Determining Water Soluble Sulfate Ion Content in Soil 1 SCOPE, LA This lest snethod cavers the de- termination of the water soluble sulfate ion content in soil. “This standard is divided imo Uwe. pars. The fist part specifies the procedae for sampling and Preparing the sample to size for testing, The second part delineates two test pro- sedores (Methods A or B) for the deter rmination of the sulfate ion content in ils. The selection of the inethod is dependent on the concentration of sulfate jon and the accuruey desired, Two meth ads are given as follows Seuuoas Heth A, (Grasse Malu fe) & Bw 16) Hettod R (Tuubiioseaie Meth Gem 8 10 26) 1.2 Method A is a primay measure or soltate ion, Method B is less time-consuming, but often more liable 10 interference thon Method A. Itis particularly usefal in the lower sulfate range and can be uscd as 4 screening test. This method is disectiy applicable over the range of 10 10 140) mpske 1.3 The values stated in SI units are to be mgareled as the standard 2, REFERENCED DOCUMENTS 24 AASHTO Standards: M92. Wite-Cloth Sicves for ‘Testing Purposes 2 Sampling of Agere ales Reducing Samples of Aggregale to Testing Size Standard Method of Test pr AASHTO DESIGNATION T 290.95 22 ASTM Standards. 1D R59 Test Method for Silica in Water 1D 1129 Standard Terminology Relating @ Ware D 1193 Standard Specification for Reagent Water Standard Practice for Analysis of Metals, Ores, and Related Ma terials by Molecular Absorption Spec Standard Practice for Deseribing and Mew. suring Performance of Ultraviolet, Visible, and Negr-Intrars Spectrophotometers F 60 E275 3. DEPINITIONS 3.1 Vor definitions of terms used in lwse ametheds, refer Definitions Ddi28, PART 1 INITIAL PREPARATION OF TEST SAMPLES 4. SCOPE 4.1 This methed covers the dey pre- paration of soil and sosl-sggregme sam: ples, as received from the fiekL, for use in determining the sulfate ion content in soils 4,2. The following applies toall spec iffed limits in this standard: For the pur- pose of determining confonuaace with these specifications, an observed value oor calculated value shall be rounded off "to the menzost unit” in the last «ight hand place of figures used in expressing the limiting value. in accordance with R LI, Recommended Pructice for Incveat- ing Which Places of Figures Are to Be Considerea Significant in Specified Lim- iting Values, APPARATUS SAL The batance shall have sufficient capacity, be readable to 0.1 percent of the sumple mass, er better, andl conform to the requitements of M231 5.2 Drying Apparatus—Aay suita ble device eopable of drying samples at a tempesature not exceeding 60” C (140° F) 5.3. Sieves—A series ot sieves of the following sizes: 63 rm Ce in), 475 mm (No, 4), 2.00 mm (Xo. 10) and a pan. ‘The sieve shall conform 10 M92, Wire Cloth Sieves for Testing Purposes (Note 1), Pulvertzing Apparatus—tither & mortar and rubber-covered pestle or any device suitable for breaking up the aggregations of soil particles without re~ ducing the size of the individual wrains (Note 2), 55. Sumpte Splitter—A suitable sif- te sampler or sample splitter for propor- tional splitting of the sample and capaale of obtaining representative portions of the sample without appreciable loss of fines. The width of the container used to feed the siffle sampler splitter soul bo equal to the total combined width of the riffle chutes, Proportional splitting ‘of the sample on a canvas cloth is also, permitted NOTE 1—the sieve sizes whieh have an opening size af 63 mm Ch in.) oF larger shall confor tothe wequirements specified in M92 exchnding.cohimn no. 7. This exclusion. Dermity the use of neavier screens in nou. Standard frames which are larger than the 203.2 mm (& in.) round frames 55656. NOTE 2—Other types of apparatus ace satitaetory if the aggregations of sil pat cles are broken wp without reducing the size of the individual prsins. SAMPLE SIZE 6:1 ‘The amount of soil material re quired & perform the individual test is as follows Apyiox Mase “Sieve Sie Tes @ Fines ‘Tan Soles 280 200 in Wo, 10) INITIAL PREPARATION OF TEST SAMPLES 7.1 The sample as received from the field may be dried in air or a di appara not exceeding 60" © C140" F) prior to sample selection (Note. 3). A represeatative test sample of the amount required to perform the. tests shall then be obtained with the sanupler, ur by splite ting or quartering, The aggregations of soil particles shall then he broken up in the pulverizing apgaratus in such a way 4s to avoid reducing the natural size of the individual paricles. NOTE. 3—Saniplas dried Jn en oven or ober drying apparains at a temperature not exceeting 607 C (140° F) are considered 10 be air died 7.2 The portion of ue sample see lected for sulfate testing shall be sepa- rated into fractions by ore of the follow jog methods TLL Alternate Method! Using 2.00 im (No. 10) Sieve—The dried sample shall be separated into two fractions using a 2.00 mm sieve, The fraction relained on the sieve shall be ground with the palverizing apparatus until he aggregation of soil particles is separated ino individaal grains. The ground soil shall then be separated into two fractions using the 2.00) mim sieve. 722 Alernate Method Using 4.75 mm and 2.00 mm (No. 4 and No, 10) Steves—The dried sample shall first he arated into two fractions usiig a 4.73 mm seve. ‘The fraction retained on this, sieve shall be ground with a pulverizing, METHODS OF SAMPLING AND TE: Apparatus until the aggregations of soil panicles are broken iote separate grains and again separsted on the 4.75 mm sieve. The fraction passing the 4:75 mm sieve shall be mized throughly and, by the use of the sampler or by spliting ancl quartering, a represensative. portion adequate for testing shall be obtained. This spht-oif portion shall thea be sepa. rated on the 2.00 mm sieve, and pro~ cessed as in Section 7.2.1 723 Ahemare Mehod Using 6.3 tr arid 2.00. mom Cy in, and No. 10) Sieves—The dried sample shall frst be separated into two fractions using a 6.3 nm sieve, The faction retained on this sieve shall he gromd with a pulverizing apparatus until the aggregations of soil particles are broken inte separate geains ain separated on the 6.3 mm sieve. ‘The fraction passing th: 6.3 mm sieve shall be mixed thoroughly ang, by the use. of the sampler or by splitting and quastering, « representative portion ade- quate for testing shall be obtained. This split-off portion shall then be separated oon the 2.00 nnn sieve, and processed as in Section 7.2.1 PART 2 DETEI MINATION OF SULFATE CONTENT Method vimnetrie Method (Sections & to 16) 8 SCOPE 8.1. This method is atilized to dater- mine the amount of water soluble suléate ion in soil. It is directly applicahle to samples containing approximately 20 to 100 mgrks of sulfate ten, Ir can’ be ex- tended to higher of lower ranges by ad- jjustng the sample size 8.2 This stundard may involve har ardous materiale, operations, and equip- ment. This standrd does. purpon to address all Ute safety problems assoei- ated with is use, It is the responsibility Uf whoever uses this standard to consult and establish appropriate safety and health practices and determine the appli- TING 1290 cability of regulutory limitutions prior to use SUMMARY OF METHOD 9.4L Sulfate ion is precipitated and the mass determined as barium sulfate after removal of silica and other insolible matter 10. INTERFERENCES 10.1 Sulfites and suttides may a» dize and precipitate vith the sulfate, Tur. Didiiy caused by silica or other insohble nuatsrial would interfere if allowed 19 he present, but removal of such interference is provided in this method, 10.2 Other substances tend to be 0 cluded or adsorbed on the barium sulfa but these do not significantly affect Ul precision and accuracy of the mettor. 11. PURITY OF REAGENTS 11.1 Reagent grade chemicals shall be used in all tests, Unless otheriise indicated, it is intended that all reagents shall conform to the. specifications of the Committee on Analytical Re the American Chemical Society. were such specifications are available. (ther gtades may be used, provided itis first ascertained that the reagent is of sufi ciently high purity to permit is use with out lessening the accuracy of the dewrm- nation, 112 Unless otherwise indicated, re erences 10 water shall be understood 10 mean ‘Type I reagent water conforming Specification D 1193. In ataition, re agent water used for these snethods shall be sultaco-free, 12. REAGENTS 12.1 _Ammoninm Hyzdroxide Gp ar 0.90)—Concentrated ammonium hy droxide (NH,OH), 12.2. Barium Chloride Solution (100 BL} Dissolve 100 x of barium chloride2H,0) in water and dilute to 12.3 Hydwochlorie Acid (+ 9)— Mix 1 volume of hydrochloric acid (HCI, sp gt 1.19) with 9 volumes of water 124 Hydrofluoric Acid 48 to SL pereent)—Concentrated —hydroflucric acid (HF), 12.5 Methyl Orange Indicator Solo tion @5 gL)—Dissolve 005 g of rethy! orange in water and dilate to 100 mi 12.6 Nitie Acid (sp sr 14—Con- centraied nitric acid (HNO). 42.7 Pictie Acid (samraced aquecas solution), 12.8 Silver Nitrate Solution (100 giL)—Dissolve 10g of silver nitrate (AgNO,) in water and dilute to 100 mi 129° Sulfuric Acid sp gr 1.84) Concentrated sulfurie seid (HsS04) 13, TEST PROCEDURE 13.1 Weigh 100 geams of the soil sample for testing, Put the tes sample into a $00-mL. Erienmeyer flask. 13.2 Add 300 wl of uistilled water Stopper the flask and shake the mix: 43.3. Ceatrifue the sample: if the sample exhibits turbidity then fitter the sample through a 0.45 micron membrane filter. A drop of concentrated nitric acid iiay’ be added, if needed, to precipitate ncly divided suspended matter (Nate 4), 13.4 Pipet 30.0 mL, or measure a {quality of the elear sample: containing sulfate fon equivalent to 20 to 50 nig of barinm sulfate (BaSO,) into a 250 mL beaker. Adjust the volume by evapora tion, or dilution with water, to approsi- mately 21K) mL. Adjust the acidity of the sample (o the methyl ormge end point and add 10 mL excess HCl (1 +9) Mf a quantity other than 30 ml. is used, substitute the volume of the aliquot into the calculation in place of 30 mb. NOTE 4 Silica nay be removed befare applying this method by dehydrstion with FCT arperchlorie acid (HCI04) in accordance With the respective procedures in Method DD 459. Ip ehis ease, ds ignition doteribed in Seotion 13.8 weed net be dene in a platinam vrueible, METHODS OF SAMPLING AND TESTING 13.5 Measuce into the heaker a quan tity ofthe clear surnple containing sulfate jon equivalent to 20 to 50 mg of baciam sulfate (139804). Adjust the volume by evaporation o: dilution with water to approximately 200) mi. Adjust ne acid ily of dhe sample «@ Ue methyl orange end point ard add 10 mL excess of KCL ary 13.6 Heat the acidified suluion te boiling. and slowly ack to it 5 mL of hot BaCl; solution (Note 5), Keep the Temperature just below boiling until the liquid has hecome clear and the precipi tote tas settled out completely. Inno ‘case shall this settling period be less than 2 hours, NOTE. 5 Faster precipitation und a coarser precipitate ean be oliaiwed by wa 10 mb of setrated pier acid selon, boiling the sample § minus before aun Bat 137 Miler me suspension of BaSO, ‘on fine, ashless filter paper, andl wash the precipitate with hot water val ihe washings are substantially free of chlo rides, as. indicated by testing the last portion of the washings with ApNOs solution (Note 6). Avoid exeessive wash ing. If any BaSQ, passes through che filter, pour the filtrate through the paper 4 second time (Note 7) NOTE 6—Do notatierp. to obwain a com- pletely negative test for ehlersde, Discontinue washing Wea uo nore than 4 Taye apales= cence is peediced in te tet, Using a stall amount of auhless fier paper pulp in the suspension will aid in filtation wi reduce the tendency for Ra8O, to pass dies filter. the NOTE 7—If the silirate is pore threwgh the paper & second time, AgNO, must nor be present in the fate 13.8 Phee the filter paper and con- tents in a tared platinum crucible (Note 4), and cher and consume the papat slowly without Maming. Ignite the. resi- due ai approximately 800° C for 1 hour. ‘or uni iis apparent that all carbon has been consumed. 13D. Auld @ drop of H.SO, and a few ctops of HF, and evaporate under hood tn exnelsitica as silicon tetaflao- 657 ride GiF,), Reipnive at akout 800° C, coo! in a desiccator, and determine ke unass of the BaS. 14. CALCULATION 14.1 Calculate the concentration of sulfate ion (SO,) in muiligeasns per kilo gram, ax follows: Sulfate, mgike = (WX 411500) where: W= prams of BrSO, and S = grams of sample used, eg 100 g soll _ 300 mL water S$ ~ 30 ml. aliquot 10g 142. Sulfate Jon Content in soil (mgrkg moisture free) [sulfates (mgykg as determined above) % LOD(100 — percent moisture} 15, REPORT 184 Report the sulfate content as ‘computed in Section 14.2 on a moisturg> free basis in units of milligrams per kilo aim (gy). Report this vale «0 the nearest whale number inaccordance with the rounding-off method 1 16, PRECISION AND BIAS 161 Data ave wot avaiable ot thi ine Method B—Turhidimetric Methoa (Sections 17 to 26) 17, SCOPE ATA This method is intended for ‘rapid routine or control tests for he water soluble sulfate fon in soil where extreme scourncy aad precision are not required Ic is dicectly applicable over the range of 10 w 10) mgvkg of sulfate jon (SO.)658, METIIODS OF SAMPLING AND TESTING 38. SUMMARY OF METHOD 18.1 Sulfate ion is converted w a barinim sulfate suspension under con- trolled conditions. Glyecrin solution and a sodium chloride solution are adled to stabilize the suspension and minimize inerferences, The resulting turbidity 16 determined by a photoelectic colori lot OF spectrophorometer and compared toa cure prepied from standard slate solutions 19, INTERFERENCES 19.1 Insoluble suspendsd mater in the sample must be removed. Dark colors that cannot be compensated for in the proceduse ineerfere with dhe -measure- ment of suspended basium sulfate (S04) 19.2 Although other tons normally found in water do not appewr to intr the formation of the barium sulfave sus- peasion is very critical. ‘This method is more suitable as a contol prosedure ‘where concentration and type of impati lies present in the water are relatively constant, Determinations that are in doubt should he checked by Method A. in some cases, or by the procedure su gested in Note 10. 20, APPARATUS 2A Photameter—A filter photom- eter or spectrophotometer suitable tor measurements hetween 350.and 425 nm, the preferable wavelength range being 380 to 400 nm. The cell for the instru ‘ment should have a light path through the sample of woproximtely 40-mm, andl should told about 50 mL. of sample. jller pholometers and photometric prac: tices prescribed in this medod shall con- form to Recommended Practice E 60; spectrophotometers shall conform 10 Recommended Practice E 275. 21. REAGENTS PAA Bariwn Chloride Crystals of barium chloride (BaCl, ¢ 2H,0) sewened to 20- to W-mech 212 Glycerin Solution (1+ 1)— Mix I volume of glycerin with 1 volume of water, NOTE 8—A stabilizing solution contain- ing sodium earboxymathylectialose (10 art) funy be wed inal Of dhe glycerin solution, 213 Sadiwn Chloride Sofution (240 gil) —Dissolye 240 g of sodium eatorice 4NaCH in water containing 20 ml. of conventuted hydrochloric acid (ICI, sp gc 1.19), and dilue 1 L with water, Filter the solucion if turbie 214 Sulfate, Standard Solution (I mL ~ 0.100 mg 50,)—Dissolve 0.1479 g 0 athydrous sodium sulfate (NazS0.) in ‘water, aud diluie withwaterte | Lina vot lumetric flask. Standardize by the proce- dure preserihed in Section 13, 22, CALIBRATION 224 Follow the provedure given in Section 2%. ning aopropriate amounts of the stundard sulfate solorion prepared jn accordance with Seetion 21.4, and prepare a calibration curve showing sul fate ion cunteat in mg/l. plotted agains the comesponding photometer readings (Note 9). Prepare standards by diluting with ware 0.0, 2.0, 5.0, 10, 15.0, 20. 30.0, 400, and 50.0 mL of standstd sul- fue solution 10 Sin volumes in vol netic Masks. These solutions wil have sulfate ion concentrations of 00. 4.0, 10.0, 2.0, 200, 400, 600, 800, and 100.0 mg. (ppm), respectively. NOTE 9—A separate eabbration curve must be prepared for eh photometer and a now curve must be prepure if i ts neceaeary to change the eel, lap, or filer, oF if any other alterations of tastument or reagents are made. Check the curve with euch series ol Tests hy running two oF move solutions of Iexosin sulfate concentuations 23, TEST PROCEDURE 28.1 Weigh 100 g of the soil sample for testing. Put the test sample into 3 500 mL Erlenmeyer flask, T29 23.2 Add 300 mL of distilled water Stopper the flask and shake the mix. 23.3 Cenicifuge the sample: if the sample exhibits turbidity then iter Ue saunple through a 0.45 micron membrane filer. A deop of eoncentrated nite acid may be added, if needed, to precipitate finely divided suspended maner (Note 4) 23.4 Pipet into a 200 aiL beaker 50 mil. of the clear sample comtaicing be tween 0.5 anid 5 my of sulfate ion (Neve 10), Date to 80 mL wide water if we quired, und adel 10.0 ml. of lyeesin sola tion (Note 8) and 50 miL of NaCl sol. tion, iffess shan $0 mL of samples use, se the appropriate diluion factor, NOTE 10—The sohility of BuSO,issich ‘uc ifficulty may be experienced inthe deter ‘nisation of sulle eonsomtrations below about Omgfts. Thiscun be overcome by concent ing te sample or by alding 5 mL of staat sulfate solution (1 mL = D.100.mg 80.) tothe sample before dlutingto 30 mL, This will dé 05 me $0 de sample, whieh mse tracted fom the inal sul 23.5 Fill a 40 cum sample esll with sample solution, wipe it with a clean, dis cloth, and place it in the cell compact ment. Set the colorimeter tw zerw absor tunce {100 percent transmission) for ¢ blank. This compensates. for any acid insoluble mater that has not been filtered ‘oul, oF for color present. or for both, 23.6 Pour the sumple solution from the cell back into the beaker and wd, with sliring, 0.3 ¢ of BaCl; « 2H,0 crystals (Now U1), Continue gently suming the solution for €0 seconds, Let il stand fu: 4 minutes, and stir again for 15 seconds, Fill the sample cell as beferc, and imme. lately make a reading with Ue photon wer. NOTE 11—The stining shoul beat acu slant rate in all determinations. The nse of + Imugnete stir: has keen found sarstetor, fe this purpose 23.7 If imerferences ate suspected, di hue the sample with an equal volume of water, and determine the sullate emeentta bon again I the value so determine is one half thal in dhe undilated semple, iterfer ‘ences may be assumed to be absent7290 4M. CALCULATION 24.1 Convent the photometer read- ings obtained with the sample to ng sulfate ion ($04) by vse of Ue calibration curve described in Sec ton 22 Selfate Jon Content Ia Soil fingikg not corrected for moistere) 10 4 soil (ppm curve) 8 METHODS OF SAMPLING AND TLSTING: where: = grams of sample used 100 300 mL, water 50 ml. aliquot S = 16.6666 g 242. Sulfate Ton Content in Soil (ang/kg moisture flee) — [Sulfates (mgeg with moisture) 100) 1100 — percent moisture) 659 25, REPORT 25.1 Report the sulfate content as computed in Section 24.2 on a moisture free basis in units of milligram pet kilo- gram (mgykg). Report this valte ta the nearest whol: numnber in seeordanee with the rounding off method RI 26, PRECISION AND BIAS 26.1 Data are not available at this sine,