Determining Water Soluble Chloride Jon Content in Soi 1. SCOPE, 11 This test method describes the procedures for sampling and testing @ fol for chloride ion costent. This sian dud is divided into two parts. The first, Dar specifies the procedure for sampling and freparing the sample 10 size for testing. The second par delineates two lest procedures (Methods ot B) for the determination of the water soluble ehloride ion content in soil. Two methods 1ue given 3 follows. Seong Memos (toh Tweaon Meow) (1107) £0018 Method 8 (Hin Meter Meads 0 02) e168) 1.2 Method A is based upon the Molirprocedue for determining chionde fon with silver nsrae. Method B utilizes a pHimV Metes By comparing the mV readings to the talibravion curve determine the chloe 13 The values sted in SI units are to be regarded as the standard 2. REFERENCED DOCUMENTS 24 AASHTO Standards T2 Sampling Ageregates T 248 Reducing Field Sam- ples of Aggregate to ‘Testing Size 22. ASTM Standards D 1129 Definitions of Terms Relating to Water D 1193 Specification for Re- agent Water D 2777 Praciee for Determi pation of Precision na Siandord Method of Test for AASHTO DESIGNATION T 291-94 and Bias of Appice be Methods of Con rites D9 on Water 1D 3370 Practices for San pling Water 3. DEFINITIONS 3.1 For definisions of terms wed in this test method, refer 19 Definitions D ms, PART 1 INITIAL PREPARATION OF ‘TEST SAMPLES 4 SCOPE 4.1 This method covers the dry prep sation of soil and soil-ageregate sam Dies, as received from the field, for use Jn determining the chlonde conten, 42 The following applies to all specified limits in this standard: For the purpose of determining conformance ‘with these specifications, an observed value or calculated valve shall be rounded off “to the asazest nit” in the Jast right hand place of Figures wsed in expressing the limiting value, in accor dance with the rounding-off method R 11, Recommended Practice For Indicat- ing Which Places Of Figures Are To ‘Be Considered Signtieant In Specified Limiting. Values 5. APPARATUS S11 Bolance—The balance sal con fon to the requirements of M231, for the class of general purpose balance re: ‘uired for the principal sainple mass of {Ge sample being tested, 52 Drying Apparans—Any.suit- able device capable of drying, samples Ba temperanire not exceeding 60°C 407), 5.3. Sieves—A series of sieves of the following sizes: 63-mm Qin), 4.75 mm (No. 4), 2.00:mm (No. 10) sieve and 2 pan. The sieve shall conform to M 92, Sieves for Testing Purposes (Note 1) SA. Pulveriting Apparatue—Either a ‘momar and rubber-covered pestle or ny evioe suitable for breaking up the egere- Enlions of soil parelee without reducing {he size of the individyl grains (Note 2) SS Sample Spliter—A suitable nf fle sampler or sample splitter for propor ‘ional spliting ofthe sample and capable of obisining representative portions of {he sample without appreciable loss of fines. The width of the container used to feed the mle sumpler splitter should bbe equal to the total combined width of the me chutes. Proportional spining of the sample on 2 canvas cloth i sso permitted NOTE 1—The seve sizes which have an ‘opening sn of 63: lei) age hal ‘conforma to the requirement specified M 92 excluding column no. 7. This exchuion Deri the use of heavier screen in tow Sandu frames hich are lager than the 208.2 (8 in) ound frames NOTE 2—Other types of apprans are ‘satisfactory if the aggegaions of sel pc ‘let are broken up without reducing te sie of We inisoual pais, 6 SAMPLE SIZE 6.1. The amount of soil material re- ‘quited to perform the individual testis 25 Follow ‘Appot. Mass Sieve Sze est ©. rer Gilonses 20 2.00 ram (e, 10T2901 7. INITIAL PREPARATION OF ‘TEST SAMPLES 7A. The sample as received ftom the field may be dred in air or a deyin apparatus not exceeding 60°C (140"F) ror to sample selection (Note 3). A representative test sample ofthe amount required wo perform the tests shall thea bbe obtained with the sampler, or by spli- ting of quartering. The aggregations of soil particles shall thea be broken up in the pulverizing apparatus ia such a way 5 1 avoid reducing the narcal size of the individual particles, NOTE SSamples died in an oven or ‘tier deying appre at 3 temperature ot ceding 40°C (IAF) ae consaered 0 be birdied 12. The portion of the sample se lected for chloride testing shall be sepa ‘ted into fractions by one of the follow ing methods: "721 Alternate Method Using 2.00- ‘mm (No, 10) Sieve—The died sample ‘hall be separated into (wo factions us- ing a 200mm sieve. The fraction se tained oo this seve shall be ground wick the pulverizing apparatus unl he aggre- sation of soil pales are separated into Incvidsal grains. The ground sol shall then be separated into to fractions using the 2.00-mm sieve. 722 Alternate Method Using 4.75- rmom and 2,00-mm (No. 4 and Wo. 10) Sieves-—The deed sarople shall be sepa fated into two fracuons using a 4.75- ‘mum sieve. The faction retained on tis sieve shall be ground with the pulven ing apparatus ntl the aggregation of soil parucles ste separated into individ- tal graias and again separated on the 475-mam sieve. The fraction passing the 14.75-mm sieve shall be mixed thoroughly and, by the use of the sampler or by splitiag and quartering, a representative portion adequate fo testing sll be ob- {ained, This spli-off portion shall ten ‘be separated on the 2.00-mum sieve, and processed as in Section 7.2L. 723 Alternate Method Using 6 mom and 2.00-rmt (ein and Wo. 10) Sieves—The dried sample shall be sepa- rated into two factions using a 6.3-am sieve, The fraction retained on this sieve ‘shal be ground wih the pulverizing ap- METHODS OF SAMPLING AND TESTING paras unl the aggregation of sll parti- les are separated jo individual grains and again separated on the 6.3mm sieve ‘The fraction passing the 6.3-mm sieve shall be mixed thoroughly and, by the tse of the sampler or by spliting and (quartering, a cepresenative portion 2d=~ (uate for testing stall be obtained. This Spliff portion shall thea be separated fon the 2.00-mm sieve, and processed as in Section 72.1. PART 2 DETERMINATION OF WATER SOLUBLE C{ILORIDE ION CONTENT BY MOER ‘TITRATION METHOD (Method A) 8. SCOPE 8:1 This method covers the test pro- cedure for the determination of water Soluble chloride convent of sols. 82 Samples conaining from 10 «© 130 mprkg of cblenide can be analyzed by thie test method, These levels are achieved by dilution as desenibed in the test method. 83. This standard may involve haz- rcous materials, operations, and equip ment, This standard does not purpor, to adress all of the salery problems seeociated with suse tise responsi= bility of whoever uses this standard to consult and establish appropriate safety nd health practices and determine the applicability of yequlatory limitations prior 1 use 9, SUMMARY OF METHOD 2 This test method is based upon the Mote procedure for determining ‘hlorde on with iver nitate, The chlo fide reacts with the silver ion before any river chromate ferms, eto the lower Solubiity of silver chlonde, The po fascium chromate indicator ceaets with ‘excess silver ion 16 form a red silver ‘hyomate precipitate. The end point is the appearace of the first permanent ‘orange color ms 92 This tex method is suitable for analyzing solutions with a pH between 60 and 85. 10, INTERFERENCES 10. Sulfide, bromide. iid. thio cyanate, cyanide, phosphate, sulfite. ca- bona, hydroxide, and iz interfere in this test method. Sulfide, sulfite, and thiosulfate can be removed with a perox- fide treatment, but usually 90 attempt is ‘made 1 remove bromide and iodide be- ‘cause they are usually present in insignif- icant quantities compared to chloride. If necessary, the pH can be raised and the hhydronices of teveral metals, including iron, can be filtered off. tro, barium, lead, and bismuth precipitate with the chromate indicator. 11, APPARATUS: W. Buret,25-ml capacity 112 Horplae. 3 Magoetc Stiver and TFE-fluo- rocarboo-Coated Stirring Bars Td Burt, $0-in. capaciy, Oak gradations. HIS Pipets. 1, $. 10, 25, 30, and 0a. 116 Beaker. 250 mL, U7 Erlenmeyer ask. $00 mL. 118 Cenzifuge with tubes capable fof holding at least 50 ml. 1.9 Phydsion papers covering pH 1 through 11 in| pH units. A pH meter is preferable if available. 0 Balance—The balance shall conform to the requirements of M 231. forthe clase of general purpose balance required fo te principal sample mass of the sample being tested. 12, REAGENTS 121 Party of Reagents—Reagent grade chemicals shal be used in all tess Ealess otherwise indicated, its intended that all reagents shall conform to the specification of the Committee ou Ana- Iyuical Reagents of the American Chem cal Society, where such specifieatin tre available, Other grades may be used. provided itis fist ascertained tat the16 reagent is of sufficiently high punty to Permit is use without lessening the acu racy of the determination 122 Narc Acid Solution (J + 19)— ‘Add | volume of HNO} (sp. gf. 1.42) «© 19 volumes of water 12.3 Punty of Woer—Uniese ether: wise indicated, references 19 water shall he understood to mean reagent water conforming to Specification D 1193, Type It 124.1 Silver nitrate solution (1 mL (of Solution is equivalent to 1m of chloride. Dissolve 479 grams of AgNO, in distied water Dilute t one ites. Ads ‘one doy concenteted nic acid (HNO,) and dilve to 1 L in a volumecie Mask The HN, wil eliminate any pesipte- tion of silver hydroxide which would change ‘ye coscenvation. Standardize against sodium chloride (NaCI), Store tu an amber-bivwn bot to paotet the soluion from light 12.4.2 Silver Nutrate Solution, ton dard (equivalent to 2 mg. Clim —For chloride concesuations slighty Bipher tian specified in Section 124.1, ths is 4 more concenaed standard. Dissolve 9.5834 g of AgNO; in approximately 700 ri of water, Add one drop concentrates rune acid (HNO,) and dilute 10 1 L an 2 volumearic flask. Standardize against sodium chloriés (NaC). Store in. an smnber-brown bate to protect the sol Vion from light 1243 Silver Nive Solution, Stan dard (equivalen) to 5 mg Clint) For éhloride concentrations slightly higher than specified in Section 12.4.2, Dissolve 23.9582 g of AzNO, in approximately 7100 mL of wate. Add 1 drop concen- ated mirc acid (HNO) and dilute to 1 L in 2 volumetie flask, The IINO, will eliminate any precipitation of silver bydroxide which would change the con- centraion, Standadize against sodium chloride (NaC) by procedure describe below, Store in an amber-brown bolle 'o protect the solusn fom light. 125.1 Dry 2 0 6 g of high purity (ini 99.5 pereent) sodiam chloride fxystals at 110 = S°C for hour and ool ina desiceatr to room tempers 1252. Weigh 1.6484 p of te Nal frystals, Transfer the crystals into a 1 LL volumetric flask, dissolve, dilute, and mix well. A quanity of 1 mL, of this solution provides 1_mg of CL 125.3" Pipet 25 mL aliquots of NaCl METHODS OF SAMPLING AND TESTING. solution wo standardize the AgNO} solue ‘on (1 mg Cen.) and dilate vo 100 mL. ‘water For th: higher concentrations use $0 mi aliguols ofthe NaCl solution to standardize the AgNOs solution (2 mg CumL) and dilute to 100 ra. with water. Use 100 mL of the NaCt solution to standardize the more concenrated ABNO, solution (5 mg of CUimL), 125.4 Add I mi-of 5 pereent indice tor solution (see Section 126). 1 2 of Sodium bicarbonate powder, and titrate 'o the appearance of a permanent orange Yor preceding red. precipitate, The snalyst mst pracice this tration to be come familiar with this color. fa. blank can be ut letermine the indicator Dank by substinwting 100 mL of reagent grade ‘water fr the sample and perform the fol- lowing: (2) Check pH wih ameter if salable for with plisdnon paper If pl en the range of 6 through &, proceed immedi stely to Step B- If te pl is below 6 24d sodium bicarbonate to adjust 10 the above range; if he pH! is above 8, add nine acid to adjust to Uhe above range (0) Add 2 érops of potassium chro mate solutien, (6) Tite with silver nitate solason ‘until the indicator begins 10 tum fom, yellow to red (2) Indicator blank is the volume of ‘AgNO, requied tothe end pont, Record this value as the blank 1256 The tive (T) of te silver nie tate solution is given in the following eauation: sed Tem ial Agno, Bhak 125.7 tthe tive (1) ofthe solutions ae nat exactly 1.0, 2.0 or 5.0 mg of CL per mL AgNO, i may be desirable £0 ‘ilue the solutions if they az too con- ceniraled o° add mote silver nitrate if oo weak. In ether cate, sestandardize the resulting solution. 126 Potassium or Sodium Chro ‘mare, Indicator Soluion—Prepare a 5- percent solution (5 g/100 mL) and adjust, the pli to 7.0 with HNO, (1.+ 19) or NaHCO, powder described in Sections 127 and 122, 12.7 Sedum bicarbonate (NaHCO Powder to adjt the sainple pH to 8.3, T2091 13, TEST PROCEDURE 13.1 Weigh 100 grams of sil into 2 S0QsmL Erlenmeyer flak, Add 300 iL of aisilled water. Stopper and shake vigorously for 20 seconds. Afier hour ‘epeat shaking. Centrifuge the sample, if the sample exhibis turbidity then fer the sample through 2 0.45-micron mem- brane filter 132. Check pi and state 4 30-mL Aliquot for chlorides as follows: (2) Check pH with a meer if available, ‘oF with phydrion paper. If pH is in the range of 6 throueh 8, proceed immedi aely to Step b. If the pH is below & 6d sodium bicarbonate to adjust v0 the above range; if the pl! is above &, add ric acid to adjust to the above range. () Add 2 drops of potassium ehro- ste solution, (6) Tite with silver neat solution luna the indicator Begins 10 tar fron yellow to red, I the uration is over 30 mL. take a smaller sample so as to keep the tration under this valve. Dilute any smaller sample to about $0 mil. with disled water before tating. () Record the volume of AgNO, re (quized to tee end point and calculate the ehloride content, (} Deduct the 0.2 blank of the blank volume as determined in Section 125.5, 14. CALCULATIONS 14.1 Caleulate the chloride content 2s follows: Chloride conten (mgihg) = (amb AgNO, used ~ B) TX 1000'S ‘where: T = tive, mg Cutal of AgNO, and B = indicator blank, 0.2 oF a deter mined in Section 125.5, S = g of sample tivated as diluted in eps 13.1 and 133, e 100 g soil _ 300 mL. water 14.2 Chloride content on a moisture free basis determine percent moistre by Sénjng at 110 = S°C and adjust above result ar291 CChlorde conten mg/kg (moisture-tree basi) = ligfg (a received) x 100)(100 ~ percent moisture) 15, REPORT 15.1 The chloride content will be reported asin Secon 14.2 on a moisure fice basis in miligrams per talogram (enghkg). This renat will be tepored to the nearest whole umber in aevondance with the rounding-off method R 11 16, PRECISION AND BIAS not available at this DETERMINATION OF WATER SOLUBLE CHLORIDE ION CONTENT UTILIZING ‘A pllm¥ METER (Method B) 1. SCoPE IT This method covers the sest procedure and apparatus forthe determi ‘ation of water soluble chore ton con- tent of soils by te use of pHa meter equipped with chloride jon electrodes) 172 Samples containing from 10 to 1000 mg/kg of chloride can be analyzed by this test method. The mange is based on the calibration curve hati developed (Note 5, 173) Tals standard may involve haz- adous materials, operations, and equip- ment. This standard does aot purport to addyes all of the safety problems sssociated with suse, eis the respoasi- Dilly of whoever uses this standard to ‘consult and establish appropeiace safety and health practices and determine the applicability of regulatory limiaions 18, SUMMARY OF METHOD 18.1 This text method wilizs a pt mV meter equipped with chionde ion Selective eleetode(s). This apparats can be used dizecly to measure concenta- METHODS OF SAMPLING AND TESTING. tions after the addition of mV ionic stuength adjustment buffer to sample(s) and standards. This procedure brings all solutions 19 the same fonic strength so ‘hat the activity coeffiients are equal ia all eases. The acivity of an ion is a Tunetion ofthe change and conceatation ofall ions present 19. INTERFERENCES 19.4 Sulfide, bromige iodide, thio cyanate, cyanide, phosphate sulfite, ear- borate, aydroxide, and izom interfere ia this test method.” Sulfide, sulfite, and thiosulfate can be removed with a perox- ‘de treatment, but usually a0 atemp® i made to remove bromide and iodide be- suse they are usually present ininsigmi jean quantities cempared to chloride. 20. APPARATUS 201 pilav Meter 202 Electrodes, (a) Reference Elecuode AgiAgcl Double Junction, (@) Chlonde Electode 203. Cenuifuge with cubes eapable of holding ac least 50 mk, 2A Glassware, Aszorted—As te- quired in the procedure 205 Balance-~The balance shall conform to the requsements of M 231, for te clas of general purpose balance required for the principal sample mass ot the sample being tested, 206 Drving Appararus—~An_ oven capable of drying samples ata tempera- sure of 110 = °C 21. REAGENTSSOLUTIONS BLL Parity of Reagents—Resgent grade chemicals shall be used in all tet Unies otherwise indicated, it is intended that all veagents shall conform t0 the specification of the Committee oa Ana Iyoeal Reagents of the American Chem sal Society, where such specifications aue avalable, Other gradee may be used, provided ii first ascertained that the reagent is of sufficiently high purity to m ‘permits use without lessening the accu racy of the detennination. L114 M KCI Solation saturated with AgCT (Purchased. reference elec- ‘wode internal chamber fil soluuon) 21.12 UM KNO, Solution. Dissolve OLLI g of Reagent grade potassuis nivate in deionized water and dilute to fone liter. (Reference electrode external ‘chamber fl solution), 213 02 M potassium nivate (KNO)} butfer. Dissolve 20.29 g af po- (assum state in deionized water and due to one liter (Note 4). NOTE 4 Other scengihs of the butler solution may be subst ia lie of the 0.2 M butler Homever, i should be noted that ‘he butler solton being bated mut be ed to develop che callin curve aswell 2 foe performing the tre, 2A Potassium Chloride Stock So- lution, Dry the potassium eblonde in an ‘oven at {10 = 5°C for & minimum of {2houes and allow to cool ina desiceator before determining the mass. Disslve 2.03 g of Reagent potassium ehloi in deionized water and diate to one liter (Note 5). This produces a stock solution of 1000 mpl, NOTE $—other soenghs of sock sole Son may be prepared nth will pa the range ofthe ener being tested 2LLS Standard Solutions. Standaré solutions are prepaied by diluang po- ‘assum chloride stdek solution, 22, SAMPLE PREPARATION 221. Sclect a representative portion ofthe material passing che .00-mam (No. 10) sieve and dry a minimum of 12 hours ato = SC, 222 To 100 g of the prepared soil ‘dd 100 mi of devonized water and agi- tae for Fifteen (15) munues on a small pint shaker. If less vigorous means of Agiation i used. a longer period of time is necessary 223. Cennfuge a $0-m portion of the mixete at approximately’ 10000 «/ smn for ten (10) to fiten (15) mioutes aad then wansfer 20 ml. of 25 ma aliquot, into 2 100 mL beaker IF the sample isturbid then filter the sample through & (0.45-micron membrane filter 23, CALIBRATION OF METER—MILLIVOLT MEASUREMENT 231 Calibrate the pHim\’ Serer— Follow the insuweuon supplied ‘ith the meter and the eleewodes, 24. PROCEDURE 241 Preparation of Calibration Curves: 24.1.1 Calibration solution, should be prepared by serial diluon of the po- lassium chloride stock solution. ‘The range of the standards should be from 10 to 1000 mg/L. Soluuons of ether strengths may be prepared which span the range of the materia being tested 24.1.2 Standards and samp = shoul be ionic stength buffered. 24.13 Construct a ealibrat mn graph fon semislog paper by ploting Se valve of the coneestration stander s on the long axis (mg/L) versus the mi! reading ‘obtained wit these standards on the ln- METHODS OF SAMPLING AND TESTING ear axis, (lon selective electrodes give 3 logarithmic response to the activites of fons rather than to their concentrations With the addition of an iosie strength adjustment buffer, the eleesades can be used direc 10 measure concentrations millivolts 25. CHLORIDE, CONCENTRATION ‘MEASUREMENT 25.1 Transfer an aliguot (25 mL to 40 mL) of ligud fom the centfupation ofthe sample into 4 100-ml. beaker 252 Buffer the samples (0% stan ards) bythe addition of an equal volume of the 0.2 M KNO, soluuon (1 to 1 by volume) 253. Rinse elettodes with deionized water, blot off exces liquid. 254 Immerse electrodes into solv on—stir gently 25.5 Allow the elecuodes to remain iw the soluion until the meter reading stabilizes, Refer to the instructions sup. lied withthe meter and te elecode(s), 25.6 After takilization, read and re cord the displayed reading (see manufac turer's operaung istvetions) 25.7 Before removing the elec ‘wode(s) from the solution refer 19 the T20 proper operating instructions supplied ‘with the meter and eectrode(s) £0 8 not to damage the mete, 258 “Remove th elecwodes from the solution, rinse and blot dry. 25.8." Consul the calibration curve ro eiermine the concentration to which displayed value io mV corresponds. 26, PRECAUTIONS 261. Periodically check the elec: lwodes for any damage. 262 The temperature ofthe tolution ved to develop the calibration curve ‘ust be the same temperature as the sample being tested 27. REPORT 211. Repon the values (mg/kg) to the nearest whole number in accordance with the rounding-off method R11 28. PRECISION AND BIAS 28.1 Data is not available at this