243, PARTS 1 AND
29、 2.5.7.1 Checking acidity of hydrogen peroxide+Hydrogen peroxide solutions (5.7) can contain appreciable acidity, especially if the pH is less than 3.5. If the pH is less than 3.5 then the acidity of the peroxide should be quantified to ascertain whether the blank is unacceptably high. Add 20 mL of
30、30% hydrogen peroxide (5.7) to 30 mL of water and note the pH. Follow the same procedure as for a sample digest, including the decomposition of peroxide with copper chloride solution and addition of KCl. Measure the pH and titrate to pH 6.5 (if required) and calculate the acidity of the blank. If th
31、e titration for the blanks yields a result in excess of the equivalent of 6 mol H /tonne, then either switch to another batch of hydrogen peroxide with lower acidity, or alternatively partially neutralize the 30% peroxide to a pH of approximately 5 with NaOH solution (5.11.2). In the latter case, re
32、peat the blank determination to ensure acceptably low acidity.5.7.2 Checking sulfur content of hydrogen peroxideAs sulfur is commonly measured in solutions following TPA determination, the sulfur content of the peroxide should be determined. Acceptable sulfur values are below0.0005%S.NOTE: Technical
33、 grade peroxides are not recommended as they are usually acid stabilized and vary considerably between bottles in both sulfur content and pH.5.8 Hydrogen peroxide H2O2 30% (w/w) (pH adjusted)NOTE: This reagent is used to oxidize ferrous ions in the final titration. This reagent is not for the digest
34、ion of samples (for which see Clause 5.7).Where pH of bulk peroxide (5.7) is less than 5.5, adjust pH to 5.5 0.1 by adding 0.05 M NaOH (5.11.2) dropwise with stirring, ensuring that this pH value remains stable thereafter.NOTE: Refer to Warning in Clause 5.7.5.9 Potassium chloride solution, 1 MDisso
35、lve 74.55 g of KCl in water, transfer to a 1 L volumetric flask and fill to the mark with water.5.10 Potassium chloride solution, 2.66 MDissolve 198.80 g of KCl in water, transfer to a 1 L volumetric flask and fill to the mark with water.5.11 Standardized sodium hydroxide (NaOH) solutionsCAUTION: SO
36、LID SODIUM HYDROXIDE IS CAUSTIC AND HYGROSCOPIC AND SHOULD BE STORED AWAY FROM WATER. DILUTE SODIUM HYDROXIDESOLUTIONSABSORBCARBONDIOXIDE.AVOID UNNECESSARY CONTACT OF THE SOLUTIONS WITH THE ATMOSPHERE.5.11.1 0.25 M NaOHDissolve 10.1 0.1 g of NaOH in water, transfer quantitatively to a 1 L volumetric
37、 flask and fill to the mark with water.Standardize against potassium hydrogen phthalate previously dried for 4 h at 105C and stored in a desiccator.The procedure shall be as follows:(a) Accurately weigh 0.25 0.05 g (6.8) of potassium hydrogen phthalate and dissolve in water.(b) Titrate (6.4) potassi
38、um hydrogen phthalate solution with NaOH solution (5.11.1) and record equivalence point volume.(c) Calculate the molarity of NaOH solution (C1).Solutions made by diluting commercially available ampoules may also be used.5.11.2 0.05 M NaOHDissolve 2.05 0.05 g of NaOH in water, transfer quantitatively
39、 to a 1 L volumetric flask and fill to the mark with water.Standardize against potassium hydrogen phthalate previously dried for 4 h at 105C and stored in a desiccator.The procedure shall be as follows:(a) Accurately weigh 0.10 0.02 g (6.8) of potassium hydrogen phthalate and dissolve in water.(b) T
40、itrate (6.4) potassium hydrogen phthalate solution with NaOH solution (5.11.2) and record equivalence point volume.(c) Calculate the molarity of NaOH solution (C2).Solutions made by diluting commercially available ampoules may also be used.NOTES:1The molarity of the standardized NaOH solutions (C1,
41、C2) should be used in the calculations(see Clause 12).2Solutions should be prepared fresh each day or alternatively may be stored in apparatus capable of excluding CO2. Solutions should be stored in high density polyethylene or borosilicate glass containers.3Absorption of CO2 changes the concentrati
42、on of NaOH solutions and decreases the extent of the reaction near the endpoint in titration of weak acids. Solutions should be standardized weekly and discarded one month after being prepared.6 APPARATUS6.1 GeneralGrade A volumetric glassware shall be used throughout. Volumetric flasks shall comply
43、 with AS 2164 and pipettes shall comply with AS 2166 and AS 2167. The use of volumetric glassware shall conform with AS 2162, Parts 1 and 2.6.2 Automatic titration instrument or pH meterWith slope adjustment and temperature control capable of measuring to an accuracy of0.01 pH units.The Standard is
44、downloaded from Standard Sharing6.3 Beaker or other containerOf at least 450 mL capacity, made of polyethylene, glass or similar inert material.6.4 BuretteA-grade, 10 mL capacity, graduated at 0.02 mL intervals, complying with Class A according to AS 2165. Alternatively, a similarly accurate digita
45、l burette, or a suitably calibrated burette from an automatic titration instrument may be used.6.5 CentrifugeCapable of centrifuging 400 mL of suspension.6.6 Dispenser (manual or automatic)Capable of accurately dispensing 80 0.5 mL.6.7 Dispenser (manual or automatic)Capable of accurately dispensing 30 0.25 mL.6.8 Electronic balance 1Capable of weighing to an accuracy of 0.0001 g.6.9 Electronic balance 2Capable of weighing to an accuracy of 0.01 g.6.10 Filter paperThick, medium speed, high retention filter paper.NOTE: Whatman No. 3 paper has been found to be suitable.6.11 FunnelMade o