Standard Methed of Test for Determining Water Soluble Chloride Ion Content in Soil AASIITO DESIGNATION T 291-94 (1996) 1. SCOPE 1A This west method Geseribes procedures for sampling and testing a soil fer chloride ion content fond is divided into wo parts, The first pant specifies rhe procedure for sampling and preparing the sample to sire for Testing. ‘The second part delineates wo lest procedures (Methoss A or B) for the determination of the water soluble hlbride ion content in soil. Twe methods are given as follows: This stan Mota’ A: (Mobi Tisation Method) (1 t0 7) 4 (810 16) Moog Bi (prey Meer Metiod) «1 to 2) © 17 to 28) 1.2. Method A is based upon the Mohr provedure for determining chloride jon with silver nitrate Method 1s utilizes a pHi Mever By comparing the mV readings 10 the ceabbration curve deterutine the chloride on content 3) The values stated in SH unis are (o be regarded ay the standard, 2, REFERENCED DOCUMENTS 21 AASHTO Standards: M92 Wire-Cleth Sieves far Testing Purposes (M231 Weighing Devices Used tn the Testing of Materia T — Sampling of Aggie- gates Reducing Sauples of Agotegate to Testing Size 22 ASTM Standards D 1129 Standard ‘Terminology Relating to Water 660 D 1193 Standard Specification for Reagent Water D 2777 Standant Practice for Determination of Proci- sion and Bias of Ap plicable Methods of Committee D-19 on Water D 3370 Pracives for Sampling Water from Closed Conduirs DEFINITIONS 3.1 For definitions ut werms ust an this west method, refer 10 Definitions D it PART 1 INITIAL PREPARATIO? 4.1 This method covers the dry preparation of soil and soilage sumples, as sozoived from the field, for use in determining the chloride content 4.2 The following applies to all specified limits ia this standrd: For the purpose of determining coaformance with these specifications, an observed value or calculated value shall he rounded off “ip the nearest uait” in the Jast tighthund place of fagares used in expressing the Tumiting value, in accor dane wilh R11, Recommended Prac: tive for Indicating Which Places af Fg: wes Ars to Le Considered Significant in Specified Limiting Valves APPARATUS. 5.1 Balance —Thebalanceshall lave suffivient capacity, he readaisleto 0.1 per ceentof the sample iass,orboler, andeon- formto the requirements of M 231 S82. Drying Appuratus—Any site be device capanle of érying samples st temperature not exceeding 6 C40" Hy 33 Sieves—A sciies of sieves of ds following sizes: 623 mam (Varin), 478 rom (No. 4), 2,09 sun (20.10) sie are 4 pan. The siave shall eoaformn to M 92 Wire-Cloth Sieves for esting Purpaes (Note 1) 54 Pulvericing Appavates—Eilhera mortar and rubber-covered peste rary device suitable for breaking up the ager gations of soil particles without edacing the size ofthe iatvidual grains (Note 2) SS Semple Sphiter—A suiiabl ni flv sampler or sample spite fo pope tional spliting of the simple ane capable oF obtaining representative postias of the sample without appreciable loss of fines. The wideh ofthe eamtainer nse 6 fees the niffle scmpler spiter shoul ke «qu W the toil combined wid of de riffle chutes. Proponicnal spitting oft sample on a canvas cloth is also per itted. NOTE 1—The sleve sizes whee hae a ‘opening size of 6.3 mm (jn) ot lange sal conform to the requirersente specifi in M 52 excluding column no. 7. This excisin ermits the eof heavier screens inotsta are frames wich are larger than the 2032 smu (8 bn) sound Frames. NOTE 2—Other types oF wppratn ae sete Jsfactory if the aggresations of soi pails sv broken up without reducing te sizeof te individual grains. SAMPLE SIZE G1 ‘The amount of soil maverial quired to perform the individual tess as follows:T201 Apex. Mas Tet Chlorides 50) 7. INECIAL PREPARATION OF TEST SAMPLES: 7.1. The sample as received fiom the field may be dried in-air or a deying appalus ol exceeding 60°C (140°F) pilor w sample selection (Now 3). A tative tox! ample of the amount repress quired to perfoom the tests shall thea bbe obtained with the sampler, oF by split ting or quartering. The agureeations of soil particles shall then be broken up ia the pulverizing appararas in such a way a to avoid reducing the mural size of the individaal pacticles NOTE 3—Samples died in an oven tier drying agpocitus at emporaure net exceeding 60? C (l40" H) are considered ‘> be alr dre. 72 The portion of the sample se lected far chforide testing shall be sep rte! into fractions by ene oF the Follow ing metods: TLL Alrernae Method Using 2.00 nun (No. 10) Sieve—The dried. sample shall be seperated into nwo fractions The fenerion retained on this sieve shall be ground with the palverizing apparatus unti the angregation af soil particles is separated into individual yrains, The ground seid shall then be seperated into two fractions using the 2.00 mm sieve. 722 Alternate Method Using 4.75 mm and 2.00 mm (No.4 ant No. 10) Siewes—The dried sample shall be septs rated inwo (wo fractions using a 475 sna Sieve, The fraction rtained on this sieve shall be ground with the palverizing ap- paratns anil the aggregation of ceil part =f is separated into mdvidual grains and ayain separated on the 4,75 mm sieve. The fraction passing the 475 mm sieve shall he mixed thorcughly and, by the use of the sampler oc by splitting and quartering, 2 representative postion adequate Jor tesing shall be obtained ‘This split portion shall then be sepa tated on the 2.00 mm sieves and pro cessed aa in Section 72.1 ‘wing a 200 mm sieve, MBSTLIODS OF SAMPLING AND TESTING 2A Altemote Method Using 63 root and 2.06 mm ("Sy ir. coud No. 19) Siewes—The dried sample shall be sep ‘red into two fructions using a 6.3 mm sieve. The fisetion retsined on this sieve shall be ground wity the pulverizing, ap- paratus until tie aggregation of soil purti= les are separated into individual grains nd agin sepsrated on the 6.3 mim sieve. The fraction passing the 6.2 uun sive shall be mixed thoronghly and, by the suse of the sempler or by spliuing and oarering, a representative portion ade- guste for esting shall be obiained. ‘This split-olf portion stull thea be separated fon the 2.00 mam sieve, and processed as in Scetion 7.2. PART 2 DETERMINATION OF WATER SOLUBLE CHLORIDE TON CONTENT BY MOUR TITRATION METHOD (Method Ay 8%. SCoPE 841 This method covers the tes pro sedare for the deieeminasion of water soluble chiotide cuntent of soils 82. Samples containing feem 10 to 150 mgrkg of chloride can he analyzed by this test med, These levels ere achieved by dilution 96 described in the est mech. 83° This standacel muy involve hee aedous materials, operations, and equip. ment, This staadsrd does not parport to address all of the safety problems assoctated wth its usa. tis the responsi bility of whucwer uses this standard to consult and establish appropriate safety and health practices and determine the applicability of regulatory Timitatens prior 10 use SUMMARY OF METHOD 9.1 This test method is based upon the Mobr procedure tor determining chloride ion with silver nitrawe. The chic Fide resets with che silver ioa before any silver chromate foans, das to the lower solubility of silver chloride, Tho po- 661 tassium chromate indiestor rencte with cexcest silver inn to form a ra silver ebiomate precipitate. The end point is the appearance ot the firs: permanent orange color Y.2. This test method is suitable for analyzing soludons with a pH between 6.0 and 85. 10. INTERFERENCES 10.1 Sulfide, bromide, iodide, thio- eyanate, cyanide, phosphate, sulle, car bone, hydroxide, and iron inerfere in this test method. Sulfide, sulfite, and thiosulfae can be removed with a perox- ide treatment, Dul usually no allemp. is made to remove bromide and iodide be- ccaase they are usually present 1m insigt= icant quautides compared to chloride, If necessary. the pll.caa be raised and the hydroxides of several metal, including ison, can be Ptoed off, un, barivin, lead and bismuth precipitate with the ehromate inliestor, IL APPARATUS TT Bret, 25 mit 12 Hotplate AL3 Magotic Stirrer and TFE- fluo rocarhon-Costed Suing ars U4 Buret. $0 mL capacity, OL aa gridations 115 Pipets. 1,5, 10,25, 30, and 80 ml 116 Beaker. 250 mL. Fflagk. 500 iL, with tubes capable ‘of holding at least 30 ml 119 Phydiion pypers covering pH 1 through L1 in | pH units, A pH meter is referable avaiable, 140 Balence—The balance shal) have sufficient capacity, bermadablet90. pereunt of the surple mess, or beter, ad ‘eenfore to the requirements of M241 pte. 12, REAGENTS A2A Parity of Revgents—Reagent [grade chernicals shall be tsed mall tests Untess otter wise indicated, ti interied ‘Dur all reagents shall conform 10 the specification of the Cammittce on Ana- lytical Reagents of the American Chen002 tal Sueiely, where such specifications are available. Other grades may be vsed, provided it i fir ascemained that the reagent is of sufficiently high purity permit tse without lessening the aceu racy of the determination 122 Mivic Acid Soluion (2 + 19}— Add | valome of HINO, (sp. oF. 1.42) 10 19 volumes of water. 123 Purity of Wexer-— Unless othet- ‘wise indented, references 10 water shall be understood « rea reagent water conforming 10 Specification D 1193, Type IIL 12.4.1 Silver nitrate solution (1 ml. of solution is equivalent to | mg of cliloride), Dissolved, 79 seams of AgNO in disilled water, Dilute to one liter. Adit one drop concentrated nitric acid (HNO} and dilate o 1 Lin a volumetric flask. The HNO, will eliminate any pre cipitation of stiver bytroxide which Would change the concentration. Stan- dandize against sodium chlocide (NaC, Store in an ambor-hrown bole to protect the solution fiom light 12.42. Silver Nitrote Solution, Stan dla feqriveters to 2-me Climh.)—For chloride concentrations slightly higher than specified in Section 12.4.1, tis is fa tiure concentrated standard. Dissolve 9.5834 g of AgNO) in approximately 700 mi. of water, Add ane drop concentrated aitie atid (HNO) aod dilute to 1 Lin a Yolumetric flask. Standardize against Sodium chloride (NaC, Store in an amberbrown bottle to protect the solu tion from light 1243 Silver Nitrore Solution, Stn land lequivelent to 5 mg Clint )-—For chloride concencrations higher than spee ificd in Section 124.2, dissolve 24.95R2 g of AgNO, in approximately 709 mi of water, Add I drop concentrated nitric acid (HNO) and dite to 1 Lin a volumetric flask. The HNOs will eliei- nate any precipiation of sliver hydroxide which would change the euneenteation, Standardize against sodium chloride (NaCl by procedure desenbed below. Store in aa amber-brown bottle protect the solution from light 128.1 Dry 2 10 6 g of high purity (oninimum 99.5 percent) sodiun: chloride rystals at 110 + SC for 1 hour and e001 in a desiccator to rou emperature. 125.2 Weigh 1.6184 g of the NeCl enptals. Transier the crystals into:a I~ L volumetrie Mask, dissolve, dute, and METHODS OF SAMPLING AND TESTING mix well. A quantity of | mL. of this solution provides 1 mg of Cl 125.2 Pipet 25 mL aliquots of NaCl solution te standardize the AgNOs sal tion (1 mg Clim) aad dilute to 100 sul ‘wth water, Mor the higher concentrations use 59 mL aliquots of the NaCl solution to standardize the AgNO, solution (2 mg Clie) and alitate 10 100 mal with water, Use 100 smb of the NaCl solution standardize the more concentrated AQNOs solution (F mg of Climly, 1254 Add | oil of 5 percent indiew tor solution (eee Section 12.6), 1 g of sodium bivurbonute powder, and titrate to the appearance of a permanent orange color preceding a red precipitate, The analyst must praciice this Liraion to be come familiar with this celor 125.5. A 0.2 mL blank can he wi lized of determine the indicator blank by substituting 1K) mL cf reagent grade water [or the sample and perform the follow (a) Check pll witha meter ifavalable, ‘or with phydrion paper If pil is in the range of 6 through 8, proceed immedi ately t0 Step 1B. If the pil is below 6: add sodium bicarbonate to adjust to the above range: if the pH is above 8, add nitric acid 9 adjust (0 the above range. (b) Add 2 drops of potassium chromate solution, (©) Titrate with siiver nitrate solution Until the iudicater begins wo tur font yellow to red (@) Trsticator blank is the volume 0 AgNO, required to the end point. Record this valve as the blank. 125.6 The tite (1) of the silver ni. trate solution is given in te follusing equation: = ie Clie nL ARNO, tequieed = Blawk 125.7 ifthe tite (1) of the solutions are not exactly 1.0, 2.0, or 3.0 mg of CL per vil AgNOs, iC may be desisable w dilute the solutions if they are too con- centrated er ald moro silver niteate if too weak, In either eae, restandurdize the resulting solation 126 Porassium or Sodium Cra mate, Indicator Soletion—Prepare a 5 percent solutien (5 g'101) mi.) and adjust, the pH 10 7.0 wilh HNO; (1 + 19) o NalICQs power deseribed in Sections 12.2 and 12.7 1291 12.7 Saito bicurboraue (NatfCOy— Power to adjust the sample pH to 6.3, 13, TEST PROCEDURE 18 Weigh 100 grams of soil int 500 mL. Eslenmeyer flask, Add 30 NL of distled water, Stopper and shake vigorously for 20 seconds, After hour sypeat shaking. Centrifuge the sample tho sample exbibis twbidity then filer the sample through a 0.48 emisron tem Wave fle. 13.2 Check pH and tate a 30 aliquot for chiorides ax follows: (2) Gheck pH with a meter if wail, or with phydrion paper. If pH i ia the tange of 6 through §, proceed immed- ately to Step 0, If the pH is below 6 cal sodium bicarbonate to adjust to the above sunge; ifthe plt is above 8, ads nitric asid to adjust to the abun rang. (hy Add deope of petassern chromate solution (6) Taeste with silver sitate salaton Until the andicator begins to turn trom yellow to ced. If the titration is over 3 ral. take 2 smaller sample so as t keep the titration under this value, Dilute a sinalie: sample (© about 50 ml. with distiled water before tating. (4) ecard me votume of AgNO) juiced wo the end paint and eae the chloride content {e) Dedset the 02 blank ofthe Bank ‘ volume as determina. in Section | 14. CALCULATIONS 14.1 Caleutate te chloride context as follows Chloride contem (mgrke) (ql. AgNOsused — BY %T ¥ 100018 where: I = titre, mg ClinL of AgNOs, and B = indicator blank, 02 or as deter mined in Section 12.5.5 S. = gf sample titrated as diluted in eps 13.L and 13.2, eg, 100 g soil _ 300 mL. water S30 ml aliquot S= WerT201 14.2 Chioriie conten’ on a moisture- foe: hasis: Determine percent moisture by drying at 110 5°C and adjust above result as Chloride content sugiky (woisiure-fice bias) — Lngfkg (as seveived) 1ODK¢1001 — percent moiszure) 18, REPORT 15.1 The chloride content vill be reported as in Section 14.2.0n a moisture- fre: tasis in milligrams per kilogram (iogrkg). This result will be reported to the nearest whole number in accordance wi BLL 16, PRECISION AND BLAS 16.1 Daa are not available at this time, DETERMINATION OF WATER SOLUBLE, CHLORIDE I0N CONTENT UTILIZING A pHimV METER (Method 1) 17. SCOPR, 171 This method covers the test procedure and apparatus forthe determi talon of water sohble catoride ion eon- tent of soils by the use of pH meter equipped with chloride ion elecuade(s). 17.2. Sampies containing feo 10 to 1000 marke of ehioride can be unalyzed by this tot method. The rnge is beeed onthe calibration eurve thats developed ote 5). 173. Thi sandaed may involve ha andous materials, operations, and equip ment, This standard does ‘not. purpor to adress all of the safety problems associated with suse. Its the respoasi- bility of whoever uses this standard to vou and establish appropriate saety snd health practices and. determine the apoticabiley of regulary limitations prior lo use METHODS Ol SAMPLING AND TESTING 18, SUMMARY OF MRTHOD, IRT This text mehod utilizes 4 pHfimV meter equipped with chloride ion selective electiode(s) This apparatus can he used diselly to measwe concente tions after the addition of mY ionic scengih adjustment busfer to sample(s) and stacdlacds, This procedure brings all solutions to the same ionic: Srengih so iat the activity eoeflivionls ae wyusl all cases. The function of the change and concentration of all ions present tivity of on ion is 4 19, INTERPERENCE 19.1 Sulfide, bromide, iodide, thio eyanate, eyanide, phosphate, salfite, Donate, hydroxide, and iron intesfexe in this test method Sulfide, sulfite, and thiosulfate can be removed with w perox. ide teaiment, but usually no attempt is made to remove bromide and iodide be- ‘euuse (hey are usually present i insigni icant quantities. compared to chloride, 2, APPARATUS 201 pHlimV Meter 20.2 Bicowodes. (a) Reference Electrode Double Junction (b) Chleride Eleerode. 20.3 Contrifoge with robes capable ‘of holding at Yeast $0) ml 204 anited in the procedure. iS Halaice—The halance shall have sufficient capacity, be readable 011 percent of the sample mass, or better, and conform co the requirements of M 2. 206 Drying Agpararus—An oven capable of drying sumnples at a tempers tue of 110 2 SC. AgIARCL Glassware, Agsoried As ree 21, REAGENTS'SOLUFIONS ZILA Purkiy of Reagenss—Reagent cals shall be used in all test. intended that all reagents shall conform to the specification of the Comaittee on Anse 663 Iytical Reagents of the American Chem cal Society, where such specifications ate available, Other grades may be used, provided it is first asceriained tht the twagenl is of sulliciently high purty 10 permait its use without lessening the acca acy of the determination, 2LAA 4M KCI Soluvion saturated with AgCl (Purchised, selerecce elee (eve intemal charnber fill solution). 2L12 1M ENO, Solution. Discolve JOLTT g of Reagent grade patassinm nitrate in deionized water and dilute 10 ‘one liter. (Reference electrode external ehamber fill solution), 2143 0.2 M_ potessivm situate (KNO3) butter. Dissolve 20.22 g of po lassium nitrate in deionized water and dilute to one liter (Note 4). NOTE 4 Otler ateongths of the bute olson may he substitied i feof the 02M butter. However, #¢ should be nord thatthe buffersoletion being substiited roast hie used to develop the calbvation curve as well as for performing the rest BLAA Potassiuns Chloride Stock So- Irion. Dry the porassinim chloride in an fovea a HO = SC for a minimum of 2 hours and allow to coo! ina desiccator hetore determining the mass, Dissolve 2.103 2 of Reagent potussiam chloride in deionized water and dilute to one liter (Note. 5). This produces a stock solution of 1000 ray. NOTE $—Ovner strengins ot sock Solus tion maybe prepared which will span the range af the materia! being tested 21.1.5 Standard Solutions. Standard solutions axe prepared by diluting. po- ‘assium chleride stock solution, 22, SAMPLE PREPARATION 2A Select a representative portion of the material passing the 2.00 mm (No, 10) sieve and dry a minimum of 12 hours. wld = 53°C. 22.2 To 100 g of the prepared soil, dé 100 mL of deionized water and aui- tate fer fifteen (15) minmes on a small pouiat shakes, If less. vigorous means of agitation is used, a longer period of time 22.3 Cenuifoge a 50 mL. portion of664 the mixture at approximately 10000 ‘min for ten (10) to fiteen (15) minutes and chen transfer 20 mL, of 25 ml. aliquot into a (00 mL beaker. If the semple is lurbid then Giller the sample trough « 01.45 micron membzune filter 28, CALIBRATION OF METER—MILIVOLT MEASUREMENT 231. Calibrawe the pHimY Merer Follow the instruction supplied with the ‘meter aud the electiodes, 24, PROCEDURE 24a Curves 24.1.1 Calibration solutions should be prepaced by serial dilution of the po. tassium chloride sack solutium. The Farge of the standards should be fiom 10 f 1000 mil. Solations of other strengths may be prepared which span the range of the material bsing tested 24.1.2. Standards and samples should be ionic strength buffered 24.1.3 Constnict a ealitration graph ‘on semi-iog payer by plotting the value Prepuration of Calibration METHODS OF SAMPLING AND TESTING. Of the concentration standards onthe Jong axis (nal.) versus the mV rendng ‘obiainedt with these standards on the: lin- car axis. (lon selective electrodes give a Jogavilirme response \o the activities oF fons rather tau to their concentrations With the audition of an ionic strength adjustment buffer, the electrodes ean be used Girectly to mensare eoncentiations oF siilivolts) 25. CHLORTE: CONCENTRATION MEASUREMENT 25.1 Transfer ao aliquot (25 mL to 40 mol) of iquid fiom the centrifugation Of the sample into a 100 mb. beaker. 25.2. Butter the sunples (or slane dards) hy the addition of an egual volume of the 0,2. M KNO) solution (1 t0 1 by volume) 25,3. Rinse electrodes with deionized water, blot off excess liquiel 25.4 Immerse electrodes inn solu- tion —stir genuly 28.5 Allow ihe electrodes to remain tn the solution vou! the meter reading slabilizes, Refer Wo the insruetions sup hed with the mnecer and the electrode(s) 25.6 After sabilizarion, read and recortl the displayed resding (ee manu factuer's cperating insirnetions), 25.7 Before removing the elec. T291 lworle(5) from the solution refer to the Ploper operating instructions. supplied ‘With the meter and eleciele(s) 50 as not to damage the moter, 258 Remove the electwsdes fiom the solution, rinse and blot dry 259° Consul the calibration exrve to ‘etemnine the concentration to which the displayed valu: in mV comespands. 26, PRECAUTIONS 264. Petiodieally check the elec trodes for any damage. 26.2. The temperature o the selution uuseel to develop the calibration curve ust be the same temperntuce as the sample being tested. 27. REPORT 27.4 Report the values (mg/kg) Wo the nearest whole umber ip usserdance with RU 28. PRECISION AND BIAS 284 Dati are not available at this